JPS61136591A - Conversion of heavy hydrocarbon oil into light oil - Google Patents

Abstract

PURPOSE:To remove heavy metal at a high removal rate and to convert a heavy oil feed stock into light oil at a reduced solvent ratio with reduced consumption of hydrogen, by mixing the heavy hydrocarbon oil feed stock with a specified amt. of a hydrogen-donating solvent followed by heavy oil cracking in the presence of a solid catalyst. CONSTITUTION:A heavy hydrocarbon oil contg. 1.0wt% or more asphaltene is converted into a light oil by cracking the heavy oil feed stock in the presence of 10-200wt%, based on the heavy hydrocarbon oil, hydrogen-donating solvent such as a hydrogenated hydrocarbon of b.p. of 150-500 deg.C and contg. 20wt% or more polycyclic aromatics, hydrogen gas and a solid catalyst such as a catalyst used for the treatment of other heavy oil, and removing at least 50wt% heavy metal contained in the heavy oil feed stock. It is pref. to keep a temp. of 380-470 deg.C and a hydrogen gas pressure of 20-150kg/cm<2>.g in the above reaction and to use said solid catalyst in the form of a fixed bed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to hydrogenation of heavy oil, particularly asphaltenes, [problems to be solved by the prior art and the invention] It is known to disassemble, lighten, and replace it with high-value products, and a number of methods have been implemented or proposed.

Here, heavy oil is a hydrocarbon oil containing 50 weight or more of a fraction with a boiling point of 350°C or higher, such as atmospheric distillation residue obtained from crude oil, vacuum distillation residue, coal, oil sand, oil shale, pitumene, etc. means oil obtained from Furthermore, the term "lightweighting" mentioned here refers to the purpose of cracking the above-mentioned heavy oil with hydrogenation to obtain light oil containing naphtha, gasoline fraction, kerosene fraction, etc. be.

One of the important problems in the above-mentioned hydrocracking of heavy oil is a decrease in catalyst activity. In other words, heavy oil contains asphaltene, which also contains heavy metals such as vanadium and nickel, which significantly poison the catalyst, which is a factor that prevents economical long-term continuous operation. . In order to solve this problem, efforts have been made to improve catalysts, and many excellent catalysts have been proposed, but the situation is still far from satisfactory.

Another important problem in hydrogen processing is the high cost of hydrogen. In the hydroprocessing of heavy oil, the heavier the feedstock oil, the greater the amount of hydrogen consumed, and the cost required for this increases enormously.

As one method to solve this problem of hydrogen cost, a hydrogenation method is known in which a polycyclic aromatic compound is hydrogenated and a compound having nine hydrogen donating properties is used (for example, U.S. Pat. No. 4,430,197), It is well known that when heavy oil is hydrocracked using a hydrogen donor compound such as the US4,294
, No. 686 and Oil & Gas Jour
nal Nov.

22.1982.1111-116).

Hydrogen-donating solvent (Hn dono)
r) is a compound obtained by hydrogenating a hydrocarbon compound having a polycyclic aromatic ring such as naphthalene, anthracene, etc., and such a hydrogen donor is heated at a high temperature (for example, 3
It is well known that carbon dioxide has the property of releasing hydrogen when heated to 80° C. or higher, and many attempts have been made to utilize this property industrially (for example, US Pat. No. 2,953,513).

It is also well known that pyrolysis oil, catalytic cracking oil, and hydrocracked oil contain such hydrogen-donating substances, and that they themselves act as effective hydrogen-donating solvents (for example, U, S, λ97o.

No. 545). In addition, Japanese Patent Publication No. 59-35955 discloses a method for hydrotreating deasphalting residue, but the solvent used here, whose main component is alkylnaphthalene, is a so-called hydrogen donor that gives hydrogen to heavy oil. Rather than acting as a body, it simply acts as a solvent to dissolve heavy oil.

The purpose of the present invention is to remove heavy metals contained in feedstock oil with a high removal rate, reduce the solvent ratio and hydrogen consumption, and ease the operating conditions.
The present invention provides a method for hydrotreating heavy oil containing at least 0% by weight using a hydrogen-donating inert solvent.

[Means for solving problems]

The object of the present invention is to provide a method for lightening heavy hydrocarbon oil containing asphaltene content of 1.0% by weight or more based on raw material heavy oil by hydrocracking.
of the heavy metals contained in the heavy hydrocarbon water sac oil.
This is achieved by a method for lightening heavy hydrocarbon oil, which is characterized by removing 0% by weight or more.

One feature of the method of the present invention is that the decomposition of heavy oil using a hydrogen-donating solvent is carried out in the presence of a solid catalyst.

In conventional decomposition using hydrogen-donating solvents, the reaction is generally carried out in an empty column. That is, a hydrogen-donating solvent and a raw material oil are introduced into a tower or a container without a packing in a high-temperature state, and the hydrogen-donating solvent is released and decomposed using nine hydrogen atoms. In contrast, the method of the present invention uses a hydrogen-donating solvent and hydrogen in the presence of a solid catalyst, and in particular effectively utilizes hydrogen in the gas phase to hydrocrack heavy oil. This product is characterized by reducing the amount of carbon dioxide and causing metals contained in the raw oil to adhere to the surface of the material.

Generally, decomposition using a hydrogen-donating solvent does not require a catalyst and is usually carried out without a catalyst. However, the present inventors discovered the following facts through experiments. That is, (1) the amount of hydrogen-donating solvent can be greatly reduced by a slight catalytic action and the presence of compressed hydrogen. (
2] The amount of the hydrogen-donating solvent used can be reduced by allowing a small amount of a highly active catalyst to be present, or by using a less active catalyst, such as a catalyst that has already been used. (3) When heavy oil is decomposed using a hydrogen-donating solvent in the presence of the solid catalyst, most of the heavy metals contained in the raw material are removed by the catalyst. To explain in more detail, regarding (1),
In the presence of a catalyst, the hydrogen-donating solvent is regenerated by compressed hydrogen gas, and as a result, even if the solvent ratio is reduced, there will be more hydrogen-donating solvent in the system. It will have excellent effects. Regarding (2), for example, direct desulfurization catalysts, demetallization catalysts, or cracking catalysts for heavy oil that have been used for several thousand hours or more have already lost most of their activity, but even such catalysts have a low solvent ratio. Effective for reducing Regarding (3), when decomposition is performed with a decomposition rate of 50% or more using a hydrogen-donating solvent, metals such as vanadium and nickel contained in the raw materials are in a state where they are very easily removed, and the catalyst etc. Due to the presence of porous material, it is easily removed.

One of the preferred examples of the hydrogen-donating solvent used in the present invention is a hydride of polycyclic aromatic hydrocarbon. Examples of the polycyclic aromatic hydrocarbon include 2 to 6 rings, preferably 2 to 6 rings.
4-ring aromatic hydrocarbons or their derivatives dE6. These aromatic hydrocarbons can be used alone or in combination of two or more. Specific examples of the aromatic hydrocarbon JE include naphthalene, anthracene, 7-enanthrene, pyrene, naphthacene, chrysene, benzopyrene, perylene, bicene, etc., or derivatives thereof.

Hydrogenated hydrocarbon oils having a boiling point of 150° C. to 500° C. and having a polycyclic aromatic hydrocarbon content of 20 wt % or more are also suitable for use as the hydrogen-donating solvent of the present invention.

A specific example of the hydrocarbon oil is a catalytic cracker (FCC)
Various products obtained from petroleum such as cycle oil, bottom oil of catalytic reforming equipment, pyrolysis oil of naphtha, etc., and various products obtained from coal such as tar oil, anthracene oil, taleonaute oil, coal liquefied oil, etc. can give.

In the present invention, an oil selected from FCC cycle oil and naphtha pyrolysis oil containing naphthalene, anthracene, etc. as main components is preferably used.

In the present invention, the above-mentioned polycyclic aromatic hydrocarbons and hydrocarbon oils may be hydrogenated in advance and charged into this apparatus, but since hydrogen gas coexists in this apparatus, hydrogenation may be carried out within this apparatus. Since it becomes a hydrogen-donating solvent, it is not necessarily necessary to hydrogenate it in advance.

The raw material oil used in the method of the present invention has an asqualtene content (bentane insoluble content) of i,o% or more, preferably 5 to 30%.
%, and the fraction with a boiling point of 350°C or higher accounts for 50% or more, such as atmospheric residual oil and vacuum residual oil obtained from crude oil, or oil obtained from coal, oil sand, oil shale, pidgemen, etc. It is.

The purpose of the solid catalyst used in the reaction tower of the present invention is not only to contribute to the decomposition of heavy oil, but also to collect and attach metals that are easily removed by decomposition. It is preferable that the adhesion capacity is high.

There are no particular restrictions on the solid catalyst, and it can be used in other heavy oil processing processes,
For example, a used catalyst used for hydrocracking, hydrodemetalization, hydrodesulfurization, etc. of heavy oil can be used. Further, a small amount of these new catalysts can be mixed, or a catalyst with relatively low activity can be used in place of the catalyst used above.

Solid catalysts include alumina, silica, silica-alumina, alumina-boria, silica-alumina-magnesia,
Examples include catalysts in which Group I metals such as nickel and cobalt and Group ViB metal oxides or sulfides such as molybdenum and tungsten are supported on an inorganic porous material such as silica-alumina-titania. Conventionally, the properties and shape of the catalyst are generally determined by heating the raw material heavy oil, hydrogen-donating solvent, and hydrogen gas in a heater, and then charging the mixture into a reaction tower containing a solid catalyst for reaction. will be carried out. The reaction temperature is 380-470°C1 hydrogen gas pressure'%d:20-
150 kp/ffl・y, loading amount of raw material heavy oil (LII
SV) (nr-1) is 0.1 to λ01, hydrogen gas supply amount (Wgo/kl raw material oil) is 200 to 1500, and hydrogen donating solvent supply amount is 10 to 200 to raw material heavy oil. weight%
, preferably in the range of 10 to 100% by weight.

In the above reaction, metals such as vanadium and nickel contained in the raw material heavy oil are removed and deposited on the catalyst. The hydrogen-donating solvent releases hydrogen in the column, but due to the presence of compressed hydrogen gas and a catalyst, it is regenerated by reacting with gaseous hydrogen gas. As for the type of reaction column, any of fixed bed, moving bed and fluidized bed may be used, but it is particularly preferable to use fixed bed.

Next, the reaction product from the reaction tower is separated into gas and liquid by a gas/liquid separator, and the liquid is separated into desired products such as gasoline naphtha fraction, kerosene fraction, light oil fraction, heavy oil fraction, etc. through separation operations such as distillation. The product is recovered by fractional distillation.

〔Example〕

EXAMPLE An experiment was conducted for the purpose of lightening heavy Arabian vacuum residue oil using the method of the present invention. In the reaction column, a direct desulfurization catalyst for atmospheric residual oil, which had already been used industrially for about 7,000 hours, was used as a downward flow fixed bed. As the reactor, a reaction tower with an inner diameter of 40 mm and a length of 1.300 m was used, and the above catalyst was filled to a length of 1,000 W. The raw material oil, hydrogen-donating solvent, and hydrogen gas shown in Table 1 were heated with a heater and then charged into the reaction tower in a downward flow.

Tetralin was added as a hydrogen-donating solvent to the raw oil at 50w.
It was added at a rate of t%. The reaction product from the reaction tower was separated into gas and liquid in a gas-liquid separator, and the liquid was used as a product after separating tetralin and naphthalene in a distillation device. The operation time was 1,500 hours continuously.

The properties of the raw material oil and the properties of the product are shown in Table 1, and the operating conditions are shown in Table 2. In addition, the temporal change in the decomposition rate is
Shown in the figure. Here, the decomposition rate was defined as follows.

α: Proportion of fraction (wt%) of α-b above 565°C in raw oil α
b: Proportion of fraction of 565° C. or higher in the product (wt%) Table 4 shows the metal removal rate in the reaction tower.

Comparative Example 1 The same raw material as in the example was hydrocracked using a conventional fixed bed reactor. However, in the reaction tower, cobalt (18wt%) and molybdenum (1t, owt%
) was used after pre-wetting. No hydrogen-donating solvent was added to the system, and the system was exposed to hydrogen. The operating conditions are shown in Table 2, and the product properties and material balance are shown in Table 1 and Table wE3, respectively. Figure 1 also shows the change in decomposition rate over time.

Note that feed oil and hydrogen gas were charged into the reaction tower in a downward flow as in the example. Table 4 also shows the decomposition rate and metal removal rate at the outlet of the reaction tower.

Comparative example 2 The experiment was conducted using the same raw materials and the same equipment as in Example 9.

However, in order to examine the effect of the catalytic action in the reaction tower, the reaction tower was filled with a catalyst carrier that did not support any metal. Other conditions were the same as in the examples, but the amount of hydrogen-donating solvent added was different from the examples as shown in Table 2. Product properties and material balance are shown in Tables 1 and 3, respectively.
[Effects of the Invention] From the results of Examples and Comparative Examples, it is clear that the present invention has the following effects.

(1) High decomposition rate.

As is clear from FIG. 3 and Table 4, the decomposition rate of the example is higher than that of comparative example 1. This indicates that the decomposition by the hydrogen-donating solvent is effectively carried out.

(2) Operating conditions are relaxed.

In the method of the present invention, decomposition is carried out effectively because the hydrogen-donating solvent is decomposed while being regenerated by the action of the solid catalyst. Therefore, it becomes possible to lower the reaction temperature, increase the amount of oil flow, etc. As shown in Reaction Table 3, the chemical hydrogen consumption of Examples is smaller than that of Comparative Examples 1 and 2.

The reason for this is thought to be that hydrogen is efficiently transferred to the feedstock heavy oil in the reaction tower in the liquid phase, and hydrogen consumption is low despite the high decomposition rate. The reason why the amount of hydrogen consumed is small even when compared with Comparative Example 2 is considered to be because in the example, the hydrogen-donating solvent is regenerated due to the presence of the catalyst, and hydrogen is used efficiently.

Comparing the total hydrogen consumption in the reaction tower with the conventional method, it is less than 80% at the same decomposition rate14) As shown in Table 2, the solvent ratio can be reduced, compared to Comparative Example 2, the Addition amount is small. Despite this, the decomposition rate is high and the metal removal rate is high because the hydrogen-donating solvent obtains gas phase hydrogen due to the presence of the catalyst and is regenerated, so even if the amount added is small, hydrogen is donated to the system. This is thought to be due to the presence of a large amount of solvent that has properties.

In lightening using a hydrogen group-donating solvent, the most important factors economically are the amount of solvent replenishment and the amount of solvent circulation. The reduction in solvent ratio is therefore a significant economic improvement over conventional methods.

(5) In conventional methods for removing metals from feedstock oil, decomposition using a hydrogen-donating solvent is generally carried out in an empty column, but in the method of the present invention, the reaction column has a catalytic effect. Since a porous material is present, the metal in the raw material is removed.

It is a graph showing leopard change.

Claims (7)

[Claims] (1) In a method for lightening heavy hydrocarbon oil containing asphaltene content of 1.0 wt% or more, the presence of a hydrogen-donating solvent, hydrogen gas, and solid catalyst in an amount of 10 to 200 wt% based on the raw material heavy oil. A method for lightening heavy hydrocarbon oil, comprising: decomposing raw material heavy oil and removing 50% by weight or more of heavy metals contained in the raw material heavy oil. (2) The reaction was carried out at a temperature of 380°C to 470°C, 20 to 1
The method according to claim 1, wherein the method is carried out while maintaining the hydrogen gas pressure at 50 kg/cm^2.g. (3) The method according to claim 1, wherein the solid catalyst is a catalyst used in another heavy oil treatment process. (4) The method according to claim 1, wherein the solid catalyst is used in the form of a fixed bed. (5) The method according to claim 1, wherein the hydrogen-donating solvent is a hydride of a polycyclic aromatic hydrocarbon. (6) The method according to claim 1, wherein the hydrogen-donating solvent is a hydrogenated hydrocarbon oil having a boiling point of 150°C to 500°C and a polycyclic aromatic content of 20% by weight or more. (7) The hydrogen donating solvent is 10 to 10% of the raw material heavy oil.
The method according to claim 1, wherein 0% by weight is added.