RU2339680C2 - Method for catalytic hydro-treatment of heavy hydrocarbons of oil and product received by this method - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: here is disclosed group of inventions related to versions of two-stage method of calalytic hydro-treatment of heavy oil hydrocarbons with high content of metals, total sulphur, pyrobitumens and total nitrogen, containing less, than 80% for volume of distillates extracted at 538°C and possessing density API lower, than 32°. According to the first version at the first stage hydrocarbons hydro-metallisation and hydrogen cracking of pyrobitumens are carried out, and at the second stage hydrocarbons hydro-desulphurisation and hydro-denitrogenation are performed; at that both stages of process are performed in a reactor with an immovable layer of catalyst. The second version includes: a) passing hydrogen and hydrocarbon raw material of heavy oil with specific mass (density) less, than 32° API and contents of distillates extracted at 538°C less, than 80% of volume through to the first stage of reaction for hydro-treatment of the said raw materials; at that the said first stage of reaction is performed in the reactor with the immovable layer of catalyst, containing a catalyst of hydro-demetallization and facilitating operation under pressure from 40 to 130 kg/cm², at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr^-1 and at ratio of hydrogen/hydrocarbon (H₂/HC) from 350 to 1.200 In/I with the result of production of hydro-treated heavy hydrocarbons; b) passing hydrogen and the said hydro-treated heavy hydrocarbons through to the second stage of reaction for hydro-treatment in the reactor with the immovable layer of catalyst containing hydro desulphurisation catalyst and facilitating operation under pressure from 40 to 130 kg/cm², at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr^-1 and at ratio of hydrogen/hydrocarbon (H₂/HC) from 350 to 1.200 In/I, at that the amount of sediments formed at each the said first and second stages of reaction is less 0.65% from weight of hydro-treated hydrocarbons. Also one of the inventions of the group refers to the product produced by the method according to the second variant. Employing of the said variant of the method facilitates high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving the product after hydro-treatment with improved characteristics.

EFFECT: facilitating high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving product after hydro-treatment with improved characteristics.

10 cl, 26 tbl, 10 ex, 1 dwg

Description

The scope of the invention

The present invention relates to an oil distillation process in which a catalytic hydroprocessing of heavy oil hydrocarbons is carried out in order to improve their properties.

BACKGROUND OF THE INVENTION

The development of the oil refining industry has led to the fact that the hydroprocessing of heavy oil hydrocarbons has acquired technological and economic importance comparable to the processes of hydrocracking and catalytic reforming. Among heavy petroleum hydrocarbons, heavy crude oils, superheavy crude oils, mixtures of heavy and light crude oils and oil residues, such as residues from distillation at atmospheric pressure or in vacuum, which have a specific gravity of less than 32 ° API (32 degrees of the American Petroleum Institute) and the content of reduced distillates at 538 ° C is less than 80% by volume.

The production of heavy oil fractions and the presence of oil residues with high sulfur and metal contents, as well as requirements regarding the need to improve the environmental quality of fuel, have led to the development and spread of hydroprocessing of these types of raw materials during oil refining.

Since the seventies, there have been reports of the hydrotreatment of oil residues, the main task of which is to extract valuable distillate fractions with a low concentration of heavy heteroatoms.

Heavy crude oil requires processing similar to the treatment of oil residues, because they are characterized by a low hydrogen / carbon ratio (N / C), high viscosity, a high content of pollutants, mainly sulfur, nitrogen and metals, and a low yield distillates.

The reactor system is part of a process in which the greatest attention is paid to the processing of this type of raw material, and this may be a reactor with a fixed catalyst bed, with a fluidized catalyst bed or with a dispersed phase of the catalyst. In oil refining, a fixed-bed reactor is mainly used.

A high concentration of metals in heavy types of oil and in oil residues leads to rapid deactivation of the catalysts, therefore, it is important that the demetallization of these raw materials be carried out in the first stage of processing, in order to maximize the removal of other contaminants in later stages, thereby increasing the time service catalysts used in these stages.

The most effective process for removing contaminants in oil refining is hydroprocessing, which is subjected to almost all fractions of oil, such as: naphtha, middle distillates, vacuum distillates, residues, etc. In the case of heavy types of oil and oil residues, when it is desirable to simultaneously remove various pollutants, mainly such as metals, sulfur, nitrogen and asphaltenes, it is necessary to make the appropriate choice of the type of reactor, catalyst with high activity and selectivity for these reactions, as well as the operating mode which makes the process cost-effective.

Improving the parameters of heavy oil hydrocarbons is associated with the need to process them to remove pollutants and increase the hydrogen / carbon ratio (N / C), usually through the use of processing schemes based on hydroprocessing.

In currently known industrial processes, the hydrotreatment of heavy oil hydrocarbons is carried out in high pressure mode, in the range from 140 to 220 kg / cm ² , for fixed-bed or fluidized-bed reactors, which allows to obtain high levels of conversion (conversion) . To maintain continuous operation in these processes, the formation of deposits and sludge is limited to a maximum content of 0.80% by weight.

The hydroprocessing of heavy oil hydrocarbons at low pressures, less than 140 kg / cm ² , is limited by the formation of deposits and sludge, which is a characteristic problem of these processes. The formation of deposits and sludge increases when the conversion of heavy fractions (boiling point> 538 ° C) to light fractions also increases, or increases with decreasing pressure in the reactors. For this reason, industrial processes for the hydrocracking of heavy hydrocarbons are carried out in the high pressure mode, above 140 kg / cm ² , in order to provide acceptable levels of heavy fraction conversion.

Note that the hydroprocessing of heavy oil hydrocarbons has already been described in various patents.

US Pat. No. 5,591,325 describes a catalytic process for hydrotreating heavy oils in two stages. The first stage is carried out in a reactor with a fixed catalyst bed to remove no more than 80% nickel + vanadium (Ni + V), and mainly to remove from 30 to 70%, although the examples of this patent indicate the removal levels from 45.3 to 47%. In this stage, the following operation mode is used: temperature from 320 to 410 ° C, pressure from 50 to 250 kg / cm ² , space velocity (LHSV - hourly average speed) from 0.1 to 2.0 hour ^-1 and the ratio of hydrogen / hydrocarbon (H ₂ / NS) from 300 to 1,200 nl / l. The second stage is carried out to remove sulfur, nitrogen and metal residues in a fluidized-bed reactor in the following operating conditions: temperature from 350 to 450 ° C, pressure from 50 to 250 kg / cm ² , LHSV from 0.2 to 10.0 h ^-1 and the ratio H ₂ / HC from 500 to 3,000 nl / L.

In this regard, it is important to note that the specified patent gives an exact example of hydroprocessing in two stages of the reaction of the residue from distillation at atmospheric pressure using the following operating conditions: pressure 150 kg / cm ² , LHSV 0.2 hour ^-1 , temperature 370 and 395 ° C for the first and second stages, respectively, and the ratio of N ₂ / HC 700 nl / l, resulting in the removal of Ni + V 109 wppm (parts by weight per million), total nitrogen 1.970 wppm, insoluble in n-C ₇ substances (asphaltenes) 6.6 % by weight and total sulfur 3.78% by weight, as well as the formation of deposits and sludge 0.01% by weight. The patent also describes the use of a catalyst based on a metal of groups VIA, VIII and V for stage I and a catalyst with a hydrogenation metal and an organic oxide support for stage II.

US Pat. No. 5,779,992, which is a partial continuation of US Pat. No. 5,591,325, describes a device that contains: a ') a fixed bed catalyst for hydrodemetallization of oil, and b') a fluidized bed reactor for hydrodesulfurization catalyst designed to hydrotreat the reactor outlet stream section a '). In this device, the heavy oil stream is first fed to the reactor with a fixed bed of hydrodemetallization catalyst of stage a '), and then the heavy oil that has passed hydrodemetallization in stage a') is fed to the reactor with a suspended layer of hydrodesulfurization catalyst of stage b ') to deepen the hydroprocessing of heavy oil . Hydrotreating can occur over a long period of time. The mode of operation is similar to that described in US patent No. 5591325.

Mexican patent MX 179301 proposes a process for hydrotreating heavy crude oil to produce synthetic petroleum feedstocks with a specific gravity of 25 to 40 degrees in degrees from the American Petroleum Institute. This method includes the following operations: catalytic hydroprocessing of heavy crude oil with a specific gravity in degrees of the American Petroleum Institute of less than 24, with a final boiling point in the range from room temperature to 800 ° C, at a pressure of 760 millimeters of mercury and with the following pollutant content substances: over 2% by weight of sulfur, 1,000 wppm of nitrogen, 150 wppm of metals (nickel and vanadium) and 5% by weight of asphaltenes; separation of the reactor effluent into a liquid phase and a vapor phase; and directing the liquid phase into a scrubber. This method allows to obtain processed or improved crude oil with a low content of pollutants, which can be 100% used as raw material in the conventional oil refining scheme, which increases the yield of distillate and its quality.

US Pat. No. 3,901,792 discloses a method for demetallization and desulfurization of crude oil or a residue from atmospheric distillation in a variety of processing steps. First, the heavy feedstock is introduced together with hydrogen into a fluidized bed reactor having the following operating mode: pressure from 68 to 170 kg / cm ² , temperature from 387 to 440 ° C, LHSV from 0.20 to 1.5 h ^-1 , whereby the degree of demetallization is obtained in the range of 50 to 80% by weight or more, depending on the amount of nickel and vanadium in the feed. The lighter fractions leave the reactor through its upper part in the form of acid gas, which is used for the subsequent extraction of light hydrocarbon fractions, while the liquid output stream is introduced into the second stage of the reaction in a mixture with a hydrogen stream for its hydrodesulfurization in a reactor with the same characteristics, as in the first stage of the reaction. A gaseous fraction is withdrawn from the upper part of the reactor for its subsequent processing, while the liquid outlet stream from this second reactor is sent for further processing or fractionation.

U.S. Patent No. 4,160,626 proposes a two-stage process for the hydrotreatment of heavy hydrocarbons such as heavy types of crude oil, stripped types of crude oil, vacuum distillation residues, or bituminous types of crude oil with a high content of asphaltenes, heavy metals, and sulfur. Heavy crude oils are treated together with a hydrogen stream in a first step for hydrodemetallization and hydrocracking of asphaltenes. The stream from the outlet of the first stage is directed to a gas-liquid separator, from which the gaseous fraction enriched with hydrogen, hydrogen sulfide and light hydrocarbons are sent to a scrubber to extract light hydrocarbons, while the liquid output stream, together with part of the recycle hydrogen, enters the second stage of the reaction, where mainly hydrodesulfurization and hydrodenitrogenation reactions take place. Then the output stream from this process step is introduced into the gas-liquid separator, from the output of which a liquid product is obtained, which is sent to another separator to obtain a light fraction and a heavy fraction. Meanwhile, the hydrogen-enriched gaseous fraction, hydrogen sulfide and light hydrocarbons are sent to a scrubber to extract light hydrocarbons and the hydrogen-enriched gaseous fraction and hydrogen, intended for wet gas purification in a subsequent unit. The process in two stages is mainly carried out with the following parameters of the operating mode: pressure from 30 to 250 kg / cm ² , temperature from 350 to 450 ° C, H ₂ / HC ratio from 100 to 2,000 normal liters per liter of load (nl / l) and LHSV from 0.1 to 10.0 hour ^-1 .

The method in accordance with the present invention differs significantly in its objectives, mode of operation and results from the methods described in these references, since it is carried out by combining a low pressure mode of operation, type of reactor and type of feedstock for hydroprocessing, which together provide a high degree of removal of metals, sulfur, nitrogen and asphaltenes, and also limit the formation of deposits and sludge, which allows to obtain a hydrotreated hydrocarbon with improved properties. This is clearly and in detail described in the following sections of the description of the invention.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a petroleum refining process in which a catalytic hydroprocessing of heavy oil hydrocarbons is carried out in two reaction stages using fixed bed reactors by combining a low pressure operating mode, a type of reactor and a type of hydroprocessing feedstock, which are combined provide a high degree of removal of metals, sulfur, nitrogen and asphaltenes, as well as reduce the formation of deposits and sludge, which allows you to get past hydrofinishing botku hydrocarbon with improved properties.

Among the heavy oil hydrocarbons that can be hydrotreated by the method of the present invention, mention is made of heavy types of crude oil, superheavy types of crude oil, as well as mixtures of heavy and light types of crude oil and oil residues, such as residues from atmospheric distillation pressure or in vacuum, which have a specific gravity in degrees of the American Petroleum Institute less than 32 ° and a reduced distillate content of 538 ° C less than 80% by volume.

Thus, the first objective of the present invention is to provide a method for catalytic hydroprocessing of heavy oil hydrocarbons by combining a low pressure operating mode, a reactor type and a type of hydroprocessing feedstock, which together limit the formation of sediment and sludge.

Another objective of the present invention is to provide a method for catalytic hydroprocessing of heavy oil hydrocarbons, which have a specific gravity in degrees of the American Petroleum Institute below 32 ° and a reduced distillate content at 538 ° C of less than 80% by volume.

An additional objective of the present invention is to provide a method for the catalytic hydroprocessing of heavy hydrocarbons of oil, due to which a hydrocarbon is obtained with improved properties, with a minimum content of sediment and sludge.

Another objective of the present invention is to provide a method for the catalytic hydroprocessing of heavy hydrocarbons, which provides a high degree of removal of metals, sulfur, nitrogen and asphaltenes, and also limits the formation of deposits and sludge.

An additional objective of the present invention is to provide a method for the catalytic hydroprocessing of heavy hydrocarbons of oil, through which receive hydrocarbons with improved properties, which can be used as raw material for the process carried out according to the usual scheme of oil refining, or can be sold as hydrocarbon oil with improved properties.

Another objective of the present invention is to provide a method for catalytic hydroprocessing of heavy hydrocarbons of oil, which can be carried out earlier than the usual process of oil refining.

Brief Description of the Drawings

Figure 1 shows the preferred flowchart of the method in accordance with the present invention, which allows to obtain a hydrotreated hydrocarbon with improved properties and with a minimum content of sediment and sludge in the form of a product.

Despite the fact that figure 1 shows a specific arrangement of equipment with which the present invention can be implemented, it should be borne in mind that such a construction is not restrictive.

DETAILED DESCRIPTION OF THE INVENTION

The following describes a preferred method for hydroprocessing heavy oil hydrocarbons in two reaction stages in fixed-bed reactors with various hydroprocessing catalysts, the main effect of which is hydrodemetallization of heavy oil hydrocarbon and hydrocracking of asphaltenes in the first stage, and hydrodesulfurization and hydrodenitrogenation of heavy oil hydrocarbon in the second stage due to the combination of low pressure operation, type of reactor and type of feedstock for hydroprocessing, which locally provide a high degree of removal of metals, sulfur, nitrogen and asphaltenes, and also limit the formation of deposits and sludge, resulting in a hydrotreated hydrocarbon with improved properties.

As a rule, there are no restrictions on the type of hydrocarbon that can be used as raw material for the implementation of the method in accordance with the present invention. Heavy oil hydrocarbons include heavy crude oils, superheavy crude oils, mixtures of heavy and light oils and oil residues, such as those from atmospheric distillation or vacuum distillation, which have a specific gravity of less than 32 ° API and reduced distillates at 538 ° C are less than 80% by volume. As examples of raw materials for implementing the method in accordance with the present invention can lead heavy types of crude oil and residues, such as residues from distillation of oil at atmospheric pressure or in vacuum.

The method in accordance with the present invention includes the following operations (reaction steps):

I. The supply of heavy oil hydrocarbons to a fixed bed reactor of a hydroprocessing catalyst, where mainly hydrodemetallization of heavy oil hydrocarbons and hydrocracking of asphaltenes occur; and

II. The supply of a heavy hydrocarbon oil that underwent hydrotreatment in step I to a fixed bed reactor of a hydrotreatment catalyst to enhance the effect of hydrodesulfurization and hydrodenitrogenation of a heavy oil hydrocarbon.

Due to the fact that heavy oil hydrocarbons contain a large number of heavy compounds, which are precursors of sediment and sludge, they (sediment and sludge) inevitably form during hydroprocessing, therefore, the method in accordance with the present invention is carried out by combining a low pressure operating mode, type of reactor and type of feedstock for hydrotreatment, which together provide a high degree of removal of metals, sulfur, nitrogen and asphaltenes, and also reduce the formation of deposits and sludge, resulting in hydrotreated hydrocarbon with improved properties is obtained.

It should be noted that sludge and deposits are compounds that are obtained during the hydrotreatment reaction due to hydrocracking of resins and light asphaltene fractions, as well as due to dealkylation of heavy asphaltenes present in heavy hydrocarbons, sedimentation and formation of sludge occur due to a decrease in their mutual solubility . Another source of scale formation is abrasion of the hydroprocessing catalyst during operation, which mainly occurs in fluidized bed reactors.

It is also important to note that the reaction in accordance with the present invention proceeds at low pressures, so that the hydrocracking of heavy fractions of heavy oil hydrocarbons proceeds moderately, so that a moderate conversion (conversion) of the feed is also provided. It was found that when the method is carried out in the low pressure mode, this contributes to the formation of deposits and sludge, therefore, the method in accordance with the present invention is carried out by combining the low pressure mode of operation, the type of reactor and the type of feedstock for hydroprocessing, which together limit formation of deposits and sludge.

The authors of the present invention unexpectedly found that the properties of the raw materials are improved and the formation of deposits and sludge in the product is reduced due to the reaction in two stages with a low pressure mode of operation, as described below:

FRAME I General low-pressure operation Parameter Total operating range Pressure, kg / cm ² 40-130 Temperature ° C 320-450 Volumetric speed (LHSV), hour ^-1 0.2-3.0 The ratio of hydrogen / hydrocarbon (H ₂ / HC), normal liters per liter of raw materials (nl / l) 350-1,200

More specifically, the authors of the present invention have found that the preferred low-pressure operating modes for each operation are as follows:

FRAME II General low-pressure operation in operation I Parameter Working range Preferred Working Range Catalyst Selective to hydrodemetallization of hydrocarbons and to hydrocracking of asphaltenes Pressure, kg / cm ² 40-130 45-90 Temperature ° C 320-450 350-450 Volumetric speed (LHSV), hour ^-1 0.2-3.0 0.2-2 The ratio of hydrogen / hydrocarbon (N ₂ / NS), nl / l 350-1,200 450-1,050

FRAME II General low-pressure operation in operation II Parameter Working range Preferred Working Range Catalyst Selective to hydrodesulfurization and hydrodenitrogenation of hydrocarbons Pressure, kg / cm ² 40-130 45-90 Temperature ° C 320-450 330-450 Volumetric speed (LHSV), hour ^-1 0.2-3.0 0.2-2 The ratio of hydrogen / hydrocarbon (N ₂ / NS), nl / l 350-1,200 450-1,050

It is important to note that the hydroprocessing catalysts used in the two stages of the reaction differ in their physical, chemical, and textural properties, which leads to different selectivities for the removal of pollutants.

Hydrocarbons that have been hydrotreated by the process of the present invention have substantially improved properties compared to the heavy hydrocarbon fed to the process inlet, the improvement mainly affecting the following specific properties: the specific gravity in degrees of the American Petroleum Institute is increased by approximately 15 degrees and the content reduced distillates at 538 ° C increases approximately by 50% by volume compared with the loading material with a minimum content Research Institute of sediments and sludge.

It should be borne in mind that although they remove large quantities of impurities from a heavy hydrocarbon oil, the method in accordance with the present invention, due to the fact that it is carried out using a combination of low pressure operation, type of reactor and type of feedstock for hydrotreating, is completely unexpectedly, it is possible to maintain a low content of sediment and sludge without blocking caused by these materials during continuous operation.

According to the method in accordance with the present invention, the mixture of heavy hydrocarbons of oil and hydrogen is preheated so that it reaches the reaction temperature in a direct fire heater.

In the first stage of the reaction, a mixture of heavy hydrocarbons of oil and hydrogen is fed into a catalytic hydroprocessing reactor under conditions necessary mainly for the hydrodemetallization and hydrocracking of asphaltenes, which results in a decrease in the amount of heavy metals (nickel and vanadium) and an increase in the volume of distillates. Other reactions take place in parallel, such as hydrodesulfurization and hydrodenitrogenation.

Then, the output stream from the first reaction stage is directed to the second stage of the hydrotreatment reaction, where the main reactions are deep hydrodesulfurization and hydrodenitrogenation, as a result of which the total sulfur content is reduced to the level necessary for processing the product in a conventional oil refining scheme. Other reactions, such as hydrodemetallization and hydrocracking, proceed in parallel.

The hydrodemetallization catalyst (HDM) used in the first reaction step is a nickel and molybdenum catalyst, while the hydrodesulfurization catalyst (HDS) used in the second reaction step is a cobalt and molybdenum catalyst; both catalysts having gamma-aluminum supports.

The HDM catalyst has small surface area and pore diameter, and the pore volume is larger than the HDS catalyst. The pores of the HDM catalyst are most concentrated in the region of 100 to 250 angstroms (~ 70%), while the pores of the HDS catalyst are most concentrated in the region of 50 to 100 angstroms (~ 60%). An HDM catalyst has approximately 20% pores with sizes greater than 250 angstroms, while an HDS catalyst has less than 0.5% pores with sizes greater than 250 angstroms (see Tables 3 and 18).

The principal advantage of the present invention is that the method of catalytic hydroprocessing of heavy oil hydrocarbons, which have a specific gravity in degrees of the American Petroleum Institute of less than 25 °, and a reduced distillate content of 538 ° C of less than 80% by volume, is carried out by a combination of modes low pressure operations, such as a reactor and a type of hydroprocessing feedstock, which together provide increased removal of metals, sulfur, nitrogen and asphaltenes, and also reduce the formation of deposits and sludge, which allows to obtain a hydrotreated hydrocarbon with improved properties. The low pressure mode of operation in which the method of the present invention is carried out mainly corresponds to that indicated in Frame I, the specific or preferred ranges of the low pressure mode of operation for each reaction step being as shown in Frame II and III.

The following describes the sequence diagram of operations shown in figure 1, which represents the best known to the applicant the way of implementing the method in accordance with the present invention.

The heavy oil hydrocarbon is sent via line (1) to the feed tank (2) and is pumped to the line (7) using a pump (3) to mix with hydrogen, which contains part (5) of fresh hydrogen and part (36) of recycle hydrogen.

Fresh hydrogen is fed via line (4) and divided into two parts, the first part (5) being introduced together with recycled hydrogen (36) into a heavy oil hydrocarbon (1) to obtain a mixture (8) for the catalytic reactor (12) of stage I , and the second part (6) is sent to the catalytic reactor (15) of stage II.

The feed mixture (8) is preheated with the outlet stream (16) from the reactor using a heat exchanger (9), and then the temperature of the mixture is raised using a direct fire heater (10). The heated effluent (11) is sent to the catalytic reactor (12) of stage I at the reaction temperature indicated in Frame II in order to carry out mainly hydrodemetallization and hydrocracking reactions, as well as, to a lesser extent, additional hydrodesulfurization and hydrodenitrogenation reactions.

The hydrotreated product (13) in the first stage of the reaction is mixed with another part of the fresh hydrogen entering the line (6) to form a stream (14) which is introduced into the catalytic reactor (15) of stage II to carry out mainly hydrodesulfurization reactions and hydrodenitrogenation, as well as, to a lesser extent, additional hydrodemetallization and hydrocracking reactions, in the low pressure mode of operation shown in Frame III.

The product (16), which has undergone hydrotreatment in two stages of the reaction, is cooled using a heat exchanger (9), washing water (18) is introduced into it, and it is additionally cooled using a heat exchanger (17), and then it is sent to a high pressure separator (19), which produce the separation of the liquid - steam.

The separated steam (21), which mainly contains hydrogen and hydrogen sulfide, is divided into two parts, and: a) the first part (23) of the steam is sent to the compressor flow tank (32), where light liquid hydrocarbons (33) are separated from the hydrogen enriched a stream (34) that is reintroduced into the process using a compressor (35); b) the second part (27) of the steam is sent for desulfurization of sour gas. In addition, in the specified high-pressure separator, an excess of residual acidic water is obtained, which is sent to water purification.

The liquid outlet stream (22), which contains ammonium salts dissolved in acidic water, is separated from the hydrotreated product and sent to water purification.

A liquid outlet stream (20) from the high-pressure separator (19) is introduced into the expansion valve (24) to obtain a liquid-vapor stream (25), which is introduced into the second low-pressure separator (26), from which the stream (28) ) the residual gas that is sent to the gas treatment plant to recover the light hydrocarbons obtained by the method in accordance with the present invention.

The liquid output stream (30) obtained in the low-pressure separator (26) is pumped into the battery by a pump (31) to process it according to the usual oil refining scheme, or sent for sale as a light oil hydrocarbon. In addition, the excess residual acidic water (29) obtained in the specified separator, is sent to the water treatment.

Examples

For a better understanding of the method in accordance with the present invention, examples are given below that are not restrictive.

Example 1

A specific example of the application of the method of catalytic hydroprocessing of heavy oil hydrocarbons in accordance with the present invention to obtain a typical feedstock for a conventional oil refining scheme or to obtain a marketable hydrocarbon with improved properties is an example of a hydrotreatment of heavy crude oil with the specific properties shown in Table 1 , due to the combination of the low-pressure operating mode, which is shown in Table 2, in two stages of the reaction with a fixed catalyst bed, using using a hydrodemetallization catalyst (HDM) and a hydrodesulfurization catalyst (HDS), the properties of which are shown in Table 3; moreover, this combination unexpectedly provides a significant removal of metals, all sulfur, asphaltenes and all nitrogen, however, with an unexpected decrease in the formation of deposits and sludge, a hydrotreated hydrocarbon with improved properties is obtained, which are shown in Table 4.

Table 1 shows that the feed does not contain deposits and sludge, as they are formed during the implementation of each of the reactions of the hydroprocessing method.

Table 4 shows that after two stages of the reaction, the metal content decreases from 353.5 wppm (parts by weight per million) to 113.8 wppm, the sulfur content decreases from 3.44% by weight to 0.66% by weight, the asphaltene content decreases from 12.4% by weight to 4.67% by weight and the total nitrogen content decreases from 3,700 wppm to 2,045 wppm.

Table 1 Properties of heavy crude oil The properties ASTM method Values Specific gravity degrees API D-287 20.91 Total sulfur, weight. % D-4294 3.44 Total Nitrogen, wppm D-4629 3,700 Asphaltenes, weight. % D-3279 12.4 Metals, wppm Ni + V 353.5 Deposits and sediment, weight. % D-487 00.0 Composition, volume. % IBP fraction 170 ° C 15.6 Fraction 170-360 ° C 25.5 Fraction 360-538 ° С 21.4 Fraction 53 ° 8С ⁺ 37.5 Fraction IBP-538 ° C ⁺ 62.5

table 2 Low pressure mode for catalytic hydroprocessing of heavy crude oil in two stages of the reaction with a fixed catalyst bed Stage Mode of operation I II Temperature ° C 400 400 Pressure, kg / cm ² 70 70 LHSV, hour ^-1 1.0 0.5 The ratio of H ₂ / NS, nl / l 890 890

In addition, these tables show that when significant removal of contaminants is achieved by hydrotreating (HDT) heavy crude oil, the formation of deposits and sludge corresponds to 0.65% by weight, which is less than an acceptable limit value of 0.8% by weight, allowing maintain the continuity of these processes.

The same tables show that the specific gravity in degrees of the American Petroleum Institute increases from 20.91 to 28.93 ° API, and the content of reduced distillates at 538 ° C increases from 62.5 to 88.1% by volume, and provide a feed conversion of 68.3% by volume.

Table 3 Properties of HDM and HDS catalysts used in each reaction step The properties HDM catalyst HDS catalyst Reaction stage I II Physical properties Particle size cm 0.254 0.158 Surface area, m ² / g 175 248 Pore volume, cm ³ / g 0.56 0.51 The average pore diameter, Å 127 91 Pore size distribution, volume. % <50 Å 3.09 18.32 50-100 Å 6.71 58.45 100-250 Å 69.09 22.84 250-500 Å 02/15 0.23 500-2000 Å 6.09 0.16 > 2000 Å - - Chemical properties Molybdenum, weight. % 10.66 12.89 Nickel, weight. % 2.88 - Cobalt, weight. % - 2.5 Sodium, wppm 412 - Titanium oxide, weight. % 3.73 3.2

Table 4 Properties and composition of the hydrotreated distillate The properties ASTM method Stage I Stage II Number of reactors one one Specific gravity, degrees API D-287 25.2 28.93 Total sulfur, weight. % D-4294 1.77 0.66 Total Nitrogen, wppm D-4629 2,616 2,045 Asphaltenes, wt.% D-3279 8.29 4.67 Metals, wppm Ni + V 228.7 113.8 Deposits and sediment, weight. % D-4870 0.12 0.65 Conversion, volume. % - 36.0 68.3 Composition, volume. % Fraction IBP-170 ° C 15.6 19.3 Fraction 170-360 ° C 28.1 37.6 Fraction 360-538 ° С 32,3 31.2 Fraction 538 ° C ⁺ 24.0 11.9 IBP-538 ° C ⁺ fraction 76.0 88.1

The results show that the method of catalytic hydroprocessing of heavy hydrocarbons in accordance with the present invention, by combining a low pressure operating mode, a reactor type and a type of hydroprocessing feedstock, allows the removal of significant amounts of contaminants and completely unexpectedly limits the formation of deposits and sludge to levels below acceptable limit level, which guarantee the continuity of the industrial production process, and a significant degree of raw material versions, which allows obtaining hydrotreated hydrocarbon with improved properties, with such ranges of pollutants, specific gravity in degrees of the American Petroleum Institute and distillates, which are usually found in raw materials suitable for typical oil refining schemes.

In this regard, it is important to note that the conversion of raw materials can be calculated using the following formula:

Conversion = [(fraction 538 ° C ⁺ in feed) - (fraction 538 ° C ⁺ in product)] / (fraction 538 ° C ⁺ in feed) × 100

Example 2

Another specific application of the method for catalytic hydrotreatment of heavy oil hydrocarbons in accordance with the present invention is the case of hydrotreatment of heavy crude oil of Example 1 with the specific properties shown in Table 1, due to the combination of low pressure operation, the parameters of which are shown in Table 5, in catalytic system, in two stages of reaction with a fixed catalyst bed and using HDM and HDS catalysts of example 1, the properties of which are shown in Table 3; this combination clearly demonstrates the limitation of the formation of deposits and sludge, and also provides a significant removal of metals, all sulfur, asphaltenes and all nitrogen, and obtaining a hydrotreated hydrocarbon with the improved properties shown in Table 6.

In contrast to the previous example, in this specific application of the invention, only the pressure (to a lower value) and the space velocity (to a higher value) are changed in the second stage of the reaction of the process in order to make the process less sharp, but other parameters are preserved without any changes low pressure operating mode, type of reactor and type of feedstock for hydrotreatment.

Table 5 Low pressure operation during catalytic hydroprocessing of heavy crude oil in two stages of the reaction with a fixed catalyst bed Stage Mode of operation I II Temperature ° C 400 400 Pressure, kg / cm ² 70 54 LHSV, hour ^-1 1.0 1.0 The ratio of H ₂ / HC, nl / l 890 890

Table 6 shows that the metal content decreased not so sharply as in example 1, but significantly, so that after two stages of the reaction, the metal content decreased from 353.5 wppm to 135 wppm, the sulfur content decreased from 3.44% by weight to 0.802% by weight by weight, the asphaltene content decreased from 12.4% by weight to 5.41% by weight and the total nitrogen content decreased from 3,700 wppm to 2,310 wppm.

Moreover, this table shows that even after significant removal of contaminants as a result of HDT heavy crude oil, the formation of deposits and sludge surprisingly corresponds to 0.32% by weight; this value is significantly less than the acceptable limit value of 0.8% by weight, which allows to maintain continuity of work in this type of process.

Table 6 Properties and composition of hydrotreated distillate The properties ASTM method Stage I Stage II Number of reactors one one Specific gravity, degrees API D-287 25.2 27.52 Total sulfur, weight. % D-4294 1.77 0.802 Total Nitrogen, wppm D-4629 2,616 2,310 Asphaltenes, weight. % D-3279 8.29 5.41 Metals, wppm Ni + V 228.7 135 Deposits and sediment, weight. % D-4870 0.12 0.32 Conversion, volume. % 36.0 42.4 Composition, volume. % Fraction IBP-170 ° C 15.6 16.8 Fraction 170-360 ° C 28.1 28.6 Fraction 360-538 ° С 32.3 33.0 Fraction 538 ° C ⁺ 24.0 21.6 IBP-538 ° C ⁺ fraction 76.0 78.4

This table shows that the specific gravity in degrees of the American Petroleum Institute increases from 20.91 to 27.52 ° API and the content of reduced distillates at 538 ° C increases from 62.5 to 78.4% by volume, which makes it possible to obtain a feed conversion of 42.4% by volume, which is less than the conversion obtained in example 1, however, the conversion is still significant, which confirms the possibility of reducing the sharpness of the process.

The results confirm that the present invention, in accordance with one of its preferred modalities, by reducing the sharpness of the process of catalytic hydroprocessing of heavy hydrocarbons by combining a low pressure operating mode, a reactor type and a type of hydroprocessing feedstock, unexpectedly limits the formation of sediment and sludge to levels significantly less than an acceptable limit value, which guarantee the continuity of the industrial production process, despite the fact that o it allows you to remove significant amounts of contaminants and provides a significant conversion of the load, while it is possible to obtain a hydrotreated hydrocarbon with improved properties.

Example 3

Another specific application of the present invention is the production of a typical feedstock for a conventional oil refining scheme or for the sale of a product as an improved hydrocarbon, which is carried out by catalytic hydroprocessing of heavy crude oil of Examples 1 and 2 with the specific properties shown in Table 1, by combining operating conditions with low pressure, the parameters of which are shown in Table 7, in the catalytic system, in two stages of the reaction with a fixed catalyst bed and using zovaniem HDM and HDS catalysts of examples 1 and 2, the properties of which are given in Table 3; moreover, this combination shows that the formation of deposits and sludge is limited in addition to the substantial removal of metals, all sulfur, asphaltenes and all nitrogen and to obtain a hydrotreated hydrocarbon with improved properties shown in Table 8.

In contrast to Example 1, in this specific application of the present invention, only the space velocity is changed (to a higher value, as in Example 2) in the second stage of the reaction of the process, in order to make the process less sharp than in Example 1, but sharper, than in example 2, while maintaining, without any change, other parameters of the low pressure operating mode, such as a reactor and the type of feedstock for hydroprocessing.

Table 7 Low pressure operation during catalytic hydroprocessing of heavy crude oil in two stages of the reaction with a fixed catalyst bed Stage Mode of operation I II Temperature ° C 400 400 Pressure, kg / cm ² 70 70 LHSV, hour ^-1 1.0 1.0 The ratio of H ₂ / NS, nl / l 890 890

Table 8 shows that the metal content decreased after two stages of the reaction, although not as sharply as in example 1, from 353.5 wppm to 119.4 wppm, the sulfur content decreased from 3.44% by weight to 0.75% by weight, the asphaltene content decreased from 12.4% by weight to 4.72% by weight and the total nitrogen content decreased from 3,700 wppm to 2,075 wppm.

Moreover, this table shows that even after significant removal of contaminants as a result of HDT heavy crude oil, the formation of deposits and sludge corresponds to 0.53% by weight; this value is significantly less than the acceptable limit value of 0.8% by weight, which allows to maintain continuity of work in this type of process.

Table 8 Properties and composition of hydrotreated distillate The properties ASTM method Stage I Stage II Number of reactors one one Specific gravity, degrees API D-287 25.2 27.99 Total sulfur, weight. % D-4294 1.77 0.75 Total Nitrogen, wppm D-4629 2.616 2,075 Asphaltenes, weight. % D-3279 8.29 4.72 Metals, wppm Ni + V 228.7 119.4 Deposits and sediment, weight. % D-4870 0.12 0.53 Conversion, volume. % 36.0 56.0 Composition, volume. % Fraction IBP-170 ° C 15.6 17.5 Fraction 170-360 ° C 28.1 33.9 Fraction 360-538 ° С 32.3 32.1 Fraction 538 ° C ⁺ 24.0 16.5 IBP-538 ° C ⁺ fraction 76.0 83.5

This table shows that the specific gravity in degrees of the American Petroleum Institute increases from 20.91 to 27.99 ° API and the content of reduced distillates at 538 ° C increases from 62.5 to 83.5% by volume, resulting in a feed conversion of 56.0% by volume, which is less than the conversion obtained in example 1, and more than in example 2, however, the conversion is still acceptable, which confirms the possibility of using the process of intermediate sharpening in comparison with examples 1 and 2.

The obtained results confirm that the method for catalytic hydroprocessing of heavy hydrocarbons in accordance with the present invention with the substantial removal of pollutants in an unexpected way allows limiting the formation of deposits and sludge to levels significantly less than an acceptable limit level, which guarantees the continuity of the industrial production process and the preparation of hydrocarbon-treated hydrocarbon with improved properties, with levels of pollutants, specific destiny density in degrees of the American Petroleum Institute and the content of distillates in the ranges in which the corresponding raw material parameters are usually found for typical well-known oil refining schemes.

Example 4

An additional case of the specific application of the present invention is the case of hydroprocessing of heavy crude oil of examples 1-3 in two runs with specific properties of crude oil, are shown in Table 1, due to the combination of low pressure operation, the parameters of which are shown in Table 9, in a catalytic system, in two stages of the reaction with a fixed catalyst bed and using HDM and HDS catalysts of examples 1-3, the properties of which are shown in Table 3; moreover, this combination unexpectedly limits the formation of deposits and sludge, so that there is a viable option that allows you to get the raw materials typical for conventional oil refining schemes or to sell the product in the form of hydrotreated hydrocarbon with improved properties, which are shown in Table 10.

In contrast to Example 1, in accordance with this specific application of the present invention, the temperature (to lower values), pressure (to lower values) and space velocity (to a higher value) are changed in the second stage of the reaction of the process to make the process even less sharp , and retain without any change other parameters of the low-pressure operation mode, type of reactor, and type of feedstock for hydroprocessing.

Table 9 Low pressure operation during catalytic hydroprocessing of heavy crude oil in two stages of the reaction with a fixed catalyst bed Stage Mode of operation I II III Temperature ° C 400 360 380 Pressure, kg / cm ² 70 54 54 LHSV, hour ^-1 1.0 1.0 1.0 The ratio of H ₂ / HC, nl / l 890 890 890

Table 10 shows that the metal content decreased, although not as sharply as in example 1, but significantly, so that after HDT the metal content decreases from 353.5 wppm to 149.7 and 138.4 wppm, the sulfur content decreases from 3.44% by weight to 1.12 and 0.89% by weight, the asphaltene content decreases from 12.4% by weight to 6.41 and 5.65% by weight and the total nitrogen content decreases from 3,700 wppm to 2,381 and 2,315 wppm, for each run at operating temperatures respectively 360 and 380 ° C in the second reaction stage.

Table 10 Properties and composition of hydrotreated distillate The properties ASTM method Stage 1 Stage II Working temperature ° C 400 360 380 Number of reactors one one one Specific gravity, degrees API D-287 25.2 26.28 26.72 Total sulfur, weight. % D-4294 1.77 1.12 0.89 Total Nitrogen, wppm- D-4629 2,616 2,381 2,315 Asphaltenes, weight. % D-3279 8.29 6.41 5.65 Metals, wppm Ni + V 228.7 149.7 138.4 Deposits and sediment, weight. % D-4870 0.12 0.21 0.26 Conversion, volume. % 36.0 36.3 39.7 Composition, vol.% Fraction IBP-170 ° C 15.6 16.2 16.5 Fraction 170-360 ° C 28.1 28.0 28.3 Fraction 360-538 ° С 32.3 31.9 32.6 Fraction 538 ° C ⁺ 24.0 23.9 22.6 IBP-538 ° C ⁺ fraction 76.0 76.1 77.4

Moreover, this table shows that even after significant removal of contaminants as a result of HDT heavy crude oil, the formation of deposits and sludge unexpectedly corresponds to only 0.21 and 0.26% by weight for each run in the second stage, at reaction temperatures of 360 and 380, respectively ° C; this value is significantly less than the acceptable limit value of 0.8% by weight, which allows to maintain continuity of work in this type of process.

The same table shows that for each run, the specific gravity in degrees of the American Petroleum Institute increases from 20.91 to 26.28 and 26.72 ° API and the content of reduced distillates at 538 ° C increases from 62.5 to 76.1 and 77.4% by volume, resulting in a conversion of raw materials 36.3 and 39.7% by volume, which is less than the conversion obtained in example 1, however, the conversion is still acceptable, which confirms the possibility of reducing the sharpness of the process.

The results confirm that the present invention, in its two preferred embodiments, by reducing the sharpness of the process of catalytic hydroprocessing of heavy hydrocarbons by combining a low pressure operating mode, type of reactor and type of hydroprocessing feedstock, unexpectedly reduces the formation of sediment and sludge to levels substantially less than an acceptable limit value, which guarantee the continuity of the industrial production process, despite the fact that it allows you to remove ety of pollutants and provides substantial load-conversion, thus possible to obtain hydrotreated hydrocarbon of improved properties.

Example 5

Another case of the specific application of the present invention is the case of obtaining a typical feedstock for a conventional oil refining scheme or the case of selling a product in the form of a hydrocarbon with improved properties as a result of hydroprocessing in two runs of the residue from atmospheric distillation with the specific properties shown in Table 11 due to the combination low pressure operating mode, the parameters of which are given in Table 12, in two stages of the reaction with a fixed catalyst bed and using a hydrodemetallization catalyst (HDM) and a hydrodesulfurization catalyst (HDS) of the above examples, the properties of which are shown in Table 3; moreover, this combination shows that despite the significant removal of metals, all sulfur, asphaltenes and all nitrogen, the formation of deposits and sludge is unexpectedly limited, which allows to obtain hydrotreated hydrocarbon with improved properties shown in Table 13.

Unlike the previous examples, for this specific application of the invention, a much heavier oil hydrocarbon (with a lower) specific gravity value, with a higher content of pollutants and with a lower content of reduced distillates at 538 ° C) was used, and the operating mode parameters were changed low pressure similarly to the examples described above, and used the same type of reactor.

Table 11 Properties of the residue from distillation at atmospheric pressure The properties ASTM method Values Specific gravity, degrees API D-287 7.14 Total sulfur, weight. % D-4294 4.60 Total Nitrogen, wppm D-4629 5,086 Asphaltenes, weight. % D-3279 17.74 Metals, wppm Ni + V 575.6 Deposits and sediment, weight. % D4870 <0.01 Composition, volume. % Fraction IBP-170 ° C 0.0 Fraction 170-360 ° C 1.1 Fraction 360-538 ° С 34.9 Fraction 538 ° С ⁺ 64.0 Fraction IBP-538 ° C ⁺ 36.0

Table 11 shows that the feedstock is almost free of deposits and sludge, since they are formed during each of the reactions of the hydroprocessing process.

Table 12 Low pressure operation during catalytic hydroprocessing of the residue from distillation at atmospheric pressure in two stages of the reaction with a fixed catalyst bed Stage Mode of operation I II II Temperature ° C 400 400 400 Pressure, kg / cm ² 70 70 70 LHSV, hour ^-1 1.0 1.0 0.5 The ratio of H ₂ / NS, nl / l 890 890 890

Table 13 shows that the metal content after the HDT unexpectedly decreases, as in Example 1, from 575.6 wppm to 277.8 and 217.5 wppm, the sulfur content decreases from 4.60% by weight to 1.18 and 1.02% by weight, the asphaltene content decreases from 17.74% by weight to 10.8 and 9.15% by weight and the total nitrogen content decreases from 5.086 wppm to 3.040 and 2.706 wppm for each run at the corresponding operating volumetric speeds (LHSV) of 1.0 and 0.5 hr ^-1 in the second reaction stage.

Moreover, this table shows that even after significant removal of contaminants as a result of the HDT residue from distillation at atmospheric pressure, the formation of deposits and sludge unexpectedly corresponds to 0.035 and 0.044% by weight for each run in the second stage, at the corresponding volumetric velocities ( LHSV) of 1.0 and 0.5 hour ^-1 ; these values are significantly less than the acceptable limit value of 0.8% by weight, which allows maintaining the continuity of work in this type of process.

Table 13 Properties and compositions of the hydrotreated residue The properties ASTM method Stage 1 Stage II Number of reactors one one one LHSV, hour ^-1 1.0 1.0 0.5 Specific gravity, degrees API D-287 13.9 16.85 17.73 Total sulfur, weight. % D-4294 42.47 1.18 1.02 Total Nitrogen, wppm D-4629 4,520 3,040 2,706 Asphaltenes, weight. % D-3279 12.76 10.8 9.15 Metals, wppm Ni + V 364.9 277.8 217.5 Deposits and sediment, weight. % D-4870 0.028 0.035 0.044 Conversion, volume. % 22.3 37.7 51.7 Composition, volume. % Fraction IBP-170 ° C 1.7 3.7 3.8 Fraction 170-360 ° C 12.9 16.3 20.6 Fraction 360-538 ° С 35.7 40.1 44.7 Fraction 538 ° C ⁺ 49.7 39.9 30.9 IBP-538 ° C ⁺ fraction 50.3 60.1 69.1

The same table shows that for each run, the specific gravity in degrees of the American Petroleum Institute increases from 7.14 to 16.85 and 17.73 ° API, and the content of reduced distillates at 538 ° C increases from 36.0 to 60.1 and 69.1% by volume, resulting in a conversion raw materials 37.7 and 51.7% by volume; these conversion levels are lower than those obtained in example 1, but they are still sufficient, which confirms the possibility of hydroprocessing a much heavier hydrocarbon oil with a lower specific gravity, with a lot more pollutants and a lower content of reduced distillates at 538 ° C.

The obtained results confirm that the present invention in its two preferred embodiments when hydrotreating an extremely heavy oil hydrocarbon by using a combination of a low pressure operating mode, a reactor type and a type of hydrotreating feedstock, removes significant amounts of contaminants and unexpectedly limits the formation of deposits and sludge to levels significantly lower than the acceptable limit value, which guarantee the continuity of the industrial process production, which also results in a significant conversion of raw materials, which allows obtaining hydrotreated hydrocarbon with improved properties, having levels of pollutants, specific gravity in degrees from the American Petroleum Institute and the content of distillates in the ranges in which the parameters of raw materials for typical known schemes are usually found oil refining.

Example 6

Another specific application of the catalytic hydrotreatment method for heavy oil hydrocarbons in accordance with the present invention is an application in accordance with which the atmospheric pressure distillation residue is hydrotreated in Example 5 with the specific properties shown in Table 11 by combining a low pressure, the parameters of which are shown in Table 14, in the catalytic system, in two stages of the reaction with a fixed catalyst bed and using HDM and HD S catalysts of the previous examples, the properties of which are shown in Table 3; moreover, this combination allows you to limit the formation of deposits and sludge, as well as to ensure significant removal of metals, all sulfur, asphaltenes and all nitrogen and get past hydrotreatment hydrocarbon with improved properties, are shown in Table 15.

Unlike the previous example, in this example, only the temperature is changed (to lower and higher values) in order to change the severity of the process in both directions, and other parameters of the low-pressure operation mode, type of reactor, and type of feedstock for hydrotreatment are kept without any changes.

Table 15 shows that the metal content after HDT decreases, as in examples 1 and 5, from 575.6 wppm to 304 and 231.9 wppm, the sulfur content decreases from 4.60% by weight to 1.32 and 0.95% by weight, the asphaltene content decreases from 17.74% by weight to 11.25 and 9.21% by weight and the total nitrogen content decreases from 5.086 wppm to 3.340 and 2.690 wppm, for each run, at the corresponding operating temperatures of 380 and 420 ° C in the second reaction stage.

Moreover, this table shows that, despite the significant removal of contaminants after the HDT residue from distillation at atmospheric pressure, the formation of deposits and sludge unexpectedly corresponds to 0.03 and 0.09% by weight for each run in the second reaction stage, at the corresponding reaction temperatures 380 and 420 ° C; unexpectedly, these values are less than the acceptable limit value of 0.8% by weight, which allows to maintain continuity of work in this type of process.

Table 14 Low pressure operation during catalytic hydroprocessing of the residue from distillation at atmospheric pressure in two stages of the reaction with a fixed catalyst bed Stage Mode of operation I II II Temperature ° C 400 380 420 Pressure, kg / cm ² 70 70 70 LHSV, hour ^-1 1.0 1.0 1.0 The ratio of H ₂ / NS, nl / l 890 890 890

The same table shows for each run that the specific gravity in degrees of the American Petroleum Institute increases from 7.14 to 14.72 and 19.39 ° API and the content of reduced distillates at 538 ° C increases from 36.0 to 56.0 and 66.0% by volume, resulting in a conversion of raw materials 31.3 and 46.9% by volume; these conversion levels are lower than those obtained in examples 1 and 5, but are still significant.

The obtained results confirm that the present invention, in its two preferred embodiments, when hydrotreating an extremely heavy oil hydrocarbon by combining a low pressure operating mode, a reactor type and a type of hydrotreating feedstock, allows significant amounts of contaminants to be removed and limits the formation of deposits and sludge to levels significantly lower than the acceptable limit value, which guarantees the continuity of the industrial production process, as a result which also receive substantial conversion of raw materials to provide hydrotreated hydrocarbon of improved properties.

Table 15 Properties and compositions of the hydrotreated residue The properties ASTM method Stage 1 Stage II Number of reactors one one one Temperature ° C 400 380 420 Specific gravity, degrees API D-287 13.94 14.72 19.39 Total sulfur, weight. % D-4294 2.47 1.32 0.95 Total Nitrogen, wppm D-4629 4,520 3.340 2.690 Asphaltenes, weight. % D-3279 12.76 11.25 9.21 Metals, wppm Ni + V 364.9 304 231.9 Deposits and sediment, weight. % D-4870 0.028 0.03 0.09 Conversion, volume. % 22.3 31.3 46.9 Composition, volume. % Fraction IBP-170 ° C 1.7 2.8 2.8 Fraction 170-360 ° C 12.9 15.9 21 Fraction 360-538 ° С 35.7 37.3 42.2 Fraction 538 ° C ⁺ 49.7 44.0 34.0 IBP-538 ° C ⁺ fraction 50.3 56.0 66.0

Example 7

Another specific application of the method for catalytic hydroprocessing of heavy oil hydrocarbons in accordance with the present invention is the application that was carried out by hydroprocessing a residue from atmospheric distillation with specific properties shown in Table 16, which differ from the properties of the material used in examples 5 and 6 due to the combination of the low pressure operating mode, the parameters of which are given in Table 17, of the catalytic system, in two stages of the reaction izhnym catalyst layer and using the two stages of the reaction mixture hydrocracking catalyst (used and new) in a proportion of 70/30% by weight of used and fresh catalyst, with the properties shown in Table 18; this combination demonstrates a significant reduction in the formation of deposits and sludge, as well as a significant removal of metals, all sulfur, asphaltenes and all nitrogen, which makes it possible to obtain hydrotreated hydrocarbon with improved properties shown in Table 19.

In contrast to Examples 5 and 6, for this specific application of the invention, the same type of hydroprocessing feedstock was used, but slightly less heavy (with a higher specific gravity, lower amount of pollutants and a higher content of reduced distillates at 538 ° C) , with a change in the space velocity (to lower values) and the hydrogen / hydrocarbon ratio (to lower values); in addition, hydrogen with a different degree of purity was used in this modality in order to vary the severity of the process in both directions, while other parameters of the low-pressure operating mode were supported similarly to the examples given earlier and a reactor of the same type was used.

Table 16 Properties and compositions of the hydrotreated residue The properties ASTM method Values Specific gravity, degrees API D-287 9-25 Total sulfur, weight. % D-4294 3.74 Total Nitrogen, wppm D-4629 4.440 Ramsbottom carbon, weight. % D-524 13.39 Asphaltenes, weight. % D-3279 10.18 Metals, wppm Ni + V 353 Deposits and sediment, weight. % D4870 0.0 Fraction 538 ° С ⁺ , volume. % 56.2 Fraction IBP-538 ° C ⁺ , volume. % 43.8

Table 17 Low pressure operation during catalytic hydroprocessing of the residue from distillation at atmospheric pressure in two stages of the reaction with a fixed catalyst bed Stage Mode of operation I and II I and II I and II Temperature ° C 400 400 400 Pressure, kg / cm ² 70 70 70 LHSV, hour ^-1 0.284 0.33 0.33 The ratio of H ₂ / NS, nl / l 534 534 534 The purity of hydrogen, mol. % 75 75 one hundred

Table 16 shows that the feed does not contain deposits and sludge, as they are formed during each reaction of the hydroprocessing process.

Table 19 shows that the metal content after the HDT unexpectedly decreases similarly to the previous examples, from 353 wppm to 126, 176 and 120 wppm, the sulfur content decreases from 3.74% by weight to 1.297, 1.75 and 1.71% by weight, the asphaltene content decreases from 10.18% by weight to 5.64, 5.41 and 5.19% by weight and the total nitrogen content decreases from 4,400 wppm to 3,515, 3,990 and 3,740 wppm, for each run at corresponding different space velocities and different hydrogen purities.

Moreover, this table shows that, despite the significant removal of contaminants after the HDT residue from distillation at atmospheric pressure, the formation of deposits and sludge, surprisingly, corresponds to a value of less than 0.05% by weight for three runs in the second stage of the reaction; this value is significantly less than the acceptable limit value of 0.8% by weight, which allows to maintain continuity of work in this type of process.

Table 18 Properties of used and new HDM catalysts used in each reaction step The properties Catalyst Used New Physical properties Size inches 1/32 1/32 Surface area, m ² / g 69.5 158 Pore volume, cm ³ / g 0.27 0.67 The average pore diameter, Å 147 148 Pore size distribution, volume. % <50Å 2.45 0.0 50-100 Å 53.94 40.0 100-250 Å 34.0 52.11 250-500 Å 4.88 4.71 500-2000 Å 4.73 3.18 Chemical properties Molybdenum, weight. % 3.64 8.33 Nickel, weight. % 2.78 2.68 Vanadium, weight. % 8.64 - Sodium, weight. % 0.18 0.037 Iron, weight. % 0.11 - Sulfur, weight. % 17.17 - Carbon, weight. % 22.59 -

Table 19 Properties and compositions of the hydrotreated residue The properties ASTM method Hydrotreated Product (Stage II) LHSV, hour ^-1 0.284 0.33 0.33 The purity of hydrogen, mol. % 75 75 one hundred Specific gravity, degrees API D-287 16.70 15.39 15.70 Total sulfur, weight. % D-4294 1.297 1.75 1.71 Total Nitrogen, wppm D-4629 3,515 3,990 3,740 Asphaltenes, weight. % D-3279 5.64 5.41 5.19 Metals, wppm Ni + V 126 176 120 Deposits and sediment, weight. % D-8470 <0.05 <0.05 <0.05

This table shows for each run that the specific gravity in degrees of the American Petroleum Institute increases from 9.25 to 16.70, 15.39, and 15.70 ° API.

The obtained results confirm that the present invention, in its three preferred embodiments, when hydroprocessing a heavy hydrocarbon oil, due to combinations of the low-pressure operating mode, type of reactor, and type of feedstock for hydroprocessing, allows to remove significant amounts of contaminants and completely reduces the formation of deposits and sludge, to levels significantly lower than an acceptable limit value, which guarantees the continuity of the industrial production process, which Will receive the hydrotreated hydrocarbon of improved properties.

Example 8

Another specific application of the method for catalytic hydroprocessing of heavy oil hydrocarbons in accordance with the present invention is the application that was carried out by hydroprocessing the same atmospheric distillation residue as in Example 7, with the specific properties shown in Table 16, by combining low pressure operating mode, the parameters of which are shown in Table 17, of the catalytic system in two stages of a reaction with a fluidized bed of catalyst, and use in two stages of the reaction of a mixture of a hydrocracking catalyst (used and new), in a proportion of 70/30% by weight of the used and new catalyst, with the properties shown in Table 18; this combination demonstrates a significant reduction in the formation of deposits and sludge, as well as a significant removal of metals, all sulfur, asphaltenes and all nitrogen, which allows to obtain a hydrotreated hydrocarbon with improved properties shown in Table 20.

In contrast to the previous example, in this specific application of the invention, only the type of reactor used in the two reaction stages (to the reactor with a fluidized catalyst bed) was changed, while maintaining the same parameters of the low-pressure operation mode as in the previous example, in order to determine the sensitivity process to such a change.

Table 20 shows that after the HDT, the metal content unexpectedly decreased, similar to the previous example, from 353 wppm to 129, 170 and 150 wppm, the sulfur content decreased from 3.74% by weight to 1.70, 1.85 and 1.76% by weight, asphaltene content decreased from 10.18% by weight to 4.78, 5.68 and 5.66% by weight and the total nitrogen content decreased from 4,400 wppm to 3,580, 3,650 and 3,610 wppm, for each run at corresponding different space velocities and hydrogen purity.

Table 20 Properties and compositions of the residue in a fluidized bed reactor The properties ASTM method Hydrotreated Product (Steps I and II) LHSV, hour ^-1 0.284 0.33 0.33 The purity of hydrogen, mol. % 75 75 one hundred Specific gravity, degrees API D-287 07.17 16.25 16.85 Total sulfur, weight. % D-4294 1.70 1.85 1.76 Total Nitrogen, wppm D-4629 3,580 3,650 3,610 Asphaltenes, weight. % D-3279 4.78 5.68 5.66 Metals, wppm Ni + V 129 170 150 Deposits and sediment, weight. % D-8470 0.56 0.47 0.54 Conversion, volume. % 7.8 9.3 14.2 Composition, volume. % Fraction IBP-170 ° C 2.5 2.4 2.4 Fraction 170-360 ° C 23.2 20.8 18.4 Fraction 360-538 ° С 22.5 25.8 31.0 Fraction 538 ° С ⁺ 51.8 51.0 48.2 IBP-538 ° C ⁺ fraction 48.2 49.0 51.8

Moreover, the table shows that, despite the significant removal of contaminants after the HDT residue from distillation at atmospheric pressure, the formation of deposits and sludge, surprisingly, corresponds to 0.56, 0.47 and 0.54% by weight for the three corresponding runs in the second reaction steps; these values are greater than in the previous example, but significantly less than the acceptable limit value of 0.8% by weight, which allows to maintain continuity of work in this type of process.

The same table shows for each run that the specific gravity in degrees of the American Petroleum Institute increases from 9.25 to 17.07, 16.25 and 16.85 ° API.

The obtained results confirm that the present invention, in its three preferred embodiments, when hydroprocessing a heavy hydrocarbon oil, by combining a low pressure operating mode, a reactor type and a type of hydroprocessing feedstock, allows to remove significant amounts of contaminants and completely unexpectedly reduces the formation of deposits and sludge to levels significantly lower than an acceptable limit value, which guarantees the continuity of the industrial production process, which Will receive the hydrotreated hydrocarbon of improved properties.

To further prove the novelty and inventive step of the present invention, the following are examples of applications that support the previous examples and show that the catalytic hydroprocessing of heavy oil hydrocarbons, carried out in a mode of operation that differs from that proposed in the present invention, improves the properties of the feedstock and allows the removal of large amounts of contaminants substances, as in accordance with the present invention, however, with significant formation of deposits and sludge in the product e, which violates the continuity of work in such processes, which is the main task of technical development in this area.

Example 9

This example does not apply to the specific application of the catalytic hydroprocessing of heavy hydrocarbons in accordance with the present invention and is shown to show that the use of the low pressure operating mode in combination with a high ratio of hydrogen to hydrocarbon (H ₂ / HC), combination with the type of reactor and the type of raw material, allows to obtain high conversion values in the range from 50 to 80%, as already mentioned in the patents cited here above for reference, as well as high levels of formation from dix and sludge.

For these purposes, the hydroprocessing of the residue from vacuum distillation was carried out in a catalytic reactor with a fluidized bed of catalyst. The specific properties of the raw materials are shown in Table 21, and the parameters of the operating mode are shown in Table 22.

As shown in Table 23, after carrying out the HDT residue from vacuum distillation in a fluidized bed reactor, the formation of deposits and sludge corresponds to 1.38% by weight. This value of sediment and sludge is higher than the maximum acceptable limit value of 0.80% by weight, allowing to maintain continuity of work in this type of process, and also higher than that obtained in all previous examples of the present invention.

Table 21 Properties of the residue from the vacuum distillation of heavy crude oil The properties ASTM method Values Specific gravity, degrees API D-287 1.87 Total sulfur, weight. % D-4294 5.07 Total Nitrogen, wppm D-4629 6,200 Ramsbottom carbon, weight. % D-524 25.41 Asphaltenes, weight. % D-3279 25.46 Metals, wppm Ni + V 777.9 Deposits and sediment, weight. % D4870 0.0 IBP fraction, volume. % 0.0

Table 22 Operating mode for catalytic hydroprocessing of the residue from vacuum distillation in a fluidized bed reactor Mode of operation Fluidized bed reactor Temperature ° C 400 Pressure, kg / cm ² one hundred LHSV, hour ^-1 0.25 The ratio of H ₂ / NS, nl / l 2,671 The purity of hydrogen, mol. % one hundred

Table 23 Properties and composition of the hydrotreated residue The properties ASTM method Hydroprocessing residue Specific gravity, degrees API D-287 21.19 Total sulfur, weight. % D-4294 0.714 Total Nitrogen, wppm D-4629 3,800 Asphaltenes, weight. % D-3279 3.67 Metals, wppm Ni + V 47 Deposits and sediment, weight. % D-8470 1.38 Conversion, volume. % 75.2 Composition, volume. % Fraction IBP-170 ° C 6.5 Fraction 170-360 ° C 36.4 Fraction 360-538 ° С 32.3 Fraction 538 ° C ⁺ 24.8 IBP-538 ° C ⁺ fraction 75.2

Example 10

This example also does not apply to the case of the specific application of the method of catalytic hydroprocessing of heavy hydrocarbons in accordance with the present invention and is shown to show that the use of high reaction pressures during hydroprocessing of the residue from vacuum distillation in a catalytic fluidized bed reactor does not reduce the formation of deposits and sludge. The specific properties of the raw materials are shown in Table 24, the parameters of the operating mode are shown in Table 25 Properties of the hydrotreated residue are shown in Table 26.

Table 26 shows that after the HDT is carried out, the residue from vacuum distillation in a fluidized bed reactor, the formation of deposits and sludge corresponds to 1.0% by weight. This value of sediment and sludge is slightly higher than the maximum acceptable limit value of 0.80% by weight, which allows to maintain continuous operation in this type of process, and also higher than that obtained in all previous examples of the present invention.

Thus, the last two examples clearly show that there is a significant difference between the processes in accordance with the prior art and the method in accordance with the present invention, it should be noted that the content of sediment and sludge in the hydrotreated hydrocarbon in the known processes is equal to or greater than 1% by weight, and in the examples in accordance with the present invention below 0.65% by weight. In this regard, it should be emphasized that in order to maintain continuity of work in the hydrotreatment of heavy oil hydrocarbons, the content of deposits and sludge should not exceed a maximum content of 0.80% by weight.

Table 24 Properties of the residue from vacuum distillation The properties ASTM method Values Specific gravity, degrees API D-287 3.73 Total sulfur, weight. % D-4294 4.507 Total Nitrogen, wppm D-4629 6,100 Conradson carbon, weight. % D-524 22.59 Asphaltenes, weight. % D-3279 17.75 Metals, wppm Ni + V 502.6 Deposits and sediment, weight. % D4870 0.0 Fraction IBP-538 ° C, volume. % 0.0

Table 25 Operating mode for catalytic hydroprocessing of the residue from vacuum distillation in a fluidized bed reactor Mode of operation Fluidized bed reactor Temperature ° C 420 Pressure, kg / cm ² 185 LHSV, hour ^-1 0.30 The ratio of H ₂ / NS, nl / l 1,335 The purity of hydrogen, mol. % one hundred

Table 26 Properties and composition of the hydrotreated residue The properties ASTM method Hydroprocessing residue API Specific Gravity D-287 18.0 Total sulfur, weight. % D-4294 2.12 Total Nitrogen, wppm D-4629 3.760 Asphaltenes, weight. % D-3279 5.58 Metals, wppm N1 + V 68.4 Deposits and sediment, weight. % D-8470 1.0 Conversion, volume. % 71.9 Composition, volume. % Fraction IBP-170 ° C 12.9 Fraction 170-360 ° C 26.0 Fraction 360-538 ° С 33.0 Fraction 538 ° C ⁺ 28.1 IBP-538 ° C ⁺ fraction 71.9

Claims (10)

1. A two-stage method for the catalytic hydroprocessing of heavy oil hydrocarbons having a high content of metals, total sulfur, asphaltenes and total nitrogen, containing less than 80% by volume of distillates recovered at 538 ° C, and having an API density below 32 °, in which at the first stage hydrodemetallization of hydrocarbons and hydrocracking of asphaltenes is carried out, and on the second, hydrodesulfurization and hydrodenitrogen generation of hydrocarbons are carried out, characterized in that both stages of the process are carried out in a reactor with a fixed catalyst bed. 2. The method according to claim 1, characterized in that the nickel-molybdenum catalyst is used in both stages. 3. The method according to claim 2, characterized in that the catalyst is mounted on a gamma aluminum substrate. 4. The method according to claim 1, in which both stages are carried out under pressure from 40 to 130 kg / cm ² , at a temperature of from 320 to 450 ° C, at a space velocity (LHSV) of from 0.2 to 3.0 h ^-1 and with a hydrogen / hydrocarbon ratio (H ₂ / HC) of 350 to 1,200 In / I. 5. The method according to claim 4, in which the first reaction stage is carried out under a pressure of from 45 to 90 kg / cm ² , at a temperature of 350 to 450 ° C, at a space velocity (LHSV) of 0.2 to 2.0 hours ^{, 1} , and with a hydrogen / hydrocarbon ratio (H ₂ / HC) of from 450 to 1,050 In / I. 6. The method according to claim 5, in which the formation of precipitation and sludge is minimized to a maximum value of 0.65% by weight of hydrotreated hydrocarbons. 7. The method according to claim 6, in which the conversion is up to 70% of the volume of raw materials. 8. The method according to claim 5, in which the product compared to raw materials has an increase in API density of approximately 15 units and an increase in the content of distillates recovered at 538 ° C, approximately up to 50% by volume. 9. A two-stage method for the catalytic hydroprocessing of heavy oil hydrocarbons having a high content of metals, total sulfur, asphaltenes and total nitrogen, including a) the transmission of hydrogen and hydrocarbon feedstocks of heavy oil having a specific gravity (density) of less than 32 ° API and a content of distillates recovered at 538 ° C of less than 80% by volume to the first reaction step for hydrotreating said feedstock, wherein said first reaction step carried out in a reactor with a fixed catalyst bed containing a hydrodemetallization catalyst and providing operation under pressure from 40 to 130 kg / cm ² , at a temperature of from 320 to 450 ° C, at a space velocity (LHSV) of from 0.2 to 3.0 hours ^{- 1} , and with a hydrogen / hydrocarbon ratio (H ₂ / HC ) from 350 to 1,200 In / I, resulting in the formation of hydrotreated heavy hydrocarbons; b) the transmission of hydrogen and these hydrotreated heavy hydrocarbons to the second stage of the reaction for hydrotreatment in a reactor with a fixed catalyst bed containing a hydrodesulfurization catalyst and providing pressure work from 40 to 130 kg / cm ² at a temperature of from 320 to 450 ° C, the space velocity (LHSV) from 0.2 to 3.0 h ^-1 , and with a hydrogen / hydrocarbon ratio (H ₂ / HC) from 350 to 1,200 In / I, and the amount of precipitation and sludge that forms in each of the first and the second stage of the reaction, is less than 0.65% by weight of the hydraulic Sent hydrocarbons. 10. The product obtained by the method according to claim 9.