RU2723633C1 - Low-viscosity marine fuel - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention discloses marine low-viscosity fuel, which can be used as fuel for low-speed engines, containing a mixture of such fractions of primary treatment of oil, as weighted diesel fuel from the top of vacuum distillation column of fuel oil. GC-3 (fraction 224–389 °C) (UDT VP GK-3); weighted diesel fuel from atmospheric distillation column. ELOU + AVT-6 (fraction 222–348 °C) (UDTAP ELOU + AVT-6); light vacuum distillate from top of vacuum distillation column of wide oil fraction of mouth. ELOU + AVT-6 (fraction 287–418 °C) (LVD ELOU + AVT-6); weighted diesel fuel from top of fuel oil vacuum distillation column. ELOU + AVT-6 (fraction 264–400 °C) (UDT VP ELOU + AVT-6) and heavy diesel fractions of secondary origin, as a still residue obtained during atmospheric-vacuum distillation of hydrogenation units of hydrogenation of heavy middle distillate fractions of primary and secondary processing oil (fraction 232–387 °C) (SR); easy catalytic cracking gasoil. GK-3 (fraction 198–331 °C) (LGKK) and depressor-dispersant additive in amount of 0.04 wt. %, characterized by that it additionally contains antioxidant additive Kerobit TP26P in amount of 0.03 wt. %.EFFECT: technical result is providing stability of low-viscosity ship during storage.1 cl, 6 tbl, 2 ex

Description

The invention relates to the field of oil refining and petrochemistry, in particular, to the production of hydrocarbon fuel compositions based on oil refined products and can be used as fuel for low-speed engines.

Low-sulfur marine fuel compositions are known (US 8987537 B1, CPC C10L 1/04, published March 24, 2015; US 9057035 B1, CPC C10L

1/04, published June 16, 2015), in which various marine fuel compositions are claimed containing from 50 to 90 wt.% Residual hydrocarbon component, and from 10 to 50 wt.% Selected from the group consisting of non-hydrotreated hydrocarbon component (light gas oil, heavy gas oil, catalytic cracking gas oil, catalytic cracking sludge oil, pyrolysis gas oil, light cracking gas oil, heavy cracking gas oil, pyrolysis light gas oil, heavy pyrolysis gas oil, thermal cracking distillate, heavy gas oil distillate, heavy oil diesel coking fraction, coking gas oil, vacuum coking gas oil, thermal cracking vacuum gas oil, thermal cracking diesel fraction, thermal cracking gas oil, gas, aromatic extracts of lubricating oil, deasphalting, kerosene fraction of coking unit, kerosene fraction of thermal cracking gas, paraffin liquid conversion, straight-run diesel fraction, straight-run kerosene fraction, straight-run gas oil and any combination thereof); hydrotreated hydrocarbon component (diesel fractions with low sulfur content up to 500 ppm and ultralow sulfur content up to 15 ppm; hydrotreated light gas oil; hydrotreated heavy gas oil; hydrotreated catalytic cracking gas oil; hydrotreated pyrolysis gas oil, hydrotreated pyrolysis gas oil, hydrotreated heavy gas oil cracked gas oil, hydrotreated heavy cracking gas oil, hydrotreated heavy coking distillate, hydrotreated heavy thermal cracking distillate, hydrotreated diesel fraction, hydrotreated coking diesel fraction, hydrotreated hydrated coking gas oil, hydrotreated hydrotreated gas cracking hydrotreated, hydrotreated thermal gas cracking diesel fraction, hydrotreated coking gas oil, hydrotreated residue, hydrocracking bases, hydrotreated vacuum thermal cracking gas oil and hydrotreated hydrocracking deasphalting, ultrafine sulfur kerosene fraction, hydrotreated jet fuel, hydrotreated kerosene fraction, hydrotreated kerosene coking unit, diesel fraction of the hydrocracking unit, kerosene fraction of the hydrocracking unit, hydrotreated thermal cracking kerosene and any combination thereof) and any combination thereof with the possibility of introducing them.

Common signs are that heavy diesel fractions, including those of secondary origin, and additives necessary to bring the operating characteristics to normalized values are involved in the fuel composition of the ship.

The analogue differs in focus on obtaining low-sulfur marine fuel, and the claimed composition relates to residual marine fuels.

The disadvantage of the analogue is the lack of study of the claimed compositions for full compliance with regulatory requirements and the stability characteristics of marine fuel during storage, including oxidative stability: the total amount of sediment, the concentration of actual resins and a color change of the product.

Known marine fuel (RU No. 2155211, IPC C10L 1/04, published on 08.27.2000), which contains 5-30% tar, up to 25% of the wide vacuum fraction 260-510 ° C or visbreaking products of the semi-tar and wide vacuum fraction 260-510 ° С, 20-25% of light catalytic cracking gas oil, 15-40% of hydrotreated diesel fuel, up to 0.05% depressant additive and up to 100% straight-run fuel oil.

Common signs are that a depressant additive is involved in the marine fuel composition, which makes it possible to produce fuel with improved low-temperature properties.

The analogue differs in its focus on expanding the raw material base for the production of naval fuel oil as marine fuel.

The disadvantage of the analogue is the lack of components that provide oxidative stability of the fuel during storage, as well as sedimentation stability of the fuel in cold storage.

Also known is the composition of marine low-viscosity fuel (RU No. 2478692, IPC C10L 1/04, published April 10, 2013), containing a mixture of distillates of atmospheric and vacuum distillation of oil. The fuel is characterized in that it contains an atmospheric distillation fraction with a boiling range of 210-365 ° C and a vacuum distillation fraction with a boiling range of 255-360 ° C in the following mass ratio of components, wt.%: Atmospheric distillation fraction with a boiling range of 210-365 ° C - 60-70; vacuum distillation fraction with a boiling range of 255-360 ° С - up to 100.

Common signs are that heavier fractions of atmospheric and vacuum distillation of oil are involved in the composition of the low-viscosity marine fuel.

The disadvantages of the analogue are the minimum number of components for the preparation of TMS, the minimum quality margin of low-temperature characteristics, increased sulfur content, and the absence of components providing oxidative stability (assessment of fuel stability during storage by oxidative stability indicators: total amount of sediment, concentration of actual resins and color change product)

The closest solution in technical essence (prototype) is the composition of low-viscosity marine fuel (RU No. 2041245, IPC C10L 1/08, published 09.08.1995), containing 1.5-15.0% of a mixture of straight-run fractions and fractions of secondary processes boiling in the range of 110-500 ° C in the mass ratio of fractions boiling in the range of 110-360 ° C and 360-500 ° C, equal to (20-80) :( 80-20); 10.0-40.0%

fractions of the secondary distillation of fuel oil in the production of oils boiling in the range 130-400 ° C; 1.0-20.0% of the fraction of vacuum distillate boiling in the range of 240-500 ° C and up to 100% of the fraction of gas oil of catalytic cracking boiling in the range of 160-400 ° C.

Common signs are that low-viscosity marine fuel in a wide assortment involves primary processing and secondary oil refining products.

The disadvantage of the prototype is the increased sulfur content, the absence of components that provide oxidative stability of the fuel during storage (assessment of the stability of the fuel during storage according to the indicators of oxidative stability: total amount of sediment, concentration of actual resins and color change of the product).

The purpose of the invention is the development of the optimal formulation of low-viscosity marine fuel.

The technical result of the claimed invention is to ensure the stability of low-viscosity marine fuel during storage and an integrated approach to its assessment.

The specified technical result is achieved by the fact that marine low-viscosity fuel containing a mixture of such fractions of the primary oil refining as heavy diesel fuel from the top of the column of vacuum distillation of fuel oil mouth. GK-3 (fraction 224 - 389 ° C) (UDT VP GK-3); weighted diesel fuel from the atmospheric distillation column ELOU + AVT-6 (fraction 222 - 348 ° С) (UDT AP ELOU + AVT-6); light vacuum distillate from the top of the column of vacuum distillation of a wide oil fraction mouth. ELOU + AVT-6 (fraction 287 - 418 ° С) (LVD ELOU + AVT-6); weighted diesel fuel from the top of the column of vacuum distillation of fuel oil mouth. ELOU + AVT-6 (fraction 264 - 400 ° С) (UDT VP ELOU + AVT-6) and heavy diesel fractions of secondary origin, as bottoms obtained in the process of atmospheric vacuum distillation of the hydrogenate of the hydrogenation unit of the hydrogenation blocks of heavy medium distillate fractions of primary and secondary processing oil (fraction 232 - 387 ° C) (KO); light gas oil catalytic cracking mouth. GK-3 (fraction 198 - 331 ° C) (LGCC) in various proportions with the introduction of a depressant-dispersant additive in an amount of 0.04% wt. to achieve the required low-temperature characteristics, according to the invention, additionally contains an antioxidant additive Kerobit TP26P in an amount of 0.03% wt.

Antioxidant additive Kerobit TP26P (AOP), stabilizes the fuel during storage, due to the chemical nature of the additive

- the ability of phenols to act as hydrogen donors, thereby stabilizing hydrocarbon or peroxide radicals.

The use of Kerobit TP26P antioxidant additives allows to stabilize the quality of fuel during storage by increasing its oxidative stability, reducing gumming and, as a result, maintaining a normalized color index.

In order to establish the effect of the low viscosity marine fuel additive, basic principles were prepared using products of secondary oil refining, the quality of which is shown in Table 1.

Table 1. Quality components for the preparation of the basic framework

Name of components Density at 15
° C, mg / kg Pour point, ° C Mass fraction of sulfur,% Temperature
flash, closed crucible, ° C Kinematic viscosity at
20 ° C, mm2 / s Kinematic viscosity at
50 ° C, mm2 / s Fractional composition, ° C Transnational corporation ten
% 50
% 90% TKK KO 838.7 3 5 · 10-4 130 12.80 4.95 232 305 330 365 387 UDT VP ELOU + AVT
-6) 889.7 1 0.59 123 18.80 6.54 264 297 334 374 400 LVD ELOU + AVT
-6 900,2 fourteen 0.68 172 - 10,4 287 327 374 403 418 UDT AP ELOU + AVT
-6 871.9 -2 0.48 97 12.52 5.20 222 293 328 342 348 LGKK 940.3 -43 1.06 76 3.75 1.98 198 232 267 309 331 UDT VP GK-3 874.6 2 0.49 98 14.36 5.50 224 292 334 371 389

The Kerobit TP26P additive was introduced in an amount of 0.03% wt. to different artificially prepared fuel bases (the composition is given in Tables 2, 3), the calculation of which was carried out by determining the optimal composition according to the standardized indicators using the indicated components by the method of mathematical modeling based on the software product PIMS (Process Industry Modeling System - Economic and Technological System of Oil Refining Modeling ) Aspen Tech. To assess the permissible composition of low-viscosity marine fuel that meets the requirements of TU 38.101567-2014, the production volumes and actual critical values of each component (pour point, mass fraction of sulfur, color, density) were introduced into the PIMS program as necessary calculation parameters. Given the possibility of adjusting the pour point using depressant-dispersant additives, this quality limit was neglected in the calculation. The process of calculating the optimal mixes of TMS using this software product allows you to take into account not only the quality characteristics of the components, but also their volumes obtained in existing plants and the possibility of their redistribution without economic losses in general. This approach to modeling the optimal formulation of TMS is of a general nature and can be used to optimize all types of multicomponent fuels.

Table 2. The basic basis of BO-1

Name of components Content,
% wt. VAT residue obtained in the process of atmospheric vacuum distillation of hydrogenated blocks
hydrogenation of heavy distillate fractions ten%

primary and secondary oil refining (KO) Weighted diesel fuel from the top of the column of vacuum distillation of fuel oil, mouth. GK-3 (UDT VP GK-
3) ten% Weighted diesel fuel from an atmospheric distillation column, ust. ELOU + AVT-6 (UDT AP
ELOU + AVT-6) 60% Light gas oil catalytic cracking, mouth. GK-3 (LGKK) ten% Column weighted diesel
atmospheric distillation GK-3 (UDT AP GK-3) ten%

Table 3. The basic basis of BO-2

Name of components Content,
% wt. Weighted diesel fuel from an atmospheric distillation column, ust. ELOU + AVT-6 (UDT AP ELOU + AVT-6) 47% Light vacuum distillate from the top of the column of vacuum distillation of a wide oil fraction, mouth.
ELOU + AVT-6
(LVD ELOU + AVT-6) 35% Weighted diesel fuel from the top of the column of vacuum distillation of fuel oil, mouth. ELOU + AVT-6 (UDT
VP ELOU + AVT-6) 12% Weighted diesel fuel from an atmospheric distillation column, ust. GK-3 (UDT VP GK-3) 2% Light gas oil catalytic cracking, mouth. GK-3 (LGKK) 4%

The effectiveness of the action of AOP - Kerobit TP26P on TMS was evaluated by the change in the total amount of precipitate obtained in accordance with GOST R EN ISO 12205 and is a measure of oxidative stability, as well as by the concentration of actual resins in TMS samples with additives relative to the results for the same indicators obtained in TMS without additives after storage. At the same time, a prerequisite for confirming the effectiveness of AOP is a decrease in actual results simultaneously for both indicators.

The invention is illustrated by examples:

Example 1

Low-viscosity marine fuel, the base base (BO-1) of which is prepared from bottoms obtained in the process of atmospheric vacuum distillation of the hydrogenate of the hydrogenation units of heavy medium distillate fractions of primary and secondary oil refining (KO) in an amount of 10% wt .; weighted diesel fuel from the top of the column of vacuum distillation of fuel oil mouth. GK-3 (UDT VP GK-3) in an amount of 10% wt .; weighted diesel fuel from the column atmospheric distillation mouth. ELOU + AVT-6 (UDT AP ELOU + AVT-6) in an amount of 60% wt .; light gas oil catalytic cracking mouth. GK-3 (LGKK) in an amount of 10% wt .; weighted diesel fuel from the column atmospheric distillation mouth. GK-3 (UDT AP GK-3) in an amount of 10% wt.

To assess the stability of marine low-viscosity fuel in this example, samples BO-1 (example 1a, table 4), BO-1 were tested with the introduction of a depressant-dispersing additive in an amount of 0.04% wt. (example 1b. table 4) and BO-1 with the introduction of depressant-dispersant additives in the amount of 0.04% wt., different from example 1b (table. 4) the introduction of antioxidant additives Kerobit TP26P in the amount of 0.03% wt. (example 1 in table. 4).

After storing the samples, the total amount of sediment in the fuel of Example 1a is 73.7 g / m3, in the fuel of Example 1b it is 86.5 g / m3, and in the fuel of Example 1c with AOP it is 27.4 g / m3. Thus, the introduction of the Kerobit TP26P antioxidant additive into the TMS sample prepared at BO-1 (Example 1B of Table 4) leads to a significant increase in oxidative stability during storage compared to that for TMS of the same composition without AOP (Table 1a, 1b) . 4).

The concentration of actual resins after storage in Example 1a (Table 4) is 35.5 mg per 100 cm3, Example 1b - 36 mg per 100 cm3, Example 1B (Table 4) - 20.5 mg per 100 cm3. It is noted that the introduction of AOP (example 1 in table. 4) led to the absence of an increase in the concentration of actual resins during storage.

During storage, the increase in the color of samples with AOP (example 1 in table 4) occurs much less than for samples of fuels without AOP (examples 1a, 1b of table 4), which meets the requirements of the consumer.

Table 4. Evaluation of the effectiveness of AOP on the stability of TMS

Example (composition) on the day of selection after storage Oxidative stability, total sediment g / m3 Example 1a (BO-1) 30.6 73.7 Example 1b (BO-1 + DDP) 35,2 86.5 Example 1c (BO-1 + DDP + AOP) 44,4 27.4 Concentration of actual resins, mg per 100 cm3 of product Example 1a (BO-1) 17 35.5 Example 1b (BO-1 + DDP) 20 36 Example 1c (BO-1 + DDP + AOP) 19.5 20.5 Colour Example 1a (BO-1) 1 3 Example 1b (BO-1 + DDP) 1 4 Example 1c (BO-1 + DDP + AOP) 1 2

Example 2

Low-viscosity marine fuel, the base base (BO-2) of which is prepared from heavy diesel fuel from an atmospheric distillation column. ELOU + AVT-6 (UDT ELOU + AVT-6) in quantity

47% wt .; light vacuum distillate from the top of the column of vacuum distillation of a wide oil fraction mouth. ELOU + AVT-6 (LVD ELOU + AVT-6) in the amount of 35% wt .; weighted diesel fuel from the top of the column of vacuum distillation of fuel oil mouth. ELOU + AVT-6 (UDT VP ELOU + AVT-6) 12% wt .; weighted diesel fuel from the column atmospheric distillation mouth. GK-3 (UDT AP GK-3) in an amount of 2% wt .; light gas oil catalytic cracking mouth. GK-3 (LGKK) in an amount of 4% wt.

To assess the stability of low-viscosity marine fuel in this example, samples of BO-2 were tested (Example 2a of Table 5), BO-2 with the introduction of a depressant-dispersant additive in an amount of 0.04% wt. (example 2b. table 5) and BO-2 with the introduction of depressant-dispersant additives in the amount of 0.04% wt., different from example 2b (table. 5) the introduction of antioxidant additives Kerobit TP26P in the amount of 0.03% wt. (example 2 in table. 5).

After storing the samples, the total amount of sediment in the fuel of Example 2a (Table 5) is 46.6 g / m3, in the fuel of Example 2b (Table 5) - 44.3 g / m3, in the fuel of Example 2c (Table 5) AOP - 34 g / m3. Thus, the introduction of the Kerobit TP26P antioxidant additive into the TMS sample prepared at BO-2 (Example 2B of Table 5) leads to an increase in oxidative stability during storage compared to that for TMS of the same composition without AOP (Example 2a, 2b of the table. five).

The concentration of actual resins after storage in Example 2a (Table 5) is 72 mg per 100 cm3, Example 2b (Table 5) 35 mg per 100 cm3, Example 2B (Table 5) 22.5 mg per 100 cm3. In the TMS samples on BO-2, the introduction of AOP led to a significant decrease in the concentration of actual resins during storage (Example 2c. Table 5).

Despite the fact that during storage of samples with AOP (example 2 in Table 5), an increase in color also occurs, the relative change in this value in them is much smaller than for samples of fuels without AOP (example 2a, 2b of Table 5), and the value this parameter lies within the limits normalized by the consumer.

Table 5. Evaluation of the effectiveness of AOP on the stability of TMS

Example (composition) on the day of selection after storage Oxidative stability, total sediment g / m3 Example 2a (BO-2) 39 46.6 Example 2b (BO-2 + DDP) 32.6 44.3 Example 2c (BO-2 + DDP + AOP) 32.1 34 Concentration of actual resins, mg per 100 cm3 of product Example 2a (BO-2) 40 72 Example 2b (BO-2 + DDP) 43 35 Example 2c (BO-2 + DDP + AOP) 48.0 22.5 Colour Example 2a (BO-2) 1 3 Example 2b (BO-2 + DDP) 1 3 Example 2c (BO-2 + DDP + AOP) 1 2

The implementation of the invention will allow to obtain TMS containing products of secondary oil refining that meets the requirements of TU 38.101567-2014 and is stable during storage by involving antioxidant additives (table. 6).

Table 6. Operational characteristics of TMS on the day of sampling (A) and after storage for 9 weeks (B).

No. Name of indicator Norm according to TU 38.10156
7-2014 TMS Example 1c Example 2c AND B AND B 1 Kinematic viscosity at 20 ° C, mm2 / s no more than 11,4 10.51 10.44 11.29 11.37 2 Flash point, in
closed crucible, ° C not lower than 61 93 95 99 105 3 Pour point, ° C no higher than minus 10 minus
28 minus
32 minus
thirty minus
24 4 Mass fraction of sulfur,% no more than 0.5 0.46 0.47 0.49 0.50 five Coking ability,% no more than 0.2 0,07 0.08 0.06 0.059 6 Density at
15 ° C, kg / m3 no more
893 876.8 876.4 884.3 884.3 7 Iodine number, g iodine per 100
g product no more than 20 2.7 2,8 2.2 2,5 8 Mass fraction of water,% traces lack of lack of lack of lack of nine Ash content,% no more
0.01 0.004 0.004 0.005 0.004 ten Mercaptan
sulfur,% no more
0,025 0.00435 0.00301 0.0029 0,00236 eleven The content of solids,% no more than 0,02 0.056 0,057 0,072 0,042 12 Water soluble x acids and
alkalis lack of lack of lack of lack of lack of 13 Color, units CNT no more than 2.5 (by
requirement
consumer) 1,0 2.0 1,0 2.0

Claims (1)

Low-viscosity marine fuel, which can be used as a fuel for low-speed engines, containing a mixture of such primary oil processing fractions as heavy diesel fuel from the top of the column of vacuum distillation of heavy fuel oil. GK-3 (fraction 224-389 ° С) (UDT VP GK-3); weighted diesel fuel from the atmospheric distillation column ELOU + AVT-6 (fraction 222-348 ° С) (UDTAP ELOU + AVT-6); light vacuum distillate from the top of the column of vacuum distillation of a wide oil fraction mouth. ELOU + AVT-6 (fraction 287-418 ° С) (LVD ELOU + AVT-6); weighted diesel fuel from the top of the column of vacuum distillation of fuel oil mouth. ELOU + AVT-6 (fraction 264-400 ° С) (UDT VP ELOU + AVT-6) and heavy diesel fractions of secondary origin, as bottoms obtained in the process of atmospheric vacuum distillation of the hydrogenate of the hydrogenation blocks of the heavy distillate fractions of primary and secondary processing oil (fraction 232-387 ° C) (KO); light gas oil catalytic cracking lips. GK-3 (fraction 198-331 ° C) (LGAA) and depressant-dispersing additive in an amount of 0.04% wt., Characterized in that it additionally contains an antioxidant additive Kerobit TP26P in an amount of 0.03% wt.