CN105368427A - Anionic surfactant and preparing method thereof - Google Patents
Anionic surfactant and preparing method thereof Download PDFInfo
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- CN105368427A CN105368427A CN201410428241.6A CN201410428241A CN105368427A CN 105368427 A CN105368427 A CN 105368427A CN 201410428241 A CN201410428241 A CN 201410428241A CN 105368427 A CN105368427 A CN 105368427A
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Abstract
The invention relates to an anionic surfactant. The anionic surfactant mainly solves the problems that a surfactant serving as an oil-displacing agent system component in the prior art is poor in adaptability to oil reservoir and poor in high temperature resistance and salt resistance. By the adoption of the anionic surfactant with a molecule general formula (see the formula in the description), R1 is an aliphatic group of C8-C30, or an aryl group substituted by a saturated and unsaturated alkyl group of a linear chain or a branched chain of C4-C20, R2 is an alkylidene group or a hydroxyl substituted alkylidene group of C1-C5, Y is COOM or SO3N, M and N are independently selected from hydrogen, alkali metal or at least one of radial groups shown as the formula NR3(R4)(R5)(R6), R3, R4, R5 and R6 are independently selected from one of H, (CH2)pOH or (CH2)qCH3, p is any integer from 2 to 4, and q is any integer from 0 to 5. According to the technical scheme, the problems are well solved, and the anionic surfactant can be applied to production of increasing the producible oil index of an oil field. R1O(CH2CH2O)m1(CH(CH3)CH2O)n(CH2CH2O)m2R2Y.
Description
Technical field
The present invention relates to a kind of anion surfactant and preparation method.
Background technology
Recovery efficiency technique is improved, i.e., the external reinforcing (EOR) being often referred to and improvement (IOR) recovery efficiency technique can be summarized as six aspects such as improving ecology, chemical flooding, heavy crude heat extraction, gas drive, microbe oil production and Physical oil recovery.At present, the raising recovery efficiency technique applied into mining site scale concentrates on thermal recovery, gas drive and chemical flooding three major types, and wherein chemical flooding yield is 5.18 × 104m3/ more than d, accounts for the 14.7% of world's EOR total outputs.Chemical flooding is by adding chemical agent in the aqueous solution, change injection fluid physicochemical properties and rheological property and with the interaction characteristic of reservoir rock and improve a kind of enhancements of recovery ratio, fast development is able in China, its main cause is that China's reservoir is stronger for continental deposit anisotropism, terrestrial origin of petroleum viscosity of crude is higher, more suitable for chemical flooding in EOR methods.
It is different according to the chemical composition of surfactant and molecular structure, surfactant can be divided into ionic and the major class of nonionic two.In current tertiary oil recovery research the species of surfactant used with anionic at most, next to that nonionic and amphoteric ion type, using it is minimum be cationic.Patent US3927716, US4018281, US4216097 of Mobil Oil Corporation are reported using caustic flooding, surfactant or caustic flooding and the result using the zwitterionic surfactant displacement of reservoir oil in succession, the zwitterionic surfactant used for different chain length carboxylic acid or sulfonate type beet alkali surface activator, in total 62000~160000mg/L of mineralising, in 1500~18000mg/L of calcium ions and magnesium ions simulation salt solution, to the interfacial tension of Texas Southern crude oil up to 10-1~10-4mN/m.The patent US4370243 of Mobil Oil Corporation is reported using oil-soluble alcohol, the oil displacement system of sulphonic acid betaine and quaternary ammonium salt composition, the system can both play a part of surfactant, it may also function as the effect of mobility control agent, wherein quaternary ammonium salt is the cationic surfactant of lipophilic group carbochain a length of 16~20, oil displacement agent is used as using 2wt% octadecyl dihydroxy ethyl propyl sulfonic acid betaine salt and 1.0% n-hexyl alcohol, inject after 1.9PV, crude oil 100% can be displaced, but surfactant adsorption loss is larger to reach 6mg/g, 2.0% tetraethylammonium bromide of relative low price is added on this basis as sacrifice agent to reduce surfactant adsorption amount.The patent US8211837 of Texas ,Usa university application, report the linear alcohol long carbon alcohol that catalytic dimerization reaction is branched at high temperature using cheap and simple, with carrying out sulfuric acid esterification after expoxy propane, ethylene oxide polymerization, relative to expensive sulfonate surfactant, low cost has synthesized big hydrophilic group polyethers sulfate surfactant, due to the presence of big hydrophilic radical, so that high temperature stability performance is excellent in the basic conditions for the sulfate surfactant, 0.3% branched-chain alcoho polyethers sulfate (C32- 7PO-6EO sulfate) with 0.3% internal olefin sulphonates (C20~24IOS) saline solution is mixed at 85 DEG C with same amount of crude oil, and its solubilization parameter is 14.The surfactant that foreign study is used receives certain limitation as oil displacement agent in actual applications because usage amount is big, high cost.Use also having been reported that for cationic surfactant, such as Chinese patent CN1528853, CN1817431, CN1066137 reports bisamide type cationic, fluorine-containing cationic type and cation Gemini surfactant containing pyridine radicals in succession, but because cation has the shortcomings that big, high cost is lost in absorption, limit its use in Oil Field.
The studies above result shows that amphion and anion surfactant have certain effect for reduction profit surface tension, solubilising etc. so that such surfactant has larger application prospect in terms of agent for improving oilfield recovery.Therefore, for reservoir characteristic, a kind of long-time Stability Analysis of Structures at the formation temperature has been invented, and the anion surfactant of ultralow interfacial tension can be formed with crude oil.Exactly this anion surfactant constitutionally stable under reservoir conditions of the present invention and preparation method.
The content of the invention
One of technical problems to be solved by the invention are that there is provided a kind of new anion surfactant for the problem of surfactant Presence of an interface activity mainly constituted as oil displacement agent system in the prior art is low, temperature-resistant anti-salt performance is poor.The aqueous solution prepared with this anion surfactant can be with crude oil formation 10 in 0.005~0.6% scope-2~10-4MN/m low interfacial tension, and under the conditions of reservoir temperature can long period holding structure it is stable so that such surfactant has improves recovery ratio application prospect well.
The two of the technical problems to be solved by the invention are the preparation methods of the anion surfactant described in one of above-mentioned technical problem.
The three of the technical problems to be solved by the invention are another preparation methods of the anion surfactant described in one of above-mentioned technical problem.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Anion surfactant, its general molecular formula is：
R1O(CH2CH2O)m1(CH(CH3)CH2O)n(CH2CH2O)m2R2Y；Formula (1)；
R1For C8~C30Aliphatic group (saturation and unsaturated alkyl of such as straight or branched) or by C4~C20The aryl of saturation and the unsaturated alkyl substitution of straight or branched, m1=1~30, m2=1~50, n=1~30, R2For C1~C5Alkylidene or hydroxyl substituted alkylene, Y be COOM or SO3N, M and N are independently selected from hydrogen, alkali metal or by formula NR3(R4)(R5)(R6) shown at least one in group；R3、R4、R5And R6To be independently selected from H, (CH2)pOH or (CH2)qCH3In one kind, any integer in p=2~4, q=0~5.
In above-mentioned technical proposal, R1Preferably C12~C24Alkyl or by C8~C12Alkyl-substituted phenyl.
In above-mentioned technical proposal, R2Preferably C1~C3Alkylidene or hydroxyl substitution propylidene.
In above-mentioned technical proposal, preferably p=2, q=0~1.
In above-mentioned technical proposal, preferred m1=2~10, m2=1~20, n=2~15.
Anion surfactant key active ingredient of the present invention is (1), those skilled in the art will know that, for the ease of transport and store or onsite application in terms of consider, various supply forms can be used, such as water-free solid-state form, either aqueous solid-state form or aqueous cream form, or aqueous solution form；Aqueous solution form includes being made into the form of concentrate with water, the solution form of concentration needed for being directly made into the live displacement of reservoir oil, and for example key active ingredient content is the live displacement of reservoir oil more suitable form for 0.005~0.6wt% solution by weight；Wherein, there is no particular/special requirement to water, can be deionized water, can also be the water containing inorganic mineral, and the water containing inorganic mineral can be running water, oil field stratum water or oilfield injection water.
To solve the two of above-mentioned technical problem, the technical solution adopted in the present invention is as follows：The preparation method of anion surfactant described in one of above-mentioned technical problem, comprises the following steps：
A, in the presence of base catalyst, R1O(CH2CH2O)m1H obtains R with the reaction of aequum expoxy propane1O(CH2CH2O)m1(CHCH3CH2O)nH；Reaction temperature is preferably 85~160 DEG C, more preferably 120~160 DEG C；Reaction pressure is preferably smaller than 0.80MPa gauge pressures, more preferably 0.30~0.60MPa gauge pressures；Wherein catalyst amount is preferably R1O(CH2CH2O)m10.3~6wt% of H mass.
B, in the presence of base catalyst, R1O(CH2CH2O)m1(CHCH3CH2O)nH obtains R with aequum reacting ethylene oxide1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H；Reaction temperature is preferably 85~160 DEG C, more preferably 120~160 DEG C；Reaction pressure is preferably smaller than 0.80MPa gauge pressures, more preferably 0.30~0.60MPa gauge pressures；Wherein catalyst amount is preferably R1O(CH2CH2O)m1(CHCH3CH2O)n0.3~6wt% of H mass.
C, in the presence of alkali metal hydroxide or alkali metal alcoholates, product and XR that step b is obtained2Y1In a solvent, in 50~120 DEG C of reaction temperature, polyether carboxylic acid or polyethers sulfonate alkali metal of the generation in 3~15 hours with following structure are reacted：
R1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2R2Y1；
Wherein Y1For COOM1Or SO3N1, M1And N1For alkali metal, X is Cl, Br or I.
In above-mentioned technical proposal, the optional alkali metal hydroxide of base catalyst (such as NaOH or potassium hydroxide), alkali metal alcoholates (such as sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide).
In above-mentioned technical proposal, R in step c1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H:XR2Y1:The mol ratio of alkali metal hydroxide is preferably 1: (1~6): (1~6).
As long as having carried out step c reaction, those skilled in the art need not pay creative work and can just separate, purify the various products form for obtaining the anion surfactant.
For example, in order to obtain purified product of the anion surfactant shown in formula (I) when M or N is H, step d and step e can be further comprised：
D, sour pH=1~3 for adjusting aqueous phase of addition, isolated organic phase in the reactant mixture that step c is obtained；
E, the organic phase being concentrated to give obtain required purified product.
For another example in order to obtain anion surfactant shown in formula (I) when M or N is for alkali metal or by formula NR3(R4)(R5)(R6) shown in group when purified product, can on the basis of step d with required alkali metal or formula NR3(R4)(R5)(R6) shown in the corresponding alkali of group neutralize, then remove solvent described in organic phase.
Alkali metal or formula NR needed for described in above-mentioned technical proposal3(R4)(R5)(R6) shown in the corresponding alkali of group, such as alkali corresponding with alkali metal be selected from alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali metal oxide or alkali metal alcoholates, with NR3(R4)(R5)(R6) the corresponding alkali of group is selected from ammonia, monoethanolamine, diethanol amine, triethanolamine, triethylamine, quaternary ammonium base etc..
XR2Y1Example have but be not limited to chloroacetic alkali metal salt (such as sodium chloroacetate), the alkali metal salt of 3- chlorine-2-hydroxyl propane sulfonic acid, 2- chloroethanes sulfonic acid alkali metal salts.
In above-mentioned technical proposal, the solvent described in step c preferably is selected from C3~C4Ketone and C6~C9Aromatic hydrocarbons at least one, such as at least one in the material group constituted by acetone, butanone, from benzene, toluene or dimethylbenzene, trimethylbenzene, ethylbenzene and diethylbenzene.
In order to solve the above-mentioned technical problem three, technical scheme is as follows：The preparation method of one of above-mentioned technical problem anion surfactant, comprises the following steps：
(a) in the presence of base catalyst, R1O(CH2CH2O)m1H obtains R with the reaction of aequum expoxy propane1O(CH2CH2O)m1(CHCH3CH2O)nH；Reaction temperature is preferably 85~160 DEG C, more preferably 120~160 DEG C；Reaction pressure is preferably smaller than 0.80MPa gauge pressures, more preferably 0.30~0.60MPa gauge pressures；Wherein catalyst amount is preferably R1O(CH2CH2O)m10.3~6wt% of H mass.
(b) in the presence of base catalyst, R1O(CH2CH2O)m1(CHCH3CH2O)nH obtains R with aequum reacting ethylene oxide1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H；Reaction temperature is preferably 85~160 DEG C, more preferably 120~160 DEG C；Reaction pressure is preferably smaller than 0.80MPa gauge pressures, more preferably 0.30~0.60MPa gauge pressures；Wherein catalyst amount is preferably R1O(CH2CH2O)m1(CHCH3CH2O)n0.3~6wt% of H mass.
(c) in the presence of alkali metal hydroxide or alkali metal alcoholates, the product and the sultone of 1,3- third that step (b) is obtained in a solvent, in 50~200 DEG C of reaction temperature, react 5~20 hours generation anion polyethers sulfonic acid alkali metal salts；The structure of the anion polyethers sulfonic acid alkali metal salts is：
R1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2CH2CH2CH2SO3M2；
Wherein M2For alkali metal.
In above-mentioned technical proposal, the optional alkali metal hydroxide of base catalyst (such as NaOH or potassium hydroxide), alkali metal alcoholates (such as sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide).
In above-mentioned technical proposal, R1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H:The sultone of 1,3- third:The mol ratio of alkali metal hydroxide is preferably 1: (1~5): (1~8).
As long as having carried out the reaction of step (c), those skilled in the art need not pay creative work and can just separate, purify the various products form for obtaining the anion surfactant.
For example, in order to obtain purified product of the anion surfactant shown in formula (I) when M or N is H, step (d) and step (e) can be further comprised：
(d) pH=1~3 of acid regulation aqueous phase, isolated organic phase are added in the reactant mixture that step (c) is obtained；
(e) organic phase being concentrated to give obtains required purified product.
For another example in order to obtain anion surfactant shown in formula (I) when M or N is for alkali metal or by formula NR3(R4)(R5)(R6) shown in group when purified product, can on the basis of step (d) with required alkali metal or formula NR3(R4)(R5)(R6) shown in the corresponding alkali of group neutralize, then remove solvent described in organic phase.
Alkali metal or formula NR needed for described in above-mentioned technical proposal3(R4)(R5)(R6) shown in the corresponding alkali of group, such as alkali corresponding with alkali metal may be selected from alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali metal oxide or alkali metal alcoholates, with NR3(R4)(R5)(R6) the corresponding alkali of group may be selected from ammonia, diethylamine, triethylamine, monoethanolamine, diethanol amine, triethanolamine, quaternary ammonium base etc..
In above-mentioned technical proposal, the solvent described in step (c) preferably is selected from C3~C4Ketone and C6~C9Aromatic hydrocarbons at least one, such as at least one in the material group constituted by acetone, butanone, from benzene, toluene or dimethylbenzene, trimethylbenzene, ethylbenzene and diethylbenzene.
Anion surfactant prepared by the present invention, due to containing polyethers and carboxylate radical or azochlorosulfonate acid anion group simultaneously, it is set to have the heat resistance of anion surfactant and the salt tolerant advantage of nonionic surfactant concurrently, so as to impart the excellent temperature resistance salt resistant character of the surfactant；Polyether carboxylic acid or sulfosalt surfactant have relatively low critical micelle concentration (cmc), less than 1~2 order of magnitude of conventional anion surfactant, so that the concentration window of the surfactant is wider, interfacial tension caused by progressively declining because of surfactant concentration during Oil Field use can be solved and rise problem, so that surfactant is in the migration process of underground, even if concentration is relatively low can still to keep ultralow oil water interfacial tension, so as to improve oil displacement efficiency.
Using the anion surfactant for preparing of the present invention, by percentage to the quality, consumption is can be with underground crude oil formation 10 under conditions of 0.005~0.6wt%-2~10-4MN/m low interfacial tension, salt resistance is up to 250000 mg/litres, wherein Mg2++Ca2+Up to 23000 mg/litres, interface performance keeps being basically unchanged after aging under oil reservoir is stable 180 days, and adsorbance is less than 3mg/g, achieves preferable technique effect.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether.
Fig. 2 is the infrared spectrogram of hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid.
Fig. 3 is absorption spirograms of the 0.3%S-1 and 0.3%S-2 in different adsorption sands.
Fig. 4 is absorption spirograms of the 0.3%S-4 in different adsorption sands.
Fig. 5 is absorption spirograms of the 0.3%S-5 in different adsorption sands.
Polyethers prepared by the present invention and polyether carboxylic acid or sulfonic acid can apply U.S.'s Nicolet-5700 spectrometers, and infrared spectrum analysis (4000~400cm of sweep limits is carried out using liquid-film method-1), the chemical constitution of sample is determined, to reach the IR Characterization to compound of the present invention.
As shown in Figure 1, wave number 3480.7cm-1For-OH characteristic peak, wave number 2968.1cm-1And 2869.2cm-1For methyl and methylene C-H telescope features peak, wave number 1109.1cm-1For the absworption peak of C-O-C ehter bonds.
As shown in Figure 2, wave number 3486.8cm-1For-COOH characteristic peak, wave number 2968.3cm-1And 2869.9cm-1For methyl and methylene C-H telescope features peak, wave number 1757.6cm-1For the carbonyl absorption peak in carboxylic acid, wave number 1112.6cm-1For the absworption peak of C-O-C ehter bonds.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
C16H33O(CH2CH2O)3(CHCH3CH2O)8(CH2CH2O)4CH2COOH.NH3
374 grams of (1 mole) hexadecanol polyoxyethylene (3) ethers, 5.6 grams of potassium hydroxide are added into the 2L pressure reactors equipped with agitating device, when being heated to 80~90 DEG C, open vacuum system, it is dehydrated 1 hour under a high vacuum, then nitrogen displacement is used 3~4 times, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 469.8 grams of (8.1 moles) expoxy propane, control pressure≤0.60MPa, temperature is adjusted to 140 DEG C again after expoxy propane reaction terminates and is slowly passed through 178.2 grams of (4.05 moles) oxirane, control pressure≤0.40MPa.After reaction terminates, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, neutralized, be dehydrated after cooling, obtain 1008.9 grams of hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether, yield 99.5%.
Hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) 507 grams of ether (0.5 mole) is mixed in the reactor of 2000 milliliters equipped with mechanical agitation, thermometer and reflux condensing tube with 112.2 grams of (2 moles) potassium hydroxide, 116.5 grams of (1 mole) sodium chloroacetates and 700 milliliters of toluene, is heated to 90 DEG C and is reacted 6 hours.Cooling, it is acidified with 25wt% sulfuric acid, divide and remove water and inorganic salts, solvent is evaporated off, obtain 494.7 grams of acid product, analyzed through high performance liquid chromatography (HPLC), hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid content is 92.3% in product.
Hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether and hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid to synthesis, using U.S.'s Nicolet-5700 infrared spectrometers, infrared spectrum analysis (4000~400cm of sweep limits is carried out using liquid-film method-1), infrared spectrum is respectively as shown in Fig. 1 and Fig. 2.
494.7 grams of the acid product of above-mentioned synthesis is mixed with 500 grams of water, with the pH=8.5 of 25% ammoniacal liquor regulation system, required hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether acetic acid ammonium anion surfactant S-1 is obtained.
【Embodiment 2】
C16H33O(CH2CH2O)3(CHCH3CH2O)8(CH2CH2O)4CH2COOH.N(CH2CH2OH)3
Together【Embodiment 1】494.7 grams of hexadecanol polyoxyethylene (3) polyoxypropylene (n=8) polyoxyethylene (4) ether acetic acid of synthesis is mixed with 500 grams of water, with the pH=8 of 98% triethanolamine regulation system, required hexadecanol polyoxyethylene (3) polyoxypropylene (n=8) polyoxyethylene (4) ether acetic acid triethanolamine salt anionic surfactant S-2 is obtained.
【Embodiment 3】
308 grams of (1 mole) Nonyl pheno (2) ethers, 1.5 grams of potassium hydroxide and 4.6 grams of Anhydrous potassium carbonates are added into the 2L pressure reactors equipped with agitating device, together【Embodiment 1】Removed water and nitrogen displacement, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 638 grams of (11 moles) expoxy propane, control pressure≤0.60MPa, after expoxy propane reaction terminates, cooling, 134.2 grams of (3.05 moles) oxirane, control pressure≤0.50MPa are slowly passed through in 140 DEG C.After reaction terminates, together【Embodiment 1】Post processing, obtains 1006.7 grams of Nonyl pheno (2) polyoxypropylene (10) polyoxyethylene (3) ether, yield 98.7%.
Nonyl pheno (2) polyoxypropylene (10) polyoxyethylene (3) 510 grams of ether (0.5 mole) is mixed in the reactor of 2000 milliliters equipped with mechanical agitation, thermometer and reflux condensing tube with 40 grams of (1 mole) NaOH, 145.6 grams of (1.25 moles) sodium chloroacetates and 500 milliliters of acetone, is heated to back flow reaction 12 hours.Cooling, it is acidified with 10wt% hydrochloric acid, divide and remove water and inorganic salts, solvent is evaporated off, obtain 523.4 grams of acid product, analyzed through high performance liquid chromatography (HPLC), Nonyl pheno (2) polyoxypropylene (10) polyoxyethylene (3) ether acetic acid content is 97.1% in product.
523.4 grams of the acid product of above-mentioned synthesis is mixed with 500 grams of water, with the pH=12 of 10% triethylamine aqueous solution regulation system, required Nonyl pheno (2) polyoxypropylene (10) polyoxyethylene (3) ether acetic acid triethylamine salt anion surfactant S-3 is obtained.
【Embodiment 4】
C13H27O(CH2CH2O)7(CHCH3CH2O)15(CH2CH2O)2CH2CH2SO3Na
254 grams of (0.5 mole) isomerous tridecanol polyoxyethylene (7) ether (BASF trade names are added into the 2L pressure reactors equipped with agitating device：TO7), 2.5 grams of potassium hydroxide, together【Embodiment 1】Removed water and nitrogen displacement, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 464 grams of (8 moles) expoxy propane, control pressure≤0.60MPa, after expoxy propane reaction terminates, cooling, 44.9 grams of (1.02 moles) oxirane, control pressure≤0.40MPa are slowly passed through in 120 DEG C.After reaction terminates, together【Embodiment 1】Post processing, obtains 717.6 grams of isomerous tridecanol polyoxyethylene (7) polyoxypropylene (15) polyoxyethylene (2) ether, yield 97.9%.
Isomerous tridecanol polyoxyethylene (7) polyoxypropylene (15) polyoxyethylene (2) 439.8 grams of ether (0.3 mole) is mixed in the there-necked flask of 2000 milliliters equipped with mechanical agitation, thermometer and reflux condensing tube with 42 grams of (0.75 mole) potassium hydroxide, 114.9 grams of (0.69 mole) 2- chloroethanes sodium sulfonates and 700 milliliters of toluene, is heated to 105 DEG C and is reacted 6 hours.Cooling, it is acidified with 35wt% sulfuric acid, divide and remove water and inorganic salts, solvent is evaporated off and obtains 450.0 grams of sulfonic acid product, analyzed through high performance liquid chromatography (HPLC), isomerous tridecanol polyoxyethylene (7) polyoxypropylene (15) polyoxyethylene (2) ether ethyl sulfonic acid content is 95.3% in product.
450.0 grams of the sulfonic acid product of above-mentioned synthesis is mixed with 500 grams of water, with the pH=13 of 15% sodium hydrate aqueous solution regulation system, required isomerous tridecanol polyoxyethylene (7) polyoxypropylene (15) polyoxyethylene (2) ether ethyl sulfonic acid sodium anion surfactant S-4 is obtained.
【Embodiment 5】
R1O(CH2CH2O)5(CHCH3CH2O)4(CH2CH2O)20CH2COONa
Wherein, R1Carbochain be distributed as：C1272.3%th, C1427.7%.
414.9 grams of (1 mole) 12/14 (C of mixing are added into the 2.5L pressure reactors equipped with agitating device12~14) alcohol polyoxyethylene (5) ether, 14.5 grams of Anhydrous potassium carbonates, together【Embodiment 1】Removed water and nitrogen displacement, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 234.9 grams of (4.05 moles) expoxy propane, control pressure≤0.50MPa, after expoxy propane reaction terminates, cooling, 924 grams of (21 moles) oxirane, control pressure≤0.40MPa are slowly passed through in 130 DEG C.After reaction terminates, together【Embodiment 1】Post processing, must mix 12/14 (C12~14) 1513.3 grams of alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether, yield 99.1%.
Mix 12/14 (C12~14) alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) 763.5 grams of ether (0.5 mole) and 70.1 grams of (1.25 moles) potassium hydroxide, 64.1 grams of (0.55 mole) sodium chloroacetates and 400 milliliters of benzene are mixed in the reactor of 2000 milliliters equipped with mechanical agitation, thermometer and reflux condensing tube, are heated to 70 DEG C and react 9 hours.Cooling, is acidified with 15wt% sulfuric acid, is divided and is removed water and inorganic salts, solvent is evaporated off, 740.9 grams of acid product is obtained, and is analyzed through high performance liquid chromatography (HPLC), and 12/14 (C are mixed in product12~14) alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether acetic acid content be 93.5%.
740.9 grams of the carboxylic acid product of above-mentioned synthesis is mixed with 900 grams of water, with the pH=10 of 40% sodium hydrate aqueous solution regulation system, (the C of mixing 12 needed for obtaining/1412~14) alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether acetic acid sodium anion surfactant S-5.
【Embodiment 6】
The simulation water of different bivalent cations and total salinity is prepared respectively, and concrete composition is shown in Table 1.
Oil water interfacial tension measure, to different oil fields, is used, viscosity of crude is shown in Table 2 with crude oil after dehydration.
A certain amount of surfactant S-1~S-5 is dissolved with the simulation salt solution A of different salinities~D, various concentrations surfactant solution is determined to the oil water interfacial tension of several crude oil, the results are shown in Table shown in 3.The TX500 types rotating interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is determined.
Surfactant simulation saline solution is fitted into 20 milliliters of peace a word used in place name bottles, is put into after sealing in baking oven, the oil water interfacial tension that surfactant after different ageing times simulates salt solution pair and crude oil is determined, it is found that oil water interfacial tension can still keep 10 after aging-3~10-4MN/m ultralow value, is shown in Table 4.The TX500 types rotating interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is determined.
Absorption waste of the surfactant on formation core is mainly explored in Static Adsorption experiment, and the possibility of oil recovery factor scene application is being improved with the surfactant for exploring embodiment synthesis.Experimentation is：After the simulation saline solution 10g of surfactant is mixed with 1g absorption with sand, 24h is shaken in formation temperature, centrifuged after cooling, take supernatant liquor, the concentration of saline solution is simulated using diphasic potential titration measuring surfactant, the adsorbance of gauging surface activating agent, unit mg/g, as a result as shown in Fig. 3-5.
【Comparative example 1】
A certain amount of contrast surfactant is dissolved with the simulation salt solution A of different salinities~D, determine oil water interfacial tension of the various concentrations contrast surfactant solution to several crude oil, and compared with surfactant prepared by corresponding embodiment, the results are shown in Table shown in 5.The TX500 types rotating interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is determined.
In table 5, S-6 is hexadecanol polyoxyethylene (3) polyoxypropylene (8) polyoxyethylene (4) ether；S-7 is hexadecanol ammonium acetate；S-8 is isomerous tridecanol polyoxyethylene (7) polyoxypropylene (15) polyoxyethylene (2) ether；S-9 is isomerous tridecanol ethyl sulfonic acid sodium；S-10：Mix 12/14 (C12~14) alcohol polyoxyethylene (5) polyoxypropylene (4) polyoxyethylene (20) ether；S-11：Mix 12/14 (C12~14) alcohol sodium acetate.
【Comparative example 2】
By (the 3rd phase volume 20 in 2002 such as Zhang Xueqin, colloid and polymer, anion/amphion complexed surfactant S-12 that the anionic (SDS) and zwitterionic surfactant lauroylamidopropyl betaine (LMB) of the research of P1~5) are formed, together【Embodiment 6】Interface performance determination test is carried out, and compared with surfactant prepared by corresponding embodiment, be the results are shown in Table shown in 6.
【Comparative example 3】
Together【Embodiment 1】, difference is not reacted step by step successively with expoxy propane and oxirane, but both are mixed into the reaction of later stepping row.Slowly it is passed through 469.8 grams of (8.1 moles) expoxy propane and 178.2 grams of (4.05 moles) ethylene oxide mixtures at 140~150 DEG C, control pressure≤0.60MPa, remaining is identical, obtains anion surfactant S-13.Together【Embodiment 6】Interface performance determination test is carried out, and compared with surfactant prepared by corresponding embodiment, be the results are shown in Table shown in 7.
【Comparative example 4】
Together【Embodiment 4】, difference is not reacted step by step successively with expoxy propane and oxirane, but both are mixed into the reaction of later stepping row.464 grams of (8 moles) expoxy propane and 44.9 grams of (1.02 moles) ethylene oxide mixtures are slowly passed through at 120~160 DEG C, remaining is identical, obtains anion surfactant S-14.Together【Embodiment 6】Interface performance determination test is carried out, and compared with surfactant prepared by corresponding embodiment, be the results are shown in Table shown in 7.
Table 1
| Simulate salt solution | Ca2+(mg/L) | Mg2+(mg/L) | TDS(mg/L) |
| A | 1200 | 400 | 32000 |
| B | 20 | 12 | 8000 |
| C | 10 | 2 | 3500 |
| D | 15000 | 8000 | 180000 |
| E | 4000 | 1250 | 250000 |
Table 2
| Crude oil | Crude oil origin | Underground crude oil viscosity (mPa.s) |
| I | Shengli Oil Field | 10.0 |
| II | Henan Oil Field | 3.4 |
| III | Jiangsu oilfield | 2.2 |
| IV | Zhongyuan Oil Field | 2.9 |
Table 3
| Surfactant | Simulate salt solution | Temperature (DEG C) | Crude oil | Concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.6 | 0.0385 |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.1 | 0.00075 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-1 | A | 85 | I | 0.025 | 0.0042 |
| S-1 | A | 85 | I | 0.01 | 0.0271 |
| S-1 | A | 85 | I | 0.005 | 0.0885 |
| S-1 | A | 85 | I | 0.001 | 0.1312 |
| S-1 | B | 85 | I | 0.1 | 0.5247 |
| S-1 | E | 85 | I | 0.1 | 0.0583 |
| S-2 | A | 85 | I | 0.3 | 0.0021 |
| S-2 | A | 85 | I | 0.05 | 0.0054 |
| S-2 | A | 85 | I | 0.01 | 0.0079 |
| S-2 | A | 85 | I | 0.005 | 0.0411 |
| S-2 | B | 85 | I | 0.3 | 0.1217 |
| S-2 | C | 85 | I | 0.3 | 0.3662 |
| S-3 | A | 85 | I | 0.6 | 0.00852 |
| S-3 | A | 85 | I | 0.3 | 0.0041 |
| S-3 | A | 85 | I | 0.05 | 0.00052 |
| S-3 | A | 85 | I | 0.025 | 0.0034 |
| S-3 | A | 85 | I | 0.01 | 0.0428 |
| S-3 | D | 85 | I | 0.05 | 0.0852 |
| S-3 | E | 85 | I | 0.05 | 0.0439 |
| S-4 | B | 80 | II | 0.4 | 0.00098 |
| S-4 | B | 80 | II | 0.2 | 0.0036 |
| S-4 | B | 80 | II | 0.1 | 0.00086 |
| S-4 | B | 80 | II | 0.05 | 0.0046 |
| S-4 | B | 80 | II | 0.01 | 0.0079 |
| S-4 | B | 80 | II | 0.005 | 0.0663 |
| S-4 | C | 80 | II | 0.1 | 0.0015 |
| S-4 | C | 80 | II | 0.005 | 0.0855 |
| S-4 | C | 85 | III | 0.6 | 0.00051 |
| S-4 | C | 85 | III | 0.3 | 0.00032 |
| S-4 | C | 85 | III | 0.05 | 0.0035 |
| S-4 | C | 85 | III | 0.01 | 0.0451 |
| S-4 | C | 85 | III | 0.005 | 0.1022 |
| S-4 | B | 85 | III | 0.05 | 0.00422 |
| S-5 | D | 95 | IV | 0.3 | 0.0056 |
| S-5 | D | 95 | IV | 0.1 | 0.00042 |
| S-5 | D | 95 | IV | 0.025 | 0.0013 |
| S-5 | D | 95 | IV | 0.01 | 0.0076 |
| S-5 | D | 95 | IV | 0.005 | 0.0233 |
| S-5 | D | 95 | IV | 0.001 | 0.3221 |
| S-5 | E | 95 | IV | 0.1 | 0.00053 |
| S-5 | E | 95 | IV | 0.01 | 0.0011 |
Table 4
| Surfactant | Simulate salt solution | Temperature (DEG C) | Crude oil | Concentration (%) | Ageing time (d) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.3 | 0 | 0.0042 |
| S-1 | A | 85 | I | 0.3 | 30 | 0.0087 |
| S-1 | A | 85 | I | 0.3 | 60 | 0.0033 |
| S-1 | A | 85 | I | 0.3 | 90 | 0.0029 |
| S-1 | A | 85 | I | 0.3 | 180 | 0.0058 |
| S-4 | B | 80 | II | 0.2 | 0 | 0.0036 |
| S-4 | B | 80 | II | 0.2 | 60 | 0.0025 |
| S-4 | B | 80 | II | 0.2 | 90 | 0.0014 |
| S-4 | C | 85 | III | 0.3 | 0 | 0.00032 |
| S-4 | C | 85 | III | 0.3 | 30 | 0.00045 |
| S-4 | C | 85 | III | 0.3 | 60 | 0.0021 |
| S-4 | C | 85 | III | 0.3 | 180 | 0.0013 |
| S-5 | D | 95 | IV | 0.3 | 0 | 0.0056 |
| S-5 | D | 95 | IV | 0.3 | 15 | 0.00075 |
| S-5 | D | 95 | IV | 0.3 | 60 | 0.00086 |
| S-5 | D | 95 | IV | 0.3 | 180 | 0.0035 |
Table 5
| Surfactant | Simulate salt solution | Temperature (DEG C) | Crude oil | Concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-6 | A | 85 | I | 0.3 | 0.0232 |
| S-6 | A | 85 | I | 0.05 | 0.0872 |
| S-7 | A | 85 | I | 0.3 | 0.0566 |
| S-7 | A | 85 | I | 0.05 | 0.1455 |
| S-4 | B | 80 | II | 0.4 | 0.00098 |
| S-8 | B | 80 | II | 0.4 | 0.0564 |
| S-9 | B | 80 | II | 0.4 | 0.0455 |
| S-5 | D | 95 | IV | 0.3 | 0.0056 |
| S-10 | D | 95 | IV | 0.3 | 0.0732 |
| S-11 | D | 95 | IV | 0.3 | 0.0299 |
Table 6
| Surfactant | Simulate salt solution | Temperature (DEG C) | Crude oil | Concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-12 | A | 85 | I | 0.3 | 0.0787 |
| S-12 | A | 85 | I | 0.05 | 0.5333 |
| S-5 | D | 95 | IV | 0.1 | 0.00042 |
| S-5 | D | 95 | IV | 0.025 | 0.0013 |
| S-12 | D | 95 | IV | 0.1 | 0.0254 |
| S-12 | D | 95 | IV | 0.025 | 0.0189 |
Table 7
| Surfactant | Simulate salt solution | Temperature (DEG C) | Crude oil | Concentration (%) | IFT(mN/m) |
| S-1 | A | 85 | I | 0.3 | 0.0042 |
| S-1 | A | 85 | I | 0.05 | 0.0024 |
| S-13 | A | 85 | I | 0.3 | 0.0087 |
| S-13 | A | 85 | I | 0.05 | 0.0065 |
| S-4 | B | 80 | II | 0.4 | 0.00098 |
| S-4 | B | 80 | II | 0.1 | 0.00086 |
| S-14 | B | 80 | II | 0.4 | 0.0043 |
| S-14 | B | 80 | II | 0.1 | 0.0039 |
Claims (9)
1. anion surfactant, its general molecular formula is：
R1O(CH2CH2O)m1(CH(CH3)CH2O)n(CH2CH2O)m2R2Y；Formula (1)；
R1For C8~C30Aliphatic group or by C4~C20The aryl of saturation and the unsaturated alkyl substitution of straight or branched, m1=1~30, m2=1~50, n=1~30, R2For C1~C5Alkylidene or hydroxyl substituted alkylene, Y be COOM or SO3N, M and N are independently selected from hydrogen, alkali metal or by formula NR3(R4)(R5)(R6) shown at least one in group；R3、R4、R5And R6To be independently selected from H, (CH2)pOH or (CH2)qCH3In one kind, any integer in p=2~4, q=0~5.
2. anion surfactant according to claim 1, it is characterised in that the R1For C12~C24Alkyl or by C8~C12Alkyl-substituted phenyl.
3. anion surfactant according to claim 1, it is characterised in that R2For C1~C3Alkylidene or hydroxyl substitution propylidene.
4. anion surfactant according to claim 1, it is characterised in that p=2, q=0~1.
5. anion surfactant according to claim 1, it is characterised in that m1=2~10, m2=1~20, n=2~15.
6. the preparation method of the anion surfactant described in claim 1, comprises the following steps：
A, in the presence of base catalyst, R1O(CH2CH2O)m1H obtains R with the reaction of aequum expoxy propane1O(CH2CH2O)m1(CHCH3CH2O)nH；
B, in the presence of base catalyst, R1O(CH2CH2O)m1(CHCH3CH2O)nH obtains R with aequum reacting ethylene oxide1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H；
C, in the presence of alkali metal hydroxide or alkali metal alcoholates, product and XR that step b is obtained2Y1In a solvent, in 50~120 DEG C of reaction temperature, polyether carboxylic acid or polyethers sulfonate alkali metal of the generation in 3~15 hours with following structure are reacted：
R1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2R2Y1；
Wherein Y1For COOM1Or SO3N1, M1And N1For alkali metal, X is Cl, Br or I.
7. the preparation method of anion surfactant according to claim 6, it is characterized in that the solvent described in step c is selected from C3~C4Ketone and C6~C9Aromatic hydrocarbons at least one.
8. the preparation method of the anion surfactant described in claim 1, comprises the following steps：
(a) in the presence of base catalyst, R1O(CH2CH2O)m1H obtains R with the reaction of aequum expoxy propane1O(CH2CH2O)m1(CHCH3CH2O)nH；
(b) in the presence of base catalyst, R1O(CH2CH2O)m1(CHCH3CH2O)nH obtains R with aequum reacting ethylene oxide1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2H；
(c) in the presence of alkali metal hydroxide or alkali metal alcoholates, the product and the sultone of 1,3- third that step (b) is obtained in a solvent, in 50~200 DEG C of reaction temperature, react 5~20 hours generation anion polyethers sulfonic acid alkali metal salts；The structure of the anion polyethers sulfonic acid alkali metal salts is：
R1O(CH2CH2O)m1(CHCH3CH2O)n(CH2CH2O)m2CH2CH2CH2SO3M2；
Wherein M2For alkali metal.
9. the preparation method of anion surfactant according to claim 8, it is characterized in that the solvent described in step (c) is selected from C3~C4Ketone and C6~C9Aromatic hydrocarbons at least one.
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