ALKOXYPOLYETHOXYPROPANE SULFONATES, PROCESS FOR THEIR PREPARATION AND METHOD FOR THEIR USE IN ENHANCED OIL RECOVERY

Abstract: Alkoxypolyethoxypropane sulfonates of the general for­ mula RO(C₂H₄O) x CH₂CH₂CH₂SO₃Na in which R is branched C₁₀-C₂₀ alkyl and x is 2 to 6 are useful as single-component surfactants for secondary water flood­ ing or tertiary oil recovery. Such compounds may be prepared by a two-stage procedure from the corresponding polyethoxylated branched alcohol and an allyl compound in the presence of strong aqueous NaOH and some final product as phase transfer agent, and in situ sulfonation of the allyl ether intermediate.

Description: ALKOXYPOLVETHOXYPROPANE SULFONATES, PROCESS FOR THEIR PREPARATION AND METHOD FOR THEIR USE IN ENHANCED OIL RECOVERY This invention relates to alkoxypolyethoxypropane sulfonates, to a process for their preparation and to an oil recovery process using them. In the recovery of oil from oil-bearing deposits, it is generally possible to recover only a portion of the original oil by so called "primary methods" which utilize only the natural forces present in the reservoir or deposit. A variety of supplemental techniques have therefore been employed in order to increase the recovery of oil from these subterranean reservoirs. The most widely used supplemental recovery technique is water flooding which involves injection of water into an oil bearing reservoir. However, there are problems associated with the water flooding technique and water-soluble surfactants have generally been required to be used for this process to be completely successful. The LTWF (Low Tension Water Flood) method using surfactants which function in conditions of low salinity (less than 3 percent) is well known but it has been found that preflushing the reservoirs with fresh or low salinity water to reduce the salinity so that the low salinity surfactants may be used is not always effective, or that preflushing is effective only for a short time and the salinity of the fresh water increases over a period of time since it is in contact with reservoir rocks and clays. Either event renders the low salinity surfactants useless and therefore it is of vital importance to have a surfactant which functions at the salinity of the reservoir water to negate the necessity of preflushing. Two different concepts have developed for using surfactants to enhance oil recovery. In the first, a solution containing a low concentration of surfactants is injected into the reservoir. The surfactant is dissolved in either water or oil and is in equilibrium with surfactant aggregates known as micelles. Large pore volumes (about 15-60% or more) of the solution are injected into the reservoir to reduce inter facial tension between oil and water and thereby increase oil recovery. Specific relationships exist between interfacial tensions of the oil against the flooding media and the percentage of recovery obtained by flooding, i.e., the efficiency of flooding increases as the interfacial tension decreases. Oil may be banked with the surfactant solution process but residual oil saturation at a given position in the reservoir will only approach zero after passage of large volumes of surfactant solution. In the second process, a relatively small pore volume (about 3-20%) of a higher concentration surfactant solution is injected into the reservoir. With the higher surfactant concentration, the micelles become a surfactant-stabilized dispersion of either water and hydrocarbon or hydrocarbon and water. The high surfactant concentrations allow the amount of dispersed phase in the microemulsion to be high in comparison to the dispersed phase of the micelles in the low concentration surfactant solutions. The injected solution (slug) is formulated with three or more components. The basic components (hydrocarbon, surfactant, and water) are sufficient to form the micellar solutions. A fourth, co-surfactant component (usually alcohol) can be added. Electrolytes, normally inorganic salts form a fifth component that may be used in preparing the micellar solutions of microemulsions. The high concentration surfactant solutions displace both oil and water and readily displace all the oil contacted in the reservoir. However, as the high concentration slug moves in the reservoir, it is diluted by formation flood and the process reverts to a low concentration flood (Enhanced Oil Recovery, Van Poolen & Associates, 1980, Tulsa, Oklahoma). Work is still in progress in the laboratory and in the field LO select the optimum method of injecting surfactant to improve oil recovery. The best process for a specific reservoir is the one having the pcWential to provide the greatest efficiency and yield regardless of the concentration of the surfactant. However, to be efficient the enemical system must be tailored to the specific reservoir. The prior art with respect to the use surfactant polymer floods to recover oil from reservoirs discloses that for a given amount of surfactant, a small slug process with a high surfactant concentration is more efficient than a large slug process with a low surfactant concentration. The former produces oil earlier but takes a smaller number of pore volumes to complete oil production. This is a favorable condition. However, it has become evident that fluid dispersion and mixing take place in the reservoirs and the slug intake routine cannot be maintained. Deterioration of the surfactant and the mobility control slug can lead to process failure or at least a reduction in process efficiency. For heterogeneous reservoirs where fluid dispersion and mixing take place to a greater extent it is desirable if not vital to have a continuous flooding process with a surfactant that is capable of moving even at very low concentrations. Propane sulfonates of various polyethoxylated alcohols are known to be effective as surfactants and various propane sulfonates are known to exhibit a high tolerance towards brine and to possess high thermal and hydrolytic stabilities. The present invention is based on the observation that certain propane sulfonate surfactants can be used alone in low concentrations over a wide range of salinity conditions in continuous flooding techniques to increase oil production during secondary water flooding or to recover tertiary oil from reservoirs that have already been water-flooded. According to the present invention, there are provided compounds of the general formula RO(C2H40 CH,CHZCHZS03Na in which R is a branched aliphatic group having from 10 to 30 carbon atoms, preferably from 12 to 20 carbon atoms, and x has a value from 2 to 6, preferably 3. Such alkoxypolyethoxypropanesulfonates have been found to be useful in enhanced oil recovery, especially when used at low concentrations, and to be especially adaptable to high salinity oil reservoirs, that is to say reservoirs having a salinity of from 4 to 30%. Such compounds can be used as single component surfactants (without the addition of any other component or co-surfactant) although it may be desirable to use a mixture of two or more such compounds or to use the surfactant in combination with a sacrificial compound such as lignin sulfonate. The present invention therefore also provides a method for recovering oil from a subterranean oil reservoir having one or more production wells and one or more injection wells in contact with the reservoir comprising injecting into the oil reservoir an aqueous medium containing as the sole surfactant a compound having a branched alkyl substituent having at least one, two-carbon atom branch, in a concentration sufficient to increase oil production from the production well during secondary water flooding or to recover residual tertiary oil when the oil reservoir has been previously flooded. The branch in the R group is preferably at least two carbon atoms in length. Both single and multiple branches are included. Particularly useful surfactants are those in which R is EMI4.1 in which each of R1 and R3 has from 7 to 26 carbon atoms and preferably from 8 to 12 carbon atoms, and R2 has from 2 to 10 carbon atoms, preferably from 4 to 6 carbon atoms. Surfactants in which R3 is C6-alkyl and R2 is C4-alkyl are highly effective in reservoirs having a salinity from about 15 to about 28 weight percent. When R3 is C7-alkyl and R2 is C5-alkyl, the surfactants are very effective in salinities of from about 10 to 20 percent, and when R3 is C8-alkyl and R2 is C6-alkyl the surfactants are highly effective in salinities of from about 4 to 10 percent. The branched sulfonates of the invention generally have their minimum inter facial tension at salinities of less than about 30%, typically at about 4 to 28%. Indeed, the surfactants can be tailored for use in particular salinity ranges by varying the overall chain length of the alkyl radical R, the length of the branch or branches, and the position of branching. In contrast to the branched surfactants of the invention whose optimum (minimum) inter facial tension occurs at salinities below about 30%, the corresponding straight chain alkyl surfactants of the prior art with the same total number of carbon atoms exhibit minimum inter facial tension at 30% salinity or higher. A consequence of this is that the branched surfactants exhibit significantly lower inter facial tension than the corresponding straight chain surfactants at salinities of most interest in chemical water flooding, that is at salinities of 30% or less. In general, at salinities of less than 30% the branched surfactants have inter facial tension values of a factor of 0.5 or less than the corresponding straight chain surfactant containing the same number of carbon atoms at the same surfactant concentration. Typically, as shown in the following Examples, the factor is much less than 0.5, rendering the branched surfactants of this invention particularly suitable for use in water flooding. The literature describes the preparation of propane sulfonates of alcohols and thiols by the reaction of alkali metal salts of the alcohols or thiols with propane sultone: EMI5.1 This is a convenient, high-yield synthesis but is not appropriate on a large scale for several reasons, especially since such a reaction requires multistep synthesis and purification of propane sultone; propane sultone is expensive to purify and its overall yield of 80-90% limits the yield in the preparation of propane sulfonates; and propane sultone is a known carcinogen. Processes involving the use of propane sultone must therefore incorporate expensive safety features but will always engender some risk. The literature also describes a two-step process for the preparation of propane sulfonates of tertiary amines (J. Amer. Oil Chem. Soc., 53, 60 (1976)] but reports that the process produces excessive quantities of undesirable "iso-sulfonate" whose presence degrades the performance of the product. This, of course, is most undesirable. The preparation of allyl ethers by the reaction of sodium or sodium methoxide with the alcohol followed by reaction with allyl chloride all in an organic solvent such as toluene or tetrahydrofuran (the Williamson ether synthesis) is well known and may be found in many standard textbooks on organic chemistry. The reaction of allyl chlorides and alcohols with NaOH is less well known but does occur in the presence of appropriate phase transfer catalysts. Hitherto, such catalysts have invariably been tetraalkylammonium salts. Thus H.H. Freedman in Tetrahedron Letters, 3251 (1975) reports that the reaction of allyl alcohol with benzyl chloride may be achieved with NaOH as base if benzyl triethylammonium chloride is used as a phase transfer catalyst. The yield is only 72%. If such a tetraalkylammonium chloride is used, it must be separated from the product and recycled in order that it does not contaminate the product or represent a loss of costly material. Such a process is therefore expensive to carry out. The reaction of NaHS03 with simple olefins has been much studied. The literature teaches that for simple water-soluble olefins or olefins that can be made soluble by the addition of small amounts of alcohols, all that is required for high conversion into the desired product is conditions in which all reagents are dissolved in a single phase. However, the early literature on the reaction of NaHOS3 with olefins indicates that S-alkylation leading to sulfonate products might be accompanied by a slight amount of O-alkylation leading to sulfites but even this slight formation is disputed and the literature for the last thirty years revels that sulfites are actually not by-products of the sulfitation of olefins. It was therefore quite surprising to find in developing the present invention that sulfitation of allyl ethers can produce as much as 100% sulfite in solvents which are taught in the literature to be acceptable for sulfitation of ordinary olefins to sulfonates. A high yield of sulfite is also surprising because the literature teaches that solvent systems which produce high conversions of olefins will product high yields of sulfonates. The present invention further provides a process for the preparation of propane sulfonates of the general formula RY(C2H40) xCH2CH2CH2SO3Na in which R is an alkyl or alkaryl group, Y is O or S and x has a value from 0 to 20, which comprises reacting together an alcohol RY(C2H40)XH, sodium hydroxide and allyl halide or tosylate to form the corresponding allyl ether RY(C2H40) CI-I2CH=CH2 and reacting the allyl ether with sodium bisulfite, the first stage of the reaction being carried out in approximately 50% for example 30-70%, especially 40 to 60%, aqueous sodium hydroxide in the presence of sufficient final product to function as a phase transfer catalyst, and the second stage being carried out without isolation of the intermediate allyl ether. This process has several inherent advantages over known processes for the production of propane sulfonates. Firstly, it uses aqueous sodium hydroxide as opposed to the sodium or sodium alcoholate and anhydrous conditions previously employed; secondly, it eliminates the use, and hence the cost of separation, recovery and recycle of organic solvent; thirdly, since intermediate product isolation is unnecessary, the process can be carried out in a single reaction vessel; and fourthly, the product is obtained in a high yield - rarely below 90% - compared to yields of 40 to 50% for many known processes. The two-stage process of the present invention can be represented schematically as follows: EMI7.1 R, V and x having the meanings given above and X being halide or tosylate. R is preferably a C1-C16 alkyl or C7-C16 alkaryl group, especially a C10-Cl6 alkyl group, and x is preferably 2 to 6, especially 3. The reaction is suitably carried out at O to 550C at ambient pressure in the presence of from 0.1 to 1 mole of final product per mole of alcohol RY(C2H40)XH. Any excess, unreacted allyl compound XCH2CH=CH2 may be distilled off at the end of the reaction. Alternatively, of course, the compounds of the invention can be prepared by the method which is in itself known for the preparation of substituted propane sulfonates, by the reaction of an alkali metal salt of the alcohol RY(C2H4O)xH with propane sultone. The following Examples illustrate the invention. EXAMPLE 1 Preparation of Branched Dodecyloxytriethoxypropane Sulfonate EMI8.1 2-Butyloctanol was reacted with an equivalent amount of phosphorous tribromide at substantially GoC. The resulting 2-butylbromooctane was purified by vacuum distillation. The distilled 2-butylbromooctane was ethoxylated by reacting with excess triethylene glycol. One equivalent of metallic sodium was first reacted with the triethylene glycol in tetrahydrofuran. This was followed by the addition of the bromo-compound and the reaction mixture was then refluxed for 4 days. The triethoxylated alcohol product was purified by vacuum distillation and the purity was checked by GC. The purified triethoxylated alcohol was reacted with 0.98 equivalent of metallic sodium in toluene followed by one equivalent of distilled propane sultone in toluene. The final product was purified by liquid chromotography. The purity of the final product was established by NMR spectroscopy. The inter facial tension of this product in aqueous solutions of various concentrations and of various salinities was then determined, against a crude oil. A spinning drop Interfacial Tensionmeter was used, and measurements were made after 30 minutes spinning at 10 or 14 msec., or longer, or until no more change in the drop took place. The width of the drop was then measured. The inter facial tension was calculated according to the equation: EMI9.1 where IFT = Interfacial Tension, dynes/cm ad = difference in density between oil and brine, g/ml Dm = diameter of oil drop, mm P = spinning speed, msec The data obtained is set out in Table 1. TABLE 1 Salinity, Percent Concentration, Percent IFT, dyne/cm 16.6 2 0.019 1 0.021 0.5 0.024 0.1 0.021 0.01 0.016 0.001 0.002 20.0 2 0.019 1 0.022 0.5 0.011 0.1 0.008 0.01 0.007 0.001 0.006 26.0 2 0.005 1 0.003 0.5 0.017 0.1 0.010 0.01 0.042 0.001 0.041 Surprisingly low tensions persisted over a span of salinity of 10 percent, and over a concentration range of three decades. EXAMPLE 2 (COMPARATIVE) Preparation of Linear Dodecyloxytriethoxypropane Sulfonate n-C12H25-0-(C2H40)3-CH2-CH2-CH2-S03Na The procedure described in Example 1 was used except that l-dodecanol was used in place of 2-butyloctanol. The interfacial tension data for the sulfonate were obtained in the manner described in Example 1 and are listed in Table 2. TABLE 2 Salinity, Percent Concentration, Percent IFT, dyne/cm 16.6 2 0.21 1 0.180 0.5 0.193 0.1 0.162 0.01 0.140 0.001 0.117 20.0 2 0.148 1 0.164 0.5 0.144 0.1 0.150 0.01 0.157 0.001 0.066 26.0 2 0.085 1 0.094 0.5 0.066 0.1 0.077 0.01 0.049 0.001 0.069 Clearly the compound of Example 2 does not produce ultra-low inter facial tension between oil and water in the specified salinity range. EXAMPLE 3 Preparation of Branched Tetradecyloxytriethoxypropane Sulfonate EMI11.1 The procedure described in Example 1 was used except that in place of 2-butyloctanol, an equivalent amount of 2-pentylnonanol was used. The interfacial tension data listed in Table 3 were obtained as described in Example 1. TABLE 3 Salinity, Percent Concentration, Percent IFT, dyne/cm 10.0 2 0.019 1 0.023 0.5 0.027 0.1 0.015 0.01 0.006 0.001 0.013 14.4 2 0.009 1 0.008 0.5 0.006 0.1 0.007 0.01 0.012 0.001 0.055 16.6 2 0.009 1 0.008 0.5 0.013 0.1 0.018 0.01 0.037 0.001 0.096 This C14-alkyl compound produces low tension at lower salinities than the C12-alkyl compound of Example 1. EXAMPLE 4 Preparation of Branched Hexadecyloxytriethoxypropane Sulfonate EMI12.1 The procedure described in Example 1 was used except that in place of 2-butyloctanol, an equivalent amount of 2-hexyldecanol was used. The interfacial tension data of the product are listed in Table 4. TABLE 4 Salinity, Percent Concentration, Percent IFT, dyne/cm 10.0 1 0.012 0.1 0.026 0.01 0.040 0.005 0.019 8.0 1 0.007 0.1 0.007 0.01 0.005 6.0 1 0.007 0.1 0.005 0.01 0.006 0.005 0.008 4.0 1 0.019 0.1 0.032 0.01 0.014 0.005 0.014 2.0 1 0.039 0.1 0.044 0.01 0.030 0.001 0.033 EXAMPLE 5 Preparation of Branched Dodecyloxytriethoxypropane Sulfonate EMI13.1 160 9. (0.8586 mole) 5-dodecanol was charged to a 4-neck flask fitted with a Dean-Stark trap, thermometer, nitrogen inlet tube and addition funnel. Mixed xylenes (700 ml.) were added. While the mixture was stirred magnetically, 25 ml. of xylene and traces of moisture were -distilled out to the Dean-Stark trap. After 3 hours of reflux the trap was emptied. Then n-butyl lithium (0.8586 mole) in hexane was introduced under nitrogen. Solvent was distilled off until the temperature rose to 1380C. After boiling had stopped 238.5 g (0.9549 mole) ofg -±2-[2-(2-Chloroethoxy)ethoxy]ethoxyg -tetrahydropyran was added and the reaction mixture was refluxed under nitrogen for 114 hours. The mixture was then cooled and filtered. Xylene was removed, the product taken up in petroleum ether and the ether solution was washed with brine and dried. The petroleum ether was then stripped off and the residue was dissolved in 1.8 1 of anhydrous alcohol. To the solution 37 g. of pyridine p-toluenesulfonate were added and the mixture was refluxed under nitrogen for 18 hours. 12.4 g. of potassium hydroxide was then added and the mixture refluxed for 2 hours. The alcohol was then stripped off and the crude product was dissolved in ether and the solution washed with water and dried. When the ether had been removed the crude product was purified by vacuum distillation. A fraction boiling at 156or to 157or at 0.3 torr. was shown to be high purity triethoxylated 5-dodecanol by GC. The purified triethoxylated alcohol was reacted with 0.98 equivalent of metallic sodium in toluene followed by reaction with one equivalent of freshly distilled propane sultone. The final product was purified by liquid chromatography. The purity of the final product was established by NMR spectroscopy. Its interfacial tension data are listed in Table 5. TABLE 5 Salinity, Percent Concentration, Percent IFT, dyne/cm 20 0.1 0.0078 0.01 0.0033 0.001 0.076 22 0.1 0.0087 0.01 0.0267 0.001 0.0667 24 0.1 0.0132 0.01 0.0406 0.001 0.108 EXAMPLE 6 Preparation of Branched Tetradecyloxytriethoxypropane Sulfonate EMI14.1 The procedure described in Example 5 was used except that 6-tetradecanol was used in place of 5-dodecanol. The interfacial tension data for the product are given in Table 6. TABLE 6 Salinity, Percent Concentration, Percent IFT, dyne/cm 6 0.1 0.0395 0.01 0.0268 0.001 0.0537 10 0.1 0.0029 0.01 0.0027 0.001 0.008 14.4 0.1 0.0054 0.01 0.0238 0.001 0.0417 16.6 0.1 0.0366 0.01 0.0449 0.001 0.091 It is surprising to see that low tensions persist over a span of salinity of 10% and over a concentration range of three decades. EXAMPLE 7 (COMPARATIVE) Preparation of Linear Dodecyloxytriethoxypropane Sulfonate n-C12H25-0-(C2H40)3-CH2-CH2-CH2-S03Na Triethylene glycol n-dodecyl ether was reacted as described in Example 5, with 0.98 equivalent of metallic sodium in toluene followed by reaction with one equivalent of freshly distilled propane sultone. The purity of the final product was established by NMR spectroscopy. The interfacial tension data of this product are given in Table 7. TABLE 7 Salinity, Percent Concentration, Percent IFT, dyne/cm 16.6 0.1 0.162 0.01 0.140 0.001 0.117 22 0.1 0.178 0.01 0.184 0.001 0.134 EXAMPLES 8-11 These Examples illustrate the process of the invention. Examples 8 and 9 illustrate specific conditions required for the second stage of the reaction and show that high allyl ether conversion can be achieved without a high yield of the desired sulfonate being obtained (Example 8) and that control over the course of the sulfonation can be achieved by appropriate choice of solvent (Example 9). Example 10 illustrates the two-stage reaction of the invention carried out in the presence of final product as a phase transfer agent; Example 11 illustrates the process of the invention carried out in the absence of such a phase transfer agent. The compounds identified as I, II, III and IV in these Examples are identified as follows (n = 4.2): EMI16.1 EMI17.1 EXAMPLE 8 A one liter, 4-neck flask equipped with a mechanical stirrer was charged witrh 120 ml methanol, 75 ml H20, 27 g sulfonate III and 66.9 g allyl ether II. The resulting homogeneous solution was stirred at about 800-1000 RPM while air was passed through the flask at about 15 ml/min and a solution of 18.72 g NaHSO3 and 11.34 g Na2S03 in 69 ml H20 was added dropwise over about one hour. Stirring was stopped occasionally and the reaction mixture analyzed by HPLC on a Water's Associates -vt-Bondapak C-18 column using 0.05M Bu4N+H2P04 in 86% methanol - 14% H2O as eluant. A W detector set for 277 nm was used. Since each of the compounds has the same UV chromophore with 3 max = 277 nm, the output of the detector could be translated directly into product yield. As the reaction proceeded the temperature rose by about 5 C. Analysis by HPLC showed three materials with retention volumes 4.3 ml, 6.7 ml, and 34.3 ml. The second and third peaks had retention volumes identical to the sulfonate III and the allyl ether II, respectively. Within two hours of the start of the reaction HPLC analysis indicated 95% of the allyl compound II had reacted but only 15% of this had been converted to sulfonate II. The rest had been converted into sulfite IV whose structure was confirmed by C-13 NMR and chemical degradation. The reaction mixture was allowed to stand overnight and then filtered from precipitated inorganic salts, evaporated on a rotary evaporator and a C-13 NMR obtained. In addition to the peaks expected for sulfonate III (by comparison to a spectrum of authentic III, two additional peaks due to one carbon each were seen at 62.9 ppm and 25.1 ppm. These are assigned to the NaO2-S-O-CH2-CH2- carbons of sulfite IV. This material was shown to be the sulfite by heating the reaction product at 600C at 0.05 mm Hg for four hours. A gas was collected in a Dry Ice trap. Infrared analysis showed this gas to be sulfur dioxide. Carbon-13 NMR of the remaining material in moist CDC13 showed the peak at 62.9 ppm to be gone and a new peak at 57.4 ppm to have appeared. This new chemical shift is identical to that of 3-methoxy-l-propanol. These results may be summarized by the reaction scheme EMI18.1 EXAMPLE 9 The procedure of Example 8 was repeated but with ethanol substituted for methanol. After three hours, the conversion of II was 99% and the yield of sulfonate III was not 14% as in Example 8 but 92%. EXAMPLE 10 HPLC was carried out by injecting samples into a Whatman ODS C-18 column and eluting at 2 ml/min with a solvent whose composition changed linearly from 70% methanol (30% H20) to 100% methanol over 15 minutes. Under these conditions, compounds III and IV had retention volumes of from 3.6 to 6.1 ml, compound I had a retention volume of 14.4 ml and compound II had a retention volume of 18.8 ml. Thus, to a four-neck 250 ml flask were added 19.3 g allyl chloride (.252 mole), 10 g 51% NaOH (.128 mole), 20.3 g I (.050 mole) and 5.05 g III (.0092 mole). The mixture was heated to reflux and stirred mechanically under argon. Aliquots were removed periodically and analyzed by HPLC. The results were as follows: Reflux Time (hours) % Reaction 1 84 3 86 6 91 22 97 At the end of the reflux period, the excess allyl chloride was distilled off, the reaction mixture was cooled, air flowed through the flask at about 15 ml/min and 40 ml 95% ethanol were added. After stirring briefly to assure air saturation, a solution of 15.7 g NaHS03 and 3.6 g Na2S03 in 42 ml H20 was added dropwise over 15 min. The temperature rose to 340C and HPLC analysis after 3 hours indicated that less than 1% allyl ether II remained. An aliquot was stripped and analyzed by C-13 NMR as described in Example 8. It showed 4% sulfite IV to be present so the overall conversion of I was 96% and the overall yield of propane sulfonate III was 92%. The flask was cooled to 150C, inorganics filtered off and the ethanol and water removed to give 33.5 g of pale yellow wax. EXAMPLE 11 Polyethyleneoxy alcohols are known to act themselves as phase transfer agents (see for example, Journal of Organic Chemistry, 45, 1095 (1980). Thus, compound I catalyzes its own reaction at the beginning of the process but as it is converted to allyl ether II the reaction slows and stops. If the alcohol is not a polyethyleneoxy alcohol but is a normal alcohol, no reaction will occur (as documented in the article by Freedman cited above). 19.3 g Allyl chloride, 30.3 9 alcohol I, and 10 g 51% NaOH were stirred and refluxed under argon and the reaction analyzed by HPLC as described in Example 10. The results were as follows: Reflux Time (hours) % Reaction 1 70 3 77 6 79 22 83 EXAMPLE 12 155.9 grams of Berea sand (less than 325 mesh) were packed into a 1.8 m glass column. The pore volume of this sand-pack column was determined to be 35 ml (by vacuum filling the dry column with West Burkburnett (WBB) brine having 16.6 percent salinity). The brine was displaced by crude oil until no more brine was produced. The crude oil in the column was equivalent to the oil in a reservoir before secondary water flooding. The column was then flooded with the 16.6 percent brine until no more oil was produced. This was, accordingly, equivalent to secondary water flooding in the field. The oil which remained in the column was equivalent to tertiary oil in the field and was determined to be 9.2 ml or 26.9 percent saturation. Into the column containing the tertiary oil a slug of 0.2 pore volume (or 7 ml) of a 2 percent solution of the sulfonate prepared in Example 1 in 16.6 percent brine was injected; nothing else was added. This slug of surfactant was followed by addition of a mobility control slug consisting of 0.1 percent Xanthan gum in 1 percent aqueous NaCl solution until no more oil was produced. By this process oil started to produce when 0.87 pore volume of fluid was pumped through; 43.5 percent oil was produced after 2 pore volumes and 45 percent was produced after 3.58 pore volumes. This clearly shows that the branched alkoxypolyethoxypropane sulfonate is suitable for use alone to enhance tertiary oil recovery without the need of a co-surfactant, even under high brine conditions. EXAMPLE 13 An oil recovery experiment similar to that described in Example 12 was performed, except that a 20 percent brine solution was used instead of a 16.6 percent solution. The results are given below: Weight of Sand: 155.8 gm Pore Volume: 36.0 ml Tertiary Oil: 9.7 ml Surfactant Slug: 1.2 pv of 2 percent surfactant in 20 percent WBB Brine Mobility Control Slug: 0.1 percent Xanthan Gum in 1 percent NaCl Oil Recovery: Started at 0.7 pv; 13.4 percent at 0.75 pv; 46.4 percent at 1.34 pv; 47.9 percent at 1.83 pv. This data further shows that the alkoxytriethoxypropane sulfonates of the invention are suitable as single component surfactants in the recovery of tertiary oil under extremely high brine conditions. EXAMPLE 14 Into a 1.8 m glass column were packed 162.8 grams of Berrea sand (325 mesh). The pore volume of this sand-pack column was determined to be 39.4 ml. (by vacuum filling the dry column with 10% West Burkburnett brine). The brine was displaced by West Burkburnett crude oil until no more brine was produced. The crude oil in the column, which is equivalent to the oil in a reservoir before secondary -water flooding, was flooded with 10% West Burkburnett brine until no more oil was produced. This was equivalent to the secondary water flooding in the field. The oil remaining in the column was the tertiary oil and was determined to be 10.0 ml or 28.6% saturation. Into the column containing the tertiary oil was injected a slug of 1 pore volume (39.4 ml.) of a 0.3% solution of the compound of Example 6 in 10% West Burkburnett brine, which also contained 1.0% lignin sulfonate and 500 ppm scleroglucan polysaccharide pusher. This slug of surfactant was followed by a first mobility control slug of 0.3 pore volume of 500 ppm of scleroglucan polysaccharide in 10% brine and a second mobility control slug of 0.2 pore volume of 250 ppm of the polysaccharide in 10% brine. These slugs were followed by 10% brine until no more oil was produced. By this process 42% of the oil was produced after 1 pore volume of fluid was pumped through; 72% was produced after 1.3 pore volumes, and 82% was produced after 2.56 pore volumes. EXAMPLE 15 An oil recovery test as described in Example 14 was performed but using 22% West Burkburnett brine with the compound of Example 5 instead of 10% brine with the compound of Example 6. The results are set out below: Weight of Sand: 158.1 g Pore Volume: 37.45 ml. Tertiary Oil: 9.7 ml Surfactant Slug: 1 pv of 0.3% surfactant with 1% lignin sulfonate and 500 ppm scleroglucan polysaccharide in 22% brine Mobility Control Slug: 0.3 pv of S00 ppm scleroglucan polysaccharide, 0.2 pv of 250 ppm polysaccharide in 22% brine, followed by 22% brine only Oil Recovery: 21.6% at 1 pv; 48.5% at 1.5 pv; 78.4% at 2.57 pv It is shown that the compound of Example 5 recovered tertiary oil under extremely high brine conditions. EXAMPLE 16 A 1.8 m sand-pack column containing 158.8 gm Berea rea sand was vacuum filled with 20% brine. The pore volume was determined to be 37.2 ml. The brine was displaced by crude oil until no more brine was produced. The oil in the column was then flooded with 20% brine until no more oil was produced leaving a residual oil of 9.85 ml or 26.5% residual oil saturation. The column was then flooded continuously. with 0.01 wt.% of the compound prepared in Example 1, in 20% brine. Oil started to produce after 0.9 pore volume; an amount of 5.2% was produced after 1.7 pv and 9% after 3.5 pv. The process is slow but incremental oil was produced. EXAMPLE 17 The procedure described in Example 16 was repeated except that the surfactant solution also contained 3% lignin sulfonate. 16% Oil was produced after 3.5 pore volume. EXAMPLE 18 The procedure described in Example 16 was repeated except that the surfactant solution was 0.1% of the compound of Example 1 in 20% brine. A recovery of 12% was achieved after 4 pore volumes. EXAMPLE 19 The procedure described in Example 18 was repeated except that the surfactant solution also contained 3% lignin sulfonate. A recovery of 50% residual oil was achieved after 3 pore volumes and 80% after 4 pore volumes. This experiment shows that lignin sulfonate significantly improves the oil recovery. EXAMPLE 20 The procedure described in Example 19 was repeated except that the surfactant solution contained 1% lignin sulfonate. A recovery of 50% was achieved after 4 pore volumes and 75% after 5 pore volumes. EXAMPLE 21 The procedure described in Example 16 was repeated except that the 20% brine was replaced by 16.6% brine. The surfactant solution contained 0.1 wt.% of the compound of Example 1 and 1 wt.% lignin sulfonate as a sacrificial chemical. The column was flooded by this surfactant solution in a continuous mode; 37% tertiary oil was recovered after 2.34 pore volume and 60% after 3.74 pore volume. EXAMPLE 22 The procedure described in Example 16 was repeated except that 12% brine was used, the surfactant solution contained 0.1 wt.% of the compound of Example 3, and 1 wt.% lignin sulfonate. The solution was injected in a continuous mode; 11.8% tertiary oil was recovered after 3.82 pore volumes, 41.2% after 5.00 and 54.1% after 6.74 pore volumes. EXAMPLE 23 The procedure described in Example 16 was repeated except 6% brine was used, the surfactant solution contained 0.1 wt.% of the compound of Example 4, and 1% lignin sulfonate. One pore volume of this surfactant solution was injected followed by a continuous injection of 0.15% polytranpolysaccharide in 6% brine. The tertiary oil was completely recovered after 1.2 pore volume of flooding. EXAMPLE 24 This example shows that incorporation of a mobility control agent results in much earlier oil production. The sand-pack with residual oil was prepared as described in Example 16. Thereafter, a surfactant solution containing 0.3 wt.% of the compound of Example 4, 1.0 wt.% lignin sulfonate as a sacrificial chemical, and 500 ppm Polytran (a nonionic polysaccharide) in 6% brine was flooded into the sand-pack column. After 1 pore volume of the surfactant solution was flooded through, tapered mobility control solutions were injected: 0.3 pore volume of 500 ppm, 0.2 pore volume of 250 ppm of Polytran in 1% NaCl followed by 1% NaC1 solution. A recovery of 45% of oil was accomplished after one pore volume and 92% after 2.4 pore volume production. No pressure build up was observed. EXAMPLE 25 Similar results to those of Example 24 were obtained when the mobility control slugs were in 6% brine instead of 1% NaCl. EXAMPLE 26 Similar results to those of Example 24 were obtained when the compound of Example 1 was used in 22S brine. EXAMPLE 27 Similar results to those of Example 24 were obtained when the compound of Example 3 was used in 12% brine.

Claims: CLAIMS: 1. A compound having the general formula RO (C2H40) xCH2CH2CH2SO3Na in which R is a branched aliphatic group having from 10 to 30 carbon atoms and x has a value from 2 to 6. 2. A compound according to claim 1, in which R is an alkyl group. 3. A compound according to claim 1 or claim 2, in which the branching in R is such that the compound has its minimum oil/water interfacial tension in brine of less than 30 percent, the minium inter facial tension being a factor of 0.5 or less than that of the corresponding compound in which R is unbranched, measured at the same percent salinity. 4. A compound according to any one of claims 1 to 3, in which R is EMI26.1 in which each of R1 and R3 has from 7 to 26 carbon atoms and R2 has from 2 to 10 carbon atoms. 5. A compound according to claim 4, in which each of R and R3 has from 8 to 12 carbon atoms and R2 has fromm 4 to 6 carbon atoms. 6. A compound according to claim 1 as specified in any one of Examples 1 and 3 to 6 herein. 7. A process for preparing a compound of the general formula RY(C2H40)xCH2CH2CH2SO3Na in which R is an alkyl or alkaryl group, Y is O or S and x has a value from 0 to 20, which comprises reacting together an alcohol RY(C2H40)XH, sodium hydroxide and allyl halide or tosylate to form the corresponding allyl ether RY(C2H40)xCH2CH=CH2 and reacting the allyl ether with sodium bisulfite, the first stage of the reaction being carried out in strong aqueous sodium hydroxide in the presence of sufficient final product to function as a phase transfer agent, and the second stage being carried out without isolation of the intermediate allyl ether. 8. A process according to claim 7, in which R is an alkyl group having from 1 to 16 carbon atoms or an alkaryl group having from 7 to 16 carbon atoms and x is zero or has a value from 2 to 6. 9. A process according to claim 7 or claim 8, in which the first stage is carried out in the presence of from 0.1 to 1 mole of the final product per mole of alcohol RY(C2H40)XH. 10. A method for recovering oil from a subterranean oil reservoir having one or more production wells and one or more injection wells in contact with the reservoir, comprising injecting into the oil reservoir an aqueous medium which includes as the sole surfactant, a compound having a branched alkyl substituent with at least one, two-carbon atom branch, in a concentration effective to increase oil production from the production well during secondary water flooding or to recover residual tertiary oil when the oil reservoir has been previously flooded. 11. A method according to claim 10, in which the oil reservoir is a high salinity reservoir. 12. A method according to claim 11, in which the oil reservoir has a salinity of from 4 to 30% brine. 13. A method according to any one of claims 10 to 12, in which the surfactant is a compound according to any one of claims 1 to 6. 14. A method according to any one of claims 10 to 13, in which the aqueous medium includes a sacrificial compound in an amount effective to substantially reduce absorption of the surfactant and thereby further increase oil production from the production well. 15. A method according to claim 14, in which the sacrificial compound is lignin sulfonate. 16. A method according to claim 15, in which the amount of lignin sulfonate is from 0.75 to 2 weight percent.

Inventors: HSIA CHEN, CATHERINE SHUIHUA, WILLIAMS, ALBERT LLOYD
Applicants: MOBIL OIL CORPORATION
Application year: 1982
Main classification: C07C143
IPC codes: C07C309, C07C43, C09K8