Hydrophobic compound emulsions free of silicon and fluorine for an oil recovering method that modifies the wettability of rocks from hydrophilic to oleophilic

Abstract

An oil recovery method by the modification of the rock wettability from hydrophilic to oleophilic using hydrophobic compounds. Specifically, the method relates to the application of oil-type emulsions in water based on hydrophobic compounds free of silicon and fluorine to increase the oil recovery in mature sandstone-type reservoirs after the injection of water.

Claims

1. A method of increasing oil production of wells in mature sandstone rock, comprising the steps of: introducing an oil-in-water emulsion into the well to modify the wettability of the sandstone rock, said emulsion comprising (1) a hydrophobic compound (A), where said compound (A) is a liquid phase at room temperature, insoluble in water and free of silicon and fluorine, and (2) an aqueous solution of an emulsifier (B), and recovering oil from the well, wherein said hydrophobic compound (A) has the formula C.sup.+Y.sup. where Y.sup. is an organic anion selected from the group consisting of chlorine, bromine, iodine, an organic carboxylate, an organic dicarboxylate, an organic sulfonate, and C.sup.+ is a cation selected from the group consisting of quaternary phosphonium cation; and an organic trialkyl sulfonium cation, and (B) is an alkyl sulfate, alkylpolyglycol ether or polyethoxylated alkyl polyphenol ether.

2. The method of claim 1, wherein the total amount of said compound (A) and emulsifier (B) is about 0.05-10% by weight based on the total weight of the emulsion.

3. The method of claim 1, wherein said aqueous solution of emulsifier (B) in said emulsion is present in an amount of 1 to 20 parts by weight per 100 parts by weight of said hydrophobic compound (A).

4. The method of claim 1, wherein said emulsifier (B) has an HLB of 10 or above and is selected from the group consisting of alkyl sulfates, alkyl ether sulfates, alkylpolyglycol ethers and polyethoxylated alkylphenol ethers having a linear or branched C.sub.8-C.sub.18 alkyl and containing 1-40 ethylene oxide or propylene oxide groups.

5. The method of claim 1, wherein said compound (A) in said emulsion has a droplet size of about 100 nm to 100 m, and where said droplet size is smaller than a pore size of said sandstone rock.

6. The method of claim 1, wherein C.sup.+ has the formula: ##STR00006## where R, R.sub.1, R.sub.2, R.sub.3 are independently selected from the group consisting of aliphatic, benzyl, aromatic, cycloalkyl and alkenyl chains, either linear or branched, with 6 to 18 carbon atoms.

7. The method of claim 1, wherein C has the formula: ##STR00007## where R, R.sub.1, R.sub.3 are independently selected from the group consisting of aliphatic, benzyl, aromatic, cycloalkyl and alkenyl chains, either linear or branched, with 6 to 18 carbon atoms.

8. The method of claim 1, wherein Y.sup. has the formula: ##STR00008## where R.sub.4 is selected from the group consisting of alkyl, cycloalkyl, benzyl, alkenyl, aromatic chains or alkyl functionalized, either linear or branched, with 1 to 18 carbon atoms and heterocyclic compounds having 4 to 10 carbon atoms that contain at least one heteroatom selected from the group consisting of nitrogen, sulfur and oxygen and with substitutes formed by alkyl, cycloalkyl, benzyl, alkenyl or aromatic chains or alkyl functionalized with 1 to 18 carbon atoms.

9. The method of claim 1, wherein Y.sup. has the formula: ##STR00009## where R.sub.4 is selected from the group consisting of alkyl, cycloalkyl, benzyl alkenyl, aromatic chains or alkyl functionalized, either linear or branched, with 1 to 18 carbon atoms and heterocyclic compounds having 4 to 10 carbon atoms that contain at least one heteroatom selected from the group consisting of nitrogen, sulfur and oxygen and with substitutes formed by alkyl, cycloalkyl, benzyl, alkenyl or aromatic chains or alkyl functionalized with 1 to 18 carbon atoms.

10. The method of claim 1, wherein said emulsion comprises 0.01-25% by weight of said hydrophobic compound (A), 0.0001-1% by weight of said emulsifier (B), and the balance water.

11. A method of increasing oil production of wells in mature sandstone rock, comprising the steps of: introducing an oil-in-water emulsion into the well to modify the wettability of the sandstone rock, said emulsion comprising (1) a hydrophobic compound that is a liquid at room temperature, insoluble in water and free of silicon and fluorine, and (2) an aqueous solution of an emulsifier (B), and recovering oil from the well, wherein said hydrophobic compound (A) has the formula C.sup.+Y.sup. where Y.sup. is an organic anion selected from the group consisting of chlorine, bromine, iodine, an alkyl carboxylate, a cycloalkyl carboxylate, a benzyl alkenyl carboxyl ate, an alkyl sulfonate, cycloalkyl sulfonate, and benzyl alkenyl sulfonate, and C.sup.+ is a cation selected from the group consisting of quaternary phosphonium cation and an organic trialkyl sulfonium cation, and (B) is a surfactant having an HLB above 10 and selected from the group consisting of a C.sub.8-18 is alkyl sulfate, C.sub.8-19 alkyl ether sulfate, a C.sub.2-40 alkylpolyglycol ether, and a C.sub.2-40 alkyl polyethoxy polyphenol ether, and where said emulsion comprises 1-5 parts by weight of said surfactant (B) based on 100 parts of said hydrophobic compound (A).

12. The method of claim 11, wherein said hydrophobic compound (A) has Y.sup. which is a C.sub.1-18 carboxylate anion.

13. The method of claim 1, wherein said hydrophobic compound is trioctylammonium octanoate.

14. The method of claim 11, wherein Y.sup. is an alkyl carboxylate anion.

15. The method of claim 1, wherein said organic trialkyl sulfonium cation is a trialkyl sulfonium cation having the formula ##STR00010## where R, R.sub.1, and R.sub.3 are independently a C.sub.6 to C.sub.18 alkyl.

16. The method of claim 1, wherein said quaternary phosphonium cation has the formula ##STR00011## where R, R.sub.1, R.sub.2, and R.sub.3 are independently a C.sub.6 to C.sub.18 alkyl.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In order to have a better understanding of the additional oil recovery method by modifying the rock wettability from hydrophilic to oleophilic using hydrophobic compound emulsions free of silicon and fluorine, the drawings featured in the present invention are described as follows:

(2) FIG. 1 depicts a diagram of the injection system used in the test, where 1 indicates the injection pumps, 2pressure differential, 3effluent collector, 4 and 5transfer cylinders, 6confinement pressure, 7rock core or sand package.

(3) FIG. 2 features a photograph of the sand packed cell.

(4) FIG. 3 displays core photographs: a) before the test, and b) after the test with the injection inlet face.

DETAILED DESCRIPTION OF THE INVENTION

(5) The present invention relates to an emulsion and to a new method for recovering additional oil after the process of injecting water in mature fields in sandstone-type reservoirs by the injection of O/W-type emulsions based on hydrophobic compounds free of silicon and fluorine. The emulsions comprise or consist of: 1) hydrophobic compound (A) in liquid phase at room temperature and insoluble in water, whose general formula is C.sup.+ Y.sup., where C.sup.+ represents an organic cation, specifically, although it is not limited to the tetralkylammonium, trialkylsulfonium and tetralkylphosphonium type, where the anion Y.sup. is represented by halides or carboxylic, sulfonic and dicarboxylic acid derivatives with different substitutes; 2) aqueous solution of an emulsifier (B), which is represented by a commercial non-ionic tensoactive derived from polyethoxyethanol with different length and ramification chains; and is soluble in water.

(6) More specifically, the present invention refers to the preparation of emulsions based on hydrophobic compounds (A) (as shown in Table 1) free of silicon and fluorine that are liquids at room temperature and immiscible in water.

(7) Emulsifier (B) can be chosen from the following surfactants with hydrophilic-lipophilic balance value (HLB) above 10: 1. Alkyl sulfates, which have an alkyl chain length from 8 to 18 carbon atoms; alkyl ether sulfates with an alkyl chain from 8 to 19 carbon atoms, which contain 1-40 unit blocks of ethylene oxide or propylene. 2. Alkylpolyglycol ethers, which have from 2 to 40 ethylene oxide units and from 2 to 40 carbon atoms in the alkyl chain which can be either linear or branched. 3. Polyethoxylated alkylpolyphenol ethers, which have from 2 to 40 ethylene oxide units and from 2 to 40 carbon atoms in the alkyl chain which can be either linear or branched.

(8) TABLE-US-00001 TABLE 1 General structure of the cations and anions that form the hydrophobic compounds (A) in the present invention. C.sup.+ (Cations) where R, R.sub.1, R.sub.2, R.sub.3 are independently aliphatic, benzyl, aromatic, cycloalkyl or alkenyl chains, which can be either linear or branched with 6 to 18 carbon atoms. Y.sup. (Anions) Cl.sup., Br.sup., I.sup. Halides where R.sub.4 is represented by alkyl, cycloalkyl, benzyl alkenyl, aromatic chains or alkyl functionalized, which can be either linear or branched, with 1 to 18 carbon atoms and heterocyclic with 4 to 10 carbon atoms that can contain at least one heteroatom such as nitrogen, sulfur or oxygen and with substitutes formed by alkyl, cycloalkyl, benzyl, alkenyl or aromatic chains or alkyl functionalized and having 1 to 18 carbon atoms.

(9) Preferably, the amount of emulsifier (B) to be used should be 1-20 parts by weight per 100 parts by weight of hydrophobic compound (A). In one embodiment, the amount of emulsifier (B) is effective within the 1-5 parts by weight per 100 parts by weight of the hydrophobic compound (A). In addition, the emulsions can contain small amounts of organic solvents.

(10) In one embodiment, C.sup.+ is a tetralkylammonium, tetralkylphosphonium or trialkylsulfonium where the alkyl can be a C.sub.1-C.sub.18 alkyl and where one or more of the alkyl group is a C.sub.6-C.sub.18 alkyl. In another embodiment, at least one of the alkyl groups is a lower alkyl group such as methyl, ethyl or propyl and one or more of the alkyl groups is a C.sub.6-C.sub.18 alkyl.

(11) The ready-to-be-used emulsion contains: a sum of hydrophobic compounds (A) in an amount of 0.01-25% by weight, preferably 0.05-10% by weight, a sum of surfactants (B) in an amount of 0.0001-1% by weight, preferably 0.0005-0.25% by weight, and the balance added water (to 100). The calculations are based on the total weight of the emulsion to be used.

(12) According to the present invention, the emulsions can be prepared by mixing the components with different combinations. The general method for the preparation of the O/W-type emulsions is carried out according to the following procedure:

(13) The emulsion preparation process is based on the formation of a system, where the disperse phase is a hydrophobic compound (A) or combinations thereof, and the continuous phase is water with emulsifier (B). In order to do so, in the first stage, a concentrated emulsion is prepared with 70% by weight of compound (A). In the second stage, the concentrated emulsion is diluted with water until it is ready-to-be-used. The preparation of the concentrated emulsion comprises or consists of emulsifier (B) at a concentration of 1-5% by weight, which is dissolved in water, forming an aqueous solution, where one or several hydrophobic compounds (A) are added slowly at a concentration of 70% by weight, mixing at the same time at speeds above 16000 rpm at room temperature.

(14) Once the concentrated emulsion has been prepared, the drop size of the disperse phase is measured. The droplet size of the disperse phase of the hydrophobic compound (A) in the prepared emulsion should range preferably from 100 nm to 100 m. The composition, droplet sizes and concentration of the disperse phase of compound (A) are adjusted according to the rock type and reservoir conditions. The particle size is selected preferably so that the drop diameter is smaller than the diameter of the rock pores. In order to determine the distribution of the droplet size in the prepared emulsions, a Malvern laser diffractometer with measuring interval of 0.02-200 m was used. In addition, zeta potential (ZP) measurements were performed in order to determine the stability of the emulsions by means of a Z-PALS equipment by Brookhaven with measurement interval of 150 to 150 mV.

(15) For the oil recovery tests, the ready-to-be-used emulsions are applied at a concentration of hydrophobic compounds (A) of 0.05-10% by weight based on the weight of the emulsion. In one embodiment, the total amount of compound (A) and emulsifier (B) is about 0.5-10% by weight of the emulsion.

EXAMPLES

(16) The following examples must not be considered as exhaustive, but just as illustrations of some of the many considered for the present invention.

(17) Likewise, it is important to mention that FIG. 1 shows a diagram of the injection system used in the test, where 1 indicates the injection pumps, 2differential pressure, 3effluent collector, 4 and 5 transfer cylinders, 6confinement pressure, 7rock core or sand package.

(18) FIG. 2 features a photograph of the sand packed cell.

(19) FIG. 3 displays core photographs: a) before the test, and b) after the test with the injection inlet face.

Example 1. Preparation of the Trioctylmethylammonium Octanoate Base Emulsion (Em 1)

(20) In the first stage, the concentrated emulsion is prepared in a reactor that is coupled to the mechanical mixing system Ultra Turrax T25 Basic, by adding 1 g of Igepal CO 890 (emulsifier B) and 29 g of deionized water. The mixture is stirred until a transparent solution is formed. Afterwards, 70 g of trioctylmethylammonium octanoate (hydrophobic compound A), which has been synthesized previously, are added dropwise. The mixture is stirred at 16000 rpm for 15 min in order to form a visually homogeneous mixture. Igepal CO 890 is a polyoxyethylene (40) nonylphenyl ether having a number average molecular weight M.sub.n of about 1,982 and an HLB of 17 from Sigma-Aldrich Co.

(21) Afterwards, in the second stage, the preparation of the ready-to-be-used emulsion is carried out. In order to do so, in a glass reactor equipped with a stirring system, 1 g of concentrated emulsion, which was obtained in the first stage, is dissolved in 34 g of deionized water.

(22) The obtained emulsion (Em 1) is analyzed in the diffractometer to determine the drop size of the disperse phase. The analysis data are shown in Table 2.

(23) TABLE-US-00002 TABLE 2 Distribution of the drop size in the emulsions Em1-Em3 by the laser dispersion technique. Drop Size Distribution No ZP (mV) D.sub.10 D.sub.50 D.sub.90 Em1 33.4 0.24 0.24 4.53 Em2 38.4 0.09 0.24 3.59 Em3 58.9 1.84 2.92 4.59 D.sub.x: Drop diameter so that the X % of the liquid total volume is in lower size drops.

(24) The emulsions Em2 and Em3 are obtained by using the same procedures described in Example 1 with the difference of using the hydrophobic compounds A and the concentrations of the ready-to-be-used emulsions different from those in Example 1.

Example 2. Oil Displacement Tests in Rock Cores

(25) The examples concerning the oil recovery tests were carried out by using Berea rock cylindrical cores (7 in FIG. 1) with a diameter of 3.8 cm and a length of 8.2 cm. First, the cores are saturated with water and afterwards with Mexican Maya crude oil with 21 API gravity. Once the rock fragment is under the established oil saturation conditions, the oil recovery is carried out by injecting bidistilled water at a flux of 10 ml/h, as shown in FIG. 1, using injection pumps (1) and transfer cylinders (4 and 5). After injecting bidistilled water, 0.4 PV (pore volume) of chemical product (Em1) are injected at the injection inlet in order to continue with the injection of bidistilled water at a flux of 10 ml/h.

(26) The oil volume recovered from the core (3 in FIG. 1) is measured and compared with the oil volume of the initial saturation of the rock core. The recovery efficiency is proportional to the displaced oil amount during the test in comparison with the total oil volume contained in the core at the beginning of the test, which is considered as 100%. The amount of additional oil displaced from the core (R.sub.emulsion) by the injection of emulsion is calculated and is referred to as the emulsion displacement efficiency.

(27) The following experiments Em2 and Em3 are performed with new rock cores and the different hydrophobic compounds as the active substance in the emulsions mentioned in Table 1.

(28) The oil production was evaluated for approximately 20 h (T) at 20 C. The pore volume (PV), porosity (), absolute permeability in milidarcies (K.sub.abs), the initial oil saturation volumes (So.sub.in), the volumes and oil recovery percentage by water injection (R.sub.water) and emulsion (R.sub.emulsion) are shown in Table 3.

Example 3. Oil Displacement Test in the Sand Packages

(29) In order to evaluate the effect of the emulsions on the oil recovery in systems with higher permeability and pore volume, the decision of producing sand packages was made. For this oil recovery tests, packed-meshed-beach-sand cells with 13 cm in length and 4.5 cm in diameter were used. The sand features a nominal diameter below 250 m, as shown in FIG. 2.

(30) TABLE-US-00003 TABLE 3 Data of the rock core tests. VP K.sub.abs So.sub.in R.sub.water R.sub.emulsion Emulsion (%) (ml) (MD) % ml % ml % ml T (h) Em1 21.5 20.4 211.2 84 17.1 58.9 10.07 15.4 2.6 24 Em2 21.8 21 228.8 74.3 15.6 66.2 10.25 22.6 3.5 20 Em3 21.7 21 246.6 80.5 16.9 57.5 9.7 22.5 3.8 20

(31) Once the cell is under the established Maya oil saturation conditions (20.1 API, 544 mPa.Math.s, 0.9317 g/mL at 20 C.; Oil 90/Water 10), the oil recovery by injection of bidistilled water at a flux of 10 ml/h is performed. After water displacement, the corresponding emulsion at 0.1 PV was injected at the inlet in order to continue injecting water at a flux of 10 ml/h. Afterwards, the injection procedure, data recovery and computations were determined as in Example 2. The results of the oil displacement in the sand packages within 30 h (T) at 20 C. are shown in Table 4.

Example 4. Modification of the Rock Wettability from Hydrophilic to Oleophilic

(32) In order to investigate water repellency and modification of the rock wettability towards oil as a consequence of the emulsions based on hydrophobic compounds, rock core samples were used before and after the oil displacement test featured in Example 2. FIG. 3 shows that the surface contact angle of the water drop was increased evidently after the emulsion treatment. In other words, the rock surface wettability was modified preferentially from water to oil wettable.

(33) TABLE-US-00004 TABLE 4 Data of the sand package tests. VP K.sub.abs So.sub.in R.sub.water R.sub.emulsion Emulsion (%) (ml) (MD) % ml % ml % ml T (h) Em1 41 85.1 300.1 88.74 75.5 46.5 35.24 3.3 2.5 30 Em2 39.6 82.2 382.1 86.9 71.5 43.2 30.9 17.7 12.7 36 Em3 39.7 82.3 326.7 82.60 68 52.2 35.5 9.6 6.5 26

(34) The emulsions used in the present invention were used as both wettability change of the sandstone towards oil wettable and additional oil recovery agents.

(35) The examples of the hydrophobic emulsions free of silicon and fluorine used in the examples regarding the recovery of additional oil and the modification of the rock wettability, in addition to the example discussing the preparation of such emulsions, must not be considered as exhaustive, but just mere illustrations of just some among the several examples considered for the present invention.