CN102220123B - Oil displacement method for tertiary oil recovery - Google Patents
Oil displacement method for tertiary oil recovery Download PDFInfo
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- 238000011084 recovery Methods 0.000 title claims abstract description 54
- 238000011549 displacement method Methods 0.000 title abstract 3
- 239000003921 oil Substances 0.000 claims abstract description 159
- 238000006073 displacement reaction Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 30
- 125000001924 fatty-acyl group Chemical group 0.000 claims abstract description 29
- 239000010779 crude oil Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 7
- -1 carboxylate salts Chemical class 0.000 claims description 187
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 79
- 239000000203 mixture Substances 0.000 claims description 63
- 239000011435 rock Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 20
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- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
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- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 claims description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
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- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
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- 239000000178 monomer Substances 0.000 claims description 2
- TUDGMESWIBQVBE-UHFFFAOYSA-N C(C=C)(=O)NC(C[Na])CCCCCCCCCC Chemical compound C(C=C)(=O)NC(C[Na])CCCCCCCCCC TUDGMESWIBQVBE-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 18
- 239000003513 alkali Substances 0.000 abstract description 9
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- 229940051841 polyoxyethylene ether Drugs 0.000 abstract 1
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract 1
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- 238000006243 chemical reaction Methods 0.000 description 40
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- 125000002252 acyl group Chemical group 0.000 description 20
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- 239000013543 active substance Substances 0.000 description 17
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 229920006395 saturated elastomer Polymers 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 5
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- 230000006378 damage Effects 0.000 description 4
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
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- 238000011160 research Methods 0.000 description 4
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
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- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 235000019082 Osmanthus Nutrition 0.000 description 2
- 241000333181 Osmanthus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
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- MJPUBYRASAZQSX-UHFFFAOYSA-N C(CCCCCCCCC)(=O)C(CCC)(N)N Chemical compound C(CCCCCCCCC)(=O)C(CCC)(N)N MJPUBYRASAZQSX-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention relates to an oil displacement method for tertiary oil recovery, which mainly aims to solve the problems that the oil displacement agent containing surface active agents has poor oil displacement efficiency and high using concentration under the high-temperature and high-salt conditions, and corrosion and scale deposition to a stratum and an oil well, caused by alkali in the ternarycompound flooding, happen in the prior art. By the oil displacement method for tertiary oil recovery, underground dehydration crude oil is contacted with an oil displacement compound in the formationwater under the conditions that the oil displacement temperature is more than or equal to 85 DEG C, the total mineralization is more than or equal to 16000mg/L and the sum of Ca2+ and Mg2 is more than or equal to 450mg/L, so that the crude oil in a core can be fully displaced, wherein the oil displacement compound comprises the following components according to mass percentage: (1) 0.01-5.0 percent of N,N-bi fatty acyl group diamine neopentanoic acid di-polyoxyethylene ether bisulphonate; (2) 0.01-3.0 percent of polymer; (3) 92.0-99.98 percent of formation water. By adopting the technical scheme, the problems can be better solved and the method is suitable for tertiary oil recovery production in the oil field.
Description
Technical field
The present invention relates to a kind of flooding method of used for tertiary oil recovery.
Background technology
Along with socioeconomic development, people are to the continuous increase of petroleum demand amount and the minimizing of prospective oil, and oil is just becoming more and more valuable as non-renewable resource.The problem that faces has one, and imbalance between supply and demand is outstanding, and the petroleum demand amount is 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 tensio-active agent is as host or as the auxiliary agent displacement of reservoir oil, all plays immeasurable effect to increasing substantially recovery ratio.Polymer displacement of reservoir oil tech is a kind of method of important raising oil recovery, compares with general water drive, and polymer flooding can 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 polymkeric substance, tensio-active agent and alkali form has carried out some field tests in China and foreign countries, has obtained good oil displacement efficiency.But 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 polymkeric substance and tensio-active agent 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 substance 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 sulfonated petro-leum is main tensio-active agent, the 2nd, alkylbenzene sulfonate is main tensio-active agent, this two classes tensio-active agent raw material is all taken from crude oil, raw material sources are wide, quantity is large, thereby also are the tensio-active agents of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is anionic, it and the divalent cation (Ca in the local water
2+, Mg
2+Deng) can precipitate, work as Ca
2+, Mg
2+Just lose oil displacement efficiency when surpassing 300 μ g/g.For this reason, also be fit to high saliferous, high Ca in continual exploitation research abroad
2+, Mg
2+The tensio-active agent that the ion stratum is used comprises the research of multi-functional tensio-active agent, Gemini surface active agent and sacrifice agent, and pays attention to the composition research of various tensio-active agents.
The moon-nonionic amphoterics is one of focus of tertiary oil recovery (EOR) area research in recent years always, owing in its molecular structure two kinds of non-ionic groups of different nature and anionic group are designed in same surfactant molecule, make it have the advantage of negatively charged ion and nonionogenic tenside concurrently, have complementary advantages, excellent property, therefore shown good application prospect, especially the binary combination flooding 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 ultra low interfacial tension with crude oil.In recent years, because Shuangzi (Gemini) tensio-active agent 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 ultra low interfacial tension, low micelle-forming concentration, low Kraff point, good lime soap dispersing power, good a series of peculiar properties such as wettability, thereby cause great concern.Gemini tensio-active agent with interface performance and rheological is expected to replace the alkali in the ternary composite driving prescription, under rational formula system, finally realizes binary displacement system, for the chemical flooding in oil field is opened up new approach.
In the patent application at beginning of the thirties late 1920s, Degroot (De Groot) just once proposed the recovery ratio that the water soluble surfactant active helps to improve oil.
At present, the main Gemini surface active agent of domestic research and development mainly is the positively charged ion double quaternary ammonium salt type, 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 pyridyl cation Gemini surfactant.The absorption loss is large because positively charged ion has, the high in cost of production shortcoming, the in recent years research and development of anionic and non-ionic type Gemini surface active agent have also obtained increasing attention, have reported the synthetic of the asymmetric Shuangzi of a kind of negatively charged ion such as Chinese patent CN 101073757.And since aniorfic surfactant to have salt tolerance poor, and non-ionic type 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 density, such as sodium hydroxide, yellow soda ash etc., in use, to bringing huge injury in stratum and oil well etc., employed tensio-active agent is difficult for being biodegradable, and human body also there is certain hazardness, as: 1991, Zhao Guoxi was at " tensio-active agent physical chemistry " P495; 1994, disclosed content among Liu Chengzai " tensio-active agent 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 ultra low 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-displacing agent that contains tensio-active agent in the prior art exists under the high temperature and high salt condition oil displacement efficiency poor, the corrosion that alkali brings stratum and oil well in the high and ternary composite driving of working concentration and the problem of incrustation injury provide a kind of flooding method of new used for tertiary oil recovery.The method will contain N, and the two carboxylate surface active agent compositions of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-are used for oil displacement process, have alkali-free, nothing corrosion and incrustation injury, and 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 flooding method of used for tertiary oil recovery, the composition that the displacement of reservoir oil is used in displacement of reservoir oil temperature 〉=85 ℃, total mineralization 〉=16000mg/L, Ca
2++ Mg
2+Under the local 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 carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% local water;
Wherein the general molecular formula of (1) component is:
In the formula: R
1Be C
9～C
17Alkyl, R
2Be C
2～C
6Alkyl, n is the adduction number of ethoxy group EO, its span is any one integer in 2～7; M is any one metal ion that is selected from potassium, sodium or the lithium.
In the technique scheme, displacement of reservoir oil temperature is preferably 85～90 ℃; Described local water total mineralization is preferably 16000～32000mg/L, Ca
2++ Mg
2+Be preferably 450～890mg/L; Polymkeric substance is preferably from above-mentioned temperature resistant antisalt polymkeric substance; The M preferred version is potassium and sodium, and more preferably scheme is for being selected from sodium; R
1It is to have best hydrophile-lipophile balance value at 3～4 o'clock that carbon number adds ratio preferable range that 1 sum and EO count n, and its aqueous solution can form 10 with crude oil
-3～10
-4Ultra low interfacial tension; N, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
1Carbonatoms is preferably nine, 11,15 or 17, R
2Carbonatoms be preferably two, four or six.
This flooding method specifically may further comprise the steps:
(a) N, the preparation of N-two fatty acyl diamines:
Be 10～18 lipid acid with the carbochain number of required proportioning, thionyl chloride and N, N-METHYLFORMAMIDE (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 transparent liquid that obtains is the carbochain number, after adding the carbochain number and be the dilution with toluene of 10～18 lipid acid quality 1/2nd, be warming up to 60～90 ℃, be 2～6 diamines with the carbochain number by required proportioning, pyridine and consumption are that the carbochain number is that slowly to splash into the carbochain number after the toluene of 10～18 lipid 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 aftertreatment.Wherein, the carbochain number is 10～18 lipid acid, thionyl chloride and N, the mol ratio of dinethylformamide is 1: 1.0～2.0: 0.03～0.1, and the carbochain number is that 10～18 fat acyl chloride, carbochain number are that 2～6 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-are 10～18 fatty acyl diamines by after required proportioning and sodium hydroxide or potassium hydroxide, the Tetrabutyl amonium bromide catalyst mix, to add N, after the tetrahydrofuran (THF) 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 again required proportioning continued back flow reaction 6～14 hours, got the white powder solid through aftertreatment.Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl diamines, sodium chloroacetate, sodium hydroxide (potassium hydroxide) and Tetrabutyl amonium bromide=1: 2～9: 3～9: 0.02～0.07.
(c) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers 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 oxyethane are 85～160 ℃ by required proportioning in temperature of reaction; pressure is less than under the 0.80MPa gauge pressure condition; the basic cpd of calcium is catalyzer; react to get N, the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy Vinyl Ethers.Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxyethane mol ratio are 1: 4～14, and catalyst levels is N, and the two carbochain numbers of N-are 0.5～5.0% of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) quality.
(d) N, the preparation of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-:
The N that step (c) is synthesized; the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy Vinyl Ethers are by required proportioning and sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide catalyst mix; take toluene as solvent; 50～130 ℃ of temperature of reaction; reacted 3～15 hours; reaction finishes to get N by aftertreatment, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-.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 Vinyl Ethers, sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide=1: 2～6: 2～8: 0.05～0.3.
(e) with the N of aequum, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-, above-mentioned temperature resistant antisalt polymkeric substance and local water evenly mix, and stirring at room 1～3 hour obtains required composition.By percentage to the quality; N; the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-, temperature resistant antisalt polymkeric substance (form with acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamido sodium laurylsulfonate and four kinds of monomer copolymerizations of allyl group oleyl ether, its molar percentage is 76: 18: 5: 1) and the proportioning of local water be 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
(f) first take total mineralization as 16000～40000mg/L, Ca
2++ Mg
2+The local water that is 450～1000mg/L is saturated with rock core, measure the volume of voids (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 (e) with composition after, water drive is calculated the percentage ratio that improves oil recovery factor to moisture 99%.
In the technique scheme, (a) the carbochain number is 10～18 lipid 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 diamines and the mol ratio of pyridine are preferably 2.5～3.5: 1: 2～3.The temperature of reaction of preparation acyl chlorides is preferably 80～95 ℃, and the temperature of reaction 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, sodium hydroxide (potassium hydroxide) and Tetrabutyl amonium bromide 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 oxyethane mol ratio be preferably 1: 6～12, catalyst levels 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 Vinyl Ethers, sodium chloroacetate, sodium hydroxide (potassium hydroxide) and Tetrabutyl amonium bromide be preferably 1: 2.5～5.5: 3～7: 0.1～0.2; temperature of reaction is preferably 70～110 ℃, and the reaction times is preferably 5～12 hours.(e) by percentage to the quality, N, the consumption preferable range of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-is 0.03～1.0%, more preferably scope is 0.1～0.3%; Above-mentioned temperature resistant antisalt polymer loading preferable range is 0.05～0.5%; More preferably scope is 0.1～0.2%, and the reaction times is preferably 1.5～2.5 hours.(f) displacement of reservoir oil temperature is preferably 85～90 ℃; The local water total mineralization 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 carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-; owing to containing simultaneously aerobic ethene non-ionic group and carboxylate anion group in its molecular structure; make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and nonionogenic tenside; and symmetrical Shuangzi constitutional features; make it have micelle-forming concentration again low; reduce the interfacial tension ability strong; the features such as the rheological of anti-high salinity and uniqueness and visco-elasticity-viscosifying action have more good performance than conventional surfactant.Do not contain aromatic ring structure in its molecule in addition, be easier to biological degradation, therefore less to the harm of human body and environment, be a kind of green surfactant that is suitable for the used for tertiary oil recovery of high temperature and high salt oil deposit.
Adopt the flooding method of used for tertiary oil recovery of the present invention, under the alkali-free condition, can be used for 85～90 ℃ of formation temperature, 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 local water and crude oil; take consumption as 0.1～0.3wt%N; the temperature resistant antisalt polymer formation above-mentioned composition oil-displacing agent that the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-and 0.1～0.2wt% are above-mentioned; measure the dynamic interface tension value between this oil-displacing agent aqueous solution and the Shengli Oil Field victory Tuo Er district crude oil, can reach 10
-3～10
-4The ultra low interfacial tension of mN/m, can on the water drive basis, can reach 16.5% by (water drive improves oil recovery factor and reaches 41.2%) raising oil recovery factor through physical simulation displacement test Lab-evaluation at this oil-displacing agent on high temperature, the high salinity reservoir, obtain preferably technique effect.
Description of drawings
Fig. 1 is N, the infared spectrum of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-.
The N of the present invention's preparation; the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-can characterize by the following method: after synthetics is purified; use U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), be 2953cm in wave number
-1, 2919cm
-1, 2850cm
-1Methyl and the flexible characteristic peak of methylene radical C-H on the alkyl chain, 1475cm appear in the place
-1C-H flexural vibration on the alkyl chain, 1856～1505cm
-1A large broad peak, comprised the charateristic avsorption band of three kinds of vC=O, 1418cm
-1The peak is the III key band C-N stretching, extension of acid amides in the place, 1106cm
-1Locate a broad peak, this peak is that the upper C-O-C asymmetric stretch of EO bands of a spectrum cause 985cm owing to having connected EO
-1Peak disappear, this peak usually associates relevantly with terminal hydroxyl, proved response has generated N really thus, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
(a) two 12 (bay) acyl group quadrol is synthetic
With lauric acid 300 grams (1.5 moles), sulfur oxychloride 267.8 grams (2.25 moles) and 4.5 gram DMF, add and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong etc., in 90 ℃ the reaction 3 hours after, decompression steams excessive thionyl chloride, obtains lauroyl chloride.When temperature is down to 60 ℃, add dry toluene 150 grams, after stirring, slowly drip the mixed solution that is formed 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 lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic
Bimonthly osmanthus acyl group quadrol 200 grams (0.47 mole) that step (a) is synthetic, 400 gram tetrahydrofuran (THF)s, 112.8 gram (2.82 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly minute five adding total amounts are the sodium chloroacetate solid of 219.0 grams (1.88 moles) after the cooling, keep back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-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 the distilled water wash solid.
(c) N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-synthetic
With the synthetic N of step (b); the basic cpd of two lauroyl ethylenediamine-N,N'-diacetic acid(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 works, whipping appts and gas distributor; when limit logical nitrogen limit heating is made 135 ℃; add 20 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, then uses nitrogen purging 3～4 times, the system temperature of reaction is transferred to 140 ℃ slowly pass into 107.6 gram (2.444 moles) oxyethane, control pressure≤0.60MPa.Reaction is used the nitrogen purging system after finishing, and neutralization after the cooling, dehydration get N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-268.5 grams, molar yield 98.5%.
(d) N, the two two carboxylate salts of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-synthetic
The N that step (c) is synthesized; the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-268.5 grams (0.30 mole) and 101.1 gram (1.80 moles) potassium hydroxide, 139.8 gram (1.20 moles) sodium chloroacetates, 10.8 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of thermometer and reflux condensing tube, to be heated to 90 ℃ of reactions 8 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, two carboxylate salts 276.0 grams of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-, molar yield is 87.3%.To synthetic N, the two two carboxylate salts of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two two carboxylate salt 0.15wt% of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory local 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 ultra low interfacial tension that forms 0.0023mN/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.
(f) first with salinity 32000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the local water of 890mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (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 85 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 41.0%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (e) with composition after, water drive records on the water drive basis and can improve oil recovery factor 16.2% again to moisture 99%.
[embodiment 2]
(a) two 12 (bay) acyl group hexanediamine is synthetic
With [embodiment 1] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexanediamine 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 lauroyl hexanediamine oxalic acid of N-synthetic
Bimonthly osmanthus acyl group hexanediamine 225.6 grams (0.47 mole) that step (a) is synthetic, 450 gram tetrahydrofuran (THF)s, 105.3 gram (1.88 moles) potassium hydroxide and 4.5 gram Tetrabutyl amonium bromides; add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to the backflow quaternization 3 hours.Slightly minute five adding total amounts are the sodium chloroacetate solid of 164.3 grams (1.41 moles) after the cooling, keep back flow reaction 9 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-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 the distilled water wash solid.
(c) N, the two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic
With [embodiment 1] (c); difference is with the N of 171.4 grams (0.288 mole); the two lauroyl hexanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 76.0g (1.728 moles); the usage quantity of the basic cpd of calcium is 4.3 grams; get N, the two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-240.7 grams, molar yield 97.2%.
(d) N, the two two carboxylate salts of lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic
The N that step (c) is synthesized; the two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-240.7 grams (0.28 mole) and 62.8 gram (1.12 moles) potassium hydroxide, 139.8 gram (1.20 moles) sodium chloroacetates, 10.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 6 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, two carboxylate salts 248.1 grams of the two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-, molar yield is 86.7%.To synthetic N, the two two carboxylate salts of lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two two carboxylate salt 0.2wt% of lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 96.5wt% Shengli Oil Field win Tuo Er district victory local 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 15.2mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.003mN/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.
(f) first with salinity 24000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the local water of 667mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 51.1%, 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 90 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 41.1%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (e) with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.9% 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) lauric acid 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 decanoyl butanediamine 186.1 grams (0.47 mole) that step (a) is synthetic, 400 gram tetrahydrofuran (THF)s, 112.8 gram (2.82 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to the backflow quaternization 3 hours.Slightly minute five adding total amounts are the sodium chloroacetate solid of 219.0 grams (1.88 moles) after the cooling, keep back flow reaction 12 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-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 the distilled water wash solid.
(c) N, two ten acyl group butanediamine oxalic acid, the two polyoxy Vinyl Ethers (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 usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 78.6g (1.788 moles); the usage quantity of the basic cpd of calcium is 3.8 grams; get N, the two ten acyl group butanediamine oxalic acid of N-two polyoxy Vinyl Ethers (n=3) 225.5 grams, molar yield 97.5%.
(d) N, the two two carboxylate salts of ten acyl group butanediamine oxalic acid, two polyoxy Vinyl Ethers (n=3) of N-synthetic
The N that step (c) is synthesized; the two ten acyl group butanediamine oxalic acid of N-two polyoxy Vinyl Ethers (n=3) 225.5 grams (0.29 mole) and 65.1 gram (1.16 moles) potassium hydroxide, 101.4 gram (0.87 mole) sodium chloroacetates, 12.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of thermometer and reflux condensing tube, to be heated to 80 ℃ of reactions 8 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, two carboxylate salts 231.2 grams of two ten acyl group butanediamine oxalic acid, the two polyoxy Vinyl Ethers (n=3) of N-, molar yield is 85.0%.To synthetic N, the two two carboxylate salts of ten acyl group butanediamine oxalic acid, two polyoxy Vinyl Ethers (n=3) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two two carboxylate salt 0.15wt% of ten acyl group butanediamine oxalic acid, two polyoxy Vinyl Ethers (n=3) of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory local 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 14.9mPa.s; Said composition and Shengli Oil Field win the ultra low 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.
(f) first with salinity 32000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the local water of 890mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (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 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 (e) with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.3% again to moisture 99%.
[embodiment 4]
(a) two 16 (palm) acyl group quadrol is synthetic
With palmitinic acid 320 grams (1.25 moles), sulfur oxychloride 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, prolong etc., in 80 ℃ the reaction 5 hours after, decompression steams excessive thionyl chloride, obtains palmityl chloride.When temperature is down to 60 ℃, add dry toluene 160 grams, after stirring, slowly drip the mixed solution that is formed 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 palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic
Two palmitoyl quadrols 251.9 grams (0.47 mole) that step (a) is synthetic, 504 gram tetrahydrofuran (THF)s, 94.0 gram (2.35 moles) sodium hydroxide and 6.0 gram Tetrabutyl amonium bromides; add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to the backflow quaternization 6 hours.Slightly minute five adding total amounts are the sodium chloroacetate solid of 164.3 grams (1.41 moles) after the cooling, keep back flow reaction 12 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-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 the distilled water wash solid.
(c) N, the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (c); difference is with the N of 190.9 grams (0.293 mole); the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-substitute 165.0 gram (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 128.9g (2.93 moles); the usage quantity of the basic cpd of calcium is 3.8 grams; get N, the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-304.9 grams, molar yield 95.3%.
(d) N, the two two carboxylate salts of palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-synthetic
The N that step (c) is synthesized; the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-304.9 grams (0.28 mole) and 67.0 gram (1.68 moles) sodium hydroxide, 130.5 gram (1.12 moles) sodium chloroacetates, 11.5 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 8 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, two carboxylate salts 298.5 grams of the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-, molar yield is 85.0%.To synthetic N, the two two carboxylate salts of ten acyl group butanediamine oxalic acid, two polyoxy Vinyl Ethers (n=5) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two two carboxylate salt 0.1wt% of ten acyl group butanediamine oxalic acid, two polyoxy Vinyl Ethers (n=5) of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.2wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory local 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 16.5mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0047mN/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.
(f) first with salinity 16000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the local water of 450mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 51.9%, 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 (e) 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) 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 palmitoyl butanediamine oxalic acid of N-synthetic
Two palmitoyl butanediamine 265.1 grams (0.47 mole) that step (a) is synthetic, 530 gram tetrahydrofuran (THF)s, 112.8 gram (2.82 moles) sodium hydroxide and 9.0 gram Tetrabutyl amonium bromides; add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to the backflow quaternization 6 hours.Slightly minute five adding total amounts are the sodium chloroacetate solid of 328.5 grams (2.82 moles) after the cooling, keep back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-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 the distilled water wash solid.
(c) N, the two palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With [embodiment 1] (c); difference is with the N of 195.6 grams (0.288 mole); the two palmitoyl butanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 101.4g (2.304 moles); get N; the two palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-282.1 grams, molar yield 94.9%.
(d) N, the two two carboxylate salts of palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
The N that step (c) is synthesized; the two palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-282.1 grams (0.27 mole) and 66.1 gram (1.65 moles) sodium hydroxide, 110.7 gram (0.95 mole) sodium chloroacetates, 12.8 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 10 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, two carboxylate salts 264.0 grams of the two palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-, molar yield is 81.9%.To synthetic N, the two two carboxylate salts of palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two two carboxylate salt 0.25wt% of palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 96.0wt% Shengli Oil Field win Tuo Er district victory local 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 14.7mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0066mN/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.
(f) first with salinity 24000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the local water of 667mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 52.3%, 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 90 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 41.2%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (e) with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.3% again to moisture 99%.
[embodiment 6]
(a) two 18 (tristearin) acyl group quadrol is synthetic
With stearic acid 497 grams (1.75 moles), sulfur oxychloride 374.9 grams (3.15 moles) and 7.5 gram DMF, add and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong etc., in 95 ℃ the reaction 3 hours after, decompression steams excessive thionyl chloride, obtains stearyl chloride.When temperature is down to 60 ℃, add dry toluene 249 grams, after stirring, slowly drip the mixed solution that is formed 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 stearoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic
Stearic bicine diester base quadrol 278.2 grams (0.47 mole) that step (a) is synthetic, 556.4 gram tetrahydrofuran (THF)s, 112.8 gram (2.82 moles) sodium hydroxide and 6.0 gram Tetrabutyl amonium bromides; add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly minute five adding total amounts are the sodium chloroacetate solid of 328.5 grams (2.82 moles) after the cooling, keep back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-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 the distilled water wash solid.
(c) N, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-synthetic
With [embodiment 1] (c); difference is with the N of 184.0 grams (0.260 mole); the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-substitute 165.0 gram (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 137.8g (3.132 moles); the usage quantity of the basic cpd of calcium is 2.9 grams; get N, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-300.8 grams, molar yield 93.6%.
(d) N, the two two carboxylate salts of stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-synthetic
The N that step (c) is synthesized; the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-300.8 grams (0.24 mole) and 80.8 gram (1.44 moles) potassium hydroxide, 139.8 gram (1.2 moles) sodium chloroacetates, 15.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, two carboxylate salts 271.8 grams of the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-, molar yield is 81.0%.To synthetic N, the two two carboxylate salts of stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two two carboxylate salt 0.2wt% of stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.1wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory local 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 16.2mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0056mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
(f) first with salinity 32000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the local water of 890mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (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 40.6%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (e) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.5% again to moisture 99%.
[embodiment 7]
(a) two 18 (tristearin) acyl group hexanediamine is synthetic
With [embodiment 6] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexanediamine 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 stearoyl hexanediamine oxalic acid of N-synthetic
Stearic bicine diester base hexanediamine 304.6 grams (0.47 mole) that step (a) is synthetic, 609 gram tetrahydrofuran (THF)s, 210.6 gram (3.76 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly the sodium chloroacetate solid of minute five adding total amount 438.0 grams (3.76 moles) after the cooling kept back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-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 the distilled water wash solid.
(c) N, the two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (c); difference is with the N of 185.6 grams (0.243 mole); the two stearoyl hexanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 106.9g (2.43 moles); the usage quantity of the basic cpd of calcium is 3.0 grams; get N, the two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-271.2 grams, molar yield 92.7%.
(d) N, the two two carboxylate salts of stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
The N that step (c) is synthesized; the two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-271.2 grams (0.23 mole) and 90.3 gram (1.61 moles) potassium hydroxide, 134.0 gram (1.15 moles) sodium chloroacetates, 15.0 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, two carboxylate salts 246.6 grams of the two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-, molar yield is 78.5%.To synthetic N, the two two carboxylate salts of stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two two carboxylate salt 0.15wt% of stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory local 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 15.9mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0012mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
(f) first with salinity 16000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the local water of 450mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (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 40.0%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (e) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.7% again to moisture 99%.
[comparative example 1]
With [embodiment 1] (e); difference substitutes 0.15wt%N with the petroleum sodium sulfonate (Wuxi refinery) of 0.15wt%; the two two carboxylate salts of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) 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] (f), record water drive and improve oil recovery factor 40.7%, 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] (e), difference substitutes the above-mentioned temperature resistant antisalt polymkeric substance of 0.15wt% take the super high molecular weight polyacrylamide (viscosity-average molecular weight 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 0.0586mN/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] (f), record water drive and improve oil recovery factor 40.9%, 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 9.5%.
Claims (6)
1. the flooding method of a used for tertiary oil recovery, the composition that the displacement of reservoir oil is used in displacement of reservoir oil temperature 〉=85 ℃, total mineralization 〉=16000mg/L, Ca
2++ Mg
2+Under the local 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 carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% local water;
Wherein the general molecular formula of (1) component is:
In the formula: R
1Be C
9～C
17Alkyl, R
2Be C
2～C
6Alkyl, n is the adduction number of ethoxy group EO, its span is any one integer in 2～7; M is any one metal ion that is selected from potassium, sodium or the lithium;
Wherein the polymkeric substance described in (2) is formed by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of allyl group oleyl ether, and its molar percentage is 76: 18: 5: 1.
2. the flooding method of used for tertiary oil recovery according to claim 1 is characterized in that described displacement of reservoir oil temperature is 85～95 ℃.
3. the flooding method of used for tertiary oil recovery according to claim 1, the total mineralization that it is characterized in that described local water is 16000～40000mg/L, Ca
2++ Mg
2+Be 450～1000mg/L.
4. the flooding method of used for tertiary oil recovery according to claim 1 is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
1Carbonatoms is nine, 11,13,15 or 17.
5. the flooding method of used for tertiary oil recovery according to claim 1 is characterized in that described N, and the carbonatoms of the R2 in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-is two, four or six.
6. the flooding method of used for tertiary oil recovery according to claim 1 is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
1Carbon number adds 1 sum and the EO adduction is counted the ratio of n between 2～4.
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| CN102373044B (en) * | 2010-08-23 | 2013-07-31 | 中国石油化工股份有限公司 | Oil displacement method suitable for MgCl2 water-type oil displacement agent |
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| CN101070468A (en) * | 2007-05-21 | 2007-11-14 | 孙安顺 | Surfactant and for mula system in oil-production process |
| CN101549266A (en) * | 2009-04-13 | 2009-10-07 | 江南大学 | Preparation of surfactant of double long-chain alkyl lycine and applications thereof |
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