Hard compound for preventing sedimentations of non-organic salts and ferrum sulfide during extraction and transportation of oil

FIELD: oil extractive industry.

SUBSTANCE: compound includes organic acidic reagent and cubic remains of amine production C17-C20, and as organic acidic reagent contains sulphamine acid with following ratio of components in percents of mass: sulphamine acid 20-70, C17-C20 the rest or mixture of sulphamine acid with nitriletetramethylphosphone acid with following ratio of components in percents of mass: sulphamine acid 10-40, nitriletetramethylphosphone acid 25-70, C17-C20 the rest.

EFFECT: higher efficiency.

2 ex, 7 tbl

 

The invention relates to the field of oil production, in particular, compositions of the solid aggregate state, intended for preventing deposition of inorganic salts and iron sulfide in the well field collection system and transport of oil, as well as in savedname oil reservoirs in secondary oil production.

Known solid composition for preventing scale deposition and sand with oil containing in wt.%: oksietilidendifosfonovaya acid (HEDP) or nitrilotriacetate acid (NTF) 5-75 and bitumen construction and the rest (RF Patent No. 2132451, CL E 21 In 37/00, 1997).

Known composition ensures the prevention of the precipitation of salts, gypsum and calcite and sand in oil production with any degree of water content and salinity of produced waters, and in any formation pressure and at elevated temperature (up to 90°).

The disadvantage of known composition is insufficient effectiveness to prevent deposits of inorganic salts and the inability to prevent the deposition of iron sulfide in wells, characterized by the presence of large quantities of sulfur in the produced fluids and the presence of sulfate reducing bacteria in the reservoir. This imposes constraints on the range of wells that can be efficiently processed.

The most effective is m to the proposed technical solution on a set of attributes is a solid compound for the treatment of watery fluids and designed, in particular, to prevent salt deposits containing scale inhibitor - oksietilidendifosfonovaya acid (HEDP) or nitrilotriacetate acid (NTF), the inhibitor asphaltoresinparaffin deposits (ARPD), corrosion inhibitor and substance-carrier - distillation residues from the production of amines With17-C20(A. SSSR No. 1543052, CL. E 21 In 37/06, 1987). Specified known composition provides a long continuous delivery of inhibitory components in effective concentrations in the produced fluids at all possible proportions of water and oil.

However, this composition is not sufficiently effective, and also does not ensure the prevention of deposits of iron sulfide, especially in wells, characterized by the presence of a large sulfur content in the produced fluids and infected sulfatoxymelatonin bacteria.

The technical result provided by the proposed solution is to increase the effectiveness of preventing deposits of inorganic salts and iron sulfide in any downhole conditions, including, in the presence of sulfate reducing bacteria in the reservoir and sulfur produced in the fluid by increasing the degree of prevention of these sediments, providing a uniform outflow of active basis, exceptions to the formation of secondary precipitation in a changing miner the implementation of fluids while maintaining a protective effect against corrosion.

This technical result is achieved solid composition for preventing deposits of inorganic salts and iron sulfide in the extraction and transportation of oil, including organic acid reagent and distillation residues from the production of amines With17-C20at the same time as the organic acid reagent composition contains sulfamic acid in the following ratio, wt.%:

sulfamic acid 20-70

distillation residues from the production

amines With17-C20the rest

or a mixture of sulfamic acid with nitrilotriethanol acid in the following ratio, wt.%:

sulfamic acid 10-40

nitrilotriacetate acid 25-70

distillation residues from the production

amines With17-C20the rest

The above technical result is ensured by the next.

Offer solid composition is delivered into the hole in the perforated container. The flow of reservoir fluids washes composition, with the gradual dissolution of still residue with an organic acid reagent in minimal concentrations, which allows to provide compatibility with produced water of any type in the changing salinity, and the exclusion of the formation of secondary precipitates. When this component is s proposed composition on the surface of the equipment creates a protective film, and besides, there is a wrapping of the already formed crystals of salts and iron sulfide, which, in the presence of a film not already adsorbed on the surface of the equipment and taken out of the wells of the extracted liquid.

And, apparently, due to the fact that sulfamic acid and distillation residues have a chemical affinity in the presence of amino groups at both substances, when dissolved sulfamic acid is mutual activation of its amino groups by conjugation with lone electron pairs of the nitrogen atoms of amino groups bottoms. As a result of this redistribution of charges occurs weakening of acidity, and because of this, blocking sulfide ions, which leads to the exclusion of the formation of new molecules of iron sulfide. And NTF has a synergistic effect on the above properties.

Due to the mutual influence of the amino groups, the pH of the formation fluid is not changed in the direction of acidification (pH remains of 5.7 to 7.2), which also contributes to the effectiveness of preventing deposits of inorganic substances, in particular of iron sulfide, which is mainly formed in an acidic medium in the presence of sulfate reducing bacteria in the reservoir.

Sulfopropyl in sulfamic acid play the role of moderator of inorganic sediments sulfate Kal the Oia. And distillation residues from the production of amines exhibit the properties of corrosion inhibitor, also slowly dissolve in water, thereby providing a longer period of validity of the claimed solid composition.

In field conditions the proposed composition is prepared by mixing and forming pellets-“sausages” in length 10-20 mm and a diameter of 2-2,2 mm, the resulting composition is placed in the container, consisting of a perforated tubing, with a diameter of 2.5 see Then the container with the composition descends into the perforations (or greater than 10-20 m) of the production well. When the well is produced, the liquid washes the composition through the perforated holes on the side walls and the ends of the container, and through the gradual dissolution of the composition of the gradual removal of components in the produced fluids. When this is achieved constant and a sufficient concentration to prevent deposits of inorganic salts and iron sulfide.

The proposed composition was obtained and tested in laboratory conditions. For its preparation were used the following substances:

- distillation residues from the production of amines C17-C20on THE other 6-02-750-87, waste production, obtained by vacuum distillation of the technical mixture of aliphatic amines C17-C20the total mass fraction of the primary and the second is cnyh amines as residue is not less than 56%, including primary - not less than 22%, the hydrocarbon content of not more than 10%; solid waxy mass of brown with a sharp odor, sparingly soluble in water, soluble in alcohol, chloroform, melting point 63-78° C;

- sulfamic acid - monoamide sulfuric acid, colorless hygroscopic crystals odourless, moderately soluble in water, used technical sulfamic acid in THE 2121-279-00204197-2001;

- nitrilotriethanol acid (NTF) TU 6-09-5283-86, white crystalline substance, soluble in water.

The inventive composition was prepared as follows.

Example 1. To obtain a composition in the laboratory took 2.5 g bottoms production of amines C17-C20, put them in a porcelain Cup, heated to 65° With, then gradually under stirring was added 2.5 g of sulfamic acid. Next, after cooling the resulting mass is formed beads-beads that had been subjected to research. Received a composition with the following ratio of components, wt.%: sulfamic acid - 50; distillation residues from the production of amines C17-C20- 50.

Example 2. For obtaining of the proposed structure in the laboratory took 2.5 g bottoms production of amines C17-C20, put them in a porcelain Cup, was heated to 70&x000B0; Since, then, while gradually stirring was added 1.5 g of sulfamic acid and 2 g NTF. Formed balls-granules, which conducted further research. Received a composition with the following ratio of components, wt.%: sulfamic acid - 25; NTF - 33 distillation residues from the production of amines C17-C20- 42.

Compositions with different content of ingredients was prepared in a similar manner.

In laboratory tests determined the following characteristics: the degree of leaching of sulfamic acid, NTF and bottoms at various watering reservoir fluids, the degree of prevention of deposits of inorganic salts (calcium sulphate, calcium carbonate and iron sulfide from various reservoir fluids; corrosivity.

The degree of leaching from the composition of sulfamic acid and NTF were determined as follows. The composition of the cut pieces with a diameter or balls with a diameter of 1-2 cm3, was placed in a cylinder with a diameter of 60 mm and a height of 300 mm with two valves: the top and bottom. Then through the funnel, the lower the crane and pieces of the composition of the fed flooded the oil, which was collected in the receiver through the top of the crane, i.e. when it was simulated the process of passage of fluid into the well through the perforated container filled with the composition. In water-cut oil passing through the composition was determined to icesto specified organic acid reagent by well-known methods by RD 0147276-212-86 photocolorimetric method. The data obtained in the tests are shown in table 1.

The degree of leaching from the composition of the bottoms of the production of amines C17-C20(hereinafter COP) was determined as follows. A portion KOPA 1 g) was placed in a conical flask and extracted with a liquid different watering, taken in an amount of 100 ml, flask was closed with a stopper and shake for 1 hour. After that, the contents of the flask was filtered under vacuum through the filter of “blue ribbon”. The filter residue was weighed.

The quantity of dissolved within 1 hour COP are shown in table 2.

The data given in tables 1 and 2 show that the composition when the claimed ratio of ingredients, provides a uniform removal of active substances under different watering reservoir fluids. When the content of sulfamic acid 70% and NTF more than 70% uniform removal is not achieved.

During tests it was determined the extent of the protective effect of the proposed structure from deposits of inorganic salts and iron sulfide on models produced water. The tests were carried out as follows. Prepared two solutions: one of them contains a soluble salt of the sulfate ion SO

2-
4
or carbonate ion FROM
2-
3
, other - soluble salt of the cation of CA2+(solution 2). In solution 1 (50 ml) for 16 hours was a flat piece of 0.5-2 cm3solid composition, then it was taken out of the solution 1 was added and a solution of 2 (50 ml). Thus, received a supersaturated solution of calcium sulfate or calcium carbonate. In the resulting solutions was determined by the content of calcium ions trigonometricheskom method. Also prepared solutions with a given amount of sulfide ions (iron sulfide). The solutions were kept in a thermostat at a temperature of 40-80° C for 6 hours. At the same time put a control sample without the composition. The extent of the protective effect of the proposed solid composition was calculated by the formula:

E=[(Cp-C0)/(Cd-C0)]:100, %

where e is the degree of protective effect, %;

Withp- the content of sedimentation ions in solution in the presence of a solid composition, after a certain experience;

Withd- the content of sedimentation ions in solution in the presence of a solid composition, certain to experience;

With0- the content of sedimentation ions in the test sample.

In solutions at the same time determined the amount of loose sediment gravimetric method. The content of iron sulfide was determined by iodometric titration.

Efficiency is Yunosti prevent sulfide ions and sulfide were evaluated on artificially prepared waters of carbonate and sulfate type in the presence of iron ions, close in chemical composition to the reservoir water oil fields. The sample was saturated with hydrogen sulfide selected concentration in the form of sodium sulfide. The effect of neutralization was determined by the method of iodometry.

The data obtained are shown in tables 3 and 4.

The data given in tables 3 and 4 show that the proposed solid composition provides high efficiency for the prevention of deposits of inorganic substances and iron sulfide.

Tests for corrosivity of the proposed composition was carried out as follows. Samples of cold-rolled steel strips (GOST 3560-73) rectangular shape with a size of 25× 20× 0.5 mm pre-weighed on an analytical balance. Then the samples (4 pieces) was fixed on a special holder and placed in a jar with the reservoir fluid, passed through the proposed structure. Specified Bank was established in the laboratory setting for conducting corrosion tests “Wheel”, which was produced by the rotation for 6 hours at a speed of 80 Rev/min and Then the samples were removed from the jars, washed with water, detergent solution, dried, and kept for 1 hour in a desiccator and weighed. The corrosion rate was calculated by the formula:

K=(Po-P1)/(F· t),

where is the corrosion rate, g/(m2·h);

Po- weight arr is SCA to test g;

P1- weight of sample after test, g;

F - area of the sample, m2;

t - time tests, including

The protective effect of the composition is determined by the formula:

Z=[(Kabout-K1)/Ko]× 100%,

where Z is a protective effect, %;

Toaboutthe corrosion rate in the reservoir fluid without composition, g/(m2·h);

K1the corrosion rate in the reservoir fluid, passed through a composition, g/(m2·h).

Evidence of the protective effect of corrosion of the proposed composition shown in table 5.

Data about the properties of oil and produced water, which is used for the above laboratory tests are presented in tables 6 and 7.

Based on the results obtained during the tests, the composition has the following advantages over the known compounds:

- permanent solid dosage composition in the produced fluids through the gradual dissolution of the active foundations in effective concentrations (is samodzielna);

- helps prevent the formation of complex inorganic salts and iron sulfide even in the presence of sulfur and sulfate reducing bacteria in the reservoir;

- provides protection for deep oil field equipment from deposits along the movement path of the water flow;

- which allows you to increase the duration of maintenance-free period of operation of the production well, in particular, the turnaround time is increased three times.

Table 1

The degree of leaching of sulfamic acid and NTF of the proposed structure
№№The contents of the ingredients in the composition, wt.%The content of sulfamic acid or NTF in oil cut, passed through a composition, g
Sulfamic acidNTFDistillation residues from the production of amines With17-C20when oil water cut 20%when the water content of the oil 70%
1.10-900,40,5
2.20-800,50,6
3.50-502,12,5
4.65-352,82,8
5.70-302,83,2
6.80-203,24,3
790-10 4,55,0
8.4025351,81,8
9.2533422,32,3
10.1070204,24,2

Table 2

Data on the extent of dissolution of the bottoms of the production of amines With17-C20
Watering water-cut oil used for experience, %The quantity of dissolved bottoms production of amines With17-C201 hour
gr.%
00,1616%
200,2121%
500,2828%
700,3535%
1000,4040%

Table 3

The extent of the protective effect of the proposed solid composition from deposits of inorganic substances and iron sulfide
№№Components predlagaemoj the solid composition, wt.%The degree of protective effect from sediments of the following substances, %
Acid reagentDistillation residues from the production of amines With17-C20Calcium carbonateCalcium sulphateIron sulfide
Sulfamic acidNTF
110-90302520
220-80985862
330-70886752
440-60917337
550-50826945
665-35555320
770-30413917
880-2038339
9 22255397,28822
1025403593,39136
11205030928660
12107020of 98.29382
13Known composition: bitumen+NTF544924

Table 5

The degree of protection against corrosion, shown predlagaemym solid composition
Component content, wt.%Corrosion protection
Sulfamic acidNTFDistillation residues from the production of amines With17-C20The corrosion rate, g/(m2h)Protective effect %
For the proposed structure
10 900,183854,78
20 800,1561 58,82
50 500,203263,14
65 350,243251,78
70 300,195857,32
80 200,120354,72
2225530,202758,32
2050300,203763,14
Known corrosion inhibitor IKB-40,218357,2

Table 6

The composition of the oil used in the tests
Place of sampling oilDensity,

kg/m3
The content in oil, %
asphaltenesresinwaxes
Constantine, PG8120,324.26 deaths5,64
Dawn, Clear8552,176,936,50

Table 7
The composition of the produced water used for testing
Place of sampling waterDensity,

kg/m3
The content of ions, mg/l
CISO4The HCO3CAMgK+Na
Constantine, PG115314013026115115301298267002
Dawn, Clear101111521,349,0204,351233,7598,75173,4

Solid composition for preventing deposits of inorganic salts and iron sulfide in the extraction and transportation of oil, including organic acid reagent and distillation residues from the production of amines With17-C20, characterized in that the organic acid reagent composition contains sulfamic acid in the following ratio, wt.%:

Sulfamic acid20-70
Distillation residues from the production of amines With17-C20Rest

or a mixture of sulfamic acid with neath latimestravel acid in the following ratio of components, wt.%:

Sulfamic acid10-40
Nitrilotriacetate acid25-70
Distillation residues from the production of amines With17-C20Rest



 

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