RU2308474C2 - Hydrocarbon gel based on ortophosphoric acid ester iron salts - Google Patents

Abstract

FIELD: oil and gas production and transportation.

SUBSTANCE: invention concerns hydrocarbon-based gel-like fluids-sand carriers used in formation rupture operations and gel-scraper compositions used for cleaning petroleum product and crude oil pipelines. Hydrocarbon gel composition comprises: gel-forming agent constituted by 55-65 vol % orthophosphoric acid esters, 15-35 vol % nitrogen-containing complexion agent, and solvent; destructor: calcium oxide or mixture of calcium oxide (10.0-60.0%) and sodium carbonate or bicarbonate (40.0-90.0); hydrocarbon liquid: gas condensate or crude oil, or diesel fuel; activator constituted by, vol %: iron sulfate containing 12 wt % Fe³⁺, 30.0-42.0, triethanolamine 0.5-8.0, cationic surfactant (neftenol GF or katamin AB, or arkvad S-50, or arkvad T-50) 8.0-20.0, ethylene glycol 5.0-12.0, acetic acid 10.0-18.0, and fresh water - the rest. Hydrocarbon gel finally contains 0.3-10.0 vol %: gel-forming agent, 0.3-10.0 vol % activator, 0.5-10.0 kg destructor per 1 m³ hydrocarbon gel, and hydrocarbon liquid in balancing amount.

EFFECT: enabled destruction of composition at required time moment at formation temperature 20-80^°C.

3 tbl, 7 ex

Description

The invention relates to the oil and gas industry and the transport of oil and oil products, in particular to compositions of gel-like hydrocarbon-based sand carriers for hydraulic fracturing, as well as gel-scraper compositions for cleaning product and oil pipelines.

A known composition of a hydrocarbon gel, including a gel, an activator and a hydrocarbon liquid, in which it contains gas condensate, or crude oil, or diesel fuel;

which, as a gelling agent, contains a composition comprising organic orthophosphoric esters, a nitrogen-containing complexing agent and a solvent, wherein, as a nitrogen-containing complexing agent, it contains dimethylethanolamine, or diethylethanolamine, or methyldiethanolamine, or ethyldiethanolamine, and as a solvent, kerosene, or den;

as an activator it contains a micellar solution including a solution of iron sulfate containing 12.0 wt.% Fe ³⁺ , triethanolamine, a cationic surfactant, ethylene glycol and fresh water, as a cationic surfactant it contains neftenol GF, or catamine AB, or Squad S-50 , or T-50 arcquad;

contains sodium carbonate or bicarbonate as a destructor [1].

The disadvantage of this composition is the prolonged destruction of the gel (more than 8 hours) at temperatures below 80 ° C.

The technical result of the invention is the creation of a hydrocarbon gel composition that is degraded in the required period of time at formation temperatures of 20-80 ° C.

The result is achieved due to the introduction of acetic acid into the activator, as well as the content of calcium oxide or a mixture of calcium oxide and sodium carbonate or bicarbonate in the destructor.

The features of the invention "hydrocarbon gel based on iron salts of organic phosphoric esters" are:

1. The water is fresh.

2. Hydrocarbon fluid.

3. As a hydrocarbon liquid - gas condensate.

4. As a hydrocarbon liquid - diesel fuel.

5. As a hydrocarbon liquid, crude oil.

6. A composition comprising organic orthophosphoric esters, a nitrogen-containing complexing agent and a solvent.

7. A solution of iron sulfate containing 12.0 wt.% Fe ³⁺ .

8. Triethanolamine.

9. Ethylene glycol.

10. Cationic surfactant.

11. As a cationic surfactant - neftenol GF.

12. As a cationic surfactant - catamine AB.

13. As a cationic surfactant - Arcvad S-50.

14. As a cationic surfactant - T-50 arcwad.

15. Acetic acid.

16. The hydrocarbon gel destructor.

17. As a hydrocarbon gel destructor, sodium carbonate or bicarbonate is used.

18. Calcium oxide is used as a hydrocarbon gel destructor.

19. A mixture of calcium oxide and sodium carbonate or sodium bicarbonate is used as a hydrocarbon gel destructor.

Signs 1-14, 16-17 are common with the prototype, and signs 15, 18-19 are essential distinguishing features of the invention.

SUMMARY OF THE INVENTION

A hydrocarbon gel composition is proposed, including a composition gelling agent, vol.%: Organic phosphoric esters 55-65, nitrogen-containing complexing agent 15-35, solvent rest, destructor, hydrocarbon liquid gas condensate or crude oil, or diesel fuel, activator comprising an iron sulfate solution containing 12.0 wt% Fe ^3+, triethanolamine, cationic surfactant, surfactant substance -. Neftenol GF or Catamin AB or arkvad S-50 or T-50 arkvad, ethylene glycol and fresh water, wherein the activator further sod rzhit acetic acid with the following ratio of components,% vol.:

the specified solution of iron sulfate  30.0-42.0 triethanolamine 0.5-8.0 cationic surfactant 8.0-20.0 ethylene glycol 5.0-12.0 acetic acid 10.0-18.0 fresh water rest

as a destructor, the composition of the hydrocarbon gel contains calcium oxide or a mixture of calcium oxide and sodium carbonate or bicarbonate in the following ratio, wt.%: calcium oxide 10.0-60.0, sodium carbonate or bicarbonate 40.0-90.0, at the following ratio of components of the composition of the hydrocarbon gel, vol.%:

specified gelling agent 0.3-10.0 specified activator 0.3-10.0 specified hydrocarbon liquid rest specified destructor 0.5-10.0 kg per m ³   hydrocarbon gel

As a result of mixing a hydrocarbon liquid, a gelling agent and an activator, a hydrocarbon gel is formed having a viscosity, depending on the amount and proportions of the introduced gelling agent and activator, as well as the substances that make up the activator.

The lower and upper limits of the concentration of iron sulfate and triethanolamine in the activator are due to the formation of viscosity and structure of the resulting hydrocarbon gel, the lower and upper limits of the concentration of cationic surfactant and ethylene glycol are due to the fact that, with a smaller amount, the activator is poorly soluble in the hydrocarbon liquid during gel preparation, and with a larger number of them decrease below the permissible limit of concentration of active substances (iron sulfate and triethanolamine), water is neutral with an agent that supplements the content of components to 100%, and the lower and upper limits of acetic acid concentrations are due to the fact that with a smaller amount the prepared gel for a long time degrades at temperatures below 80 ° C (more than 8 hours), and with a larger amount it falls below the permissible limit concentration of active substances (iron sulfate and triethanolamine).

The lower limit of the concentration of gelling agent and activator is due to the possibility of obtaining a gel, and the upper limit is the necessary viscosity sufficient to use hydrocarbon gel in oil and gas production and transportation of oil and oil products.

For research were used:

1. Gas condensate.

2. Diesel fuel, GOST 305-82 with the following physico-chemical characteristics:

- density at 20 ° C, ρ ₂₀ = 830 kg / m ³ ;

- flash point in a closed crucible, t = 40 ° C;

- pour point, t = -45 ° C;

- kinematic viscosity at 20 ° C, μ ₂₀ = 4.0 mm ² / s.

3. Oil of the Salym field with the following physicochemical characteristics:

- density at 20 ° C, ρ ₂₀ = 826 kg / m ³ ;

- dynamic viscosity at 20 ° C, η ₂₀ = 5.5 cP;

- wt.% the content of fractions boiling up to 300 ° C - 49.0;

- wt.% water content - traces.

4. For the preparation of the gelling agent, Himeko TU 400 MP "X" -2075-227-001-93, which is a surfactant consisting of a complex mixture of monophosphate and diesters of alkylphosphoric acids, is used as organic orthophosphoric esters. primary fatty, oxa and low molecular weight alcohols - a mobile liquid from colorless to light brown in color. Mass fraction of the main substance - not less than 95%.

As a complexing agent for the gelling agent, dimethylethanolamine TU 6-02-1086-91, diethylethanolamine TU 6-02-701-76, methyldiethanolamine and ethyldiethanolamine, which are viscous liquids with a specific amine odor, possessing the properties of amines and alcohols, are used.

As a solvent for the gelling agent are used:

TS brand kerosene - GOST 10227-86, denormalizate - GOST 305-82 and diesel fuel - GOST 305-82.

5. To prepare the activator, a solution of iron sulfate is used, containing 12.0 wt.% Fe ³⁺ , triethanolamine - TU 6-02-916-79, cationic surfactants: Neftenol GF TU 2484-035-17197708-97, catamine AB - TU 2482-012-13164401-94, Arquad S-50 and Arquad T-50, acetic acid - GOST 19814-74, fresh water.

6. For the preparation of the destructor, sodium carbonate or bicarbonate is used, calcium oxide - TU 6-18-107-74.

Examples of the preparation of compounds.

Example 1

In 99.4 ml (99.4%) of gas condensate at a temperature of 20 ° C, while stirring on a paddle mixer, 0.3 ml (0.3 vol.%) Of a gelling agent was prepared, prepared as follows: in 55 ml (55.0 vol. %) of organic orthophosphoric esters (Himeko alkyl phosphate) with stirring on a paddle stirrer, 15 ml (15.0 vol.%) of dimethylethanolamine was introduced, and then, after obtaining a homogeneous mass, 30 ml (30.0 vol.%) of kerosene was introduced into the mixture after which the gelling agent was ready for use, and 0.3 ml (0.3 vol.%) of activator prepared as follows: in 30 ml (30.0 vol.%) of sulfate an iron containing 12.0 wt.% Fe ³⁺ , with stirring on a paddle mixer, 0.5 ml (0.5 vol.%) of triethanolamine, 8 ml (8.0 vol.%) of neftenol GF, 5 ml ( 5.0 vol.%) Ethylene glycol, 10 ml (10 vol.%) Acetic acid and 46.5 ml (46.5 vol.%) Fresh water and mixed until a homogeneous solution was obtained, after which the activator was ready for use; mixing of the resulting gel was continued for 15 min, after which its rheological characteristics were studied at a temperature of 20 ° C.

Example 2

In a 94.0 ml (94.0 vol.%) Oil of the Salym field at a temperature of 20 ° С, 3.0 ml (3.0 vol.%) Of a gelling agent was prepared with stirring on a paddle mixer, prepared as follows: in 58 ml (58 , 0 vol.%) Of organic orthophosphoric esters (Himeko alkyl phosphate) with stirring on a paddle stirrer, 22 ml (22.0 vol.%) Of diethylethanolamine were introduced, and then, after obtaining a homogeneous mass, 20 ml (20.0 vol. .%) denormalizate, after which the gelling agent was ready for use, and 3.0 ml (3.0 vol.%) of the activator, prepared as follows: 33 ml (33.0 vol.%) Of ferrous sulfate containing 12.0 wt.% Fe ³⁺ with stirring on a paddle mixer was introduced successively 2.0 ml (2.0 vol.%) Of triethanolamine, 11 ml (11.0 vol.%) of catamine AB, 7 ml (7.0 vol.%) of ethylene glycol, 12 ml (12 vol.%) of acetic acid and 35 ml (35.0 vol.%) of fresh water and stirred until a homogeneous solution, after what the activator was ready for use; mixing of the resulting gel was continued for 15 min, after which its rheological characteristics were studied at a temperature of 20 ° C.

Example 3

In a 88.0 ml (88.0 vol.%) Oil of the Salym field at a temperature of 20 ° C, 6.0 ml (6.0 vol.%) Of a gelling agent was prepared with stirring on a paddle mixer, prepared as follows: in 62 ml (62 , 0 vol.%) Of organic orthophosphoric esters (Himeko alkyl phosphate) with stirring on a paddle mixer, 28 ml (28.0 vol.%) Of methyldiethanolamine were introduced, and then, after obtaining a homogeneous mass, 10 ml (10.0 vol. .%) of diesel fuel, after which the gelling agent was ready for use, and 6.0 ml (6.0 vol.%) of the activator prepared as follows way:. 36 ml (. 36.0 vol%), ferrous sulfate containing 12.0 wt% Fe ^3+, while stirring at a paddle stirrer was added sequentially 4 mL (4.0 vol.%) triethanolamine, 14 ml (14 , 0 vol.%) S-50 arcquad, 9.0 ml (9.0 vol.%) Of ethylene glycol, 14 ml (14 vol.%) Of acetic acid and 23 ml (23.0 vol.%) Of fresh water and stirred until a homogeneous solution is obtained, after which the activator was ready for use; mixing of the resulting gel was continued for 15 min, after which its rheological characteristics were studied at a temperature of 20 ° C.

Example 4

In 80.0 ml (80.0 vol.%) Of diesel fuel at a temperature of 20 ° С with stirring on a paddle mixer, 10.0 ml (10.0 vol.%) Of a gelling agent was prepared, prepared as follows: in 65 ml (65, 0 vol.%) Of organic orthophosphoric esters (Himeko alkyl phosphate) with stirring on a paddle mixer, 35 ml (35.0 vol.%) Of ethyl diethanolamine were added and stirring was continued until a homogeneous mass was obtained, after which the gelling agent was ready for use, and 10, 0 ml (10.0 vol.%) Of the activator, prepared as follows: in 42 ml (42.0 vol.%) Of iron sulfate containing 12.0 wt. % Fe ³⁺ , with stirring on a paddle mixer, 8.0 ml (8.0 vol.%) Of triethanolamine, 20 ml (20.0 vol.%) T-50 arquad, 12 ml (12.0 vol. %) ethylene glycol and 18 ml (18 vol.%) acetic acid and stirred until a homogeneous solution, after which the activator was ready for use; mixing of the resulting gel was continued for 15 min, after which its rheological characteristics were studied at a temperature of 20 ° C.

Example 5 (example 1 of the prototype)

In 99.4 ml (99.4 vol.%) Of gas condensate at a temperature of 20 ° C, with stirring on a paddle mixer, 0.3 ml (0.3 vol.%) Of a gelling agent was prepared, prepared as follows: in 55 ml (55.0 vol.%) of organic orthophosphoric esters (Himeko alkylphosphate) with stirring on a paddle stirrer, 15 ml (15.0 vol.%) of dimethylethanolamine were added, and then after obtaining a homogeneous mass, 30 ml (30.0 vol. %) kerosene, after which the gelling agent was ready for use, and 0.3 ml (0.3 vol.%) of the activator prepared as follows: in 40 ml (40.0 vol.%) sulfate and iron containing 12.0 wt.% Fe ³⁺ , with stirring on a paddle mixer, 0.5 ml (0.5 vol.%) of triethanolamine, 15 ml (15.0 vol.%) of neftenol GF, 5 ml (5.0 vol.%) Ethylene glycol and 39.5 ml (39.5 vol.%) Fresh water and mixed until a homogeneous solution, after which the activator was ready for use; mixing of the resulting gel was continued for 15 min, after which its rheological characteristics were studied at a temperature of 20 ° C.

Example 6 (example 2 of the prototype)

In a 94.0 ml (94.0 vol.%) Oil of the Salym field at a temperature of 20 ° С, 3.0 ml (3.0 vol.%) Of a gelling agent was prepared with stirring on a paddle mixer, prepared as follows: in 58 ml (58 , 0 vol.%) Of organic orthophosphoric esters (Himeko alkyl phosphate) with stirring on a paddle stirrer, 22 ml (22.0 vol.%) Of diethylethanolamine were introduced, and then, after obtaining a homogeneous mass, 20 ml (20.0 vol. .%) denormalizate, after which the gelling agent was ready for use, and 3.0 ml (3.0 vol.%) of the activator, prepared as follows: 43 ml (43.0 vol.%) Of iron sulfate containing 12.0 wt.% Fe ³⁺ , 5 ml (5.0 vol.%) Of triethanolamine, 17 ml (17.0 vol. .%) catamine AB, 8 ml (8.0 vol.%) ethylene glycol and 27 ml (27.0 vol.%) fresh water and mixed until a homogeneous solution, after which the activator was ready for use; mixing of the resulting gel was continued for 15 min, after which its rheological characteristics were studied at a temperature of 20 ° C.

Example 7 (example 4 of the prototype)

In 80.0 ml (80.0 vol.%) Of diesel fuel at a temperature of 20 ° С with stirring on a paddle mixer, 10.0 ml (10.0 vol.%) Of a gelling agent was prepared, prepared as follows: in 65 ml (65, 0 vol.%) Of organic orthophosphoric esters (Himeko alkyl phosphate) with stirring on a paddle mixer, 35 ml (35.0 vol.%) Of ethyl diethanolamine were added and stirring was continued until a homogeneous mass was obtained, after which the gelling agent was ready for use, and 10, 0 ml (10.0 vol.%) Of the activator, prepared as follows: in 50 ml (50.0 vol.%) Of iron sulfate containing 12.0 wt. .% Fe ³⁺ with stirring on a paddle mixer, 15 ml (15.0 vol.%) Of triethanolamine, 20 ml (20.0 vol.%) Of T-50 arquad, 15 ml (15.0 vol.%) Of ethylene glycol were successively introduced and mixed until a homogeneous solution is obtained, after which the activator was ready for use; mixing of the resulting gel was continued for 15 min, after which its rheological characteristics were studied at a temperature of 20 ° C.

The dynamic viscosity of the obtained gels at a temperature of 20 ° C was determined on a Rheotest-2 rotational viscometer at a shear rate of 3 s ^-1 ; the consistency coefficient "k", "Pa · s ⁿ " and the coefficient of non-Newtonian behavior "n" were determined by mathematical processing of the rheological curves obtained as a result of studies.

The compositions of the obtained gels are shown in table 1. The results of studies of the compositions of the gels according to table 1 are shown in table 2. For comparison, tables 1 and 2 show the characteristics of the gels according to the prototype.

Table 1.
The composition of hydrocarbon gels (without a destructor) №№
p / p The composition of the gel, ml (vol.%) The composition of the activator, vol.% gelling agent activator hydrocarbon liquid iron sulfate triethanol min Surfactant ethylene glycol acetic acid fresh water one 2 3 four 5 6 7 8 9 10 one 0.3 0.3 Gas condensate, 99.4 ml thirty 0.5 8 5 10 46.5 2 3.0 3.0 Salym oil, 94.0 ml 33 2 eleven 7 12 35 3 6.0 6.0 Salym oil, 88.0 ml 36 four fourteen 9 fourteen 23 four 10.0 10.0 Diesel, 80.0 ml 42 8 twenty 12 eighteen 5 0.3 0.3 Gas condensate, 99.4 ml The gel composition of the prototype (example 1) 6 3.0 3.0 Salym oil, 94.0 ml The gel composition of the prototype (example 2) 7 10.0 10.0 Diesel, 80.0 ml The composition of the gel according to the prototype (example 4)

Table 2.
Rheological characteristics of the gels at a temperature of 20 ° C No. of composition according to table 1 Dynamic viscosity at a shear rate of 3 s ^-1 , cP Consistency coefficient "k", Pa * s ⁿ Non-Newtonian behavior coefficient, "n" one 1500 2.5 0.18 2 60,000 105.0 0.15 3 100,000 195.0 0.12 four 157500 390.0 0,07 5 (prototype No. 1) 1200 2.0 0.20 6 (prototype No. 2) 52000 105.0 0.15 7 (prototype No. 4) 150800 380.0 0,07

As can be seen from table 2, when using the proposed compositions were obtained hydrocarbon gels with a higher viscosity compared with the viscosity of the gel from the prototype, since the content of acetic acid activator in the solution increases the viscosity of the hydrocarbon gel.

Studies of the coefficients of consistency "k" and the coefficients of non-Newtonian behavior "n" showed that the gels of the proposed compositions are also highly structured, as well as the gel compositions of the prototype.

It is known that the most structured gels have the greatest sand-holding ability, as well as the lowest pressure loss on friction in the pipes, so the proposed composition will allow to obtain high-quality hydrocarbon-based hydraulic fracturing fluids, and high viscosity and structure of highly concentrated hydrocarbon gels (up to 10 vol.% Gel and activator) will allow you to get gel scrapers of the necessary rigidity for product and oil pipelines.

For destruction, a destructor was introduced into the obtained gels. Sodium carbonate, sodium bicarbonate, calcium oxide and a mixture of calcium oxide and sodium carbonate or sodium bicarbonate were used in an amount of 0.5-10.0 kg / m ^{3 of the} gel.

The lower concentration of the destructor is determined by the possibility of destruction, and the upper - by practical and economic feasibility.

Table 3 presents the results of the destruction of the proposed composition, as well as the composition of the prototype at a temperature of 75 ° C.

Table 3.
Hydrocarbon gel degradation No. of composition according to table 1 The amount of destructor, kg / m ³ The dynamic viscosity of the gel, cP, without a destructor at a shear rate of 3 s ^-1 , at a temperature of 75 ° C (measured on a Rheotest-2 viscometer) The dynamic viscosity of the gel, cP, after holding it with the addition of a destructor at a temperature of 75 ° C (measured on a glass viscometer) The time of complete destruction of the hydrocarbon gel, h Sodium carbonate Bicarbonate of soda Calcium oxide one 0.4 - 0.1 1000 2 2 80 twenty wt.% wt.% 2 - 1.4 0.6 38000 12 6 70 thirty wt.% wt.% 3 - - 5 55,000 5 8 5 (prototype 0.5 - - 1300 2 24 No. 1) 6 (prototype - 1,0 - 48500 12 24 No. 2) 7 (prototype - 10.0 - 147000 5 24 No. 4)

Information sources

1. Patent (prototype) No. 2184222, ЕВВ 43/26, published on June 27, 2002, Bull. Number 18.

Claims (1)

The composition of the hydrocarbon gel, including the gelling agent of the composition, vol.%: Organic orthophosphoric esters 55-65, nitrogen-containing complexing agent 15-35, solvent - the rest, destructor, hydrocarbon liquid - gas condensate or crude oil, or diesel fuel, activator, including iron sulfate solution, containing 12.0% of the mass. Fe ³⁺ , triethanolamine, a cationic surfactant surfactant - Neftenol GF or Catamine AB, or Squad S-50, or Squad T-50, ethylene glycol and fresh water, characterized in that the activator additionally contains acetic acid in the following ratio of components, about.%: the specified solution of iron sulfate 30.0-42.0 triethanolamine 0.5-8.0 cationic surfactant 8.0-20.0 ethylene glycol 5.0-12.0 acetic acid 10.0-18.0 fresh water rest as a destructor, the composition of the hydrocarbon gel contains calcium oxide or a mixture of calcium oxide and sodium carbonate or bicarbonate in the following ratio, wt.%: calcium oxide 10.0-60.0, sodium carbonate or bicarbonate 40.0-90.0, at the following ratio of components of the composition of the hydrocarbon gel, vol.%: specified gelling agent 0.3-10.0 specified activator 0.3-10.0 specified hydrocarbon liquid rest the specified destructor of 0.5-10.0 kg per m ³ hydrocarbon gel.