CN111068594B

CN111068594B - Fluidized bed reactor, application thereof and hydrocarbon oil desulfurization method

Info

Publication number: CN111068594B
Application number: CN201811214214.3A
Authority: CN
Inventors: 朱丙田; 侯栓弟; 毛俊义; 朱振兴; 毛安国; 张同旺; 刘凌涛; 韩颖
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2018-10-18
Filing date: 2018-10-18
Publication date: 2021-10-08
Anticipated expiration: 2038-10-18
Also published as: CN111068594A

Abstract

Fluidized bed reactor and application and hydrocarbon oil desulfurization method thereof, fluidized bed reactor include reaction section (3) and the settling section on upper portion of lower part, separate the settling section for settling section upper portion space and settling section lower part space by separating member (14), separating member (14) constitute by class cone and unloading pipe (17), its top cone shirt rim and reactor wall seamless connection, settling section upper portion space in set up fluid guide structure (9), fluid guide structure (9) pass through conveyer pipe (8) separating member (14), open in settling section lower part space, the unloading pipe (17) bottom opening of separating member (14) is in reaction section (3), settling section upper portion space top sets up gas outlet (13). The fluidized bed reactor provided by the invention can convey the separated catalyst fine powder particles to the dense bed layer of the reactor in time, remarkably reduce the suspension amount of the catalyst particles in the settling zone of the fluidized bed reactor, and prolong the operation period of the device.

Description

Fluidized bed reactor, application thereof and hydrocarbon oil desulfurization method

Technical Field

The invention relates to a fluidized bed reactor in the field of oil refining chemical industry and an application method thereof, in particular to a fluidized bed reactor and a gasoline adsorption desulfurization method adopting the fluidized bed reactor.

Background

With the increasing environmental protection requirements, the indexes of gasoline sulfur content are becoming more and more strict. This puts higher demands on gasoline desulfurization technology. The fluidized bed gasoline desulfurization process is an important gasoline desulfurization process.

CN1658965A proposes a method and apparatus for removing sulfur from a hydrocarbon-containing fluid, wherein the sulfur removal is enhanced by improving the contact of the hydrocarbon-containing fluid with sulfur-absorbing solid particles in a fluidized bed reactor. The reactor adopts a fluidized bed reactor, and the reactor comprises a catalyst bed layer straight-tube section for reaction, an expanding section and a straight-tube section for particle sedimentation from bottom to top; the top of the reactor is provided with a filter for gas-solid separation. The reactor bed zone is provided with a series of vertically spaced members for enhancing gas-solid contact. This reactor configuration has the disadvantage that catalyst fines suspended in the settling space above the reactor cannot be discharged from the reactor in a timely manner.

CN101780389A proposes a fluidized bed reactor for gasoline desulfurization. The reactor sequentially comprises a separation section, an expansion section and a reaction section from top to bottom. The reactor is internally provided with an automatic back-flushing filter, a dust remover, a catalyst bed layer, a backflow prevention distributor and an anti-impact distributor, and is externally connected with a reducer and a receiver. The device can timely, automatically and efficiently recover the filtering performance of the filter and reduce the labor intensity; catalyst particles are prevented from flowing back to the lower part of the reactor. Thereby enabling the gas to be uniformly distributed on the whole cross section of the reactor; the dust content of the gas is effectively reduced, so that the load of the automatic backwashing filter is greatly reduced, and the operation period of the automatic backwashing filter is effectively prolonged; the gas flowing into the reactor is prevented from impacting the backflow prevention distributor, so that the gas is uniformly distributed, and the benefit of the reactor is improved. But the presence of catalyst fines in the settling space above the reactor, suspended above the reactor, does not allow for timely discharge from the reactor.

The fluidized bed gasoline desulfurization process adopts a fluidized adsorption reactor, reaction products leave the reactor through a dust filter arranged at the top of the reactor, and separated solid particles of a catalyst are led out of the reactor through a discharge pipe arranged below the material level of a bed layer on the upper part of the reactor and then enter a regenerator and a reducer for regeneration and reduction. However, in the fluidized adsorption reactor, the fine powder of the catalyst and the fine powder generated by long-term abrasion of the particles can be elutriated into a settling space of the fluidized bed for long-term suspension, so that suspended particles have no chance to return to a dense bed layer of the fluidized bed and can not be discharged out of the reactor, and the stable operation of the device is influenced after long-term abrasion. The reason why the particles are difficult to settle in the settling space of the gasoline adsorption desulfurization reactor is that: the gas flows from bottom to top, and the gas moves upwards basically on the radial section, so that the particles in most areas on the section of the settling space have more chances to be subjected to the upward drag force of the gas, and once the velocity of the particles is less than the terminal velocity of the particles, the particles are difficult to settle.

Therefore, it is required to provide a new adsorption desulfurization reactor which not only can realize adsorption desulfurization, but also can remove catalyst fine powder formed in the reactor out of the reaction system in time to realize stable and long-term operation of the apparatus.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a fluidized bed reactor capable of recovering particles in a settling space of the reactor to a catalyst bed layer and an application method of the fluidized bed reactor on the basis of the prior art, wherein the fluidized bed reactor can obviously reduce the suspension amount of catalyst particles in the settling area of the fluidized bed reactor.

A fluidized bed reactor comprises a reaction section 3 at the lower part and a sedimentation section at the upper part, and is characterized in that the sedimentation section is divided into a sedimentation section upper space and a sedimentation section lower space by a partition member 14, the partition member 14 consists of a cone-like body and a blanking pipe 17, the skirt edge of the cone at the top part is in seamless connection with a reactor cylinder body, a fluid guide structure 9 is arranged in the sedimentation section upper space, the fluid guide structure 9 passes through the partition member 14 through a conveying pipe 8 and is opened in the sedimentation section lower space, the bottom of the blanking pipe 17 of the partition member 14 is opened in the reaction section 3, and a gas outlet 13 is arranged at the top of the sedimentation section upper space;

the fluid guide structure 9 consists of a gas collection chamber 95, an outlet channel 96 and a feeding channel 98, wherein the feeding channel 98 is vertically arranged below the gas collection chamber, one end of the feeding channel is communicated with the gas collection chamber, and the other end of the feeding channel is communicated with the conveying pipe 8; the outlet passage 96 is horizontally arranged, one end of the outlet passage is communicated with the gas collection chamber 95, and the other end of the outlet passage is opened in the upper space of the settling section.

The cone-like body is a single cone surface or a multi-surface cone surface which is formed by a plurality of planes in a surrounding mode and has a large upper part and a small lower part.

The application method of the fluidized bed reactor comprises the steps that fine powdery catalyst particles are filled in the fluidized bed reactor, raw materials enter from the bottom of the fluidized bed reactor and are in contact with the catalyst particles to react, and meanwhile, the catalyst particles are driven to move upwards to be in a fluidized state; part of catalyst particles rise to the settling section along with the reaction oil gas, gas-solid fluid enters the fluid guide structure through the conveying pipe, enters the upper space of the settling section in a rotational flow mode through an outlet channel of the fluid guide structure, is separated and settled under the action of the rotational flow, enters a discharging pipe of the separating member and returns to a catalyst bed layer of the reaction section, and the other part of particles are adsorbed on the filter, fall off when the filter is subjected to reverse blowing and settle into a discharging pipe of the separating member; and the oil gas product after gas-solid separation enters a subsequent separation system through a gas outlet.

A method for desulfurizing hydrocarbon oil adopts the fluidized bed reactor, the fluidized bed reactor is filled with an adsorption desulfurization catalyst, a sulfur-containing hydrocarbon oil raw material enters from the bottom of the fluidized bed reactor, contacts with the adsorption desulfurization catalyst under the condition of adsorption desulfurization to react, and simultaneously drives catalyst particles to move upwards so as to enable the catalyst particles to be in a fluidized state; part of catalyst particles rise to a settling section along with reaction oil gas, gas-solid fluid enters a fluid guide structure through a conveying pipe, enters a settling space at the upper part in a rotational flow mode through an outlet channel of the fluid guide structure, part of particles are separated and settled and enter a discharging pipe of a separation member to return to a catalyst bed layer of the reaction section, the other part of particles are adsorbed on a filter, fall off when the filter is subjected to reverse blowing, settle in the discharging pipe of the separation member, and an oil gas product subjected to gas-solid separation enters a subsequent separation system through a gas outlet.

The fluidized bed reactor and the application method thereof and the hydrocarbon oil desulfurization method adopting the fluidized bed reactor have the beneficial effects that:

according to the fluidized bed reactor provided by the invention, the separation member separates the settling zone into the upper area of the settling section and the lower area of the settling section, gas-solid fluid is conveyed through the conveying pipe, and the gas-solid separator is not arranged on the conveying pipe in the lower area of the settling section, so that the structural design of the device is simplified on one hand, and the crushing effect of the gas-solid separator on particles is reduced on the other hand. Is especially suitable for catalyst reaction system with low wear strength and fragility.

And the fluid from the lower area of the settling section enters the upper area of the settling section through the conveying pipe, and the gas-solid fluid generates rotational flow through the fluid guide structure. The outlet channel of the fluid guide structure has a constraint effect on fluid flow, on one hand, a rotational flow is formed, and on the other hand, the cross section normal direction of the special outlet channel enables fluid to flow out of the outlet channel without impacting the wall of the reactor and the filter, so that particle breakage and particle adsorption on the filter are avoided. Most particles can be settled through the rotational flow, the settled particles return to the catalyst bed layer through the blanking pipe of the separation member and then are discharged out of the reactor through the catalyst discharge port, and the content of fine powder in the reactor is reduced; when the filter is subjected to back flushing, because the gas on the radial section of the upper area of the settling section does not flow vertically upwards but flows at an uneven flow rate, a filter cake on the filter can be settled after the back flushing, falling particles are prevented from being carried by rising gas, the suspension concentration of catalyst fine powder in the settling section is effectively reduced, and the accumulation of the catalyst fine powder in the upper area of the settling section is avoided, so that the fluidized bed reactor can stably run for a long period, and a good and stable reaction effect is obtained.

Because the desulfurization adsorbent used for hydrocarbon oil desulfurization has low strength and is easy to crush, the fluidized bed reactor provided by the invention can obviously reduce the crushing of the desulfurization adsorbent into fine powder, and has good economic benefit.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a schematic structural view of a first embodiment of a fluidized bed reactor provided by the present invention;

FIG. 2 is a schematic structural view of a second embodiment of a fluidized bed reactor provided by the present invention;

FIG. 3 is a top view of a fluid directing structure in a reactor;

FIG. 4 is a front view of a fluid directing structure;

FIG. 5 is a top view of a fluid directing structure;

description of reference numerals:

1-raw material feed pipe 2-catalyst feed pipe

3-reaction section 4-settling section lower space

8-conveying pipe 9-fluid guiding structure

10-settling section outer wall 11-settling section upper space

12-Filter 13 gas Outlet

14-partition member 15-partition plate

17-blanking tube 18-blanking tube bottom opening

19-catalyst outlet 95-gas collection chamber

121-external profile of filter 951-plenum boarding

952-lower bounding wall 953 of gas-collecting chamber-inner bounding wall of gas-collecting chamber

954-gas collection chamber peripheral board 955, 956-gas collection chamber two side enclosing board

96-outlet channel 98-feed channel

961-Top Ends of outlet channels 962-peripheral plates of outlet channels

963-inner bounding wall 964 of the outlet channel-lower bounding wall of the outlet channel.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In order to solve the problems that the settling space of the gasoline adsorption desulfurization reactor is difficult to settle and the concentration of particles is continuously increased, the separation member is added in the settling space, so that the non-uniformity of gas flow of gas-solid fluid in the radial section of the settling space is changed, the stress uniformity of the particles in the radial section of the settling space is reduced, the drag force borne by the particles in a local area is reduced, and the particles are promoted to settle.

A fluidized bed reactor comprises a lower reaction section 3 and an upper settling section, and is characterized in that the settling section is divided into a settling section upper space 11 and a settling section lower space 4 by a partition member 14, the partition member 14 consists of a cone-like body and a blanking pipe 17, the skirt edge of the cone at the top of the partition member is in seamless connection with a reactor cylinder, a fluid guide structure 9 is arranged in the settling section upper space, the fluid guide structure 9 passes through the partition member 14 through a conveying pipe 8, the bottom of the fluid guide structure is opened in the settling section lower space, the bottom of the blanking pipe 17 of the partition member 14 is opened in the reaction section 3, and the top of the settling section upper space 11 is provided with a gas outlet 13;

the fluid guiding structure 9 is composed of a gas collection chamber 95, an outlet passage 96 and a feeding passage 98. The feeding channel 98 is vertically arranged below the gas collection chamber, one end of the feeding channel is communicated with the gas collection chamber 95, and the other end of the feeding channel is communicated with the conveying pipe 8; the outlet passage 96 is horizontally arranged, one end of the outlet passage is communicated with the gas collection chamber 95, and the other end of the outlet passage is opened in the upper space of the settling section.

Preferably, a catalyst outlet 19 is provided at the upper portion of the reaction zone 3, and the outlet 18 of the blanking pipe 17 of the partition member 14 and the catalyst outlet 19 are located at substantially the same horizontal line.

Preferably, the cone of the partition member 14 is a single cone or a plurality of polygonal openings surrounded by the inclined baffle; the included angle between the conical surface angle of the single cone or the included angle between the inclined baffles and the horizontal plane is 35-60 degrees.

Preferably, the cross section of the outlet passage 96 is rectangular, and the outlet passage is a region surrounded by four surrounding plates, namely an upper surrounding plate, a lower surrounding plate, an outer surrounding plate and an inner surrounding plate, wherein the height-to-width ratio of an opening of the outlet passage is 2-5: 1.

preferably, the outlet channel 96 is circular arc-shaped on the horizontal section, the included angle between the normal direction of the circular arc-shaped channel outlet and the circular tangent line of the channel outlet, which takes the center of the cross section of the settling space as the center of the circle, is 6-20 degrees, preferably 8-15 degrees, and the ratio of the radius R1 of the outer edge of the circular arc-shaped channel to the radius R of the upper space of the settling section of the reactor is 0.6-0.95, preferably 0.7-0.9.

Preferably, the circumference of the outer edge of the outlet channel is 200-800 mm, and more preferably 300-600 mm.

Preferably, a filter is arranged at the top of the upper space of the settling section, and the upper space of the settling section is communicated with the gas outlet through the filter.

Preferably, the lowermost end of said outlet passage is axially higher than the lowermost end of the filter.

Preferably, the ratio of the cross-sectional area of the conveying pipe 8 to the cross-sectional area of the settling section is 0.01 to 0.04, and more preferably 0.02 to 0.03.

In the fluidized bed reactor provided by the present invention, the partition member 14 may be non-axisymmetric, and the upper opening cross-section thereof is an irregular polygon. The partition member 14 is surrounded by a baffle plate with a certain inclination angle at the upper part, and the bottom part is connected with a discharging pipe 17; the baffle can be made of plates with various structural forms such as flat plates, circular arc plates and the like, and only a structure similar to a cone can be formed.

Furthermore, the radial section of the cone is large at the top and small at the bottom, the side wall of the cone is composed of 1 or more enclosing plates, and the included angle between the conical surface angle of the single cone or the inclined baffles and the horizontal plane is 30-70 degrees, preferably 35-60 degrees.

The number of the partition members 14 may be plural, preferably 1 to 9.

Each cone-shaped component is connected with a blanking pipe 17, the blanking pipe of each cone can extend into the catalyst bed layer, preferably, the blanking pipes of the cones converge to form a blanking pipe outlet, and the inclination angle of the middle connecting pipeline of each cone blanking pipe manifold to form a dipleg is larger than 45 degrees.

And a catalyst discharge pipe 19 is arranged at a position of the reaction section 3 close to the settling section, and an outlet 18 of a discharge pipe 17 of the separation member extends into the catalyst bed layer and is close to the position of the catalyst discharge port 19.

The number of the fluid guiding structures 9 may be one or more, and when the number of the fluid guiding structures is plural, the outlet directions of the fluid guiding structures are arranged in the same manner.

The position of the fluid guide structure in the settling space is as follows: the lower edge of the outlet of the fluid guide outlet structure is at least not lower than the lowest end of the filter tube of the filter.

A gas outlet of the reactor is provided with a filter 12, and the filter 12 extends into the upper area of the settling section; the filter is provided with an automatic blowback device capable of blowing off particulate matter deposited on the filter.

The ducts 8 communicate with the fluid directing structure directly through the partition, the number of ducts 8 being the same as the number of fluid directing outlet structures 9.

Preferably, the nozzle below the delivery pipe 8 extends beyond the separating member 14, and the distance between the nozzle below the delivery pipe 8 and the conical surface of the separating member 14 is preferably 10-200 mm.

Preferably, the circumference of the outer edge of the arc-shaped outlet channel is 200-800 mm, and more preferably 300-600 mm.

The application method of the fluidized bed reactor provided by the invention comprises the following steps that fine powdery catalyst particles are filled in the fluidized bed reactor, raw materials enter from the bottom of the fluidized bed reactor and contact with the catalyst particles to react, and meanwhile, the catalyst particles are driven to move upwards to be in a fluidized state; part of catalyst particles rise to the settling section along with the reaction oil gas, gas-solid fluid enters the fluid guide structure through the conveying pipe, enters the upper space of the settling section in a rotational flow mode through an outlet channel of the fluid guide structure, part of the particles are separated and settled to enter a discharging pipe of the separating member and return to the reaction section, and the other part of the particles are adsorbed on the filter, fall off during the back blowing of the filter and settle to the discharging pipe of the separating member; and the oil gas product after gas-solid separation enters a subsequent separation system from a gas outlet.

In the application method of the fluidized bed reactor, the gas velocity of the outlet channel of the fluid guide structure is 3-12 m/s, and preferably 4-9 m/s.

The fluidized bed reactor provided by the invention is suitable for a hydrocarbon oil adsorption desulfurization reaction system.

A method for desulfurizing hydrocarbon oil adopts the fluidized bed reactor, the fluidized bed reactor is filled with an adsorption desulfurization catalyst, a sulfur-containing hydrocarbon oil raw material enters from the bottom of the fluidized bed reactor, contacts with the adsorption desulfurization catalyst under the condition of adsorption desulfurization to react, and simultaneously drives catalyst particles to move upwards so as to enable the catalyst particles to be in a fluidized state; part of catalyst particles rise to the settling section along with the reaction oil gas, gas-solid fluid enters the fluid guide structure through the conveying pipe, enters the upper space of the settling section in a rotational flow mode through an outlet channel of the fluid guide structure, part of the particles are separated and settled and enter a discharging pipe of the separation member to return to a catalyst bed layer of the reaction section, the other part of the particles are adsorbed on a filter, the particles fall off during reverse blowing of the filter, settle in the discharging pipe of the separation member, and an oil gas product after gas-solid separation enters a subsequent separation system through a gas outlet.

In the hydrocarbon oil desulfurization method provided by the invention, the sulfur-containing hydrocarbon oil raw material is sulfur-containing naphtha, including hydrocarbon oil fractions such as catalytic cracked naphtha, straight run gasoline and the like.

The adsorption desulfurization catalyst is composed of active components Ni and/or Co and one or more heat-resistant inorganic oxide carriers of ZnO, matrix alumina and silicon oxide.

The adsorption desulfurization conditions are as follows: the reaction temperature is 350-440 ℃, and hydrogen gas is usedThe mol ratio of the gasoline to the gasoline is 0.1-0.4, and the weight hourly space velocity is 0.2-0.6 h^-1Absolute pressure is 2.0-3.0 MPa.

The following detailed description of the embodiments of the fluidized bed reactor according to the present invention is provided with reference to the accompanying drawings:

fig. 1 is a schematic structural diagram of an embodiment of a fluidized bed reactor according to the present invention, and as shown in fig. 1, an inner space of a fluidized bed reactor main body includes a reaction section 3 and a settling section from bottom to top. The settling section is provided with a partition member 14 dividing the settling section into a settling section upper space 11 and a settling section lower space 4, wherein the settling section upper space is provided with a filter 12 and a fluid guiding structure 9. The gas outlet of the filter 12 communicates with the gas outlet 13 of the fluidized bed reactor. The fluid guiding structure 9 is provided with a conveying pipe 8 passing through a partition plate 15, the conveying pipe 8 is opened in the lower space of the settling section, gas-solid fluid from the lower space 4 of the settling section is introduced into the upper area 11 of the settling section, and the flowing direction of the fluid is changed to enter the upper area 11 of the settling section in a swirling manner, so that the settling of fine particle catalyst is increased and the collision of catalyst particles is reduced.

The partition member 14 comprises a plurality of members enclosed by partition plates 15 to form a cone-like structure, and a discharge pipe 17 is connected to the bottom of the partition member 14 and used for collecting particles settled in the upper area of the settling section and returning the particles to the bed of the reaction zone.

FIG. 2 is a schematic structural diagram of another embodiment of a fluidized bed reactor provided by the present invention. As shown in FIG. 2, the partition member 14 comprises a plurality of members having a cone-like structure, the upper edges of the cones of adjacent members are welded together, and the discharge pipes 17 of the cone members are collected on a dipleg. The partition plate member is provided with a plurality of cone-like members, which contributes to saving of a settling space in the axial direction occupied by the main body portion (i.e., the cone portion) of the member.

FIG. 3 is a top view of a fluid directing structure in a fluidized bed reactor; FIG. 4 is a front view of a fluid directing construction; FIG. 5 is a top view of a fluid directing structure; as can be seen in fig. 4, the fluid directing structure 9 consists of a plenum 95, an outlet channel 96 and a feed channel 98. The feeding channel 98 is vertically arranged below the gas collection chamber, one end of the feeding channel is communicated with the gas collection chamber 95, and the other end of the feeding channel is communicated with the conveying pipe 8; the outlet passage 96 is horizontally arranged, one end of the outlet passage is communicated with the gas collection chamber 95, and the other end of the outlet passage is opened in the upper space of the settling section.

As shown in fig. 3, the fluid guiding structure 9 is installed in the settling zone of the fluidized bed reactor, the outlet channel 96 is defined by an outlet channel inner surrounding plate 963, an outlet channel outer surrounding plate 962, an outlet channel upper surrounding plate 961 and an outlet channel lower surrounding plate 964, the horizontal sections of the outlet channel inner surrounding plate 963 and the outlet channel lower surrounding plate 962 are arc-shaped, and an included angle a between a normal direction of an outlet of the arc-shaped outlet channel and a tangent line of a circle at the outlet of the channel and with the center of the cross section of the settling space as a center is 6 to 20 degrees, preferably 8 to 15 degrees. As shown in the attached figure 5, the ratio of the radius R1 of the outer edge of the arc-shaped outlet channel to the radius R of the upper space of the settling section of the reactor is 0.6-0.95, preferably 0.7-0.9.

The fluidized bed reactor of the present invention and the method and effect of its application are illustrated by examples below.

In the examples and comparative examples:

the catalyst used was an S Zorb catalyst manufactured by the Zhongpetrochemical Nanjing catalyst plant under the designation FCAS-R09, the properties of which are listed in Table 1.

The sulfur-containing hydrocarbon oil was sulfur-containing gasoline obtained from Yanshan petrochemical division, a product of petrochemical industries, Ltd., China, and the properties thereof are shown in Table 2.

The reaction conditions in the fluidized bed reactor include: the contact temperature is 400 ℃, the absolute pressure meter is used, the pressure is 2.8MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon raw material is 4h^-1。

The main analysis and test method comprises the following steps:

the particle size is measured by a Malvern laser particle measuring instrument, and the pore volume is measured by a mercury intrusion method. The specific surface area is measured by the BET method, and other parameters are conventional analytical methods.

The method for measuring the dilute phase density comprises the following steps: by measuring the pressure difference P1 at different positions (spacing L) in the axial direction of the settling space, the dilute phase particle density is equal to P1/(g L) -hydrocarbon density, and g is the gravity acceleration.

The catalyst loss calculating method includes setting gas-solid separator in the settling space of the regenerator, introducing the gas separated in the gas-solid separator into the fine powder collecting tank and collecting the fine powder entrained in the gas. The ratio of the quality of the fine powder collected by the fine powder collecting tank to the gasoline processing in a certain time is the catalyst consumption.

TABLE 1

TABLE 2

Example 1:

the fluidized bed reactor shown in FIG. 1 is adopted, and the structure is as follows: the settling zone of the reactor is internally provided with 1 separating member, the inclination angle of the baffle 15 is 60 degrees, and the section of the opening of the separating member is circular. The upper part of the settling zone is provided with a metal filter tube type filter, and the space at the lower part of the settling section is not provided with a gas-solid separation device. The number of the delivery pipes and the fluid guiding structures entering the upper settling space is 2, and the delivery pipes and the fluid guiding structures are uniformly distributed along the circumference, and the distance that the pipe orifices of the delivery pipes 8 extend out of the separation members 14 is 200 mm. The aspect ratio of the outlet channel opening of the fluid directing structure is 3: 1, the ratio of the radius of the enclosing plate outside the outlet channel to the radius of the sedimentation area is 0.9, the included angle a between the outlet normal direction of the outlet channel and the tangent line of the arc-shaped channel outlet, which takes the center of the radial section of the sedimentation space as the center of the circle, is 10 degrees, and the outer edge of the outlet channel is 400 mm. The ratio of the cross-sectional area of the transfer pipe 8 to the cross-sectional area of the settling zone was 0.02. The outlet gas velocity of the fluid-conducting outlet structure 9 was 9 m/s.

Hydrogen and sulfur-containing gasoline were mixed at a ratio of 0.3: a molar ratio of 1 is fed via feed line 1 into the reaction zone of the fluidized bed reactor (superficial gas velocity of 0.3 m/s) and contacted with catalyst fed via catalyst feed line 2 to remove at least a portion of the elemental sulfur from the sulfur-containing hydrocarbon feedstock.

The gas-solid fluid entering the lower space of the settling section firstly enters the fluid guide structure through the conveying pipe 8 and then enters the upper space of the settling section in a rotational flow mode, part of particles are separated and settled under the action of the rotational flow and enter the blanking pipe of the separation member to return to the catalyst bed layer of the reaction section, and the other part of particles are adsorbed on the filter under the action of the airflow, fall off when the filter is subjected to reverse blowing and settle in the blanking pipe of the separation member. The oil gas product after gas-solid separation enters a subsequent separation system.

The apparatus was operated continuously for 500 hours. During the reaction, the following indicators were monitored: (1) a filter pressure drop; (2) the dilute phase density in the headspace above the settling section of the fluidized bed reactor and the results are given in table 3. The unit was operated for 500 hours with an average catalyst consumption of 0.06kg catalyst per ton of oil treated.

TABLE 3

Time/h	100	200	300	400	500
						Filter pressure drop/kPa	6	6.1	6.1	6.1	6.1
Dilute phase density/(kg/m) in upper settling zone³）	0.6	0.6	0.6	0.6	0.6

Example 2

Example 2 a fluidized bed reactor as shown in figure 1 was used, differing from example 1: the ratio of the radius R1 of the outer edge of the arc-shaped outlet channel to the radius of the upper space of the settling section of the reactor is 0.6, the included angle a between the normal direction of the outlet channel and the tangent line of the circle at the outlet of the arc-shaped channel and taking the center of the radial section of the settling space as the center of the circle is 8 degrees, and the perimeter of the outer edge of the outlet channel is 600 mm. The ratio of the cross-sectional area of the transfer pipe 8 to the cross-sectional area of the settling zone was 0.025. The outlet gas velocity of the fluid guiding structure 9 is 6 m/s.

The reaction method, sulfur-containing hydrocarbon oil raw material, and reaction conditions were the same as in example 1.

The apparatus was operated continuously for 500 hours. During the reaction, the following indicators were monitored: (1) a filter pressure drop; (2) the dilute phase density in the headspace above the settling zone of the fluidized bed reactor and the results are given in table 4. The unit was operated for 500 hours with an average catalyst consumption of 0.055kg catalyst per ton of oil treated.

TABLE 4

Time/h	100	200	300	400	500
						Filter pressure drop/kPa	6.1	6.2	6.2	6.2	6.2
Dilute phase density/(kg/m) in upper settling zone³）	0.56	0.59	0.60	0.59	0.6

Example 3

Embodiment 3 adopts a fluidized bed reactor as shown in fig. 2, a separation member is arranged in a settling zone of the reactor, the separation member is a cone-like shape formed by 9 small cones and a blanking pipe thereof, an included angle between a partition plate 15 forming the separation member and a horizontal plane is 45 degrees, and the opening section of each separation member is an irregular polygon. The upper part of the settling area is provided with a metal filter

tube type filter

13, and 3 conveying pipes and fluid guide outlet structures which enter the settling space at the upper part are uniformly distributed along the circumference. The aspect ratio of the outlet channel opening of the fluid directing outlet structure 9 is 4: 1, the ratio of the radius of the enclosing plate outside the outlet channel to the radius of the settling zone is 0.9. The included angle a between the outlet normal direction of the arc-shaped outlet channel and the circle tangent line which takes the center of the radial section of the sedimentation space as the center of a circle at the outlet of the channel is 15 degrees, and the peripheral length of the outer edge of the outlet channel is 300 mm. The ratio of the cross-sectional area of the transfer pipe 8 to the cross-sectional area of the settling zone was 0.03.

The outlet gas velocity of the fluid-directing outlet structure 9 was 4 m/s.

The reaction method, sulfur-containing hydrocarbon oil raw material, and reaction conditions were the same as in example 1. The apparatus was continuously operated for 500 hours. During the reaction, the following indicators were monitored: (1) a filter pressure drop; (2) the dilute phase density in the headspace above the settling zone of the fluidized bed reactor and the results are given in table 5. The unit was operated for 500 hours with an average catalyst consumption of 0.053kg of catalyst per ton of oil treated.

TABLE 5

Time/h	100	200	300	400	500
						Filter pressure drop/kPa	4.5	4.6	4.6	4.6	4.6
Dilute phase density/(kg/m) in upper settling zone³）	0.45	0.45	0.45	0.45	0.45

Comparative example 1

The same fluidized bed reactor as in example 1 was used and the top of the settling section of the reactor was provided with the same metal filter tube filter as in example 1. Except that the settling zone of the reactor is not provided with the partition member of the present invention.

The apparatus was continuously operated for 500 hours. During the reaction, the following indicators were monitored: (1) a filter pressure drop; (2) the dilute phase density in the headspace above the settling zone of the fluidized bed reactor and the results are given in table 6. The unit was operated for 500 hours with an average catalyst consumption of 0.053kg of catalyst per ton of oil treated.

TABLE 6

Time/h	100	200	300	400	500
						Filter pressure drop/kPa	7	7.2	7.7	8	9
Dilute phase density/(kg/m) in upper settling zone³）	0.9	0.95	1.0	1.1	1.2

Example 4

The same fluidized bed reactor as in example 1 was used, except that the fluid guide outlet structure into the upper settling space was a straw hat structure: namely, a herringbone annular baffle is arranged above the opening of the conveying pipe penetrating through the separation member. The herringbone annular baffle is positioned below the filter. The ratio of the cross-sectional area of the transfer pipe 8 to the cross-sectional area of the settling zone was 0.02.

The apparatus was continuously operated for 500 hours. During the reaction, the following indicators were monitored: (1) a filter pressure drop; (2) the dilute phase density in the headspace above the settling zone of the fluidized bed reactor and the results are given in Table 7. The unit was operated for 500 hours with an average catalyst consumption of 0.09kg of catalyst per ton of oil treated.

TABLE 7

Time/h	100	200	300	400	500
						Filter pressure drop/kPa	6.5	6.7	6.9	7	8
Dilute phase density/(kg/m) in upper settling zone³）	0.8	0.85	0.88	0.9	1.0

Example 5

The fluidized bed reactor as in example 1 was used, except that a common cyclone separator was provided in the lower space of the settling section, and the fluid guide structure was of a common cyclone structure, which is equivalent to the angle a between the outlet normal of the outlet channel of the fluid guide structure in example 1 and the tangent to a circle at the outlet of the channel, which is centered on the center of the radial cross-section of the settling space, was 0 °. The ratio of the cross-sectional area of the flow to the transfer pipe 8 to the cross-sectional area of the settling zone was 0.03.

The apparatus was continuously operated for 500 hours. During the reaction, the following indicators were monitored: (1) a filter pressure drop; (2) the dilute phase density in the headspace above the settling zone of the fluidized bed reactor and the results are given in Table 8. The plant was operated for 500 hours with an average catalyst consumption of 0.08kg catalyst per ton of oil treated.

TABLE 8

Time/h	100	200	300	400	500
						Filter pressure drop/kPa	6.5	6.7	6.8	6.7	6.7
Dilute phase density/(kg/m) in upper settling zone³）	0.50	0.51	0.51	0.51	0.51

Thus, it can be seen from the results of examples 1 to 5 that the use of the reactor component of the present invention for gasoline desulfurization can effectively reduce the pressure drop of the filter and contribute to the extension of the device operation cycle.

It can be seen from the results of examples 1 and 2 and comparative example 1 that, in example 2, the dilute phase density of the upper chamber of the settling zone is small and does not change substantially with time during continuous operation, so that the fluidized bed reactor of the present invention can effectively reduce the particle suspension concentration in the settling zone of the fluidized bed reactor by providing the partition member, and thus the continuous operation period can be prolonged.

Comparing example 2 with example 4, it can be seen that by changing the structural parameters of the fluid directing outlet structure entering the upper settling space, the increase in filter pressure drop can be significantly reduced, resulting in a significant reduction in the particles entering the upper space of the settling zone and a reduction in the dilute phase space particle concentration, as compared to example 4.

From the results of examples 1 and 2 and example 5, it can be seen that although the lower settling space is provided with a gas-solid separator to help reduce the particle concentration in the upper settling space, the pressure drop and the attrition of the filter are increased, which illustrates that the present invention is advantageous in that the pressure drop of the filter of the fluidized bed reactor can be effectively reduced and the operation period of the apparatus can be prolonged.

The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A fluidized bed reactor comprises a lower reaction section (3) and an upper settling section, and is characterized in that the settling section is divided into a settling section upper space and a settling section lower space by a partition member (14), the partition member (14) consists of a cone-like body and a blanking pipe (17), the top cone skirt of the partition member is in seamless connection with a reactor cylinder, a fluid guide structure (9) is arranged in the settling section upper space, the fluid guide structure (9) penetrates through the partition member (14) through a conveying pipe (8) and opens into the settling section lower space, the bottom of the blanking pipe (17) of the partition member (14) opens into the reaction section (3), and a gas outlet (13) is arranged at the top of the settling section upper space;

the fluid guide structure (9) consists of a gas collection chamber (95), an outlet channel (96) and a feed channel (98), the feed channel (98) is vertically arranged below the gas collection chamber, one end of the feed channel is communicated with the gas collection chamber, and the other end of the feed channel is communicated with the conveying pipe (8); the outlet channel (96) is horizontally arranged, one end of the outlet channel is communicated with the gas collection chamber (95), and the other end of the outlet channel is opened in the upper space of the settling section;

the horizontal section of the outlet channel (96) is arc-shaped, the included angle a between the normal direction of the outlet of the arc-shaped channel and the tangent line of the circle at the outlet of the channel, which takes the center of the cross section of the settling space as the center of the circle, is 6-20 degrees, and the ratio of the radius R1 of the outer edge of the arc-shaped channel to the radius R of the upper space of the settling section of the reactor is 0.6-0.95.

2. Fluidized bed reactor in accordance with claim 1, characterized in that a catalyst outlet (19) is provided in the upper part of the reaction section (3), the opening of the feeding pipe (17) of the partition member and the catalyst outlet (19) being located at substantially the same level.

3. Fluidized bed reactor in accordance with claim 1, characterized in that the cone-like shape of the partition member (14) is a single cone surface or a multi-faceted cone surface with a large top and a small bottom surrounded by a plurality of planes; the included angle between the conical surface angle of the single cone or the included angle between the planes and the horizontal plane is 35-60 degrees.

4. Fluidized bed reactor in accordance with claim 1, characterized in that the outlet channel (96) has a rectangular cross-section and is surrounded by an upper and a lower outer and an inner 4 bounding walls, and the outlet channel opening has an aspect ratio of 2 to 5: 1.

5. the fluidized bed reactor according to claim 1, wherein an angle a between a normal direction at the outlet of the circular arc-shaped passage and a tangent to a circle at the outlet of the passage centered on the center of a cross section of the settling space is 8 to 15 °.

6. The fluidized bed reactor in accordance with claim 1, wherein the ratio of the radius R1 of the outer edge of the circular arc-shaped channel to the radius R of the upper space of the settling section of the reactor is 0.7 to 0.9.

7. Fluidized bed reactor in accordance with claim 1, characterized in that a filter (12) is arranged at the top of the headspace of the settling section, said headspace of the settling section being in communication with the gas outlet via the filter.

8. Fluidized bed reactor in accordance with claim 7, characterized in that the lowermost end of the outlet channel (96) is higher in axial position than the lowermost end of the filter.

9. Fluidized bed reactor in accordance with claim 1, characterized in that the ratio of the cross-sectional area of the duct (8) to the cross-sectional area of the settling section is 0.01-0.04.

10. Fluidized bed reactor in accordance with claim 9, characterized in that the ratio of the cross-sectional area of the duct (8) to the cross-sectional area of the settling section is 0.02 to 0.03.

11. The fluidized bed reactor as set forth in claim 1, wherein said circular arc type passage has an outer circumference of 200 to 800 mm.

12. The fluidized bed reactor as set forth in claim 11, wherein said arcuate passageway has an outer circumference of 300 to 600 mm.

13. The application method of the fluidized bed reactor as claimed in any one of claims 1 to 12, characterized in that the fluidized bed reactor is filled with fine powdery catalyst particles, and the raw material enters from the bottom of the fluidized bed reactor, contacts with the catalyst particles to react, and drives the catalyst particles to move upwards to be in a fluidized state; part of catalyst particles rise to the settling section along with the reaction oil gas, gas-solid fluid enters the fluid guide structure through the conveying pipe, enters the upper space of the settling section in a rotational flow mode through an outlet channel of the fluid guide structure, is separated and settled to enter a discharge pipe of the separation member and return to a catalyst bed layer of the reaction section, and the other part of particles are adsorbed on the filter, fall off when the filter is subjected to back blowing and settle to the discharge pipe of the separation member; and the oil gas product after gas-solid separation enters a subsequent separation system through a gas outlet.

14. The method of using a fluidized bed reactor as defined in claim 13 wherein the fluid directing structure outlet channel has a superficial gas velocity of 3 to 12 m/s.

15. The method of using a fluidized bed reactor as defined in claim 14 wherein the fluid directing structure outlet channel has a superficial gas velocity of 4 to 9 m/s.

16. A method for desulfurizing hydrocarbon oil is characterized in that a fluidized bed reactor as claimed in any one of claims 1 to 12 is adopted, an adsorption desulfurization catalyst is filled in the fluidized bed reactor, a sulfur-containing hydrocarbon oil raw material enters from the bottom of the fluidized bed reactor, contacts with the adsorption desulfurization catalyst under the adsorption desulfurization condition to react, and simultaneously drives catalyst particles to move upwards to enable the catalyst particles to be in a fluidized state; part of catalyst particles rise to the settling section along with the reaction oil gas, gas-solid fluid enters the fluid guide structure through the conveying pipe, enters the upper space of the settling section in a rotational flow mode through an outlet channel of the fluid guide structure, part of the particles are separated and settled and enter a discharge pipe of the separation member and return to a catalyst bed layer of the reaction section, the other part of the particles are adsorbed on a filter, the particles fall off during reverse blowing of the filter, settle in the discharge pipe of the separation member, and an oil gas product after gas-solid separation enters a subsequent separation system through a gas outlet.

17. The method for desulfurizing hydrocarbon oil according to claim 16, wherein said sulfur-containing hydrocarbon oil feedstock is a gasoline fraction; the adsorption desulfurization catalyst is composed of active components Ni and/or Co and a heat-resistant inorganic oxide carrier of one or more of ZnO, matrix alumina and silicon oxide; the adsorption desulfurization conditions are as follows: the reaction temperature is 350-440 ℃, the molar ratio of hydrogen to gasoline is 0.1-0.4, and the weight hourly space velocity is 0.2-0.6 h^-1Absolute pressure is 2.0-3.0 MPa.