JP2008143917A - Hydrocarbon oil hydroforming process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coke precursor capable of grasping in advance the ease of coke deterioration of the hydrocarbon oil in the hydrotreating method of hydrocarbon oil containing asphaltene and generating coke deterioration at a later stage. A method for suppressing coke deterioration in a hydrodemetallation treatment step and a hydrodemetallation catalyst used in the step are provided.
The hydrodemetallation process is performed when hydrodemetallation treatment is performed on a hydrocarbon oil containing asphaltene and then hydroreforming treatment such as hydrodesulfurization treatment or hydrocracking treatment is performed in a subsequent stage. In this method, the hydrocarbon oil is supplied to the process at a temperature lower than the 1% by mass reduction temperature by the thermobalance measurement of asphaltenes contained therein. It is.
[Selection figure] None

Description

  The present invention relates to a hydrocracking method for hydrocarbon oils, and more particularly, in a hydrotreating method for hydrocarbon oils containing asphaltenes, to suppress coke deterioration of hydrodesulfurization catalysts and hydrocracking catalysts in the subsequent stage. In order to extend the service life, the present invention relates to a method characterized by the hydrodemetallation process in the previous stage.

  In the oil refining industry, in order to hydrotreat a hydrocarbon oil containing asphaltene, which is a raw material, in general, hydrodemetallation treatment is performed in the former stage, followed by hydrodesulfurization catalyst and hydrocracking catalyst metal in the latter stage. A method for suppressing deterioration is employed. However, depending on the type of hydrocarbon oil containing asphaltene as a raw material, a coke precursor is generated from asphaltene by the progress of demetallation in the hydrodemetallation process, which induces coke deterioration of the catalyst in the subsequent stage. It has been found that the catalyst life is often shortened. However, what kind of hydrocarbon oil is likely to cause coke deterioration, and methods and indicators for avoiding coke deterioration have been unknown so far. The reality is that they are forced to perform trial and error operation management while monitoring the deterioration status.

In hydrotreating of hydrocarbon oil containing asphaltenes, a method for improving the demetallization activity by adding a third component to the hydrodemetallation catalyst in order to suppress metal degradation (for example, Patent Document 1, Patent Document) 2), a method of switching the hydrodemetallation process in parallel and switching it during operation (Patent Document 3) has been proposed.
Any of these methods is a method for enhancing the demetalization activity of the catalyst or maintaining a high activity, and was devised from the viewpoint of suppressing metal degradation, and is considered effective for metal degradation. However, these methods are not sufficient from the viewpoint of inducing coke deterioration, and the catalyst life is still not satisfactory.
Also, depending on the nature of the raw material hydrocarbon oil to be reformed, there are those that are prone to metal degradation and those that are prone to coke degradation. It was a very important issue.

JP-A-9-276712 Japanese Patent Laid-Open No. 9-248460 JP-A-4-224891

  The present invention has been made under such circumstances, and in a hydrogenation reforming method of hydrocarbon oil containing asphaltene as a raw material oil, it is possible to grasp in advance how easily the coke deterioration of the raw material oil occurs, and An object of the present invention is to provide a method for suppressing excessive decomposition of asphaltenes in the preceding hydrodemetallation step, which is considered to generate a coke precursor that causes coke degradation in the process, and a hydrodemetallation catalyst used in the step Is.

In order to achieve the above object, the present inventor conducted extensive research on the combination of various catalysts, reaction conditions, etc. in physical property measurement, analysis, analysis and hydrotreating treatment of asphaltenes in various raw hydrocarbon oils. The inventors have found the following matters and have completed the present invention.
(A) A material having a low 1% by mass reduction temperature as measured by thermobalance of asphaltenes in a raw material hydrocarbon oil is a raw material that easily causes coke deterioration. Therefore, supplying the raw hydrocarbon oil to the hydrodemetallation step at a temperature lower than this temperature is effective in suppressing coke deterioration.
(B) In the hydrodemetallation step, as a catalyst used in the hydrodemetallation treatment, the supported amount of metals belonging to Groups 8, 9 and 10 of the periodic table which are active metals is a specific range as a metal oxide. A catalyst in which the supported amount of a metal belonging to Group 6 of the periodic table, which is a promoter metal, is in a specific range as a metal oxide, preferably a catalyst supporting a metal belonging to Group 5 of the periodic table Moreover, coke deterioration can be suppressed by using more than a certain ratio with respect to all the catalysts in a hydrodemetallation process.

That is, the present invention
(1) A hydrocracking method for hydrocarbon oil containing asphaltenes, wherein the hydrodemetallation is performed when hydrodesulfurization treatment is performed on the hydrodesulfurization treatment after hydrodemetallation treatment of the hydrocarbon oil. In the treatment step, the hydrocarbon oil is supplied to the step at a temperature lower than the 1% by mass reduction temperature by the thermobalance measurement of asphaltenes contained therein. Quality method,
(2) A method for hydrotreating a hydrocarbon oil containing asphaltenes, wherein the hydrocarbon oil is hydrodemetallized, hydrocracked, and then hydrodesulfurized to hydroreform. At the time, in the hydrodemetallation treatment step, the hydrocarbon oil is supplied to the step at a temperature lower than a 1% by mass reduction temperature by thermobalance measurement of asphaltenes contained therein, Hydrocarbon oil hydroforming method,
(3) Hydrocarbon reforming method for hydrocarbon oil containing asphaltenes, wherein the hydrocarbon oil is hydrodemetallized, hydrodesulfurized, and then hydrocracked and hydrodesulfurized sequentially And when hydrotreating the hydrocarbon oil, in the hydrodemetallation treatment step, the hydrocarbon oil is heated at a temperature lower than the 1% by mass reduction temperature by thermobalance measurement of asphaltenes contained therein. , A method for hydrotreating hydrocarbon oil, characterized by being supplied to the process,
(4) In the hydrodemetallation treatment step, the catalyst used in the step is a metal oxidation of at least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table on the support. A catalyst comprising at least one metal selected from 2% by weight to 8% by weight and a metal belonging to Group 6 of the periodic table as a metal oxide as a metal oxide. A method for hydrotreating a hydrocarbon oil according to any one of the above (1) to (3),
(5) In the hydrodemetallation treatment step, the catalyst used in the step is a metal oxidation of at least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table on the support. 2% by mass to 8% by mass as a product and 0.5% by mass to 5% by mass of at least one metal selected from metals belonging to Group 6 of the periodic table as a metal oxide, and the catalyst surface area The hydrogen of the hydrocarbon oil according to any one of (1) to (4) above, wherein the coverage of the metal belonging to Group 6 of the periodic table is in the range of 5 to 25% on the oxide basis Reforming method,
(6) In the hydrodemetallation treatment step, the catalyst used in the step is a metal oxidation of at least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table on the support. 2% by mass to 8% by mass as a product and 0.5% by mass to 5% by mass of at least one metal selected from metals belonging to Group 6 of the periodic table as a metal oxide, and the catalyst surface area The catalyst in which the coverage of metals belonging to Group 6 of the periodic table is in the range of 5 to 25% on the oxide basis is such that the content in the total catalyst used in the step is 35% by volume or more. A hydrocracking method for hydrocarbon oils according to any one of the above (1) to (5), wherein
(7) In the hydrodemetallation treatment step, at least 35% by volume or more of the catalyst used in the step is selected from metals belonging to Groups 8, 9 and 10 of the periodic table 0.5% by mass to 5% by mass of at least one metal selected from 2% by mass to 8% by mass as a metal oxide and a metal belonging to Group 6 of the Periodic Table. % Of the hydrocarbon oil according to any one of the above (1) to (6), which is a catalyst that is supported on at least one metal selected from metals belonging to Group 5 of the periodic table. Reforming method,
(8) At least one metal selected from metals belonging to Groups 8, 9 and 10 of the Periodic Table is included in the carrier as a metal oxide in an amount of 2 to 8% by mass and Group 6 of the Periodic Table. At least one metal selected from the metals belonging to the catalyst is supported by 0.5% by mass to 5% by mass as a metal oxide, and the coverage of the metal belonging to Group 6 of the periodic table with respect to the catalyst surface area is based on the oxide. Hydrocarbon oil hydrodemetallation catalyst, characterized in that it is in the range of 5 to 25%, and (9) the support was selected from metals belonging to Groups 8, 9 and 10 of the Periodic Table At least one metal selected from 2% by mass to 8% by mass as a metal oxide and at least one metal selected from metals belonging to Group 6 of the Periodic Table is 0.5% by mass to 5% as a metal oxide. It is supported by mass% and belongs to Group 6 of the periodic table for the catalyst surface area. A hydrocarbon oil having a genus coverage in the range of 5 to 25% on an oxide basis and further supporting at least one metal selected from metals belonging to Group 5 of the periodic table Hydrodemetallation catalyst,
Is to provide.

  According to the present invention, in the hydrogenation reforming method of hydrocarbon oil containing asphaltenes, it is possible to grasp in advance the ease of coke degradation of the raw hydrocarbon oil, and to produce a coke precursor that causes coke degradation at a later stage. It is possible to provide a method for suppressing excessive decomposition of asphaltenes in a conceivable preceding hydrodemetallation step. In addition, it is possible to design an optimal catalyst system and set the operation method according to the characteristics of the raw hydrocarbon oil in order to minimize coke deterioration in hydrotreating of hydrocarbon oil containing asphaltenes. . This leads to an improvement in the operating rate of the hydrocracking apparatus and a reduction in catalyst costs, so an improvement in the profits of the oil refining industry is expected.

  There are the following three methods for the catalytic hydrogenation reforming method for the hydrocarbon oil of the present invention. That is, after hydrodemetallation treatment of petroleum hydrocarbon oil containing asphaltenes, (1) hydrodesulfurization treatment, (2) hydrocracking, and then hydrodesulfurization treatment, (3) hydrodesulfurization treatment Then, hydrocracking treatment and hydrodesulfurization treatment are sequentially performed. Thus, when hydrotreating the hydrocarbon oil, in the hydrodemetallation treatment step, the raw hydrocarbon oil is contained therein. At least selected from metals belonging to Groups 8, 9 and 10 of the periodic table for supplying to the process at a temperature lower than the 1% by mass reduction temperature by thermobalance measurement of the asphaltenes contained 0.5% by mass of at least one metal selected from 2% by mass to 8% by mass as a metal oxide as a metal oxide and at least one metal selected from metals belonging to Group 6 of the periodic table as a promoter metal A hydrocracking method for hydrocarbon oil, characterized in that a catalyst supported by ~ 5% by mass is used so that the content in the total catalyst used in the step is 35% by volume or more. . The process schematic of these three methods is shown in FIGS.

Each item will be described in turn.
(1) Raw material hydrocarbon oil In this invention, the hydrocarbon oil containing 1 mass% or more of asphaltenes is used. The content of asphaltenes is preferably 2% by mass or more, and more preferably 4% by mass or more from the viewpoint of the hydrogenation reforming effect. Moreover, although there is no restriction | limiting in particular about an upper limit, 15 mass% is preferable on an apparatus driving | operation. As this hydrocarbon oil, those containing vanadium and nickel of 10 mass ppm or more and sulfur content of 0.1 mass% or more are advantageous in that the hydroreforming effect is effectively exhibited.
Examples of the hydrocarbon oil include petroleum-based hydrocarbon oils such as atmospheric residue oil, reduced pressure residue oil, crude oil, overhead crude oil, history oil, history residue oil, cracked oil, cracked residue oil, and mixed oils thereof. It is done. The hydrocarbon oil may contain synthetic crude oil obtained from non-petroleum coal liquefied oil, tar sand oil, oil sand oil, oil shale oil, orinocotal, and the like.

(2) Pretreatment When there is much salt content, it is desirable to desalinate and to make sodium chloride content 10 mass ppm or less. When there are many solid substances, it is desirable to pass through a filter of about 10 μm.
(3) Heating process It heats up to desired temperature through a heat exchanger and a heating furnace. At this temperature increase, in order to suppress coke deterioration in the hydrodesulfurization catalyst or hydrocracking catalyst in the latter stage, a temperature that does not exceed the 1% by mass reduction temperature by thermobalance measurement of asphaltenes in the raw hydrocarbon oil. It is necessary to keep it down.
Specifically, in differential thermal analysis, the temperature at which the mass reduction of asphaltenes by thermobalance measurement begins is presumed as the thermal decomposition start temperature of asphaltenes. Further, it is presumed that this mass decrease start temperature is also a temperature at which asphaltenes start to generate a coke precursor that causes thermal degradation of coke and causes coke deterioration. Therefore, in the heating step for supplying the raw hydrocarbon oil to the hydrodemetallation step described later, the temperature can be raised to as high a temperature as possible without exceeding the 1% mass reduction temperature of asphaltene by the thermobalance measurement. It is effective. More preferably, the temperature is raised to as high a temperature as possible without exceeding the 0.5% mass reduction temperature of asphaltenes.
From the above viewpoint, the heat of asphaltenes is measured by ESR (Electron Spin Resonance) measurement using the property of absorbing microwaves of a specific frequency when unpaired electrons (radicals) are placed in a strong magnetic field. It is also effective to measure the radical generation temperature by decomposition and adjust the temperature as high as possible at a temperature not exceeding the radical generation temperature as the feed temperature of the raw hydrocarbon oil to the hydrodemetallation process.

(4) Hydrodemetallation process The raw hydrocarbon oil is heated under pressure and subjected to hydrodemetallation in the first stage hydrodemetallation process together with hydrogen. This process consists of one tower or a plurality of reaction towers.
Catalysts used in this hydrodemetallation step include porous inorganic oxides such as alumina, silica, silica-alumina or sepiolite, and active metals for carriers such as natural minerals. A period in which at least one active metal selected from metals belonging to the group is 2% by mass to 8% by mass, preferably 2% by mass to 4% by mass, and a promoter metal based on the total amount of the catalyst. It is preferable that at least one metal selected from metals belonging to Group 6 of the Table is supported as metal oxide in an amount of 0.5% by mass to 5% by mass, preferably 1% by mass to 5% by mass. Specifically, the metals belonging to Groups 8, 9 and 10 of the periodic table which are active metals are more preferably nickel, cobalt and rhodium, and the metals belonging to Group 6 of the periodic table which are promoter metals are More preferred are molybdenum and tungsten.
Moreover, what carried | supported so that the coverage with respect to the catalyst surface area by a promoter metal carrying | support might become the range of 5-25% on an oxide basis is preferable.
Furthermore, it is preferable to use the catalyst in an amount of 35% by volume or more of the total catalyst in the hydrodemetallation step. The reason for this is not clear, but when the amount of active metal supported is large or the amount of promoter metal supported is large, the asphaltene is excessively decomposed beyond the hydrogenation capacity of the catalyst. It may be promoted. More preferably, 60% by volume or more is used. In addition, this catalyst and the remaining catalyst may be filled into the reactor in layers, or may be mixed and filled. The catalyst preferably has an average pore diameter of 10 nm or more, and particularly preferably 15 to 20 nm. The remaining catalyst may be a general hydrodemetallation catalyst, and has an average pore diameter of 10 nm or more formed by supporting about 3 to 30% by mass of the active metal as an oxide on the support. Is preferred. Also, a hydrodemetallation step of a catalyst comprising 1 to 4% by mass of at least one metal selected from metals belonging to Group 5 of the periodic table as oxides on a catalyst carrier together with the active metal In order to suppress coke deterioration, it is preferable to use 35% by volume or more based on the total amount of the catalyst. Vanadium and niobium are preferable as the at least one metal selected from metals belonging to Group 5 of the periodic table. The reason why the vanadium-containing catalyst leads to the suppression of coke degradation is unknown, but vanadium previously supported on the catalyst is combined with other active metals such as nickel to strengthen the binding force between vanadium, It is thought that there is an effect of attracting vanadium in the oil into the catalyst pores at a low temperature. As a result, it is possible to adsorb and remove vanadium in the raw material oil at a low temperature and to evenly adsorb vanadium having a property of being unevenly distributed and adsorbing in the vicinity of the catalyst surface to the inside of the pore. For this reason, it is considered that the hydrogenation active points of the entire catalyst pores function effectively and the hydrogenation reforming of the coke precursor is not promoted.
The hydrodemetallation catalyst is preferably used in an amount of 10 to 50% by volume based on the metal concentration in the raw hydrocarbon oil relative to the total amount of catalyst used in all steps.
The treatment conditions for the hydrodemetallization step, a hydrogen partial pressure of 3 to 20 mPa · G, preferably 10~18MPa · G, a hydrogen / oil ratio 200~2,000Nm ³ / kl, preferably 400 to 800 nm ³ / kl, LHSV (liquid hourly space velocity) is 0.1 to 10 hr ⁻¹ , preferably 0.3 to 5 hr ⁻¹ . This is because when the hydrogen partial pressure and the hydrogen / oil ratio are below the ranges, the reaction efficiency decreases, and when they exceed the ranges, the economic efficiency decreases. On the other hand, when LHSV is below the range, the economic efficiency is lowered, and when it exceeds the range, the reaction efficiency is lowered.

(5) Hydrodesulfurization process If the hydrodemetallized oil or the hydrocracked oil described later is required to control the reaction temperature, the fluid temperature is lowered by a heat exchanger. Let If the reaction temperature can be controlled by hydrogen gas quenching or oil quenching, the hydrodesulfurization treatment is performed in the hydrodesulfurization process as it is without installing a heat exchanger. This process consists of one tower or a plurality of reaction towers.
The catalyst used in this hydrodesulfurization step may be a normal heavy oil hydrodesulfurization catalyst. That is, based on the total amount of the catalyst, at least one selected from metals belonging to Groups 5, 6, 8, 9 and 10 of the periodic table is used as a support of alumina, silica, silica-alumina, zeolite or a mixture thereof. Alumina-phosphorus as disclosed in JP-A-7-305077 and JP-A-5-98270 is a catalyst having an average pore diameter of 8 nm or more supported as an oxide in an amount of about 3 to 30% by mass. Among the metals belonging to Groups 5, 6, 8, 9 and 10 of the periodic table among carriers selected from carriers, alumina-alkaline earth metal compound carriers, alumina-titania carriers, alumina-zirconia carriers, alumina-boria carriers, etc. A catalyst that supports at least one selected from the above is preferable because the reforming effect of the kerosene oil fraction is high.
The treatment conditions in this step include a reaction temperature of 300 to 450 ° C., preferably 300 to 420 ° C., a hydrogen partial pressure of 3 to 20 MPa · G, preferably 10 to 18 MPa · G, and a hydrogen / oil ratio of 200 to 2,000 Nm ³ / kl, preferably 400~800Nm ³ / kl, LHSV (liquid hourly space velocity) 0.1 to 10 hr ^-1, preferably 0.2~2hr ^-1.
This is because if the reaction temperature, hydrogen partial pressure, and hydrogen / oil ratio are below the range, the reaction efficiency is lowered, and if the range is exceeded, the economic efficiency is lowered. On the other hand, when LHSV is below the range, the economic efficiency is lowered, and when it exceeds the range, the reaction efficiency is lowered. Moreover, about the order of a hydrocracking process and a hydrodesulfurization process, when using a catalyst with a high hydrogenation function as shown to following (6), you may change the order of the process. Further, the hydrodesulfurization step may be arranged again after the hydrodesulfurization step and the hydrocracking step.

(6) Hydrocracking Step The batch hydrodemetallized oil or the aforementioned batch hydrodesulfurized oil is then batch hydrocracked in the hydrocracking step. This process consists of one tower or a plurality of reaction towers.
As the catalyst used in this hydrocracking step, a catalyst produced by the technique disclosed in Japanese Patent No. 3341011 can be used. That is, it consists of a zeolite compounded with titanium group metal oxide ultrafine particles on the inner surface of the mesopore, and the atomic ratio [Al] / [Si] of aluminum and silicon contained in the zeolite is 0.01 to 0.1, Preferably, a modified zeolite in the range of 0.03 to 0.08 is used as a carrier, and when the raw hydrocarbon oil is light, the activity is controlled by adding 10 to 50% by mass of alumina or the like to the modified zeolite. Also good. The carrier carries at least one selected from metals belonging to Groups 6, 8, 9 and 10 of the periodic table as a hydrogenation active metal, and belongs to Group 6 of the Periodic Table As tungsten, molybdenum is preferable, and the metals in groups 8 to 10 of the periodic table may be used singly or in combination with a plurality of metals. However, the hydrogenation activity is particularly high and the deterioration is small. From the viewpoint, a combination of nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, nickel-cobalt-molybdenum is preferable.
The treatment conditions in this hydrocracking step include a reaction temperature of 300 to 450 ° C., preferably 360 to 420 ° C., a hydrogen partial pressure of 3 to 20 MPa, preferably 10 to 18 MPa, and a hydrogen / oil ratio of 200 to 2,000 Nm ³ / kl. , Preferably 400 to 800 Nm ³ / kl, LHSV (liquid hourly space velocity) 0.1 to 10 hr ⁻¹ , preferably 0.2 to 2 hr ⁻¹ .
This is because if the reaction temperature, hydrogen partial pressure, and hydrogen / oil ratio are below the range, the reaction efficiency is lowered, and if the range is exceeded, the economic efficiency is lowered. On the other hand, when LHSV is below the range, the economic efficiency is lowered, and when it exceeds the range, the reaction efficiency is lowered.

(7) Separation process In this way, the oil subjected to the batch hydrodemetallation treatment, the batch hydrocracking treatment, and the batch hydrodesulfurization treatment is introduced into the separation step according to a conventional method, and processed in a plurality of separation tanks. It is separated into a gas part and a liquid part. Among these, after removing hydrogen sulfide, ammonia and the like, the gas portion is subjected to treatment for improving hydrogen purity, etc., and after being combined with new supply gas, it is recycled to the reaction step.
The liquid portion obtained in the separation step is introduced into an atmospheric pressure separation column called a stripper to remove hydrogen sulfide accompanying desulfurization and to separate a light fraction from the produced oil.
(8) Type of reaction tower In the present invention, there is no particular limitation on the type of reactor in the batch hydrodemetallation treatment, batch hydrocracking treatment, and batch hydrodesulphurization treatment. For example, fixed bed, moving bed, fluidized bed A boiling bed, a slurry bed, etc. can be adopted.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

  Arabian heavy atmospheric residue and Latawi atmospheric residue were used as the raw material hydrocarbon oil. Table 1 shows the properties. The asphaltene concentration contained in the residual oil was measured by the method specified in International Standard IP143.

  3 mg of each asphaltene contained in Arabian heavy normal pressure residue and Latawi normal pressure residual oil was measured at 10 ° C./min under a nitrogen gas flow (500 ml / min) using a Shimadzu differential thermal analyzer (TG-DTA). The mass change was measured while the temperature was raised at a rate of. Table 2 shows the measurement results.

In the differential thermal analysis, the temperature at which the mass loss of asphaltenes begins is assumed to be the thermal decomposition start temperature of asphaltenes. Further, it is presumed that this mass decrease start temperature is also a temperature at which asphaltenes start to generate a coke precursor that causes thermal degradation of coke and causes coke deterioration. From Table 2, it is expected that the Latawi normal pressure residual oil will thermally decompose asphaltene at a temperature about 40 ° C. lower than the Arabian heavy normal pressure residual oil to produce a coke precursor.
Table 3 shows the properties of the catalyst used in the reaction.

  In addition, the hydrocracking catalyst D supported cobalt (Co) and molybdenum (Mo) on the support | carrier prepared by the method described in Example 1-5 of the patent 3341011 gazette.

[Comparative Example 1]
The hydrodemetallation catalyst C28% by volume, hydrocracking catalyst D33% by volume and hydrodesulfurization catalyst E39% by volume shown in Table 3 were charged in this order into a 100 ml reaction tube and connected in series in this order. And reacted. As the raw material hydrocarbon oil, the Arabian heavy normal pressure residue and the Latawi normal pressure residual oil shown in Table 1 are supplied, the hydrogen partial pressure is 13.2 MPa · G, the hydrogen / oil ratio is 800 Nm ³ / kl, and the reaction temperature is hydrogen. The hydrodesulfurization catalyst C was 380 ° C., the hydrocracking catalyst D was 400 ° C., and the hydrodesulfurization catalyst E was adjusted so that the sulfur content of the product oil was 0.7% by mass. The LHSV was 5,000 hours per hour at 0.18 per hour. FIG. 4 shows the change in the temperature of the hydrodesulfurization catalyst E required to obtain 0.7% by mass of the sulfur content of the Arabian Heavy normal pressure residue and the Latawi normal pressure residual oil, and the accumulated metal content on the catalyst. The figure plotted against (Metal On Catalyst: hereinafter referred to as MOC) is shown. The result of supplying Latawi normal pressure residual oil to the hydrodemetallation process at a temperature higher than the 1% mass reduction temperature of asphaltenes by thermobalance measurement is the result of hydrogenation at a temperature lower than the 1% mass reduction temperature of asphaltenes by thermobalance measurement It is clear from FIG. 4 that significant coke degradation has occurred compared to the result of supplying Arabian heavy atmospheric residue in the metal removal process. From this, it is clear that those having a low 1 wt% reduction temperature measured with an asphaltene thermobalance in the raw hydrocarbon oil are raw materials that are prone to coke degradation.

[Examples 1 to 5 and Comparative Examples 2 and 3]
An example of a method for suppressing coke deterioration of raw material hydrocarbon oil that easily causes coke deterioration is shown below.
A hydrodesulfurization catalyst A, B, C or a mixture thereof shown in Table 3 and a hydrodesulfurization catalyst E in a proportion shown in Table 4 are charged into a reaction tube having a catalyst amount of 300 ml. The Latawi normal pressure residual oil shown in Table 1 is supplied, the hydrogen partial pressure is 13.2 MPa · G, the hydrogen / oil ratio is 800 Nm ³ / kl, the reaction temperature is 340 ° C. for the hydrodemetallation catalyst, and the hydrodesulfurization catalyst E is Maintained at 380 ° C., the LHSV was oiled for 720 hours each at 0.15 hour.

FIG. 5 shows changes in sulfur concentration in the product oil. From FIG. 5, in Comparative Examples 2 and 3, initial deterioration is observed, whereas in Examples 1 to 5, initial deterioration that is considered to be caused by coke is suppressed.
From these, the following points became clear.
(A) In the hydrodemetallation process, supplying the raw hydrocarbon oil at a temperature lower than the thermal decomposition start temperature of asphaltenes in the raw hydrocarbon oil is effective in suppressing coke deterioration.
(B) In the hydrodemetallation treatment step, the supported amount of active metal as a catalyst used in the hydrodemetallation treatment is 2% by mass to 8% by mass as a metal oxide, and the amount of promoter metal supported is metal. Coke degradation is suppressed by using 35% by volume or more of the total catalyst in the hydrodemetallation process using a catalyst that is 0.5% by mass to less than 5% by mass as oxide and further supporting vanadium. Can do.
Until now, in the hydroreforming reaction of hydrocarbon oils containing asphaltenes, it was thought that coke degradation appeared particularly prominently in the early stage of the reaction, but as seen in the examples, the coke degradation was observed in the early stage of the reaction. Being restrained is a surprising result.

It is one of the process schematics for implementing this invention (1st invention). It is one of the process schematics for implementing this invention (2nd invention). It is one of the process schematics for implementing this invention (3rd invention). It is a deterioration behavior comparison figure of the Arabian heavy normal-pressure residual oil and the Latawi normal-pressure residual oil in the comparative example 1. It is a time-dependent change figure of the sulfur content of the production | generation oil at the time of the Latawi normal-pressure residual oil hydrogenation reforming process in Examples 1-5 and Comparative Examples 2 and 3. FIG.

Explanation of symbols

1: Hydrodemetallation process 2: Hydrodesulfurization process 3: Hydrocracking process

Claims (9)

A method for hydrotreating hydrocarbon oil containing asphaltene, wherein the hydrocarbon oil is hydrodemetallized and then hydrodesulfurized to hydroreform, A method for hydrotreating a hydrocarbon oil, characterized in that the hydrocarbon oil is supplied to the process at a temperature lower than a 1% by mass reduction temperature as measured by thermobalance of asphaltenes contained therein. A hydroforming method for hydrocarbon oil containing asphaltenes, wherein the hydrocarbon oil is subjected to hydrodemetallation, hydrocracked, and then hydrodesulfurized to hydrotreat. In the hydrodemetallation process, the hydrocarbon oil is supplied to the process at a temperature lower than a 1% by mass reduction temperature by thermobalance measurement of asphaltenes contained therein. Hydrogenation reforming method. A hydrocracking method for hydrocarbon oil containing asphaltenes, wherein the hydrocarbon oil is hydrodemetallized and then hydrodesulfurized, then hydrocracked and hydrodesulfurized sequentially, When hydrotreating a hydrocarbon oil, in the hydrodemetallation treatment step, the hydrocarbon oil is treated at a temperature lower than a 1% by mass reduction temperature as measured by a thermobalance of asphaltenes contained therein. Hydrocarbon reforming method for hydrocarbon oil, characterized by being supplied to In the hydrodemetallation treatment step, the catalyst used in the step is 2 as a metal oxide with at least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table as a support. A catalyst comprising 0.5% by mass to 5% by mass of at least one metal selected from mass% to 8% by mass and a metal belonging to Group 6 of the periodic table as a metal oxide. The hydrocarbon reforming method of hydrocarbon oil in any one of 1-3. In the hydrodemetallation treatment step, the catalyst used in the step is 2 as a metal oxide with at least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table as a support. 0.5% by mass to 5% by mass of at least one metal selected from mass% to 8% by mass and a metal belonging to Group 6 of the periodic table as a metal oxide, and a periodic rule with respect to the catalyst surface area The method for hydrotreating hydrocarbon oil according to any one of claims 1 to 4, wherein the coverage of the metal belonging to Group 6 of the Table is in the range of 5 to 25% on the oxide basis. In the hydrodemetallation treatment step, the catalyst used in the step is 2 as a metal oxide with at least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table as a support. 0.5% by mass to 5% by mass of at least one metal selected from mass% to 8% by mass and a metal belonging to Group 6 of the periodic table as a metal oxide, and a periodic rule with respect to the catalyst surface area Use a catalyst having a coverage of a metal belonging to Table Group 6 in the range of 5 to 25% on an oxide basis so that the content in the total catalyst used in the step is 35% by volume or more. The method for hydrotreating a hydrocarbon oil according to any one of claims 1 to 5. In the hydrodemetallation treatment step, the catalyst to be contained in an amount of 35% by volume or more in all the catalysts used in the step is at least one selected from metals belonging to Groups 8, 9 and 10 of the periodic table. At least one metal selected from 2% by mass to 8% by mass as a metal oxide and a metal belonging to Group 6 of the periodic table is supported as 0.5% by mass to 5% by mass as a metal oxide. The hydrocarbon oil hydroforming method according to any one of claims 1 to 6, further comprising a catalyst supporting at least one metal selected from metals belonging to Group 5 of the periodic table. At least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table is 2% by mass to 8% by mass as a metal oxide and a metal belonging to Group 6 of the Periodic Table. At least one metal selected from the inside is supported as a metal oxide in an amount of 0.5% by mass to 5% by mass, and the coverage of the metal belonging to Group 6 of the periodic table with respect to the catalyst surface area is 5 to 5 on an oxide basis. A hydrodemetallation catalyst for hydrocarbon oils, characterized by being in the range of 25%. At least one metal selected from metals belonging to Groups 8, 9 and 10 of the periodic table is 2% by mass to 8% by mass as a metal oxide and a metal belonging to Group 6 of the Periodic Table. At least one metal selected from the inside is supported as a metal oxide in an amount of 0.5% by mass to 5% by mass, and the coverage of the metal belonging to Group 6 of the periodic table with respect to the catalyst surface area is 5 to 5 on an oxide basis. A hydrodemetallation catalyst for hydrocarbon oil, characterized in that it is in the range of 25% and further supports at least one metal selected from metals belonging to Group 5 of the periodic table.

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