RU2213125C1 - Process of production of environmentally safe low-viscosity marine engine fuel - Google Patents

Abstract

FIELD: petroleum processing and petrochemistry. SUBSTANCE: process comprises atmospheric vacuum distillation of petroleum to isolate fraction 240-500 C, which is subjected to catalytic cracking in fluidized bad of microspherical zeolite-containing catalyst resulting in formation of light catalytic gas oil fraction 180-350 C. The latter is hydrogenised on aluminasupplemented nickel-tungsten sulfide catalyst, purged, alkalinized, washed with water, and subjected to atmospheric vacuum distillation yielding fraction 195-315 C. This fraction is combined (i) with vacuum gas oil or thermal gas oil fraction at weight ratio from 99:1 to 75:25 or (ii) with light catalytic gas oil fraction 180-350 C or light coke gas oil fraction at weight ratio from 99:1 to 50:50. Resulting mixtures are supplemented by composition of antioxidant (ionol) and antiwear additive (distilled oil acids) in amounts 0.002-0.004 wt % each. Invention enables lowering sulfur level in obtained low-viscosity marine engine fuel, improving environmental characteristics of fuel owing to reduced emission of sulfur and nitrogen compounds and light hydrocarbons, increased chemical stability of fuel, reduced lacquer and carbon deposition, improved low-temperature characteristics and, increased cetane number. EFFECT: improved working and environmental characteristics of fuel. 2 cl, 5 tbl

Description

 The invention relates to methods for producing fuel for marine engines and can be used in the oil refining industry.

 Low-viscosity marine fuel is intended for use in medium-speed and high-speed diesel engines instead of scarce diesel fuel in accordance with GOST 305-82 consumed in water transport.

 The consumer has stringent requirements for the operational characteristics of low-viscosity marine fuel (SMT): improving chemical stability, lubricating and calorific value, reducing corrosion activity and carbon formation, improving low-temperature properties, along with which, the creation of an environmentally friendly SMT with low sulfur content remains an urgent task, using which in diesel engines would reduce emissions of sulfur, nitrogen compounds and light hydrocarbons into the atmosphere s, as well as harmful carcinogens generated during the combustion of fuels in the engine.

A known method of producing low-viscosity marine fuel (RF patent 2074232, C 10 C 57/00, BI 6, 1997) by distillation of oil at the ABT unit with the separation of fractions: 160-360 ^o C, 160-420 ^o C and 300-480 ^o With their subsequent mixing in a mass ratio of 40: 40: 20-60: 30: 10 to obtain a direct distillate distillate; fraction 250-550 ^o C obtained at the ABT installation, is subjected to catalytic cracking on a special zeolite-containing catalyst of the type "EMKAT" on the installation G-43/102. A fraction of 160-400 ^{° C. is} isolated from the catalate and compounded with a direct distillation distillate in a ratio of 20: 80-60: 40.

 In the known method for the production of SMT, light fractions of direct distillation of oil and catalytic cracking are used, which leads to a decrease in flash point, cetane number, calorific value and lubricity of the fuel. In addition, in this method for the production of SMT, a very laborious and obsolete catalytic cracking process is used in the moving layer of a coarse-grained ball catalyst, leading to a deterioration in fuel quality.

The closest technical solution to the claimed invention is a method for producing low-viscosity marine fuel (RF patent 2149888, C 10 G 1/04, C 10 G 55/06, BI 15, 05/27/2000) by atmospheric vacuum distillation of oil with separation of fractions , catalytic cracking of vacuum gas oil, compounding of these fractions, fractions of 155-360 ^° C, 155-435 ^° C, 220-500 ^° C and 240-560 ^° C are isolated during atmospheric vacuum distillation, the first three fractions are mixed in a weight ratio of 40 : 55: 5-55: 35: 10 to obtain a distillate oil direct distillation and fraction 240-560 ^o C is subjected to thrust roochistke alyumokobaltmolibdenovom on the catalyst, and then catalytically cracked in a fluidized bed of a microspheroidal catalyst separation from the product obtained fractions 155-420 ^o C at a weight ratio in a catalytic cracking distillate fractions 155-325 ^o C and 325-420 ^o C fraction 90: 10-99: 1 followed by compounding it with a direct distillation distillate in a mass ratio of 15: 85-65: 35.

The disadvantages of this method (prototype) are: the presence of light fractions of direct distillation of oil and catalytic cracking in the production of SMT, which increases the volatility of the fuel and leads to the release of light hydrocarbons into the atmosphere, worsening the environment; and the presence of a rather high content of high boiling fractions leads to carbon formation in a diesel engine; A disadvantage of the known method for producing SMT is also a high sulfur content in the fuel, including mercaptan sulfur and aromatic hydrocarbons in the catalytic cracking distillate, boiling in the range 155-420 ^o C, which leads to high varnish and carbon formation in the engine, increased wear of cylinder piston parts groups, incomplete combustion of fuel and increased smoke haze and the release of carcinogens into the environment. In turn, mercaptan sulfur causes corrosion of fuel equipment and parts of the cylinder-piston group (CPG) of the engine itself. In addition, when fuel is burned in the engine, sulfur and sulfur anhydrides are formed, causing corrosion of exhaust valves and increased wear of ICE rings, which also leads to pollution of the atmosphere of river basins, seas, oceans and disturbance of ecological balance.

 The invention solves the technical problem of reducing sulfur content and the almost complete removal of mercaptan sulfur in the SMT obtained by the proposed method, improving its environmental friendliness by reducing emissions of sulfur, nitrogen compounds and light hydrocarbons into the atmosphere, by decreasing the volatility of fuel, increasing its chemical stability, and decreasing its propensity to varnish and carbon formation, improving low temperature properties and increasing cetane number.

This problem is solved by the fact that in the known method for producing SMT, including the separation of fractions by atmospheric vacuum distillation, catalytic cracking of vacuum gas oil, compounding of the fractions according to the invention, a fraction of 240-500 ^° C is isolated by atmospheric vacuum distillation, which is subjected to catalytic cracking in fluidized bed microspheroidal catalyst layer to obtain a fraction 180-350 ^o C gas oil and light catalytic hydrogenation subsequent to its nickel-tungsten sulfide with the addition of al oxide minum catalyst with separation of the hydrogenate obtained by atmospheric and vacuum distillation fraction 195-315 ^o C, which is mixed with the fraction of vacuum gas oil or thermo gas in a ratio of 99: 1-75: 25 (.% by weight), respectively, or fraction of 195-315 ^o C is mixed with a fraction of 180-350 ^o With a light catalytic gas oil or a fraction of 180-350 ^o With a light coke oven gas oil in a ratio of 99: 1-60: 40 (wt.%), respectively, or with domestic heating fuel in a ratio of 99: 1-50: 50 ( wt.%), respectively, then an antioxidant composition (ionol) and other tivoiznosnoy (distilled oil acid according to GOST 13302-77) additives in an amount of 0.002-0.004 wt.% each.

 Tables 1 and 2 show the quality indicators of SMT components. The characteristics of vacuum gas oil and thermal gas oil in accordance with the requirements of TU 38.10113-04-90 and TU 38.1011254-89, respectively, are given in Table 1. Vacuum gas oil (TU 38.1011304-90) is a straight-run product obtained by vacuum distillation of fuel oils. Thermogasoil (TU 38.1011254-89) is obtained by thermal cracking of catalytic gas oils, extracts from oil production, thermal cracking gas oils and delayed coking, as well as by coking these products, cracking residues.

Oven household fuel (TU 38.101656-87) is produced from diesel fractions of direct distillation and secondary origin - thermal cracking and coking distillates. The main physicochemical quality indicators of industrial samples of heating oil, light catalytic and light coke oven gas oils, as well as the 195-315 ^o C fraction of the hydrogenated process of deep hydrogenation (T-6 fuel) are presented in Table 2.

 The selection in the proposed method by direct distillation of oil fractions with a higher boiling point and lower boiling point compared with the prototype provides a low volatility of the fuel and a lower emission of light hydrocarbons into the atmosphere, resulting in improved ecology. Lowering the temperature of the end of boiling makes it possible to reduce the content of high boiling fractions and, therefore, significantly reduce the varnish and carbon formation in a diesel engine.

Catalytic cracking in the proposed method is subjected to a vacuum gas oil fraction of 240-500 ^o With a lightweight fractional composition with a boiling point not exceeding 500 ^o C, which is due to the adverse effect of high-boiling fractions on the quality of the products obtained, causing coking of the catalyst.

The proposed hydrogenation of light catalytic gas oil 180-350 ^o C on the block of deep hydrogenation of high pressure in the system in the presence of a nickel-tungsten sulfide catalyst with the addition of aluminum oxide leads to increased chemical stability of the fuel and a decrease in deposits in the fuel system due to the removal of heteroorganic (sulfur , nitrogen-, oxygen-containing) and unsaturated (including aromatic) compounds. In this case, the total sulfur content reaches 0.03-0.05%, and mercaptan sulfur is completely absent.

 The method is as follows.

1. A vacuum gas oil fraction of 240-500 ^{° C.} isolated by direct distillation of oil is subjected to catalytic cracking in a fluidized bed of a microspherical zeolite-containing catalyst in a unit of type 1A-1M or GK-3, which makes it possible to obtain a light catalytic gas oil (LCG), fraction 180-350 ^o C, which as a feedstock is sent to a high-pressure deep hydrogenation unit:
System pressure, ata, no less than - 260
Temperature, ^o С - 300 - 420
Volumetric feed rate, hour ^-1 , not higher - 1.0
The ratio of hydrogen-containing gas: raw materials, nm ³ / m ³ , not less than - 2000: 1
The hydrogen content in the circulating gas, vol.%, Not less than - 75
Table 3 shows the requirements for the quality of the feedstock of deep hydrogenation units.

 The hydrogenation process is carried out on a nickel-tungsten sulfide with the addition of alumina catalyst. The obtained unstable hydrogenate is subjected to blowing from hydrogen sulfide and alkalized with an alkali solution and water washing. Hydrogenated hydrogen stripping from hydrogen sulfide is carried out in a stripping column in accordance with the requirements of the technological regulations.

Alkalization of the hydrogenate with an alkali solution and water washing are carried out in accordance with the regulations. After alkalization and water washing from an unstable hydrogenate by atmospheric vacuum distillation, a fraction of 195-315 ^o C. is isolated ^.

The fraction extracted from the unstable hydrogenate must meet the requirements that correspond to the fuel for T-6 jet engines according to GOST 12308-89:
Density at 20 ^o С, kg / m ³ , not less than - 840
Kinematic viscosity at 20 ^o C, mm ² / s, not more than 4.5
Fractional composition, ^o C:
a) the temperature of the start of distillation, not lower - 195
b) 10% is distilled off at a temperature of no higher than 220
c) 50% is distilled off at a temperature not higher than 255
d) 90% is distilled off at a temperature not higher than 290
d) 98% is distilled off at a temperature not higher than 315
Flash point in a closed crucible, not lower - 62
Acidity, mg KOH per 100 cm ^{3 of} fuel, in the range - 0.4 - 0.7
Test on a copper plate at 100 ^o C for 4 hours - Endurance.

The temperature of crystallization onset, ^o С, not higher - Minus 60
The content of water-soluble acids and alkalis - Ots.

 Water and solids content - Ots.

Iodine number, g iodine per 100 g of fuel, not more than - 0.8
Mass fraction,%, no more than:
Aromatic hydrocarbons - 10
Total sulfur - 0.05
Mercaptan Sulfur - Ots.

Ash content,%, no more - 0,003
Then, the fraction 195-315 ^° C extracted from the unstable hydrogenate is mixed with the fraction of vacuum gas oil or thermal gas oil in a ratio of 99: 1-75: 25 (wt.%), Respectively, or with the fraction 180-350 ^° C of light catalytic gas oil or the fraction 180-350 ^° With light coke oven gas oil in a ratio of 99: 1-60: 40 (wt.%), Respectively, or with domestic heating fuel in a ratio of 99: 1-50: 50 (wt.%), Respectively.

To improve the antioxidant and antiwear properties, a mixture of ionol and distilled petroleum acids is added to the resulting mixture of distillates in the amount, wt.%:
Yonol - 0.002 - 0.004
Petroleum acids - 0.002 - 0.004
Received marine low-viscosity fuel after the introduction of additives must satisfy the following requirements of TU 38.101567-00:
Viscosity:
conditional at 20 ^o С, ^o ВУ, no more - 2.0
Corresponding kinematic, mm ² / s, not more than - 11.4
Cetane number, not less than - 40
Temperature, ^o С: flashes in a closed crucible, ^o С, not lower - 62
Stiffening, not higher - Minus 10
Mass fraction,%, no more than:
Sulfur
I view - 0.5
II view - 1.0
III view - 1.5
Mercaptan Sulfur - 0.025
Water - Traces
Mechanical impurities - 0.02
Coking ability,%, no more - 0.2
Ash content,%, no more - 0,01
The content of water-soluble acids and alkalis - Ots.

Density at 20 ^o С, kg / m ³ , not more than - 890
Iodine number, g iodine per 100 g of fuel, not more than - 20
Table 4 presents the component composition, table 5 - quality indicators obtained by the proposed method of environmentally friendly SMT.

 An example of obtaining SMT.

Example 1. Oil on the installation of ABT is subjected to distillation with the release of the fraction of vacuum gas oil 240-500 ^o C.

The fraction of 240-500 ^{° C. of} vacuum gas oil is subjected to catalytic cracking in a fluidized bed of a microspherical zeolite-containing catalyst at a temperature of 490 ^° C. The fraction of 180-350 ^{° C. is} isolated from the catalysis and subjected to deep hydrogenation on a nickel-tungsten sulfide with the addition of aluminum oxide catalyst at a pressure of 260 at a temperature of 350 ^o C. Then the unstable hydrogenate is subjected to blowing, alkalization and water washing. Then, by atmospheric vacuum rectification, a fraction of 195-315 ^° C is isolated from the hydrogenate, which is mixed with a fraction of vacuum gas oil in a ratio of 99: 1 (wt.%). The additive composition is introduced into the resulting mixture: ionol and distillate petroleum acids in an amount of 0.003 wt.%, Respectively.

Example 2. The parameters of the processes and the sequence of their implementation are similar to example 1. The fraction 195-315 ^o C isolated from the hydrogenate is mixed with the thermogasoil fraction in a ratio of 99: 1 (wt.%). The additive composition is introduced into the resulting mixture: ionol and distillate petroleum acids in an amount of 0.003 wt.%, Respectively. The results are shown in table 5.

Example 3. The parameters of the processes and the sequence of their implementation are similar to example 1. The fraction 195-315 ^o C isolated from the hydrogenate is mixed with the fraction of vacuum gas oil in a ratio of 75:25 (wt.%). The additive composition is introduced into the resulting mixture: ionol and distillate petroleum acids in an amount of 0.003 wt.%, Respectively. The results are shown in table 5.

Example 4. The parameters of the processes and the sequence of their implementation are similar to example 1. The fraction 195-315 ^o C isolated from the hydrogenate is mixed with the thermogasoil fraction in a ratio of 75:25 (wt.%), Respectively. Then enter the composition of additives in an amount of 0.003 wt.% Each (yonol and distilled petroleum acids).

Example 5. Similar to example 1, only the 195-315 ^o C fraction isolated from the hydrogenate is mixed with the 180-350 ^o C fraction of light catalytic gas oil in a ratio of wt. % 99: 1, respectively. Then, an additive composition is introduced in an amount of 0.003 wt.% Each (ionol and distilled petroleum acids). The results are shown in table 5.

Example 6. Similar to example 1, only the 195-315 ^o C fraction isolated from the hydrogenate is mixed with the 180-350 ^o C fraction of light catalytic gas oil in a ratio of wt. % 60:40 respectively. Then, an additive composition is introduced in an amount of 0.003 wt.% Each (ionol and distilled petroleum acids). The results are shown in table 5.

Example 7. The parameters of the processes and the sequence of their implementation are similar to Example 1. The 195-315 ^o fraction isolated from the hydrogenate is mixed with the 180-350 ^o C fraction of light coking gas oil in a ratio of 99: 1 (wt.%), Respectively. Then, an additive composition is introduced in an amount of 0.003 wt.% Each (ionol and distilled petroleum acids). The results are shown in table 5.

Example 8. The parameters of the processes and the sequence of their implementation are similar to Example 1. The 195-315 ^o C fraction isolated from the hydrogenate is mixed with the 180-350 ^o C fraction of light coking gas oil in a ratio of 60:40 (wt.%), Respectively. Then enter the composition of additives in an amount of 0.003 wt.% Each (yonol and distilled petroleum acids). The results are shown in table 5.

Example 9. The parameters of the processes and the sequence of their implementation are similar to example 1. The fraction 195-315 ^o C isolated from the hydrogenate is mixed with domestic heating oil in a ratio of 99: 1 (wt.%), Respectively. Then, an additive composition is introduced in an amount of 0.003 wt.% Each (ionol and distilled petroleum acids). The results are shown in table 5.

Example 10. The parameters of the processes and the sequence of their implementation are similar to example 1. The fraction 195-315 ^o C isolated from the hydrogenate is mixed with furnace household fuel in a ratio of 50:50 (wt.%), Respectively. Then, an additive composition is introduced in an amount of 0.003 wt.% Each (ionol and distilled petroleum acids). The results are shown in table 5.

 The analysis of samples according to examples 1-10 showed that compared with the prototype, the content of total and mercaptan sulfur significantly decreased, evaporation decreased, chemical stability and fuel purity increased, the tendency to varnish and carbon formation decreased, low-temperature properties significantly improved, and the cetane number increased, which allowed to reduce emissions of harmful substances into the atmosphere and improve the environment.

 The proposed technology for producing SMT will be widely used at refineries to produce environmentally friendly fuels for marine diesel engines.

Claims (2)

1. A method of producing environmentally friendly marine low-viscosity fuel, including atmospheric-vacuum distillation of oil with separation of fractions, catalytic cracking of vacuum gas oil, compounding of fractions, characterized in that a fraction of 240-500 ^o C is isolated during atmospheric vacuum distillation, which is subjected to catalytic cracking with obtaining a fraction of 180-350 ^o With light catalytic gas oil and subsequent hydrogenation of the obtained fraction on a nickel-tungsten sulfide with the addition of alumina catalyst with separation from irradiated hydrogenated by atmospheric vacuum distillation of the fraction 195-315 ^o With, which is mixed with a fraction of vacuum gas oil or thermogas oil in a ratio of 99: 1-75: 25 wt. %, respectively, or a fraction of 195-315 ^o With mixed with a fraction of 180-350 ^o With a light catalytic gas oil or with a fraction of 180-350 ^o With a light coke oven gas oil in a ratio of 99: 1-60: 40 wt. %, respectively, or with domestic heating fuel in a ratio of 99: 1-50: 50 wt. %, respectively, then the composition is additionally introduced the composition of antioxidant and antiwear additives in an amount of 0.002-0.004 wt. % of each.  2. The method according to p. 1, characterized in that ionol is used as an antioxidant and distilled petroleum acids are used as antiwear.

Images