WO2017111764A1

WO2017111764A1 - Method for processing heavy hydrocarbon feedstock

Info

Publication number: WO2017111764A1
Application number: PCT/UA2016/000132
Authority: WO
Inventors: Евгений Ефимович ДОМАНОВ; Владимир Васильевич РОМАНЬКОВ; Вадим Викторович СТУДЕННИКОВ
Original assignee: Евгений Ефимович ДОМАНОВ; Владимир Васильевич РОМАНЬКОВ; Вадим Викторович СТУДЕННИКОВ
Priority date: 2015-12-24
Filing date: 2016-11-10
Publication date: 2017-06-29
Also published as: US20180371329A1; CA3009626A1; EA035887B1; PE20181211A1; RU2018121020A; MX2018007689A; RU2018121020A3; EA201891513A1; BR112018012882A2; CO2017013225A2; CN108463537A

Abstract

The method for processing heavy hydrocarbon feedstock, predominantly heavy crude oil, comprises pre-treatment of an initial feedstock and an auxiliary gaseous mixture at a pre-set pressure, introducing the pre-treated auxiliary gaseous mixture into the pre-treated feedstock and mixing thereof, cavitation treatment of the resulting mixture, separating liquid and gaseous products followed by isolating the final petroleum product. The novelty is in that gaseous hydrocarbons having the activation energy comparable with the molecule dissociation energy of the main components of the heavy hydrocarbon feedstock, are used as auxiliary gaseous mixture; and the pre-treatment of the initial heavy hydrocarbon feedstock and the auxiliary gaseous mixture, both of which are in the liquid state, is performed at a pressure which exceeds the saturated vapour pressure of the auxiliary gaseous mixture. The technical result is the improved physical and chemical characteristics of the final petroleum product by virtue of changing the composition and structure thereof, more particularly, by reducing its density, viscosity, and initial boiling point, by increasing the light fraction yield during refining, and by increasing the efficiency and the effectiveness factor of processing heavy hydrocarbon feedstock.

Description

METHOD FOR PROCESSING HEAVY HYDROCARBON RAW MATERIALS

Technical field

The invention relates to the refining, petrochemical and chemical, as well as to the fuel and energy industry, and specifically to a method for processing heavy hydrocarbons, and can be used in the preparation and processing of heavy oil, residues of oil refining and petrochemical industries, and other liquid hydrocarbon media, production of hydrocarbon fuels, petrochemical and chemical products, as well as the transportation of heavy oil.

State of the art

An urgent task in the transportation of heavy hydrocarbon feedstocks (heavy oil) is to reduce its viscosity and density, as well as reduce the boiling point and increase the yield of light products during distillation. Currently, for transportation of heavy oil, before injection into the pipeline, it is usually diluted with light gasoline fractions (naphtha), while the volume of diluents can reach 15-20% of the volume of heavy oil. If delivery to the terminal of naphtha for oil dilution is impossible, then to reduce the viscosity it is heated throughout the transportation.

The viscosity and density of heavy oil can also be reduced by treating it in a cavitation reactor both in pure form and in the presence of auxiliary additives. The technology allows to exclude or significantly reduce the volume of diluents, as well as to exclude heating or reduce the temperature of the heating of the pipeline.

A known method of processing heavy oil, including the preparation of oil, the preparation of auxiliary additives, mixing the components, cavitation treatment of the mixture, where pentane gas is used as an auxiliary additive [1].

The disadvantage of this method is the low efficiency of the process due to the use of pentane as an auxiliary additive. The pentane activation energy under the same temperature conditions is several times higher than the activation energy of the high molecular weight components of heavy oil. Due to the significant difference in activation energies, the concentration of free radicals of light components in the mixture is significantly lower than the concentration of free radicals of heavy components. The fragments of the high molecular weight components of the oil do not get the right amount of light radicals to react with them, so they recombine with each other. The reduction in the density and viscosity of heavy oil with this processing technology occurs mainly not due to the destruction of high molecular weight compounds of heavy oil, but due to its dilution with pentane.

Closest to the proposed method for processing heavy hydrocarbons is a method of processing oil [2], including the preparation of oil, the preparation of an auxiliary additive (gas mixture), mixing the components, processing them in a cavitation reactor and separation of liquid and gaseous products, where associated gas is used as an auxiliary additive (gas mixture). For the processing of oil associated natural gas applied jet-cavitation method. At the same time, oil processing using associated gas involves heating associated gas at a pressure of 0.6-0.8 MPa to a temperature of 120 ⁹ C, its acceleration to supersonic speeds of more than 400 m s in the expansion of the Laval nozzle, acceleration of the oil flow under pressure 1.6 MPa at a temperature of 80-90 ° C in the profiled channel and its spraying in a cavitation jet gas-liquid mixer with the formation of a volumetric cavitation cavity into which a supersonic natural gas stream is fed coaxially and in the same direction with the oil flow, by which interaction and mixing of oil and gas flows in a two-phase medium moving locally at a supersonic speed to produce a mixture in which the gas concentration is at least 10% of the mass of the oil being processed, the resulting mixture is directed through a profiled expanding channel, where its velocity drops even at When crossing the sound barrier, a compaction jump occurs, in which the dissolution of natural gas in oil is completed, in order to stabilize the mixture and remove excess natural gas through the separator The torus for reuse is carried out by Re-cavitation treatment in a passive cavitator-homogenizer.

The disadvantages of this method, according to the prototype, should include its high energy intensity, low oil processing efficiency and low process efficiency. At the same time, high molecular weight oil components (fractions boiling in the temperature range 350-550 ° C), as well as their fragments, have a relatively high reactivity and easily enter into the addition and oxidation reactions [3], Associated gas contains mainly methane (70 -96%), which as a representative protozoa gaseous paraffin hydrocarbons possesses' high chemical stability [4]. As a result, the oil-gas working mixture in the reaction zone, even in the presence of catalysts, must have a temperature of at least 350 ° C. Cavitation processing of a mixture of associated gas (according to the prototype) occurs at a temperature of 80-90 ° C under pressure, a maximum of 1.6 MPa. This means that the heavy hydrocarbon feed is in a liquid state, and methane is in a gaseous state and the temperature is insufficient to activate it.

For the maximum reaction effect, it is necessary that the reacting components have a comparable activation energy and, accordingly, an approximately equal number of donors and acceptors among the free radicals formed. Non-compliance with this rule dramatically reduces the efficiency of the process, which takes place in the prototype.

Disclosure of invention

The present invention provides a method for processing heavy hydrocarbon feedstocks, which allows, in comparison with the prototype, to process oil and petroleum products of high viscosity and density as fully and efficiently as possible with an improvement in the physicochemical parameters of the final petroleum product by changing its composition and structure at low cost.

The basis of the invention is the task of improving the method of processing heavy hydrocarbon raw materials, in which through the use of other auxiliary gas mixture and other conditions for the preparation of raw materials and auxiliary gas mixture, the physico-chemical parameters of the processed heavy hydrocarbon raw materials are improved by changing the composition, structure and a high degree of conversion of heavy hydrocarbons, namely: a decrease in density, viscosity, boiling point and increase yield of light fractions during distillation, increase the processing efficiency of heavy hydrocarbons and its efficiency, due to this, a reduction in the energy intensity of the process is achieved.

The problem is solved in that in a method for processing heavy hydrocarbon feedstocks, mainly heavy oil, including preparing oil, preparing auxiliary gas mixture at a given pressure, introducing prepared auxiliary gas mixture into the raw materials, and mixing them, cavitational processing of the mixture, separation of liquid and gaseous products with the further isolation of the final oil product, according to the invention, gaseous hydrocarbons having energy a are used as auxiliary gas mixture activation, comparable with the breaking energy of the molecules of the main components of a heavy hydrocarbon feedstock, and the preparation of the initial heavy hydrocarbon feedstock and auxiliary gas mixture in a liquid state is carried out at a pressure exceeding the saturated vapor pressure of the auxiliary gas mixture.

In addition, in some cases, the use of the proposed method for processing heavy hydrocarbons, mainly heavy oil, the proposed method is characterized in that:

- heavy oil residues (fuel oil, tar, semi-tar), oil sludge (asphalt-resin-paraffin deposits, fuel-oil, reservoir, paraffin, etc.), used motor oils and lubricating oils, heavy oil fractions, heavy oils are used as heavy hydrocarbon feedstocks; mixtures: oil-fuel oil, oil-semi-tar, oil-tar, in various ratios;

- as a raw material for the auxiliary gas mixture using gases of high temperature catalytic cracking of oil and gas.

In General, the distinguishing features of the proposed processing method heavy hydrocarbon feedstocks are essential and necessary to achieve a new technical result compared to the prototype.

As a result of using the claimed invention, it is possible to obtain a technical result consisting in improving the physicochemical parameters of the final oil product by changing its composition, structure, namely: reducing its density, viscosity, boiling point, increasing the yield of light fractions during distillation and increasing efficiency processing of heavy hydrocarbons and its efficiency.

The use of gaseous hydrocarbons with an activation energy comparable to the breaking energy of the molecules of the main components of a heavy hydrocarbon feedstock as an auxiliary gas mixture makes it possible to improve the physicochemical parameters of the final oil product, namely, by increasing the yield of light fractions during distillation and lowering the boiling point, An improvement in composition and structure is achieved, which is expressed in a decrease in density and viscosity. And preliminary preparation of the initial heavy hydrocarbon feedstock and auxiliary gas mixture (auxiliary additive) - gaseous hydrocarbons in a liquid state and having an activation energy comparable to the breakdown energy of the molecules of the main components of the heavy hydrocarbon feedstock, at a pressure exceeding the saturated vapor pressure of the auxiliary gas mixtures, provides a high concentration of reacting components in a cavitation reactor. As a result of cavitation treatment of a mixture of pre-prepared heavy hydrocarbon feedstocks and auxiliary gas mixture, due to the fact that the heavy hydrocarbon feedstock and gas auxiliary mixture have comparable activation energy, provides the necessary concentration of free radicals of the donor and acceptor in the cavitation reactor. The maximum concentration of active donor and acceptor molecules in the processed mixture is the main principle of increasing the yield of the target product as a result of the effect of cavitation on the mixture of processed substances under the selected conditions. During cavitation treatment of the mixture, gasoline and salt fractions are formed due to the destruction of high molecular weight compounds of heavy hydrocarbon feedstocks, and as a result, the density and viscosity of the processed oil products decrease. An increase in the content of gasoline and solar fractions leads to a decrease in the boiling point of the processed heavy oil products and an increase in the yield of light fractions during distillation.

All this leads to an improvement in the physicochemical parameters of the processed heavy hydrocarbon feedstocks, and also increases the efficiency of processing heavy oil products and process efficiency.

The absence in comparison with the prototype in the technological process of the proposed method for processing heavy hydrocarbon feedstocks of the stage of preheating the feedstock and auxiliary gas mixture leads to a decrease in the energy intensity of the process and an increase in the efficiency of processing heavy oil products and its efficiency.

Brief Description of the Drawings

The invention is illustrated by graphic material, where Fig. 1 is a flow chart of a process for processing heavy hydrocarbon feeds, Fig. 2 shows a graph of the density of heavy oil depending on the percentage of auxiliary gas mixture that is introduced into the feed before cavitation treatment, and Fig. .3 - Graph of changes in the viscosity of heavy oil depending on the percentage of auxiliary gas mixture, which is introduced into the feed before cavitation treatment.

An alleged embodiment of the invention An embodiment of the proposed method for processing heavy hydrocarbon feedstocks is illustrated by the Technological scheme of the process (see Figure 1), where it is indicated: 1 - feedstock, 2 - auxiliary gas mixture, 3 - prepared raw materials, 4 - prepared auxiliary gas mixture, 5 - mixing of raw materials 3 and auxiliary gas mixture 4, 6 - cavitation treatment of the mixture, 7 - oil-gas separation, 8 - finished oil product. In Fig.2 and Fig.Z designated: 1 - known (prototype), 2 - proposed.

The claimed method for processing heavy hydrocarbons, mainly heavy oil, is implemented using known standard equipment and devices used in this industry.

The proposed method for processing heavy hydrocarbon feeds, mainly heavy oil, is as follows (see FIG. 1): feedstock 1 and auxiliary gas mixture 2 are prepared at a given pressure, for which they are compressed to a pressure above the saturated vapor pressure of the auxiliary gas mixture. Prepared raw materials 3 and auxiliary gas mixture 4 are mixed 5, for example, in a mixer. Then carry out cavitation treatment 6 of the resulting mixture in a cavitation installation. Then, 7 liquid and gaseous products are separated, for example, in an oil-gas separator, with a further release of the final oil 8 and unreacted gases, which are returned to the auxiliary gas mixture tank 2. For example, some of the gases after separation of low-boiling components - hydrogen methane, ethane, etc. can be reused as raw material for the preparation of auxiliary gas mixture. Moreover, as auxiliary gas mixture 2, gaseous hydrocarbons having activation energy comparable with the breakdown energy of the molecules of the main components of a heavy hydrocarbon feedstock, and the preparation of feedstock 1, 3 and auxiliary gas mixture 2, 4 in a liquid state is carried out at a pressure exceeding the saturated vapor pressure of the auxiliary gas mixture 2.

The proposed method for processing heavy hydrocarbon feeds is carried out by the method of catalytic cracking in a cavitation reactor, where a mixture of hydrocarbons having an activation energy comparable to the breaking energy of the molecules of the main components of the heavy hydrocarbon feed is used as an auxiliary gas mixture (additive), and cavitation is used as a catalyst. Hydrodynamic cavitation units work effectively when liquid with a viscosity of not more than 5000 cSt is supplied to their input. The higher the viscosity and density of the feedstock, the greater the percentage of auxiliary gas mixture (additive) must contain the mixture before cavitation treatment. Based on this limitation, for the processing of feedstock with a viscosity, for example, 20,000 cSt, it is necessary to introduce 2% of the mass of the auxiliary gas mixture, and for the processing of raw materials with a viscosity of 120,000 cSt from 12 to 15% of the mass of the auxiliary gas mixture. The pressure at which the preliminary preparation of the heavy hydrocarbon feedstock and auxiliary gas mixture (additive) is carried out must be higher than the saturated vapor pressure of the auxiliary gas mixture, that is, the gases must be in a liquefied state. For example, when using gas catalytic cracking of oil and gas, the pressure should not be lower than the pressure of saturated vapors of propylene (a component of the mixture having the highest saturated vapor pressure of all components), which at 25 ° C is 1.132 MPa.

During cavitation action on a mixture of components, when the energy of breaking the bonds of molecules of heavy hydrocarbons and the energy activation of the auxiliary gas mixture of hydrocarbons (additives) have close values, the concentration of free radicals that are formed as a result of the destruction of heavy molecules of hydrocarbons and free radicals of auxiliary substances will be approximately equal, with the appropriate selection of mass coefficients.

A decrease in the viscosity and density of heavy hydrocarbon feedstocks occurs due to a decrease in the average molecular weight of the hydrocarbon mixture, in which, after processing, the content of gasoline and solar fractions increases. As a result of the process, a finished oil product is formed with improved physicochemical parameters, namely, with a reduced density, viscosity, boiling point and an increased yield of light fractions.

The effectiveness of the invention was tested on a GUL-180 cavitation unit with a capacity of up to 700 l / h and was evaluated by changing the physicochemical parameters of heavy hydrocarbons before and after processing, such as viscosity, density, boiling point, light fractions. Pacific Rubiales oil with parameters at 20 ° С was used as a heavy hydrocarbon feedstock: density - 0.976 g / cm, viscosity - 22500 cSt. The boiling point is 242 ° C. The check was carried out depending on the quantitative ratio of heavy oil products and auxiliary gas mixture. As an auxiliary gas mixture, hydrocarbon gases were used that have an activation energy comparable to the breaking energy of the molecules of the main components of a heavy hydrocarbon feedstock, namely, a mixture of catalytic cracking gases with a propylene content of at least 65% and a total amount of unsaturated hydrocarbons of at least 80% by volume. The processing of heavy oil was carried out according to the technological scheme (see Figure 1) in a flow mode once with the following parameters: initial temperature 22-25 ° C, pressure 1.6 MPa and raw material productivity 450 l / h. Heavy oil 1 and auxiliary gas mixture 2 after their preliminary preparation 3, 4 under a pressure of 1.6 MPa were mixed and the mixture was fed to the inlet of the working chamber of the cavitation unit 6, where the mixture was processed. After cavitation treatment, the liquid entered the receiving tank - degasser 7. The number of products formed is determined by the physicochemical parameters of the raw material (viscosity, density, fractional and group composition) and auxiliary additives (boiling point, saturated vapor pressure at the operating temperature, degree of unsaturation of chemical bonds ), the intensity of hydrodynamic fluctuations and the residence times of the liquid in the treatment zone (productivity). After the cycle of processing the sample of heavy oil, the excess pressure from the system was released, and the oil was degassed to a residual dissolved gas content of less than 1% of the mass. The viscosity and density of the initial oil 1 and the finished oil product 8 obtained as a result of cavitation treatment were measured under standard conditions (20 ° C).

The results of experiments to determine the changes in the physicochemical parameters of heavy oil depending on the percentage of auxiliary gas mixture introduced into the initial heavy hydrocarbon feed before cavitation treatment are presented in the Table below.

Table.

The change in the physicochemical parameters of heavy oil depending on the percentage of auxiliary gas mixture introduced into the feed before cavitation treatment. Processing method The amount of auxiliary gas mixture, which is introduced into the raw material before cavitation treatment,% of the mass.

0 2 4 6 8 10

No processing

density, g / cm ³ 0.976

viscosity, cSt 22500

Famous

(prototype)

density, g / cm ³ 0.968 0.965 0.961 0.962 0.965 viscosity, cSt 16000 15000 14000 13500 13000

Proposed

density, g / cm 0.943 0.939 0.928 0.928 0.928 viscosity, cSt 4200 3000 2400 2200 2000

The test results shown in the table are also shown in the attached graphs (see Fig.2 and Fig.Z). Based on the data presented in the attached graphs, the following conclusions can be drawn. When processing heavy oil from Pacific Rubiales, the decrease in oil density after processing by the proposed method is 0.033-0.048 g / cm (average 0.0405 g / cm), and according to the prototype

3 3

0.008-0.015 g / cm, (average 0.0115 g / cm). Thus, the change in density in the reduction side, in the proposed method is 3, 5 times higher than in the prototype. The viscosity of heavy oil after its processing by the proposed method is reduced by more than 8 times, and by the prototype 1.6 times.

To compare the physicochemical parameters before and after processing heavy hydrocarbons, as well as determining the efficiency and efficiency of the process, Pacific Rubiales oil was fractionally distilled before and after processing. As tests have shown, crude oil boiling point 242 ° C, the yield of light fractions 55.5% by volume, oil processed according to the prototype, the boiling point 181 ° C, the yield of light fractions 63%, and processed by the proposed method, the boiling point 127 ° C the yield of light fractions was 74.5% by volume.

Industrial applicability

The proposed method for processing heavy hydrocarbon feedstocks can be used to process multicomponent liquids, including for the modification of oil and petroleum products in order to improve their consumer characteristics, in particular, to reduce their viscosity and density. The invention is industrially applicable and may be practicable by methods known in the industry using known means and equipment.

The tests showed that the processing of heavy oil by the proposed method allowed to reduce the density by an average of 0.0405 g / cm, viscosity by more than 8 times, reduce the boiling point by 115 ° C and increase the yield of light fractions by 19% volume.

The foregoing indicates the possibility of implementing the present invention and achieving the above technical result when implementing the totality of the features of the invention set forth in the claims. Using the entire set of essential features of the claimed invention allows to create a technology for the processing of heavy hydrocarbons with improved consumer characteristics, which are higher than in the known ones, with a low energy intensity of the process and high efficiency of the process.

The proposed method for processing heavy hydrocarbons can be used to reduce viscosity and density before transportation in the pipeline, as well as to increase the yield of light fractions during oil distillation. Information sources.

1. Patent US 8105480 B2 IPC C10G 9/00, priority March 6, 2007, published January 31, 2012.

2. Patent RU 2436834, IPC C10G 015/00, C10G 04732, priority

03/15/2010, publication date 12/20. 201 1 (prototype).

3. Chemistry of oil and gas. Ed. V. A. Proskuryakova and A.E. Drabkina. -M .: Chemistry, 1995.S. 294.

4. E.V. Smidovich. Oil and gas processing technology. Part 2. Petroleum cracking and hydrocarbon gas processing. M .:

Chemistry, 1980.S. 52.

5. Reference petrochemist. Ed. S.K. Ogorodnikova. T. 1.L .: Chemistry, 1978.P. 67.

Claims

CLAIM

1. A method of processing heavy hydrocarbon feedstocks, mainly heavy oil, including preparing the feedstock and auxiliary gas mixture at a given pressure, introducing the prepared auxiliary gas mixture into the prepared raw materials and mixing them, cavitation treatment of the resulting mixture, separation of liquid and gaseous products, with further isolation the final oil product, characterized in that as auxiliary gas mixture using gaseous hydrocarbons having an activation energy of nimuyu molecules with an energy gap major components of a heavy hydrocarbon feedstock and preparation of raw materials and heavy hydrocarbon. auxiliary gas mixture in a liquid state is carried out at a pressure exceeding the saturated vapor pressure of the auxiliary gas mixture.

2. The method of processing heavy hydrocarbon feedstocks according to claim 1, characterized in that heavy hydrocarbon residues (fuel oil, tar, semi-tar oil), oil sludge (asphalt-resin-paraffin deposits, fuel oil, reservoir, paraffin, etc.) are used as heavy hydrocarbon feedstocks. , used motor and lubricating oils, heavy oily fractions, heavy oils, mixtures: oil-fuel oil, oil-semi-tar, oil-tar, in various ratios.

3. The method for processing heavy hydrocarbon feeds according to claim 1, characterized in that natural gas, or associated gas, or propane-butane mixtures, or high-temperature catalytic cracking oils and gas are used as raw materials for the auxiliary gas mixture.