JPS59179142A - Method for packing catalyst - Google Patents

Abstract

PURPOSE:To control exothermic reaction in a reaction vessel by packing metallic wire netting containers contg. hydrogenation catalyst sealed therein in combination with empty metallic wire netting containers in a reaction vessel for a fixed bed catalytic reaction for hydrocarbons. CONSTITUTION:H2 and liquid oil 1 are passed through layers 4 packed with a catalyst and empty spaces 5 and lower mol. wt. oil and H2 are discharged out of the system. Spherical catalyst having 5mm.phi grain size are packed in the catalyst packing layer 4 for the reaction. Preferred mesh of the metallic wire netting constituting a cylindrical wire netting structure body 6 is 3mm.. The catalyst packing layers 4 are constituted of the metallic wire netting structure body 6 packed with 5mm.phi spherical catalyst, and the empty spaces 5 are constituted of the metallic wire netting structure body 6 contg. no catalyst. Said catalyst packing layer 4 and said empty space 5 are arranged alternately in the reaction vessel.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of loading a catalyst in a hydrocracking reactor for treating hydrocarbon oils with hydrogen in the presence of the catalyst.

More particularly, the present invention relates to a method for loading a catalyst in an apparatus for hydrocracking or hydrodesulfurization by catalytic treatment of heavy hydrocarbon slag.

Although hydroprocessing of heavy oils is economically preferable,
There were many problems. Seven of them were associated with formation of coke on the catalyst material and clogging of the catalyst layer. A second problem is that when the reaction that occurs is significantly exothermic, it is difficult to maintain a stable and satisfactory reaction temperature.

An object of the present invention is to provide a compact catalyst packing method that can suppress exothermic reactions in a fixed bed reactor and can be easily packed into the reactor.

Regarding the method of bringing liquid into contact with waste, please refer to U.S. Shipping License 29.
This is disclosed in the specification of No. 87465. This method completely eliminates the large pressure drop and difficulty of blockage caused by carbon formation.
No. 87465 describes that the solid is in an expanded state,
For bringing gases, liquids and solids into contact in a gas-liquid system in which the mass occupies a volume that is at least 10% larger than its resting state and operates irregularly in a gas-liquid system. (・However, since this method uses a boiling layer or fluidization, it is necessary to flow the liquid oil at a speed higher than the minimum speed necessary for fluidization.・This method uses more power than necessary. , and the reaction source is clearly worse than that of a fixed bed.Furthermore, a type of fluidized bed, a type of fluidized bed,
The disadvantage is that the suitable operating conditions are narrow,
Incorrect operation can cause various troubles. An example of a hydrogenolysis reaction is shown below.

As another method, a process using a fixed bed filled with spherical catalysts has been considered. However, if a fixed bed filled with these spherical catalysts is applied to the hydrogenation of liquid oil treated in the present invention, the fixed bed will be clogged with soot and dust that accumulates, increasing pressure loss and making it difficult to operate the equipment smoothly. It is difficult to maintain a stable and satisfactory reaction temperature because it causes problems in operation and is not practical (also, it causes localized heat generation due to explosion reaction).

The present invention has been made to overcome these drawbacks of the conventional methods, and provides a method for packing a catalyst that does not increase pressure loss over time, allows temperature control, and is compactly packaged. It is something.

That is, the present invention provides a fixed bed reactor using a catalyst for +l) hydrocarbons.
For example, a cylindrical or rectangular wire mesh container, for example, in which a spherical, cylindrical, or ellipsoidal catalyst is sealed, and a wire mesh container that is not filled with the catalyst are combined and placed in the reactor. (2) A method for charging a catalyst (hereinafter referred to as the first invention) characterized by charging a fixed bed reactor with a hydrocarbon catalyst.
For example, a cylindrical or rectangular wire mesh container, for example, is filled with a spherical, cylindrical or elliptical catalyst, and the wire mesh container is pierced with a light filler that does not participate in the reaction. This invention relates to a method for charging a catalyst (hereinafter referred to as the second invention), characterized in that the catalyst is charged into the reactor at a rate of interest.

The method of the present invention will be explained below with reference to the drawings.

FIG. 1 shows a spherical catalyst packed bed according to a conventional method, and FIG. 2 shows a catalyst bed according to the first invention of the present invention.

In Figure 1, hydrogen and liquid oil 1 enter the catalyst packed bed 3 from the reactor inlet, and inside, the liquid oil reacts with hydrogen on the catalyst, and then becomes oil with a smaller molecular weight and hydrogen 2. Go outside the system.

In FIG. 2, similarly, hydrogen and liquid oil 1 pass through the catalyst packed bed 4 and the space 5 from the reactor inlet and exit as oil and hydrogen 2 with smaller molecular weights to the outside of the yarn. However, in the reactor, the catalyst packed bed 4 was filled with a spherical catalyst of 5 uφ. Next, the filling method will be described using Fig. 6. In Fig. 6, 6 is a cylindrical wire mesh structure, and the size of the wire mesh used was one with a wire mesh spacing of 3 m. The catalyst packed bed 4 is composed of this wire mesh structure 6 filled with 5-diameter spherical catalyst, and the space 5 is made of a wire mesh structure 6 that is not filled with the catalyst.
It is composed of 6 structures. This catalyst packed bed 4 and space 5
were arranged alternately in the reactor.

When using the reactor according to the method of the present invention, exothermic reactions are much less likely to occur compared to packed bed reactors according to the conventional method.
In addition, filling and removal operations are easy.

FIGS. 4 and 5 show the axial temperature distributions of the packed bed according to the conventional method and the reactor according to the method of the present invention, respectively. The conventional method has a cooling section inside the reactor, so when an exothermic reaction occurs, the temperature changes in the direction of oil flow as shown in the temperature distribution shown in Figure 4, so the temperature rise due to heat generation. This further accelerates the reaction rate and further increases the temperature, resulting in a so-called explosive reaction that creates heat spots and increases the temperature.

As an example of the hydrocracking reaction, in the case of the hydrocracking of 7-nthracene oil shown below, -ΔH=500kco//
m N (N2), and is a considerably exothermic reaction.

On the other hand, in the case of the method of the present invention, there is a space 5 between the four layers 4 of the light 1fj.
exists as a cooling section, so the reaction section and the cooling section are arranged alternately as shown in Figure 5, which averages out the temperature distribution and makes explosive reactions extremely likely.

Next, FIG. 6 shows a conventional reactor in which a packed bed is divided.

In the figure, 4 is a catalyst filling part, and 5 is a space part. In the case of this reactor, due to the restriction that it is a room pressure vessel, in order to charge the catalyst, it is necessary to supply the catalyst from each of the points A, B, and C in Fig. 6, making it extremely difficult to fill the reactor. It is difficult and difficult to completely fill the catalyst.

On the other hand, in the method of the present invention shown in FIG. 2, even if heat is generated in the catalyst filling section 4, the gases are mixed very well in the space 5 that does not participate in the reaction, and the temperature distribution in the gas flow direction is small. Regarding catalyst filling, Figure 2 shows two types: one in which the catalyst is filled in a wire gauze from the top of the reactor, and one in which the catalyst is not filled in at all.
Since the reactor is filled with the catalyst by combing them together alternately, the catalyst can be filled with the catalyst, and filling is also easy, and cracking due to falling of the catalyst during filling can be prevented.

Next, FIG. 7 shows the change in pressure loss within the reactor over time.

Usually, liquid oil contains impurities (caulking),
And because coking products are generated during the hydrogenation reaction,
When using a reactor packed with a 1.5 Mφ catalyst in a normal packed bed shape as shown in Figure 1, a reactor packed with a 6 Mφ catalyst is used as shown in Comparative Example 1 in Figure 7. In this case, as shown in Comparative Example 2 in Fig. 7, the pressure loss increases over time with the operating time, but when using the reactor shown in Fig. 2 according to the method of the present invention, as shown in Inventive Example 1 in Fig. 7. No such trend was observed. The reason for this is that because there is a space between the catalyst parts, explosive reactions do not occur (therefore, there is no possibility that a local reaction will occur and a coking substance will be partially formed). can be given.

The relationship between catalyst particle size and adhesion by coking substances differs depending on the target oil type. The results shown in FIG. 7 are obtained when oils having the compositions shown in Table 1 below were used. The reaction conditions are as follows:
Hydrogen supply amount 15m'N/Hr, liquid oil supply amount 5.28-
It was set as e/Hr. The products obtained at this time are also shown in Table 1.

Table 1 In Table 1, BS indicates benzene soluble content, BI indicates benzene insoluble content, and THFS indicates gutrahydrofuran soluble content.

Next, the reactor according to the method of the present invention has a fixed catalyst, so the relative velocity with the fluid (hydrogen or liquid oil) is high (therefore, the mixing It has the advantage that the reactor volume can be compact to obtain the same hydrocracking conversion rate.

Although the catalyst used in the above explanation is a cobalt-molybdenum-silica-alumina spherical catalyst, it has been confirmed that similar results can be obtained with thin cylindrical, elliptical, etc. catalysts.

In addition to this Go-M□-silica alumina, the types of catalysts include N1-W-silica alumina and N1-M.

-7/L/Mina, N1W-Silica Alumina, N1W-Alumina, Ni-Co-Mo-Flumina, Pd-7
/I/, Pd-Y type zeolite, pt-alumina,
There are ZnO1 and the like.

Next, the overall flow will be described using FIG. The feed liquid oil 8 and the feed hydrogen 7 are injected into the reactor 13 according to the filling method of the present invention, and the pressure in the reactor is about 150 to 200 atmospheres.
Hydrocracking is carried out at a temperature of 550 to 450°C, and then the gas-liquid mixture 14 is sent to the gas-liquid separator 9, where it is separated into a gas product 10, a liquid product 11, and a hydrogen circulation stream 12. Stream 12 is combined with feed hydrogen 7 and reused.

9 and 10 show a catalyst layer according to the second aspect of the present invention.

In FIG. 9, hydrogen and liquid oil 1 pass through the catalyst packed bed 4 and the packed bed 15 that does not participate in the reaction from the reactor inlet.
It exits the system as oil with a smaller molecular weight and hydrogen 2. However, the reactor was constructed using a wire mesh structure A shown in FIG. It is made from original seeds.

In the 10th section, the wire mesh structure 6 shown in FIG.
．． In this example, a structure 4 filled with a catalyst consisting of 0 mm φ and a structure 15 filled with a filler that does not participate in the reaction in a wire mesh structure B are arranged alternately. On the other hand, the length of the catalyst part/1.12. /3
is made gradually longer to accommodate exothermic reactions. In addition, in this example, from the top, the wire mesh structure filled with the catalyst 4 and the wire mesh structure filled with a packed layer that does not participate in the reaction are alternately stacked, so the size of the wire mesh is There is an advantage that the filling height of the catalyst and filler can be adjusted arbitrarily by changing the height of the catalyst and filler. Further, since the packings M15a and 15b are provided to sandwich the catalyst portion, it is possible to suppress adhesion of caulking material to the catalyst layer and a decrease in catalyst activity caused by adhesion.

The reason why the temperature distribution is gradually increased to /1.12.13 is because the temperature distribution in the flow direction of a packed bed is normally lower near the inlet and higher near the outlet, as shown in Figure 5. It is better to shorten the height of the packed bed closer to the height of the reactor than to divide the height of the packed bed into equal parts.
This is to become.

The second invention of the present invention described above uses the same catalyst as the first invention described by MiJ, and fillers that do not participate in the reaction include silica alumina, alumina, zeolite, etc., which are catalyst carriers. It will be done.

Next, the raw oils shown in Table 1 were hydrogenated using the reactor shown in FIG. The catalyst used was co-M, the same as that used in the experiment of the first invention. - Silica alumina was used, silica alumina was used as a filler not involved in the reaction, and the reaction conditions were the same as in the experiment of the first invention. As a result, the pressure loss was as shown in Invention Example 2 in FIG. 7, and the products were as shown in the table below.

As is clear from the above description, the method of the present invention has the following effects.

1) It is easy to charge and remove the catalyst, and the inside of the reactor can be fully utilized.

2) When filling the reactor with the catalyst, the metal mesh structure is placed in the reactor, which prevents the catalyst from falling and causing cracks.

3) Since the catalyst-packed parts and unreacted parts are arranged alternately, the unreacted parts have a cooling effect and can easily cope with exothermic reactions.

4) The arrangement of the catalyst part and the filler not involved in the reaction can be easily changed.

5) Because the temperature distribution within the reactor is relatively uniform, local coking is less likely to occur, and therefore there is little change in pressure loss within the reactor over time.

6) Because it is a packed bed (fixed bed), mixing is extremely good (and the hydrocracking conversion method is also expensive) compared to ebullated beds and suspended beds.Therefore, the reactor volume can be compact.

7) Does not participate in the reaction (due to the presence of fillers,
Activity 41 decrease due to catalyst adhesion of caulking materials is less likely to occur.

[Brief explanation of drawings]

FIG. 1 is a diagram showing a filled 304 layer according to a conventional method, FIG. 2 is an explanatory diagram of an embodiment of the first invention of the present invention, and FIG. 6 is a wire mesh 44'' for catalyst filling or for holding a space. Fig. 4 shows the axial temperature distribution of the catalyst in the conventional packed bed shown in Fig. 1, and Fig. 5 shows the axial temperature distribution of the catalyst in the reactor of the present invention shown in Fig. 2. Figure 6 is a diagram showing a reactor with multiple packed beds according to the conventional method, Figure 7 is a graph showing the effects of the method of the present invention, and Figure 8 is a diagram showing a reactor using a hydrocracking reactor according to the method of the present invention. A diagram showing the overall flow when
FIG. 9 and FIG. 1D are explanatory diagrams of an embodiment of the second invention of the present invention. Fukudaikonjin 1) Meikakari agent Ryo Hagiwara - Rei 3 Figure 6 Light 7 Figure 8

Claims (1)

[Claims] (11) In a fixed bed reactor using a catalyst for hydrocarbons, a combination of a wire mesh container filled with a catalyst and a wire mesh container filled with nothing are filled into the reactor. (2) In a fixed bed reactor using a hydrocarbon catalyst, a catalyst is sealed in a wire mesh container, and a filler that does not participate in the reaction is sealed in the wire mesh container. A method for filling a catalyst, comprising filling the reactor with a combination of the above.