JPS5896685A - Hydrogenation process - Google Patents

Abstract

PURPOSE:To enable the hydrogenation with a compact apparatus, and to facilitate the temperature control, by passing a liquid oil and hydrogen through the catalyst layer composed of honeycomb or plate catalyst wherein the surface of the catalyst is arranged parallel to the flow of the liquid oil and hydrogen. CONSTITUTION:A mixture of a liquid oil and hydrogen is supplied through the line 3 to the reactor 2 containing a plurality of vertically stacked catalyst layers wherein the catalyst surface (longitudinal direction) of a honeycomb or plate catalyst is arranged parallel to the flow of the liquid oil and hydrogen. The liquid oil is hydrocracked to light oil and hydrocarbon gas at the catalyst layers 1 by the action of hydrogen and catalyst. The produced light oil and hydrocarbon gas are discharged from the system through the line 4 at the bottom of the reactor 2.

Description

[Detailed Description of the Invention] Improved method of processing with elements, more details. In the present invention, heavy hydrocarbon oils are treated by the action of a catalyst.

It relates to a method of hydrocracking or hydrodesulfurization. Although the hydroprocessing of heavy oils is an economically preferable method, it produces coke on the catalyst, clogging the catalyst bed, and causes problems when the reaction is extremely exothermic. It has drawbacks such as difficulty in stably maintaining an appropriate reaction temperature.

Edwin, S., Johnson/U.S. Patent No. 29B74
At step 65, liquid and gas are flowed upward in parallel flow into a reactor filled with a large amount of solid particles to form an ebullated bed, thereby effectively bringing the liquid and gas into contact and reducing pressure loss and blockage. Although an invention relating to a method is disclosed.

In this method, in order to form an ebullated bed, it is necessary to flow the liquid oil at a rate higher than the minimum velocity necessary to fluidize the solid particles. The superficial liquid velocity of the liquid must be 2 to 3 crrL/see or higher, and the liquid must be constantly circulated. Also,
In the reaction of hydrogenating hydrocarbons, the superficial velocity of hydrogen must be at least 1 to 2 times higher than the liquid superficial velocity. In this method, all phases are in the boiling bed.

Since it supplies and circulates large amounts of liquid and gas, it has the disadvantage of requiring a large amount of power, and in order to maintain a stable boiling state, the optimum flow rate range of liquid and gas must be selected and maintained. The disadvantage is that it is difficult to operate.

As another method, a process using a fixed bed reactor packed with a single spherical catalyst has been considered. However, if a fixed bed reactor filled with these spherical catalysts is applied to the hydrogenation treatment of liquid oil treated in the present invention, the fixed bed will become clogged with deposits that adhere and accumulate on the fixed bed, resulting in increased pressure loss. 2. It may interfere with the smooth operation of the equipment.

This method is not preferred in practice, and also has the disadvantage that it is difficult to remove the heat of two reactions in a fixed bed reactor, making it difficult to stably maintain an appropriate reaction temperature.

The present inventors have conducted extensive research in order to develop an excellent hydrotreating method that can solve the above-mentioned drawbacks of conventional hydrotreating methods. As a result, the catalytic surface ( By passing liquid oil and hydrogen through a catalyst layer in which the longitudinal direction of the catalyst is arranged parallel to the flow of liquid oil and hydrogen, it is possible to prevent blockage of the catalyst layer and increase in pressure loss due to the formation of coke on the catalyst 1-. The present inventors have discovered that the hydrogenation process can be carried out using a compact apparatus that is free from heat and temperature control and that the present invention is based on this knowledge. That is, the present invention provides a method for hydrotreating liquid oil by the action of hydrogen and a catalyst, in which the catalytic surface of a honeycomb-shaped or plate-shaped catalyst is arranged parallel to the flow of the liquid oil and hydrogen. This paper proposes a hydrogenation treatment method characterized by contacting with a catalyst layer.

The present invention will be explained below based on embodiment examples. FIG. 1 is an illustration of a reactor used in the present invention. In FIG. 1, a mixture of liquid oil and hydrogen is produced in a catalyst layer (a catalyst layer) formed by installing honeycomb-shaped or plate-shaped catalysts in multiple vertical stages with their catalytic surfaces (longitudinal direction) parallel to the flow of liquid oil and hydrogen.
The liquid oil is supplied from the pipe (3) at the top of the reactor (2) to the reactor (2), which has a built-in tray), and in the catalyst layer (1), the liquid oil is hydrocracked by the action of hydrogen and the catalyst to produce light oil. and hydrocarbon gases are produced. Hydrogen and generated light oil and hydrocarbon gas are discharged to the outside of the system through a pipe (41) at the bottom of the reactor (2).

The catalyst used in the present invention is a honeycomb-shaped catalyst (the cross-sectional shape is not particularly limited to hexagonal, square, circular, etc., and is formed in the longitudinal direction) or a plate-shaped catalyst, examples of which are shown in FIGS. 2 and 3. . FIG. 2 is a perspective view of several examples of honeycomb-shaped catalysts, (a) has a hexagonal cross section, (b) has a square cross section, (
C) is a catalyst with a diamond-shaped cross section, and (d) is a catalyst with a triangular cross-section.

FIG. 3 is a perspective view of an example of a plate-shaped catalyst. Plate catalyst (5
) are combined in large numbers parallel to each other and integrated.

It is used with the catalyst surface parallel to the flow of liquid oil and gas.

Deposits are deposited at the inlet and outlet of fluids (liquid oil and hydrogen) at the top and bottom of the catalyst bed.

Although it varies depending on the concentration and composition of the liquid oil and the solid content contained in the liquid oil, it is greatly influenced by the equivalent diameter of the bee-shaped catalyst or the spacing between the plates of the plate-shaped catalyst. According to experiments conducted by the present inventors, the preferred equivalent diameter of the honeycomb catalyst is 2 to 1 (approximately 111111 mm) when the solid content concentration in the liquid oil is low, regardless of whether the cross-sectional shape is polygonal or circular. When the diameter was high, it was about 10 to 30 dragons.The equivalent diameter is defined as follows.

The outer circumference of the cross-sectional area of the fluid flow and the preferred spacing between the plates of the plate-shaped catalyst are 5 to 10 mm when the solids concentration in the liquid oil is low, and 10 to 10 mm when the solids concentration is high. It was around 2011. In actual applications, the smaller the equivalent diameter of the catalyst or the plate spacing, the larger the catalyst area per volume, which is advantageous. Considering the contact efficiency of oil and gas with the catalyst, the equivalent diameter for honeycomb catalysts is 2 to 30 m, preferably 2 to 151 m, and the plate spacing for plate catalysts is 5 to 50 m.
The appropriate length is preferably about 5 to 201 m.

As mentioned above, in the present invention, a honeycomb-shaped catalyst or a plate-shaped catalyst is used, and the catalyst surface is arranged parallel to the flow of liquid oil and gas. There are few loss factors, so there is an advantage that pressure loss is small.

Next, since the pressure loss is small, the fluid linear velocity at the pressure loss allowed for the device is compared with that of the 2-spherical catalyst packing method, and the figure on the left is obtained by taking a larger value. As a result, the gas (hydrogen) flow becomes turbulent, and gas diffusion in the gas phase becomes active, so that the reaction is promoted and a high hydrogenolysis rate is obtained.

In addition, one possible means to deal with the large heat generated by the hydrocracking reaction is to introduce a cold hydrogen stream stepwise into various positions of the reactor to suppress the hydrocracking reaction. case.

Since the pressure loss is small, the fluid linear velocity of the liquid oil and hydrogen can be greatly changed, and by introducing a large amount of hydrogen, the amount of liquid oil supplied can be suppressed, and the temperature can be controlled more easily than before.

In addition, the flow of liquid oil and hydrogen is parallel to the catalyst surface, and since there is no flow of fluid (liquid oil and hydrogen) that forces deposits (caulking) against the catalyst surface, even if deposits adhere to the surface, Even in this case, the shear I force of the fluid flow causes re-scattering, and no increase in deposit adhesion is observed over time.

Next, the effects of the present invention will be explained in more detail using an experimental example using a honeycomb catalyst (a hexagonal catalyst having a cross-sectional shape of 4Ⅲ length across opposite sides) used in the present invention.

FIG. 4 is a graph showing the relationship between the pressure loss of the catalyst layer and the superficial liquid velocity when a 7 w yj spherical catalyst is used as the present experimental example and a comparative example. As is clear from this, in this experimental example, the pressure loss is only lower than that of the spherical catalyst packed bed, and one experiment is performed when the allowable pressure loss of the catalyst layer is 100 meters of water per 1 meter of height of one layer. In the example, a superficial liquid velocity of 20 crn/see is allowed, but in the case of two spherical catalyst packings, the superficial liquid velocity is only 1.7 cm/sec. FIG. 5 is a graph showing the change in pressure loss of the catalyst layer over time. As is clear from this, the pressure loss increases over time with the operating time in the 3-diameter spherical catalyst packed bed of Comparative Example 1 and the 7I1-diameter spherical catalyst packed bed in Comparative Example 2, but no increasing trend was observed in this example. I couldn't. Figure 6 shows LH8V (=supplied liquid oil acid/
It is a graph showing the relationship between the superficial liquid velocity of liquid oil and the hydrocracking rate under a constant condition of reactor volume)=o7s (1/Hr). As is clear from this, the hydrocracking rate hardly changes depending on the superficial liquid velocity of the liquid oil.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 FIG. 7 is a process flow sheet in the case of no external liquid circulation flow in the hydrotreating method of the present invention. In Fig. 7, the supplied liquid oil (8) and the supplied hydrogen (GE) are injected into a reactor (6) filled with a bee-shaped catalyst or a plate-shaped catalyst, and the pressure in the two reactors (6) is approximately 150 to 200 atmospheres. , temperature 350°C
~450'C! After that, the gas-liquid mixture I is sent to the gas-liquid separator (9) to produce gas products 01. It was separated into a liquid product αl and a hydrogen circulation stream 0, and the hydrogen circulation stream Q2 was combined with the supplied hydrogen (7) and recycled.

In addition.

The active components of the catalyst include CQMO-silica alumina, Ni, Mo-7 lyca alumina, Nr, MoP
20s-alumina was used. As a result, a high hydrocracking rate was obtained with a compact device, and stable hydrocracking could be performed with low power.

Example 2 FIG. 8 is a process 70-sheet in the case of external liquid circulation flow in the hydrotreating method of the present invention. In Fig. 8, supplied liquid oil (8) and supplied hydrogen (7) are injected into a reactor (6) filled with a honeycomb catalyst or a plate catalyst.
6) Pressure approximately 150 to 200 atm, temperature 350℃ to 4
Hydrogenolysis was carried out at 50°C, and the degassed liquid mixture α
The gaseous product 01. The liquid product 0υ is separated into a hydrogen circulating stream O3 and an external liquid circulating stream 0, and the hydrogen circulating stream O3 joins the supplied hydrogen (7) and is used for circulation, and the external liquid circulating flow αj is used as the supplied hydrogen (7) and the external liquid circulating stream 0. Combines with liquid oil (8) and reactor (6)
and circulated. Note that Co, Mo-silica alumina, Ni, Mo-silica alumina, Ni, Mo-P2O5-alumina were used as active components of the catalyst. As a result, a high hydrocracking rate was obtained with a compact device, and stable hydrocracking could be performed with low power. In this case, there is an advantage that the volume of one reactor is compact due to the external liquid circulation flow 01m, and it is possible to circulate a large amount of liquid oil, but the pressure loss and the power of the external liquid circulation flow αJ are Considering this, it is appropriate that the superficial velocity of liquid oil in the reactor is 5o cm/see or less,
It is economical to use hydrogen at a superficial velocity of 1 m/see or less.

As explained in detail above, the present invention has low pressure loss and
We propose a hydroprocessing method that does not increase pressure loss over time, consumes little power, and can achieve a high hydrocracking rate with a compact reactor, and that can easily suppress the large heat generated by the hydrogenation reaction. This is very useful in practice.

[Brief explanation of the drawing]

Figure 1 is an illustrative diagram of the reactor used in the present invention, Figure 2 is a perspective view of a honeycomb catalyst, Figure 3 is a perspective view of a plate catalyst, and Figure 4 is a diagram showing the pressure loss of the catalyst layer and the liquid empty column. Graph showing the relationship between speed, Figure 5 is a graph showing the change in pressure loss of the catalyst bed over time, Figure 6 is a graph showing the relationship between the superficial liquid velocity of liquid oil and the hydrocracking rate, and Figure 7 is a graph showing the relationship between the surface velocity of liquid oil and the hydrocracking rate. The gross flow route of the hydrotreating method when there is no external liquid circulation flow, Figure 8 shows the water reactor when there is an external liquid circulation flow, 7...Supplied hydrogen,
8... Supply liquid oil, 9... Gas-liquid separation device, 10...
- Gaseous product, II...Liquid product, +2...
Hydrogen circulation flow, 13... External liquid circulation flow, 14... Gas-liquid mixture Figure 1 Figure 2 (C) (t) Figure 3 Figure 4 Figure 5 erase nM (H) Figure 5 (night Σ month r4 return (“/]a)

Claims (1)

[Claims] In a method of hydrotreating liquid oil by the action of hydrogen and a catalyst, hydrogen and liquid oil are applied to a catalyst layer in which the catalytic surface of a honeycomb-shaped or plate-shaped catalyst is arranged parallel to the flow of the hydrogen and liquid oil. A hydrogenation treatment method characterized by contacting