RU2425209C2 - Treatment method of carbonate and carbonate-containing formations (versions) - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: as per one version, in treatment method of carbonate and carbonate-containing formations by pumping to the formation through the well of helium-forming acid solution containing production waste of synthetic zeolite, lignosulphonate -LS, chlorhydric acid -CA and water; liquid production waste of synthetic zeolite NaX and/or NaA + NaA-Y is used as waste; pumping is performed in two stages with water flush to formation and stop for the period of helium formation, by using at the first stage the above solution at the following ratio of components, wt %: the above waste 50.0-60.0, LS 0.5-5.0, CA 7.0-12.0, water is the rest, at the second stage - the above solution at the following ratio of components, wt %: the above waste 20.0-40.0, LS 0.5-5.0, CA 10.0-15.0, and water is the rest. As per the other version, in treatment method of the above formations by pumping to formation through the well of helium-forming acid solution containing production waste of synthetic zeolite, LS, CA and water, liquid production waste of synthetic zeolite NaX and/or NaA-Y is used as the waste at the following ratio of components, wt %: the above waste 20.0-40.0, LS 0.5-5.0, CA 10.0-15.0, and water is the rest, and subsequent pumping of 7-12% CA solution, the first buffer of fresh water, liquid production waste of the above zeolite containing 2-5 wt % LS, the second buffer of fresh water, 7-12% CA solution and water flushing is performed in the volume of tubing string and wellhead of equipment.

EFFECT: higher treatment efficiency of formations and larger temperature limits of method application.

10 cl, 3 tbl, 6 ex

Description

The invention relates to the oil and gas industry, in particular to the production of oil and gas from heterogeneous waterlogging formations at any stage of the development of gas and oil fields, in particular to methods using reagents, acids and gelling compositions based on silicates.

The invention can be used to increase the efficiency of processing the bottom-hole zone of a carbonate and carbonate-containing formation due to better insulation of the flooded pore-crack transport channels and increase the depth of acid penetration into the formation.

Hydrochloric acid treatments (SKO) are the main way to influence carbonate formations. The main disadvantages of hydrochloric acid treatments are the decrease in efficiency with increasing exposure and the low efficiency or absence of a positive effect in flooded formations. The effectiveness of the RMS can be increased by increasing the depth of penetration of the treatment composition into the reservoir while maintaining its dissolving and corrosive properties, which, in turn, is achieved by reducing the rate of dissolution of the rock in acid and using hydrochloric acid in combination with water-insulating compositions.

There is a known method of treating a carbonate formation, in which a reverse emulsion is pumped into the formation, then alternating portions of acid and a hydrophobizing agent. As a hydrophobizing composition, a 20% hydrocarbon solution of washed tall oil pitch is pumped into the formation [A.S. USSR No. 1624134, MKI E21B 43/27, publ. 01/30/1991]. This method has insufficient efficiency, the acid reacts with carbonates rather quickly and the depth of treatment is insufficient, the reaction products are extracted with severe complication due to emulsification, the reduction in water cut in the production of the well is insignificant.

A known method of processing formations, which uses a composition comprising hydrochloric acid and liquid glass [V.I. Kudinov, B.M. Suchkov. "Methods of increasing the productivity of wells", Samara: Prince. Publishing House, 1996, p. 95]. Its main disadvantage is the low efficiency associated with the small depth of penetration of the acid composition into the reservoir due to the high reaction rate with the carbonate rock.

Thus, in order to increase processing efficiency, it is important to deliver acid that has not reacted as deep as possible into the formation. It is known that aluminosilicates (nepheline, syenite concentrate or zeolite) and lignosulfonates (dry or liquid lignosulfonates, lignin, etc.) are inhibitors of the rate of dissolution of carbonate in hydrochloric acid. Known methods for treating formations using an acidic composition that reduces the rate of dissolution of carbonate by 10-50 times (depending on the depth of the reaction) [Lozin EV, Khlebnikov VN The use of colloidal reagents to enhance oil recovery. - Ufa, ed. BashNIPIneft, 2003]. The use of highly mineralized water (with a density of more than 1100 kg / m ³ ) or its mixture with methanol allows using the acid composition in the autumn-winter period and additionally slowing down the rate of dissolution of carbonates.

A known method of regulating the permeability of an inhomogeneous formation, including a two-stage injection of a gelling acid solution into the formation through a well, pumping it into the formation with water and stopping for a period of gelling, using a gelling solution in the form of an acidic solution of aluminosilicate or liquid glass, said gelling solution being pumped in the first stage with a concentration above the gelation threshold, and in the second stage, the same solution is pumped with a concentration below the gelation threshold [patent t of the Russian Federation No. 2184841, ЕВВ 43/22, publ. 07/10/2002].

The closest in essence and the achieved result is a method for controlling the permeability of an inhomogeneous formation, which includes injecting a gel-forming acid solution into the formation through a well, pumping it into the formation with water and stopping for the period of gelation using a gel-forming solution containing, wt.%: Aluminosilicate (in terms of dry matter) 0.5-10.0, lignosulfonate (in terms of dry matter) 0.5-10.0, hydrochloric acid - the rest, and aluminosilicates can be used natural or synthetic, including Isla and waste production zeolite - zeolite slurries, hydrochloric acid is prepared by mixing concentrated acid with fresh or saline water [RF patent №2194157, E 21 B 43/22, publ. 12/10/2002].

These methods are not effective enough, since the reduction in water cut in the production of the well is small due to the insufficient density of the formed gel and the insufficient penetration of active acid, there are technological difficulties in the preparation of working solutions in the well.

The aim of the invention is to increase the processing efficiency of fractured porous carbonate and carbonate-containing formations and to expand the temperature limits of the application of the method due to better insulation of irrigated pore-fissure transport channels, increase the depth of acid penetration into the formation and cover the bottom-hole formation zone by exposure.

This goal is achieved in that in a method for treating carbonate and carbonate-containing formations, including injecting into the formation through a well a gel-forming acid solution containing synthetic zeolite production waste, lignosulfonate, hydrochloric acid and water, which use liquid waste from the production of synthetic zeolite NaX and / or NaA + NaA-U, injection is carried out in two stages with water being poured into the formation and stopped for the time of gelation, using the specified solution in the first stage, followed by it ratio of its components, wt.%:

Indicated waste 50.0-60.0 Lignosulfonate 0.5-5.0 Hydrochloric acid 7.0-12.0 Water rest

and in the second stage, the specified solution in the following ratio of its components, wt.%:

Indicated waste 20,0-40,0 Lignosulfonate 0.5-5.0 Hydrochloric acid 10.0-15.0 Water rest

Moreover, the mixing of the hydrochloric acid solution and the specified waste with the addition of lignosulfonate is carried out at the mouth by injection through a wave mixer installed at the wellhead, the shoe of the tubing is equipped with a hydraulic wave generator, and all solutions are injected into the formation through this hydraulic wave generator used for selling water additionally contains methanol in the following ratio of components, wt.%:

Methanol 50-60 Mineralized water, ρ = 1.1-1.24 g / cm ³ rest

used in the second stage, the specified solution additionally contains 20-32 wt.% methanol.

This goal is also achieved by the fact that, according to another variant, in the method for treating carbonate and carbonate-containing formations, including injecting into the formation through a well a gelling acid solution containing synthetic zeolite production waste, lignosulfonate, hydrochloric acid and water, synthetic production liquid is used as said waste zeolite NaX and / or NaA + NaA-Y in the following ratio of components, wt.%:

Indicated waste 20,0-40,0 Lignosulfonate 0.5-5.0 Hydrochloric acid 10.0-15.0 Water rest

and pre-sequentially injecting a 7-12% solution of hydrochloric acid, a first fresh water buffer, liquid waste from the production of synthetic zeolite NaX and / or NaA + NaA-U containing 2-5% lignosulfonate, a second fresh water buffer, 7-12 % hydrochloric acid solution and water supply in the volume of tubing and wellhead piping equipment.

Moreover, with large volumes of injected solutions, 2-4 cycles of consecutive injections are performed in the indicated sequence with the injection after the last part of the hydrochloric acid solution, the shoe of the tubing is equipped with a hydraulic wave generator, and all solutions are injected into the formation through this hydraulic wave generator used for selling water additionally contains methanol in the following ratio of components, wt.%:

Methanol 50-60 Mineralized water, ρ = 1.1-1.24 g / cm ³ rest

said solution further comprises 20-32 wt.% methanol.

The difference of the proposed method from the known one is that an acid gelling solution is used in the form of an acid solution of sodium silicate and sodium sulfate, with a residual content of aluminosilicates, which is a liquid waste from the production of synthetic zeolite NaX (according to TU 38.10281-88) and / or NaA and NaA- For (according to TU 2163-003-05766557-97) containing the Na ₂ O, Al ₂ O ₃ , SiO ₂ , H ₂ O system, a surfactant of lignosulfonate was added to this solution, and in the first stage an acid gelling solution is pumped with silicate concentration sodium, which provides the creation of a denser and less permeable gel, and in the second stage the same solution is injected with a concentration of sodium silicate, which slows down the process of dissolution of carbonates with hydrochloric acid, the acid-forming gel solution additionally contains lignosulfonate to strengthen the gel and enhance its adhesion to the surface of the pore-crack space, and in the second stage, lignosulfonate is involved in slowing down the reaction of acid with carbonates, additionally providing deeper penetration into the formation actively acid. A decrease in the concentration of the chemical reagent in the subsequent rim and the use of differences in the physicochemical properties of the gel solutions at gel concentrations above and below the gel threshold is known (RF patent 2184841), however, the claimed combination of essential features, namely, the use of a new acid as a gel former to further slow down the reaction component - liquid waste from the production of synthetic zeolite NaX (according to TU 38.10281-88) and / or NaA and NaA-U (according to TU 2163-003-05766557-97), which was not previously used, and bavlenie lignosulfonate allows the same chemical reagents in the first step more significantly reduce the permeability of high permeability zones and seams, and the second stage - to increase permeability and low srednepronitsaemyh not covered by filtration, inhomogeneous reservoir portions. In addition, the proposed sequence of operations in combination with the substances used has not been previously used. Based on the foregoing, we can conclude that the proposed method meets the criterion of "inventive step".

For the preparation of delayed acid and gelling compositions were used:

- liquid waste from the production of synthetic zeolite NaX (according to TU 38.10281-88) and / or (NaA and NaA-U) (according to TU 2163-003-05766557-97) containing the system Na ₂ O, Al ₂ O ₃ , SiO ₂ , H ₂ O, which is a solution with a content of sodium silicate 6.5-12.0 wt.%, Sodium sulfate 3.5-8.5 wt.%, Sodium aluminosilicate in the form of impurities up to 1.5 wt.%;

- surfactant - lignosulfonate;

- hydrochloric acid produced in accordance with TU 212204200203306-98.

Laboratory experiments were conducted to determine the necessary concentrations of the components of the processing solutions at different stages of the technological process of processing the formation. When sodium silicate is added to the composition of a hydrochloric acid solution, two types of solutions are obtained (Table 1) - delayed hydrochloric acid (with a concentration of sodium silicate of 4% or less, experiments No. 1-11) and a gel-forming composition (with a concentration of sodium silicate of 5% and more, experiments No. 12-22).

Table 1 The effect of the content of sodium silicate (CH) and hydrochloric acid in solution on the gelation process (excess carbonate - at least 50%, t = 20 ° C) Experience number Concentration% results Experience number Concentration% results CH Hcl CH Hcl one 2 10 Suspension 12 6 6 Part of the volume is a suspension, part is a gel 2 3 10 Suspension 13 6 10 Thick gel 3 four 10 Suspension fourteen 7 10 Thick gel four 5 10 Suspension fifteen 8 10 Thick gel 5 2 12 Suspension 16 9 10 Thick gel 6 3 fifteen Suspension 17 12 10 Thick gel 7 four 12 Suspension eighteen 7 7 Thick gel 8 5 fifteen Suspension 19 8 8 Thick gel 9 3 3 Suspension twenty 9 9 Thick gel 10 four four Suspension 21 10 10 Thick gel eleven 5 5 Part of the volume is a suspension, part is a gel 22 12 12 Thick gel

Lignosulfonate along with silicates slows down the reaction of hydrochloric acid with carbonate rock. Therefore, the use of lignosulfonate together with silicate will increase the depth, and hence the processing efficiency. The mechanism of a joint inhibitory effect on the reaction of hydrochloric acid with carbonates of silicate and lignosulfonate is as follows. The colloidal and polymeric nature of the solutions of silicates and lignosulfonates in hydrochloric acid leads to a decrease in the rate of diffusion of hydrogen ions in the solution. As a result of the interaction of an acid solution of silicate and lignosulfonate with carbonates, a protective gel-like layer forms on the surface of pores and cracks, which is accompanied by a decrease in the rate of reaction of the acid with a carbonate or carbonate-containing rock. Lignosulfonate increases the adhesion of the gel on the surface of the pore-fissure space and the density of the gel layer on this surface.

The addition of lignosulfonate increases the strength of the resulting gel and, accordingly, its water-insulating properties. Lignosulfonate, having surfactant properties, increases the adhesion strength of the resulting gel with the surface of the pore-fissure space. The presence of lignosulfonate increases the viscosity of the gel-forming solution, and it enters the largest cracks and pores, which makes the method selective. The presence of a surfactant in an acidic solution provides a decrease in surface tension at the halyard interface and a deeper penetration of the acidic solution into the formation.

The addition of methanol to the delayed acid solution and squeezing solution on the one hand lowers the freezing temperature of the solutions, which expands the applicability of the method to lower negative temperatures, on the other hand, the presence of methanol in the acid solution further slows down the reaction of the acid with carbonates, increasing the depth of the acid treatment, and at the same time, it facilitates the cleaning of the bottom-hole zone from reaction products when the inflow is called and the well is flared, in addition, methanol is an inhibitor of hyd atom formation. That is, the use of methanol in this case gives a comprehensive positive effect.

Tests of the processing method of carbonate and carbonate-containing formations were carried out on the installation UIPK-1M. The reservoir model was represented by core samples with a size of 030 mm, length 1 = 40 mm. The results of experiments with an acid gelling composition based on hydrochloric acid and a waste product from the production of synthetic zeolite NaX and NaA containing sodium silicate, and additionally lignosulfonate are presented in Table 2.

table 2 Assessment of the degree of water isolation when using a composition containing hydrochloric acid, a waste product from the production of synthetic zeolite NaX and NaA and lignosulfonate in the method for treating carbonate and carbonate-containing formations. Experience number Solution composition The permeability of the core before processing, water, 10 ^-3 microns ² Pressure gradient in determining permeability, MPa / m After processing Water permeability, 10 ^-3 μm ² / reduction ratio The pressure gradient at which the filtration occurred, MPa / m / multiplicity of increase in the pressure gradient one No. 13 table 1 113 1.8 4.9 / 23.1 2.8 / 1.5 2 No. 16 table 1 119 1.8 5.7 / 20.9 2.9 / 1.6 3 No. 13 table 1 + 0.5% lignosulfonate 137 1.8 4.6 / 29.8 3.6 / 2.0 four No. 16 table 1 + 0.5% lignosulfonate 121 1.8 4.0 / 30.2 3.8 / 2.1 5 No. 13 table 1 + 2.0% lignosulfonate 194 1.8 6.2 / 31.3 3.7 / 2.1 6 No. 16 table 1 + 2.0% lignosulfonate 197 1.8 6.1 / 32.3 3.7 / 2.1 7 No. 13 table 1 + 5.0% lignosulfonate 312 1.8 9.4 / 33.2 4.0 / 2.2 8 No. 16 table 1 + 5.0% lignosulfonate 328 1.8 9.7 / 33.8 4.2 / 2.3 9 Prototype (nepheline 8% + HCl 8%) 189 1.8 10.8 / 17.5 2.5 / 1.4 10 Prototype (nepheline 8% + HCl 8%) 123 1.8 9.2 / 13.4 2.0 / 1.1

According to the data in Tables 1 and 2, it can be seen that, depending on the concentration of the components, the composition proposed for use in the method for treating carbonate and carbonate-containing formations exhibits the properties of a gel-forming composition capable of isolating the influx of water, or of a slowed acid composition, which makes it possible to comprehensively solve the problem of water isolation and intensification of oil and gas inflow into the well. And also it is seen that the waterproofing capabilities of the proposed method is higher than that of the prototype (table 2).

According to the physicochemical parameters, the sodium silicate-containing composition complies with the requirements and values given in table 3.

Table 3 Name of indicator Value Test method 1. Appearance Light brown to dark brown liquid visually 2. Density at 20 ° C, kg / m ³ 1.0-1.25 GOST 18995.7-73 3. The mass concentration of sodium sulfate, g / DM ³ within 35-85 GOST 27025-86 4. Mass concentration of silicon oxide (IV), g / DM ³ 40-80 GOST 27025-86 5. The mass concentration of sodium oxide, g / DM ³ within 25-40 GOST 27025-86

Injection of the components of the processing solution (hydrochloric acid solution and liquid waste from the production of synthetic zeolite NaX, and / or NaA and NaA-U with the addition of lignosulfonate) through a wave mixer installed at the wellhead [Ganiev RF, Ukrainian LE, Andreev V.E., Kotenev Yu.A. Problems and prospects of wave technology of multiphase systems in the oil and gas industry. - SPb .: Nedra LLC, 2008. - 214 p. P.83, 176-177] allows you to achieve a high degree of mixing of the components and uniformity at a high injection speed, which reduces the time of preparatory work and achieve greater processing efficiency. At the same time, the wave action through the existing hydraulic channel (tubing string) will be transmitted to the bottom of the well and to the bottomhole formation zone, which, in turn, also positively affects the processing efficiency [Ganiev R.F., Ukrainian L.E. , Andreev V.E., Kotenev Yu.A. Problems and prospects of wave technology of multiphase systems in the oil and gas industry. - SPb .: Nedra LLC, 2008. - 214 p.].

When the shoe of the tubing is equipped with a hydraulic wave generator and all solutions are injected into the formation through this wave generator, a high degree of mixing of the components and uniformity of the solution obtained in the bottomhole zone is achieved, which naturally reduces the time of preparatory work. However, in parallel with this, there is a wave effect on the bottom-hole zone of the formation, which allows more thoroughly filling the pore-fissure space of the rock with a gel-forming composition and creating a more dense and impenetrable gel screen (barrier), and at the stage of acid exposure due to wave effects, the acid solution penetrates better formation, and then a large area around the well, which was not previously covered by filtration, is subjected to treatment. These processes increase the efficiency of water isolation and acid treatment to intensify the influx of oil and gas [Ganiev RF, Ukrainian L.E., Andreev V.E., Kotenev Yu.A. Problems and prospects of wave technology of multiphase systems in the oil and gas industry. - SPb .: Nedra LLC, 2008. - 214 p.].

Example 1. For processing, a producing oil well was selected that operates an irrigated reservoir with a thickness of 15 m, the roof of the reservoir is at a depth of 2020 m. The porosity of the reservoir is m = 0.2. The well was cased with a production string of 146 mm, tubing pipes (tubing) with a diameter of 73 mm were lowered to a depth of 2000 m. The reservoir pressure was 20.5 MPa, and the reservoir temperature was 78 ° C. The injectivity determined at the beginning of the work is 280 m ³ / day at 12 MPa.

The first working solution was prepared: the pump unit CA-320 pumped 9 m ^{3 of} liquid waste from the production of synthetic zeolite NaX into the process tank, the acid unit SIN-32 pumped 6 m ^{3 of a} 23% hydrochloric acid solution with simultaneous stirring in a circular manner using the pump unit CA- 320, 250 kg of lignosulfonate was added and stirred for 30 minutes. in a circular pattern using a pump unit CA-320.

Tied wellhead fittings with the pump unit CA-320. With an open annular space (connected to a circulation tank): 2 m ^{3 of} fresh (technical) water, 5 m ^{3 of the} prepared first working solution of the composition, wt.%: Liquid waste from the production of synthetic zeolite NaX 60,0, lignosulfonate 1.7, hydrochloric acid 9.2, water 29.1; closed the annulus and sequentially pumped: 10 m ^{3 of the} specified prepared first working solution, 7 m ^{3 of} industrial water. The wellhead was sealed and the well was left alone for 48 hours, for gelation.

A second working solution was prepared (delayed acid solution): 6 m ^{3 of} liquid waste from the production of synthetic zeolite NaX and 9.1 m ^{3 of} fresh water were pumped into the technological tank with a CA-320 pumping unit, 14.9 m ³ 23% was pumped into the SIN-32 acid aggregate hydrochloric acid solution with simultaneous stirring in a circular pattern using the CA-320 pump unit, 200 kg of lignosulfonate was added and stirred for 30 minutes in a circular pattern using the CA-320 pump unit.

Tied wellhead fittings with the pump unit CA-320. The pressure line was compressed with a pressure of 18 MPa. With an open annular space (connected to a circulation tank): 6 m ^{3 of the} prepared second working solution of the composition, wt.%: Liquid waste from the production of synthetic zeolite NaX 20.0, lignosulfonate 0.7, hydrochloric acid 13.7, water 65, 6: closed the annular space and sequentially pumped: 24 m ³ prepared the specified second working solution, 6.7 m ³ technical water. The wellhead was sealed and the well was left alone for 2 hours for reaction.

By injecting inert gases into the annulus, the SD-9 compressor lowered the liquid level in the well. A well was launched to clean the bottom-hole zone of the formation from reaction products to the flare and worked out on washers of ÷8 ÷ 12 mm for 36 hours. Next, the well was launched into a loop for operation. There is no water inflow into the wellbore. Well production increased by 23%.

Example 2. For processing, a producing oil well was selected that operates an 18-m-thick flooded formation; the formation roof is at a depth of 1980 m. The porosity of the formation is m = 0.2. The well was cased with a production string of 146 mm, tubing pipes (73) with a diameter of 73 mm were lowered to a depth of 1990 m. The reservoir pressure was 20 MPa and the reservoir temperature was 78 ° C. The injectivity determined at the beginning of the work is 300 m ³ / day at 12 MPa.

A wave mixer was installed at the mouth and connected to the tube space, two pressure lines for supplying reagents were connected to it, and the first was connected to the CA-320 pump unit, and the second to the SIN-32 acid unit. A solution of liquid waste from the production of synthetic zeolite NaA and NaA-U with lignosulfonate was prepared, for which 24 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U (1: 1 ratio) was pumped into the process vessel with a pump unit CA-320, 800 kg of lignosulfonate was added and mixed for 15 minutes in a circular pattern using a pump unit CA-320. Then, through a wave mixer, 2.4 m ^{3 of} 23% hydrochloric acid (SIN-32 acid aggregate) and 3.6 m ^{3 of the} production of synthetic zeolite NaA and NaA-U with an additive were simultaneously pumped into the well with an open annulus (connected into a circulation tank) lignosulfonate (pump unit CA-320); closed the annulus and simultaneously pumped 13.6 m ^{3 of} 23% hydrochloric acid (SIN-32 acid aggregate) and 20.4 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U with the addition of lignosulfonate (pump aggregate CA-320); then they sold 6.5 m ^{3 of} industrial water. The wellhead was sealed and the well was left alone for 36 hours for gelation.

A solution of liquid waste from the production of synthetic zeolite NaA and NaA-U (in the ratio 1: 1) with lignosulfonate was prepared, for which 15 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U and 8 m ^{3 were} pumped into the technological tank fresh water, 900 kg of lignosulfonate were added and mixed for 15 min in a circular manner using a CA-320 pump unit. Then, through the wave mixer, 3.7 m ^{3 of} 23% hydrochloric acid (SIN-32 acid aggregate) and 2.3 m ³ of liquid waste solution from the production of synthetic zeolite NaA and NaA- were simultaneously pumped into the well with an open annulus (connected into a circulation tank) U with the addition of lignosulfonate (pump unit CA-320); closed the annulus and simultaneously pumped 33.3 m ³ 23% hydrochloric acid (SIN-32 acid aggregate) and 20.1 m ³ liquid waste from the production of synthetic zeolite NaA and NaA-U with the addition of lignosulfonate (pump aggregate CA-320); then they sold 6.5 m ^{3 of} industrial water.

The wellhead was sealed and the well was left alone for 1.5 hours for reaction.

By injecting inert gases into the annulus, the SD-9 compressor lowered the liquid level in the well. A well was launched to clean the bottom-hole zone of the formation from reaction products to the flare and worked out on washers of ÷8 ÷ 12 mm for 36 hours. Next, the well was launched into a loop for operation. There is no water inflow into the wellbore. Well production increased by 29%.

Example 3. For processing, a producing gas well was selected that operates a 19 m waterlogged formation; the formation roof is at a depth of 2080 m. The porosity of the formation is m = 0.24. The well was cased with a production string of 168 mm, tubing pipes (73) with a diameter of 73 mm were lowered to a depth of 2060 m. The reservoir pressure was 21.2 MPa and the reservoir temperature was 79 ° C. The injectivity determined at the beginning of the work is 380 m ³ / day at 12.3 MPa.

Two pressure lines for supplying reagents were connected to the tube space through a tee and connected the first with the CA-320 pump unit, the second with the SIN-32 acid unit. A water-methanol solution was prepared for sale, for which 3 m ³ (56 wt.%) Of mineralized water with p = 1.14 g / cm ³ and 3.5 m ³ (44 wt.%) Methanol were pumped into the tank, mixed for 5 minutes. A solution of liquid waste from the production of synthetic zeolite NaX + NaA (1: 1 ratio) with a lignosulfonate was prepared, for which a pump unit CA-320 pumped 20 m ^{3 of} liquid waste from the production of synthetic zeolite NaA into a process vessel, 1 ton of lignosulfonate was added with simultaneous stirring and mixed for 20 min in a circular pattern using a pump unit CA-320. At the same time, 20 m of a 12% hydrochloric acid solution was prepared, for which 9.9 m ^{3 of} fresh water was pumped into the second technological tank, and 10.1 m ^{3 of a} 23% hydrochloric acid solution (commercial hydrochloric acid) was pumped into the SIN-32 aggregate and mixed into for 10 min in a circular pattern using an acid aggregate SIN-32. Then, 6.2 m ³ 12% hydrochloric acid (SIN-32 acid unit) was pumped into the well with an open annulus (connected into a circulation tank) (SIN-32 acid unit), the annulus was closed and pumped sequentially: 3.8 m ³ 12% hydrochloric acid (12 wt. .% acid and 88 wt.% water); 0.5 m ³ fresh water; 20 m ³ (25 wt.%) Of liquid waste from the production of synthetic zeolite NaX with the addition of 5 wt.% Lignosulfonate (pump unit CA-320); 0.5 m ³ fresh water; 10 m ³ 12% (... 12 wt.% Acid and ... 88 wt.% Water) hydrochloric acid (acid unit SIN-32) and 6.5 m ³ water-methanol solution (pump unit CA-320). The wellhead was sealed and the well was left alone for 10 hours to gel.

We prepared 60 m ^{3 of} slowed-down acid solution, for which 18 m ^{3 of} liquid waste from the production of synthetic zeolite NaX and 5 m ^{3 of} fresh water were pumped into the technological tank by the CA-320 pumping unit; 37 m ³ 23% hydrochloric acid (SIN-32 acid aggregate) was pumped into the same process vessel and mixed for 20 min in a circular manner using the CA-320 pumping unit; then 800 kg of lignosulfonate was added and mixed for 15 min in a circular manner using a CA-320 pump unit (wt.%: 30 waste, 14.2 ... acid, ... 54.5 water and 1.3 ... lignosulfonate). A water-methanol solution was prepared for sale, for which 3 m ³ (... 56 wt.%) Of mineralized water with p = 1.14 g / cm ³ and 3.5 m ³ (... 44 wt.%) Methanol were pumped into the tank, mixed into within 5 minutes Then, 6.2 m ^{3 of} delayed acid solution (SIN-32 acid aggregate) was pumped into the well with an open annulus (connected into a circulation tank); closed the annulus and pumped 53.8 m of the slowed-down acid solution (SIN-32 acid aggregate), then 6.5 m ^{3 of the} water-methanol solution was pushed. The wellhead was sealed and the well was left alone for 2 hours for reaction.

By injecting inert gases into the annulus, the SD-9 compressor lowered the liquid level in the well. They launched a well to clean the bottom-hole zone of the formation from reaction products to the flare and worked it out on washers of ÷8 ÷ 14 mm for 60 hours. Next, the well was launched into a loop for operation. There is no water inflow into the wellbore. Well production increased by 33.4%.

Example 4. For processing, a producing oil well was selected that operates a 16 m thick flooded formation; the formation roof is at a depth of 2120 m. Formation porosity m = 0.21. The well was cased with a production string of 146 mm, tubing pipes (73) with a diameter of 73 mm were lowered to a depth of 2128 m, the shoe of the tubing was equipped with a wave generator of the SGGK type (design of the Scientific and Scientific Center for High-Temperature Metals, Russian Academy of Sciences). The reservoir pressure is 21 MPa, the reservoir temperature is 78 ° C. The injectivity determined at the beginning of the work is 240 m ³ / day at 11.8 MPa.

The first working solution was prepared: 10 m ^{3 of} liquid waste from the production of synthetic zeolite NaX + NaA + NaA-Y was pumped into the process tank by the pumping unit CA-320, 6 m ^{3 of a} 23% hydrochloric acid solution was pumped into the SIN-32 acid unit while stirring in a circular pattern using the CA-320 pump unit, 640 kg of lignosulfonate were added and mixed for 30 min in a circular manner using the CA-320 pump unit (wt.%: waste 60.0, ... 10.0 acid, 26.0 ... water and ... 4.0 lignosulfonate).

Tied wellhead fittings with the pump unit CA-320. With an open annulus (connected into a circulation tank), the following was pumped in sequence: 2 m ^{3 of} fresh (technical) water, 6.4 m ^{3 of the} prepared first working solution; closed the annulus and sequentially pumped: 9.6 m ^{3 of the} prepared first working solution, 7 m ^{3 of} industrial water. The wellhead was sealed and the well was left alone for 48 hours to gel.

A second working solution was prepared (delayed acid solution): 12.8 m ^{3 of} liquid waste from the production of synthetic zeolite NaX + NaA + NaA-Y and 1.9 m ^{3 of} fresh water were pumped into the technological tank by the CA-320 pumping unit, and the SIN-32 acidic unit 17.3 m ^{3 of a} 23% hydrochloric acid solution was pumped with simultaneous stirring in a circular pattern using a CA-320 pump unit, 200 kg of lignosulfonate was added and stirred for 30 minutes in a circular pattern using a CA-320 pump unit (wt.%: 40.0 ... waste, ... 12.4 acids, ... 47.0 water and ... 0.6 lignosulfonate )

Tied wellhead fittings with the pump unit CA-320. With an open annular space (connected to a circulation tank), successively pumped: 6.4 m ^{3 of the} prepared solution; closed the annulus and sequentially pumped: 24 m ^{3 of the} prepared second working solution, 7 m ^{3 of} industrial water. The wellhead was sealed and the well was left alone for 2 hours for reaction.

By injecting inert gases into the annulus, the SD-9 compressor lowered the liquid level in the well. A well was launched to clean the bottom-hole zone of the formation from reaction products to the flare and worked out on washers of ⌀8 ÷ 12 mm for 40 hours. Next, the well was launched into a loop for operation. There is no water inflow into the wellbore. Well production increased by 30.2%.

Example 5. For processing, a gas producing well was selected that operates a 40 m thick flooded formation; the formation roof is at a depth of 3080 m. The porosity of the formation is m = 0.25. The well was cased with a production string of 168 mm, tubing pipes (89) with a diameter of 89 mm were lowered to a depth of 3111 m, the shoe of the tubing was equipped with a wave generator of the SGGK type (design of the Scientific and Scientific Center for High-Temperature Metals, Russian Academy of Sciences). The reservoir pressure is 29.5 MPa, the reservoir temperature is 91 ° C. The injectivity determined at the beginning of the work is 420 m ³ / day at 13 MPa.

Two pressure lines for supplying reagents were connected to the tube space through a tee and connected the first with the CA-320 pump unit, the second with the SIN-32 acid unit. A solution of the liquid waste from the production of synthetic NaX zeolite with lignosulfonate was prepared, for which 60 m ^{3 of the} liquid waste from the production of synthetic zeolite NaX was pumped into the process vessel with the CA-320 pumping unit, 1600 kg of lignosulfonate was added with simultaneous stirring and stirred for 20 min in a circular manner using pump unit ЦА-320. At the same time, 60 m ^{3 of a} 10% hydrochloric acid solution was prepared, for which 35.4 m ^{3 of} fresh water was pumped into the second technological tank, and 24.6 m ^{3 of a} 23% hydrochloric acid solution (commercial hydrochloric acid) was pumped into the SIN-32 unit and mixed for 10 min in a circular pattern using an acid aggregate SIN-32. Then, 10 m ³ 12% hydrochloric acid (SIN-32 acid aggregate) 0.5 m ³ fresh water was pumped into the well with an open annulus (connected into a circulation tank); 3.5 m ^{3 of} liquid waste from the production of synthetic zeolite NaX with the addition of lignosulfonate (pump unit CA-320); closed the annulus and pumped sequentially: 16.5 m ^{3 of} liquid waste from the production of synthetic zeolite NaX with the addition of lignosulfonate (pump unit CA-320); 0.5 m ³ fresh water; 20 m ³ 12% hydrochloric acid (acid aggregate SIN-32); 0.5 m ³ fresh water; 20 m ^{3 of} liquid waste from the production of synthetic zeolite NaX with the addition of lignosulfonate (pump unit CA-320); 0.5 m ³ fresh water; 20 m ³ 12% hydrochloric acid (acid aggregate SIN-32); 0.5 m ³ fresh water; 20 m ^{3 of} liquid waste from the production of synthetic zeolite NaX with the addition of lignosulfonate (pump unit CA-320); 0.5 m ³ fresh water; 10 m ³ 12%) of hydrochloric acid and 14.5 m ^{3 of} industrial water (pump unit CA-320). The wellhead was sealed and the well was left alone for 12 hours for gelation.

We prepared 70 m ^{3 of} slowed-down acid solution, for which 14 m ^{3 of} liquid waste from the production of synthetic zeolite NaX and 18 m ^{3 of} fresh water were pumped into the technological tank by the CA-320 pumping unit; 38 m ³ 23% hydrochloric acid (SIN-32 acid aggregate) was pumped into the same technological vessel (SIN-32 acid aggregate) and mixed for 20 min in a circular pattern using a TsA-320 pump aggregate; then 1 ton of lignosulfonate was added and mixed for 16 min in a circular manner using a CA-320 pump unit. Then, 14 m ^{3 of} delayed acid solution (SIN-32 acid aggregate) was pumped into the well with an open annulus (connected into a circulation tank); they closed the annulus and pumped 56 m ^{3 of} slowed-down acid solution (SIN-32 acid aggregate), then 14.5 m ^{3 of} process water was pushed. The wellhead was sealed and the well was left alone for 2.5 hours for reaction.

By injecting inert gases into the annulus, the SD-9 compressor lowered the liquid level in the well. A well was launched to clean the bottom-hole zone of the formation from reaction products to the flare and worked out on washers of ÷8 ÷ 14 mm for 72 hours. Next, the well was launched into a loop for operation. There is no water inflow into the wellbore. Well production increased by 35.8%.

Example 6. For processing, a gas producing well was selected that operates a 38 m thick flooded formation, the formation roof is at a depth of 3240 m. The porosity of the formation is m = 0.26. The well was cased with a production string of 168 mm, tubing pipes (89) in diameter with a diameter of 89 mm were lowered to a depth of 3260 m, the shoe of the tubing was equipped with a wave generator of the SGGK type (design of the Scientific and Scientific Center for High-Temperature Metals, Russian Academy of Sciences). The reservoir pressure is 30.5 MPa, the reservoir temperature is 91 ° C. The injectivity determined at the beginning of the work is 460 m ³ / day at 13 MPa.

Two pressure lines for supplying reagents were connected to the tube space through a tee and connected the first with the CA-320 pump unit, the second with the SIN-32 acid unit. A water-methanol solution was prepared for sale, for which 5.2 m ^{3 of} mineralized water with ρ = 1.15 g / cm ³ and 9.8 m ^{3 of} methanol (42.8 ... and 57.2 ... wt.%, Respectively) were pumped into the tank, mixed within 5 minutes A solution of liquid waste from the production of synthetic zeolite NaA and NaA-U (in a ratio of 0.5: 1.5, respectively) with a lignosulfonate was prepared, for which 60 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA- was pumped into the process tank. U, 2 tons of lignosulfonate were added with simultaneous stirring and stirred for 20 min in a circular pattern using a CA-320 pump unit. At the same time, 60 m ^{3 of a} 9% hydrochloric acid solution was prepared, for which 38 m ^{3 of} fresh water was pumped into the second technological tank, and 22 m ^{3 of a} 23% hydrochloric acid solution (commercial hydrochloric acid) was pumped into the SIN-32 aggregate and mixed for 10 minutes in a circular pattern using an acid aggregate SIN-32. Then, 10 m ³ 9% hydrochloric acid (acid aggregate SIN-32) 0.5 m ³ fresh water was pumped into the well with an open annulus (connected into a circulation tank); 4.2 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U with the addition of lignosulfonate (pump unit CA-320) (wt.%: 9.0 ... acid, 39.3 ... water, 50.0 ... waste and 1.7 ... lignosulfonate) ; closed the annulus and pumped sequentially: 15.8 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U with the addition of lignosulfonate (pump unit CA-320); 0.5 m ³ fresh water; 20 m ³ 9% hydrochloric acid (acid aggregate SIN-32); 0.5 m ³ fresh water; 20 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U with the addition of lignosulfonate (pump unit CA-320); 0.5 m ³ fresh water; 20 m ³ 9% hydrochloric acid (acid aggregate SIN-32); 0.5 m ³ fresh water; 20 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U with the addition of lignosulfonate (pump unit CA-320); 0.5 m ³ fresh water; 10 m ³ 9% hydrochloric acid and 15 m ³ water-methanol solution (pump unit CA-320). The wellhead was sealed and the well was left alone for 14 hours for gelation.

A water-methanol solution was prepared for sale, for which 5.2 m ^{3 of} mineralized water with ρ = 1.15 g / cm ³ and 9.8 m ^{3 of} methanol were pumped into the tank, mixed for 5 minutes. We prepared 80 m ^{3 of} slowed-down acid solution, for which 16 m ^{3 of} liquid waste from the production of synthetic zeolite NaA and NaA-U (in the ratio of ... 1: ... 1) and 18 m ^{3 of} methanol were pumped into the technological tank by the pumping unit CA-320; 46 m ³ 23% hydrochloric acid (SIN-32 acid aggregate) was pumped into the same technological vessel (SIN-32 acid aggregate) and mixed for 20 min in a circular pattern using a TsA-320 pump aggregate; then 1 ton of lignosulfonate was added and mixed for 16 min in a circular manner using a CA-320 pump unit. Next, they injected into the well with an open annulus (connected into a circulation tank) 14.7 m ^{3 of a} slowed-down acid solution (acid aggregate SIN-32); closed the annulus and pumped 65.3 m ^{3 of the} slowed-down acid solution (SIN-32 acid aggregate), then 15 m ^{3 of the} water-methanol solution was pushed. The wellhead was sealed and the well was left alone for 2.5 hours for reaction.

By injecting inert gases into the annulus, the SD-9 compressor lowered the liquid level in the well. A well was launched to clean the bottom-hole zone of the formation from reaction products to the flare and worked out on washers of ÷8 ÷ 14 mm for 72 hours. Next, the well was launched into a loop for operation. There is no water inflow into the wellbore. Well production increased by 38%.

Thus, the examples of implementation of the invention show its compliance with the criterion of "practical applicability".

The method has been successfully tested on flooded wells in the summer and winter periods, at temperatures from -25 ° C to + 25 ° C, and showed positive results, its use allowed to obtain additional oil and gas production, as well as savings from reduced associated water withdrawal.

The method is recommended for processing wells developing flooded fractured-porous reservoirs having high absorption capacity.

Claims (10)

1. A method of processing carbonate and carbonate-containing formations, including injecting into the formation through a well a gel-forming acid solution containing synthetic zeolite production waste, lignosulfonate, hydrochloric acid and water, characterized in that liquid waste from the production of synthetic zeolite NaX and / or NaA + NaA-Y, injection is carried out in two stages with water being poured into the formation and stopped for the time of gelation, using the specified solution in the first stage in the following ratio of components entov, wt.%:
Indicated waste 50.0-60.0 Lignosulfonate 0.5-5.0 Hydrochloric acid 7.0-12.0 Water rest,
and in the second stage, the specified solution in the following ratio of components, wt.%:
Indicated waste 20,0-40,0 Lignosulfonate 0.5-5.0 Hydrochloric acid 10.0-15.0 Water rest 2. The method according to claim 1, characterized in that the mixing of a solution of hydrochloric acid and the specified waste with the addition of lignosulfonate is carried out at the mouth by injection through a wave mixer installed at the wellhead. 3. The method according to claim 1, characterized in that the shoe of the tubing is equipped with a hydraulic wave generator and all solutions are injected into the formation through this hydraulic wave generator. 4. The method according to any one of claims 1 to 3, characterized in that the water used for the sale additionally contains methanol in the following ratio of components, wt.%:
Methanol 50-60 Mineralized water, ρ = 1.1-1.24 g / cm ³ rest 5. The method according to any one of claims 1 to 4, characterized in that the solution used in the second step further comprises 20-32 wt.% Methanol. 6. A method of treating carbonate and carbonate-containing formations, including injecting into the formation through a well a gel-forming acid solution containing synthetic zeolite production waste, lignosulfonate, hydrochloric acid and water, characterized in that liquid waste from the production of synthetic zeolite NaX and / or NaA + NaA-Y in the following ratio of components, wt.%:
Indicated waste 20,0-40,0 Lignosulfonate 0.5-5.0 Hydrochloric acid 10.0-15.0 Water rest,
and pre-sequentially injecting a 7-12% solution of hydrochloric acid, the first fresh water buffer, liquid waste from the production of synthetic zeolite NaX and / or NaA + NaA-U, containing 2-5 wt.% lignosulfonate, the second fresh water buffer, 7 -12% hydrochloric acid solution and selling water in the volume of tubing and wellhead piping equipment. 7. The method according to claim 6, characterized in that for large volumes of injected solutions, 2-4 cycles of consecutive downloads are performed in the indicated sequence with the sale after the last part of the hydrochloric acid solution. 8. The method according to claim 6 or 7, characterized in that the shoe of the tubing is equipped with a hydraulic wave generator and all solutions are injected into the formation through this hydraulic wave generator. 9. The method according to any one of claims 6 to 8, characterized in that the water used for the sale additionally contains methanol in the following ratio of components, wt.%:
Methanol 50-60 Mineralized water, ρ = 1.1-1.24 g / cm ³ rest 10. The method according to any one of claims 6 to 9, characterized in that said solution further comprises 20-32 wt.% Methanol.