KR20180046981A - Hydrogenation treatment method of heavy hydrocarbon fraction - Google Patents

Abstract

Disclosed is a method for processing hydrogenation of heavy oil, which is for efficient utilization of a demetallization catalyst, maximization of the performance of a desulfurization catalyst, an increase in light oil capable of increasing production of heavy oil, and efficient utilization of a catalyst in a process of hydriding heavy oil such as atmospheric residual oil, vacuum residual oil, and the like. The method for processing hydrogenation of heavy oil, which performs hydrogenization in a series reactor divided into a desulfurization catalyst filling unit and a demetallization catalyst filling unit, comprises the steps of: filling a desulfurization catalyst and a demetallization catalyst in the desulfurization catalyst filling unit and the demetallization catalyst filling unit, respectively; adding a sulphidizing agent in the series reactor to perform sulfurization; and performing a hydrogenization processing reaction by adding hydrogen while passing heavy oil through the series reactor. The average temperature of the desulfurization catalyst filled in the desulfurization catalyst filling unit and the average temperature of the demetallization catalyst filled in the demetallization catalyst filling unit are set to be independently controlled. The difference between the average temperatures of the desulfurization catalyst and the demetallization catalyst is maintained at 15 to 50 deg. C.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for hydrotreating a heavy oil component,

More particularly, the present invention relates to a process for hydrotreating a heavy oil fraction such as atmospheric residual oil and reduced-pressure residual oil, The present invention relates to a process for hydrogenation of heavy oil components for efficient utilization of catalysts and for the production of light oils capable of increasing production of light oil components.

Generally, a conventional hydrogenation treatment process in a commercial refinery is a process in which a desulfurization catalyst and a desulfurization catalyst are packed in a series reactor under high-temperature and high-pressure hydrogen conditions to remove sulfur (S), nitrogen (N) , CCR (Conradson Carbon Residue), Ni (Ni), and Vanadium (V) to produce feedstock for L / S Fuel Oil or downstream heavy oil contact cracking process .

In addition, under the high-temperature and high-pressure hydrogenation treatment conditions, decomposition reaction for molecules having a large molecular weight also progresses, and it is possible to produce light oil having high added value.

Among these series reactors, a de-metal catalyst for removing metals such as nickel (Ni) and vanadium (V) is filled in advance to remove the metal which is a permanent poison of the catalyst first, followed by sulfur (S), nitrogen ), CCR (Conradson Carbon Residue), and the like.

In particular, the metal components present in the heavy oil fraction are converted to nickel sulfide or V sulfide through a metal removal catalytic reaction, which is deposited in the catalyst pores and catalyst layer voids. Such a demetalization reaction gradually stabilizes after an abrupt reaction at the initial stage of operation. In this process, metal components such as Ni and V are deposited in the pores of the catalyst to cause pore mouth plugging, and coking due to the high reaction heat causes deterioration in catalyst performance as well as increase in process pressure .

The object of the present invention is to efficiently utilize a demetallation catalyst and to maximize the performance of a desulfurization catalyst in the process of hydrotreating a heavy oil fraction such as an atmospheric residual oil and a reduced pressure residual oil, The present invention provides a method for hydrogenation treatment of heavy oil.

According to another aspect of the present invention, there is provided a method for hydrotreating a heavy oil fraction, the hydrogenation treatment being performed in a series reactor divided into a desulfurization catalyst filling unit and a demetallation catalyst filling unit, Filling the desulfurization catalyst and the desulfurization catalyst with a desulfurization catalyst and a demetallation catalyst, respectively; Adding a sulphurizing agent to the series reactor to perform sulphation; And performing a hydrogenation treatment by passing a heavy oil component through the series reactor, wherein an average temperature of the desulfurization catalyst packed in the desulfurization catalyst packed part and an average of the demetallation catalyst packed in the demetallation catalyst packed part The temperature is set to be controlled independently and the difference between the average temperature of the desulfurization catalyst and the average temperature of the demetallation catalyst is maintained at 15 to 50 캜.

The method for hydrotreating a heavy oil fraction according to the present invention is characterized in that it comprises a desulfurization catalyst (HDM Catalyst) for mainly removing sulfur (S), nitrogen (N) and CCR (Conradson Carbon Residue) (HDS Catalyst) which mainly removes nickel (Ni) and vanadium (V) from the average temperature of the desulfurization catalyst and the average temperature of the desulfurization catalyst, And is controlled to 15 to 50 캜.

Accordingly, the method of hydrogenation treatment of heavy oil according to the present invention can be applied to high-quality low-sulfur fuel oil (L / S fuel oil) or high-quality residual oil It is possible to produce a feedstock for the catalytic cracking process.

In addition, the method for hydrotreating a heavy oil fraction according to the present invention can increase the life-time of a hydrogenation treatment of a heavy oil fraction and reduce the possibility of problems such as generation of differential pressure.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a process for explaining a hydrogenation treatment method of heavy oil according to an embodiment of the present invention. FIG.
2 is a view for explaining an average temperature difference between a desulfurization catalyst and a demetallization catalyst between the present invention and the prior art.
3 is a graph showing the results of measurement of impurity conversion rates of a desulfurization catalyst and a demetalization catalyst for Examples 1 to 4;

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for hydrotreating heavy crude oil according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a process flow chart showing a method for hydrogenating heavy crude oil according to an embodiment of the present invention, and FIG. 2 is a view for explaining an average temperature difference between a desulfurization catalyst and a demetallization catalyst between the present invention and a conventional technology.

1 and 2, a method for hydrotreating heavy crude oil according to an embodiment of the present invention includes a desulfurization catalyst and a demetallation catalyst filling step (S110), a sulfurization treatment step (S120), and a hydrogenation treatment reaction step (S130 ).

Desulfurization catalyst and Metal removal  catalyst Filling

In the desulfurizing catalyst and the demetallating catalyst filling step (S110), the desulfurizing catalyst and the demetallating catalyst are filled in the desulfurizing catalyst filling part and the demetallating catalyst filling part, respectively.

At this time, the desulfurization catalyst means a catalyst used for hydrocracking, hydrotreating, etc., and can be used without limitation. In addition, the metal removal catalyst also means a catalyst used for hydrocracking, hydrotreating, etc., and can be used without limitation.

That is, each of the desulfurization and demetallation catalysts may include a support composed of at least one metal selected from group VIB, at least one metal selected from group VIII, or at least one metal selected from group VIB and group VII and oxides, .

It is preferable that the desulfurization catalyst and the demetallization catalyst are filled using a series reactor which is divided into a desulfurization catalyst filling part and a demetallating catalyst filling part. As described above, in the present invention, a desulfurization catalyst and a demetallization catalyst are filled in a series reactor divided into a desulfurization catalyst filling part and a demetallization catalyst filling part which have different reaction temperature sections.

In this case, it is preferable that the average temperature of the desulfurization catalyst packed in the desulfurization catalyst charging part and the average temperature of the demetallization catalyst packed in the desulfurization catalyst charging part are independently controlled. In particular, it is preferable to set the difference between the average temperature of the desulfurization catalyst and the average temperature of the demetallation catalyst at 15 ° C or higher, and a detailed description thereof will be described later.

Sulfation treatment

In the sulfiding step (S120), a sulfiding agent is added to the series reactor to carry out the sulfiding treatment.

At this time, DMDS (dimethyl disulfide) may be used as a sulfurizing agent to be added in the series reactor. In this sulphiding treatment, a light diesel having a sulfur concentration adjusted to 2 to 3 vol% by adding a sulfurizing agent can be used.

Hydrogenation treatment reaction

In the hydrogenation treatment reaction step (S130), hydrogen is added while passing the heavy oil fraction through the series reactor, and the hydrogenation treatment reaction is carried out.

At this time, the pressure of the series reactor may be set to 13 to 200 kg / cm ³ , the liquid space velocity (LHSV) to 0.1 to ^{1 hr -1} and the H ₂ / oil ratio to be 100 to 1000 NL / L.

Here, the heavy oil fraction may include any one of an atmospheric residue, a decompressed residue, a bitumen, and a tar sand.

In particular, it is preferable to maintain the difference between the average temperature of the desulfurization catalyst and the average temperature of the demetallation catalyst at 10 to 50 ° C, more preferably 20 to 35 ° C. For this purpose, it is preferable to maintain the average temperature of the demetallization catalyst at 330 to 400 ° C. and maintain the average temperature of the desulfurization catalyst at 350 to 420 ° C. to perform the hydrogenation treatment.

Further, in the hydrogenation treatment, it is more preferable to raise the temperature of the demetalization and desulfurization catalyst at a temperature raising rate of 0.01 to 1 占 폚 / day.

Meanwhile, as shown in FIG. 2, in the present invention, the average temperature of the demetalization catalyst is limited to 330 to 400 ° C. and the average temperature of the desulfurization catalyst is limited to 350 to 420 ° C.

In particular, the difference between the average temperature of the desulfurization catalyst and the average temperature of the demetallation catalyst was maintained at 15 to 50 ° C, more preferably 20 to 35 ° C.

As described above, the present invention can effectively remove metal components such as nickel (Ni) and vanadium (V) contained in the heavy oil component while applying an average temperature of the metal removal catalyst lower than that of the conventional art, It is possible to remove most of the impurities such as sulfur (S), nitrogen (N), and CCR (Conradson carbon residue) present in the heavy oil fraction together with the remaining metal component at the average temperature of the catalyst.

Particularly, the present invention makes it possible to maintain the catalytic performance over the entire impurity conversion rate in the conventional technology for the entire operation period, despite the temperature raising method different from the conventional technology. As a result, in the present invention, the demetalization has an impurity conversion of 80% or more, and the desulfurization has an impurity conversion of 82% or more.

That is, in the present invention, by maintaining the average temperature of the desulfurization catalyst at a relatively high level, it is possible to increase the yield of light oil in the product to about several vol% compared with the conventional one, and to maintain the average temperature of the demetallation catalyst relatively low Through the suppression of the rapid precipitation of the metal component removed by the metal removal reaction, the performance of the metal removal catalyst can be maintained constant over the entire operation period, and the lifetime can be extended.

In addition, in the present invention, the average temperature of the demetallation catalyst and the desulfurization catalyst is effectively controlled, so that the amount of hydrogen consumed in the reaction can be reduced to about 15 to 25% of the conventional amount.

As described above, the method of hydrogenating heavy crude oil according to an embodiment of the present invention is characterized in that sulfur (S), nitrogen (N), and CCR (Conradson Carbon Residue) The average temperature of the desulfurization catalyst (HDM Catalyst) and the average temperature of the desulfurization catalyst (HDS catalyst), which primarily remove nickel (Ni) and vanadium (V), are independently controlled and the average temperature of the desulfurization catalyst And the difference between the average temperatures of the demetallation catalysts is controlled to 15 to 50 캜.

Accordingly, the method for hydrotreating heavy crude oil according to an embodiment of the present invention can provide high-quality low-sulfur fuel oil (L / S fuel oil) or high-quality It is possible to produce a feedstock for the residual contact catalytic cracking process.

In addition, the method for hydrotreating a heavy oil portion according to an embodiment of the present invention can increase the life-time of a hydrogenation treatment of a heavy oil component and reduce the possibility of problems such as generation of differential pressure.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

1. Experimental Method

Example  One

Of the series reactors, 200 cc of HDS Catalyst was charged to Reactor 1 and 300 cc of HDM Catalyst was charged to Reactor 2.

Next, DMDS (dimethyl disulfide), which is a sulfurizing agent, was added to the series reactor, and sulfurization was carried out using light oil having a sulfur concentration adjusted to 2.2 vol%.

Next, the atmospheric residue was passed through the series reactor and hydrogenation treatment was carried out for 300 days.

At this time, the pressure of the series reactor was set to 140 kg / cm ³ , the liquid space velocity (LHSV) was set to 0.2 hr ^-1 , the ratio of H ₂ / oil was set to 850 NL / L, The average temperature of the desulfurization catalyst was maintained at 360 ° C and the average temperature of the demetallation catalyst was maintained at 345 ° C so that the difference between the average temperature of the catalyst was 15 ° C. The temperature of the demetalization and desulfurization catalyst was continuously increased by keeping the temperature increase rate at 0.1 ° C / day.

Example  2

The difference between the average temperature of the desulfurization catalyst and the average temperature of the demetallation catalyst was 25 ° C, the average temperature of the desulfurization catalyst was maintained at 370 ° C, and the average temperature of the demetallation catalyst was maintained at 345 ° C. The hydrogenation treatment of the heavy oil fraction was carried out in the same manner as in Example 1.

Example  3

Except that the difference between the average temperature of the desulfurization catalyst and the average temperature of the demetallation catalyst was 30 ° C, the average temperature of the desulfurization catalyst was maintained at 375 ° C and the average temperature of the demetallation catalyst was maintained at 345 ° C. The hydrogenation treatment of the heavy oil fraction was carried out in the same manner as in Example 1.

Example  4

Except that the difference between the average temperature of the desulfurization catalyst and the average temperature of the demetallation catalyst was 50 占 폚, the average temperature of the desulfurization catalyst was maintained at 395 占 폚, and the average temperature of the demetallation catalyst was maintained at 345 占 폚 The hydrogenation treatment of the heavy oil fraction was carried out in the same manner as in Example 1.

Comparative Example  One

Of the series reactors, 200 cc of HDS Catalyst was charged to Reactor 1 and 300 cc of HDM Catalyst was charged to Reactor 2.

Next, DMDS (dimethyl disulfide), which is a sulfurizing agent, was added to the series reactor and sulfurization was carried out using light diesel oil adjusted to a sulfur concentration of 2.2 vol%.

Next, the atmospheric residue was passed through the series reactor and the hydrogenation treatment was carried out for 50 days.

At this time, the pressure of the series reactor was set to 140 kg / cm ³ , the liquid space velocity (LHSV) was set to 0.2 hr ^-1 , the H ₂ / oil ratio was set to 850 NL / L, The average temperature of the desulfurization catalyst was maintained at 355 deg. C, and the average temperature of the demetalization catalyst was maintained at 345 deg.

2. Property evaluation

Table 1 shows the measurement results of the impurity conversion rates of the desulfurization catalyst and the demetalization catalyst for Examples 1 to 4, and FIG. 3 shows the results of measurement of the impurity conversion rates of the desulfurization catalyst and the demetalization catalyst for Examples 1 to 4 Fig.

1) The conversion of sulfur (S) which is a desulfurization catalyst impurity was defined as follows.

HDS (wt%) = {(wt% S) _feedstock (wt% S) _product} / (wt% S) _feed × 100

2) Conversion rates of nickel (Ni) and vanadium (V) which are impurity metals of the demetalization catalyst were defined as follows.

HDM (wt%) = {(wt ppm Ni + V) _feedstock- (wtppm Ni + V) _product } / (wt ppm Ni + V) _Feedstock x 100

[Table 1]

As shown in Table 1 and FIG. 3, in Examples 1 to 4, as the difference between the average temperature of the desulfurization (HDS) catalyst and the mean temperature of the demetalization (HDM) catalyst increases, It was confirmed that the impurity conversion ratio was the most excellent in the case of Example 2 adjusted by the temperature difference of 25 캜.

On the other hand, Table 2 shows the results of measurement of the impurity conversion rates of the desulfurization catalysts and the demetalization catalysts according to the reaction period for Example 2 and Comparative Example 1.

[Table 2]

Referring to Table 2, although the hydrogenation treatment was performed at a relatively low demetallation reaction temperature condition as compared with Comparative Example 1, in the case of Example 2, the impurity conversion rate of the demetalization catalyst was about 2 ~ 9%, and it was confirmed that the decomposition reaction rate of the desulfurization catalyst was also improved by about 2 ~ 7%.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. These changes and modifications may be made without departing from the scope of the present invention. Accordingly, the scope of the present invention should be determined by the following claims.

S110: Desulfurization catalyst and demetalization catalyst charging step
S120: Sulfurization step
S130: hydrogenation treatment reaction step

Claims (6)

A method for hydrogenation of a heavy oil fraction subjected to a hydrogenation treatment in a series reactor divided into a desulfurization catalyst charging section and a demetallation catalyst charging section,
Filling the desulfurization catalyst and the desulfurization catalyst with a desulfurization catalyst and a demetallation catalyst, respectively;
Adding a sulphurizing agent to the series reactor to perform sulphation; And
And performing hydrogenation treatment by adding hydrogen while passing the heavy oil fraction through the series reactor,
The average temperature of the desulfurization catalyst charged in the desulfurization catalyst charging part and the average temperature of the demetallation catalyst packed in the demetallization catalyst charging part are set to be controlled independently,
Wherein the difference between an average temperature of the desulfurization catalyst and an average temperature of the demetallation catalyst is maintained at 15 to 50 캜.
The method according to claim 1,
Wherein the difference between an average temperature of the desulfurization catalyst and an average temperature of the demetallation catalyst is 20 to 35 ° C.
The method according to claim 1,
The average temperature of the demetalization catalyst was maintained at 330 to 400 ° C.,
Wherein the average temperature of the desulfurization catalyst is maintained at 350 to 420 占 폚 and hydrogenated.
The method according to claim 1,
The heavy oil fraction
A method for hydrotreating a heavy oil, comprising at least one of an atmospheric residue, a decompressed residue, a bitumen, and a tar sand.
The method according to claim 1,
In the hydrogenation treatment,
Wherein the temperature of the demetallating and desulfurizing catalyst is raised at a rate of temperature increase of 0.01 to 1 占 폚 / day while passing the heavy oil fraction through the series reactor to perform the reaction.
The method according to claim 1,
The metal removal has an impurity conversion of 80% or more,
Wherein the desulfurization has an impurity conversion of 82% or more.

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