RU2546158C2 - Composition for removal of asphaltene-resin-paraffin deposits - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: composition contains a surface active substance based on a polymer of ethylene oxide - ITPS 806 reagent grade B 0.1-5.0 wt % and a mixture of aliphatic and aromatic hydrocarbons in the form of ITPS 010 reagent grade A is the rest.

EFFECT: invention provides high dissolving, dispersing and washing activity of a composition in relation to asphaltene-resin-paraffin deposits of a different type, and reduction of oil viscosity in a treated zone.

4 tbl, 4 ex

Description

The invention relates to the oil industry, in particular to compositions for removing asphalt and tar and paraffin deposits, and can be used to dissolve and remove paraffin deposits from the bottom-hole formation zone, from oilfield equipment, tanks and oil pipelines in oil companies both in solid form and dissolved in oil .

A known composition for removing asphalt-resin-paraffin deposits (AFS), containing in its composition, wt.%: 16-35 nonionic surfactant (surfactant) OP-7 or OP-10, 4,5-10,3 sulfonol and the rest is aromatic solvent (see RF Patent No. 2173328, MKI C09K 3/00, E21B 37/06, publ. 2001).

The disadvantage of this composition is its narrow focus - the removal of paraffin wax contained in paraffinic oils and oil condensates with a low content of resins and asphaltenes.

A known composition for removing asphaltene-resin-paraffin deposits, containing, wt.%: 0.15-0.30 a mixture of surfactants from ethoxylated monoalkylphenols of the General formula (I):

RC ₆ H ₄ (OC ₂ H ₄ ) mOH,

where: m = 6-10

R = C ₉ H ₁₉ -C ₁₂ H ₂₅ ,

hydroxyethylated products of the general formula (II):

R ₁ (OC ₂ H ₄ ) qOH,

where: q = 10-12

R ₁ = C ₁₂ H ₂₅ -C ₁₄ H ₂₉ ,

and sulfonated products of the general formula (III):

R ₂ C ₆ H ₄ (OC ₂ H ₄ ) mOSO ₃ H,

where: m = 6-10,

R ₂ = C ₉ H ₁₉ -C ₁₂ H ₂₅ ,

when the ratio in the mixture of these surface-active substances is (I + II): III = 1: 3-4 and I: II = 1: 1.1: 2 or 2: 1, 30-70 aromatic solvent and the rest is an aliphatic hydrocarbon solvent (see RF Patent No. 2137796, MKI C09K 3/00, E21B 37/06, publ. 1999).

The known composition exhibits low efficiency in the removal of paraffin wax with a high content of paraffins, asphaltenes, resins and sulfur.

Closest to the proposed invention in technical essence and the achieved result is a composition containing in vol.%: 0.5-5.0 one block copolymer of ethylene oxide and propylene oxide based on glycerol, 30 aromatic hydrocarbon and the rest is an aliphatic hydrocarbon (see RF patent No. 2323954, MKI C09K 8/524, publ. 2008).

However, this composition exhibits low efficiency for the removal of paraffin contained in viscous oils.

The aim of the invention is the development of a composition for removing asphaltene-resin-paraffin deposits, which has a high dissolving, dispersing and washing activity in relation to various types of paraffin deposits, including those with a high sulfur content and to reduce oil viscosity in the treated area.

The goal is achieved by creating a composition for removing asphaltene-tar-paraffin deposits containing a surfactant based on an ethylene oxide polymer and a hydrocarbon solvent is a mixture of aromatic and aliphatic hydrocarbons, and it contains an ITPS 806 grade B reagent as a surfactant based on an ethylene oxide polymer and as a hydrocarbon solvent - reagent ITPS-010 grade A, with the following ratio of components, wt.%:

Reagent ITPS 806 grade B 0.1 - 5.0

Reagent ITPS 010 grade A - the rest.

Reagent ITPS 806 grade B is produced according to TU 2458-016-27913102-2010 and is a mixture of surfactants in an organic or in an aqueous-organic solvent. Reagent ITPS 010 grade A is a composition based on a hydrocarbon solvent - a mixture of aliphatic and aromatic hydrocarbons and is produced according to TU 2458-014-27913102-2010. The following can be used as aliphatic hydrocarbons: a wide fraction of volatile hydrocarbons (BFLH) according to TU 38.101524-93, stable gasoline (BGS) according to TU 0272-003-00135817-00, oil solvent (NR) according to TU 38.101303-85 , petroleum ether according to GOST 11992 - 66, white spirit according to GOST 3134-78, Nefras-S 50/170 according to GOST 8505-80. The following can be used as aromatic hydrocarbons: xylene according to TU-6-09-3825-78, petroleum toluene according to GOST 14710-78, Nefras Ar 120/200 according to TU 38101809-80, butylbenzene fraction according to TU 2414-076-05766563-2005 , ethylbenzene fraction according to TU 2415 195 00203335-2010.

The proposed composition can be prepared both in industrial production conditions, and immediately before use by mixing the components of the composition in the claimed quantities using tankers with circulation.

The composition is a liquid from light yellow to dark brown in color, shows stability for a long time at a temperature of + 30 ° C to -40 ° C.

We give examples of the preparation of the proposed composition for the removal of paraffin, the compositions are shown in table 1.

Example 1 (the claimed composition). 99.9 g of ITPS 010 grade A reagent and 0.1 g of ITPS 806 grade B reagent are successively poured into a 250 ml vessel, the mixture is stirred by shaking the vessel with the cork closed with rotational movements until the components are completely mixed (see table 1, example 1).

Examples 2 and 3. Similarly, prepare other compositions, changing the number of the claimed reagents.

Example 4 (prototype).

In a 100-ml chemical vessel, I successively pour 1.0 ml of Laprol 3603-2-12, 30.0 ml of ethylbenzene and 69.0 ml of n-hexane. the vessel is closed with a ground stopper and the resulting composition is mixed with agitation (see table 1, example 4).

Table 1 Composition numbers The content of components in the composition, wt.% ITPS 806 grade B ITPS 010 grade A Composition 1 0.1 99.9 Composition 2 0.5 99.5 Composition 3 5,0 95.0 Prototype Laprol 3603-2-12-1.0 Hydrocarbon solvent - 99.0 Composition 4

The effectiveness of the claimed composition is due to the use of a variety of hydrocarbon solvents - aliphatic of various lengths of the carbon chain, aromatic of various molecular weights. The use of ethylene oxide in the composition of surfactants based on a polymer leads to a decrease in surface tension at the composition / paraffin boundary, and effectively destroys sulfur-containing paraffin deposits. All components for the preparation of the claimed composition are available, inexpensive and manufactured in Russia.

To prove the effectiveness of the claimed composition, experiments are conducted in laboratory conditions to determine the dissolving, dispersing and washing ability of the composition when exposed to samples of paraffin deposits of various oil producing institutions of the Republic of Tatarstan.

The test procedure is as follows. An AFS sample weighing 2.00 g is formed in the form of a cylinder and placed in a weighed basket made of steel mesh with a mesh size of 1.5 × 1.5 mm. A basket with an AFS sample is weighed to the second decimal place and the mass of an AFS sample is found. A basket with an AFS sample is placed using a wire in a glass sealed bottle with 100 ml of the test composition. Hold for 3 hours at room temperature. Next, the basket with the remains of the paraffin is taken out and dried at room temperature in suspension for 24 hours, then weighed.

The washing ability (X ₁ ) in% is calculated by the formula:

X ₁ = ((m ₀ -m ₁ ) / m ₀ ) * 100%,

where: m ₀ - the mass of paraffin in the basket before the test, g;

m ₁ - the mass of paraffin in the basket after the test,

The contents of the bottle are filtered through a filter. The bottle is rinsed with a filtered solution several times until the paraffin particles are completely transferred to the filter. The filter with particles of paraffin is dried at room temperature to constant weight.

The solvent capacity (X ₂ ) in% is calculated by the formula:

X ₂ = ((m ₀ -m ₁ + m ₂ ) / m ₀ * 100%,

where: m ₀ - the mass of paraffin in the basket before the test, g;

m ₁ - the mass of paraffin in the basket after the test, g:

m ₂ - the mass of paraffin filtered after the test,

Dispersing ability (X ₃ ) in% is calculated by the formula:

X ₃ = X ₁ -X ₂ .

The result is the arithmetic mean of two parallel measurements. The test results are shown in table 2.

table 2 №№ per item AFS sample numbers, well numbers Compositions from table 1 Washing ability, X ₁ ,% Solvent ability, X ₂ ,% Dispersing ability, X ₃ ,% one 2 3 four 5 6 one 1, well 32461 one 74.8 64.7 10.1 2 2, well 21062 one 79.9 72.5 7.4 3 3, well 11096 one 84.3 75,4 8.9 four 4, well 6177 one 75.1 57.4 17.7 5 6, well 11759 one 68.7 57.4 11.3 6 7, well 1489 one 93.5 76.7 16.8 7 8, well 23655 one 82,2 68.7 13.5 8 9, well 12445 one 93.9 79.8 14.0 9 11, well 3515 one 69.7 57.7 12.0 10 12, well 10037 one 55.5 50.3 5.2 eleven 13, well 6329 2 99.0 75,4 23.6 12 14, well 6177 2 84.6 65,4 19.2 13 15, well 7685 2 one hundred 85,2 14.8 fourteen 16, well 10219 2 85.5 73,4 12.1 fifteen 17, well 15265 2 78.0 63.8 14.2 16 18, well 9347 2 79.5 67.7 11.8 17 21, well 6379 2 94.6 84.2 10,4 eighteen 22, well 3540 3 82.3 72.7 9.6 19 23, well 22628 3 83.5 70.3 13,2 twenty 24, well 10542 3 55,4 50.6 4.8 21 25, well 11321 3 54.1 48.0 6.1 22 26, well 13508 3 53.5 45,2 8.3

one 2 3 four 5 6 23 28, well 32280 3 96.5 77.6 18.9 24 29, well 10004 3 98.0 83.3 14.7 25 30, well 20957 3 68.9 56.0 12.9 26 prototype 1, well 32461 Composition No. 4 41.6 32.3 9.3

As can be seen from the data in table 2, the washing and dissolving efficiencies of the claimed composition exceed the efficacy data of the prototype by 11.9-58.4% and 12.9-52.9%, respectively. The dispersing ability of the compounds have comparable values.

Table 3 shows the physico-chemical characteristics of the oils of the Ashalchinskoye oil field of the Nurlatneft oil and gas production unit, including wells No. 230, 232 and 15210. These oils contain the sulfur element and are highly viscous oils.

Table 3 Parameters of oil samples Number of wells surveyed Number of samples taken Value range Average value Mass content,% - sulfur eleven 38 2.8-4.95 3.98 - silica gel resins eleven eighteen 19-33.18 24.4 - asphaltenes eleven 41 4.19-18.09 8.74 - paraffins eleven 22 0.09-0.47 0.288 - coke eleven 32 4.5-13.6 9.8 - mechanical impurities 6 6 06.06-14.85 2.61

For research to reduce the viscosity of oil using three samples of high viscosity oil from wells 230, 232, 15210. Studies are carried out at a temperature of 20 ° C. Viscosity is determined with a FAN 35SA viscometer at a rotor speed of 100 rpm. For this, the test composition is added in the indicated amount to 100 ml of oil, stirred with a glass rod and the readings of the viscometer are taken. The research data are shown in table 4.

Table 4 No. of experience Well number Composition from table 1 Indicators of oil viscosity, SPZ, (decrease in oil viscosity from the original,%) The amount of composition introduced into the oil, vol. % 0 one 1.5 2 3 four 5 one 2 3 four 5 6 7 8 9 10 one Well 230 one 160 122 (23.8) 115 (28.1) 109 (31.9) 96 (40.0) 85 (46.9) 85 (49.9) 2 160 137 (14.4) 118 (26.3) 101 (36.9) 95 (40.6) 88 (45.0) 81 (49.4) 3 160 143 (10.6) 125 (21.9) 112 (30.0) 110 (31.3) 99 (38.1) 92 (42.5) Prototype 160 156 (2.5) 155 (3.1) 141 (12.5) 123 (23.1) 120 (25.0) 112 (30.0) 2 Well 232 one 212 179 (15.6) 160 (24.5) 129 (39.2) 115 (45.8) 96 (54.7) 92 (56.6) 2 212 186 (12.2) 157 (25.9) 114 (46.2) 100 (52.8) 88 (58.5) 86 (59.4) 3 212 191 (9.9) 146 (31.1) 108 (49.1) 98 (53.8) 84 (60.4) 83 (60.8) Prototype 212 202 (4.7) 196 (7.5) 177 (10.6) 160 (24.5) 148 (30.2) 142 (33.0) 3 Well 15210 one 129 95 (26.4) 89 (31.0) 74 (42.6) 69 (46.5) 50 (61.2) 48 (62.8) 2 129 107 (17.1) 90 (30.2) 76 (41.1) 61 (52.7) 48 (62.8) 42 (67.4) 3 129 90 (30.2) 86 (33.3) 69 (46.5) 53 (58.9) 47 (63.6) 45 (65.1) Prototype 129 112 (86.8) 92 (28.7) 83 (35.7) 70 (45.7) 61 (52.7) 54 (58.1)

From the data of table 4 it follows that for the most viscous oil - from well 232, the inventive composition reduces the viscosity of oil by 23.6-27.8% more than the prototype. The decrease in viscosity of the claimed composition for oils from wells 230 and 15210 is higher than the composition of the prototype by 12.5-19.9% and 4.7-9.3%, respectively.

Thus, the inventive composition, which is an original composite mixture, selected taking into account the characteristics of the group composition of paraffin, provides a high dissolving, dispersing and washing activity with respect to deposits in a wide range of operating temperatures. The use of the inventive composition will reduce the complexity of removing deposits, increase the inter-treatment period and productivity of wells, improve the economic performance of oil production.

Claims (1)

The composition for removing asphaltene-tar-paraffin deposits containing a surfactant based on an ethylene oxide polymer and a hydrocarbon solvent is a mixture of aliphatic and aromatic hydrocarbons, characterized in that the ITPS 806 grade B reagent is used as a surfactant based on an ethylene oxide polymer, and in the quality of the hydrocarbon solvent is reagent ITPS 010 grade A, with the following ratio of components, wt.%:
Reagent ITPS 806 grade B 0.1-5.0 Reagent ITPS 010 grade A Rest