RU2258079C1 - Multipurpose depressor additive - Google Patents

Abstract

FIELD: petroleum processing.

SUBSTANCE: invention aims at lowering freezing temperature, dynamic viscosity, and limiting transverse strain of petroleums as well as preventing formation of asphalt-tar-paraffin deposits during transportation and storage of petroleum. Additive contains 43-60% of product of joint oxidation of heavy pyrolysis resin with atactic polypropylene taken at weight ratio 10:(0.5-1.5) and 43-60% of alkylaromatic hydrocarbons.

EFFECT: enhanced efficiency and broadened spectrum of additive activity.

12 tbl, 4 ex

Description

The invention relates to the oil industry and can be used to reduce the pour point, reduce dynamic viscosity, ultimate shear stress of oils, and also as a means of preventing the formation of asphalt resin-paraffin deposits (AFS) during transportation and storage of oil.

Currently, many compounds are described that have, to one degree or another, depressant activity with respect to oil and oil products (Sablina Z.A. and Gureev A.A. Additives to motor fuels. M: Chemistry, 1977, p. 221). Many low molecular weight and polymeric organic compounds are used as depressants. Industrial alkylaromatic depressants (AzNII, ROS, paraflow, santopur), polymethacrylate (PMA-D), ethylene vinyl acetate copolymers and others (Terteryan R.A. Depressor additives for oils, fuels and oils) are most widely used. M .: Chemistry, 1990, p. 238). Also known is the additive DT-1, which is a copolymer of methacrylic acid esters and vinyl acetate for diesel fuel (US Pat. RF 2016890, C 10 M 145/14, 1994).

But the most commonly used additive is based on a copolymer of ethylene with vinyl acetate. With the introduction of such additives in oil and petroleum products in small quantities (up to about 0.1%), their pour point decreases by 20-30 ° C. The disadvantage of these and the above additives is their poor solubility in oils and petroleum products, a narrow spectrum of action, the high cost of additives, as well as high requirements for storage and operation.

Compositions are known where the 130-220 ° C fraction is used as the main component, which is formed as a distillate in the preparation of petroleum polymer resins (by the method of thermopolymerization of liquid pyrolysis products), and, depending on the variant, either the bottom residue from distillation of liquid pyrolysis products with boiling point above 220 ° C, or oxidized bitumen, or used motor oil [RF patent 2092677]. But the degree of inhibition is not more than 7-38%.

The closest in technical essence to the claimed invention relates to the use of heavy residues of oil refining, namely, the use of heavy pyrolysis resin (TPS) as a depressant (Zagidullin PM and others // Oil refining and petrochemicals, M .: 1979, No. 5, p. 9 -12). But in this case, high concentrations of TPN are used (from 1 to 10%) and the depressant effect does not exceed 4-10 ° C.

The objective of the invention is the creation of a new effective depressant additive with a complex effect to reduce the pour point of paraffinic and high-paraffin oils, improve the rheological properties of high-paraffin oils and prevent the sedimentation process of paraffin deposits during oil production, transportation and storage. As well as expanding the raw material base and assortment of depressants and inhibitors based on waste and by-products of various hydrocarbon feedstocks.

The problem is solved in that the additive contains the product of the joint oxidation of TPN with atactic polypropylene (APP), taken in ratios by weight of 10: (0.5-1.5), and alkyl aromatic hydrocarbons in the following ratio of components,% wt .:

The product of co-oxidation of TPN with APP - 43-60

Aromatic hydrocarbons (xylene, toluene) - the rest

The technical result is achieved by introducing into the oil the proposed depressant additive with a complex effect, the concentration of the additive is 0.03-0.05% by weight of the oil.

Joint oxidation of TPN with APP was carried out at temperatures of 190–210 ° С in the presence of cobalt resinate for 2–3 hours. Air consumption and other experimental conditions are similar to those described in the methodology [RF Patent 2158276, BI No. 30, 2000]. The product is a black resinous compound with the following characteristics:

1. Appearance - black bitumen-like product.

2. The density is 1.12-1.22 g / cm ³ .

3. The softening temperature (according to KiSh) 116-126 ° C.

4. Elemental analysis (%) - C (89.44), H (8.83), O (1.72).

Depressor properties of the additive were established by determining the pour point (according to GOST 20287-74). Depressor effect, ΔT is calculated by the formula:

where T _{Zast. Ex.} - pour point of the original oil, ° C;

T _{Zast.S pri.} - pour point of the oil with the additive, ° C.

A quantitative assessment of the process of sedimentation was carried out on the installation, developed on the basis of the well-known method of the "cold rod", under the following test conditions: the temperature of the test oil sample - 30 ° C, the temperature of the metal rod - 12 ° C and the duration of a single experiment - 60 minutes. The inhibitory ability of additives to prevent the formation of oil sludge on the "cold rod" was calculated by the formula:

where S _And - the degree of inhibition,% wt .;

W ₀ is the sediment yield of the original oil, g;

W ₁ - the output of oil sediment with an additive,

Example 1.1 The depressor and inhibitory properties of the additive using toluene as a solvent (the product of co-oxidation of TPS with APP is 60% by weight (with a ratio of TPS to APP by weight of 10: 0.5), toluene is 40% by weight) were established for oil from the Sobolinoye field (the content of paraffin hydrocarbons is 2.5% by weight).

The use of additives reduces the pour point of oil by 7.5-16.0 ° C at a concentration in oil of 0.03-0.05% wt. respectively (table. 1.1.1), the effective viscosity of 30.1% (at 10 ° C), 37.0% (at - 20 ° C) at 0.05% wt. in oil (table. 1.1.2) and prevents the process of sedimentation by 24.3-40.3% at a concentration in oil of 0.03-0.05% wt. (table 1.1.3).

Table 1.1.1
Change in oil pour point
Sable deposit when using a depressant additive. The concentration of additives in oil,% wt. T. st., ° C Depressor effect, ΔТ, ° С 0.00 -23.0 - 0,03 -30.5 7.5 0.05 -39.0 16,0 Table 1.1.2
Change in effective viscosity (rotation speed 81 s ^-1 ) of Sobolinoye oil using 0.05% wt. depressant additives at temperatures close to pour point. Temperature ° C Effective viscosity, η [MPa · s] Δη,% rel. Source oil Additive Oil 10 189.2 132.3 30.1 -20 498.1 313.8 37.0

Table 1.1.3
Inhibitory ability of oil additives
Sobolinny deposit. The concentration of additives in oil,% wt. The amount of paraffin in oil, g / 100 g of oil Inhibitory ability,% 0.00 4.65 - 0,03 3.52 24.3 0.05 2.77 40.3

Example 1.2 Depressor and inhibitory properties of the additive, using xylene as a solvent (the product of co-oxidation of TPS with ALL - 50 wt.% (With a ratio of TPS to APP by weight - 10: 1.0), xylene - 50 wt.%) were established for the oil of the Sobolin field (the content of paraffin hydrocarbons is 2.5% by weight).

The use of additives, using xylene as a solvent, for the oil of the Sobolinoye field reduces the pour point of oil by 7.5-15.0 ° C at a concentration in the oil of 0.03-0.05% wt. respectively (table. 1.2.1), the effective viscosity of 33.1% (at 10 ° C), 39.2% (at - 20 ° C) at 0.05% wt. in oil (table. 1.2.2) and prevents the process of sedimentation by 21.5-51.2% at a concentration in oil of 0.03-0.05% wt. (table 1.2.3).

Table 1.2.1
Change in oil pour point
Sable deposit when using a depressant additive. The concentration of additives in oil,% wt. T. st., ° C Depressor effect, ΔТ, ° С 0.00 -23.0 - 0,03 -30.5 7.5 0.05 -38.0 15.0 Table 1.2.2
Change in effective viscosity (rotation speed 81 s ^-1 ) of Sobolinoye oil using 0.05% wt. depressant additives at temperatures close to pour point. Temperature ° C Effective viscosity, η [MPa · s] Δη,% rel. Source oil Additive Oil 10 189.2 126.6 33.1 -20 498.1 302.8 39.2 Table 1.2.3
The inhibitory ability of additives for oil Sobolinoye field. The concentration of additives in oil,% wt. The amount of paraffin in oil, g / 100 g of oil Inhibitory ability,% 0.00 4.65 - 0,03 3.65 21.5 0.05 2.27 51,2

Example 2.1 Depressor and inhibitory properties of the additive, using toluene as a solvent (the product of co-oxidation of TPS with APP is 57% by weight (with a ratio of TPS to APP by weight of 10: 1.5), toluene is 43% by weight), were established for oil from the Archinsky field (the content of paraffin hydrocarbons is 8.74% by weight).

The use of a depressant additive, using toluene as a solvent, for oil of the Archinsky field reduces the pour point of oil by 20.0-22.0 ° C at a concentration in the oil of 0.03-0.05% wt. (table. 2.1.1.), the effective viscosity of 33.1% (at 10 ° C), 39.2% (at - 20 ° C) at 0.05% wt. in oil (table. 2.1.2) and prevents the process of sedimentation by 20.9-33.7% at a concentration in oil of 0.03-0.05% wt. (table. 2.1.3).

Table 2.1.1
Change in the pour point of oil of the Archinsky field when using a depressant additive. The concentration of additives in oil,% wt. T. st., ° C Depressor effect, ΔT ° C 0.00 3.0 - 0,03 -17.0 20,0 0.05 -19.0 22.0 Table 2.1.2
Change in effective viscosity (rotation speed 81 s ^-1 ) of Sobolinoye oil using 0.05% wt. depressant additives at temperatures close to pour point. Temperature ° C Effective viscosity, η [MPa · s] Δη,% rel. Source oil Additive Oil twenty 1997,1 1579.7 20.9 10 5077,4 3366,3 33.7 Table 2.1.3
The inhibitory ability of additives for oil Sobolinoye field. The concentration of additives in oil,% wt. The amount of paraffin in oil, g / 100 g of oil Inhibitory ability,% 0.00 4,5 - 0,03 3.08 31.53 0.05 3.48 22.59

Example 2.2 Depressor and inhibitory properties of the additive, using xylene as a solvent (the product of co-oxidation of TPS with APP is 55% by weight (with a ratio of TPS to APP by weight of 10: 1.3), xylene is 45% by weight), were established for oil from the Archinsky field (the content of paraffin hydrocarbons is 8.74% by weight).

The use of a depressant additive, using xylene as a solvent, for the oil of the Archinsky field reduces the pour point of oil by 19.0-21.5 ° C at a concentration in the oil of 0.03-0.05% wt. (table 2.2.1), effective viscosity by 33.1% (at 10 ° C), 39.2% (at - 20 ° C) at 0.05% wt. in oil (table. 2.2.2) and prevents the process of sedimentation by 20.9-32.3% at a concentration in oil of 0.03-0.05% wt. (table 2.2.3).

Table 2.2.1
Change in the pour point of the Archinskoye oil when using a depressant additive. The concentration of additives in oil,% wt. T. st., ° C Depressor effect, ΔT ° C 0.00 3.0 - 0,03 -16.0 19.0 0.05 -18.5 21.5

Table 2.2.2
Change in effective viscosity (rotation speed 81 s ^-1 ) of Sobolinoye oil using 0.05% wt. depressant additives at temperatures close to pour point. Temperature ° C Effective viscosity, η [MPa · s] Δη,% rel. Source oil Additive Oil twenty 1997,1 1649.6 17.4 10 5077,4 3625.3 28.6 Table 2.2.3
The inhibitory ability of additives for oil Sobolinoye field. The concentration of additives in oil,% wt. The amount of paraffin in oil, g / 100 g of oil Inhibitory ability,% 0.00 4,5 - 0,03 3.15 32.3 0.05 3.68 20.9

Thus, the use of a new depressant additive obtained by the joint oxidation of TPN with APP allows lowering the pour point and viscosity characteristics of paraffinic and high-paraffin oils, as well as preventing the process of sedimentation.

Claims (1)

Complex depressant additive based on heavy pyrolysis resin, characterized in that the additive contains the product of co-oxidation of heavy pyrolysis resin (TPS) with atactic polypropylene (APP), taken in a mass ratio of 10: (0.5-1.5), and alkyl aromatic hydrocarbons in the following ratio of components, wt.%: The product of co-oxidation of TPN with APP 43-60 Aromatic hydrocarbons Rest