Method of producing oil from underground deposit of medium-to-high salinity

专利摘要:
The invention relates to the extraction of oil. The goal is to increase the efficiency of the process. A fluid is injected into the reservoir in the form of an emulsion containing, as an emulsifier, carboxymethylated oxyethylate of a general form (see description) in a quantity of 0.5-15% in terms of the aqueous phase of the emulsion. Formation water is used as the aqueous phase of the emulsion. The injection is carried out at t-re phase inversion of the system of oil-reservoir water-hydroxyethylates equal to or 10 ° C higher than the t-ry of the deposit. The phase inversion t-ru is determined by measuring the conductivity. Other than oil, oils, mixtures of oils, partially refined fractions of oil, gas oil, kerosene or gasolines, and mixtures thereof with oil can also be used to prepare the emulsion. Suitable organic phase emulsions are also mixtures of pure hydrocarbons. The volume of the injected emulsion, the ratio of its phases, the content of surfactants and possible additives, as well as the type and amount of polymer solution controlling the mobility can be optimized by flooding the model. 1 tab.
公开号:SU1549486A3
申请号:SU823389161
申请日:1982-02-16
公开日:1990-03-07
发明作者:Бальцер Дитер；Коссвиг Курт
申请人:Хемише Верке Хюльс Аг (Фирма)；
IPC主号:

专利说明:

This invention relates to the extraction of oil from an underground reservoir containing medium or high salinity water.
The purpose of the invention is to increase the eco-economic process.
The phase inversion temperature is determined by measuring the conductivity. At the same time, an emulsion is prepared consisting of oil (if necessary, gasified oil), formation water from the corresponding reservoir (phase ratio 1: 1), surfactant (2 or 5% in terms of the aqueous phase) and possible additives. If a
for a tertiary oil recovery should be injected other than the above emulsion, from which it can only be different in oil phase, this emulsion is also prepared by the above method. The conductivity of the resulting emulsion or the resulting two emulsions are then measured depending on the temperature ..
At the phase inversion temperature, an emulsion like oil in water turns into an emulsion like water in oil or vice versa, and the conductivity decreases or increases abruptly. This temperature limit
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includes only a few degrees Celsius. As the phase inversion temperature perHCTpnpVeTCH, such is the temperature at which the electrical conductivity reaches the average value between the upper (in the case of an oil-in-water emulsion) and lower (in the case of a water-in-oil emulsion).
Carboxymethylated hydroxyethylates used as surfactants can be obtained by reacting hydroxyethyl atoms of the formula R- (0-CHC CH4) -OH with a salt of chloroacetic acid in the presence of alkali or alkaline earth metal hydroxide. However, other methods of preparation are possible. B here means a saturated or unsaturated, unbranched or branched alkyl radical with Ce-Ceo, preferably, or an unsubstituted or disubstituted alkylaryl radical with in the alkyl radical n - 2 ... 30, preferably 3 ... 15. The cation can be sodium, potassium, lithium, ammonium, calcium or magnesium. As alcohols whose hydroxyethyls are the starting materials of carboxymethylates, for example, hexyl, octyl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, palmitic, and stearyl alcohols, as well as unsaturated alcohols, can be used. oleyl alcohol. Alkyl chain can be with a normal or branched chain. Mixtures of these alcohols are suitable, preferably with chain lengths differing from one another by no more than 4 carbon atoms.
As alkyl, can be used, for example, butylphenol, pentylphenol, hexylphenol, octylphenol, nonyl phenol, decylphenol, undecylphenol, dode cyphenol; tridecylphenol, tetradecylphenol, as well as corresponding dialkylphenols. The alkyl chain may be straight chained or branched. In particular, mixtures of alkylphenols are suitable, preferably with chain lengths differing from one another by no more than 4 carbon atoms.
Oxyethylation can be carried out in the presence of catalytic amounts of alkali metal hydroxide
from 3 to 30, preferably from 3 to 15 mol of ethylene oxide / mol of hydroxyl compound. Depending on the preparation conditions, the degree of carboxymethylation of the oxyethylates obtained is 10-100%, preferably 70 ... 100%. Carboxymethylated hydroxyethylates are dissolved or at least well dispersed in ordinary formation waters in the absence of sediments. With a degree of carboxymethylation of up to 10%, the total recovery of oil in its pure form does not exceed 80%. Their selection is carried out as follows.
At a known temperature or temperature range of a reservoir of oil, produced water, and in the presence of gas in the reservoir and suitable carboxymethylated hydroxyethyl acid of the above formula, the phase inversion temperatures are measured. This measurement should be repeated using further surfactants and, if necessary, additives.
On the basis of the data obtained, the final selection of carbocyte simethylated hydroxyethyl is carried out. The degree of oil production efficiency for the corresponding reservoir system can be revealed by preliminary experiments in a layer of sand as a model formation or in an original core.
An injection emulsion is prepared by known methods from oil, produced water, surfactant, and, if necessary, additives, and the required shear forces should not be very high. It is also possible to heat the mixture consisting of oil, water, surfactant and, if necessary, additives to the phase inversion temperature and form an emulsion consisting of very thin drops under soft stirring, stabilize with rapid cooling. At temperatures of 15 ° C below the temperature of the inversion, the phases of the emulsion are relatively stable, with very high degree of salinity, gentle mixing in the tank is recommended.
Oil, oils, mixtures of oils, partially refined fractions of oil, gas oil kerosene or gasolines, and mixtures thereof can also be used to prepare the emulsion.
with oil. Suitable organic phase emulsions are also mixtures of pure hydrocarbons, the use of which, however, is uneconomical.
The volume of the injected emulsion, its phase ratio, surfactant content and possible additives, as well as the type and amount of polymer solution controlling the mobility can be optimized by flooding the model.
Based on the results of preliminary tests, the emulsion is pumped into the reservoir either continuously or in the form of a rim, i.e. accurately limited volume from 0.02 to 2 OP (pore volume) deposits. The size of the rim of the emulsion depends on the concentration of the surfactant and on the efficiency of the process. The emulsifier concentration in terms of the aqueous phase is, for example, 0.1 ... 30%, preferably 1 ... 20%. The ratio of the phases of the emulsion, oil and water is 1: 20-4: 1. Before emulsion flooding, it is advisable to conduct flooding with water, and the produced formation water is used as a liquid. The value of this water sludge is 0.01 ... 4 OD, preferably 0.05 ... 1.0 OD. After the emulsion is fed into the reservoir, it is advisable to inject a polymer rim, which serves to control mobility, as well as to protect the emulsion from ingress of produced water. At the same time, the polymer or polymer mixture is dissolved at such a concentration in the formation water that the viscosity is 2-6 times greater than the viscosity of the oil. For deposits of medium or high salinity (from 3 to 28% of total salinity), biopolymers are suitable, such as polysaccharides or cellulose derivatives, which, in the presence of elevated salt concentrations, have sufficient viscosity and do not precipitate. For reservoir waters that are relatively poor in alkaline earth metal ions, it is advisable to add soluble alkaline earth metal salts to the emulsion, as well as to the previously and additionally supplied reservoir water. When coordinated, the surfactant is active with the deposit, i.e. when measuring the phase inversion temperature, these additives must be considered.
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After the injection of the polymer solution, it is advisable to carry out a normal water flooding. This is carried out until oil production is no longer profitable.
The higher efficiency of the proposed method in comparison with the known is due to the lower degree of delay of hydroxyethyl in the deposit, i.e. in this case, the maximum degree of retention of hydroxyethyl is 1.1 sand, while according to a known method it is at least 3 mg / g of sand.
Example 1. To obtain an artificial reservoir, quartz sand with rounded edges is filled with a high-pressure thermostatic tube, 70 cm long and 5 cm in diameter, equipped with a temperature measuring device and a pressure gauge, which can be locked on both sides with threaded valves with a capillary inlet and containing a pressure valve valve outlet. Then the sand layer is saturated with formation water A using a high-pressure dosing pump and the thermostat is set to the desired temperature.
After that, the permeability of the sand layer is determined. 0.44 OD (1 OD approximately 750 ml) of an emulsion consisting of crude oil A, produced water A (phase ratio 1: 1) and 9.4 g (4, 5% (based on the aqueous phase) of the carboxymethylated nonylphenoloxyethylate with 6 mol of ethylene oxide / mol of a hydroxyl compound with a degree of carboxymethylation of 80%. Then, 0.4 OP of the polymer solution and 3 OP of formation water are injected at the same rate of flooding.
The temperature of the deposit is 55 ° C and thus lies in the region of the phase inversion temperature (approximately 56 ° C), with which the stability of the emulsion is additionally loaded. The reservoir pressure is 60 bar, the porosity of the artificial reservoir is 47%, its permeability is 1C 100 mD. Reservoir water A contains,%: NaCl 20; KS1 0.1; CaClul, 2; MEC120,4. Hydroxyethylcellulose (0.25% dissolved in formation water A, viscosity at 60 ° C, 60 mPa-s) serves as the polymer. As oil And use
71
paraffin-based oil with I, 486, 0.863 g / cm3 and 7. MPa-s. From 172 ml of oil that are fed into the sand layer as an emulsion by flooding, 1.6 ml can be separated and 117 ml obtained in emulsifiable form. 46 ml of oil and 594 g of surfactant in a relatively homogeneous distribution were detected analytically in the sand layer.
EXAMPLE 2 An artificial formation was prepared according to Example 1, saturated with formation A water, and permeability measured. Then it is saturated with crude oil A, and the content of adsorbed water is simultaneously determined. Water flooding begins at a speed of 2 m / day. After the introduction of 1.5 OD of formation water, with a water content of 98 „„ 100% being achieved, the emulsion is injected as a rim. It is followed as a rim polymer solution (0.4 OP) and 3.0 OP formation water. The supply of surfactant, polymer and additional injection of produced water is carried out at a rate of 1 m / day water flooding.
The reservoir porosity is 49%, the permeability is 1,600 mD, the content of adsorbed water is 26% and the temperature of the deposit is 46 C.
0.44 OD of the emulsion (oil A, formation water A at a 1: 1 phase ratio), 10.1 g (6.6% based on the aqueous phase) of carboxymethylated nonylphenol oxoxylate with 5.5 mol of ethylene oxide / mole hydroxyl compounds with a carboxymethylation degree of 80%. The phase inversion temperature of this emulsion is 49 ° C. Water flooding achieves an oil recovery rate of 76%, which, at 1.3 OP, after the start of water flooding with an emulsion, can be increased by 24% to 100% total oil recovery, with water content decreasing to 40%. The average pressure gradient is 0.5 bar / m,
In the sand layer, 4.5 g of a surfactant were detected by analysis in relative homogeneous distribution.
EXAMPLE 3 An artificial formation was obtained analogously to Example 2, but using 0.5 OD of an emulsion consisting of 86 wt.% N-dodecane.


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9486
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five
40
45
50
55
eight
and 14% by mass of toluene, formation water A (Phase ratio 1: 1) and 12 g (6.6%) of carboxymethylated nonylphenol hydroxyethyl acetate with 5.5 mol of ethylene oxide / mole of hydroxyl compound with a degree of carboxymethylation of 80%. The temperature of the deposit is 46 ° C, the phase inversion temperature of the injected emulsion is 49 ° C. Water flooding results in a 78% recovery of oil, which, at 1.2 ° F, after the start of emulsion flooding, rises to 100% of the total oil recovery. During tertiary oil production, an average pressure gradient of 0.8 bar / m.
EXAMPLE 4 A thicker artificial layer is prepared as in Example 2, moistened with formation water A and saturated with oil A (porosity 42%, permeability 310 mD, adsorbed water content 26%, temperature of the reservoir 53 ° C). After water flooding, resulting in 69% recovery of oil, the rim of the emulsion 0.25 OD, consisting of oil A, produced water A (phase ratio 1: 1) and 5.3 g (6.6%) carcass, is injected. - bauximethylated nonylphenoloxyethylate with 6 mol of ethylene oxide / mol of hydroxyl compound with a carboxymethylation degree of 99% (phase inversion temperature of the oil emulsion 56 C) and a water flooding rate of 1.1 m / day, then 0.4 OD of polymer solution and approximately 3 OD formation water. At approximately 1.3 OP, 100% oil recovery is achieved after the start of emulsion flooding. At the time of oil transportation through the reservoir, the average pressure gradient is 1.5 bar / m. After water flooding, 3.2 g of a surfactant were found homogeneously unstitched on the sand layer.
Example 5 A reservoir (porosity 42%, permeability 240 mD), as in Example 4, is moistened with formation water B and then saturated with oil B. The content of adsorption water is 26%, temperature 41 ° C. After water flooding with formation water B, resulting in 68% to extract oil, a rim of an emulsion of 0.3 OD, consisting of oil B, formation water (phase ratio 1: 1) and 7 g of carboxymethylated nonylphenoloxyethyl acetate (6.6%) with approximately 5 mol of ethylene oxide is injected. mole hydroxyl compound91549486Y
with a carboxymethylation degree of 1.2 m / day, then 0.4 OD of 97% (phase temperature of the emulsion polymer solution (Example 1) is injected) and
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these are 43 C) and the water velocity is 1.2 m / day. Analogously to example 2, polymer is introduced as a rim and then water-flooding is carried out by means of produced water B. At 1 OD after the start of emulsion flooding, a total oil recovery of 100% is achieved, and the water content is reduced to 20%. The average pressure gradient is 2 bar / m.
Reservoir water contains,%: NaCl 10; Cacile2,2; MgCU 0.5 and minor amounts of KC1 and SrCle. Oil B is paraffin-based, pg ° 1.480, density, 86, viscosity 9 mPa s.
Example 6 “Plast (porosity...... ....
43%, permeability (1,400 mD) meant a 5 mol of ethylene oxide containing fluid (but Example 2 is moistened with hydroxyl compound with hydroxy A and then saturated with oil A. With a 97% degree of carboxymethylation, the content of adsorbed water is 1% , 1 m / day, followed by 27%, temperature 54 ° C. After-25 SchЈy filing 0.4 OP rims polymer15
3 OD of formation water A. A total oil recovery of 87% is achieved, the average pressure gradient is approximately 0.8 bar / m.
Example Analogously to example 2, a layer with a porosity of 44% and a permeability of 1200 mD is moistened with formation of water B and then saturated with oil B. The content of adsorption water is 25%, temperature 43 ° C. After hydration with reservoir water, resulting in the recovery of 71% of oil, 0.3 OD of the emulsion rim is injected with an extraction temperature of Phases 43 C, consisting of oil B, produced water B ((Phase ratio 1: 2) and 7 g of carboxymethy - cast nonylphenoxyethylene,
solution and 3.00 OP formation water. With the supply of 1.2 OP emulsion, 100% oil recovery is achieved. The average pressure gradient is 0.5 bar / m.
as a rim, the OD emulsion consisting of oil A, produced water A (phase ratio 1: 1) and 73 g (6.6%) carboxymethylated alphol-1214-hydroxyethyl with 4.5 mol of ethylene oxide / mol of hydroxyl compound with a degree of carboxymethylation (phase inversion temperature of 56 ° C) and a waterflood rate of 1.2 m / day. Then, as in Example 1, 0.4 OD of the polymer solution and 3 OD of formation water are injected. Emulsion at 1.3, OD achieved 100% total oil recovery. The average pressure gradient is 0.9 bar / m.
Example. The reservoir (porosity 41%, permeability 650 similar to 30
35
40
solution and 3.00 OP formation water. With the supply of 1.2 OD emulsion, 100% oil recovery is achieved. The average pressure gradient is 0.5 bar / m.
EXAMPLE 9. Similarly, Example 2, a layer with a porosity of 47% and a permeability of 2500 mD is moistened with formation water A and then inflated with oil. С holding adsorption water is 22%, temperature. After flooding with reservoir water, resulting in the recovery of 74% of oil, it will pump 0.3 OD of the emulsion rim with a phase extraction temperature of 60 ° C consisting of oil A, formation water A (phase ratio 1: 2) and 6.5 g carbox of methylated dinonylphenol oxoate containing 13.5 moles of oxide of eth
But Example 2 is wetted with formation water per mole of hydroxyl compound Doi A and then saturated with A. Co with a degree of carboxymethylation.
holding adsorbed water is 21%, temperature 61 ° C. After flooding with reservoir water, resulting in 68% recovery of oil, an emulsion of 0.3 OD consisting of oil A, formation water A (phase ratio 1: 1) and 7.2 g (B, 6 %) carboxymethylated alfol-16-oxyethylate with 7 mol of ethylene oxide / mol hydroxyl compound with a carboxymethylation degree of 90X (phase inversion temperature of 65PC) and filling rate
. . . . . . ....
containing 5 mol of ethylene oxide / mol hydroxyl compound with a carboxymethylation degree of 97% and a speed of 1.1 m / day, followed by a feed of 0.4 OD of the rim polymer
3 OD of formation water A. A total oil recovery of 87% is achieved, the average pressure gradient is approximately 0.8 bar / m.
Example Analogously to Example 2, a layer with a porosity of 44% and a permeability of 1200 mD is wetted with formation water B and then saturated with oil B. The content of adsorption water is 25%, temperature 43 ° C. After flooding with reservoir water, resulting in the recovery of 71% of oil, 0.3 OP of the emulsion rim with the extraction temperature of Phases 43 C, consisting of oil B, produced water B ((Phase ratio 1: 2) and 7 g carboxymethylated nonylphenoxyethylate,
containing 5 mol of ethylene oxide / mol hydroxyl compound with a carboxymethylation degree of 97% and a speed of 1.1 m / day, followed by a feed of 0.4 OD of the rim polymer
solution and 3.00 OP formation water. With the supply of 1.2 OP emulsion, 100% oil recovery is achieved. The average pressure gradient is 0.5 bar / m.
PRI me R 9. Analogously to example 2, a layer with a porosity of 47% and a permeability of 2500 mD is moistened with formation water A and then inflated with oil. The content of adsorption water is 22%, temperature. After flooding with reservoir water, resulting in the recovery of 74% of oil, 0.3 OP of the emulsion rim with a phase extraction temperature of 60 ° C consisting of oil A, formation water A (phase ratio 1: 2) and 6.5 g of carboxymethylated dinonylphenoloxyethyl are injected. - the one containing 13.5 mol of ethyl oxide0
five
85% and a speed of 1.2 m / day, followed by a feed of 0.6 OD of the rim of the polymer solution and 1.5 OP of the reservoir Gvoda. With a supply of 1.3 OP emulsion, 99% oil recovery is achieved. The average pressure gradient is 0.4 bar / m.
In examples 1-9, the average degree of delay of the emulsifier is 1 mg / g of sand.
Examples 10-16. Example 2j is repeated with the difference shown in the table.
In addition, in examples 10-13, hydroxyethylate is used in the form of sodium, in examples 14 and 16 in the form of potassium, and in example 15, in the form of ammonium salts.

权利要求:
Claims (1)
[1]
Invention Formula
The method of extracting oil from an underground deposit of medium or high salinity JQ by injection into the reservoir of a liquid containing carboxymethylated hydroxyethyl of the general Formula
R- (OCH2CH7) n - OSIg - SOOM, 15
where R is C, 0 — C., is alkyl, an alkyl aromatic residue with 6 to 12 carbon atoms in the alkyl group;
M is sodium, potassium or ammonium;
p - 1.5 ... 15,
moreover, the injection is carried out at the temperature of the inversion of the phases of the system oil – formation water – carboxymethylated hydroxyethylates equal to or 10 ° C higher than the temperature of the deposit, in order to increase the efficiency of the process, the liquid is injected into the deposit in the form of an emulsion, containing as an emulsifier specified oxyethylate, in the amount of 0.5-15% in terms of the aqueous phase of the emulsion, which is used as formation water.

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NO155898C|1987-06-17|

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AT7165T|1984-05-15|

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EP0058371B1|1984-04-18|

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US4457373A|1984-07-03|

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NO820491L|1982-08-19|

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RO87465A|1985-08-31|

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EP0058371A1|1982-08-25|

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HU191239B|1987-01-28|

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CA1179115A|1984-12-11|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE3105913A|DE3105913C2|1981-02-18|1981-02-18|Process for the extraction of oil from underground reservoirs by emulsion flooding|

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