SU1508967A3 - Method of producing residual oil - Google Patents

Abstract

The invention relates to the oil industry. The goal is to reduce the interfacial tension between the oil and water. Surfactants are injected into an underground oil reservoir to displace oil from the reservoir in an amount sufficient to reduce the interfacial tension between the oil and water. As a surfactant, a mixture containing the following components is introduced into the reservoir with their ratio: 1-7% of a mixture of mono- and dialkyl-substituted aromatic hydrocarbon, obtained by alkylating the aromatic hydrocarbon with an olefinic hydrocarbon containing 10-13 carbon atoms in the chain, in the presence of hydrogen fluoride in alkylation conditions, and 2% lower alkyl alcohol containing 3-6 carbon atoms or 0.4% non-ionic ethoxylated normal alcohol containing 12-15 carbon atoms. The use of this surfactant provides greater extraction of tertiary oil with a correspondingly smaller amount of final residual oil. 5 tab.

Description

The invention relates to the oil industry, in particular to the extraction of residual oil from a formation.

The aim of the invention is to reduce the interfacial tension between oil and water.

The method consists in introducing an aqueous surface-active agent into the underground oil reservoir in order to displace oil from the reservoir, and the surface-active agent is used in an amount sufficient to reduce the interfacial tension between the oil and water. Improvement. : consists of using an aqueous mixture containing 1-10% sulfonate as a surface-active agent

I mixtures of mono- and dialkyl-substituted aromatic hydrocarbons obtained by alkylation of an aromatic hydrocarbon with a straight or branched chain olefinic hydrocarbon containing 6-22 carbon atoms of c. chains in the presence of a catalyst containing fluoride, hydrogen in the state of alkylation, and 1 to 10% lower alkyl alcohol containing 3 to 6 carbon atoms, or 0, t to 2% non-ionic ethoxylated normal alcohol containing 12 to 15 carbon atoms. The proposed method uses an aqueous surface-active agent to reduce the interfacial tension between the oil and water, and this

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the agent contains a mixture consisting of neutralized sulphonates of a mixture of mo-moalkyl- and dialkyl-substituted aromatic hydrocarbons, obtained by alkylating benzene with an olefinic hydrocarbon in the presence of hydrogen fluoride at temperatury ranging from ambient to C0, with aromatic hydrocarbons present in the reaction mixture at mole The ratio is from 3: 1 to 1:10 mol of aromatic compound per 1 mol of olefinic hydrocarbon, while the aforementioned sulfonate is neutralized by the addition of sodium compound , Lower alkyl alcohol having 3-6 carbon atoms, or a nonionic surfactant - agent comprising an ethoxylated n-alcohol, with 12 - 15 carbon atoms. Sulfonated dialkyl aromatics, used as one of the components of the surfactant according to the invention, provide the possibility of reducing the interfacial tension between the oil present in the subterranean formation and water to 10 dyne / cm, which makes this system industrially cost-effective when extracting oil. In addition, mono- and dialkyl-substituted aromatic hydrocarbons used in the surface-active agent withstand the presence of sodium chloride, which

 usually present in saline solution and exhibits a tendency to precipitate sulfonates, especially sulfonates derived from petroleum. This precipitation of petroleum sulfonates reduces the effect of the sulfonate as a surface-active agent. Other advantages of mono- and dialkyl-substituted aromatic hydrocarbons are the tolerance of calcium and magnesium to the sulfonate and in preventing the exchange of sodium ions used to neutralize the sulfonate with subsequent 1m precipitation, as well as the relatively good stability of the sulfonate in water.

The surface-active agent contains, as one of its components, a sulfonate of mono- and dialkyl-substituted aromatic hydrocarbons with a low content of 2-aryl. Olefinic hydrocarbons used as alkylating agents for semi

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The compounds you are looking for may be linear or branched. Linear alkenes preferred as starting materials in the formation of mono- and di-alkyl aromatic hydrocarbons are usually a mixture of olefins obtained by dehydrating normally saturated hydrocarbons to form unsaturated hydrocarbons, and this dehydration is carried out by using a solid acid-free catalyst. containing a metal or compound of a metal or its mixtures, and the catalytic component of this catalyst is usually chosen from groups IVB and VIII of the Periodic Table of the Elements. The olefin product obtained by dehydration of this type usually contains olefins with 10–22 carbon atoms in the chain and, due to the dehydration process, has a high degree of internal non-condensation, i.e. unsaturated alkene bonds present on carbon atoms that are not terminal in the chain. Olefins of the type, which is preferably alkylating, 1; s agents are olefins, in which the internal unsaturation is 90-94%, the remainder of this unsaturation is final.

The desired olefins can be separated from the hydrocarbon mixture containing unreacted alkenes by treating the hydrocarbon mixture in the liquid phase with a fixed bed of solid sorbent, which can be aluminosilicate. These olefins are adsorbed on the aluminosilicates and recovered.

Olefinic hydrocarbons may contain a branched-chain compound obtained from other reactions, and they are used as alkylating agents to produce mono- and dialkyl-substituted aromatic hydrocarbons. Suitable aromatic hydrocarbons that can be alkylated with olefinic hydrocarbons include benzene, naphthalene, anthracene or aromatic compounds containing lower alkyl substituents, for example toluene, o-xylene, p-xylene, ethylbenzene, isomeric dietbenzenes and ToPo Other aromatic compounds In addition to hydrocarbons, for example, phenol and isomeric cresols, it is also possible to alkylate according to the proposed method and use it in an aqueous surface-active agent, although not necessarily with equivalent results. Aplylation of mono- and diaplyl-substituted aromatic hydrocarbons, which is desirable for obtaining mono- and dialkyl-substituted aromatic hydrocarbons can be carried out under alkylation conditions, including from 2 to atmospheric, up to 50 atm, and elevated pressures are obtained by introducing inert gas, for example nitrogen, gels, argon, etc., in the reaction vessel. To accelerate the dialkylation of this aromatic compound, the reagents must be present in a molar ratio of from 3: 1 to 1:19 mol of aromatic hydrocarbons — per 1 mol of olefinic hydrocarbons. In addition, the amount of hydrofluoric i

: The catalyst used in the process must be such that the resulting temperatures range from 25 to 100 ° C and pressures from

The ratio of organic material to catalyst is from 10: 1 to 1: 3 in weight units.

Alkylation of an aromatic hydrocarbon with an olefinic hydrocarbon can be carried out in an autoclave, loading an aromatic hydrocarbon into an autoclave containing a hydrogen fluoride catalyst, followed by the addition of an olefinic charge. After the alkylation was carried out under the reaction conditions in the above ranges for a predetermined time, which can be 0.1-0.5 h, during which the reaction mixture is continuously stirred, heating is stopped and after returning to room temperature relieve excess pressure At the end of the residence time, the mixture is allowed to separate into aqueous and organic layers, followed by separation, and the organic layer is neutralized by adding caustic, resulting in entrapped or trapped hydrogen fluoride present in the organic layer, is recovered. Mono- and dialkyl-substituted aromatic hydrocarbons thus obtained with a low 2-phenyl content can then be sulphonated by treatment.

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mono- and dialkyl-substituted aromatic hydrocarbons in the reaction flask with a sulphating agent, such as sulfur trioxide or sulfuric acid, in the presence of an organic solvent, which may include paraffin, for example, cyclopentane, methylcyclopentane, cyclohexane, etc.

10 Mono- and dialkyl-substituted aromatic hydrocarbons can be loaded into the reaction flask along with the solvent, and then the liquid sulfur trioxide is loaded under a layer of nitrogen into

J5. Reaction apparatus. The addition of three sulfur oxides to mono- and dialkyl-substituted aromatic hydrocarbons can be carried out at ambient temperature or at temperatures nos20. How many exceed the surrounding, i.e. approximately 60 ° C for 1–10 hours or more. Upon completion of the reaction, the mixture is neutralized by adding an alkaline component, which can

25 to be selected and a group consisting of ammonium hydroxide or a salt or hydro- (metal oxide group IA or IIA of the Periodic Table, for example sodium hydroxide, potassium hydroxide, lithium, magnesium, calcium, strontium, ammonium carbonate j

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sodium, potassium, lithium, magnesium, calcium, strontium, etc. When the pH of Bbmie 7 is reached, water is added to the reaction mixture along with an equal amount of alcohol, for example, x isopropyl alcohol. After thorough mixing, the mixture is heated to 50-75 ° C for a predetermined period of time and then allowed to cool. The alkaline sulphonate, which OT-V is made by cooling, is then removed by conventional means, for example by filtration, centrifugation, etc., and then the mixture is allowed to stand and it is not divided into two layers. The bottom layer, water-alcohol, can then be removed with an organic solvent, such as hexane, before the bleaching extracts. The upper, organic layer, together with the combined extracts, can then be washed with water, added to the aqueous layer. Thereafter . the aqueous layer is allowed to evaporate to dryness or else a drying device, such as a steam bath, is used to obtain neutralized mono- and dialkyl-substituted aromatic hydrocarbon sulfonate derivatives.

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The second component of the surfactant contains a surfactant active agent consisting of 11, of alkyl alcohol containing 3-6 carbon atoms, for example n-5 propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol , n-amyl alcohol, sec-amyl alcohol, n-hexyl alcohol, second hexyl alcohol, etc.

The third component of the surfactant contains a non-ionic surfactant containing ethoxylated normal 15

. alcohol with 12-15 carbon atoms in length (ethoxy-n-dodecyl alcohol, ethoxy-n-tridecyl alcohol, ethoxy-n-tetradecyl alcohol, ethoxy-n-pentadecyl alcohol, etc.). 20

The amount of all three components of the surfactant is usually 1-10% of the neutralized sulfonate of mono- and dialkyl-substituted aromatic hydrocarbons, 25 to extract oil into the layer an additional 1-10% of the surface-active agent is injected into the amount a lower alkyl alcohol base to displace the surface and 0.1-2% non-ionic surface-active agent and oil, and the ethoxy-based active agent, thus the oil is extracted into the molded n-alcohol. It may be added in such a quantity that the process of proving a method of increased extraction of L, T. In the process of enhanced oil recovery, an underground reservoir containing oil can be pre-washed with water in order to displace water used in the secondary process, which may have high salinity and / or hardness, from the flow channels in the reservoir. After washing, a surfactant is injected until a desired amount of surfactant is in the oil reservoir. Due to the presence of various components, including gas oil sulphonates and thermally cracked coal, the surfactant reduces the interfacial tension between oil and water and thus contributes to the displacement of oil through the formation in the well and through the wells to the surface to collect it. After

Chlorine sodium is also absent. in the amount of 1–5%. However, the presence of this salt is not necessary for the operation of a surface-active agent to reduce the interfacial tension between oil and sludge. .

Using a surface-active agent containing the described components, it is possible to carry out the continuous extraction of oil, in which the oil remaining in the subterranean formation can be forced out of this formation and from the voids of relatively porous rocks.

Surface-active agents can be obtained by mixing a specified amount of the mentioned neutralized sulfonate derivatives of mono- and dialkyl-substituted aromatic hydrocarbons to a surface-active agent and a non-ionic surface-active agent, and they are mixed in an aqueous medium.

The aqueous medium selected for the surfactant must contain produced water, which in many cases contains a low specific gravity brine. The surfactant thus obtained is then used for tertiary

Extraction of oil into the layer is additionally injected with water in an amount sufficient to displace the surface-active agent and oil, and thus the oil is extracted in such a quantity that the process of enhanced recovery of non-ferrous. In the process of enhanced oil recovery, an underground reservoir containing oil can be pre-washed with water in order to displace water used in the secondary process, which may have high salinity and / or hardness, from the flow channels in the reservoir. After washing, a surfactant is injected until a desired amount of surfactant is in the oil reservoir. Due to the presence of various components, including gas oil sulphonates and thermally cracked coal, the surfactant reduces the interfacial tension between oil and water and thus contributes to the displacement of oil through the formation in the well and through the wells to the surface to collect it. After

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Example 1. The autoclave with a stirrer was purged with nitrogen and 33 ml (0.3713 mol) of benzene were charged into it. After that, the autoclave was cooled to 10 ° C and 2000 g of hydrogen fluoride was loaded into it. The autoclave was brought to the reaction temperature of 40 ° C and 2635 ml (1.458 mol) of an alkylating agent containing QMecb olefins with 10 to 13 carbon atoms in the chain were added over 15 minutes. After completion of the addition of olefins, the mixture was transferred at 40 ° C for 15 minutes. At the end of this time period, the stirring was stopped, the autoclave was cooled to 10 ° C, and hydrogen fluoride was removed through a sight glass in a bucket with ice. Then a mixture of water and calcium carbonate was lowered into the hydrocarbon layer to neutralize the residual hydrogen fluoride. After holding, the hydrocarbon product layer was separated and the aqueous phase was washed with pentane. The organic layers were dried on sodium sulfate, filtered, and fractionated in a column to remove paraffins, benzenes, and olefin. Alkylated products were subjected to qualitative and quantitative gas chromatography as well as mass spectrometry. The yield is 38.6% monoalkylate, 40.2% dialkylate together with 18.0% unknown compounds.

For the preparation of sodium sulfonate derivatives, an alkylirovan product 50.0 g of alkylate was mixed with the same

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The alkyl product was sulfonated as described in Example 1, treating it with liquid sulfur trioxide at 40 ° C. After neutralization and recovery, the desired product yield is:. sodium sulphonate was 76%. Equivalent weight of sodium sulphonate determined by titration

the amount of hexane and the mixture of peretaka Qi free sulfonic acids with sodium hydroxide, was 421 with a theoretical equivalent weight of 400,

Example 3 In a similar manner, benzene was alkylated by stripping and heating to 60 ° C. A quantity of liquid sulfur trioxide, equimolar to the amount of alkylate, was placed in a bubbler and introduced into the alkylate solution for 3 hours as a 5% gas treatment component. propylene tetramer with a branched nitrogen mixture. After being completed with a chain, the reaction was added with sulfur trioxide and the mixture was stirred at the reaction temperature, sparged with nitrogen for 1–3 hours. After that, the mixture was neutralized to 20 pH 8 using 50% w / w sodium hydroxide in water, removing water as anisotropic using isopropyl alcohol. The precipitated sodium sulfonate was removed from the solution from 25% to 21% of the monoalkylated propyl alcohol product by filtration, 37.4% of the dialkylated product. In addition, unreacted and 42.7% of the unknown compounds, the alkylate was extracted by

demineralized water isoxane hexane. Example 4, The product was measured for interphasicpropyl alcohol, Desired-30 tension of sodium sulfonate

were mixed in a one-liter autoclave with a stirrer in the presence of a hydrofluoric catalyst with a total reaction time of 60 minutes. The reagents containing benzene and tetramer were present in a molar ratio of 0.33: 1 mol of benzene per 1 mol of tetramer. A gas chromatograph analysis of the product showed

 the sodium sulfonate derivative of alkylated benzene was isolated, allowing the solution to evaporate to dryness on

.steam bath By titrating free sulfonic acids with ac hydroxide; frames 1 and 2, it was measured relative to sodium that the equivalent sulfonate and sulfonate compounds were measured

The sulphonate salt weight was 348 with a theoretical equivalent devil of 374.

Example 2 240 g of monoalkylated benzene, in which the alkyl part of the molecule contained 10 to 13 carbon atoms, was loaded into a liter. An autoclave purged with nitrogen. The autoclave was cooled to 10 ° C and 195 MP of an alkylating agent consisting of an olefin containing 11 carbon atoms in the chain was added to it within 15 minutes. Then the autoclave was mixed in

fractions derived from alkylation with aluminum chloride catalysis do not have the same composition as hydrogen fluoride alkylates. The surfactant compositions used in the interfacial tension test contained an aqueous solution containing 0.07% of the sodium sulfonate derivative of various alkyl aromatic compounds.

for 15 minutes, maintaining a temperature of 40 ° C and a pressure of 4.236 kg / cm. B1.0% of sodium chloride and 2.0 vol.% At the end of the reaction period, the stirring was stopped, the autoclave was cooled to 10 ° C and hydrogen fluoride was removed. The hydrocarbon layer was then treated as described above, and determined by gas chromatography that the alkylated product contained 29.8% of the dialkylated product.

Sue sodium was 421 with a theoretical equivalent weight of 400,

Example 3 In a similar way, benzene was alkylated by treating with a branched propylene tetramer, and the reaction with a wire of 21% monoalkylated product, 37.4% of dialkylated product 42.7% of unknown compounds,

branched chain tetramer, with a wire reaction of 21% monoalkylated product, 37.4% dialkylated product and 42.7% unknown compounds,

were mixed in a one-liter autoclave with a stirrer in the presence of a hydrofluoric catalyst with a total reaction time of 60 minutes. The reagents containing benzene and tetramer were present in a molar ratio of 0.33: 1 mol of benzene per 1 mol of tetramer. A gas chromatograph analysis of the product showed

derived diaptylamine aromatic compounds. Solutions of dialkyl-substituted aromatic compounds: which were obtained according to the example

, lei, derived from the lower fraction, i obtained from the distillation of monoalkyl- | benzenes of the detergent grade, Neft-40 NOW sulfonate and data sulfonates

fractions derived from alkylation with aluminum chloride catalysis do not have the same composition as hydrogen fluoride alkylates. The surfactant compositions used in the interfacial tension test contained an aqueous solution containing 0.07% sodium sulfonate derivative of various alkyl aromatic compounds.

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surfactant agent, the results of measurements are given in Table. 1, in which: A is dialkylsubstituted benzene according to example 1, B is dialkyl benzene according to example 2, C is the lower fractions of monoalkylbenzene derived from aluminum chloride, D is the lower fractions catalyzed by fluorine

hydrogen monoalkylbenzene, E - petroleum sulfonate.

Example 5. The test for tolerance to sodium chloride of various surface-active agents was carried out by mixing the initial solutions of the surface-active agent and alcoholic co-surface agents with the initial solutions of aqueous sodium chloride. The concentration of surfactants was maintained at a level of 2.5% by weight in the final solutions, while the concentration of sodium chloride and alcohols varied from 1.0 to 5.0% by weight. After 24 hours, the condition of the test solutions was observed. Different states have occurred: bright, slightly turbid, turbid, precipitate, separation into light layers and separation into layers, followed by precipitation. Light or slightly turbid solutions can then be used in tests of continuous displacement of the core. The test results for 2.5% by weight of surface-active agent, 2.0% by weight of sodium chloride and 2.0% by weight of n-butanol are as follows:

A. Slightly turbid

Lightly muddy

Slightly muddy

D separation into two

bright layers

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Example 6 To evaluate the use of sulfonated mono- and dialkyl-substituted hydrocarbons obtained by alkylation using hydrogen fluoride as a catalyst in comparison with other sulfonated derivatives, a water-flooding test was performed. In the first trial, a procedure was used to water the core of a diluted surface-active agent, in which a radial core consisting of Berea sandstone was burned for 3 hours. After that, the sandstone core was filled with field brine using a pump. After saturation of the field brine was injected, crude oil was injected into the core at a frontal flow velocity of 0.152 m / day. Upon completion of the injection of crude oil, 2.0 pore volumes of field brine were injected at the same rate.

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Roots of frontal fluid advance 0.152 m / day. After that, 0.15 pore volume of diluted over-1

 the notably active agent was injected at the same frontal velocity.

: fluid advancement followed by injection of 0.85 polymer pore volume and 1.50 fresh water pore volume. Dilution The surface active agents tested in these experiments included surface active agent F, which is a mixture of the sodium sulfonate sodium product obtained in example 1, plus co-surface agent containing ethoxylated alcohol sulfate. The surfactant agent G contains a sulfonate sodium derivative of an alkylate derived from petroleum, plus the indicated co-surface-active agent, whereas the surfactant agent H is a sulfate sodium derivative of a mixture containing 10% monoalkylates, 45% dialkylates, 40% diphenylalkyl - lats and 5% synthetic sulfonate plus co-surfactant. The results of these tests are shown in Table. 2, in which the extraction of oil is presented through the volume of production, the volume of pores obtained and the amount of oil produced as a percentage of the amount of oil present in the core just before

 extraction. In this table 3, means the percentage of residual oil saturated with water. A residual oil recovery test was also used to reduce the interfacial tension of only one.

polymer

From the comparison of the results presented in Table. 3, it is clear that the surface active agent in which is-. , use sodium sulfonate derivatives of a mixture of mono- and dialkyl-substituted aromatic hydrocarbons derived from alkylation in the presence of hydrofluoric aromatic hydrocarbon catalyst with olefinic hydrocarbon, as one of its components, results in a larger amount of oil recovered by the method of tertiary oil, as well as the same amount of tertiary oil produced with a correspondingly smaller amount of final residual oil j present in the core, fe compared with the amount chennym using other surface-active agents containing other derivatives sulfonatnatrievye monoalkylates and other dialkyl kilatovo The order of the tertiary oil recovery systems between the diluted surface-active agent and the polymer system will only Q F G H polymer.

Table 3 compares the interfacial tension characteristics of the three Surfactants.

Example 7. In a series of tests 5, a micelle evaluation of the properties of surface-active agents of various compositions was carried out. Given in tlbl. 4, the evaluation of diluted surfactants was performed with 2.0% Q / V / V) Isham, while the test micelle structure / polymer was submerged using the ratio of 7% (V / V) surfactant. The surfactants used in this comparison test were identical in nature to the surfactants shown in Example 6.

Surface-active agents were used to prepare a microemulsion by adding a surface-active agent to fresh water and adding to it a secondary surface-active agent in the form of sulfate. 35 ethoxylated alcohol. As ethoxylated alcohol sulfate, neodal 25-39 is used, which is a mixture of ethoxylation of alcohols with 12-15 carbon atoms. If-. 40 is the number of surfactants present, i.e. ethoxylated alcohol, 0.4%. This microemulsion was used as described in example 6, by injection of the Berea sandstone 45 into the radial core after the sandstone was saturated with field brine and oil. The results of this series of tests are given in Table. four.

These results also show that the 50 4TO surface agent offered provides greater extraction of tertiary oil with a correspondingly smaller amount of the residual oil present in the core 55 than when using

Claims (1)

other surface-active compounds or one polymer. The order of tertiary recovery of oil from micelle / polymer blends and the system from the polymer only is: F polymer only. Invention Formula A method for extracting residual oil by introducing a surfactant into an underground oil reservoir to displace oil from the reservoir in an amount sufficient to reduce the interfacial tension between said oil and water, characterized in that in order to reduce the interfacial tension between the oil and water, as a surfactant injected into. . A mixture containing 1 to 7% of a mixture of a mono- and dialkyl-substituted aromatic hydrocarbon obtained by alkylation of an aromatic hydrocarbon with an olefinic hydrocarbon, containing 10-13 carbon atoms in the chain, in the presence of hydrogen fluoride under alkylation conditions and 2% lower alkyl alcohol containing 3 -6 carbon atoms, or. 0.4% non-ionic ethoxylated normal alcohol containing 12-15 carbon atoms. T a b l and c a Determined by the method of Clayias et al. Surface-active agent is n-butanol. Surface active agent is isobutanol. The surfactant is isoamyl alcohol. 15 150896716 table 2 Table 3 Table 4