RU2276252C1 - Asphalt-tar-paraffin deposit removing composition (variants) - Google Patents

Abstract

FIELD: oil production, particularly compositions for asphalt-tar-paraffin deposits removing in bottomhole formation zone, from oil production equipment surfaces, from reservoirs and oil accumulation tanks and from pipelines.

SUBSTANCE: composition comprises solvent taken in amount of 67.0-98.9% by weight, polar nonelectrolyte, namely butyl alcohol still residues taken in amount of 1-30% by weight, surfactant taken in amount of 0.1-3.0% by weight. In accordance with the first embodiment the solvent is liquid pyrolysis product or 30-180°C hydrocarbon fraction obtained by above liquid pyrolysis product rectification or mixture thereof in arbitrary combination of above substances in the mixture. In accordance with the second embodiment the solvent is 145-180°C hydrocarbon fraction, obtained by liquid pyrolysis product rectification or absorbent rectification or mixture including liquid pyrolysis products and absorbent, wherein above hydrocarbon fractions may be used separately or compose mixture to which 2-7% of vinylbenzene is added. In accordance with the third embodiment the solvent is liquid pyrolysis product and/or 30-180°C hydrocarbon fraction, obtained by liquid pyrolysis product rectification and 145-180°C hydrocarbon fraction, obtained by liquid pyrolysis product or absorbent rectification or mixture including liquid pyrolysis product and absorbent taken in arbitrary amounts and vinylbenzene added in amount of 2-7%.

EFFECT: increased tar-paraffin deposit dissolving ability at high temperatures, widened raw material source, possibility to use petrochemical waste products.

3 cl, 3 tbl

Description

The invention relates to the field of oil production, in particular to compositions for removing asphalt tar and paraffin deposits (AFS), and can be used to remove and dissolve deposits of paraffin and asphalt tar substances in the bottomhole formation zone, from the surface of oilfield equipment, in reservoirs and oil collectors, oil pipelines.

A known composition for dissolving paraffin, containing ethylbenzene and butylbenzene fractions, light pyrolysis resin (US Pat. RF No. 2098443). The disadvantage of this composition is the relatively low efficiency of removing paraffin from production wells of oil fields, characterized by a high content of resins, asphaltenes and high molecular weight paraffins. In addition, the components of this composition are valuable scarce petrochemical raw materials.

Closest to the proposed invention in technical essence is a composition for removing paraffin (Pat. RF No. 2228432) containing a hydrocarbon fraction of 70-165 ° C - a solvent obtained from the gasoline fraction of the reforming process with the addition of 15.9-17.3% dicyclopentadiene or the specified fraction obtained by rectification of liquid pyrolysis products, which includes 15.9-17.3% of a mixture of cyclopentadiene and dicyclopentadiene, as well as non-ionic surfactants OP-7 and OP-10 and surfactant neonols and polar non-electrolyte, represented by aliphatic alcohols : methyl vym, isopropyl, n-butyl, isobutyl. The components of the composition are taken in the ratio, wt.%:

Solvent 98.8-99.2 Surfactant 0.3-0.5 Polar non-electrolyte 0.5-0.7

The disadvantage of this composition is the low efficiency of the removal of paraffin deposits in the so-called "harsh conditions" - when at high temperatures the deposits form a dense layer on the surface of the metal of oilfield equipment, oil pipelines. The specified composition is characterized by insufficient dissolution efficiency of paraffin wax with a high content of refractory paraffins with a high molecular weight.

The technical result of the present invention is to increase the dissolving ability of the composition in relation to paraffin under "harsh conditions", the expansion of the raw material base, including and involving waste from petrochemical production.

The composition for removing asphalt-resin-paraffin deposits according to the first embodiment, including a solvent, a surfactant and a polar nonelectrolyte, contains as a solvent a liquid product of pyrolysis of the grade E-1, E-3, E-5 or a hydrocarbon fraction of 30-180 ° C obtained by distillation the specified liquid pyrolysis product, or a mixture thereof in an arbitrary combination with each other, and as a polar non-electrolyte, bottoms of butyl alcohol production in the following ratio of components, wt.%:

Solvent 67.0-98.9 Polar non-electrolyte 1-30 Surface-active substance 0.1-3.0

The liquid pyrolysis products used as the hydrocarbon fraction are produced by industry according to TU 38.402-62-144-93. As a hydrocarbon fraction with a boiling point of 30-180 ° C, hydrostabilized petroleum condensate pyrocondensate PL 1-2 is used in accordance with TU 38.1011149-91E or a mixture of these products.

The composition for removing asphalt-resin-paraffin deposits according to the second embodiment, including a solvent, a surfactant and a polar nonelectrolyte, contains as a solvent a hydrocarbon fraction of 145-180 ° C obtained by rectification of a liquid pyrolysis product of grades E-1, E-3, E-5, E-13 or absorbent grade A-8, or a mixture of liquid pyrolysis products of grade E-1 or E-3, or E-5 and E-13, and absorbent grade A-8, while these hydrocarbon fractions can be used individually , and in any combination with each other, with the addition of by adding 2-7% vinylbenzene to them, and bottoms of butyl alcohol production in the following ratio of components, wt.%:

Solvent 67.0-98.9 Polar non-electrolyte 1-30 Surface-active substance 0.1-3.0

The composition for removing asphalt-resin-paraffin deposits according to the third embodiment, including a solvent, a surfactant and a polar nonelectrolyte, contains as a solvent a liquid pyrolysis product of the grade E-1, E-3, E-5 and / or a hydrocarbon fraction of 30-180 ° C, obtained by rectification of said liquid pyrolysis product, as well as a hydrocarbon fraction of 145-180 ° C, obtained by rectification of liquid pyrolysis product of grade E-1, E-3, E-5, E-13 or absorbent grade A-8, or a mixture of liquid pyrolysis products grades E-1 or E-3, or E-5 and E-13, and absorb coagulant A-8, in an arbitrary combination with each other with the addition to the hydrocarbon fractions 145-180 ° C vinylbenzene in an amount of 2-7%, and as the polar nonelectrolyte - bottoms production butyl alcohol in the following ratio, wt.%:

Solvent 67.0-98.9 Polar non-electrolyte 1-30 Surface-active substance 0.1-3.0

In all cases, still bottoms of butyl alcohols are used as polar non-electrolyte (TU 2421-101-05766575-2001).

The surfactant surfactant is represented by the sodium salt of carboxymethylated isononylphenol ethoxylate, produced according to TU 2484-088-05766575-2001, or other nonionic surfactants: OP-7, OP-10 (GOST 8433-81), as well as surfactants - neonols (TU 2483 077-05766801-98).

The increase in the effectiveness of the removal of paraffin deposits by the proposed composition is provided, apparently, by the following mechanism of its effect on deposits. When the ARPD is in contact with the solvent, the interaction process begins at the solvent – paraffin interface, therefore, resins and asphaltenes located on the surface of the sediments, which form the framework of the sediments, are chemically exposed. The destruction of the carcass-forming elements occurs due to the action of aromatic hydrocarbons that make up the hydrocarbon part of the solvent.

Vinylbenzenes contained in liquid pyrolysis products have a modifying effect on the resinous components of paraffin. These hydrocarbons pass into the fraction of 30-180 ° C obtained by rectification of the liquid pyrolysis products. In support of this conclusion, it was the creation of compositions with the addition of vinylbenzene to hydrocarbon fractions that initially did not contain it (option 2). Thanks to this, it was possible to expand the raw material base by using previously unsuitable petrochemical production wastes for the production of highly effective compositions for the removal of paraffin deposits.

Such a conclusion does not follow with obviousness from the existing level of technology and therefore can be considered as meeting the patentability criterion of "inventive step".

The mechanism of action of surfactants in this composition is traditional, aimed at creating a proppant effect in relation to ARPD, which increases the area available for dissolution and the efficiency of removing ARPD from the equipment surface.

Polar nonelectrolyte ensures the distribution and retention of surfactants in the composition and performs the function of a co-solvent. The use of bottoms of the production of butyl alcohols as a polar non-electrolyte on the one hand allows expanding the raw material base, and through the use of production wastes, on the other hand, increasing the share of this component in the composition and thereby achieving a more efficient distribution of surfactants.

The procedure for obtaining the proposed composition in each of the examples is as follows. In a flask with a capacity of 150 ml, a hydrocarbon fraction containing vinylbenzene is added sequentially (option 1), or with its preliminary addition to the hydrocarbon fraction (option 2), or both together (option 3), then a surfactant and bottoms production of butyl alcohols. Compositions were prepared with different proportions of components for each option, the data are summarized in table 1, where examples 1-18 relate to the first option, examples 19-34 to the second option, and examples 35-40 to the third option.

For testing, three types of paraffin deposits were used, differing in their content of paraffins, resins and asphaltenes. Data on the composition of the tested paraffin are shown in table 2.

When conducting laboratory tests, we studied the dissolution efficiency of the ARPD of the proposed composition using the method STP-03-153-2001 "Laboratory method for determining the dissolving and removing ability of ASPO solvents" (method A and B). Method "A" is designed to determine the solvent and penetration in the so-called "harsh conditions" - when at an elevated temperature the deposits form a dense layer on the surface of the metal. Method "B" is designed to determine the solvent and destructive abilities of the solvent deposits, not subjected to heat treatment.

Method A. Deposits of paraffin deposits are placed in a heat-resistant chemical glass, which is placed in a water bath with t = 70-90 ° C (depending on the melting point of paraffin deposits) and left until the deposits are completely melted. Metal plates 10 × 55 × 2 mm made of steel of grade 20 are treated with sanding paper No. 0, wiped with acetone, dried and lowered into a glass with molten deposits so that the plate is immersed in the deposits to a height of 45 mm (N). Then remove the plate with the deposited deposits on it and dry for 2 hours. The sediment layer should be 1.5-2.0 mm thick. In case deposits are applied in a thin layer, the plate is lowered into the molten deposits in several stages, with each layer being pre-dried for 20-30 minutes. The prepared composition is poured into a glass cylinder in an amount of 10 cm ³ and the plate is lowered there by% of the height (35 mm) of the applied layer (h). Every 15-30 minutes, changes that occur with deposits within 2 hours are recorded: swelling, staining of the solvent, peeling, cleaned surface in%. For 100%, the surface of deposits deposited to a height of h is taken. At least two parallel tests are carried out for each sample.

Method B. In a glass cylinder with a capacity of 25 cm ³ pour solvent in an amount of 10 cm ³ . Balls with a diameter of 10-12 mm are formed from AFS samples, which, after weighing on an analytical balance, are placed on a metal mesh, which is placed in a glass cylinder with the studied solvent. Tests are carried out for 2 hours, and every 15 minutes, changes in the physical state of deposits are recorded. If after 2 hours deposits remained on the grid, they are removed from the solvent, dried and weighed on an analytical balance. The calculation of the effectiveness of the solvent is carried out according to the following formula:

where m is the mass of paraffin, taken for the experiment, g;

m _, is the mass of deposits after the experiment, g.

The test results are summarized in table 3.

As can be seen from table 3, all formulations that contain vinylbenzene (option 1, examples No. 1-18), and into which it is additionally introduced (option 2, examples No. 19-34), both together (option 3, examples No. 35-40), have a high efficiency removal of paraffin. Significantly worse result shows the composition of the prototype (for an example of the prototype, see the beginning of table 3). According to the prototype for the same period of time (according to method A), only 50-55% of deposits are removed.

The interchangeability of components for the preparation of compositions positively affects the flexibility of the process of their preparation based on the presence (or absence) of a product.

To illustrate the effect of vinylbenzene on the solvent capacity of solvents, they were taken in pure form (examples 1, 2, 7, 8, 13, 14 option 1; examples 19, 20, 29, 30 option 2; examples 35, 36 option 3). The content in the solvent (option 1) or the addition to it (option 2) of already 2% vinylbenzene significantly increases the efficiency of removing deposits in comparison with the prototype, which does not contain vinylbenzene. A further increase in the proportion of vinylbenzene weakly affects the improvement of the quality of the solvent, see examples 2, 8, 14, 20, 30, where its content reaches 7% (maximum content in liquid pyrolysis products), and the removal efficiency increases only by 1-5%.

From this table 3 it is also seen that the effectiveness of the compositions is strongly influenced by the fraction of the polar nonelectrolyte contained in them. In example No. 4, 6, 10, 12, 16 and 18 (table 1), its share is 30%, while the most effective removal of deposits from almost all samples is observed. If we consider that the polar non-electrolyte according to this invention is a waste of petrochemical production, then in addition to efficiency, the economic indicators of the process of deposit removal as a whole are also improved.

Thus, the proposed compositions successfully solve the problem of removal of paraffin deposits while expanding the raw material base and improving the technical and economic indicators of the process by involving production waste and increasing the flexibility of the preparation process.

Table 1
Data on the content of ingredients in the studied formulations No. The content of ingredients, wt. % The content of vinylbenzene in the hydrocarbon fraction, wt. % an example Liquid Pyrolysis Product
brands E-1, E-3, E-5 Hydrocarbon fraction 30-180 ° C obtained by rectification of the liquid pyrolysis product
brands E-1, E-3, E-5 A mixture of liquid pyrolysis products of grade E-1, E-3, E-5 and a hydrocarbon fraction of 30-180 ° C obtained by rectification of the liquid pyrolysis product
brands E-1, E-3, E-5 Surfactant Polar nonelectrolyte, bottoms of butyl alcohol production one one hundred - - - 2 2 one hundred - - - 7 3 98.9 - 0.1 one 2 four 67 - 3 thirty 2 5 98.9 - 0.1 one 7 6 67 - 3 thirty 7 7 - one hundred - - - 8 - one hundred - - 7 9 - 98.9 0.1 one 2 10 - 67 3 thirty 2 eleven - 98.9 0.1 one 7 12 - 67 3 thirty 7 13 - - one hundred - - 2 fourteen - - one hundred - - 7 fifteen - - 98.9 0.1 one 2 16 - - 67 3 thirty 2 17 - - 98.9 0.1 one 7 eighteen - - 67 3 thirty 7

Table 1 (continued)
Data on the content of ingredients in the studied formulations Example No. The content of ingredients, wt. % The content of vinylbenzene in the hydrocarbon fraction, mass%. Hydrocarbon fraction 145-180 ° C obtained by rectification of liquid pyrolysis products of grade E-1, E-3, E-5 Hydrocarbon fraction 145-180 ° C obtained by rectification of the absorbent grade A-8 The hydrocarbon fraction 145-180 ° C, obtained by rectification of the liquid product of the pyrolysis grade E-13 Hydrocarbon fraction 45-180 ° C obtained by distillation of a mixture of liquid pyrolysis products of grades E-1, E-3, E-5 and E-13, and absorbent grade A-8 Surfactant Polar nonelectrolyte, bottoms of butyl alcohol production 19 one hundred - - 2 twenty one hundred - - 7 21 98.9 0.1 one 2 22 67 3 thirty 2 23 98.9 0.1 one 7 24 67 3 thirty 7 25 67 3 thirty 2 26 67 3 thirty 7 27 67 3 thirty 2 28 67 3 thirty 7 29th one hundred - - 2 thirty one hundred - - 7 31 98.9 0.1 one 2 32 67 3 thirty 2 33 98.9 0.1 one 7 34 67 3 thirty 7

Table 1 (continued)
Data on the content of ingredients in the studied formulations Example No. The content of ingredients, wt. % A mixture of a hydrocarbon fraction of 145-180 ° C obtained by distillation of liquid pyrolysis products of the grade E-1, E-3, E-5, E-13, absorbent grade A-8 and a hydrocarbon fraction of 30-180 ° C obtained by rectification of the liquid pyrolysis products brands E-1, E-3, E-5 Surfactant Polar nonelectrolyte, bottoms of butyl alcohol production The content of vinylbenzene in the hydrocarbon fraction, wt. % 35 one hundred - - 2 36 one hundred - - 7 37 98.9 0.1 one 2 38 67 3 thirty 2 39 98.9 0.1 one 7 40 67 3 thirty 7

table 2
Paraffin composition data Sample No. The composition of paraffin, wt.% Paraffins Resins Asphaltenes ASPO-1 40.7 14.3 11.2 ASPO-2 11.5 45.3 12.8 ASPO-3 15.6 12,2 43.8

Table 3
Data on the properties of the known and proposed compounds Example No. (by
table 2) The dissolution efficiency (method A),% The dissolution efficiency (method B),% ASPO-1 ASPO-2 ASPO-3 ASPO-1 ASPO-2 ASPO-3 According to the prototype 55 65 fifty 83.5 80.2 73,4 one 61 69 58 84.3 82.0 75.1 2 60 71 62 85,2 83,4 78.2 3 65 74 65 83.6 89.1 82.5 four 70 79 69 84.5 90.1 84.1 5 66 73 66 84.7 89.7 83.0 6 75 81 70 87.4 90,4 85.3 7 81 84 79 82.6 85.3 79,4 8 84 86 81 82.0 86.7 80.2 9 83 85 83 81.7 85,4 81.7 10 91 89 82 94.2 88.1 85,2 eleven 98 96 90 99.1 95.6 94.7 12 one hundred one hundred 95 one hundred one hundred 97.5 13 80 83 78 81.8 84.3 78.1 fourteen 82 85 77 81.1 84.2 79.1 fifteen 81 83 80 79,4 84.7 79.5 16 93 87 81 93.2 86.4 84.3 17 97 95 78 97.3 93.6 92.8 eighteen one hundred 98 99 one hundred 99.1 96.4 19 63 72 60 86.7 85.0 77.8 twenty 65 73 67 87.5 85.9 80.5 21 67 76 67 85,4 90,4 84,4 22 74 82 71 87.9 93.5 83.9 23 69 75 68 86.5 90.3 85.7 24 77 84 72 89.1 92.6 87.3 25 73 80 71 86.5 92.9 84.2 26 76 83 73 88.9 91.3 86.9 27 71 78 69 85.6 92.1 83.8 28 73 80 72 89.0 93.2 85,4 29th 63 73 60 86.2 84.5 78.1 thirty 66 72 68 87.9 85.1 81.3

Table 3 (continued)
Data on the properties of the known and proposed compounds Example No. (according to Table 2) The dissolution efficiency (method A),% The dissolution efficiency (method B),% ASPO-1 ASPO-2 ASPO-3 ASPO-1 ASPO-2 ASPO-3 According to the prototype 55 65 fifty 83.5 80.2 73,4 31 68 77 65 86.2 89.9 85.3 32 75 83 73 87.5 94.5 84.6 33 70 74 68 85.9 91.1 85,4 34 76 84 73 90.1 90.3 88.7 35 83 85 81 83.5 85,2 79.1 36 85 87 78 84.2 86.4 81.6 37 83 85 83 81.5 86.7 81.5 38 95 89 83 95.2 88.4 86.2 39 98 96 80 98.3 95.6 94.8 40 99 97 89 one hundred 97.2 96.9

Claims (3)

1. The composition for removing asphalt-resin-paraffin deposits, including a solvent, a surfactant and a polar non-electrolyte, characterized in that it contains as a solvent a liquid product of pyrolysis of grade E-1, E-3, E-5 or a hydrocarbon fraction of 30-180 ° C obtained by distillation of said liquid pyrolysis product, or a mixture thereof in an arbitrary combination with each other, and bottoms of butyl alcohol production in the following ratio of components, wt.%: As a polar nonelectrolyte Solvent 67.0-98.9 Polar non-electrolyte 1-30 Surface-active substance 0.1-3.0 2. A composition for removing asphalt-resin-paraffin deposits, including a solvent, a surfactant and a polar non-electrolyte, characterized in that it contains a hydrocarbon fraction of 145-180 ° C obtained by rectification of a liquid pyrolysis product of grade E-1, E-3, E-5, E-13, or grade A-8 absorbent, or a mixture of liquid pyrolysis products of grade E-1 or E-3, or E-5 and E-13 and grade A-8 absorbent, with these hydrocarbon fractions be used both individually and in arbitrary combination with each other with Adding thereto 2-7% vinylbenzene, and as the polar nonelectrolyte - bottoms production butyl alcohol in the following ratio, wt.%: Solvent 67.0-98.9 Polar non-electrolyte 1-30 Surface-active substance 0.1-3.0 3. A composition for removing asphalt-resin-paraffin deposits, including a solvent, a surfactant and a polar non-electrolyte, characterized in that it contains a liquid product of the pyrolysis of grade E-1, E-3, E-5 and / or a hydrocarbon fraction 30- 180 ° C obtained by distillation of said liquid pyrolysis product, as well as a hydrocarbon fraction of 145-180 ° C obtained by rectification of liquid pyrolysis product of grade E-1, E-3, E-5, E-13 or absorbent grade A-8, or mixtures of liquid pyrolysis products of grade E-1, or E-3, or E-5 and E-13 and a Sorbent A-8 in an arbitrary combination with each other with the addition to the hydrocarbon fractions 145-180 ° C vinylbenzene in an amount of 2-7%, and as the polar nonelectrolyte - bottoms production butyl alcohol in the following ratio, wt.%: Solvent 67.0-98.9 Polar non-electrolyte 1-30 Surface-active substance 0.1-3.0