Gas-solid reaction device, application thereof and method for producing low-carbon olefin

Abstract

The invention discloses a gas-solid reaction device and application thereof and a method for producing low-carbon olefin, the gas-solid reaction device comprises a reaction part, a separation part and a flow guide part, the reaction part comprises a gas-solid contact cavity, a solid-phase feeding piece and a gas-phase feeding piece; the sprayed gas-phase raw material and the solid-phase raw material fed through the solid-phase feeding part can be in cross-flow contact in the gas-solid contact cavity through the gas-phase feeding part, and gas-solid mixed fluid containing product gas is generated; a separation cavity is formed in the separation part, and the gas-solid contact cavity is communicated with the separation cavity so that the gas-solid mixed fluid can enter the separation part from the side face of the separation cavity; and the flow guide part is arranged in the separation cavity and is used for guiding the gas-solid mixed fluid entering from the side surface of the separation cavity to move downwards. The method has the advantages of high gas-solid contact efficiency, short contact time and high target product selectivity.

Description

Technical Field

[0001] The present invention relates to the field of methanol processing, and particularly to a gas-solid reaction device, its application, and a method for producing light olefins. Background Art

[0002] China is a country rich in coal but short of oil. The shortage of oil resources means that the country's crude oil supply has long been largely dependent on imports. However, China is relatively rich in coal resources. Therefore, vigorously developing C1 chemistry will effectively improve the existing resource short board and has important strategic significance for sustainable economic development. Coupled with the continuous breakthroughs in methanol-to-olefins technology in recent years, after 2010, a large number of large-scale MTO industrial plants have been put into operation, becoming an important supplement to the crude oil preparation route.

[0003] At present, the industrial application of domestic MTO technology has formed a scale, and the proportion of coal-to-olefins and methanol-to-olefins is about 17%. The competition among many coal-to-olefins technologies is extremely fierce. As the most core device in the entire coal-to-olefins project, the methanol-to-olefins process technology requires more extensive and in-depth research and innovation.

[0004] According to the hydrocarbon pool mechanism, in the reaction process of methanol being converted to hydrocarbons in the MTO reaction, it will go through the step of methanol to reaction intermediates. The main reaction intermediates generated are polymethylbenzenes, and the reaction rate from reaction intermediates to olefins is very fast. At present, the gas-solid contact time of common MTO technologies is within 2 to 8 seconds, and there are still about 14 to 17% of propane and C4+ by-products. Further reducing the gas-solid contact time is beneficial to further improving the selectivity of light olefin products.

[0005] US4499327A discloses a process for applying a silicoaluminophosphate molecular sieve catalyst to the conversion of methanol to olefins. SAPO-34 is preferably used as the catalyst for the methanol-to-olefins process. This catalyst has a very high selectivity for light olefins and high activity, enabling the reaction time for converting methanol to light olefins to reach less than 10 seconds, and even within the reaction time range of the riser.

[0006] CN104437274A discloses a dense fluidized bed reactor that can be used for methanol conversion to olefins. The reactor uses a gas pre-lift pipe with a special structure. By extending a gas distributor into the bed layer of the dense fluidized bed reactor and introducing gas radially into the bed layer, combined with the special baffle design in the reactor, the gas-solid contact efficiency in the bed layer is improved, and the selectivity of light olefins in the reaction products is improved. This method improves the selectivity of the target product by strengthening mass transfer and heat transfer, rather than by reducing the reaction time. There are limitations for the dense gas-solid fluidized bed reactor with respect to gas velocity. If the gas velocity is reduced to the millisecond level by increasing the intake gas volume to increase the gas velocity, it may cause changes in the fluidized bed shape, resulting in a decrease in bed density and even serious catalyst loss.

[0007] CN111054277A discloses a reactor and method for producing light olefins. Using a raw material gas stream with a high tangential velocity ejected from multiple upper and lower partitions, entraining the solid-phase catalyst to form a near-wall dense thin layer by swirling around the axis. The raw material gas simultaneously passes rapidly through the solid-phase thin layer radially to achieve rapid gas-solid contact reaction, so as to improve the selectivity of light olefins in the MTO reaction tail gas. The gas-solid contact time can be as low as less than 2 s. However, since the raw material gas approximately enters the reactor tangentially, it will continue to swirl around the central axis after passing through the catalyst thin layer. Before being discharged through the central draft tube, the tail gas will continue to stay in the reactor for a long time and may continue to undergo a series of side reactions at the reaction temperature of MTO, affecting the final product composition.

[0008] As mentioned above, in the MTO process, the selectivity of light olefins in the product is improved by optimizing gas-solid distribution to strengthen mixing and controlling the rapid separation after gas-solid contact. However, how to develop a reactor structure specifically from the perspective of fitting the reaction process to further improve the selectivity of light olefins is a major issue in the continuous development of the MTO process. Summary of the Invention

[0009] The purpose of the present invention is to overcome the problem of low selectivity of the target product existing in the prior art, and provide a gas-solid reaction device, its application and a method for producing light olefins, which have the advantages of high gas-solid contact efficiency, short contact time, and high selectivity of the target product.

[0010] To achieve the above purpose, on the one hand, the present invention discloses a gas-solid reaction device, which includes:

[0011] A reaction section, including a gas-solid contact chamber, a solid-phase feed member, and a gas-phase feed member. The gas-phase feed member enables the injected gas-phase raw material and the solid-phase raw material fed through the solid-phase feed member to cross-flow contact in the gas-solid contact chamber, generating a gas-solid mixed gas stream containing product gas;

[0012] A separation section is internally provided with a separation chamber. The gas-solid contact chamber is communicated with the separation chamber so that the gas-solid mixed gas flow can enter from the side of the separation chamber.

[0013] A flow guiding section is arranged in the separation chamber and is used for guiding the gas-solid mixed gas flow entering from the side of the separation chamber to move downward.

[0014] The second aspect of the present invention discloses the application of the gas-solid reaction device of the present invention in the production of olefins by methanol conversion, catalytic cracking or fluidized bed propane dehydrogenation.

[0015] The third aspect of the present invention discloses a method for producing light olefins. This method uses the gas-solid reaction device of the present invention and includes:

[0016] Feeding catalyst particles through a solid-phase feeding member, and spraying methanol raw material gas through a gas-phase feeding member, so that the methanol raw material gas and the catalyst particles are in cross-flow contact in the gas-solid contact chamber to generate a gas-solid mixed gas flow containing product gas.

[0017] Making the gas-solid mixed gas flow enter from the side of the separation chamber and pass through the flow guiding section to be converted into a downward gas flow and enter the separation chamber for gas-solid separation.

[0018] Through the above technical solutions, the gas-solid reaction device of the present invention can enable full contact between gas and solid, and convert the horizontally sprayed gas-solid mixed fluid into a downward fluid through the flow guiding section, so that the solid phase obtains a further increased downward speed, resulting in that most of the solid phase detaches from the gas phase main body and flows downward concentratedly after the mixed fluid leaves the flow guiding section and enters the separation chamber. Compared with the structure without a flow guiding section, the dispersion degree of the solid phase in the reactor is greatly reduced, realizing effective and rapid gas-solid separation. Further, the coiled pipe section for heat removal of the present invention is used to reduce the temperature of the tail gas after the reaction, further limiting the generation of side reactions, and at the same time further reducing the solid phase entrainment in the tail gas. When the present invention is applied to the production of olefins by methanol conversion, the light olefin composition in the tail gas can be significantly improved. Description of the Drawings

[0019] Figure 1 It is a schematic structural diagram of a gas-solid reaction device according to an embodiment of the present invention;

[0020] Figure 2 It is a schematic structural diagram of a gas-solid reaction device including size marks according to an embodiment of the present invention;

[0021] Figure 3 It is Figure 2 A three-dimensional structural diagram of the circled part in

[0022] Figure 4 It is Figure 2 A top view structural diagram of the gas-solid reaction device;

[0023] Figure 5It is a schematic diagram of the solid-phase feed inlet of the gas-solid reaction device;

[0024] Figure 6 It is a schematic layout structure of the nozzles of the gas-phase feed component of the gas-solid reaction device;

[0025] Figure 7 It is a schematic structural diagram of the baffle of the gas-solid reaction device

[0026] Figure 8 It is a schematic cross-sectional view of the coiled pipe in the separation chamber;

[0027] Figure 9 A process flow diagram of an embodiment of the present invention.

[0028] Explanation of reference numerals

[0029] 1 Solid-phase feed component; 2 Gas-phase feed component; 3 Gas-solid contact chamber; 4 Baffle; 5 Separation chamber; 6 Solid-phase outlet; 7 Coiled pipe; 8 Gas-phase outlet; 9 Gas-solid reaction device; 10 Cyclone separator; 11 Catalyst regenerator; 12 Mixer; 13 Inclined baffle; 14 Baffle; 15 Turbulence plate; 41 Flow baffle. Detailed implementation manners

[0030] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0031] In the present invention, unless otherwise stated, the orientation terms such as "upper, lower, top, bottom" are usually in terms of the direction shown in the drawings or in terms of the vertical, perpendicular or gravitational directions for the description of the relative positional relationship of each component; "inside, outside" refers to inside and outside the chamber relative to the chamber or radially inside and outside relative to the center of the circle.

[0032] As Figures 1-9 shown, the first aspect of the present invention discloses a gas-solid reaction device, including a reaction part, a separation part and a diversion part, wherein,

[0033] The reaction part is internally provided with a gas-solid contact chamber 3 and includes a solid-phase feed component 1 and a gas-phase feed component 2. The gas-phase feed component 2 enables the sprayed gas-phase raw material to cross-flow contact with the solid-phase raw material fed through the solid-phase feed component 1, generating a gas-solid mixed gas flow containing product gas;

[0034] The separation part is arranged outside the reaction part and is internally provided with a separation chamber 5. The top end of the separation chamber 5 is communicated with the gas phase outlet 8, and the bottom end is communicated with the solid phase outlet 6. The gas-solid contact chamber 3 is located on the side of the separation chamber 5 and is communicated with the separation chamber 5, so that the gas-solid mixed gas flow can enter from the side of the separation chamber 5;

[0035] The flow guiding part is arranged in the separation chamber 5 and is used for guiding the gas-solid mixed gas flow entering from the side of the separation chamber 5 to enter the separation chamber 5 downward for separation.

[0036] The gas-solid reaction device of the present invention can realize the rapid contact and rapid separation of gas-solid two phases, so as to improve the product selectivity and the yield.

[0037] For the convenience of describing the relative positions of various components, in the accompanying drawings of the present invention, the vertical or perpendicular direction is defined as the Z direction, the first horizontal direction is the X direction, and the second horizontal direction is the Y direction. Among them, the X direction, the Y direction and the Z direction are perpendicular to each other in pairs.

[0038] In order to realize the cross-flow contact between the solid phase and the gas phase, in the present invention, as Figures 1-2 shown, the feeding direction of the solid phase feeding part 1 and the feeding direction of the gas phase feeding part 2 are arranged at an angle in the ZX plane, preferably perpendicular to each other. For example, the gas phase raw material enters the gas-solid contact chamber 3 horizontally, and the solid phase raw material can enter the gas-solid contact chamber 3 vertically from top to bottom, and the two are in vertical contact.

[0039] In some embodiments of the present invention, a solid phase inlet is formed on the top chamber wall of the gas-solid contact chamber 3 to form the solid phase feeding part 1. As Figure 5 shown, the cross-section of the solid phase inlet in the XY plane can be oval or rectangular. Among them, the length of the solid phase inlet in the length direction (X direction or Y direction) is defined as b 0 .

[0040] In some embodiments of the present invention, the gas phase feeding part 2 includes a plurality of nozzles 21. The plurality of nozzles 21 are arranged on the side chamber wall of the gas-solid contact chamber 3 and are arranged opposite to the separation chamber 5 to spray the gas phase material into the gas-solid contact chamber. Among them, as Figure 6 shown, preferably, the plurality of nozzles 21 are arranged in a single row form arranged at equal intervals along the Y direction as shown in A in Figure 6 or a multi-row form arranged at intervals along the Z direction as shown in B and C in Figure 6 . In the multi-row form, the number of nozzles arranged at equal intervals along the Y direction in each row is equal or unequal; to further improve the gas-solid contact efficiency, more preferably, when the plurality of nozzles 21 are arranged in multiple rows, the adjacent two rows of nozzles 21 can be arranged in a Figure 6 dislocation arrangement as shown in C.

[0041] To further improve the gas-solid contact efficiency, in some embodiments of the present invention, the relationship between the solid phase inlet and the plurality of nozzles 21 is b + c ≥ b0 and b ≤ b 0 , where, as Figure 6 shown, c is the distance between two adjacent nozzles 21 in the same row of nozzles 21, b is the distance between the two nozzles 21 that are farthest apart in the gas-phase feed member 2 in the arrangement direction (Y-direction) of the nozzles 21, as Figure 5 shown, referring to the foregoing, b 0 is the distance of the solid-phase inlet in its own length direction.

[0042] To further improve the gas-solid contact efficiency, in some embodiments of the present invention, as Figure 3 shown, the distance c between the bottom end surface of the solid-phase inlet and the nozzle 21 in the vertical direction (Z-direction) 0 ≤ 10 cm.

[0043] It should be noted that, to avoid the accumulation of solid phase in the gas-solid contact chamber, as Figure 1 shown, in the present invention, an inclined plate inclined downward is provided in the gas-solid contact chamber 3, and the bottom end of the gas-solid contact chamber 3 is communicated with the separation chamber 5. The inclined plate enables the solid phase that has fallen after contacting the gas-phase raw material to fall into the separation chamber 5 and be discharged from the solid-phase outlet 5. In some embodiments of the present invention, as Figure 1 shown, the gas-solid contact chamber 3 can be arranged to extend into the separation chamber 5 along the X-direction. Thus, since the size of the separation chamber 5 is set larger than that of the gas-solid contact chamber 3, the gas velocity immediately decreases significantly after the gas leaves the gas-solid contact chamber 3, reducing the ability to entrain the solid phase, and the solid phase can enter the separation chamber faster to accelerate the separation process.

[0044] To enable the solid phase to fall into the separation chamber 5 more smoothly, in some embodiments of the present invention, the angle θ between the inclined plate and the vertical direction is 45° ≤ θ ≤ 75°.

[0045] According to a preferred embodiment of the present invention, as Figures 1-3 shown, the guiding portion includes an arc-shaped plate bent against the gas flow direction. Here, the gas flow direction refers to, for example, the gas flow spraying from the nozzle to the side where the separation chamber is located along the X-direction, and the arc-shaped plate also arches toward the side where the separation chamber is located. Among them, the upper end of the arc-shaped plate is connected to the top chamber wall of the gas-solid contact chamber 3, and the lower end extends downward to form a baffle 4. Thus, after the gas-solid material is fed, on the premise of sufficient gas-solid contact, the guiding portion converts the gas-solid mixed gas flow that is sprayed almost horizontally into a downward gas flow, and the solid phase obtains a further increase in downward velocity, resulting in that most of the solid phase detaches from the gas-phase main body and flows downward concentratedly after the mixed gas flow leaves the guiding portion and enters the separation chamber. Compared with the structure without the guiding portion, the dispersion degree of the solid phase in the reactor is greatly reduced, realizing effective and rapid gas-solid separation.

[0046] In the present invention, as Figures 1-2As shown, side plates are respectively arranged on both sides of the arc section of the arc-shaped plate in the Y direction. The two side plates, the arc-shaped plate and a part of the cavity wall of the separation cavity 5 enclose a channel for strengthening the air flow.

[0047] To further improve the gas-solid separation efficiency, according to a preferred embodiment of the present invention, as Figure 2 shown, the preferred baffle is arranged at an interval from the cavity wall of the separation cavity 5, and the horizontal distance (X direction) from the closer cavity wall is L 1 , 0.2D ≤ L 1 ≤ 0.5D, where D is the diameter of the separation cavity 5.

[0048] In some embodiments of the present invention, side plates are not arranged on both sides of the baffle 4 (i.e., both sides in the Y direction), and a baffle piece 14 extending towards the channel is provided at the bottom end in the Z direction. In this way, local backflow can be formed to strengthen the gas-solid mixing. The included angle between the baffle piece 14 and the baffle 4 is Φ, 45° ≤ Φ ≤ 90°, and preferably Φ is 90°.

[0049] To further improve the gas-solid separation efficiency, as Figure 7 shown, a plurality of material passing openings are formed in the baffle 4. Thus, when the gas-solid mixed fluid passes through, a part of the solid phase and the gas phase pass through the material passing openings in advance and enter the separation cavity 5, reducing the residence time of the gas-solid in the gas-solid reaction device. Due to the action of the baffle 4, the gas phase can flow radially, and the main body of the solid phase can flow axially downward.

[0050] To further improve the gas-solid separation efficiency, in some embodiments of the present invention, the opening ratio of the preferred baffle 4 is greater than 0.5 and less than 0.78.

[0051] In some embodiments of the present invention, the baffle 4 includes a plurality of baffle plates 41 equally spaced in the height direction (Z direction). The gap between two adjacent baffle plates 41 forms a material passing opening. It can be understood that as long as the material passing opening can enable a part of the solid phase and the gas phase to pass through the material passing opening in advance and enter the separation cavity 5, reducing the residence time of the gas-solid in the gas-solid reaction device, the present invention is not limited to the foregoing setting form. For example, as Figure 7 shown, the material passing opening can not only be set in the form of the gap between adjacent baffle plates, but also in the form of dense holes or grid-shaped spaced long openings. The present invention will not elaborate on this anymore.

[0052] Preferably, an inclined baffle piece 13 is connected to the inner side of each baffle plate 41 (the side located in the channel in the X direction). By arranging the inclined baffle piece 13 on the baffle, the guiding effect on the gas-solid mixed fluid is strengthened, the proportion of the fluid entering the separation cavity 5 in advance through the gap between the baffle plates 41 is increased, the separation efficiency of the separation cavity is improved, and the entrainment of the solid phase in the reaction part is reduced, and the backmixing of the solid-phase catalyst is reduced.

[0053] To further strengthen the diversion effect on the gas-solid mixed fluid, as Figure 7 shown, the included angle β between the inclined baffle 13 and the baffle plate 4 is 20° ≤ β ≤ 50°. In the embodiments of the present invention, 4 baffle plates 4 spaced along the height direction are taken as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0054] In the present invention, a heat exchange member and a flow disturbing member are provided in the separation chamber 5. The heat exchange member is used to reduce the temperature of the gas-solid mixed gas flow after entering the separation chamber and prevent side reactions from occurring. The flow disturbing member is used to disturb the gas-solid mixed gas flow after the reaction and further reduce the entrainment of the gas phase to the solid phase. In some embodiments of the present invention, the heat exchange member and the flow disturbing member can be separately provided. Preferably, as Figure 1 and Figure 2 shown, the coil section 7 is passed through a heat exchange medium to form a heat exchange member. Specifically, in some embodiments of the present invention, as Figures 1-2 shown, preferably the flow disturbing member is set as the coil section 7. The coil section 7 includes multiple layers of coils 71 arranged at equal intervals along the axial direction (Z direction) of the separation chamber. Between each layer of coils 71, the inlet and outlet of the heat exchange medium can be separately provided without connection, or a unified inlet and outlet of the heat exchange medium can be provided with connection between each layer of coils 71 (for example, as Figure 1 shown, the heat exchange medium can enter from c1 and flow out from c2). The present invention has no special requirements for this and can be set according to actual needs. Among them, as Figure 4 shown, each layer of coils 71 extends circuitously along the radial direction (X direction or Y direction) of the separation chamber 5. In this way, the coil section 7 provided in the separation chamber has the functions of heat exchange and flow disturbance. For example, in the application of the MTO reaction, on the one hand, it cools the gas phase after the reaction to prevent side reactions, and on the other hand, it increases the interfacial disturbance when the gas flow entraining a small amount of catalyst particles passes through, as well as the collisions between particles and between particles and the wall surface, reducing the amount of fine particles entrained and removed from the top product gas outlet.

[0055] To further enhance the heat exchange and flow disturbance effects, in some embodiments of the present invention, the height h of the coil section 7 ≤ 0.5H, where H is the main height of the separation chamber 5.

[0056] To further enhance the heat exchange and flow disturbance effects, in some embodiments of the present invention, the length of each layer of coils 71 in the radial direction of the separation chamber 5 is L 2 , where (L 1 +L 2 ) ≥ 0.8D.

[0057] To further enhance the heat exchange and flow disturbance effects, in some embodiments of the present invention, as Figure 8 shown, this figure is the cross-section of the coil pipeline in the ZY plane. Among them, a downwardly inclined flow disturbing plate 15 is provided on the outer wall of the pipeline of the coil 71.

[0058] In some embodiments of the present invention, preferably, the outer wall of the pipe of the coiled pipe is tangent to the spoiler 15, and the spoiler 15 can be symmetrically arranged on both sides of the pipe in the Y direction.

[0059] To further enhance the heat exchange and flow disturbance effects, in some embodiments of the present invention, the angle ψ between the spoiler 15 and the longitudinal section (ZX plane) of the pipe where it is located satisfies 22° ≤ ψ ≤ 69°.

[0060] In the present invention, the gas-solid reaction device further includes some conventional settings in gas-solid reactions, such as a catalyst regenerator 11, a mixer 12, a cyclone separator 10, etc. Among them, the positional relationship and connection mode of the catalyst regenerator 11, the mixer 12, and the cyclone separator 10 are set according to the conventional settings in the prior art and connected according to actual needs, or as Figure 9 shown in the figure, and the present invention will not elaborate on this.

[0061] The second aspect of the present invention discloses the application of the gas-solid reaction device of the present invention in the production of olefins from methanol conversion, catalytic cracking, or fluidized bed propane dehydrogenation.

[0062] The third aspect of the present invention discloses a method for producing light olefins, which uses the gas-solid reaction device of the present invention and includes:

[0063] Feeding catalyst particles through the solid-phase feeding member 1, spraying methanol raw material gas through the gas-phase feeding member 2, so that the methanol raw material gas and the catalyst particles are in cross-flow contact in the gas-solid contact chamber 3 to generate a gas-solid mixed gas stream containing product gas;

[0064] Making the gas-solid mixed fluid enter from the side of the separation chamber 5 and be converted into a downward mixed fluid through the diversion part and enter the separation chamber 5 for gas-solid separation.

[0065] In the present invention, the methanol raw material gas is preheated and then sprayed through the gas-phase feeding member. Among them, the preheating temperature is 150 - 200 °C; the injection gas velocity u of the methanol raw material gas f is 10 - 50 m / s, preferably 15 - 25 m / s.

[0066] According to a preferred embodiment of the present invention, the gas-solid contact conditions include: a reaction temperature of 450 - 500 °C and a reaction pressure of 0.01 - 1 Mpa.

[0067] According to a preferred embodiment of the present invention, the gas-solid average contact time between the methanol feed gas and the catalyst in the gas-solid reaction device is 0.1 - 1.5 s, preferably in the range of 0.1 - 0.5 s. It should be noted that the gas-solid average contact time refers to the mathematical expectation of the residence time distribution of the catalyst solid phase entering and leaving the reaction device. Since the flow of the solid phase is not plug flow after contacting with the gas phase in the device, when the solid phase passes through the outlet of the reaction device, the response value of the outlet to the solid phase concentration presents a curve similar to a normal distribution, denoted as F(t). When the distribution curve is discrete data,

[0068]

[0069] where t m is the mathematical expectation of the solid phase residence time distribution curve, that is, the average contact time is considered. The average residence time of the gas phase in the examples is also obtained by the above formula, which refers to the mathematical expectation of the residence time distribution of the gas phase entering and leaving the reaction device.

[0070] According to a preferred embodiment of the present invention, the temperature in the separation chamber 5 is controlled to be ≤ 300 °C.

[0071] In the present invention, the spent catalyst discharged from the solid phase outlet 6 is regenerated and then sent to the gas-solid contact chamber 3. The regeneration conditions include: the regeneration operation temperature is 550 - 700 °C.

[0072] In some embodiments of the present invention, as shown in Figure 9 , the methanol feed gas f enters the gas-solid contact chamber 3 horizontally through the nozzle and vertically contacts with the reaction catalyst g falling vertically from above to carry out the reaction. At the same time, the catalyst particles entrained by the gas flow are affected by the arc plate, and the flow direction is converted to downward flow. When passing through the pores of the baffle, some particles and gas leave the reaction zone and enter the separation chamber. When the remaining gas phase and solid phase reach the baffle at the bottom of the baffle, most of them leave the reaction zone from both sides, and the other part flows back to the front end of the reaction zone, strengthening the mixing contact between the feed gas and the catalyst just entering the reaction zone; due to inertia, most of the catalyst particles leaving the reaction zone are discharged downward through the solid phase outlet, and a small amount of fine catalyst particles continue to be entrained upward by the gas flow. When passing through the coil section 7, while the gas phase temperature drops, the catalyst particles leave the gas flow main body and move downward due to increased disturbance and collision, and the tail gas after the reaction is discharged from the gas phase outlet 8 at the top. After removing the possible entrained trace fine powder through the cyclone separator 10 again, it enters the subsequent process unit; the spent catalyst e discharged from the bottom of the separation chamber 5 is transported to the catalyst regenerator 11 through the riser for regeneration, or directly sent to the mixer 12 as the reaction catalyst g in the reaction process and returned to the solid phase inlet.

[0073] The present invention will be described in detail below through examples, but the present invention is not limited thereto.

[0074] Adopt Figures 1-9 The gas-solid reaction device shown, the gas-solid reaction device includes a reactor and a separator. Among them, the reactor is set as a reaction part with a gas-solid contact chamber 3, and the separator is set as a separation part with a separation chamber 5. The top chamber wall of the gas-solid contact chamber 3 is provided with a solid-phase material port as a solid-phase feed part 1. The side wall of the gas-solid contact chamber 3 is provided with a plurality of nozzles perpendicular to the solid-phase inlet. The plurality of nozzles form a gas-phase feed part 2. Among them, the top chamber wall of the gas-solid contact chamber 3 is connected with an arc-shaped plate. The lower end of the arc-shaped plate extends downward to form a baffle. On both sides of the arc section of the arc-shaped plate, side plates are respectively arranged. The two side plates and the arc-shaped plate and a part of the chamber wall of the separation chamber 5 enclose a channel. The chamber wall of the gas-solid contact chamber 3 is set to be inclined downward, so that the gas-solid contact chamber 3 forms a roughly trapezoidal shape. The bottom of the gas-solid contact chamber 3 is also communicated with the separation chamber; the plurality of nozzles are arranged at intervals in the radial direction of the separation chamber 5. The top of the separation chamber 5 is provided with a gas-phase outlet 8, and the bottom is provided with a solid-phase outlet 6. The solid-phase outlet 6 is communicated with the catalyst regenerator 11. The catalyst regenerator 11 is communicated with the mixer 12. The mixer 12 is communicated with the solid-phase outlet 6 and the solid-phase inlet. The gas-phase outlet 8 is communicated with the cyclone separator 10.

[0075] The method includes: feeding the methanol raw material gas f horizontally into the gas-solid contact chamber 3 through the nozzle, vertically contacting and reacting with the reaction catalyst g falling vertically from the solid-phase inlet to generate a gas-solid mixed gas stream containing the product gas. The gas-solid mixed gas stream enters the separation area for separation. The separated gas phase p is discharged from the gas-phase outlet 8 at the top and is further removed of the possible entrained trace fine powder through the cyclone separator 10; the spent catalyst e discharged from the bottom of the separation chamber 5, a part of it is transported to the catalyst regenerator 11 through the riser for regeneration and then sent to the mixer 12 to be mixed with another part of the spent catalyst e, and then returned to the solid-phase inlet as the reaction catalyst g; due to the very short gas-solid contact time during the reaction process, the single-pass catalyst has less carbon deposition. Generally, the catalyst can be directly recycled, and the spent catalyst is regenerated periodically as needed.

[0076] Example 1

[0077] The setting form of the gas-solid reaction device includes: the setting form and quantity of the nozzles are as Figure 6 in (C), where c is 0.28b 0 , b is 0.86b 0 , satisfying the relationship (b + c) ≥ b 0 and b ≤ b 0 , c 0 is 2 cm; the angle θ between the inclined plate and the vertical direction is 65°; the horizontal distance between the baffle 4 and the chamber wall of the separation chamber 5 is L 1 = 0.3D. A retaining piece is arranged at the bottom end of the baffle. The angle Φ between the retaining piece 14 and the baffle 4 is 90°. The setting form of the baffle is Figure 7As shown in (C), the opening ratio of the baffle 4 is 0.6, and four baffle plates 41 are evenly distributed at equal intervals along the height direction. The gap between two adjacent baffle plates 41 forms a material passage. An inclined baffle 13 is connected to the inner side of each baffle plate 41, and the included angle β between the inclined baffle 13 and the baffle 4 is 40°.

[0078] A coil pipe section 7 is arranged in the separation chamber 5. The coil pipe section 7 includes multiple layers of coil pipes 71 arranged at intervals along the axial direction of the separation chamber. Each layer of coil pipe 71 extends circuitously along the radial direction of the separation chamber 5, and a heat exchange medium is introduced into the coil pipe section. Among them, the height h of the coil pipe section 7 = 0.5H, and the length of each layer of coil pipe 71 in the radial direction of the separation chamber 5 is L 2 , L 2 = 0.6D; Turbulence plates 15 are arranged tangent to the outer wall of the pipe of the coil pipe. The included angle ψ between the turbulence plate 15 and the longitudinal and cross-sectional planes of the pipe where it is located is 23.5°.

[0079] The method includes: preheating methanol and then spraying it through a nozzle, and making it cross-flow contact with a solid catalyst (active component SAPO-34 molecular sieve catalyst). Among them, the preheating temperature is 200 °C, the injection gas velocity u of methanol f is 20 m / s, the reaction temperature is 480 °C, and the reaction pressure is 125 kPa; controlling the temperature in the separation chamber 5 to be 300 °C; the average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 0.18 s; the average residence time of the gas phase in the reaction device is 11.0 s. After analyzing the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 88.6 wt%, and the single-pass conversion rate of the reaction is 92.1 wt%.

[0080] Example 2

[0081] The setting form of the gas-solid reaction device includes: the setting form and quantity of the nozzles are as Figure 6 shown in (C), where c is 0.26b 0 , b is 0.8b 0 , satisfying the relationship (b + c) ≥ b 0 and b ≤ b 0 , c 0 is 5 cm; the included angle θ between the inclined plate and the vertical direction is 45°, and the horizontal distance between the baffle 4 and the chamber wall of the separation chamber 5 is L 1 = 0.2D. A baffle is arranged at the bottom end of the baffle, and the included angle Φ between the baffle 14 and the baffle 4 is 70°. The setting form of the baffle is Figure 7 shown in (A), and the opening ratio of the baffle 4 is 0.7.

[0082] A coil pipe section 7 is arranged in the separation chamber 5. The coil pipe section 7 includes multiple layers of coil pipes 71 spaced axially along the separation chamber. Each layer of coil pipe 71 extends circuitously in the radial direction of the separation chamber 5, and a heat exchange medium is introduced into this coil pipe section. Among them, the height h of the coil pipe section 7 = 0.4H, and the length of each layer of coil pipe 71 in the radial direction of the separation chamber 5 is L 2 , L 2 = 0.65D; spoiler plates 15 are tangentially arranged on the outer wall of the pipe of the coil pipe, and the angle ψ between the spoiler plate 15 and the longitudinal and transverse cross-sections of the pipe where it is located is 30°.

[0083] The method includes: preheating methanol and then spraying it through a nozzle, and making it cross-flow contact with a solid catalyst (active component SAPO-34 molecular sieve catalyst). Among them, the preheating temperature is 200 °C, the injection gas velocity u of methanol f is 15 m / s, the reaction temperature is 480 °C, the reaction pressure is 125 kPa; controlling the temperature in the separation chamber 5 to be 300 °C; the average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 0.35 s; the average residence time of the gas phase in the reaction device is 20.0 s. After analyzing the tail gas of the reactor, the selectivity of diolefins (ethylene + propylene) is 85.3 wt%, and the single-pass conversion rate of the reaction is 94.3 wt%.

[0084] Example 3

[0085] The setting form of the gas-solid reaction device includes: the setting form and quantity of the nozzle are as Figure 6 in (C), where c is 0.3b 0 , b is 0.9b 0 , satisfying the relationship (b + c) ≥ b 0 and b ≤ b 0 , c 0 is 10 cm; the angle θ between the inclined plate and the vertical direction is 75°, and the horizontal distance between the baffle 4 and the chamber wall of the separation chamber 5 is L 1 = 0.4D. A retaining piece is arranged at the bottom end of the baffle, and the angle Φ between the retaining piece 14 and the baffle 4 is 45°. The setting form of the baffle is Figure 7 shown in (B), and the opening ratio of the baffle 4 is 0.6.

[0086] A coil pipe section 7 is arranged in the separation chamber 5. The coil pipe section 7 includes multiple layers of coil pipes 71 spaced axially along the separation chamber. Each layer of coil pipe 71 extends circuitously in the radial direction of the separation chamber 5, and a heat exchange medium is introduced into this coil pipe section. Among them, the height h of the coil pipe section 7 = 0.4H, and the length of each layer of coil pipe 71 in the radial direction of the separation chamber 5 is L 2 , L 2 = 0.5D; spoiler plates 15 are tangentially arranged on the outer wall of the pipe of the coil pipe, and the angle ψ between the spoiler plate 15 and the longitudinal and transverse cross-sections of the pipe where it is located is 60°.

[0087] The method includes: preheating methanol and then spraying it through a nozzle, and making cross-flow contact with a solid catalyst (active component SAPO-34 molecular sieve catalyst). Among them, the preheating temperature is 200°C, the injection gas velocity u of methanol f is 30 m / s, the reaction temperature is 480°C, and the reaction pressure is 125 kPa; controlling the temperature in the separation chamber 5 to be 280°C; the average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 0.67 s; the average residence time of the gas phase in the reaction device is 7.5 s. After analyzing the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 83.1 wt%, and the single-pass conversion rate of the reaction is 86.8 wt%.

[0088] Example 4

[0089] The number of nozzles is the same as that in Example 1. Different from Example 1, the arrangement form of the nozzles is as Figure 6 shown in (A) therein.

[0090] Result: The average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 0.57 s; the average residence time of the gas phase in the reaction device is 10.5 s.

[0091] After analyzing the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 85.9 wt%, and the single-pass conversion rate of the reaction is 89.6 wt%.

[0092] Example 5

[0093] Different from Example 1, c is 0.2b 0 , b is 0.6b 0 , not satisfying the relationship (b + c) ≥ b 0 and b ≤ b 0 , c 0 is 8 cm.

[0094] Result: The average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 0.37 s; the average residence time of the gas phase in the reaction device is 10.6 s.

[0095] After analyzing the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 80.7 wt%, and the single-pass conversion rate of the reaction is 87.2 wt%.

[0096] Example 6

[0097] Different from Example 1, no baffle piece is provided at the bottom of the baffle, and no material passing port is provided on the baffle. Instead, the baffle is set as a whole piece.

[0098] Result: The average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 1.12 s; the average residence time of the gas phase in the reaction device is 17.8 s.

[0099] The reactor tail gas was analyzed. The selectivity of dienes (ethylene + propylene) was 82.2 wt%, and the single-pass conversion rate of the reaction was 88.3 wt%.

[0100] Example 7

[0101] Different from Example 1, the horizontal distance between the baffle 4 and the chamber wall of the separation chamber 5 is L 1 = 0.1D. A retaining piece is provided at the bottom end of the baffle. The included angle Φ between the retaining piece 14 and the baffle 4 is 135°. The porosity of the baffle 4 is 0.3, and the included angle β between the inclined retaining piece 13 and the baffle 4 is 90°.

[0102] Result: The average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 1.34 s; the average residence time of the gas phase in the reaction device is 13.6 s.

[0103] The reactor tail gas was analyzed. The selectivity of dienes (ethylene + propylene) was 81.9 wt%, and the single-pass conversion rate of the reaction was 93.6 wt%.

[0104] Example 8

[0105] Different from Example 1, the coil section 7 is not provided inside the reaction device for heat exchange and flow disturbance of the fluid;

[0106] Result: The average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 0.44 s; the average residence time of the gas phase in the reaction device is 8.6 s.

[0107] The reactor tail gas was analyzed. The selectivity of dienes (ethylene + propylene) was 82.4 wt%, and the single-pass conversion rate of the reaction was 95.2 wt%.

[0108] Example 9

[0109] Different from Example 1, the flow disturbance plate 15 is not provided.

[0110] Result: The average gas-solid contact time of methanol and the catalyst in the gas-solid reaction device is 0.23 s; the average residence time of the gas phase in the reaction device is 9.8 s.

[0111] The reactor tail gas was analyzed. The selectivity of dienes (ethylene + propylene) was 86.3 wt%, and the single-pass conversion rate of the reaction was 92.6 wt%.

[0112] Example 10

[0113] Different from Example 1, the height h of the coil section 7 = 0.8H, and the length of each layer of coil 71 in the radial direction of the separation chamber 5 is L 2 , L 2 = 0.3D; the flow disturbance plate 15 is tangentially provided on the outer wall of the pipeline of the coil, and the included angle ψ between the flow disturbance plate 15 and the cross-section of the pipeline is 15°.

[0114] Result: The average gas-solid contact time between methanol and the catalyst in the gas-solid reaction device is 0.69 s; the average residence time of the gas phase in the reaction device is 10.2 s.

[0115] After analysis of the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 82.2 wt%, and the single-pass conversion rate of the reaction is 86.3 wt%.

[0116] Example 11

[0117] Differing from Example 1, the injection gas velocity u of the methanol feed gas f is 100 m / s;

[0118] Result: The average gas-solid contact time between methanol and the catalyst in the gas-solid reaction device is 1.43 s; the average residence time of the gas phase in the reaction device is 4.2 s.

[0119] After analysis of the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 79.6 t%, and the single-pass conversion rate of the reaction is 76.7 wt%.

[0120] Example 12

[0121] Differing from Example 1, the temperature in the separation chamber 5 is controlled at 500 °C;

[0122] Result: The average gas-solid contact time between methanol and the catalyst in the gas-solid reaction device is 0.18 s; the average residence time of the gas phase in the reaction device is 11.1 s.

[0123] After analysis of the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 78.9 wt%, and the single-pass conversion rate of the reaction is 98.3 wt%.

[0124] Comparative Example 1

[0125] Differing from Example 1, the arc plate and baffle are not provided, that is, the flow guiding part is not provided in the gas-solid reaction device of this comparative example, and the gas-solid mixed gas flow in the gas-solid contact chamber 3 directly enters the separation chamber 5 from the side;

[0126] Result: The average gas-solid contact time between methanol and the catalyst in the gas-solid reaction device is 4.7 s; the average residence time of the gas phase in the reaction device is 13.5 s.

[0127] After analysis of the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 80.6 wt%, and the single-pass conversion rate of the reaction is 94.2 wt%.

[0128] Comparative Example 2

[0129] Use the reactor and method for producing light olefins disclosed in CN111054277A.

[0130] Results: The average gas-solid contact time between methanol and the catalyst in the gas-solid reaction device is 0.5 s; the average residence time of the gas phase in the reaction device is 39.3 s.

[0131] After analysis of the reactor tail gas, the selectivity of diolefins (ethylene + propylene) is 85.8 wt%, and the single-pass conversion rate of the reaction is 90.7 wt%.

[0132] Comparative Example 3

[0133] In the continuous reaction and regeneration fluidized bed industrial production of methanol to olefins, a catalyst with an active component of SAPO-34 molecular sieve is used, and a fast bed reactor is used. The reaction temperature in the reactor is 480 °C, the reaction pressure is 125 kPa, and the single-pass selectivity of diolefins (ethylene + propylene) is 81.2 wt%.

[0134] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A gas-solid reaction device, characterized in that, the gas-solid reaction device comprises: a reaction part, which is internally provided with a gas-solid contact chamber (3) and includes a solid-phase feeding member (1) and a gas-phase feeding member (2), and the gas-phase feeding member (2) enables the injected gas-phase raw material and the solid-phase raw material fed through the solid-phase feeding member (1) to cross-flow contact in the gas-solid contact chamber (3) to generate a gas-solid mixed gas flow containing product gas; a separation part, which is internally provided with a separation chamber (5), and the gas-solid contact chamber (3) is communicated with the separation chamber (5) so that the gas-solid mixed gas flow can enter from the side of the separation chamber (5); a diversion part, which is arranged in the separation chamber (5) and is used for guiding the gas-solid mixed gas flow entering from the side of the separation chamber (5) to move downward.

2. The gas-solid reaction device according to claim 1, characterized in that, the feeding direction of the gas-phase feeding member (2) and the feeding direction of the solid-phase feeding member (1) are arranged at an angle in a vertical plane, preferably perpendicular to each other; and / or a solid-phase inlet is formed on the top chamber wall of the gas-solid contact chamber (3) to form the solid-phase feeding member (1); and / or the gas-phase feeding member (2) includes a plurality of nozzles (21), and the plurality of nozzles (21) are arranged on the side chamber wall of the gas-solid contact chamber (3) and are arranged opposite to the separation chamber (5); preferably, the plurality of nozzles (21) are arranged in a single row or multiple rows, and more preferably, when the plurality of nozzles (21) are arranged in multiple rows, the nozzles (21) in adjacent two rows are arranged in a staggered manner.

3. The gas-solid reaction device according to claim 2, characterized in that, The relationship between the solid-phase inlet and the multiple nozzles (21) is (b + c) ≥ b 0 and b ≤ b 0 , where c is the distance between two adjacent nozzles (21) in the same row of nozzles (21), b is the distance between the two nozzles (21) farthest apart in the gas-phase feed member (2) in the nozzle (21) arrangement direction, and b 0 is the distance of the solid-phase inlet in its own length direction; and / or The distance c in the vertical direction between the bottom end surface of the solid phase inlet and the nozzle (21) 0 ≤ 10 cm.

4. The gas-solid reaction device according to claim 1, characterized in that, an inclined plate inclined downward is arranged in the gas-solid contact chamber (3), and the angle θ between the inclined plate and the vertical direction is 45° ≤ θ ≤ 75°; and / or The flow guiding part includes an arc-shaped plate bent against the air flow direction. The upper end of the arc-shaped plate is connected to the top cavity wall of the gas-solid contact cavity (3), and the lower end extends downward to form a baffle (4); preferably, the horizontal distance between the baffle (4) and the cavity wall of the separation cavity (5) is L 1 , 0.2D ≤ L 1 ≤ 0.5D, where D is the diameter of the separation cavity (5).

5. The gas-solid reaction device according to claim 4, characterized in that, a baffle piece (14) is arranged at the bottom end of the baffle (4), and the angle Φ between the baffle piece (14) and the baffle (4) is 45° ≤ Φ ≤ 90°; and / or a plurality of material passing openings are formed on the baffle (4), preferably, the opening ratio of the baffle (4) is greater than 0.5 and less than 0.

78.

6. The gas-solid reaction device according to claim 4 or 5, characterized in that, the baffle (4) includes a plurality of baffle plates (41) spaced apart in the height direction, and the gap between adjacent two baffle plates (41) forms a material passing opening, preferably, an inclined baffle piece (13) is connected to the inner side of each baffle plate (41), and preferably, the angle β between the inclined baffle piece (13) and the baffle plate (41) is 20° ≤ β ≤ 50°.

7. The gas-solid reaction device according to claim 1, characterized in that, a heat exchange member and a flow disturbance member are arranged in the separation chamber (5); preferably, the flow disturbance member is arranged as a coil pipe section (7), and the coil pipe section (7) includes a plurality of coil pipes (71) spaced apart along the axis of the separation chamber, and each layer of coil pipe (71) extends circuitously along the radial direction of the separation chamber (5); More preferably, the coiled pipe section (7) is passed through by a heat exchange medium to form the heat exchange member.

8. The gas-solid reaction device according to claim 7, characterized in that the height h of the coiled pipe section (7) ≤ 0.5H, where H is the main body height of the separation chamber (5); and / or The length of each coil pipe (71) in the radial direction of the separation chamber (5) is L 2 , where, (L 1 +L 2 ) ≥ 0.8D; and / or a spoiler (15) inclined downward is provided on the outer wall of the pipe of the coiled pipe (71); preferably, the spoiler (15) is tangent to the outer wall of the pipe of the coiled pipe (71); and / or preferably, the included angle ψ between the spoiler (15) and the longitudinal and transverse cross-section of the pipe where it is located is 22° ≤ ψ ≤ 69°.

9. Application of the gas-solid reaction device according to any one of claims 1-8 in methanol conversion to produce olefins, catalytic cracking or fluidized bed propane dehydrogenation.

10. A method for producing light olefins, characterized in that this method uses the gas-solid reaction device according to any one of claims 1-8, and includes: feeding catalyst particles through a solid-phase feeding member (1), and spraying methanol raw material gas through a gas-phase feeding member (2), so that the methanol raw material gas and the catalyst particles are in cross-flow contact in a gas-solid contact chamber (3) to generate a gas-solid mixed gas stream containing product gas; making the gas-solid mixed fluid enter from the side of the separation chamber (5) and pass through a diversion part to be converted into a downward mixed fluid and enter the separation chamber (5) for gas-solid separation.

11. The method according to claim 10, wherein the methanol raw material gas is preheated and then sprayed through the gas-phase feeding member, wherein the preheating temperature is 150-200°C; and / or The injection gas velocity u of the methanol feed gas f is 10 to 50 m / s, preferably 15 to 25 m / s; and / or the average gas-solid contact time of the methanol raw material gas and the catalyst in the gas-solid reaction device is 0.1-1.5 s, preferably in the range of 0.1-0.5 s; and / or controlling the temperature in the separation chamber (5) ≤ 300°C.

12. The method according to claim 10 or 11, wherein the gas-solid contact conditions include: reaction temperature 450-500°C, reaction pressure 0.01-1 Mpa; and / or the conditions for regenerating the spent catalyst discharged from the separation chamber (5) include: regeneration operation temperature 550-700°C.

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