CN111068591B

CN111068591B - Liquid-solid axial moving bed reaction and regeneration device and application thereof

Info

Publication number: CN111068591B
Application number: CN201811230209.1A
Authority: CN
Inventors: 刘铮; 侯栓弟; 胡立峰; 唐晓津; 毛俊义; 朱振兴; 张久顺; 赵志海; 李永祥; 袁清; 张同旺
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: 2018-10-22
Filing date: 2018-10-22
Publication date: 2021-03-12
Anticipated expiration: 2038-10-22
Also published as: CN111068591A

Abstract

The invention relates to the field of liquid-solid reaction devices, and discloses a liquid-solid axial moving bed reaction and regeneration device and application thereof, wherein the device comprises: the device comprises an axial moving bed reactor, a spent catalyst receiver, a catalyst regenerator and a regenerant receiver which are sequentially connected, wherein a catalyst outlet of the regenerant receiver is communicated with a catalyst inlet of the axial moving bed reactor; the axial moving bed reactor is provided with at least two catalyst bed layers which are arranged up and down, and a feed inlet is arranged above each catalyst bed layer; a catalyst conveying pipe is arranged between two adjacent catalyst bed layers, so that the catalyst can move from top to bottom in the axial moving bed reactor. The liquid-solid axial moving bed reaction and regeneration device provided by the invention not only can realize the continuous and stable operation of the solid acid alkylation reaction, but also can improve the selectivity of target products.

Description

Liquid-solid axial moving bed reaction and regeneration device and application thereof

Technical Field

The invention relates to the field of liquid-solid reaction devices, in particular to a liquid-solid axial moving bed reaction and regeneration device and application thereof.

Background

At present, one of the most important tasks of the oil refining industry is to provide transportation fuel, and gasoline is widely used in transportation industry and other industries as an important transportation fuel. With the increase of gasoline consumption and the stricter environmental protection standards, it is a hot point for research and discussion to focus on how to solve the problem of clean gasoline production.

Under the action of strong acid, the technology of using isoparaffin (mainly isobutane) and olefin (C3-C5 olefin) as raw materials to generate alkylate provides possibility for clean production of gasoline. The alkylate oil has higher octane value and lower vapor pressure, mainly consists of saturated hydrocarbon, and does not contain substances such as sulfur, nitrogen, olefin, aromatic hydrocarbon and the like, so the alkylate oil is called clean gasoline and is an ideal blending component for aviation gasoline and motor gasoline. Alkylation techniques can be divided into liquid acid alkylation and solid acid alkylation in terms of catalyst form. At present, about 90% of the world's alkylation energy is provided by liquid acid alkylation technology (sulfuric acid process and hydrofluoric acid process), and although the liquid acid alkylation technology is mature and has better reaction selectivity, there are many problems, such as severe corrosion of equipment in the liquid acid alkylation process. In addition, for the sulfuric acid method, the acid consumption in the process is huge, a large amount of waste acid has certain potential safety hazards in transportation and treatment, and for the hydrofluoric acid method, hydrofluoric acid has strong corrosivity and toxicity and is easy to volatilize, so that great harm is caused to human bodies. Therefore, compared with the prior art, the solid acid is adopted as the catalyst, so that the environment is not polluted, the problem of equipment corrosion does not exist, the method can be regarded as a green alkylation process technology, and the method has a good development prospect. However, since the solid acid catalyst is easily deactivated during the solid acid alkylation process and frequent regeneration operation is required to maintain a certain reaction activity, it is very important to develop a reactor technology capable of continuously performing the reaction and regeneration process to promote the development of the solid acid alkylation technology.

US8373014 discloses a solid acid alkylation reaction process using an overlapping radial moving bed as reactor. In the method, a structure similar to a catalytic reforming overlapped radial moving bed is adopted, and a single-section reactor is internally provided with an annular barrel with the periphery playing a role in distributing reaction materials, a central pipe playing a role in collecting materials and a reaction bed layer area clamped between the annular barrel and the central pipe; and a catalyst material conveying pipe is adopted between the two sections of reactors to convey the catalyst in the upper section of the catalyst bed layer to the reaction bed layer area of the lower section of the reactor. The effluent material in the middle reactor is divided into two parts, one part is pumped back to the upstream reactor and is mixed with fresh raw materials by the mixer to be used as the feeding material of the upstream reactor, and the part can be called as recycling material; the other part is mixed with fresh raw materials before being introduced into a feed mixer of the downstream reactor and then used as the feed of the downstream reactor, and the part is directly used without pump pressurization. In addition, the recycle stream portion also needs to be passed through a heat exchanger to extract the heat of reaction.

CN1879956A discloses a fluidized bed solid acid alkylation technology, which mainly comprises a riser reactor, a fluidized bed reactor, a loop regenerator and a moving bed regenerator. Wherein the liquid velocity range in the riser reactor is 0.1-3 m/s, and the liquid velocity range in the fluidized bed reactor is 0.26-7.68 cm/s. The regeneration process may determine the form of the regeneration reactor according to the regeneration time, and if the regeneration time is several seconds to several tens of seconds, a loop regenerator alone may be used. If the regeneration time is dozens of seconds to dozens of minutes, a moving bed regenerator can be independently adopted, and the liquid velocity of the regeneration liquid is 0.2-3 cm/s.

CN1113906A discloses a fluidized bed solid acid aromatic alkylation process technology, which mainly comprises a liquid-solid ascending reactor, a spent catalyst settling and backwashing tower, a liquid-solid parallel flow ascending regenerator and a regenerated catalyst settling and backwashing tower. The particle size of the catalyst is required to be 0.05-0.8 mm, the liquid velocity of the liquid which can carry the catalyst to flow upwards in the reactor and the regenerator is 1-15 times of the settling velocity of the particle terminal, the catalyst is washed and regenerated by adopting the washing liquid flowing from bottom to top in the settling and backwashing tower, and the flow velocity of the washing liquid is 0.5-5 times of the settling velocity of the particle terminal.

In order to realize continuous and stable operation of a reaction device, at least more than two reactors are required for switching operation of a fixed bed alkylation technology and a fluidized bed alkylation technology disclosed in the prior art, a catalyst in a bed layer is subjected to high-temperature regeneration at intervals, and a high-temperature bed layer is subjected to cooling operation after deep regeneration. In addition, in the prior art, the catalyst in the solid acid alkylation reaction device is difficult to maintain stable and high target product selectivity.

Disclosure of Invention

The invention provides a liquid-solid axial moving bed reaction and regeneration device and application thereof, aiming at overcoming the problems that the solid acid alkylation reaction in the prior art can not continuously and stably operate and the selectivity of a target product needs to be further improved. The liquid-solid axial moving bed reaction and regeneration device provided by the invention not only can realize the continuous and stable operation of the solid acid alkylation reaction, but also can improve the selectivity of target products.

In order to achieve the above object, a first aspect of the present invention provides a liquid-solid axial moving bed reaction and regeneration apparatus, comprising:

the device comprises an axial moving bed reactor, a spent catalyst receiver, a catalyst regenerator and a regenerant receiver which are sequentially connected, wherein a catalyst outlet of the regenerant receiver is communicated with a catalyst inlet of the axial moving bed reactor;

the axial moving bed reactor is provided with at least two catalyst bed layers which are arranged up and down, and a feed inlet is arranged above each catalyst bed layer;

a catalyst conveying pipe is arranged between two adjacent catalyst bed layers, so that the catalyst can move from top to bottom in the axial moving bed reactor.

Preferably, a reaction material baffle is arranged between two adjacent catalyst bed layers and used for enhancing the mixing of the reacted material and the liquid fresh raw material fed from the feeding port.

Preferably, a catalyst distribution piece is arranged between two adjacent catalyst beds and used for dispersing the catalyst at the outlet of the catalyst conveying pipe.

The second aspect of the invention provides the application of the liquid-solid axial moving bed reaction and regeneration device in the solid acid alkylation reaction.

The liquid-solid axial moving bed reaction and regeneration device provided by the invention has the following advantages:

1) compared with the fixed bed alkylation technology, the continuous and stable operation of the reaction device can be realized only by using one reactor;

2) compared with the fluidized bed alkylation technology, the liquid-solid axial moving bed reaction and regeneration device provided by the invention can realize the service life distribution of the catalyst, and can remove part of the inactivated catalyst out of the system and then supplement fresh catalyst; the fluidized bed reactor cannot realize the service life distribution of the catalyst;

3) the liquid-solid axial moving bed reaction and regeneration device provided by the invention uses an axial moving bed reactor, and a single set of equipment can meet the requirements, so that the investment cost of the device is reduced, in addition, the inactivated catalyst particles are led out of the reactor for deep regeneration, so that the continuous operation of the catalyst reaction and regeneration is realized on the premise of not influencing the stable operation of the reaction device, the catalyst in the device has stable balance activity, and the selectivity of a target product in the alkylate oil is improved.

Drawings

FIG. 1 is a liquid-solid axial moving bed reaction and regeneration apparatus according to one embodiment of the present invention;

FIG. 2 is a schematic view of a baffle according to the present invention;

FIG. 3 is a liquid-solid axial moving bed reaction and regeneration apparatus according to an embodiment of the present invention.

Description of the reference numerals

1-axial moving bed reactor 2-feed inlet 3-catalyst bed layer

4-catalyst regenerator 5-spent agent receiver 6-regenerant receiver

7-fluid removal filter 8-regenerated medium filter 10-separating element

11-reaction Material baffle 111-Main shaft 112-conveying Member

113-baffle 12-conical distribution baffle 13-horizontal distribution baffle

15-liquid-withdrawing material outlet 16-catalyst conveying pipe 17-pipeline

19-first branch line 20-second branch line 21-third branch line

25-first particle flow regulator 30-regenerated medium inlet 31-regenerated medium outlet

32-liquid phase feed make-up inlet 33-second particle flow regulator 37-bottom catalyst collection zone

38-catalyst buffer tank

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 use of directional terms such as "upper" and "lower" generally means upper and lower as generally described with reference to the drawings, unless otherwise specified. Use of the terms of orientation such as "inner and outer" refer to inner and outer relative to the profile of the respective component itself.

In a first aspect, the present invention provides a liquid-solid axial moving bed reaction and regeneration apparatus, as shown in fig. 1, comprising:

the device comprises an axial moving bed reactor 1, a spent catalyst receiver 5, a catalyst regenerator 4 and a regenerant receiver 6 which are connected in sequence, wherein a catalyst outlet of the regenerant receiver 6 is communicated with a catalyst inlet of the axial moving bed reactor 1;

the axial moving bed reactor 1 is provided with at least two catalyst bed layers 3 which are arranged up and down, and a feed inlet 2 is arranged above each catalyst bed layer 3 of the axial moving bed reactor 1;

a catalyst conveying pipe 16 is arranged between two adjacent catalyst beds 3, so that the catalyst can move from top to bottom in the axial moving bed reactor 1.

In the present invention, the sequential connection means that the catalyst outlet of the axial moving bed reactor 1 is connected to the catalyst inlet of the spent catalyst receiver 5, the catalyst outlet of the spent catalyst receiver 5 is connected to the catalyst inlet of the catalyst regenerator 4, and the catalyst outlet of the catalyst regenerator 4 is connected to the catalyst inlet of the regenerant receiver 6. The catalyst outlet of the regenerant receiver 6 communicates with the catalyst inlet of the axial moving bed reactor 1 to feed the regenerated catalyst into the axial moving bed reactor 1.

The axial moving bed reactor refers to a moving bed reactor with the moving direction of a catalyst being axial.

According to the device provided by the invention, the axial moving bed reactor 1 is provided with at least two catalyst bed layers which are arranged up and down, and preferably 3-8 catalyst bed layers 3 which are arranged up and down. The thickness of the catalyst bed 3 is not particularly limited in the present invention, and preferably, the thickness of each catalyst bed 3 is each independently 10 to 30% of the height of the axial moving bed reactor 1.

In the embodiment of the present invention, the height of the axial moving bed reactor 1 is 15m and the inner diameter is 600mm, but the present invention is not limited thereto. Those skilled in the art can make appropriate adjustments according to actual conditions.

According to the device provided by the invention, the axial moving bed reactor 1 is provided with a feeding hole 2 above each catalyst bed layer 3. Liquid fresh raw materials are fed into the axial moving bed reactor 1 from a feed inlet 2 of the axial moving bed reactor 1 to carry out contact reaction with the catalyst filled in the catalyst bed layer 3. The catalyst in the uppermost catalyst bed 3 of the axial moving bed reactor 1 is in contact reaction with the liquid fresh raw material, and the catalyst in the other catalyst beds 3 is in contact reaction with the mixture of the liquid fresh raw material and the reacted material from the upstream catalyst bed 3. By adopting the device provided by the invention, the liquid fresh raw materials can be fed into the axial moving bed reactor 1 through different feed inlets 2, which is more beneficial to controlling the temperature rise.

The catalyst transport pipe 16 of the present invention is not particularly limited as long as it allows the catalyst to move from top to bottom in the axial moving-bed reactor 1. Specifically, the catalyst transport tube may be cylindrical. One catalyst conveying pipe 16 may be provided between two adjacent catalyst beds 3, or two or more catalyst conveying pipes 16 may be provided. The inner diameter and the number of the catalyst transport pipes 16 are appropriately selected in accordance with the inner diameter of the axially moving bed reactor 1. For example, 2 to 5 catalyst transfer pipes 16 may be provided between two adjacent catalyst beds 3 with respect to the axial moving bed reactor 1 having an inner diameter of 600mm, and the inner diameter of the catalyst transfer pipe 16 may be 15 to 50 mm.

According to a preferred embodiment of the present invention, the reaction material outlet (preferably arranged at the bottom) of the axially moving bed reactor 1 communicates with the uppermost feed inlet 2 of the axially moving bed reactor 2 to circulate the reaction material obtained by the axially moving bed reactor 1 back to the axially moving bed reactor 1. With this preferred embodiment, it is more advantageous to control the alkane-olefin ratio of each catalyst bed 3, and it is more advantageous to control the temperature rise of the catalyst bed 3.

According to a preferred embodiment of the present invention, a separating member 10 is disposed between two adjacent catalyst beds 3, the separating member 10 is communicated with a catalyst conveying pipe 16, the separating member 10 is used for separating materials and catalysts after reaction of the upstream catalyst bed, and the catalysts separated by the separating member 10 move downwards through the catalyst conveying pipe 16. The reacted material and catalyst in the upstream catalyst bed are separated by the separating part 10 to obtain the reacted material and catalyst, the catalyst moves downwards through the catalyst conveying pipe 16, and the reacted material is mixed with the liquid fresh material fed from the feeding port above the catalyst bed 3 in the space between two adjacent catalyst beds (referred to as the bed space before the reaction bed in the invention) and then flows into the downstream catalyst bed.

According to an embodiment of the present invention, the separating member 10 may be a screen having holes (the hole diameter may be determined according to the size of the catalyst particles) for allowing the reacted material to pass through, so as to separate the reacted material from the catalyst.

In order to mix the reacted material and the liquid fresh material flowing into the downstream catalyst bed layer more uniformly, a reaction material baffle 11 is preferably arranged between two adjacent catalyst bed layers 3, and the reaction material baffle 11 is used for enhancing the mixing of the reacted material and the liquid fresh material fed from the feed inlet 2.

The present invention is not particularly limited to the specific structure of the reaction material baffle 11, as long as it can enhance the mixing of the reacted material and the liquid fresh raw material. In particular, the reaction material baffles 11 are placed in the space of the bed layer in front of the reaction bed layer, and the number of the baffles can be 1 or more than two, and preferably 1-6.

According to a first preferred embodiment of the invention, as shown in fig. 2, the reaction material baffle 11 comprises a main shaft 111 and a conveying member 112 extending helically in the axial direction of the main shaft. Specifically, the inlet of the spirally extending flow channel formed by the conveying member 112 is set according to the position of the feed port 2 so that the reacted material and the liquid fresh raw material flow from the spirally extending flow channel formed by the conveying member 112, thereby achieving mixing.

According to a second preferred embodiment of the present invention, as shown in fig. 1, the reaction material baffle 11 comprises a plurality of baffles 113, the plurality of baffles 113 are arranged obliquely in the axial direction of the axial moving-bed reactor 1, and the plurality of baffles 113 are arranged alternately with each other to form flow passages through which the reaction material can pass. The plurality of baffles 113 may be disposed obliquely downward or obliquely upward in the axial direction of the axial moving-bed reactor 1 (as shown in fig. 1). Preferably, the baffle 113 extends at an angle of 5-60 °, more preferably 10-40 ° to the horizontal.

The baffles 113 are arranged in a staggered manner in the invention, which means that no closed area is formed between the baffles 113, so that the reaction materials can smoothly flow downwards. According to one embodiment of the present invention, as shown in fig. 1, a part of the baffles 113 is fixedly connected to the wall of the axially moving bed reactor 1, a part of the baffles 113 is fixedly connected to the wall of the catalyst transport pipe 16, and the baffles 113 are arranged in parallel with each other. Preferably, the distance between adjacent baffles 113 is 15-60 mm.

According to a preferred embodiment of the present invention, a catalyst distribution member is disposed between two adjacent catalyst beds 3, and the catalyst distribution member is used for distributing the catalyst at the outlet of the catalyst conveying pipe 16. If no catalyst distribution member is provided, the catalyst at the outlet of the catalyst transfer pipe 16 is liable to form a conical pile in the downstream catalyst bed. Preferably, the catalyst distribution member comprises a conical distribution baffle 12, and the conical distribution baffle 12 is coaxially arranged with the catalyst conveying pipe 16. The catalyst at the outlet of the catalyst conveying pipe 16 falls on the tip of the conical distribution baffle 12 under the action of gravity, and is dispersed to the two horizontal sides of the catalyst conveying pipe 16 through the dispersion action of the conical distribution baffle 12. It is further preferred that the number of the conical distribution baffles 12 and the number of the catalyst conveying pipes 16 are the same.

According to a preferred embodiment of the present invention, the catalyst distribution member further comprises a horizontal distribution baffle 13 disposed below the conical distribution baffle 12, and the horizontal distribution baffle 13 is provided with holes for catalyst to pass through. In the present invention, the number of the horizontal distribution baffles 13 is not particularly limited, and may be 1, or two or more, and it is preferable that each horizontal distribution baffle is provided at a radially intermediate position (and an axially lower position) of each of two adjacent conical distribution baffles 12. The radial and axial directions refer to the radial and axial directions of the axial moving-bed reactor 1.

Further preferably, the holes of the horizontal distribution baffle 13 become gradually larger in a horizontal outward direction along the center of the axial moving bed reactor 1. With this preferred embodiment, the part of the catalyst that is dispersed near the center of the axial moving bed reactor 1 and passes through the tapered distribution baffle 12 passes through the holes of the horizontal distribution baffle 13, and the part of the catalyst that cannot pass through is dispersed to the edge of the axial moving bed reactor 1, which is more beneficial to ensuring the uniform dispersion of the catalyst.

Further preferably, the horizontal distribution baffle 13 may be a circular distribution plate with a low open area in the middle area and a high open area in the side walls.

The catalyst in each catalyst bed layer of the axial moving bed reactor 1 is gradually deactivated along with the reaction, and simultaneously gradually falls to the catalyst bed layer further downstream, finally reaches the bottom of the axial moving bed reactor 1, and then is conveyed to a spent catalyst receiver 5 through a catalyst conveying pipeline.

According to a preferred embodiment of the present invention, the axially moving bed reactor 1 is provided with a bottom catalyst collection zone 37 at its lower part. The catalyst passing through the most downstream catalyst bed is delivered to the bottom catalyst collection zone 37, and a certain amount of catalyst is collected and delivered to the spent catalyst receiver 5.

According to an embodiment of the present invention, as shown in fig. 1, material pipeline valves between the containers are respectively disposed on communicating pipelines of the axial moving bed reactor 1 and the spent agent receiver 5, the spent agent receiver 5 and the catalyst regenerator 4, the catalyst regenerator 4 and the regenerant receiver 6, and the regenerant receiver 6 and the axial moving bed reactor 1.

According to a preferred embodiment of the invention, the spent agent receiver 5 (preferably the bottom) is provided with a spent liquor outlet 15. The invention can remove the liquid phase materials carried in the catalyst in the spent catalyst receiver 5 by directly reducing the pressure or introducing high-pressure hydrogen, nitrogen and other pressurizing modes, and the liquid phase materials can be output through the liquid phase material outlet 15. Preferably, a liquid removing filter 7 is arranged on the liquid-returning material conveying line which is sent out from the liquid-returning material outlet 15. The liquid removal filter 7 is used for blocking fine catalyst powder or fine particles.

The catalyst after the liquid removal in the spent catalyst receiver 5 is sent to the catalyst regenerator 4 for regeneration. The catalyst regenerator 4 is provided with a regeneration medium inlet 30 and a regenerated medium outlet 31. The regeneration medium is fed into the catalyst regenerator 4 through the regeneration medium feed inlet 30 to contact with the catalyst to regenerate (preferably completely regenerate) the catalyst, and the regenerated medium is discharged through the regenerated medium discharge outlet 31. Preferably, a regenerated media filter 8 is provided on the regenerated media delivery line that is sent from the regenerated media outlet 31. The filter is used for blocking the catalyst of the regenerator from flowing into a gas circulation pressurization device at the downstream and collecting fine powder or fine particles generated by friction or purging in the regeneration process. The regeneration medium of the invention can be air or a mixed gas of air and nitrogen.

According to a preferred embodiment of the present invention, the catalyst regenerator 4 may also be provided with a fresh catalyst inlet for fresh catalyst to enter the catalyst regenerator 4. By providing a fresh catalyst feed port in the catalyst regenerator 4, a catalyst partially deactivated or a catalyst that is difficult to recover the initial activity can be replaced with a fresh catalyst, ensuring the treatment capacity of the apparatus. Specifically, a pump is provided on the fresh catalyst delivery line in communication with the fresh catalyst feed inlet.

The regenerated catalyst will flow through the catalyst transfer line at the bottom of the catalyst regenerator 4 into the regenerant receiver 6. Preferably, the regenerant receiver 6 is provided with a liquid phase feed makeup inlet 32. The gas in the catalyst gap is replaced by the liquid phase material such as alkane in the reaction raw material or liquid phase material after the reaction, etc. introduced into the regenerant receiver 6 through the liquid phase material replenishment inlet 32.

The regenerated catalyst returns to the axial moving bed reactor 1 through a catalyst conveying pipeline between the regenerant receiver 6 and the axial moving bed reactor 1, continuously participates in the reaction until the catalyst is deactivated and then is conveyed to the spent catalyst receiver 5, and the catalyst circulates according to the flow.

According to a preferred embodiment of the invention, the spent catalyst receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are sequentially arranged from top to bottom, and catalyst flow lines among the spent catalyst receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are vertically arranged or obliquely arranged at an included angle of not less than 40 degrees with the horizontal plane. By adopting the preferred embodiment, the catalyst granules can smoothly flow from top to bottom, and the material is prevented from being accumulated or remaining in a pipeline to influence the valve tightness or the catalyst regeneration effect.

According to a preferred embodiment of the present invention, a first particle flow regulator 25 is disposed on a communicating line between a catalyst outlet of the axial moving bed reactor 1 and a catalyst inlet of the spent catalyst receiver 5; a second particle flow regulator 33 is provided on a communicating line of the catalyst outlet of the regenerant receiver 6 and the catalyst inlet of the axial moving bed reactor 1. The first particle flow rate adjuster 25 and the second particle flow rate adjuster 33 are not particularly limited in the present invention as long as the flow rate of the catalyst particles can be adjusted. Further preferably, the first particle flow regulator 25 and the second particle flow regulator 33 are each independently an L-shaped or approximately L-shaped material delivery valve group. Specifically, the L-shaped or approximately L-shaped material conveying valve group is also communicated with at least one liquid phase material feeding pipeline. The flow resistance of the granular materials can be increased by arranging the granular flow regulator, and meanwhile, the regulator is communicated with at least one liquid-phase material feeding pipeline for increasing the flow driving force of the granular materials and reducing the flow resistance of the granular materials. The L-shaped or approximately L-shaped material conveying valve group is arranged, and the discharge rate of the catalyst can be adjusted by changing the flow of the liquid-phase material entering the valve group, so that the falling rate and the retention time of the catalyst in each reaction bed layer in the reactor can be controlled and adjusted.

According to a preferred embodiment of the invention, the device further comprises a catalyst buffer tank 38, the catalyst buffer tank 38 is arranged between the axial moving bed reactor 1 and the spent agent receiver 5, a catalyst inlet of the catalyst buffer tank 38 is communicated with a catalyst outlet of the axial moving bed reactor 1, and a catalyst outlet of the catalyst buffer tank 38 is communicated with a catalyst inlet of the spent agent receiver 5. The catalyst buffer tank 38 is used for storing the catalyst discharged from the axial moving bed reactor 1 during the period of discharging the spent catalyst receiver from the liquid phase material and the catalyst to the catalyst regenerant, and ensures the continuity of the catalyst material flow in the axial moving bed reactor 1 and the smoothness of the device operation.

The liquid-solid axial moving bed reaction and regeneration device provided by the invention can realize continuous and stable operation of solid acid alkylation reaction and regeneration of deactivated catalyst, improves the selectivity of target products and the flexibility of device operation, greatly reduces the investment cost of catalyst and improves the economic competitiveness of the device. Accordingly, in a second aspect the present invention provides the use of a liquid-solid axial moving bed reaction and regeneration apparatus as described above in a solid acid alkylation reaction.

The following is a specific embodiment of the liquid-solid axial moving bed reaction and regeneration apparatus of the present invention and its application in solid acid alkylation reactions, but the present invention is not limited thereto.

As shown in fig. 1, three catalyst beds 3 are arranged in an axial moving bed reactor 1, a spent catalyst receiver 5, a catalyst regenerator 4 and a regenerant receiver 6 are sequentially arranged from top to bottom, and catalyst flow pipelines among the three are vertically arranged. The fresh olefin raw material containing isobutane is introduced from a pipeline 17, mixed with a circulating material through a first branch pipeline 19, enters a reaction zone of the axial moving bed reactor 1 from the feeding hole 2 to be in contact reaction with the first catalyst bed layer 3, and is fed from the feeding hole 2 through a second branch pipeline 20 and a third branch pipeline 21 to be in contact reaction with a reacted material of an upstream catalyst bed layer to be mixed in a bed layer space in front of the reaction bed layer of the axial moving bed reactor 1. A separating piece 10 is arranged between two adjacent catalyst bed layers 3, the reacted materials pass through the separating piece 10, and the catalyst which does not pass through the separating piece 10 moves downwards through a catalyst conveying pipe 16. A reaction material baffle 11 is arranged between two adjacent catalyst bed layers 3, and the reaction material and the fresh material flow passing through the separating piece 10 are intensively mixed under the action of the reaction material baffle 11. And a catalyst distribution piece (comprising a conical distribution baffle 12 and a horizontal distribution baffle 13, wherein the conical distribution baffle 12 is coaxial with the catalyst conveying pipe 16, and the horizontal distribution baffle 13 is arranged below the conical distribution baffle 12) is also arranged between every two adjacent catalyst beds 3, and the catalyst at the outlet of the catalyst conveying pipe 16 is dispersed and falls to the downstream catalyst beds 3 under the action of the catalyst distribution piece. The lower part of the axially moving bed reactor 1 is provided with a bottom catalyst collecting zone 37. The catalyst passing through the most downstream catalyst bed is delivered to the bottom catalyst collection zone 37, and a certain amount of catalyst is collected and delivered to the spent catalyst receiver 5. A first particle flow regulator 25 is arranged on a communicating pipeline of the catalyst outlet of the axial moving bed reactor 1 and the catalyst inlet of the spent catalyst receiver 5 so as to regulate the flow of the catalyst particles. A liquid-phase material outlet 15 is arranged at the bottom of the spent agent receiver 5, liquid-phase materials carried in the catalyst are removed from the spent agent receiver 5, and a liquid-removing filter 7 is arranged on a liquid-phase material conveying pipeline sent out from the liquid-phase material outlet 15 to block fine catalyst powder or fine particles. The catalyst after liquid removal in the spent catalyst receiver 5 is sent to a catalyst regenerator 4 for regeneration, and the catalyst regenerator 4 is provided with a regeneration medium feeding port 30 and a regeneration medium discharging port 31. The regenerated medium is fed into the catalyst regenerator 4 through the regenerated medium feed inlet 30 to contact with the catalyst for regenerating the catalyst, and the regenerated medium is discharged through the regenerated medium discharge outlet 31. A regenerated medium filter 8 is disposed on the regenerated medium delivery line fed out from the regenerated medium outlet 31 to block fine powder or fine particles. The catalyst regenerator 4 may also be provided with a fresh catalyst inlet for fresh catalyst to enter the catalyst regenerator 4. By providing a fresh catalyst feed port in the catalyst regenerator 4, a catalyst partially deactivated or a catalyst that is difficult to recover the initial activity can be replaced with a fresh catalyst, ensuring the treatment capacity of the apparatus. The regenerated catalyst flows into the regenerant receiver 6 through a catalyst transfer line at the bottom of the catalyst regenerator 4, and the regenerant receiver 6 is provided with a liquid phase feed make-up inlet 32. Gas in the liquid phase replacing catalyst interstice is introduced into the regenerant receiver 6 through the liquid phase make-up inlet 32.

The regenerated catalyst returns to the axial moving bed reactor 1 through a catalyst conveying pipeline between the regenerant receiver 6 and the axial moving bed reactor 1 to continuously participate in the reaction until the catalyst is deactivated and then conveyed to the spent catalyst receiver 5, and the catalyst circulates according to the process. A second particle flow regulator 33 is provided on a communicating line of the catalyst outlet of the regenerant receiver 6 and the catalyst inlet of the axial moving bed reactor 1 to regulate the catalyst particle flow.

The present invention will be described in detail below by way of examples.

Example 1

This example was carried out on a liquid-solid axial moving bed reaction and regeneration apparatus as shown in FIG. 1. Wherein, the axial moving bed reactor 1, the spent catalyst receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are connected in sequence through pipelines.

The inner diameter of the axial moving bed reactor 1 is 600mm, the height is 15m, the height of each section of catalyst bed 3 (respectively marked as a first catalyst bed, a second catalyst bed and a third catalyst bed) which is provided with three catalyst beds 3 from top to bottom is 3.5m, and the distance between adjacent catalyst beds 3 is 1.2 m. 2 cylindrical catalyst conveying pipes 16 are respectively arranged between the first catalyst bed layer and the second catalyst bed layer and between the second catalyst bed layer and the third catalyst bed layer, and the inner diameter of each catalyst conveying pipe 16 is 20 mm. Separating pieces 10 (wedge-shaped filter screens with the gap width of 0.2 mm) are respectively arranged below the first catalyst bed layer and the second catalyst bed layer. 1 reaction material baffle 11 shown in fig. 2 is respectively arranged between the first catalyst bed layer and the second catalyst bed layer and between the second catalyst bed layer and the third catalyst bed layer, the reaction material baffle 11 comprises a main shaft 111 and a conveying part 112 spirally extending along the axial direction of the main shaft, and the inlet of a spirally extending flow channel formed by the conveying part 112 is positioned below the feed inlets 2 of the fresh olefin raw materials of the second branch pipeline 20 and the third branch pipeline 21. Reactant flow baffles 11 are disposed in the annular space between the central region of catalyst transfer tube 16 and the reactor wall. Still be provided with 3 among first catalyst bed, the second catalyst bed and between second catalyst bed, the third catalyst bed respectively and taper distribution baffle 12 (highly being 0.1m) with the coaxial setting of

catalyst conveyer pipe

16, 3 sets up horizontal distribution baffle 13 (circular distribution board) of taper distribution baffle 12 below is provided with the hole that supplies the catalyst to pass through on the horizontal distribution baffle 13, along axial moving bed reactor 1's central level to the outside direction, the hole on the horizontal distribution baffle 13 progressively enlarges, and the biggest hole aperture sets up to 25mm, and the minimum hole aperture sets up to 5 mm. The lower part of the axially moving bed reactor 1 is provided with a bottom catalyst collecting zone 37.

The spent catalyst receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are sequentially arranged from top to bottom, and catalyst flow pipelines among the spent catalyst receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are vertically arranged. The diameter of the spent catalyst receiver 5, the diameter of the catalyst regenerator 4 and the diameter of the regenerant receiver 6 are all 1200mm, and the height of each straight pipe section is 6 m. The diameter of the material circulation line was 250 mm.

After the mixture of reaction fresh raw materials of isobutane, normal butane, butylene and the like is fed from a fresh material feeding pipeline 17, the reaction fresh raw materials are divided into three paths to enter the corresponding catalyst bed layers 3, and the molar ratio of alkane to alkene of the mixed material entering each catalyst bed layer 3 is 700: 1, the flow rate of the recycled material in the reactor was 1.9m/s, the corresponding total fresh feed rate was 482kg/h, and the olefin mass space velocity was 0.25h^-1. The residence time of the catalyst in the axially moving bed reactor 1 was 72 h. The catalyst used is a molecular sieve spherical catalyst with FAU structure, and the average particle size is 1.8 mm. The preparation method comprises the steps of removing sodium ions on a NaY type molecular sieve with an FAU structure produced by China petrochemical catalyst division through steps of ion exchange and the like; the molecular sieve was then mixed with alumina in a ratio of 65: 35, mixing uniformly, preparing into small balls by adopting an oil ammonia column forming method, and further drying and roasting to prepare the catalyst. ShaftThe reaction temperature in the moving bed reactor 1 was 70 ℃ and the reaction pressure was 2.5 MPa.

Fresh materials and circulating materials are mixed and fed into the axial moving bed reactor 1 from the feeding hole 2 to be in contact reaction with the catalyst filled in the first catalyst bed layer, the reacted materials obtained by separation of the separating piece 10 and the fresh materials from the first branch pipeline 19 are fed into the second catalyst bed layer to be reacted through reinforced mixing of the baffle piece 11, the catalyst obtained by separation of the separating piece 10 dispersedly falls to the downstream catalyst bed layer under the action of the catalyst distributing piece through the catalyst conveying pipe 16, and finally the catalyst falls to the catalyst collecting region 37 at the bottom. The catalyst obtained from the bottom catalyst collecting zone 37 is sent to the spent catalyst receiver 5 through the catalyst outlet. A first particle flow regulator 25 (an L-shaped material conveying valve group) is arranged on a communicating pipeline between a catalyst outlet of the axial moving bed reactor 1 and a catalyst inlet of the spent catalyst receiver 5, and the L-shaped material conveying valve group is also communicated with a liquid-phase material feeding pipeline to control the flow (20kg/h) of the catalyst. And introducing nitrogen into the spent catalyst receiver 5 to remove liquid-phase materials carried in the catalyst, outputting the liquid-phase materials through a liquid-withdrawing material outlet 15, and arranging a liquid-removing filter 7 on a liquid-withdrawing material conveying pipeline sent out from the liquid-withdrawing material outlet 15. The catalyst after liquid removal in the spent catalyst receiver 5 is sent into a catalyst regenerator 4 for regeneration, a mixed gas of nitrogen and air (the volume concentration of oxygen is 1-21 vol% and is adjusted from small to large, the apparent gas velocity is 0.1m/s) is used as a high-temperature deep regeneration medium of the catalyst, the period of high-temperature (350-. The catalyst regenerator 4 may also be provided with a fresh catalyst inlet for fresh catalyst to enter the catalyst regenerator 4.

The regenerated catalyst will flow through the catalyst transfer line at the bottom of the catalyst regenerator 4 into the regenerant receiver 6. The regenerant receiver 6 is provided with a liquid phase material supplement inlet 32, gas in the catalyst gap is replaced by the reacted oil-containing liquid phase material introduced into the regenerant receiver 6 through the liquid phase material supplement inlet 32, and the obtained catalyst slurry is circulated to the top of the axial moving bed reactor 1. A second particle flow regulator 33 (an L-shaped material conveying valve group) is arranged on a communicating pipeline between a catalyst outlet of the regenerant receiver 6 and a catalyst inlet of the axial moving bed reactor 1, and the L-shaped material conveying valve group is also communicated with a liquid-phase material feeding pipeline to control the flow (20kg/h) of the catalyst slurry.

Example 2

The solid acid alkylation reaction was carried out on the apparatus shown in FIG. 3. The difference from the example 1 is only that the device is also provided with a catalyst material buffer tank 38 with the diameter of 500mm and the height of a straight pipe section of 4.2m between the axial moving bed reactor 1 and the spent catalyst receiver 5.

The catalyst material buffer tank 38 is added in this embodiment, so that when the spent catalyst receiver performs the liquid removal operation and transfers the catalyst into the regenerator, the catalyst in the reactor still keeps moving downwards slowly at the original speed, and after the operation is completed, the catalyst accumulated in the catalyst buffer tank is gradually discharged to the spent catalyst receiver, so that the continuity of the catalyst material flow in the axial moving bed reactor 1 and the stability of the device operation are ensured.

Example 3

The solid acid alkylation reaction was carried out on the apparatus shown in FIG. 1. The difference is that the reaction material baffle 11 shown in fig. 2 is replaced by the reaction material baffle 11 shown in fig. 1, the reaction material baffle 11 comprises 8 parallel baffle plates 113 which are arranged in a staggered manner, the included angle between the extension direction of the baffle plates 113 and the horizontal plane is 25 degrees, the baffle plates 113 are arranged upwards along the axial inclination of the axial moving bed reactor 1, 4 baffle plates 113 are fixedly connected to the wall of the axial moving bed reactor 1, 4 baffle plates 113 are fixedly connected to the tube wall of the catalyst conveying tube 16, and the distance between the adjacent baffle plates 113 is 25 mm.

Comparative example 1

The solid acid alkylation reaction is carried out on two fixed bed medium-sized test devices which are connected in parallel, and the specific operation process is that when the first reactor is in the alkylation reactionWhen the device is used, the second reactor carries out high-temperature deep regeneration operation, and the two fixed bed reactors connected in parallel are switched for use, so that the device can continuously and stably operate. Each fixed bed reactor had an internal diameter of 200mm and a height of 2500 mm. The catalyst charged in the reactor was prepared in the same manner as in example 1 except that the diameter of the pellets was 2.7mm, the loading was 28kg and the loading height was 1500 mm. The reaction raw material is a mixture of isobutane and butene, the mole ratio of alkane and alkene in the reactor is 800:1, the feeding quantity of fresh mixed alkene is 6.3kg/h, and the mass space velocity of the alkene is 0.09h^-1. The catalyst in the bed layer needs to be subjected to high-temperature deep regeneration once every 24 hours, the temperature of the mixed gas of nitrogen and air (same as that in example 1) is increased from normal temperature to 480 ℃, the catalyst in the bed layer is subjected to high-temperature oxidation regeneration for 3 hours under normal pressure, the bed layer needs to be cooled after regeneration, and the whole regeneration period is 24 hours. And after the regeneration is finished, returning the materials in the reactor in the reaction state to the reactor after the regeneration is finished, continuing to carry out an alkylation reaction experiment by using the regenerated catalyst, and switching the reactor after the reaction materials are returned into the regeneration operation, thus repeatedly circulating.

After the apparatus of the above examples and comparative examples were continuously and stably operated for 1000 hours, the obtained alkylate was measured, and the test results are shown in Table 1.

TABLE 1

	RON	MON	Olefin C5+ yield	TMP/DMH	C9+ product wt.%
						Example 1	95.5	91.5	1.99	3.53	5.12
Example 2	95.8	92.0	2.0	3.62	5.08
						Example 3	95.7	92.0	2.0	3.60	5.11
Comparative example 1	95.2	91.3	1.96	3.24	6.76

As can be seen from Table 1, the octane number of the alkylate obtained by using the device provided by the invention is slightly superior to that of the fixed bed technology, the olefin yield in the alkylate is higher, the alkylate has higher selectivity of the target product (trimethylpentane), and the yield of the C9+ product is lower. Compared with the example 1, the example 2 with the catalyst buffer tank has better product yield and target product selectivity. From the view of device operation, for the fixed bed alkylation technology, in order to realize the continuous and stable operation of the reaction device, at least more than two reactors are required to be switched (as comparative example 1), the catalyst in the bed layer is regenerated at high temperature at regular intervals, the high temperature bed layer is cooled after deep regeneration, and the device frequently switches between the reaction temperature and the regeneration temperature, so that a plurality of problems are brought to the continuous and stable operation in industrial application, but the single (set) device can meet the requirements by adopting the liquid-solid axial moving bed reaction and regeneration device provided by the invention, the investment cost of the device is reduced, in addition, the continuous operation of the catalyst reaction and the regeneration is realized by leading the deactivated catalyst particles out of the liquid-solid axial moving reactor for deep regeneration on the premise of not influencing the stable operation of the reaction device, the catalyst in the device has stable equilibrium activity, and the selectivity of the target product in the alkylate oil is improved. Therefore, the liquid-solid axial moving bed reaction and regeneration device provided by the invention has better industrial application prospect.

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

1. A liquid-solid axial moving bed reaction and regeneration apparatus, comprising:

the device comprises an axial moving bed reactor (1), a spent catalyst receiver (5), a catalyst regenerator (4) and a regenerant receiver (6) which are connected in sequence, wherein a catalyst outlet of the regenerant receiver (6) is communicated with a catalyst inlet of the axial moving bed reactor (1);

the device comprises an axial moving bed reactor (1), a feed inlet, a feed outlet and a feed outlet, wherein the axial moving bed reactor (1) is provided with at least two catalyst bed layers (3) which are arranged up and down, and the feed inlet (2) is arranged above each catalyst bed layer (3) of the axial moving bed reactor (1);

a catalyst conveying pipe (16) is arranged between two adjacent catalyst bed layers (3) so that the catalyst can move from top to bottom in the axial moving bed reactor (1);

a reaction material baffling piece (11) is arranged between every two adjacent catalyst bed layers (3), and the reaction material baffling piece (11) is used for enhancing the mixing of the reacted materials and the liquid fresh raw materials fed by the feeding port (2).

2. A liquid-solid axial moving bed reaction and regeneration apparatus according to claim 1, wherein the reaction material outlet of the axial moving bed reactor (1) communicates with the uppermost feed inlet (2) of the axial moving bed reactor (1) to circulate the reaction material obtained from the axial moving bed reactor (1) back to the axial moving bed reactor (1).

3. A liquid-solid axial moving bed reaction and regeneration apparatus according to claim 1, wherein,

be provided with separator (10) between two adjacent catalyst bed (3), separator (10) and catalyst conveyer pipe (16) intercommunication, separator (10) are used for the separation of upstream catalyst bed reaction back material and catalyst, and the catalyst that separator (10) separation obtained passes through catalyst conveyer pipe (16) and moves down.

4. A liquid-solid axial moving bed reaction and regeneration apparatus according to claim 1, wherein the reaction material baffle (11) comprises a main shaft (111) and a conveying member (112) extending spirally in the axial direction of the main shaft.

5. A liquid-solid axial moving bed reaction and regeneration apparatus as claimed in claim 1, wherein the reaction material baffle (11) comprises a plurality of baffles (113), the plurality of baffles (113) are disposed obliquely in the axial direction of the axial moving bed reactor (1), and the plurality of baffles (113) are disposed alternately with each other to form flow passages through which the reaction material can pass.

6. A liquid-solid axial moving bed reaction and regeneration apparatus as claimed in any one of claims 1 to 5, wherein a catalyst distribution member is provided between two adjacent catalyst beds (3) for dispersing the catalyst at the outlet of the catalyst transport pipe (16).

7. A liquid-solid axial moving bed reaction and regeneration apparatus according to claim 6, wherein the catalyst distribution member comprises a conical distribution baffle (12), the conical distribution baffle (12) being arranged coaxially with the catalyst transport pipe (16).

8. A liquid-solid axial moving bed reaction and regeneration apparatus according to claim 7, wherein the number of the conical distribution baffles (12) and the number of the catalyst transfer pipes (16) are the same.

9. A liquid-solid axial moving bed reaction and regeneration apparatus according to claim 7, wherein the catalyst distribution member further comprises a horizontal distribution baffle (13) disposed below the conical distribution baffle (12), and the horizontal distribution baffle (13) is provided with holes for passing the catalyst.

10. A liquid-solid axial moving bed reaction and regeneration apparatus according to any one of claims 1 to 5, wherein the catalyst regenerator (4) is provided with a fresh catalyst inlet for fresh catalyst to enter the catalyst regenerator (4).

11. The liquid-solid axial moving bed reaction and regeneration device according to any one of claims 1 to 5, wherein the spent catalyst receiver (5), the catalyst regenerator (4) and the regenerant receiver (6) are arranged sequentially from top to bottom, and catalyst flow lines between the spent catalyst receiver (5), the catalyst regenerator (4) and the regenerant receiver (6) are arranged vertically or inclined at an angle of not less than 40 degrees with respect to the horizontal plane.

12. A liquid-solid axial moving bed reaction and regeneration apparatus as claimed in any one of claims 1 to 5, wherein a first particle flow regulator (25) is provided on a communicating line between the catalyst outlet of the axial moving bed reactor (1) and the catalyst inlet of the spent catalyst receiver (5); a second particle flow regulator (33) is arranged on a communicating pipeline between the catalyst outlet of the regenerant receiver (6) and the catalyst inlet of the axial moving bed reactor (1).

13. A liquid-solid axial moving bed reaction and regeneration apparatus according to claim 12, wherein the first particle flow regulator (25) and the second particle flow regulator (33) are each independently an L-shaped or nearly L-shaped material delivery valve block.

14. A liquid-solid axial moving bed reaction and regeneration apparatus according to any one of claims 1 to 5, wherein the apparatus further comprises a catalyst buffer tank (38), the catalyst buffer tank (38) is arranged between the axial moving bed reactor (1) and the spent agent receiver (5), a catalyst inlet of the catalyst buffer tank (38) is communicated with a catalyst outlet of the axial moving bed reactor (1), and a catalyst outlet of the catalyst buffer tank (38) is communicated with a catalyst inlet of the spent agent receiver (5).

15. Use of a liquid-solid axial moving bed reaction and regeneration apparatus according to any one of claims 1 to 14 in solid acid alkylation reactions.