RU2610845C1 - Method of processing heavy oil residues - Google Patents

Abstract

FIELD: oil industry.

SUBSTANCE: present invention relates to processing of heavy oil residues in order to obtain light oil products. Method consists in direct contact of oil residues with oxygen-containing gas in a cracking reactor at high temperature and pressure, includes removal of gaseous products from upper part of cracking reactor and heavy cracking products from lower part of reactor and extraction of light hydrocarbon fractions by rectification. Processing of heavy oil residues is performed in presence of unsaturated carboxylic acids and/or derivatives thereof.

EFFECT: method increases output of light fractions and specific efficiency.

1 cl, 1 dwg, 7 ex

Description

The invention relates to petrochemistry, in particular to the processing of heavy oil residues (TNO) in order to obtain an additional amount of light oil products (gasoline and diesel fuel).

A known method of processing TNO, including their processing with a gas containing ozone, followed by thermal cracking of the obtained ozonated product at 400-430 ° C, 0.5-3.0 MPa and a space velocity of 1-2 h ^-1 (RU 2184761).

The disadvantages of this method is the need to use special equipment for producing ozone-containing gases, as well as the formation in this case of a significant amount of coke 0.2-0.25% of the amount of TNO supplied, which creates problems when implementing the process in a continuous mode.

A TNO thermal cracking unit is known in which the TNO stream preheated to 100-200 ° C is mixed in an injector with air at 50-250 ° C, 0.5-1 MPa, and then it is divided into two streams in a separator: gaseous (exhaust air) ) and liquid (the so-called activated TNO). The liquid stream is heated to 380-410 ° C in a tubular furnace and sent to a portable TNO thermal cracking reactor, where the thermal TNO cracking reaction takes place. The liquid and vaporous reaction products obtained in the reactor are separated into fractions in the separation unit with the release of hydrocarbon gas, liquid fractions, and heavy cracking residue, respectively.

Depending on the type of TNO, hydrocarbon gas and light fractions are obtained: gasoline (HC - 180 ° C), diesel (180-350 ° C) and vacuum gas oil (350-450 ° C), as well as fuel oil 450 ° C (in case of use as raw materials for straight-run fuel oil) or bitumen (in the case of using tar as a raw material). The yield of cracking products is not given in the patent (RU 2232789).

The main disadvantage of this installation is its complexity.

A known method of processing TNO, including feeding a stream of preheated feedstock to 430-450 ° C to the upper part of the reactor and feeding preheated to 500-530 ° C air to the lower part of the reactor, draining the heavy residue from the bottom of the reactor and feeding it to the quenching apparatus or stripping column and discharge from the upper part of the light cracking products and their subsequent supply to the separation unit (RU 2335525).

When processing straight-run fuel oil at 440 ° C, 8.5–9 atm and a contact time of 10 min, the yield of light fractions (including gas) was 63%; fuel oil brand M100 - the rest.

When processing oil tar with the addition of 5% oil sludge at 450 ° C and an air temperature of 530 ° C, its consumption is 2.8 kg / 100 kg of feedstock, the pressure in the reactor is 1.2 atm and the cracking contact time is 9 min, the yield of light fractions is 36 %, gaseous products 5%, fuel oil M100 - the rest.

The main disadvantage of this method and installation is their complexity, as well as the large yield of gaseous cracking products.

There is a method of thermooxidative cracking of TNO at elevated temperature and pressure, including preheating the feed streams and oxygen-containing gas and feeding them into a cracking reactor, in which heated streams are mixed before being fed to the reactor, and the resulting gas-liquid mixture is sent to the reactor in the form of one or more streams .

The process by this method allows to reduce the yield of gaseous products to 3.6-4.6% with a fairly high yield (28-37%) of light fractions (RU 2458967).

The disadvantage of this method is the relatively low yield of light fractions and the need to use special mixers of liquid TNO and air.

The closest analogue to the claimed method is a continuous method of processing TNO at elevated temperature and pressure, including the processing of all raw materials with air directly in the thermal cracking reactor, when heated TNO is supplied to the upper part of the reactor, and air to the lower part. A product stream is diverted from the upper part of the reactor, containing mainly pairs of light hydrocarbon fractions (gasoline and diesel fractions), C ₁ -C ₅ hydrocarbons, nitrogen; from the bottom is a stream of heavy cracking residue. Both flows are directed to a separation unit, from the upper part of which light products are selected, from the lower part - naval or boiler fuel oil (RU 2289607, figure 2).

The disadvantage of this method is the relatively low yield of light fractions and specific productivity.

An object of the invention is to increase the yield of light fractions and specific productivity.

This problem is solved by a method of processing heavy oil residues upon direct contact with an oxygen-containing gas in a cracking reactor at elevated temperature and pressure, including the removal of vaporous products from the upper part of the cracking reactor and heavy cracking residue from the lower part of the reactor and the separation of light hydrocarbon fractions by distillation, in which the processing of heavy oil residues is carried out in the presence of unsaturated carboxylic acids and / or their derivatives.

As unsaturated carboxylic acids, C ₁₀ -C ₂₀ carboxylic acids can be used, their esters or salts as their derivatives.

Preferably, used vegetable oils are used as derivatives of unsaturated carboxylic acids.

The following examples illustrate the method.

To illustrate the method, tar and vacuum gas oil of the Moscow Oil Refinery, as well as fuel oil of the Ryazan NPK, were used as TNO. As a reactor, a hollow vertical column-type apparatus of 1 liter volume was used. However, the use of other TNO and reactor types is not contraindicated.

A schematic diagram of a TNO processing plant is shown in FIG. one.

Example 1 (comparative)

Raw materials, Moscow refinery sludge from container 1 pump 2 at a rate of 2.6 kg / h is fed into a furnace 3 where it is heated to a temperature of 450 ± 5 ^{° C} and then fed to a cracking reactor 6. Return the compressor 4 at a rate of 150 l / hour serves pre-heated in the furnace 5 to a temperature of 470 ^about With a stream of air.

Due to the simultaneous occurrence of partial oxidation reactions and destruction of raw materials, the temperature in the reactor 6 was 440 ± 5 ° C. The pressure in the reactor is 0.5 ± 0.1 MPa.

The vaporous reaction products in a mixture with nitrogen from the upper part of the reactor 6 are sent to the middle part of the distillation column 7.

Heavy products (stream IV) are removed from the lower part of the reactor 6 in terms of the level in the reactor, which are sent to the lower part of the distillation column 7.

A gasoline fraction (NK-180 ° C) at a rate of 0.15 kg / h (stream V) and a diesel fraction (180-350 ° C) at a rate of 0.68 kg / hour (stream VI), bottoms (stream VIII) are taken from the distillation column at a speed of 1.66 kg / h, as well as gaseous products (stream VII) containing nitrogen and C ₁ -C ₅ hydrocarbons - the rest.

The yield of light hydrocarbon fractions was 31.9%. Specific productivity - 0.83 kg / (l * hour).

Example 2

The processing process is carried out in the presence of linoleic acid. Raw materials, Moscow refinery sludge containing 0.3 wt.% Linoleic acid, from vessel 1 pump 2 at a rate of 2.8 kg / h is fed into a furnace 3 where it is heated to a temperature of 450 ± 5 ^{° C} and then fed to a cracking reactor 6. There the compressor 4 at a speed of 150 l / h serves pre-heated in the furnace 5 to a temperature of 470 ^about With a stream of air.

Due to the simultaneous occurrence of partial oxidation and destruction reactions, the temperature in reactor 6 was 440 ± 5 ° C. The pressure in the reactor is 0.5 ± 0.1 MPa.

The vaporous reaction products in a mixture with nitrogen from the upper part of the reactor 6 are sent to the middle part of the distillation column 7.

Heavy products (stream IV) are removed from the lower part of the reactor 6 in terms of the level in the reactor, which are sent to the lower part of the distillation column 7.

A gasoline fraction (NK-180 ° C) at a speed of 0.25 kg / h (stream V) and a diesel fraction (180-350 ° C) at a speed of 0.73 kg / h (stream VI), bottoms (stream VIII) are taken from the distillation column at a speed of 1.71 kg / h, as well as gaseous products (stream VII) containing nitrogen and C ₁ -C ₅ hydrocarbons - the rest.

The yield of light hydrocarbon fractions was 35.0%. Specific productivity - 0.98 kg / (l * hour).

Example 3 (comparative)

Raw oil Ryazan NPK of the container 1 pump 2 at a rate of 1.7 kg / h is fed into a furnace 3 where it is heated to a temperature of 455 ± 5 ^{° C} and then fed to a cracking reactor 6. Return the compressor 4 at a flow rate of 50 l / hour serves pre-heated in the oven 5 to a temperature of 470 ^about With a stream of oxygen-containing gas composition, vol.%: oxygen - 45; nitrogen and inert - the rest.

Due to the simultaneous occurrence of partial oxidation reactions and destruction of raw materials, the temperature in reactor 6 was 445 ± 5 ° C. The pressure in the reactor is 0.8 ± 0.2 MPa.

The vaporous reaction products in a mixture with nitrogen from the upper part of the reactor 6 are sent to the middle part of the distillation column 7.

From the lower part of the reactor 6, heavy products are diverted in level (stream IV), which are sent to the lower part of the distillation column 7.

A gasoline fraction (NK-180 ° C) at a rate of 0.16 kg / h (stream V) and a diesel fraction (180-350 ° C) at a rate of 0.67 kg / hour (stream VI), bottoms (stream VIII) are taken from the distillation column at a speed of 0.8 kg / h, as well as gaseous products (stream VII) containing nitrogen and C ₁ -C ₅ hydrocarbons - the rest.

The yield of light hydrocarbon fractions was 48.8%. Specific productivity - 0.83 kg / (l * hour).

Example 4

Raw oil Ryazan NPK containing 0.8 wt.% Of methyl ester of oleic acid, of the container 1 pump 2 at a rate of 1.9 kg / h is fed into a furnace 3 where it is heated to a temperature of 455 ± 5 ^{° C} and then fed to a cracking reactor 6. Return the compressor 4 at a flow rate of 50 l / h is fed into the preheated furnace 5 to a temperature of 470 ^{° C} oxygen-containing gas stream composition, volume%: oxygen - 45;. nitrogen and inert - the rest.

Due to the simultaneous occurrence of partial oxidation reactions and destruction of raw materials, as well as due to the return of condensate to the reactor, the temperature in reactor 6 was 450 ± 5 ° С. The pressure in the reactor is 0.8 ± 0.2 MPa.

The vaporous reaction products in a mixture with nitrogen from the upper part of the reactor 6 are sent to the middle part of the distillation column 7.

From the lower part of the reactor 6, heavy products are diverted in level (stream IV), which are sent to the lower part of the distillation column 7.

A gasoline fraction (NK-180 ° C) at a rate of 0.29 kg / h (stream V) and a diesel fraction (180-350 ° C) at a rate of 0.78 kg / h (stream VI), bottoms (stream VIII) are taken from distillation column 9 ) at a speed of 0.73 kg / h, as well as gaseous products (stream VII) containing nitrogen and C ₁ -C ₅ hydrocarbons - the rest.

The yield of light hydrocarbon fractions was 56.3%. Specific productivity - 1.07 kg / (l * hour).

Example 5 (comparative)

Raw, vacuum gas oil refinery Moscow, from the tank 1 pump 2 at a rate of 2.1 kg / h is fed into a furnace 3 where it is heated to a temperature of 455 ± 5 ^{° C} and then fed to a cracking reactor 6. Return the compressor 4 is fed, preheated in an oven 5 to a temperature of 460 ^about With a stream of oxygen-containing gas composition, vol.%: Oxygen - 40; nitrogen and inert - the rest, with a flow rate of 80 l / h.

Due to the simultaneous occurrence of partial oxidation reactions and destruction of raw materials, the temperature in reactor 6 was 450 ± 5 ° C. The pressure in the reactor is 1.0 ± 0.2 MPa.

The vaporous reaction products in a mixture with nitrogen from the upper part of the reactor 6 are sent to the middle part of the distillation column 7.

From the lower part of the reactor 6, heavy products are diverted in level (stream IV), which are sent to the lower part of the distillation column 7.

From the distillation column 7, a gasoline fraction (NK-180 ° C) at a rate of 0.23 kg / h (stream V) and a diesel fraction (180-360 ° C) at a rate of 0.98 kg / h (stream VI), bottoms ( stream VIII) at a rate of 0.80 kg / h, as well as gaseous products (stream VII) containing nitrogen and C ₁ -C ₅ hydrocarbons - the rest.

The yield of light hydrocarbon fractions was 57.6%. The yield of gaseous products (C ₁ -C ₅ hydrocarbons) is 4.2%. Specific productivity - 1.21 kg / (l * hour).

Example 6

Raw materials, vacuum gas oil of the Moscow refinery, containing 0.4 wt.% Sodium oleate, 0.1 wt.% Oleic acid, from tank 1, pump 2, with a flow rate of 2.3 kg / h is fed to furnace 3, where it is heated to a temperature of 455 ± 5 ^{° C} and then fed to a cracking reactor 6. Return the compressor 4 is fed into the preheated furnace 5 to a temperature of 460 ^{° C} oxygen-containing gas stream composition,% vol .: oxygen - 40; nitrogen and inert - the rest, with a flow rate of 80 l / h.

Due to the simultaneous occurrence of partial oxidation reactions and destruction of raw materials, as well as due to the return of condensate to the reactor, the temperature in reactor 6 was 450 ± 5 ° С. The pressure in the reactor is 1.0 ± 0.2 MPa.

The vaporous reaction products in a mixture with nitrogen from the upper part of the reactor 6 are sent to the middle part of the distillation column 7.

From the lower part of the reactor 6, heavy products are diverted in level (stream IV), which are sent to the lower part of the distillation column 7.

A gasoline fraction (NK-180 ° C) at a rate of 0.30 kg / h (stream V) and a diesel fraction (180-360 ° C) at a speed of 1.23 kg / h (stream VI), bottoms (stream VIII) are selected from distillation column 7 ) at a speed of 0.65 kg / h, as well as gaseous products (stream VII) containing nitrogen and C ₁ -C ₅ hydrocarbons - the rest.

The yield of light hydrocarbon fractions was 66.5%. The specific productivity is 1.53 kg / (l * hour).

Example 7

The process is carried out analogously to example 2, feeding the tar of the Moscow refinery containing 1.5 wt.% Rapeseed oil to the reactor inlet.

The yield of light hydrocarbon fractions was 36.1%. The specific productivity is 1.09 kg / (l * hour).

Example 8

The process is carried out analogously to example 2, feeding to the reactor inlet a tar of the Moscow refinery, containing 4.5 wt.% Of used deep-frying oil, composition, wt.%: Spent sunflower oil - 68.0; used olive oil - 32.0.

The yield of light hydrocarbon fractions was 38.5%. Specific productivity - 1.26 kg / (l * hour).

Carrying out the process by this method allows to increase the yield of light fractions from 31.9 to 37.5% (in the processing of tar); from 48.8 to 56.3% (during the processing of fuel oil); from 57.6 to 66.5% (in the processing of vacuum gas oil), as well as increase the specific productivity from 0.83-1.21 to 1.26-1.53 kg / (l * hour).

Claims (2)

1. A method of processing heavy oil residues upon direct contact with an oxygen-containing gas in a cracking reactor at elevated temperature and pressure, including the removal of vaporous products from the upper part of the cracking reactor and heavy cracking products from the lower part of the reactor and the separation of light fractions of hydrocarbons by distillation, characterized in that the processing of heavy oil residues is carried out in the presence of unsaturated carboxylic acids and / or their derivatives. 2. The method according to claim 1, characterized in that used vegetable oils are used as a source of carboxylic acid derivatives.

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