RU2490296C2 - Composition for removing asphaltene-resin-paraffin deposits - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to oil industry and can be used in removing asphaltene-resin-paraffin deposits (ARPD) during oil extraction. The composition for removing ARPD, which contains a non-aromatic hydrocarbon solvent; an additive - oxyethylated alkylphenol with 9-12 oxyethyl groups or alkylbenzene sulphonate, an organic amine with general formula R-R'-NH, where R, R'=CH₃, C₂H₅ C₃H₇, or mixtures thereof in weight ratio from 1:1:10 to 10:5:1; organosulphur compounds - a mixture of oil and gas refining by-products - dialkyl disulphides of a complex composition having general formula R-S-S-R', where R, R'=CH₃, C₂H₅, C₃H₇, C₄H₉, with the following ratio of components, wt %: said organosulphur compounds 10-50; said additive 0.01-0.9; said solvent - the balance.

EFFECT: efficient removal of ARPD of a different hydrocarbon composition with high content of paraffin wax and asphaltene-resin substances.

3 tbl, 5 ex, 1 dwg

Description

The invention relates to the oil industry and may find application in the removal of asphaltene-resin-paraffin deposits (paraffin) in the process of oil production.

In connection with the increase in the share of heavy oils with a high content of asphaltene-resinous substances and high molecular weight paraffins, leading to deposits in the bottomhole zone, oilfield equipment, there is a need to create an effective method of processing wells.

A known composition for the removal of paraffin, which contains at least one block copolymer of ethylene oxide and propylene oxide based on glycerol and a hydrocarbon solvent is a mixture of aromatic and aliphatic hydrocarbons,% vol .: at least one specified block copolymer of 0.5- 5.0, aromatic hydrocarbon 30, aliphatic hydrocarbon - the rest [Auth. St. RU No. 2323954, C09K 8/524, 2008, BI No. 19]. However, this composition has a lack of effective removal of paraffin.

A known composition for removing paraffin, including a hydrocarbon solvent and an additive. As an additive, the composition contains a nitrogen-containing block copolymer of ethylene oxide and propylene oxide with a molecular weight of ~ 5000, or a by-product of the production of isopropylbenzene - a polyalkylbenzene resin, or a mixture thereof in a ratio of 1: 0.5: 10, respectively. The established ratio of components, wt.%: Nitrogen-containing block copolymer of ethylene oxide and propylene oxide with a molecular weight of ~ 5000, or polyalkylbenzene resin, or a mixture thereof in a ratio of 1: 0.5: 10, respectively, hydrocarbon solvent - the rest [Aut. St. RU No. 2163916, C09K 3/00, E21B 37/06, 2001, BI No. 13]. However, this composition is ineffective for deposits with a high content of asphaltenes.

The closest to the present invention is a composition for removing paraffin, including ethoxylated alkyl phenol with the number of hydroxyethyl groups 4-6 in an amount of 0.001-5 wt.%, The condensation product of diethylene triamine and oleic acid in a molar ratio of 1: 1 ÷ 1: 2 in an amount of 0.001-5 wt.%, hydrocarbon solvent - the rest. An advantageous embodiment of the invention is a composition comprising hydroxyethylated alkyl phenol with the number of hydroxyethyl groups 4-6, a condensation product of diethylene triamine and oleic acid at a temperature of 160 ° C in a molar ratio of 1: 1 ÷ 1: 2, 2-butoxyethanol and a hydrocarbon solvent [USSR Patent No. 2064954, C09K 3/00, 1996]. The disadvantage of this composition is the low removal efficiency of paraffin wax with a paraffin content of more than 40%, as well as the high temperature of synthesis of the condensation product.

The present invention is to develop a more effective composition for the removal of paraffin in a wide range of ratios of the most difficult to remove group components: asphaltenes and paraffins.

The problem is solved by the development of a composition for the removal of paraffin, including a non-aromatic hydrocarbon solvent, which contains as an additive ethoxylated alkyl phenol with the number of hydroxyethyl groups 9-12 or alkylbenzenesulfonate, or an organic amine with the general formula R-R'-NH, where R, R '= CH ₃ , C ₂ H ₅ , C ₃ H ₇ , or mixtures thereof in a mass ratio of 1: 1: 10 to 10: 5: 1, and additionally contains organosulfur compounds - a mixture of by-products

oil and gas processing - complex dialkyl disulfides with the general formula RSS-R ', where R, R' = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , in the following ratio of components, wt.%:

these organosulfur compounds 10-50 specified additive 0.01-0.9 specified solvent rest.

The presence in the developed composition of organosulfur compounds contributes to an increase in the dissolving ability of high molecular weight heteroatomic compounds in the structure of resins and asphaltenes.

The introduction of an additive reduces the surface tension at the ARPD – solvent interface, which increases the efficiency of dissolution and destruction of ARPD, and the presence of solvating components leads to the solvation of dispersed particles of asphaltenes and paraffins, preventing them from sticking together.

As a hydrocarbon solvent, the composition contains the following components and their mixtures in any ratio: hexane fraction, or unstable gasoline, or a wide fraction of light hydrocarbons, or gasoline - Nefras S-2-80 / 120 solvent. The main characteristics of the hydrocarbon solvent are shown in table 1.

The proposed composition was tested for the effectiveness of the removal of paraffin in static conditions at a temperature of 20 ° C according to the method developed by NPO Neftepromkhim. The essence of the method consists in determining the change in the mass of the ARPD sample as a result of dissolution and dispersion in a certain volume of solvent under isothermal conditions. The characteristics of the studied paraffin samples are presented in table 2.

To prove the compliance of the invention with the criterion of "industrial applicability" and illustrate the developed composition, examples of its preparation and effectiveness assessment for different types of paraffin deposits are given below (see Table 3).

The above examples do not limit the possibility of using this composition.

Example 1 (prototype). 141 g of oleic acid are mixed with 51.5 g of diethylene triamine. The mixture is heated at 160 ° C until the water is completely distilled off. The resulting product is a condensation product of diethylene triamine and oleic acid in a molar ratio of 1: 1. To 5 g of the condensation product in a 1: 1 molar ratio, add 0.001 g of Neonol AF 9-6, 10 g of butyl cellosolve (2-butoxyethanol), n-hexane - the rest. The mixture is stirred until a homogeneous product is obtained, cooled to 20 ° C, after which the effectiveness of the prepared composition on the AFS samples is determined by the above procedure (see table 3).

Example 2 (proposed). A mixture of dialkyl disulfides, consisting mainly of dimethyl disulfide, diethyl disulfide, methylethyl disulfide, methylpropyl disulfide, which is an organo-sulfur by-product of oil and gas processing with the general formula RSS-R ', is a non-organic solvent, 20 g in weight, is poured into a mixer reactor 1, the diagram of which is shown in the figure, with a volume of 500 ml - unstable gasoline taken in an amount of 179.6 g, an additive is added - the ethoxylated product "Neonol AF 9-9" with the number of hydroxyethyl groups 9, in an amount of 0.4 g. Next, I will dissolve spruce with an additive is poured into a mixture of dialkyl disulfides in a mixing reactor 1. The contents of the reactor are thermostated using a thermal relay 2, an internal refrigerator 3 and a heating element 4 with a LATR transformer 5 with constant stirring with an electric mixer 6 for 40 min at a temperature of 30 ° C, supported by a contact thermometer 7, it is cooled to 20 ° C, after which the effectiveness of the prepared composition on AFS samples is determined according to the above procedure (see table 3).

Example 3. In the reactor-mixer 1 in example 2, a mixture of dialkyl disulfides, analogous to example 2, weighing 40 g, is poured into the amount of 159 g of Nefras S-2-80 / 120 non-aromatic hydrocarbon solvent, and the sulfonated product “Sulfanol- P "(alkylbenzenesulfonate) in an amount of 1 g. The contents of the reactor are thermostated with constant stirring for 60 min at a temperature of 25 ° C, cooled to 20 ° C, and then determine the effectiveness of the composition on AFS samples (see table 3).

Example 4. A mixture of dialkyl disulfides, analogous to Example 2, weighing 40 g, a non-aromatic hydrocarbon solvent Nefras C-2-80 / 120 in an amount of 159 g, and diethylamine (an organic amine) are poured into the reactor-mixer 1 of Example 2 ) in an amount of 1 g. The contents of the reactor are thermostated with constant stirring for 60 min at a temperature of 25 ° C, cooled to 20 ° C, after which the effectiveness of the composition on the AFS samples is determined (see Table 3).

Example 5. In the reactor-mixer 1 in example 2, a mixture of dialkyl disulfides, similar to example 2, in an amount of 60 g is poured, a non-aromatic hydrocarbon solvent — a hexane fraction in an amount of 138.2 g, as an additive — a mixture consisting of Neonol AF 9- 9 "," Sulfanol-P and diethylamine (organic amine), in a mass ratio of components 4: 4: 2; the total amount of the additive mixture introduced is 1.8 g. The contents of the reactor are thermostated with constant stirring for 30 min at a temperature of 40 ° C; cooled to 20 ° C, and then determine the effectiveness of the composition on the AFS samples (see table 3).

As additives in the proposed composition for the removal of paraffin can also be used, for example:

- from a number of ethoxylated alkyl phenols - “Neonol AF 9-10”, “Neonol AF 9-12”;

- from a number of alkylbenzenesulfonates - “Sulfanol NP-1”, “Sulfanol NP-3”;

- from a number of organic amines - triethylamine, propylamine, tripropylamine.

The composition of the mixture of dialkyl disulfides used as components of the proposed composition may vary, which is associated with the features of the technological process of obtaining this mixture as a by-product of oil and gas processing from various manufacturers.

As shown by the research results, a composition containing organosulfur compounds and an additive in various ratios is more effective than the prototype when removing ARPDs of various group composition. The developed composition can be obtained by mixing the available components at a low temperature.

Composition for removing asphaltene-resin-paraffin deposits

Table 1 Physico-chemical properties of hydrocarbon solvents The name of indicators Solvent Density, g / cm ³ 0.689 ÷ 0.876 Fractional composition, ° C Start of boil 35 ÷ 85 97% return 90 ÷ 120 The content of aromatic hydrocarbons, wt.% 0.01 ÷ 1.5

table 2 The content of group components in paraffin No. Mechanic impurities, wt.% Asphaltenes, wt.% Paraffins, wt.% Resins, oils, wt.% ASPO1 2.60 4.06 40.09 53.25 ASPO2 3.68 4.82 8.49 83.01 ASPO3 2,32 8.74 71.97 16.97

Table 3 Experience number Component Content The removal efficiency,% ASPO1 ASPO2 ASPO3 for prototype one Neonol AF 9-6 condensation product of diethylene triamine and oleic acid 2-butoxyethanol n-hexane fifty 70 49 mass% 5 5 90 for the proposed composition Sulfur containing Additive Carbohydrate solvent 2 R-S-S-R ' Neonol AF 9-9 Unstable gasoline 67.0 72.0 66.0 mass% 10 0.2 89.8 3 R-S-S-R ' Sulfanol-P Nefras 90.8 89.6 67.0 mass% twenty 0.5 79.5 four R-S-S-R ' Diethylamine Nefras 83.0 74.0 76,2 mass% twenty 0.5 79.5 5 R-S-S-R ' Neonol AF 9-9
Sulfanol-P
Diethylamine Hexane fraction 81.5 76.8 73.0 mass% thirty 0.9 69.1

Claims (1)

Composition for removing asphaltene-resin-paraffin deposits (AFS), comprising a non-aromatic hydrocarbon solvent, characterized in that it contains as an additive ethoxylated alkyl phenol with the number of hydroxyethyl groups 9-12, or alkylbenzenesulfonate, or an organic amine with the general formula R-R ' -NH, where R, R '= CH ₃ , C ₂ H ₅ C ₃ H ₇ , or a mixture thereof in a mass ratio of 1: 1: 10 to 10: 5: 1 and additionally contains organosulfur compounds - a mixture of by-products of oil and gas processing - complex dialkyl disulfides with the general formula RSS-R ', where R, R '= CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , in the following ratio of components, wt.%:
these organosulfur compounds 10-50 specified additive 0.01-0.9 specified solvent rest