RU2316641C1 - Method to produce asphalt-tar-paraffin deposit removal composition - Google Patents

Abstract

FIELD: oil production, particularly devices to remove asphalt-tar-paraffin deposits from well bottom zone, discharge lines of oil-gathering reservoirs, oil-field equipment, oil production and refinery plants.

SUBSTANCE: method involves mixing initial components in the following succession: mixing FLEK-IP-102 inhibitor and HPP-004 inhibitor to obtain mixture and adding DP-65 depression additive, which is 40% jet-fuel solution. The DP-65 depression additive is mixed with two-component mixture including FLEK-IP-102 and HPP-004 inhibitors after 15 min of said inhibitor mixture preparation.

EFFECT: increased efficiency.

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Description

The invention relates to the field of oil production, in particular, can be used to remove paraffin deposits from the bottomhole formation zone, flow lines of oil collecting manifolds of oilfield equipment of oil producing and oil refining enterprises.

The AFS process worsens the technical and economic performance of oil production: the overhaul period of wells is reduced, oil losses and energy consumption are increased, accident rates at facilities are increased, conditions are created for the spread of oil contamination in the field, etc. (Olenev L.M., Mironov T.P. Use of solvents for the prevention of AFS formations. M.: VNIIOUENG, 1994).

A known method of obtaining a composition for removing paraffin deposits with a high content of asphaltenes and resins from the wellbore and bottomhole formation zone [SU, No. 1696449 A1, С09К 3/00, ЕВВ 37/06] containing bottoms from the production of butyl alcohols and corrosion inhibitor Ural-2 - a mixture of aromatic and aliphatic amino compounds in toluene, comprising mixing the components of the composition with the following optimal ratio of components wt.%:

VAT bottoms production of butyl alcohols 45-55 Corrosion inhibitor Ural-2 - a mixture of aromatic and aliphatic amino compounds in toluene 45-55

The claimed method differs from the known one in that it involves preparing the composition by mixing the starting reagents in the following sequence: a FLEK-IP-102 inhibitor, an inhibitor of HPP-004 and a depressant additive DP-65, in the form of a 40% solution in jet fuel. In the claimed method, the dependence of the efficiency of inhibition, as well as the effect of synergy on the order of mixing of the reagents in the mixture, is revealed.

Currently, to prevent the formation and removal of paraffin, various inhibitors are used, depressant additives, as a rule, of single-functional action.

So known is the FLEK-IP-102 inhibitor, which is produced by FLEK LLC according to TU 2483-007-24084384-01. The inhibitor is a colorless to dark brown gel. The composition of the inhibitor includes: toluene, technical ethylbenzene, xylene petroleum, petroleum solvent [RD 39-0148311-328-88, Selection of paraffin scale inhibitors].

The disadvantage of the FLEK-IP-102 inhibitor is its low efficiency, which does not exceed 30% in the range of concentrations up to 1000 g / t (studies were carried out on oil from the Kharampur field).

The KhPP-004 inhibitor, designed to prevent the formation of paraffin deposits and remove hydrate deposits in oilfield equipment and pipelines during oil production and transportation, manufactured according to TU 39-43122541-OP-14-98, is a mixture of organophosphorus compounds, monoethanolamine and hydroxyalkylated alcohols and urethane derivatives in a mixture of solvents: methanol, oil solvent (Nefras A-130/150 or A-120/200).

Appearance of the inhibitor HPP-004: a homogeneous transparent liquid from light yellow to yellow.

The disadvantage of the KhPP-004 inhibitor, as well as the FLEK-IP-102 inhibitor, is its low efficiency, which does not exceed 47% in the concentration range up to 1000 g / t (studies were carried out on oil from the Kharampur field).

The depressant additive DP-65 according to TU 6-02-594 is a solid low-toxic substance from brown to dark brown.

DP-65 is polyamides - condensation products of FFA fraction C ₂₁ -C ₂₅ and polyethylene polyamines in various ratios. Additive DP-65, designed to reduce the pour point of oils and petroleum products containing high-melting solid hydrocarbons, is ineffective in diesel fuels. It also has an inhibitory effect on paraffin. The inhibition efficiency is 33% in the concentration range up to 1000 g / t (studies were carried out on oil from the Kharampur field).

The technical challenge facing the inventor is to develop a method for producing a highly effective three-component composition of paraffin inhibitors by mixing the starting reagents.

To solve this problem, the compositions of three-component mixtures of paraffin deposition inhibitors, which differ in the order of mixing of the starting reagents, were studied. The compositions are designed to remove asphalt-resin-paraffin deposits in wells and oilfield equipment.

During the preparation of the three-component composition, various results were visually obtained.

A study of the effectiveness of formulations differing in the order of mixing of the reagents was carried out in laboratory conditions at the Cold Rod facility on jet fuel with the addition of an AFS of the Kharampur field in an amount of 10 wt.% According to the known method described in RD 39-0148070-003VNII-86.

Solutions were prepared immediately prior to testing.

The results of the study are shown in table 1.

Each of the components of the initial inhibitors has its own specific effect on a certain type of paraffin.

The optimal ratio of components, which determines high efficiency, wt.%:

FLEK-IP-102 inhibitor 53.3 inhibitor of hpp-004 26.7 depressant additive DP-65, in the form of a 40% solution in jet fuel 20,0

(I method of mixing).

The dependence of the inhibition efficiency of the three-component composition on the content of DP-65 (40% solution in jet fuel) depending on the order of mixing of the reagents at a flow rate of 50 g / t (Table 2) allows us to conclude that the order of mixing actually affects the efficiency of inhibition . The composition prepared according to the I method of mixing [(FLEK-IP-102 + KhPP-004) + DP-65] is much more active than the compositions prepared according to II and III methods. Maximum efficiency (75.4%) is achieved with a content of 20% additive DP-65 (40% solution in jet fuel) in the composition prepared by the first method.

The synergism was quantified by comparison with the additivity curve. According to the additivity rule, the mass of a mixture of components is equal to the sum of the masses of the components that make up this mixture, multiplied by the corresponding mass fractions in the mixture.

where m ₁ is the mass of paraffin deposits deposited on the rod in the experiment with the addition of one inhibitor, g;

m ₂ - the mass of paraffin deposits deposited on the rod in the experiment with the addition of a second inhibitor, g;

m ₃ is the mass of paraffin deposits deposited on the rod in the experiment with the addition of a third inhibitor, g;

n ₁ - mass fraction of the first inhibitor in a three-component mixture;

n ₂ is the mass fraction of the second inhibitor in the mixture;

n ₃ is the mass fraction of the third inhibitor in the mixture.

The effectiveness of the additivity of the mixture (EA) is found by the calculation method:

where m _o is the mass of paraffin in the control experiment, g;

m _a - additive mass of paraffin, calculated by the formula (1),

We denote the efficiency obtained in this way as the additivity efficiency. For a quantitative assessment, we use the ratio S = Esm / Ea. If Esm / Ea> 1, then a synergistic effect is manifested, and if Esm / Ea <1, then the effect is antagonistic.

The results are shown in table 2.

According to the results of Table 2, one can track the dependence of Esm / EA on the content of DP-65 (40% solution in jet fuel) for three-component compositions that differ in the order of mixing of the reagents. The compositions prepared according to methods I and II have a synergistic effect. Moreover, for the composition prepared according to method I, the phenomenon of synergism is observed over the entire content of DP-65, and for the composition (FLEK-IP-102 + DP-65) + HPP-004 [II method] in the range of 27-100%. For the composition (KhPP-004 + DP-65) + FLEK-IP-102, a relatively low efficiency of inhibiting mixtures was obtained in the entire region, which indicates the preparation of a composition with worse physicochemical properties, i.e. due to the emulsion.

The physicochemical properties of the compositions of inhibitors of paraffin inhibitors KhPP-004, FLEK-IP-102 and depressant additives DP-65 (40% solution in jet fuel) depend on the order of mixing of the reagents. The structure of the mixture varies from an ideal solution to a stable emulsion. The color of the mixtures varies from transparent to brown (solutions) and to white (emulsion).

Three-component compositions with good mutual solubility have the greatest efficiency, and emulsions have the least efficiency. Moreover, the synergistic effect is characteristic of true colored solutions, for white emulsions, in general, there is a decrease in efficiency and the phenomenon of antagonism, with the exception of the mixture with the content of the additive solution in the ternary mixture in the amount of 40 wt.% (III method, Table 2, p.12).

Thus, based on the above data, we can conclude that the order of mixing of the reagents has a significant impact on the effectiveness and synergistic effect. This is possibly due to the formation of associative bonds between the reagents in the mixture. This fact must be taken into account when developing and compiling various compositions.

The results obtained are associated with the mechanisms that occur during the formation of the mixture.

In order to study the mechanism of the formation of three-component compositions of paraffin inhibitors, which differ in the order of mixing, the spectra of three-component compositions and initial reagents were studied.

The study was performed by infrared spectroscopy with a spectrometer FTIR AVATAR 330 FT-IR "Thermo Nicollet" in the wave range of 400-4000 cm ^-1.

The dependence of the optical density on the wave number was obtained for individual inhibitors and their mixtures prepared in different ways, but with the same composition.

The IR spectra of the mixtures depend both on the composition of the mixtures and on the order of mixing of the reagents. The more different are the efficiencies of mixtures prepared in different ways, the more clearly are the differences in their spectra.

The structure of the mixtures and their color depend on the mixing order of the starting reagents. With a different mixing order, both true colored solutions and white emulsions are formed with the same final mixture composition.

The effectiveness and synergy of the three-component mixtures depend on the mixing order of the starting reagents. The effectiveness of the mixtures varies from 5 to 70%, and the synergy from 0.2 (antagonism) to 2.2 with the same final composition of the mixture. Moreover, the mixtures forming the true solution have the greatest efficiency and synergism, while mixtures in the state of emulsion have the lowest efficiency and exhibit antagonism.

Differences in the IR spectra of mixtures having the same composition but differing in the order of mixing of the reagents were revealed. The spectra of synergistic mixtures and their changes indicate that there is an interaction between the reagents, which increases the efficiency and enhances the manifestation of the synergistic effect.

The composition, structure and energy of the intermolecular bonds of the complexes formed in the mixture of paraffin inhibitors, in all probability, determines the synergy of the starting reagents and, ultimately, the effectiveness of the mixture.

The developed method of mixing the starting reagents in order to obtain highly effective inhibitors of paraffin can be used at reagent manufacturing enterprises and at oil production and pumping plants to increase the technological and economic efficiency of inhibitor protection against asphaltene-tar-paraffin deposits in wells, oil pipelines and other oilfield equipment.

The implementation of the results will solve the problem of mixing various inhibitors in a chaotic manner, i.e. will make it possible to obtain highly effective compounds with the correct order of mixing of the reagents.

The compositions are prepared as follows.

I method Two-component mixture FLEK-IP-102: KhPP-004 is prepared in four containers with ground stoppers in a percentage of 67:33 in a water bath (Tbani = + 35-40 ° С), periodically mixed for 15 minutes. Then, a 40% solution of DP-65 in jet fuel in the amount of 20, 40, 80 wt.% In terms of the active part is added to the three double-mix bottles. Stand for another 15 minutes in a water bath, stirring every 2 minutes.

II method. First, FLEK-IP-102 and a 40% solution of DP-65 in jet fuel are mixed in the bucks, heated in a water bath and stirred periodically for 15 minutes, then the inhibitor of HPP-004 is added, heated and stirred for 15 minutes.

III method. The two-component mixture is prepared from an inhibitor of HPP-004 and a 40% solution of the additive in jet fuel, then the FLEK-IP-102 inhibitor is added.

Table 1
The results of the effectiveness of the three-component compositions of the FLEK-IP-102, KhPP-004 inhibitors with the addition of a 40% solution of DP-65 in jet fuel in an amount of 20, 40, 80 wt.%, Differing in the order of mixing of the reagents ASPO inhibitors and their mixtures in various ratios The effectiveness of the inhibitors and their mixtures (%) at wt. flow rate 50 g / t I cooking method FLEK-IP-102 mixture: HPP-004 67.0: 33.0 * 42.3 40% solution of DP-65 in jet fuel 29.0 FLEK-IP-102: KhPP-004: rd DP-65 53.3: 26.7: 20.0 75,4 FLEK-IP-102: KhPP-004: solution DP-65 40.0: 20.0: 40.0 47.0 FLEK-IP-102: HPP-004: solution DP-65 13.3: 6.7: 80.0 70,2 II cooking method FLEK-IP-102 mixture: HPP-004 = 67.0: 33.0 * 45.8 40% solution of DP-65 in jet fuel 28,2 FLEK-IP-102: rr DP-65: KhPP-004 53.3: 20.0: 26.7 31.25 FLEK-IP-102: rr DP-65: KhPP-004 40.0: 40.0: 20.0 49.9 FLEK-IP-102: rr DP-65: KhPP-004 13.3: 80.0: 6.7 48,4 III method of preparation FLEK-IP-102 mixture: HPP-004-67.0: 33.0 * 47.1 40% solution of DP-65 in jet fuel 26.8 KhPP-004: rr DP-65: FLEK-IP-102 26.7: 20.0: 53.3 36.0 KhPP-004: rr DP-65: FLEK-IP-102 20.0: 40.0: 40.0 41.3 KhPP-004: rr DP-65: FLEK-IP-102 6.7: 80.0: 13.3 5,0 Note * The differences in the performance indicators of the FLEK-IP-102: KhPP-004 mixture in the ratio of 67.0: 33.0 and 40% solution of DP-65 in jet fuel indicated in paragraphs I, II, III are due to the fact that the results were obtained under conditions of intralaboratory precision (under conditions of varying time), while experiments on each preparation method were carried out at different times independently of each other.

table 2
The results of determining the synergistic effect for the three-component compositions of the FLEK-IP-102, KhPP-004 inhibitors with the addition of a 40% DP-65 solution in an amount of 20, 40, 80 wt.%, Differing in the order of mixing of the reagents at a flow rate of 50 g / t Reagent mixing procedure Indicator The content of a 40 percent solution of DP-65 in the mixture,% 0 twenty 40 80 one hundred I way Color and structure of the double mixture Transparent. solution Transparent. solution Transparent. solution Transparent. solution - FLEK-IP-102 + KhPP-004 (FLEK-IP-102 + KhPP-004) + DP-65 Color and structure of the triple mixture Transparent. solution Orange Brown solution Light brown solution Brown emulsion Dark brown emulsion. Esm 42.3 75,4 47 70,2 29.0 Ea 42.3 39.7 37.0 31.7 29.0 S = Esm / Ea one 1.9 1.3 2.2 one II method Color and structure of the double mixture Light orange. solution Light orange. solution Orange solution Brown solution - FLEK-IP-102 + DP-65 (FLEK-IP-102 + DP-65) + KhPP-004 Color and structure of the triple mixture Light orange. solution White emulsion Light orange. solution Light brown solution Dark brown emulsion. Esm 45.8 31,2 49.9 48,4 28,2 Ea 45.8 38.1 32,5 21.3 28,2 S = Esm / Ea one 0.8 1,5 2,3 one III method Color and structure of the double mixture White emulsion White emulsion White emulsion White emulsion - HPP-004 + DP-65 (KhPP-004 + DP-65) + FLEK-IP-102 Flowering triple mixture structure White emulsion White emulsion White emulsion White emulsion Dark brown emulsion. Esm 47.1 36.0 41.3 5 26.8 Ea 47.1 43.0 39.0 30.9 26.8 S = Esm / Ea one 0.8 1,1 0.2 one

Claims (1)

A method of obtaining a composition for removing asphalt-resin-paraffin deposits, comprising preparing the composition by mixing the starting reagents in the following sequence: a FLEK-IP-102 inhibitor and an HPP-004 inhibitor to form a mixture and a depressant additive DP-65 in the form of a 40% solution in jet fuel, introduced into a two-component mixture PDEK-IP-102: an inhibitor of HPP-004 15 minutes after preparation of a mixture of inhibitors.