TWI408219B - Method of Transfer of Moving Contact Decomposition Catalyst - Google Patents

Abstract

A method for transporting a fluid catalytic cracking catalyst which can greatly reduce friction at a bend of a transportation piping when a fluid catalytic cracking catalyst (FCC catalyst) is transported therein in a dry state. The method for transporting a FCC catalyst comprises a step for transporting a FCC catalyst on a gas by feeding the gas in the transportation piping having a bend. The transportation piping is formed of a metal material and the bend consists of a first portion in the shape of a straight pipe, and a second portion in the shape of a straight pipe connected with the first portion. In the transportation step, the superficial air velocity of the gas is set at 5-20 m/s, the direction of the gas flowing through the second portion makes an angle of 45°-90° to the direction of the gas flowing through the first portion, and the density of the FCC catalyst is set at 5-10 g/L or 15-20 g/L.

Description

Flow contact decomposition catalyst transfer method

The present invention relates to a transfer method of a flow contact decomposition catalyst in a flow contact decomposition process of heavy petroleum.

In view of environmental problems or ease of use, the demand for hydrocarbon oils having a boiling point below light oil is relatively increased, and how to convert heavy oil into light oil has become an important issue. Among them, as one of the heavy oil treatment processes, the importance of FCC (Fluid Catalytic Cracking) as a raw material oil is enhanced. Here, the flow contact decomposition means that the feedstock oil (petroleum hydrocarbon) is brought into contact with a fluid contact decomposition catalyst (hereinafter also referred to as "FCC catalyst"), thereby decomposing, thereby obtaining gasoline, liquefied petroleum gas, A method of alkylating a product such as a raw material or a middle distillate mixture.

Here, the raw material oil contains metals such as nickel, vanadium, iron, and copper. Therefore, when the raw material oil is subjected to flow contact decomposition, the metals are deposited on the FCC catalyst, which is remarkable. These metals are present in the stock oil due to contact with the crude oil, or the transport device, the storage device, or the treatment device, and are usually present in the feedstock oil as an organometallic compound typified by a porphyrin ring structure. Therefore, if the feedstock oil is in contact with the FCC catalyst at a high temperature, the organometallic compound will decompose and the metals will deposit on the FCC catalyst.

If these metals are deposited on the FCC catalyst, not only will the activity of the FCC catalyst be reduced, but the selectivity of the FCC catalyst will also decrease. That is, the metals have hydrogenation and dehydrogenation functions, and therefore, under the reaction conditions of flow contact decomposition, the dehydrogenation reaction of hydrocarbons is promoted, and as a result, the amount of hydrogen or coke produced as a poor product increases. The production of better liquefied petroleum gas, gasoline, and light oil is reduced.

Therefore, in order to avoid such a decrease in the amount of production of liquefied petroleum gas, gasoline, and light oil, there is known a method of using a magnetic separation device when performing flow contact decomposition on heavy oil or residual oil having a large metal content. Periodically or fixedly take out part of the FCC catalyst in the circulation system, that is, the FCC catalyst with reduced activity and selectivity, and put in a new FCC catalyst to keep the activity of the FCC catalyst in the circulation system as a whole. Fixed (for example, refer to Patent Document 1).

Patent Document 1: Japanese Patent Laid-Open No. 2006-187761

However, in order to take out a FCC catalyst having a decreased activity and replace it with a new FCC catalyst, it is necessary to transfer the FCC catalyst in a dry state. In general, there is a problem that in the FCC catalyst transfer step, the FCC catalyst is transferred by blowing dry air, but when the FCC catalyst passes through the bent portion of the transfer pipe, the FCC catalyst collides with the bent portion of the transfer pipe. The wall is worn, and the transfer pipe is worn, so that the bent portion of the transfer pipe forms a hole.

Therefore, an object of the present invention is to provide a method for transferring a flow contact decomposition catalyst which can greatly reduce abrasion of a bent portion of a transfer pipe when a flow contact decomposition catalyst (FCC catalyst) is transferred in a dry state.

The method for transferring a flow contact decomposition catalyst according to the present invention includes a step of flowing a gas in a transfer pipe having a bent portion, and transferring a flow contact decomposition catalyst by a gas, wherein the transfer pipe is formed of a metal material, and the bent portion is formed It is composed of a first portion of a straight tubular shape and a second tubular portion connected to the first portion; in the transfer step, the empty cylinder speed of the gas is 5 m/s or more and 20 m/s or less. The angle between the flow direction of the gas flowing through the second portion and the flow direction of the gas flowing through the first portion is 45° or more and 90° or less, and the ratio of the flow contact decomposition catalyst contained in the gas is set. It is 5 g/L or more and 10 g/L or less, or 15 g/L or more, and 20 g/L or less.

In the transfer method of the flow contact decomposition catalyst of the present invention, in the transfer step of flowing the gas into the transfer pipe made of the metal material having the bent portion and transferring the flow contact by the gas, the transfer step is performed under the following specific conditions. By transferring the flow contact decomposition catalyst, it is possible to reduce the frictional force applied to the transfer pipe by the flow contact decomposition catalyst. As a result, the wear of the bent portion of the transfer piping can be greatly reduced.

According to the present invention, it is possible to provide a transfer method of a flow contact decomposition catalyst which can greatly reduce abrasion of a bent portion of a transfer pipe when a flow contact decomposition catalyst (FCC catalyst) is transferred in a dry state.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

(Composition of flow contact decomposition system)

First, the configuration of the flow contact decomposition system 1 will be described with reference to Fig. 1 . The fluid contact decomposition system 1 has a reactor 10, a regeneration column 12, and a magnetic separation device 14. Further, in Fig. 1, the flow of the feedstock oil and the gasoline is indicated by a broken line, and the flow of the FCC catalyst is indicated by a solid line.

In the reactor 10, the feedstock oil and the flow contact decomposition catalyst (FCC catalyst) transferred from the regeneration tower 12 are reacted to generate gasoline. Here, the FCC catalyst used in the reaction is again transferred to the regeneration tower 12. As a contact method of a raw material, an FCC catalyst, and an additive, there is a method of contacting with a fluidized bed of FCC catalyst, and a riser cracking of the FCC catalyst and the raw material moving together in the tube, but The invention is applicable to any one of the ways.

The reaction conditions of the reactor 10 are not particularly limited, and usual reaction conditions can be employed. For example, the reaction temperature can be set to about 480 ° C to 650 ° C, and the pressure in the reactor 10 can be set to about 0.1 MPa to 0.3 MPa, and the ratio of the FCC catalyst to the raw material oil (FCC catalyst/raw material oil) can be set to From 1 to 20, the contact time is set to be about 0.1 second to 10 seconds.

In the present embodiment, as the heavy petroleum used as the feedstock oil, heavy petroleum oil containing a heavy metal such as nickel or vanadium and a distillation residue component such as asphaltene is used. Specific examples thereof include an atmospheric distillation residue oil of crude oil, a vacuum distillation residue oil, or a mixture obtained by hydrogenation treatment, or a mixture thereof. The FCC catalyst may be an FCC catalyst which is generally used in the contact decomposition of petroleum, and examples thereof include a zeolite-based catalyst. The particle size of the FCC catalyst is not particularly limited, but is usually about 5 μm to 200 μm, preferably about 20 μm to 150 μm.

In the regeneration tower 12, the regeneration treatment of the FCC catalyst used in the reaction with the feedstock oil in the reactor 10 is performed. Specifically, on the FCC catalyst that has reacted with the feedstock oil in the reactor 10, the coke formed by the contact decomposition with the feedstock oil adheres to the surface of the FCC catalyst, so that the FCC catalyst is heated at a high temperature. And burn the coke on the surface of the FCC catalyst. The FCC catalyst regenerated in the above manner is again transferred to the reactor 10 for contact decomposition of the feedstock oil.

The magnetic separation device 14 selectively separates the FCC catalyst (hereinafter also referred to as "deterioration catalyst") whose activity and selectivity are lowered, and discards the deterioration catalyst. Specifically, since the raw material oil contains metals such as nickel, vanadium, iron, and copper, when the feedstock oil is subjected to flow contact decomposition in the reactor 10, the metals are deposited on the FCC catalyst to form a deterioration catalyst. Therefore, focusing on the metal content of the FCC catalyst, magnetic separation is used to separate the deteriorated catalyst. The FCC catalyst (the FCC catalyst whose activity and selectivity are not reduced) which is not separated as the deterioration catalyst in the magnetic separation device 14 is transferred to the regeneration tower 12, and thereafter, is transferred to the reactor 10 for the feedstock oil. Contact decomposition.

Further, in the flow contact decomposition system 1, since the deterioration catalyst is discarded as described above in the magnetic separation device 14, in order to ensure that the FCC catalyst in the regeneration tower 12 reaches a fixed amount, the amount of the deteriorated catalyst is discarded. A new FCC catalyst (hereinafter also referred to as "new catalyst") is supplied to the regeneration tower 12. Further, in the fluid contact decomposition system 1, the FCC catalyst is randomly (randomly) discarded from the regeneration tower 12 regardless of whether the activity or selectivity of the FCC catalyst is lowered.

Next, the transfer piping 16 including the transfer piping for supplying the new catalyst to the regeneration tower 12, and the transfer piping for discarding the FCC catalyst from the regeneration tower 12, for the transfer piping 16, will be described with reference to Fig. 2; a transfer pipe for transferring the FCC catalyst of the regeneration column 12 to the magnetic separation device 14; a transfer pipe for transferring the FCC catalyst whose activity and selectivity are not reduced to the regeneration column 12 by the magnetic separation device 14; The magnetic separation device 14 discards the transfer piping of the deteriorated catalyst (hereinafter, collectively referred to as "transfer piping"). In addition, one part of the transfer piping 16 is shown in FIG.

The transfer pipe 16 is transferred to the FCC catalyst. When the FCC catalyst is transferred, a gas is used, but if the gas contains excess water, the FCC catalyst will absorb water, and the FCC catalyst in the reactor 10 or the regeneration tower 12 will not easily flow, or the FCC in the state containing moisture. Since the catalyst is at a high temperature and the FCC catalyst is hydrothermally deteriorated, it is preferred to use a dry state gas (for example, dry air) having a moisture content of less than 1% by volume. The transfer piping 16 is formed of a metal material such as stainless steel or carbon steel. Further, when the transfer piping 16 is formed of a material such as acrylic or vinyl chloride other than a metal material, it is melted by a high-temperature FCC catalyst, and thus such materials are not used.

The transfer pipe 16 has a bent portion 18 composed of a straight tubular first portion 18a and a straight tubular second portion 18b. The first portion 18a and the second portion 18b are joined by, for example, welding.

As shown in Fig. 2, in the transfer pipe 16, dry air flows so as to flow from the first portion 18a to the second portion 18b. At this time, the angle between the flow direction of the gas flowing through the first portion 18a and the flow direction of the gas flowing through the second portion 18b (hereinafter simply referred to as "angle") θ is 45° or more and 90° or less. . When the angle θ is 25° or more and less than 45°, the FCC catalyst tends to collide with the transfer pipe, and the wear of the curved portion 18 of the transfer pipe 16 tends to increase. When the angle θ is less than 25°, the transfer pipe is transferred. The wear of the curved portion 18 of 16 does not reach the above level, but the layout of the transfer piping 16 tends to be complicated and the economy is deteriorated; when the angle θ exceeds 90. In consideration of the layout of the transfer piping 16, it is not used.

The empty cylinder speed of the gas in the transfer pipe 16 is set to 5 m/s or more and 20 m/s or less. If the empty cylinder speed is less than 5 m/s, there is a tendency that it is difficult to transfer the FCC catalyst. When the empty cylinder speed exceeds 20 m/s, the abrasion of the curved portion 18 of the transfer pipe 16 tends to increase due to the collision of the FCC catalyst and the transfer pipe. In addition, the "empty speed" means a value obtained by dividing the flow rate [m ³ /s] of the dry air per unit time in the transfer pipe 16 by the sectional area [m ² ] of the transfer pipe 16 .

The ratio of the FCC catalyst contained in the gas (that is, the concentration of the FCC catalyst) when the FCC catalyst is transferred by the transfer pipe 16 is set to 5 g/L or more and 10 g/L or less, or 15 g/L or more and 20 g/ L or less. If the concentration of the FCC catalyst is less than 5 g/L, the amount of the FCC catalyst relative to the gas will be small, so that the transfer efficiency tends to be poor; if the concentration of the FCC catalyst exceeds 10 g/L and is less than 15 g/L, In the case where the FCC catalyst collides with the transfer pipe, the wear of the bent portion 18 of the transfer pipe 16 tends to increase. If the concentration of the FCC catalyst exceeds 20 g/L, it is necessary to increase at least the need for transferring the FCC catalyst. The amount of gas has a tendency to deteriorate economically.

In the above-described embodiment, in the transfer step of using the transfer pipe 16 made of a metal material and transferring the FCC catalyst via a gas, the FCC catalyst is transferred under the above-described specific conditions, so that the FCC catalyst can be reduced. The friction applied by the transfer pipe 16 is transferred. As a result, the wear of the bent portion 18 of the transfer piping 16 can be greatly reduced.

(Example)

Here, a test was conducted to confirm that the transfer of the transfer piping can be reduced by the transfer method of the FCC catalyst of the present invention. The test piece measures the abrasion resistance of the test piece 20 in accordance with ASTM-C 704 "Standard Test Method Abrasion Resistance of Refractory Materials at Room Temperature". Specifically, as shown in FIG. 3, the test piece 20 which can be changed with respect to the inclination angle Φ [°] in the vertical direction is simultaneously sprayed with SiC particles in the vertical direction from the nozzle 22 disposed above the test piece 20 and compressed and dried. Air was passed to cause the SiC particles to collide with the test piece 20, whereby the wear rate [%] of the test piece 20 was calculated. The test conditions are set to

The material of the test piece 20: SUS-304BA and SUS-316BA

Test piece 20 size: 100mm × 100mm × 2mm

Spraying pressure of compressed dry air: 0.01MPa~0.5MPa

Injection amount of SiC particles: 500g~3kg

SiC particle size: 0.3mm~0.85mm

The diameter of the spray nozzle 20: 4.74 mm

The linear distance between the spray nozzle 20 and the test piece 20 is 203 mm. Further, the wear rate is such that when the weight of the test piece 20 before the test is set to W ₀ [g], and the weight of the test piece 20 after the test is set to W ₁ [g], according to (W _{0 -} W ₁ ) / W ₀ × 100 is calculated.

First, the empty cylinder speed of the compressed dry air was set to 55 m/s, and the concentration of the SiC particles was set to 11.5 g/L, and the inclination angles Φ of the test piece 20 were measured to be 15°, 30°, 45°, 60°, respectively. Wear rate at 75° and 90°. As a result, the wear rates were 0.18%, 0.22%, 0.21%, 0.18%, 0.14%, and 0.13%, respectively. Therefore, as shown in FIG. 4, it can be confirmed that the peak of the wear rate is when the inclination angle Φ is set to about 30°, and as the inclination angle Φ becomes smaller from about 30°, the wear rate is decreased; The inclination angle Φ becomes larger from about 30°, and the wear rate is reduced.

Then, the concentration of the SiC particles was set to 11.5 g/L, and the inclination angle Φ of the test piece 20 was set to 90°, and the empty tube speeds of the compressed dry air were measured to be 10 m/s, 15 m/s, 20 m/s, and 30 m, respectively. /s, wear rate at 55 m/s. As a result, the wear rates were 0%, 0%, 0.01%, 0.04%, and 0.13%, respectively. Therefore, as shown in FIG. 5, it can be confirmed that the larger the empty cylinder speed of the compressed dry air is, the larger the wear rate is. In particular, when the empty cylinder speed of the compressed dry air is greater than 20 m/s, the rate of increase of the wear rate is higher. Significant.

Then, the empty cylinder speed of the compressed dry air was set to 55 m/s, and the inclination angle Φ of the test piece 20 was set to 90°, and the concentrations of the SiC particles were determined to be 0 g/L, 7 g/L, 10 g/L, and 11.5 g, respectively. Wear rate at /L, 15g/L, 20g/L, and 32.5g/L. As a result, the wear rates were 0%, 0.05%, 0.07%, 0.08%, 0.07%, 0.02%, and 0.01%, respectively. Therefore, as shown in FIG. 6, it can be confirmed that the peak of the wear rate is when the concentration of the SiC particles is about 12 g/L to 13 g/L, and the concentration of the SiC particles f is from about 12 g/L to 13 g. When /L becomes smaller, the wear rate decreases; moreover, as the concentration of SiC particles increases from about 12 g/L to 13 g/L, the wear rate decreases.

In the above test, the SiC particles were used instead of the FCC catalyst, but after the same experiment was performed using the FCC catalyst (the maximum particle diameter was 0.15 mm), the relationship between the inclination angle and the wear rate was confirmed. The relationship between the empty cylinder speed and the wear rate is also the same as that of the SiC particles when using the FCC catalyst.

Specifically, first, the empty cylinder speed of the compressed dry air is set to 55 m/s, and the concentration of the FCC catalyst is set to 6 g/L, and the inclination angle Φ of the test piece 20 is determined to be 0°, 15°, and 30°, respectively. The wear rate at 45° and 90° resulted in wear rates of 0%, 0.015%, 0.018%, 0.01%, and 0%, respectively. Therefore, as shown in FIG. 7, it can be confirmed that the peak value of the wear rate is when the inclination angle Φ is set to about 30°, and as the inclination angle Φ becomes smaller from about 30°, the wear rate is decreased; As the tilt angle Φ increases from about 30°, the wear rate decreases.

Then, the concentration of the FCC catalyst was set to 6 g/L, and the inclination angle Φ of the test piece 20 was set to 90°, and the empty tube speeds of the compressed dry air were determined to be 0 m/s, 10 m/s, 15 m/s, and 25 m, respectively. The wear rate at /s, as a result, the wear rates were 0%, 0.002%, 0.005%, and 0.018%, respectively. Therefore, as shown in FIG. 8, it can be confirmed that the larger the empty cylinder speed of the compressed dry air, the larger the wear rate, especially when the empty cylinder speed of the compressed dry air is greater than 20 m/s, the rate of increase of the wear rate is remarkable. .

Therefore, in view of the above test results, the SiC particles are harder than the FCC catalyst, and the gas cylinder speed is set to 5 m/s or more, 20 m/s or less, and the angle θ is 45 or more and 90. When the concentration of the FCC catalyst is 5 g/L or more and 10 g/L or less, or 15 g/L or more and 20 g/L or less, the bending portion of the transfer pipe 16 can be reduced even when the FCC catalyst is used. 18 wear.

1. . . Flow contact decomposition system

10. . . reactor

12. . . Regeneration tower

14. . . Magnetic separation device

16. . . Transfer piping

18. . . Bending

18a. . . part 1

18b. . . part 2

20. . . Test piece

twenty two. . . nozzle

Fig. 1 is a view showing the configuration of the flow contact decomposition system 1.

Fig. 2 is a view showing a part of a transfer pipe.

Fig. 3 is a view for explaining the abrasion resistance test of the test piece.

Fig. 4 is a view showing the correspondence relationship between the inclination angle and the wear rate when SiC particles are used.

Fig. 5 is a graph showing the relationship between the velocity of the hollow cylinder and the wear rate when SiC particles are used.

Fig. 6 is a graph showing the relationship between the concentration of SiC particles and the wear rate.

Fig. 7 is a view showing the correspondence relationship between the inclination angle and the wear rate when the FCC catalyst is used.

Fig. 8 is a view showing the correspondence relationship between the speed of the empty cylinder and the wear rate using the FCC catalyst.

1. . . Flow contact decomposition system

10. . . reactor

12. . . Regeneration tower

14. . . Magnetic separation device

Claims (2)

A method for transferring a flow contact decomposition catalyst, comprising: flowing a gas into a transfer pipe having a bent portion, and transferring a particulate flow contact contact decomposition catalyst by a gas; wherein the transfer pipe is formed of a metal material The curved portion is composed of a first portion of a straight tubular shape and a second tubular portion connected to the first portion. In the transfer step, the empty cylinder speed of the gas is set to 5 m/s or more. And 20 m/s or less, the angle formed by the flow direction of the gas flowing through the second portion with respect to the flow direction of the gas flowing through the first portion is 45° or more and 90° or less. The ratio of the flow contact decomposition catalyst contained in the gas contained in the gas is 5 g/L or more, 10 g/L or less, or 15 g/L or more, and 20 g/L or less. A magnetic separation device for selectively separating a particle-shaped flow contact decomposition catalyst having activity and selective decrease; wherein the magnetic separation device is connected with a metal material and having a bending portion In the piping, the curved portion includes a first portion of a straight tubular shape and a second tubular portion connected to the first portion; and the gas flows from the magnetic separation device to another device by flowing a gas into the transfer pipe Or from other devices to the above magnetic separation When the device transfers the particulate flow contact decomposition catalyst, the empty cylinder speed of the gas is set to 5 m/s or more and 20 m/s or less, and the flow direction of the gas flowing through the second portion is relative to the flow. The angle formed by the flow direction of the gas in the first portion is 45° or more and 90° or less, and the ratio of the flow contact decomposition catalyst contained in the gas is 5 g/L or more. And 10 g / L or less, or 15 g / L or more, and 20 g / L or less.