CN111054281A - Catalyst fluidized bed reactor, reaction system and method using system - Google Patents

Catalyst fluidized bed reactor, reaction system and method using system Download PDF

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Publication number
CN111054281A
CN111054281A CN201811210765.2A CN201811210765A CN111054281A CN 111054281 A CN111054281 A CN 111054281A CN 201811210765 A CN201811210765 A CN 201811210765A CN 111054281 A CN111054281 A CN 111054281A
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gas
catalyst
chamber
pipe
reactor
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CN111054281B (en
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张同旺
朱丙田
刘凌涛
韩颖
朱振兴
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/006—Separating solid material from the gas/liquid stream by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/20—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

The invention relates to the field of catalyst fluidized bed reactors, and discloses a catalyst fluidized bed reactor, a reaction system and a method using the system, wherein the catalyst fluidized bed reactor comprises a reaction chamber, a gas stripping chamber and a gas locking chamber, a partition plate is arranged between the reaction chamber and the gas stripping chamber, and a gas distribution plate is fixed between the gas stripping chamber and the gas locking chamber; a feeding distribution plate is fixed at the lower end of the reaction chamber, and a discharging pipe is fixed at the lower end of the feeding distribution plate; a gas baffle is fixed at the opening position of the gas distribution plate, which is opposite to the feeding pipe, a plurality of gas locking pipes are fixed on the lower end surface of the gas distribution plate, and the gas locking pipes are communicated with the gas stripping chamber and the gas locking chamber; the vertical distance H between the lower end surface of the blanking pipe and the gas distribution plate meets the following conditions:
Figure DDA0001832379670000011
r1 is the circumference radius of the orthographic projection of the gas locking pipe on the gas distribution plate, R2 is the radius of the gas baffle plate, α is the angle of repose of the solid catalyst.

Description

Catalyst fluidized bed reactor, reaction system and method using system
Technical Field
The invention relates to the field of catalyst fluidized bed reactors, in particular to a catalyst gas-solid countercurrent fluidized bed reactor, a reaction system containing the reactor and a method for carrying out continuous reaction and regeneration of solid catalyst transfer by utilizing a non-mechanical valve of the reaction system.
Background
The catalysts used in the field of petrochemical industry are usually solid catalysts, and the activity and the service cycle of the selected catalyst are different according to different processes. For the catalyst with long service life and low airspeed, a fixed bed reactor is mostly adopted; for short-life, high space velocity catalysts, fluidized bed or riser reactors are mostly used. For catalysts with a single-pass life of hours to days, a moving bed or fluidized bed reactor can be adopted, and the moving bed or fluidized bed reactor usually comprises a plurality of reaction zones and regeneration zones, so that the catalyst can be repeatedly regenerated, and the service life of the catalyst is prolonged.
For moving bed or fluidized bed reactors comprising a plurality of reaction zones and regeneration zones, mechanical throttling devices or non-mechanical throttling means are generally used in order to eliminate mixing of fluids between different reaction zones. However, the mechanical throttling device is influenced by solid catalyst particle erosion, particle blockage, particle abrasion, air seal failure and the like, the maintenance and nursing cost is higher, and the price is exponentially increased along with the size enlargement.
CN102612625A discloses a method and apparatus for chemical looping combustion with independent solids looping control, which includes at least one fluidized bed reduction reaction zone, at least one fluidized bed oxidation reaction zone, at least one ascending circulation device for circulating the particles from the reduction reaction zone to the oxidation reaction zone. The ascending circulation device adopts a non-mechanical throttling means to adjust the flow of solid particles, the fluidized bed reactors used in the reduction reaction area and the oxidation reaction area of the fluidized bed are conventional circulating fluidized beds, the conventional circulating fluidized beds have poor air seal effect, and the fluidization effect of the solid catalyst is influenced.
CN101683602A discloses a moving bed reactor device with a catalyst capable of continuous reaction and regeneration and a method for using the same, wherein the top of the moving bed reactor device is provided with an upper lock hopper, and the bottom of the moving bed reactor device is provided with a lower lock hopper. The gas flow in the moving bed reactor is controlled by the matching of the upper lock hopper and the lower lock hopper.
CN202570114U discloses a moving bed radial reactor with a gas lock structure, which comprises a reactor shell, wherein a gas lock valve is installed on the top of the reactor shell to regulate and control the gas flow rate in the reactor.
However, the gas locking function of the moving bed reactor in the prior art can be realized only by matching with a mechanical gas locking valve, and the mechanical gas locking valve is easy to wear and block, has high maintenance cost, and influences the fluidization effect of the solid catalyst in the moving bed reactor. Accordingly, there is a need for a fluidized bed reactor that overcomes the drawbacks of the prior art using mechanical gas lock.
Disclosure of Invention
The invention aims to solve the problems of abrasion and particle blockage caused by mechanical gas locking in the prior art, and provides a catalyst fluidized bed reactor, a reaction system and a method for applying the system.
In order to achieve the above object, the first aspect of the present invention provides a catalyst fluidized bed reactor, comprising a reaction chamber, a stripping chamber and a gas lock chamber, which are connected in sequence from top to bottom; a baffle plate is arranged between the reaction chamber and the air lock chamber, and an air distribution plate with a plurality of air lock pipe through holes and air lock gas through holes is fixed between the air lock chamber and the air lock chamber; a feeding distribution plate is fixed at the lower end of the reaction chamber, and a discharging pipe is fixed at the lower end of the feeding distribution plate; a gas baffle is fixed at the opening position of the gas distribution plate, which is opposite to the feeding pipe, a plurality of gas locking pipes are fixed on the lower end surface of the gas distribution plate, and the gas locking pipes are communicated with the gas stripping chamber and the gas locking chamber;
wherein, the vertical distance H between the lower end surface of the blanking pipe and the gas distribution plate meets the following conditions:
Figure BDA0001832379650000021
and is
Figure BDA0001832379650000022
R1 is the radius of the circumference formed by the orthographic projection of the gas locking pipe on the gas distribution plate, R2 is the radius of the gas baffle plate, and α is the angle of repose of the solid catalyst.
The second aspect of the invention provides a catalyst fluidization regeneration reaction system, which comprises a reaction unit and a regenerator, wherein the reaction unit comprises a plurality of reactors, a solid catalyst inlet of a first reactor in the reaction unit is communicated with a solid catalyst outlet of the regenerator, and a solid catalyst outlet of a last reactor in the reaction unit is connected with the regenerator; wherein, the adjacent reactors, the last reactor and the regenerator and the first reactor are connected by non-mechanical valves; the reactor and the regenerator are each independently a catalyst fluidized bed reactor as described in the first aspect.
In a third aspect, the invention provides a use of the catalyst fluidized regeneration reaction system of the second aspect in the desulfurization of hydrocarbons.
In a fourth aspect of the present invention, there is provided a hydrocarbon desulfurization method, wherein a sulfur-containing hydrocarbon material is subjected to a countercurrent contact reaction with a catalyst in a system, wherein the system is the catalyst fluidized regeneration reaction system of the second aspect.
In a reaction chamber of the catalyst fluidized bed reactor, a solid catalyst is in countercurrent contact with gas, a gas stripping chamber and a gas locking chamber are sequentially arranged at the lower end of the reaction chamber, the gas flow in the reaction chamber is adjusted by adjusting the flow of stripping gas, and the gas locking function in the catalyst fluidized bed reactor is adjusted in a non-mechanical mode.
The catalyst fluidized bed reactor is matched with a non-mechanical valve to form a catalyst fluidized regeneration reaction system, solid catalyst particles are driven to move in different reactors in a pneumatic mode, the isolation of gases in different reaction sections is realized, and the system is easy to amplify.
The invention can avoid the mixing of gases in different reactors under the condition of no mechanical valve throttling, simultaneously can ensure that the solid moves according to the expected direction, and can also improve the desulfurization effect of the sulfur-containing hydrocarbon material.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic diagram of the structure of a catalyst fluidized bed reactor according to the present invention;
FIG. 2 is a schematic view of a connection structure of two reactors and one regenerator in an embodiment according to the present invention;
FIG. 3 is a schematic view of a reactor-regenerator connection according to an embodiment of the present invention;
FIG. 4 is a top view of a gas distribution plate;
FIG. 5 is a schematic diagram showing the positional relationship among the feed pipe, the gas distribution plate and the gas-lock pipe.
Description of the reference numerals
1. Reaction chamber 11, feeding distribution plate 12 and blanking pipe
121. Differential pressure transmitter 13, fluid inlet 14, fluid outlet
15. Catalyst inlet 2, partition 3, stripping chamber
31. Gas stripping gas outlet 4, gas distribution plate 41 and gas stripping gas through hole
42. Air baffle 43, air locking pipe through hole 5 and air locking chamber
51. Gas lock pipe 52, catalyst outlet 53 and stripping gas inlet
6. Cyclone 61, return pipe 62, gas outlet
7. Filter A1 first reactor A2 second reactor
B regenerator 81, horizontal pipe 82 and vertical pipe
Detailed Description
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 the present invention, the catalyst fluidized-bed reactor and the regenerator are both vertically arranged, and in the case where no description is given to the contrary, the terms of orientation such as "upper, top, and top" are generally used to refer to the inlet direction of the solid catalyst, and "lower, bottom, and bottom" are generally used to refer to the outlet direction of the solid catalyst.
The invention provides a catalyst fluidized bed reactor, which comprises a reaction chamber 1, a stripping chamber 3 and a gas-locking chamber 5 which are sequentially connected from top to bottom as shown in figure 1. A partition plate 2 is arranged between the reaction chamber 1 and the gas stripping chamber 3, and a gas distribution plate 4 with a plurality of gas stripping through holes 41 and gas locking pipe through holes 43 is fixed between the gas stripping chamber 3 and the gas locking chamber 5; a feeding distribution plate 11 is fixed at the lower end of the reaction chamber 1, and a blanking pipe 12 is fixed at the lower end of the feeding distribution plate 11; the air baffle plate 42 is fixed on the opening position of the air distribution plate 4 facing the feeding pipe 12, a plurality of air locking pipes 51 are fixed on the lower end face of the air distribution plate 4, the air locking pipes 51 are fixed on the through holes 43 of the air locking pipes, and the air locking pipes 51 are communicated with the air stripping chamber 3 and the air locking chamber 5.
With reference to fig. 4 and 5, the vertical distance H between the lower end surface of the blanking pipe 12 and the gas distribution plate 4 satisfies the following condition:
Figure BDA0001832379650000051
r1 is lock gasThe radius of the circumference defined by the orthographic projection of the tube 51 on the gas distribution plate 4, R2 is the radius of the gas barrier 42, and X is the angle of repose of the solid catalyst.
The reaction chamber 1 is used for the contact reaction of the solid catalyst and the reaction raw materials, and the baffle plate 2 separates the reaction chamber 1 from the gas stripping chamber 3, so that the reaction chamber 1 is communicated with the gas stripping chamber 3 through the feeding pipe 12. The solid catalyst can enter from the upper end of the reaction chamber 1 and flow out from the blanking pipe 12. The fluid passes through the feed distribution plate 11 from the lower end of the reaction chamber 1 into the reaction chamber 1 to be in counter-current contact with the solid catalyst in the reaction chamber 1.
The stripping chamber 3 and the gas lock chamber 5 are separated by a gas distribution plate 4, and the gas distribution plate 4 is preferably a porous plate or a metal sintered plate, so that the gas distribution plate 4 is a porous plate. The holes on the gas distribution plate 4 are stripping gas through holes 41 (the stripping gas through holes are too small and not shown in the figure), and the stripping gas through holes 41 are smaller than the outer diameter of the solid catalyst. In order to deposit the solid catalyst flowing out from the blanking pipe 12 on the gas distribution plate 4, a gas baffle plate 42 is fixed at a position where the gas distribution plate 4 faces the lower end opening of the blanking pipe 12, and the gas baffle plate 42 can be integrally formed with the gas distribution plate 4 or can be fixed on the gas distribution plate 4 by welding or other means. The gas baffle plate 42 shields part of the gas stripping through holes 41, when the stripping gas passes through the gas distribution plate 4 from bottom to top, the middle gas flow is shielded by the gas baffle plate 42, the falling of the solid catalyst cannot be influenced, and the gas-blocking device has a primary gas-blocking effect on the reaction chamber 1. Meanwhile, the differential pressure transmitter 121 is arranged on the blanking pipe 12, so that the material level of the solid catalyst in the blanking pipe 12 can be monitored conveniently, the gas stripping gas amount can be adjusted conveniently, and the catalyst fluidized bed reactor has a good gas locking effect.
The lower end face of the gas distribution plate 4 is also fixedly provided with a plurality of gas locking pipes 51, the gas locking pipes 51 are communicated with the stripping chamber 3 and the gas locking chamber 5, and the plurality of gas locking pipes 51 preferably surround the center of the gas distribution plate 4 as a circle center to form a circumference so as to facilitate the catalyst accumulated on the gas distribution plate 4 to slowly flow to the gas locking pipes 51. The solid catalyst passes through the blanking pipe 12 and is accumulated between the blanking pipe 12 and the gas distribution plate 4, and slowly flows into the gas locking pipe 51 from the blanking pipe 12 under the synergistic action of a structure formed by the blanking pipe 12, the gas distribution plate 4 and the gas locking pipe 51, gas stripping gas and a pressure difference transmitter 121 arranged on the blanking pipe 12, the solid catalyst is in a fluidized state in the catalyst fluidized bed reactor, and the catalyst fluidized bed reactor still keeps a good gas locking effect in the flowing process of the solid catalyst.
More preferably, when the vertical distances H between the lower end surface of the blanking pipe 12 and the gas distribution plate 4, and R1, R2, and α satisfy the above relationship, the solid catalyst is free to fall onto the gas distribution plate 4 and is deposited on the gas distribution plate 4 without being blown by the stripping gas, and does not fall from the gas lock pipe, and after being blown by the stripping gas, the solid catalyst falls through the gas lock pipe 51 and is collected at the solid catalyst outlet 52, and the catalyst fluidized bed reactor has a preferable gas lock effect.
In order to further improve the gas locking effect of the catalyst fluidized bed reactor, the blanking pipe 12 passes through the partition plate 2 and extends into the gas stripping chamber 3, and the differential pressure transmitter 121 is fixed on the blanking pipe 12. The side wall of the lower end of the reaction chamber 1 is provided with a fluid inlet 13, the top of the reaction chamber 1 is provided with a fluid outlet 14, the side wall of the upper end of the reaction chamber 1 is provided with a solid catalyst inlet 15, the bottom of the air lock chamber 5 is provided with a solid catalyst outlet 52, a solid catalyst enters the reaction chamber 1 from the solid catalyst inlet 15 and flows out of the catalyst outlet 52 through a feeding pipe 12 and an air lock pipe 51, and the fluid passes through a feeding distribution plate 11 from the fluid inlet 13 and enters the reaction chamber 1 to be in countercurrent contact with the solid catalyst; the side wall of the air locking chamber 5 is provided with an air stripping air inlet 53, the side wall of the air stripping chamber 3 is provided with an air stripping air outlet 31, and stripping air enters the air locking chamber 5 from the air stripping air inlet 53, passes through the air stripping air through hole 41, enters the air stripping chamber 3 and is discharged from the air stripping air outlet 31.
The fluid inlet 13 is opened at a position near the lower end portion of the sidewall of the reaction chamber 1 to facilitate the fluid to pass through the feed distribution plate 11 into the reaction chamber 1. The stripping gas inlet 53 is opened at a position near the upper end of the gas-lock chamber 5 so as not to influence the flow of the stripping gas to fall the solid catalyst through the gas-lock pipe 51.
In order to further improve the gas locking effect of the reactor, it is preferable that the vertical height H between the lower end surface of the blanking pipe 12 and the gas distribution plate 4 satisfies the following condition: h is less than R3, and R3 is the radius of an inscribed circle formed by the orthographic projection of the gas locking pipe 51 on the gas distribution plate 4.
And H meets the condition, and the gas locking effect of the catalyst fluidized bed reactor is better by matching the relationship between the vertical distance H between the lower end surface of the blanking pipe and the gas distribution plate and the R1 and R2.
In order to further improve the gas locking effect of the catalyst fluidized bed reactor, the included angle β between the central connecting line of the outer edge of the gas baffle plate 42 and the lower end face of the blanking pipe 12 and the horizontal plane meets the condition that tan α < tan β < tan2 α is the angle of repose of the solid catalyst.
β is also the included angle formed by the generatrix of the cone formed by the centers of the gas baffle 42 and the lower end face of the blanking pipe 12 and the horizontal plane of the gas baffle 42, so as to facilitate the accumulation of the solid catalyst on the gas distribution plate 4, and slowly pass through the gas-locking pipe 51 to fall under the action of gas lift H and β, under the condition of satisfying the above relationship, the gas-locking effect of the catalyst fluidized bed reactor can be further effectively improved, the fluidization effect of the solid catalyst in the moving bed reactor can be improved, and the desulfurization effect can be further improved.
Preferably, the bottom surface of the gas-lock chamber 5 is in an inverted cone shape, and an included angle γ between a generatrix of the inverted cone shape and a horizontal plane is greater than X, so as to ensure that the solid catalyst can slide down to the catalyst outlet 52.
According to the invention, the diameter of the gas locking pipe 51 is smaller than half of the diameter of the blanking pipe 12, the height-diameter ratio of the blanking pipe 12 is larger than 20, the height-diameter ratio of the gas locking pipe 51 is larger than 10, so that the solid catalyst can conveniently slide to the catalyst outlet 52, and the gas locking effect is improved.
According to the invention, the feeding distribution plate 11 is in an inverted cone shape, the blanking pipe 12 is connected with and communicated with the bottom end of the feeding distribution plate 11, and the side wall of the inverted cone-shaped feeding distribution plate 11 can be a porous plate or a metal sintered plate, so that fluid can pass through the inverted cone-shaped feeding distribution plate. The aperture of the feeding distribution plate 11 is smaller than the particle size of the solid catalyst, so that the solid catalyst can slide down the side wall of the feeding distribution plate 11 to the blanking pipe 12 without falling through the feeding distribution plate 11.
The blanking pipe 12 is preferably fixed at the center of the feed distribution plate 11, and there may be a plurality of blanking pipes 12. Correspondingly, if there are a plurality of blanking pipes 12, the air-lock pipe 51 is correspondingly provided with a plurality of matching with the blanking pipes 12.
According to the invention, a cyclone separator 6 is arranged at the fluid outlet 14, a solid particle return pipe 61 is connected between the bottom of the cyclone separator 6 and the side wall of the lower end part of the reaction chamber 1, and the solid returns to the reaction chamber 1 after the material flowing out from the fluid outlet 14 is separated; preferably, the cyclone separator 6 has a gas outlet 62 at the upper end thereof, and a filter 7 is installed at the gas outlet 62.
A certain amount of solid catalyst particles may be entrained at the fluid outlet 14 of the reaction chamber 1, and a cyclone separator 6 is installed at this position to coarsely swirl the solid catalyst particles, and the separated solid particles flow back into the reaction chamber 1, so that the solid catalyst particles in the reaction chamber 1 have a certain fine powder amount, and the whole solid catalyst in the reaction chamber 1 has a fluidization effect. The cyclone separator 6 and the filter 7 are matched to further separate ultrafine particles.
In order to improve the gas locking effect of the catalyst fluidized bed reactor and enable the solid catalyst to slowly fall down, the gas stripping chamber 3 maintains a positive pressure difference to the reaction chamber 1, and preferably, the gas stripping gas outlet 31 is provided with a back pressure valve.
The invention also provides a catalyst fluidization regeneration reaction system, which comprises a reaction unit and a regenerator, wherein the reaction unit comprises n reactors which are communicated in series; the solid catalyst inlet 15 of the 1 st reactor is communicated with the solid catalyst outlet 52 of the regenerator, and the solid catalyst outlet 52 of the nth reactor is communicated with the solid catalyst inlet 15 of the regenerator; wherein, the adjacent reactors, the nth reactor and the regenerator, and the 1 st reactor are connected by non-mechanical valves; the reactor and regenerator are the catalyst fluidized bed reactor of the first aspect.
In the present invention, the number of reactors in the reaction unit may be one or more.
If there is only one reactor in the reaction unit, the solid catalyst outlet 52 of the reactor is communicated with the solid catalyst inlet 15 of the regenerator, and the solid catalyst inlet 15 of the reactor is communicated with the solid catalyst outlet 52 of the regenerator.
As shown in fig. 3, the catalyst fluidized regeneration reaction system comprises a reaction unit and a regenerator B, wherein one reactor is arranged in the reaction unit, n is 1, and the reactor is named as a first reactor a 1. The solid catalyst outlet 52 of the first reactor a1 is connected to the solid catalyst inlet 15 of the regenerator B, and the solid catalyst inlet 15 of the first reactor a1 is connected to the solid catalyst outlet 52 of the regenerator B to form a system in which the solid catalyst circulates.
The first reactor a1 and the regenerator B have the same structure, and the internal structure of both reactors is the same as that of the catalyst fluidized bed reactor. The connection between the first reactor A1 and the regenerator B is realized by adopting a non-mechanical valve, so that the mixing of the gases in the first reactor A1 and the regenerator B can be avoided.
If a plurality of reactors are arranged in the reaction unit, n is more than or equal to 2, the solid catalyst outlet 52 of the nth reactor in the reaction unit is communicated with the solid catalyst inlet 15 of the (n + 1) th reactor, and the like, so that the reactors are communicated in series.
As shown in fig. 2, the catalyst fluidized regeneration reaction system comprises a reaction unit and a regenerator B, wherein the reaction unit comprises a first reactor a1 and a second reactor a 2. The solid catalyst inlet 15 of the first reactor a1 is connected with the solid catalyst outlet 52 of the regenerator B, the solid catalyst outlet 52 of the second reactor a2 is connected with the solid catalyst inlet 15 of the regenerator B, and the solid catalyst outlet 52 of the first reactor a1 and the solid catalyst inlet 15 of the second reactor a2 are connected to form a system in which the solid catalyst circulates.
According to the invention, the non-mechanical valve comprises a cross pipe 81/a chute and a vertical pipe 82 which are in communication with each other, the angle between the chute and the horizontal being smaller than the angle of repose of the solid catalyst, the solid catalyst being pneumatically transported in the cross pipe 81/the chute and the vertical pipe 82.
The non-mechanical valve in the application refers to a valve which utilizes gas to drive the solid catalyst to move along a certain path, so that the solid catalyst can be transferred in different reactors, and the solid catalyst can circularly move in the whole reaction system.
In the horizontal pipe 81, the inclined pipe or the vertical pipe 82 in the non-mechanical valve, a gas conveying port is left in the feeding direction of the solid catalyst, so that the ventilation is convenient, and the solid catalyst is driven to move along the horizontal pipe 81, the inclined pipe or the vertical pipe 82. The gas amount can be adjusted according to the gas locking effect of the catalyst fluidized bed reactor.
Typically, non-mechanical valves are used in which cross pipe 81 and standpipe 82 are mated, and if this connection is used, gas transfer ports are left in cross pipe 81 and standpipe 82 in the direction of feed of the solid catalyst. The non-mechanical valve can also adopt a mode of matching the inclined pipe with the vertical pipe 82, if the connection mode is adopted, the included angle between the inclined pipe and the horizontal direction is smaller than the repose angle of the solid catalyst, so that the solid catalyst cannot automatically slide off, and only when gas is conveyed, the solid catalyst can move forwards, and the gas locking effect of the catalyst fluidized bed reactor is ensured.
The adjacent reactors and the regenerator are connected by non-mechanical valves. The non-mechanical valve can select any one of the two connection modes, or the combination of the two connection modes. The included angle between the inclined tube and the horizontal direction is smaller than the repose angle of the solid catalyst. The solid catalyst is moved by the transfer gas to the end of the cross tube 81/inclined tube and into the vertical tube 82, and the lower end of the vertical tube 82 is blown so that the solid catalyst is lifted into the next reactor or regenerator.
According to the present invention, a differential pressure transmitter is connected to the standpipe 82 for measuring the volume fraction of particles in the standpipe 82 so that solid catalyst particles are dense phase transported in the vertical pipe.
Use of a catalyst fluidized regeneration reaction system according to the second aspect for the desulfurization of hydrocarbons.
The invention also provides a hydrocarbon desulfurization method, wherein the sulfur-containing hydrocarbon material is in countercurrent contact reaction with the catalyst in a system, and the system is the catalyst fluidization regeneration reaction system of the second aspect.
The reactor is filled with solid catalyst, and the fluid in the reaction chamber 1 of the reactor is the material to be reacted and hydrogen, which is in countercurrent contact with the solid catalyst. The fluid in the reaction chamber 1 of the regenerator is air, and the solid catalyst is regenerated. The gas used for stripping and the gas used in the non-mechanical valve can be chosen from inert gases or water vapor, such as nitrogen, argon.
According to the invention, the superficial gas velocity v of the stripping chamber 3Watch (A)Initial fluidization velocity v with catalyst particlesFlow ofSatisfies 0.5vFlow of<vWatch (A)<2vFlow ofAnd a positive pressure differential is maintained across the stripping chamber 3 relative to the reaction chamber 1.
To further enhance the desulfurization effect, preferably, the reaction conditions under which the sulfur-containing hydrocarbon material is contacted with the catalyst in the reactor of the system include: the temperature is 350-450 ℃, the pressure is 1-3.5MPa, preferably 1.3-2.5MPa, and the mass space velocity of the catalyst is 1-10h-1。
When v isWatch (A)＝vFlow ofDuring the process, catalyst particles are accumulated to the catalyst outlet 52, the gas stripping chamber 3 is pressurized, so that the pressure difference between the gas stripping chamber 3 and the gas locking chamber 5 is at least larger than 0.1MPa, and the particle material level in the feeding pipe 12 at the bottom of the reactor is ensured not to drop.
The sulfur-containing hydrocarbon material is desulfurized in the catalyst fluidized regeneration reaction system under the conditions, so that the catalyst loss is low, the desulfurization effect is better, and the system can keep running for a long time.
The present invention will be described in detail below by way of examples. In the following examples, the superficial gas velocity is calculated from the feed pump volume via the gas equation of state, the particle circulation volume is calculated from the differential pressure of the transfer standpipe, and the sulfur content of the feedstock is measured by a carbon-sulfur meter.
FCC gasoline is purchased from Yanshan hydrocarbon catalyst, and the catalyst is FCAS-II type catalyst prepared by petrochemical engineering research institute.
Mass space velocity (h) of the catalyst-1) Raw material mass flow (kg/h)/catalyst dosage (kg)
Catalyst loss is expressed as mass of catalyst consumed per ton of feed oil.
Example 1
This example illustrates a fluidized catalyst regeneration system according to the present invention.
Catalyst fluidization regeneration reaction system:
as shown in fig. 3, it includes a first reactor a1 and a regenerator B. The first reactor A1 has the same structure as the regenerator B, the solid catalyst outlet 52 of the first reactor A1 is communicated with the solid catalyst inlet 15 of the regenerator B, and the solid catalyst inlet 15 of the first reactor A1 is communicated with the solid catalyst outlet 52 of the regenerator B.
The first reactor a1 and the regenerator B are connected by a non-mechanical valve, taking the connection mode of the solid catalyst outlet 52 of the first reactor a1 and the solid catalyst inlet 15 of the regenerator B as an example. Wherein, the solid catalyst outlet 52 of the first reactor A1 is connected with a horizontal pipe 81, the horizontal pipe 81 is communicated with the solid catalyst outlet 52, and a gas conveying port is reserved at one end of the horizontal pipe 81 close to the solid catalyst outlet 52 to drive the solid catalyst to move in the pipe. The position of the horizontal pipe 81 far away from the solid catalyst outlet 52 is connected with a vertical pipe 82, the horizontal pipe 81 is communicated with the vertical pipe 82, a gas conveying port is reserved at one end of the vertical pipe 82 close to the horizontal pipe 81 so as to drive the solid catalyst to move upwards in the vertical pipe 82, and one end of the vertical pipe 82 far away from the horizontal pipe 81 is communicated with the solid catalyst inlet 15 of the regenerator B.
The diameter of the first reactor A1 is 92mm, the height is 2000mm, the vertical distance H between the lower end face of the feeding pipe 12 and the gas distribution plate 4 is 5mm, the radius R1 of the circumference formed by the gas locking pipe 51 on the gas distribution plate 4 by taking the center of the gas distribution plate 4 as the center is 23mm, the radius R2 of the gas baffle 42 at the center of the gas distribution plate 4 is 2mm, the radius R3 of an inscribed circle formed by enclosing the gas locking pipe 51 is 20mm, the included angle β between the central connecting line of the outer edge of the gas baffle 42 and the lower end face of the feeding pipe 12 and the horizontal plane is 40 degrees, the diameter of the feeding pipe 12 is 7.6mm, the height is 200mm, the diameter of the gas locking pipe 51 is 3.5mm, and the height is 200 mm.
The hydrocarbon desulfurization process was carried out on a catalyst fluidized regeneration reaction system as shown in fig. 3:
the addition amount of the solid catalyst was 4.5kg, and FCAS-II type catalyst was selected as the solid catalyst, and the angle of repose was 32 °. The temperature of the first reactor A1 was adjusted to 400 ℃ and the apparent pressure of the first reactor A1 to 1.3MPa, the temperature of the regenerator B was adjusted to 500 ℃ and the apparent pressure of the regenerator B was adjusted to 0.2 MPa. The hydrocarbon feedstock and hydrogen in the first reactor a1 were fed into the reaction chamber 1 through the fluid inlet 13 at a feed rate of 22kg/h and a hydrogen rate of 25 SLPM.Air in regenerator B enters the reaction chamber 1 through the fluid inlet 13, and the air feeding amount is 15SLPM, so as to facilitate the regeneration treatment of the solid catalyst. The stripping gas in the first reactor A1 and the regenerator B both used nitrogen, the stripping gas amount in the first reactor A1 was 5SLPM, and the stripping gas amount in the regenerator B was 15 SLPM. The mass space velocity of the catalyst is 4.9h-1。
In the non-mechanical valve, nitrogen is used as the gas for providing power in both the horizontal pipe 81 and the vertical pipe 82, the gas delivery rate in the horizontal pipe 81 is 1.2SLPM, and the gas delivery rate in the vertical pipe 82 is 14 SLPM.
At the beginning, no stripping gas and raw material were introduced into the first reactor a1 and the regenerator B, and the solid catalyst in the first reactor a1 was deposited on the gas distribution plate 4 through the feed pipe 12 and did not fall down. Thereafter, a stripping gas is passed through the first reactor a1 and the regenerator B, and a transport gas is passed through the non-mechanical valve, establishing circulation of the solid catalyst between the first reactor a1 and the regenerator B.
Stopping gas delivery of the regenerator B, stopping transferring the regenerator B to the first reactor A1, recording the change of the material level in the regenerator B, measuring the circulation amount of the solid catalyst to be 80g/h, ensuring that the material level of the first reactor A1 is 700mm water column, the value of the differential pressure transmitter 121 of the blanking pipe 12 is 50kPa, and the value of the differential pressure transmitter on the vertical pipe 82 is 20kPa, so as to ensure the gas locking effect of the first reactor A1 and the regenerator B and avoid the mixing of the gases of the reaction chamber 1 in the first reactor A1 and the regenerator B.
The superficial gas velocity v of the stripping chamber 3 of the first reactor A1 was adjustedWatch (A)0.03m/s, initial fluidization velocity vFlow of0.042m/s, P gas stripping chamber > P reaction chamber. The heated olefin feed (containing 465ppm of sulfur in the olefin feed) enters the reaction chamber 1 through the fluid inlet 13, and after 35 seconds of reaction, the sulfur content in the product is 9 ppm.
When the method is used for carrying out the desulfurization treatment on the olefin raw material, the operation period can be prolonged by 3 months, and the reaction does not need to be interrupted in the middle. The whole system is more stable, and the service life can be prolonged to 40 days. The catalyst fluidization regeneration reaction system does not need the size of a limited mechanical valve and is easy to enlarge.
Example 2
The hydrocarbon desulfurization process was carried out using the system of example 1:
the addition amount of the solid catalyst was 4.5kg, and FCAS-II type catalyst was selected as the solid catalyst, and the angle of repose was 32 °. The temperature of the first reactor A1 was adjusted to 400 ℃ and the apparent pressure of the first reactor A1 to 2MPa, the temperature of the regenerator B was adjusted to 500 ℃ and the apparent pressure of the regenerator B was adjusted to 0.2 MPa. The hydrocarbon feedstock and hydrogen in the first reactor a1 were fed into the reaction chamber 1 through the fluid inlet 13 at a feed rate of 7.5kg/h and a hydrogen rate of 8.4 SLPM. Air in regenerator B was fed into chamber 1 through fluid inlet 13 at an air feed rate of 27.2SLPM to facilitate the regeneration of the solid catalyst. The stripping gas in the first reactor A1 and the regenerator B both used nitrogen, the stripping gas amount in the first reactor A1 was 2.5SLPM, and the stripping gas amount in the regenerator B was 2.5 SLPM. The mass space velocity of the catalyst is 1.67h-1。
In the non-mechanical valve, nitrogen is used as the gas for providing power in both the horizontal pipe 81 and the vertical pipe 82, the gas conveying amount in the horizontal pipe 81 is 2SLPM, and the gas conveying amount in the vertical pipe 82 is 5 SLPM.
At the beginning, no stripping gas and raw material were introduced into the first reactor a1 and the regenerator B, and the solid catalyst in the first reactor a1 was deposited on the gas distribution plate 4 through the feed pipe 12 and did not fall down. Thereafter, a stripping gas is passed through the first reactor a1 and the regenerator B, and a transport gas is passed through the non-mechanical valve, establishing circulation of the solid catalyst between the first reactor a1 and the regenerator B.
Stopping gas delivery of the regenerator B, stopping transferring the regenerator B to the first reactor A1, recording the material level change of the regenerator B, measuring the circulation amount of the solid catalyst by 80g/h, ensuring that the material level of the first reactor A1 is 700mm water column, the value of the differential pressure transmitter 121 of the blanking pipe 12 is 50kPa, and the value of the differential pressure transmitter on the vertical pipe 82 is 20kPa, so as to ensure the gas locking effect of the first reactor A1 and the regenerator B and avoid the mixing of the gases in the reaction chamber 1 of the first reactor A1 and the regenerator B.
Adjusting the superficial gas velocity v of the stripping chamber 3 in the first reactor A1Watch (A)0.03m/s, initial fluidization velocity vFlow ofIs 0.042m/s, PAir stripping chamber＞PReaction chamber. The heated olefin feed (the sulfur content in the olefin feed is 465ppm) enters the reaction chamber 1 from the fluid inlet 13, and the sulfur content in the product is 5.6ppm after the reaction for 42 seconds.
When the method is used for carrying out the desulfurization treatment on the olefin raw material, the operation period can be prolonged by 3 months, and the reaction does not need to be interrupted in the middle. The whole system is more stable, and the service life can be prolonged to 40 days. The catalyst fluidization regeneration reaction system does not need the size of a limited mechanical valve and is easy to enlarge.
Example 3
The hydrocarbon desulfurization process was carried out using the system of example 1:
the addition amount of the solid catalyst was 4.5kg, and FCAS-II type catalyst was selected as the solid catalyst, and the angle of repose was 32 °. The temperature of the first reactor A1 was adjusted to 400 ℃ and the apparent pressure of the first reactor A1 to 2.5MPa, the temperature of the regenerator B was adjusted to 500 ℃ and the apparent pressure of the regenerator B was adjusted to 0.2 MPa. The hydrocarbon feedstock and hydrogen in the first reactor a1 were fed into the reaction chamber 1 through the fluid inlet 13 at a feed rate of 7.5kg/h and a hydrogen rate of 8.4 SLPM. Air in regenerator B was fed into chamber 1 through fluid inlet 13 at an air feed rate of 27.2SLPM to facilitate the regeneration of the solid catalyst. The stripping gas in the first reactor A1 and the regenerator B both used nitrogen, the stripping gas amount in the first reactor A1 was 2.5SLPM, and the stripping gas amount in the regenerator B was 2.5 SLPM. The mass space velocity of the catalyst is 1.67h-1。
In the non-mechanical valve, nitrogen is used as the gas for providing power in both the horizontal pipe 81 and the vertical pipe 82, the gas conveying amount in the horizontal pipe 81 is 2SLPM, and the gas conveying amount in the vertical pipe 82 is 5 SLPM.
At the beginning, no stripping gas and no fluid are introduced into the first reactor a1 and the regenerator B, and the solid catalyst in the first reactor a1 is deposited on the gas distribution plate 4 through the feeding pipe 12 and does not fall down. Thereafter, a stripping gas is passed through the first reactor a1 and the regenerator B, and a transport gas is passed through the non-mechanical valve, establishing circulation of the solid catalyst between the first reactor a1 and the regenerator B.
Stopping gas delivery of the regenerator B, stopping transferring the regenerator B to the first reactor A1, recording the material level change of the regenerator B, measuring the circulation amount of the solid catalyst to be 100g/h, ensuring that the material level of the first reactor A1 is maintained at 700mm water column, the value of the differential pressure transmitter 121 of the blanking pipe 12 is 30kPa, and the value of the differential pressure transmitter on the vertical pipe 82 is 20kPa, so as to ensure the gas locking effect of the first reactor A1 and the regenerator B and avoid the mixing of the gases in the reaction chamber 1 of the first reactor A1 and the regenerator B.
Adjusting the superficial gas velocity v of the stripping chamber 3 in the first reactor A1Watch (A)0.025m/s, initial fluidization velocity vFlow ofIs 0.042m/s, PAir stripping chamber＞PReaction chamber. The heated olefin feed (containing 465ppm of sulfur in the olefin feed) enters the reaction chamber 1 from the fluid inlet 13, and after 50 seconds of reaction, the sulfur content in the product is 2.1 ppm.
When the method is used for carrying out the desulfurization treatment on the olefin raw material, the operation period can be prolonged by 3 months, and the reaction does not need to be interrupted in the middle. The whole system is more stable, and the service life can be prolonged to 40 days. The catalyst fluidization regeneration reaction system does not need the size of a limited mechanical valve and is easy to enlarge.
Example 4
The hydrocarbon desulfurization process was carried out using the system of example 1:
the addition amount of the solid catalyst was 2.2kg, and FCAS-II type catalyst was selected as the solid catalyst, and the angle of repose was 32 °. The temperature of the first reactor A1 was adjusted to 350 ℃ and the superficial pressure of the first reactor A1 to 1MPa, the temperature of the regenerator B was adjusted to 450 ℃ and the superficial pressure of the regenerator B was adjusted to 0.2 MPa. The hydrocarbon feedstock and hydrogen in the first reactor a1 were fed into the reaction chamber 1 through the fluid inlet 13 at a feed rate of 22kg/h and a hydrogen rate of 25 SLPM. Air in regenerator B enters the reaction chamber 1 through the fluid inlet 13, and the air feeding amount is 15SLPM, so as to facilitate the regeneration treatment of the solid catalyst. The stripping gas in the first reactor A1 and the regenerator B both used nitrogen, the stripping gas amount in the first reactor A1 was 5SLPM, and the stripping gas amount in the regenerator B was 15 SLPM. The mass space velocity of the catalyst is 10h-1。
Example 5
The hydrocarbon desulfurization process was carried out using the system of example 1:
the solid catalyst is added in 10kg, FCAS-II type catalyst is selected as the solid catalyst, and the angle of repose is 32 degrees. The temperature of the first reactor A1 was adjusted to 450 ℃ and the superficial pressure of the first reactor A1 to 3.5MPa, the temperature of the regenerator B was adjusted to 500 ℃ and the superficial pressure of the regenerator B was adjusted to 0.5 MPa. The hydrocarbon feedstock and hydrogen in the first reactor a1 were fed into the reaction chamber 1 through the fluid inlet 13 at a feed rate of 22kg/h and a hydrogen rate of 25 SLPM. Air in regenerator B enters the reaction chamber 1 through the fluid inlet 13, and the air feeding amount is 15SLPM, so as to facilitate the regeneration treatment of the solid catalyst. The stripping gas in the first reactor A1 and the regenerator B both used nitrogen, the stripping gas amount in the first reactor A1 was 5SLPM, and the stripping gas amount in the regenerator B was 15 SLPM. The mass space velocity of the catalyst is 2.2h-1。
Comparative example 1:
system for carrying out the hydrocarbon desulfurization process of example 1:
the diameter of the first reactor A1 is 92mm, the height is 2000mm, the vertical distance H between the lower end face of the feeding pipe 12 and the gas distribution plate 4 is 15mm, the radius R1 of the circumference formed by the gas lock pipe 51 on the gas distribution plate 4 by taking the center of the gas distribution plate 4 as the center of a circle is 20mm, the radius R2 of the gas baffle plate 42 at the center of the gas distribution plate 4 is 3mm, the radius R3 of the gas distribution plate 4 is 17mm, the included angle β between the connecting line of the outer edge of the gas baffle plate 42 and the lower end face of the feeding pipe 12 and the horizontal plane is 40 degrees, the diameter of the feeding pipe 12 is 7.6mm, the height is 200mm, the diameter of the gas lock pipe 51 is 3.5mm, and the height.
The addition amount of the solid catalyst was 4.5kg, and FCAS-II catalyst was selected as the solid catalyst, and the angle of repose was 34 °.
When the system is used for carrying out the desulfurization reaction of the hydrocarbon raw material, the solid catalyst slowly falls down when the gas is not introduced and is lifted, the gas locking effect is not good, and a mechanical valve is required to be matched. The amounts of the hydrocarbon feedstock and the catalyst added and the reaction conditions were the same as in example 1, and the specific test results are shown in table 1.
Comparative example 2:
system for carrying out the hydrocarbon desulfurization process of example 1:
the first reactor a1 used was selected from a conventional fluidized bed reactor having an inverted conical shape, and a mechanical valve was installed at the lower end of the fluidized bed reactor.
When the system is adopted to carry out the desulfurization reaction of the hydrocarbon raw material, the mechanical valve is frequently switched, the service life of the system is short, the reaction needs to be interrupted for many times to replace the valve, and the system is unstable in operation. The amounts of the hydrocarbon feedstock and the catalyst added and the reaction conditions were the same as in example 1, and the specific test results are shown in table 1.
Comparative example 3:
the hydrocarbon desulfurization process was carried out using the system of example 1:
the addition amount of the solid catalyst was 4.5kg, and FCAS-II type catalyst was selected as the solid catalyst, and the angle of repose was 32 °. The temperature of the first reactor A1 was adjusted to 300 ℃ and the superficial pressure of the first reactor A1 to 0.6MPa, the temperature of the regenerator B was adjusted to 500 ℃ and the superficial pressure of the regenerator B was adjusted to 0.2 MPa. The hydrocarbon feedstock and hydrogen in the first reactor a1 were fed into the reaction chamber 1 through the fluid inlet 13 at a feed rate of 22kg/h and a hydrogen rate of 25 SLPM. Air in regenerator B enters the reaction chamber 1 through the fluid inlet 13, and the air feeding amount is 15SLPM, so as to facilitate the regeneration treatment of the solid catalyst. The stripping gas in the first reactor A1 and the regenerator B both used nitrogen, the stripping gas amount in the first reactor A1 was 5SLPM, and the stripping gas amount in the regenerator B was 15 SLPM. The amounts of the hydrocarbon feedstock and the catalyst added were the same as in example 1, and the specific test results are shown in table 1.
The results of the catalyst loss (i.e., the mass of catalyst consumed per ton of feed oil), the catalyst life, the system run time, and the product sulfur content in the above examples and comparative examples are shown in table 1.
TABLE 1
Figure BDA0001832379650000181
From the above analysis, it can be seen that when the catalyst fluidized regeneration reaction system of the present embodiment is used to perform the desulfurization reaction of the hydrocarbon raw material, the catalyst loss is smaller, and the desulfurization effect is better. And the system can be kept running for a long time without interrupting the reaction.
If the conditions of H in the first reactor a1 are:
Figure BDA0001832379650000182
the catalyst fluidization regeneration reaction system has poor gas locking effect, needs to be matched with a mechanical valve, has large catalyst loss amount and reduces the desulfurization effect on hydrocarbon raw materials.
If a conventional fluidized bed reactor is adopted, a mechanical valve needs to be continuously opened and closed in the reaction process, the equipment is easy to wear, the loss of the catalyst is large, and the service life is shortened; and the desulfurization effect on the hydrocarbon feedstock is reduced.
If the temperature and the pressure of the catalyst fluidization regeneration reaction system are relatively reduced, the desulfurization effect of the system on the hydrocarbon raw material is influenced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. A catalyst fluidized bed reactor comprises a reaction chamber (1), a gas stripping chamber (3) and a gas lock chamber (5) which are sequentially connected from top to bottom; a partition plate (2) is arranged between the reaction chamber (1) and the gas stripping chamber (3), and a gas distribution plate (4) with a plurality of gas stripping through holes (41) and gas locking pipe through holes (43) is fixed between the gas stripping chamber (3) and the gas locking chamber (5); a feeding distribution plate (11) is fixed at the lower end of the reaction chamber (1), and a blanking pipe (12) is fixed at the lower end of the feeding distribution plate (11); an air baffle plate (42) is fixed at the opening position of the air distribution plate (4) opposite to the discharging pipe (12), a plurality of air locking pipes (51) are fixed on the lower end surface of the air distribution plate (4), and the air locking pipes (51) are communicated with the air stripping chamber (3) and the air locking chamber (5);
wherein, the vertical distance H between the lower end surface of the blanking pipe (12) and the gas distribution plate (4) meets the following conditions:
Figure FDA0001832379640000011
and is
Figure FDA0001832379640000012
R1 is the radius of the circumference formed by the orthographic projection of the gas locking pipe (51) on the gas distribution plate (4), R2 is the radius of the gas baffle plate (42), and α is the angle of repose of the solid catalyst.
2. The catalyst fluidized bed reactor in accordance with claim 1, wherein a feed pipe (12) extends through the partition (2) into the stripping chamber (3), the feed pipe (12) having a differential pressure transmitter (121) secured thereto;
preferably, the side wall of the lower end of the reaction chamber (1) is provided with a fluid inlet (13), the top of the reaction chamber (1) is provided with a fluid outlet (14), the side wall of the upper end of the reaction chamber (1) is provided with a solid catalyst inlet (15), and the bottom of the air lock chamber (5) is provided with a solid catalyst outlet (52); the solid catalyst enters the reaction chamber (1) from a solid catalyst inlet (15) and flows out from a catalyst outlet (52) through a discharge pipe (12) and an air locking pipe (51), and fluid passes through a feed distribution plate (11) from a fluid inlet (13) and enters the reaction chamber (1) to be in countercurrent contact with the solid catalyst;
a stripping gas inlet (53) is formed in the side wall of the air locking chamber (5), and a stripping gas outlet (31) is formed in the side wall of the stripping chamber (3); the stripping gas enters the air lock chamber (5) from the stripping gas inlet (53), passes through the stripping gas through hole (41), enters the stripping chamber (3), and is discharged from the stripping gas outlet (31).
3. The catalyst fluidized bed reactor according to claim 1, wherein the vertical height H of the lower end face of the blanking tube (12) from the gas distribution plate (4) satisfies the following condition: h is less than R3, and R3 is the radius of an inscribed circle formed by the orthographic projection of the gas locking pipe (51) on the gas distribution plate (4) in a surrounding manner.
4. The catalyst fluidized bed reactor according to claim 3, wherein the angle β between the horizontal plane and the line connecting the outer edge of the gas baffle (42) and the center of the lower end face of the downcomer (12) satisfies the condition that tan α < tan β < tan2 α is the angle of repose of the solid catalyst.
5. The catalyst fluidized bed reactor as set forth in claim 1, wherein the bottom surface of the gas-lock chamber (5) is in the shape of an inverted cone, and the included angle γ between the generatrix of the inverted cone and the horizontal plane is greater than α.
6. A catalyst fluidized bed reactor as claimed in any one of claims 1 to 5, wherein the diameter of the gas-lock tube (51) is less than half the diameter of the feed tube (12);
preferably, the height-diameter ratio of the blanking pipe (12) is more than 20, and the height-diameter ratio of the air locking pipe (51) is more than 10;
preferably, the feeding distribution plate (11) is in an inverted cone shape, and the discharge pipe (12) is connected with the bottom end of the feeding distribution plate (11).
7. A catalyst fluidized bed reactor as claimed in any one of claims 1 to 5, wherein a cyclone (6) is installed at the fluid outlet (14), a solid particle return pipe (61) is connected between the bottom of the cyclone (6) and the lower end side wall of the reaction chamber (1), and the solids are returned to the reaction chamber (1) after the separation of the material flowing out from the fluid outlet (14); preferably, the upper end of the cyclone separator (6) is provided with a gas outlet (62), and a filter (7) is arranged at the gas outlet (62);
preferably, the stripping gas outlet (31) is fitted with a back pressure valve.
8. A catalyst fluidization regeneration reaction system comprises a reaction unit and a regenerator, wherein the reaction unit comprises n reactors which are communicated in series; the solid catalyst inlet (15) of the 1 st reactor is communicated with the solid catalyst outlet (52) of the regenerator, and the solid catalyst outlet (52) of the nth reactor is communicated with the solid catalyst inlet (15) of the regenerator; wherein, the adjacent reactors, the nth reactor and the regenerator, and the 1 st reactor are connected by non-mechanical valves; the reactor and the regenerator are each independently a catalyst fluidized bed reactor according to any one of claims 1 to 7.
9. The catalyst fluidized regeneration reaction system according to claim 8, wherein the non-mechanical valve comprises a cross pipe (81)/a chute and a vertical pipe (82) which are communicated with each other, the included angle between the chute and the horizontal direction is smaller than the repose angle of the solid catalyst, and the solid catalyst is conveyed in the cross pipe (81)/the chute and the vertical pipe (82) in a pneumatic mode;
preferably, a differential pressure transmitter is connected to the standpipe (82).
10. Use of a catalyst fluidized regeneration reaction system according to claim 8 or 9 for the desulfurization of hydrocarbons.
11. A process for desulfurizing hydrocarbons by countercurrent contact reaction of sulfur-containing hydrocarbon material with catalyst in a system, wherein the system is the fluidized regeneration reaction system of catalyst as claimed in claim 7 or 8.
12. Process for the desulfurization of hydrocarbons according to claim 11, wherein the superficial gas velocity v of the stripping chamber (3)Watch (A)Initial fluidization velocity v with catalyst particlesFlow ofSatisfies 0.5vFlow of<vWatch (A)<2vFlow of。
13. A process for the desulfurization of hydrocarbons according to claim 11, wherein the reaction conditions under which the sulfur-containing hydrocarbon material is contacted with the catalyst in the reactor of the system include: the temperature is 350-450 ℃, the pressure is 1-3.5MPa, and the mass space velocity of the catalyst is 1-10h-1。
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