Compound for removal of asphalt-resin-paraffin precipitations and hydrophobization of face-adjacent bed zone

FIELD: oil industry.

SUBSTANCE: compound has processed cyclohexane fraction, processed tallic or rapeseed oil, additionally has modified high-dispersion polysyl-grade silica with following ratio of components in percents of mass: processed cyclohexane fraction 69.9-78.0, processed tallic or rapeseed oil 20.0-30.0, polysyl 0.1-2.0.

EFFECT: higher efficiency.

3 ex, 4 tbl

 

The invention relates to the oil industry and can be used to remove asphaltoresinparaffin, resin and paraffin deposits from oil-field equipment, wells and bottom-hole formation zone, as well as for the waterproofing layer zones for enhanced oil recovery and enhanced oil recovery.

Known compositions for removal of deposits, which contain hexane, ethylbenzol fraction (A.S. USSR №1620465, From 09 To 3/00, B. I. 2, 1991) and hexane fraction and a light pyrolysis resin (A.S. USSR №1092164, From 09 To 3/00, B. I. 18, 1984).

The disadvantage of these compounds is their low efficiency in relation to the deposits in a wide range of content of asphaltenes, resins and waxes.

Known composition for removing asphaltoresinparaffin deposits, which contains, wt%: a byproduct of the petrochemical production - hexane fraction or a product of oil refining - fraction gasoline - reagent-2” - 25 - 75, monoalkyl ether of polyethylene glycol on the basis of primary fatty alcohols of General formula CnH2n+1About (C2H4)mH, where n=10-18, m=8-10, or ethoxylated isononylphenol with a degree of oksietilirovannye 9-12-0,5-5,0, a by-product of organic synthesis based on aromatic hydrocarbons - the rest (RF Patent 2131901, From 09 To 3/00, E 21 In 37/06, B. I. 17, 1999).

The disadvantage of e the second part is the low boiling point of hexane and gasoline fractions, the use of components containing aromatic hydrocarbons, which have a harmful impact on people and the environment, as well as lack of effectiveness for deposits with a high content of waxes, resins and asphaltenes.

Closest to the proposed composition is a composition for removing deposits containing a mixture of hydrocarbons, wt.%: waste cyclohexane fraction - 70-80, waste tallow or canola oil - 20-30 (RF Patent 2185412, From 09 To 3/00, E 21 In 37/06, epubl).

The composition has good dissolving ability in relation to deposits with a high content of paraffins, asphaltenes and resins. However, the composition has insufficient detergent, emulsifying and stabilizing action of the contaminated surface with respect to asphaltenesresinous sediments with a high content of paraffins, asphaltenes and resins.

The task of the invention is to increase detergent, emulsifying and stabilizing action of the contaminated surface with respect to asphaltenesresinous sediments with a high content of paraffins, asphaltenes and resins, as well as the increase in oil-driving properties of the composition by increasing the hydrophobization of the reservoir rock.

The problem is solved in that the composition for removing asphaltoresinparaffin deposits and hydrophobization p is Sabinas zone of the reservoir, containing waste cyclohexane fraction, enriched tall oil or rapeseed oil, characterized in that it further comprises a modified fine silica mark Policy in the following ratio, wt.%:

Proven cyclohexane fraction 69,9-78,0

Waste tallow or canola oil 20,0-30,0

Policy 0,1-2,0

Proven cyclohexane fraction represents a departure from the production of plastic products containing, in wt.%: cyclohexanone - 71,4-75,0, heptane-2 - 4,6-of 5.29, cyclohexane 1,43-1,71, Cyclopentanone 2,40-2,86, cyclohexanol 13,1-14,8, cyclohexen 0,70-0,86, water of 2.0 to 3.0.

The enriched tall oil mainly contains, wt%: fatty acids (oleic, linoleic and other) 30-60, resin acids 30-60, neutral substances 8-20, oxidized substances 4-10, moisture to 8.0.

Waste rapeseed oil, wt.%: oleic acid to 20.0, erucic acid 56,0-65,0, linoleic acid to 14.0.

The mixture of exhaust components are yellow oily liquid with a density at 20° - 944 kg/m3with a water content of 2.0% and a flash point in closed crucible - 45,5°C.

As Policie use of chemically modified silica (SiO2), which, depending on how modifications can have a hydrophobic (Policy-P1) or debiliny and (POLYSIL-AF) properties.

Policy is a trademark of chemically modified silica (SIO, SIS2) (Trademark “Policy”, certificate No. 196999 from 06.12.2000 year).

Policy-P1 has a strong hydrophobic and organophilic properties, which means is a superfine powder on the basis of silicon dioxide, chemically modified organosilicon compound has a bulk density a 0.035-0.14 g/cm3particle size of 0.005 to 0.04 μm, specific surface area 300 m2/g, the effective contact angle for the surface-treated Policrom-P1 140-170°, working temperature range - 60 to +180°With the degree of hydrophobicity is 99% (THAT 2169-001-0470693-93).

Policy-DF has the properties of a solid nonionic surfactants due to the chemical structure of the grafted surface layer possesses emulsifying properties, has a bulk density a 0.035-0.14 g/cm3particle size of 0.005 to 0.04 μm, specific surface area 300 m2/g, the effective contact angle for the surface-treated Policrom-DF, 0°, working temperature range - 60 to +180°With the degree of hydrophobicity is 100% (THE 2311-002-04706-93).

Chemically modified superfine powder brand Policy is chemically inert powder that will have no adverse impact on human health and the environment, in accordance with the “Primary Toxicological-hygienic new passport with the unity, approved by the RF Ministry of health, this class of materials is according to GOST 12.007-76 4-the class of low-hazard substances. Storage conditions of Policie: dry location at temperatures from - 50 to +50°C.

Unlike the prototype of the proposed composition additionally contains a new component - chemical conversion of highly disperse silica mark Policy.

Fine-grained hydrophobic silica mark Policy, introduced into the composition, having a submicron particles easily penetrate into the pores and microcracks formation, changes the energy surface (wettability). This qualitatively changes the filtration characteristics of the reservoir for water and for oil.

The proposed composition containing finely dispersed hydrophobic silica with the degree of hydrophobicity of 99-100%, largely hydrofobicity the rock surface. The hydrophobization of the surface of the breed is the result of a consolidation of fine material in the pore volume due to the small size of its particles and due to forces of adhesion, but also due to changes in wetting angle to 170-178° and reduce surface tension.

The composition may contain modified silica mark POLYSIL-DF. Due to the structure of the grafted surface layer POLYSIL-DF has the properties of a solid nonionic surfactant.

In the result of consolidation in the pore volume due to the small size of its particles and due to forces of adhesion Policy-AF dramatically reduces the surface tension at the phase boundary water-rock-oil, increasing permeability of the fluid.

Add material brand Policy-DF in the composition enhances the cleaning effect of the contaminated surfaces and leads to emulsification of the fat and oil pollution, dispersion and stabilization of the particles of solid impurities (ASPO).

In the proposed structure as a component that increase the hydrophobic properties of the composition, using a modified hydrophobic silica mark POLYSIL-P1. Chemical surface modification of silicon dioxide to produce organic silicon compound of General formula Cl4-nSiRnwhere n=1-3; R=H, methyl, ethyl, Cl - methyl, phenyl, followed by treatment with a compound selected from the group consisting of tetramethoxysilane or tetraethoxysilane, or polymethylsilane.

The enriched tall oil mainly contains fatty carboxylic acids (oleic, linoleic, and others), resin acids, and waste rapeseed oil - oleic acid, linoleic acid, which are oil-soluble surface-active substances.

In addition, the composition contains cyclohexane fraction, which contains Ali Ilichevsky alcohol - the cyclohexanol, and alicyclic ketones - cyclohexanone, heptanone and Cyclopentanone. When mixed with tallow or canola oil, they form a complex mixture of derivatives of acids of tall oil or rapeseed oil in a hydrocarbon solvent, which are an effective oil soluble surfactant.

The above fatty carboxylic acid and a complex mixture of derivatives of acids of tall oil or rapeseed oil in the hydrocarbon solvent are effective emulsifiers.

For injection into permeable oil reservoir above oil-soluble surfactants form when mixed with reservoir water reverse emulsions (type water in oil”).

Prospects and high efficiency reverse emulsions is due to a number of their positive qualities. First, the dispersed nature of inverse emulsions allows them to selectively filter in the most permeable zones of the reservoir, and secondly, the ability to thickening and structuring during the mechanical mixing with formation water during the filtration in the depth of the reservoir, and Vice versa, for liquefaction at dispersing the oil, which ensures their high selectivity, thirdly, the presence in their composition of the oil-soluble surfactant with high adhesion to hydrophilic rock formation in the water-washed areas gives them the ability as when driving on Phi is tracyanum channels, and after decomposition to gidrofobizatory skeleton manifold increase in its permeability to oil and reduce water.

The presence of highly dispersed hydrophobic silica in the above emulsions increases their viscosity, stabilize and hydrofobicity emulsion.

When increasing the concentration of fine hydrophobic silica introduced into the composition, increases the stabilizing and fobissea its action, which allows to obtain a stable emulsion.

The presence of calcium chloride and magnesium and other electrolytes in formation water increases the stability of emulsions with increasing temperature. This affects mainly through chemical transformations of emulsifier in the emulsion and changes in the composition of the adsorption layer. The presence of metal cations (calcium, magnesium and others) contributes to the behavior of metabolic reactions of formation of metal Soaps of higher carboxylic acids present in the composition of the emulsifier, which leads to a sharp decrease in interfacial tension, more effective detergent, emulsifying and stabilizing action of the contaminated surface with respect to deposits with a high content of paraffins, asphaltenes and resins.

The proposed composition containing waste cyclohexane fraction, waste tallow or RA is its oil and fine hydrophobic silica mark Policy, has a high solvent power, and by increasing detergency, emulsifying and stabilizing ability in relation to ASPO will more effectively be used to remove deposits with a high content of paraffins, asphaltenes and resins, but at the expense of waterproofing reservoir rock, that is, increasing the relative permeability of the reservoir for hydrocarbon phase compared with water there is an increase in oil-driving properties of the composition.

Research on the effectiveness of the dissolution of the deposits was carried out by the method of “cold core” installation that simulates the well (the prototype). A metal rod put approximately 1 g of sediment. In a vessel pour 50 ml of the composition, which is prepared by mixing the starting components at a temperature of 40-50°C for 15 min Rod suspended by a flexible thread through skip performs reciprocating motion in the vertical plane by an electric motor. As a result of these movements is flush ASPO studied composition.

To test selected compounds of deposits with a high content of paraffins, asphaltenes and resins, selected in the oil industry “Tapescript and Kielnet” Samara region.

The compositions are given in table. 1.

Conducted research on the effectiveness of the dissolution of the compositions of deposits with a high content of the W paraffins, asphaltenes and resins.

The results of the efficiency of dissolution of deposits in the proposed composition compared to the prototype are presented in table. 2 and 3 at a temperature of 20°C.

The data table. 2 and 3 show that the proposed composition at different ratios of the components has a high dissolving ability in relation to deposits with a high content of paraffins, asphaltenes and resins.

In addition, the proposed structure has the best compared to the prototype oil-driving properties. Data filtering through the water-washed oil-saturated core (simulation processing rinsed with water saturated zone thickness) of the compositions proposed composition and prototype are presented in table. 4.

Example. 1. Prepare a song on the proposed composition: 74 g spent the cyclohexane fraction added with stirring 25 g of extract tall oil, then with stirring in small portions administered 1 g of silica mark POLYSIL-DF.

The proposed composition is filtered through washed oil-saturated core filtration plant (simulation processing rinsed with water saturated zone thickness) to increase oil-driving ability of the composition in terms of Tootmine of residual oil on the linear model for the homogeneous reservoir.

The linear model represents the core of stainless steel, the soup became a length of 220 mm and an inner diameter of 32 mm, which is filled with a mixture containing 95% quartz sand and 5% montmorillonite clay. The model under vacuum saturated with water, the weight method to determine the permeability of the water column.

After that in the model under pressure is pumped oil until until exit appears clean (without water) oil, determine the initial oil saturation, which is 63,5-71,0%. In the filtration works use natural oil density 842 kg/m3and a dynamic viscosity of 8.5 MPa·20°C. the Initial displacement is performed with water (three pore volume) and determine the ratio of oil displacement by water. After that filtered through the model one pore volume of the prepared composition the proposed composition and three pore volumes of water, determine the growth rate and total fertility rate of oil displacement.

The results of the filtration tests oil-driving ability of the compositions of the proposed structure are presented in table. 4.

Example. 2. Prepare the composition of the prototype: 75 g spent the cyclohexane fraction added with stirring 25 g of extract tall oil.

The prepared composition is filtered through washed oil-saturated core filtration plant (simulation processing rinsed with water saturated zone thickness) to increase nepaviesinau is her ability composition in terms of Tootmine of residual oil on the linear model for the homogeneous reservoir.

Through the above core (see example 1) one filter pore volume of the prepared compositions of the prototype and three pore volumes of water, determine the growth rate and total fertility rate of oil displacement.

The results of the filtration tests oil-driving ability of the compositions of the prototype are presented in table 4.

Example. 3. Prepare a song on the proposed composition: 69 g spent the cyclohexane fraction added under stirring 30 g of waste rapeseed oil, then with stirring in small portions administered 1 g of silica mark POLYSIL-P1.

The proposed composition is filtered through washed oil-saturated core filtration plant (simulation processing rinsed with water saturated zone thickness) to increase oil-driving ability of the composition in terms of Tootmine of residual oil on the linear model for the homogeneous reservoir.

Through the above core (see example 1) one filter pore volume of the prepared composition the proposed composition and three pore volumes of water, determine the growth rate and total fertility rate of oil displacement.

The results of the filtration tests oil-driving ability of the compositions of the proposed structure are presented in table 4.

Data tables 1-3 show that the proposed structure has high dissolving ability, the institutional capacity in relation to deposits with a high content of paraffins, asphaltenes and resins.

In addition, filtration studies have shown that the proposed structure has a higher oil-driving properties in comparison with the prototype. Increase the displacement efficiency of the proposed structure increases from 0.24 to 0.30 (see table 4.).

When the content in the proposed composition of Policie less than 0.1 wt.% increase the displacement efficiency of oil differs little from the prototype, so the concentration of 0.1 wt.% Policie taken for the minimum content in the composition. The upper limit of the content of Policie in the proposed part - 2.0 wt.% due to the element of the adequacy of the achieved result, since the increase in the content of Policie to 2.5 wt.% results in a negligible increase the displacement efficiency of oil (see table 4).

Technical result: as a result of the injection of the proposed composition containing waste cyclohexane fraction, enriched tall oil or rapeseed oil and additionally fine-grained hydrophobic silica mark POLYSIL having high dissolving ability in relation to the AFS, there is an increase detergent, emulsifying and stabilizing action of the contaminated surface of particles of solid impurities (ASPO), significantly reduced the water content and increasing oil production rate, which is achieved for accounts which improve the waterproofing of the reservoir rock.

Technology of preparation of the composition according to the proposed structure simple.

In an elaborate cyclohexane faction in the number of 69.9-78,0 wt.% add with stirring waste tallow or canola oil in the amount of 20-30 wt.%, then small portions enter silica mark Policy in the quantity of 0, 1-2,0 wt.%, thoroughly mixed and the composition is ready to use.

Table 1
№ p/pThe compositions of paraffin, wt.%
Waxesasphaltenes + resins
136,763,3
270,929,1
373,626,4
Table 2

Results the efficiency of dissolving paraffin composition
№ p/pRatio

ASPO - composition
The efficiency of dissolution, %
30 min60 min90 min
11:5051,387,197,7
21:5050,886,297,4
31:50a 50.5is 83.896,5
Note: part 2 of table 3 example 4.

The composition for removing asphaltoresinparaffin sediments and the waterproofing layer zones containing waste cyclohexane fraction, enriched tall oil or rapeseed oil, characterized in that it further comprises a modified fine silica mark Policy in the following ratio, wt.%:

Proven cyclohexane fraction 69,9-78,0

Waste tallow or canola oil 20,0-30,0

Policy 0,1-2,0



 

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