Method of thermal craking of heavy oil products "ИТЭР"

FIELD: mining.

SUBSTANCE: invention refers to method of thermal cracking of heavy oil products consisting in their supply together with active donor-hydrogen additive as source raw material into zone of cracking and its heat treatment; as donor-hydrogen additive water is used at amount of 10-50 wt %; source raw material is supplied into zone of cracking in form of water-oil emulsion under overcritical pressure 22.5-35.0 MPa, at which heat treatment is performed at the temperature of 320-480°C.

EFFECT: creating high technological method of thermal cracking of heavy oil residues with increased depth of raw material processing and with increased output of light distillate fractions.

1 ex, 1 tbl

 

The present invention relates to the field of oil refining, in particular to a process for thermal cracking of heavy oil feedstock, and can be used when directed processing of heavy crude oils, residues, their atmospheric or vacuum distillation, waste oil refining - oil sludge.

In refining, the main task is to increase the refining depth, i.e. the maximum receiving light oil.

Technologically increase refining depth depends on the redistribution of the balance of the hydrogen/feedstock carbon and the balance sheets of the obtained oil and residue materials. In this regard, the gas component and gasoline are products with a high content of hydrogen, and here we consider the problem of maximum receipt diesel fractions with minimal hydrogen content in the range of light distillate fractions.

The existing technologies of thermal cracking are characterized by the fact that reactions take place simultaneously with the reactions of condensation and polymerization of resins and asphaltenes, which does not allow the process of thermal cracking units (visbreaking) oil residue to obtain a sufficient depth of processing more than 50 wt.%, not having the balance of a significant amount of coke.

A method of refining heavy oil path and the processing sonadoras gas to ozone absorption in the amount of preferably 0.05 to 0.5 wt.% with subsequent thermal cracking of the resulting product at a temperature of preferably 400-430°C, the pressure of 0.5-3.0 MPa and flow rate of the raw material into thermal reactor 1-2 h-1the output of light oil products is about 70% when coxworthy 0,2-0,25% (see Russian Federation patent No. 2184761, CL C10G 27/14, C10G 9/00, 2001.07.18).

However, this method does not allow to regulate the receipt of diesel fractions, requires the use of ozone in large enough quantities of 0.05-0.5%. And the fact that industrial ozone generators with this capacity is not produced, makes the specified method is hardly applicable in the industry,

Also known is a method of processing oil, including an introduction to crude oil catalyst activation donors of hydrogen and a hydrogenation crude oil. Hydrogenation is subjected to native crude oil with a water content of 2-10 wt%, the catalyst used in the form of a water-soluble metal compounds VI and VIII group elements of the periodic system and dissolve it in the water contained in the crude oil, with the formation of a true solution, and as the hydrogen donors use their own fraction and a crude oil obtained from oil fractions.

This is achieved by increasing the depth of oil refining up to 95,0% light oil (see U.S. Pat. Of the Russian Federation No. 2255959, CL C10G 47/02, 2004.02.03).

However, this method is only suitable for processing (preparation) of crude oil requires the presence of the Oia hydrogen pressure of 3.5-7.0 MPa, consumable catalyst in large enough quantities of 0.01 to 1.0 wt.% in the calculation of the metal - Mo, Ni, Co, Fe, introduction of large quantities of hydrogen donors, obtained from crude oil fractions, under the donor hydrogen understand fractions obtained by distillation of the products of the hydrogenation of crude oil and Hydrotreating fractions with a boiling temperature of 300-400°C. in a separate production stage, all this makes this method very difficult and hardly applicable in the processing of crude oil (in particular, heavy oil) and not applicable for processing existing oil residue.

Closest to the proposed method is a method of thermal cracking of heavy petroleum products, including filing jointly with an active donor-hydrogen additive selected from the group: ordinary or enriched shales of different genetic types, the mineral part of oil shale, zeolite-containing catalysts, a mixture of raw oil shale and ceritadewasa aluminosilicate catalysts, as feedstock in the cracking zone and its heat treatment at atmospheric pressure in the temperature range 400-430°C. the Content of these additives is 8-12 wt.%, time isothermal aging the reaction mixture at finite temperature in the reactor is from 30 to 180 minutes, the light distillate (depth of processing) to 65.8% downloadable mix see the patent of Russian Federation №2288940, CL C10G 47/22, 2005.07.20).

The disadvantages of this method are its relatively low technology, the need for preliminary preparation of raw material, availability of huge amounts of solid additives is 8-12%, the need for long-term isothermal exposure of the reaction mass is 30-180 minutes, all this makes this method difficult and hardly applicable in the industrial processing of heavy petroleum residues.

In addition, the depth of processing of raw materials is not high enough, a relatively small output of light distillate fractions, in particular diesel.

The technical result of the proposed solution is the creation of high-tech method of thermal cracking of heavy oil residues with increasing depth of processing of raw materials and higher output of light distillate fractions, in particular diesel.

This technical result is achieved by a method of thermal cracking of heavy petroleum products ITER, including the filing jointly with an active donor-hydrogen additive as feedstock in the cracking zone and its heat treatment, and the donor-hydrogen additives use water in an amount of 10-50 wt.%, the feedstock is fed to the cracking zone in the form of water-in-oil emulsion under supercritical pressure of 22.5-35,0 MPa, at which the om conduct heat treatment at a temperature of 320-480°C.

The technical essence of the method ITER is that heavy oil in conjunction with water as the feedstock served in the reaction tube cracking furnace in which the process begins, develops and ends. When using the socket-camera process terminates in the socket chamber. Water at operating temperatures 320-480°C and supercritical pressure of 22.5-35,0 MPa is thermally and catalytically active in this process, allowing you to use it as a donor-hydrogen additives. Special preparation of raw materials is not required - water is fed either directly into the flow of crude oil before entering the convection and/or radiation chamber of the furnace cracking, or the flow of crude oil to the high pressure pumps, or water originally associated with the heavy oil feedstock in the case of sludge processing.

The present invention allows to significantly simplify the hardware design of the cracking process (compared to cedrelinga and hydrocracking) and get a higher depth of processing of heavy petroleum residues, up to 90%, with the receipt of gas cracking less than 1% and the set of products of components of motor fuels, fuel GOST 10585-99 and bitumen of various grades. This technology can be processed not only fuel oils and tars, and oil sludge with sod is a neigh mechanical impurities up to 30 wt.%, the processing of which is usually a vital task.

The proposed method of thermal cracking is waste-free and allows, within certain limits, to vary the ratio between benzimidazoles fraction and the resulting oily residue.

To organize the optimal reactions of cracking of the formed emulsion water - in-oil raw materials in the reaction tube cracking furnace is regulated by the structure and the flow velocity in pipes by submission (dosage) of water in each stream of the reaction tubes cracking furnaces. Water, as a rule, is at the entrance to the convection section of the cracking furnace, the water amount is determined on the basis of practical experience in relation to the specific parameters of crude oil and ranges from 10% to 50% wt. from the mass of crude oil. At the outlet of the furnace cracking in the vapor-liquid food mixture may be supplied with a cooling agent - "quench", which serves as chilled water or gas oil cracking. Quench is served in the stream after reducing valve-pressure regulator direct action to itself for termination reactions of cracking, as well as to achieve the temperature of the mixture corresponding to the optimal temperature profile in a flow manufacturing line.

Vapor-liquid mixture, cooled to the temperature of condensation in which Moisiu water the obtained oil product, due to the large difference in the densities of well stratified, and water technologically easily separated from the oil, In future petroleum potential content of light fractions up to 80% wt., can either be shipped in the form of boiler fuels and commodity oil, or be subjected to further refining - distillation, Hydrotreating, etc. and the remainder in the form of tar to be processed in the bitumen.

Example 1

The feedstock is old netany sludge open barn storage, Perm region, former Ust-Sylvenska farm, gkrellkam.

Characteristics of sludge

Specific gravity at 20°C is 0.975 g/cm3

Fractional composition of petroleum frequent:

Start boiling360°C
NC-160°C0%
160-360°C0%,
360-500°C15%
500° C and above85%

The presence of water - 30,0%

The sulfur content of 2.7%

Solids content of 5.5 wt.%.

Raw materials with a water content of 30% is heated in a steam heat exchanger to a temperature of 90°C, nacosa the high pressure is served in the reaction furnace coil cracking under the pressure of 28.0 MPa. Passing the raw material through the coil, it is heated flue gases to 420°C and further to regulate the pressure valve to itself relieve pressure up to 1.0 MPa. The obtained liquid-vapor mixture is cooled in the heat exchanger. The resulting product condense. After water separation is carried out analyses of the obtained oil product.

Characteristics of the obtained oil product

Specific gravity at 20°C - 0,838 g/cm3

Fractional composition of the obtained product (water separated):

Start boiling42°C
NC-160°C8%
160-360°C64%,
360-500°C12%
500° and above15%

Gas C1-C5 1,0%

The sulfur content in gasoline to 0.6%, diesel fuel - 1,4%

Further examples of the method are summarized in table.

As follows from the above examples, the inventive method is a good and reliable solution of the problem with the achievement of the claimed technical result.

The proposed method for thermal cracking of heavy petroleum products ITER differs from other known ways of doing process the sa processing of petroleum residues, such as: thermal cracking (visbreaking), catalytic cracking, hydrocracking, Hydrotreating residual oil fractions, delayed coking, etc. and the difference lies in the fact that processing of oil residue is water in the reaction tube cracking furnace with working temperatures 320-480°C, at supercritical pressure of 22.5-35,0 MPa treated emulsion water - in-oil raw materials, without the use of solid additives and catalysts, without special preparation of the raw materials. Water-in-oil emulsion is obtained by adding (dosing) 10-50 wt.%. water in the flow of heavy oil raw material supplied for processing.

The proposed method for thermal cracking of heavy petroleum products ITER allows you to suppress the polymerization reaction so that you have the ability to process even the "dirty" raw materials with a content up to 30% solids, while receiving additional quantity of oil in the conversion of organic part of mechanical impurities in the hydrocarbon fraction. This process allows a selectivity of up to 90% wt. get only the diesel fraction with getting gas cracking less than 1% wt.

The proposed solution meets the condition of patentability "novelty", as in the prior art does not contain a solution, the contest is gosia thermal cracking of heavy oil residues, essential features which coincide with all the essential features of the present invention.

The proposed solution also meets the condition of patentability "inventive step", as in the prior art is not identified technical solutions, the hallmarks of which is aimed at the solution of the technical problem of the present invention.

In addition, the proposed solution meets the criterion of "industrial applicability"that follows from the above examples.

All of the above, according to the author, allows to consider the proposed solution meet the criteria of the invention, which could be protected by a patent.

1
Table
№ p/pCrude oilThe addition of water, wt.%Temperature, t, °CThe pressure P, MPaThe original product, fraction of NK-360°C, % wt.The resulting product
fractions NK-360°C, % wt.fractions of 360° - QC % wt.gas + loss % wt.
23456796
1Old sludge, former Ust-Sylvenska NR3042028,0072,02710
2The slime JSC "salavatneftorg-synthesis"5032030,0074,025,40,6
3Mazut M100 JSC "salavatneftorg-synthesis"2048022,5063,235,90,9
4Mazut M100 Novo-Ufa refinery40480 30,0062,836,50,7
5Mazut M100 Yaroslavl refinery3046528,00to 59.440,20,4
6Mazut M-40 LLC Antipinsky oil refinery3048025,0091,97,40,7
7Mazut M100 JSC Moscow oil refinery"1042035,0072,326,80,9

The method of thermal cracking of heavy petroleum products, including filing jointly with an active donor-hydrogen additive as feedstock in the cracking zone and its heat treatment, characterized in that as the donor-hydrogen additives use water in an amount of 10-50 wt.%, raw materials p is given in the cracking zone in the form of water-in-oil emulsion under supercritical pressure of 22.5-35,0 MPa, at which conduct the heat treatment at a temperature of 320-480°C.



 

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