Fluidized bed reactor for the ammoxidation of aromatic hydrocarbons, its use and the reaction process

Abstract

The present application relates to a kind of aromatic aminooxidation fluidized bed reaction device, including fluidized bed reactor, first distributor and second distributor are arranged in the fluidized bed reactor, double distributor area is formed between the first distributor and second distributor, isolation unit is arranged in the double distributor area;The isolation unit includes multiple isolation components, the isolation component is the cylinder structure, so that the cylinder structure inside forms fluidization unit area, the area formed with cylinder outside in the double distributor area is lattice oxygen supplement unit area.The device of the present application has obvious advantages in fluidized reaction, is used for aromatic aminooxidation reaction, cooperates corresponding reaction method under the condition of guaranteeing reducing total ammonia ratio, air ratio, reaches the purpose of energy saving, consumption reduction, emission reduction.

Description

Technical Field

[0001] This invention relates to a fluidized bed reactor for the ammonia oxidation of aromatics, its application, and the reaction method thereof. Background Technology

[0002] The ammoxidation of aromatics mainly involves fixed-bed and fluidized-bed processes. The reaction generates a significant amount of heat, making temperature control a key challenge. Localized overheating is prone to occur, leading to difficulties in temperature control and increasing the likelihood of side reactions such as deep oxidation. This results in reduced yields of the target product and catalyst deactivation. Therefore, using a fluidized-bed reactor is a better solution. Fluidized-bed reactors ensure good gas-solid contact, achieving uniform temperature distribution and effective heat dissipation. In highly exothermic reactions, they can effectively control the reaction temperature, thus enabling stable production.

[0003] The increasing international demand for aromatic nitrile compounds has prompted producers to expand their production capacity. Increasing the number of reactors and raising the ammonia and air ratios to expand capacity, while reducing equipment manufacturing costs, is considered a primary means of capacity expansion. If a fluidized bed reactor could be developed that achieves higher yields without increasing existing equipment size, maintaining low total ammonia and air ratios, and avoiding side reactions or equipment damage due to overheating, the social benefits would be significant. Summary of the Invention

[0004] The purpose of this invention is to solve the problems of high ammonia ratio, high air ratio, and low raw material utilization in existing aromatic ammonia oxidation fluidized beds. It provides a fluidized bed reactor and its application and reaction method that can improve heat exchange efficiency, flexibly adjust the heat in the reactor, and improve the utilization rate of raw materials while ensuring a reduction in total ammonia ratio and air ratio, thereby achieving the goals of energy saving, consumption reduction, and emission reduction.

[0005] To achieve the above objectives, the present invention provides a fluidized bed reactor for the ammonia oxidation of aromatics, comprising a fluidized bed reactor, wherein a first distributor and a second distributor are disposed within the fluidized bed reactor, a dual distributor region is formed between the first distributor and the second distributor, an isolation unit is disposed within the dual distributor region, the isolation unit comprising a plurality of isolation components, the isolation components being cylindrical structures, such that a fluidized unit region is formed inside the cylindrical structure, and the region formed between the dual distributor region and the outside of the cylindrical structure is a lattice oxygen replenishment unit region;

[0006] The fluidization unit region is used for contact and mixing of reactants and catalyst particles, and for carrying out ammonia oxidation reaction;

[0007] The lattice oxygen replenishment unit region is used to replenish the lattice oxygen of the catalyst particles.

[0008] Preferably, the second distributor is provided with a fluidizing nozzle and a supplementary nozzle, the upper end of the fluidizing nozzle being connected to the fluidizing unit region; the upper end of the supplementary nozzle being connected to the lattice oxygen supplementary unit region; and the fluidizing unit region being connected to the lattice oxygen supplementary unit region.

[0009] Preferably, the ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.2 to 0.7.

[0010] Preferably, the fluidized bed reactor is provided with a primary heat drain pipe, and the isolation member surrounds and wraps around the primary heat drain pipe, with its vertical center coinciding with that of the primary heat drain pipe; the ratio of the cross-sectional area of ​​the primary heat drain pipe to the cross-sectional area of ​​the isolation member is 0.01 to 0.5.

[0011] Preferably, the side opening ratio of the isolation member is 0-15%.

[0012] Preferably, the ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.03 to 0.1.

[0013] Preferably, the ratio of the vertical distance between the upper and lower surfaces of the isolation member to the vertical distance between the first distributor and the second distributor is 0.4 to 0.9.

[0014] Preferably, the isolation unit includes a plurality of isolation members arranged evenly along the horizontal direction, and preferably the distance between two adjacent isolation members is greater than 50 mm, and more preferably 200-500 mm.

[0015] Preferably, a baffle is provided in the fluidization unit area, and the baffle has a structure with holes and / or slits. Preferably, the vertical angle between the baffle and the primary hot water discharge pipe is 5 to 45°.

[0016] This invention provides the application of the apparatus described herein in oxidation reactions, preferably in ammonia oxidation reactions.

[0017] This invention provides a reaction method corresponding to solving the technical problem. The method is carried out in the aromatic hydrocarbon ammonia oxidation fluidized bed reactor and includes the following steps:

[0018] (a) A stream of air participating in the reaction is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor region of the fluidized bed reactor. It reacts with the raw material and ammonia from the first distributor under the action of the catalyst in the fluidization unit region to generate product gas.

[0019] (b) Another stream of air enters the lattice oxygen replenishment unit area within the dual distributor region of the fluidized bed reactor from the second distributor, and comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0020] Preferably, in the fluidized bed reactor, the raw material is a hydrocarbon and / or hydrocarbon derivative, preferably a C2-C6 alkane or olefin, a C7-C8 aromatic hydrocarbon and / or a C7-C8 aromatic hydrocarbon derivative, the molar ratio of raw material, ammonia and air is 1:(1-9):(10-40), the reaction temperature is 320-450℃, the pressure is 0.01-0.11MPa, and the apparent linear velocity of the gas is 0.2-1.2m / s.

[0021] Preferably, one stream of air participating in the reaction is ejected from the fluidizing nozzle of the second distributor, and another stream of air is ejected from the supplementary nozzle of the second distributor, wherein the volume ratio of the total air flow rate from the supplementary nozzle to the total air flow rate from the fluidizing nozzle is 0.05 to 0.8.

[0022] This invention forms a dual-distributor region by setting up a first distributor and a second distributor. An isolation unit is provided within the dual-distributor region, dividing it into a fluidization unit region and a lattice oxygen replenishment unit region. By combining and coupling the fluidization unit region and the lattice oxygen replenishment unit region, the system's thermal balance can be maintained efficiently and stably, thereby improving product distribution, increasing the yield of the target product, and extending the long-cycle operation time. Furthermore, it effectively avoids the excessive supply of air and ammonia or other raw materials during fluidization processes, such as ammonia oxidation reactions, as is common in existing technologies, significantly improving economic efficiency.

[0023] According to a preferred embodiment of the present invention, the isolation unit preferably includes at least one set of isolation members, the center of which coincides with the center of the primary hot water discharge pipe. The isolation members surround and enclose the hot water discharge pipe. Due to the adhesion effect, the primary hot water discharge pipe is conducive to the fluidization of particles. At the same time, the local temperature difference around the primary hot water discharge pipe is small, which is conducive to the reaction.

[0024] The technical solution of this invention is applied to the ammonia oxidation reaction of aromatics. While ensuring that the local ammonia ratio and air ratio meet the process requirements, it improves the fluidization quality and heat exchange level of the fluidized bed, effectively reduces the total ammonia ratio and total air ratio, improves the utilization rate of raw materials, achieves the purpose of energy saving, consumption reduction and emission reduction, improves product yield, and achieves good technical results. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the aromatic hydrocarbon ammoxidation reaction apparatus and reaction method of the present invention;

[0026] Figure 2 This is a partial schematic diagram of the dual distributor region of the aromatic hydrocarbon ammonia oxidation reactor of the present invention;

[0027] Figure 3 A schematic diagram of an arrangement within the fluidization unit region of the present invention.

[0028] Explanation of reference numerals in the attached figures

[0029] 1 is the gas collection chamber; 2 is the fluidized bed reactor;

[0030] 3 is the secondary hot water disconnection pipe; 4 is the primary distributor;

[0031] 5 is the raw material; 6 is ammonia;

[0032] 7 is the second distributor; 8 is the air feedstock;

[0033] 9 is the air inlet pipe; 10 is the isolation component;

[0034] 11 is a cyclone separator; 12 is product gas;

[0035] 13 is the primary hot water pipe; 14 is the fluidization unit area;

[0036] 15 represents the lattice oxygen replenishment unit region; 20 represents the fluidizing nozzle;

[0037] 21 is a supplementary nozzle; 30 is a baffle. Detailed Implementation

[0038] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0039] This invention provides a fluidized bed reactor device, including a fluidized bed reactor 2. A first distributor 4 and a second distributor 7 are disposed inside the fluidized bed reactor 2. A dual distributor region is formed between the first distributor 4 and the second distributor 7. An isolation unit is disposed within the dual distributor region. The isolation unit includes a plurality of isolation components 10. The isolation components 10 are cylindrical structures, so that a fluidized unit region 14 is formed inside the cylindrical structure. The region formed between the dual distributor region and the outside of the cylindrical structure is a lattice oxygen replenishment unit region 15.

[0040] The fluidization unit region 14 is used for contact and mixing of reactants and catalyst particles, and for carrying out ammonia oxidation reaction;

[0041] The lattice oxygen replenishment unit region 15 is used to replenish the lattice oxygen of the catalyst particles.

[0042] According to the present invention, for example, the lattice oxygen replenishment unit region 15 is used to replenish the lattice oxygen from the deactivated catalyst particles from the fluidization unit region 14.

[0043] In this invention, any cylindrical structure, such as a rectangular cylinder or a circular cylinder, that can form a fluidized cavity structure is applicable to this invention.

[0044] According to a preferred embodiment of the present invention, the second distributor 7 is provided with a fluidizing nozzle 20 and a supplementary nozzle 21. The upper end of the fluidizing nozzle 20 is connected to the fluidizing unit region 14; the upper end of the supplementary nozzle 21 is connected to the lattice oxygen supplementary unit region 15; and the fluidizing unit region 14 is connected to the lattice oxygen supplementary unit region 15.

[0045] Specifically, the gas ejected from the supplement nozzle is used to replenish the catalyst in the fluidized lattice oxygen replenishment unit. The gas ejected from the fluidizing nozzle pushes the catalyst of the fluidizing unit upwards after it flows out of the fluidizing unit. The gas chamber at the bottom is replenished by the catalyst of the lattice oxygen replenishment unit and continues to rise, forming a particle circulation. By combining the circulation and coupling of the fluidizing unit region and the lattice oxygen replenishment unit region, the device of the present invention can be used for ammonia oxidation reaction. While ensuring that the local ammonia ratio and air ratio meet the process requirements, it improves the fluidization quality and heat exchange level of the fluidized bed, effectively reduces the total ammonia ratio and total air ratio, improves the utilization rate of raw materials, achieves the purpose of energy saving, consumption reduction, and emission reduction, improves product yield, and achieves good technical results.

[0046] According to a preferred embodiment of the present invention, the ratio of the vertical distance between the supplementary nozzle 21 and the first distributor 4 to the vertical distance between the first distributor 4 and the second distributor 7 is 0.2 to 0.7.

[0047] According to a preferred embodiment of the present invention, the fluidized bed reactor 2 is provided with a primary heat drain pipe 13, and the isolation member 10 surrounds the primary heat drain pipe 13 and coincides with the vertical center of the primary heat drain pipe 13; the ratio of the cross-sectional area of ​​the primary heat drain pipe 13 to the cross-sectional area of ​​the isolation member 10 is 0.01 to 0.5.

[0048] Specifically, the primary hot water pipe, due to its adhesion effect, facilitates the fluidization of particles, and the local temperature difference around the primary hot water pipe is small, which helps the reaction to proceed.

[0049] According to a preferred embodiment of the present invention, the side opening ratio of the isolation member 10 is 0 to 15%.

[0050] According to a preferred embodiment of the present invention, the ratio of the vertical distance between the first distributor 4 and the second distributor 7 to the vertical height of the fluidized bed reactor 2 is 0.03 to 0.1.

[0051] According to a preferred embodiment of the present invention, the ratio of the vertical distance between the upper and lower surfaces of the isolation member 10 to the vertical distance between the first distributor 4 and the second distributor 7 is 0.4 to 0.9.

[0052] According to a preferred embodiment of the present invention, the isolation unit includes a plurality of isolation members 10 arranged uniformly in a horizontal direction, preferably with a distance between two adjacent isolation members 10 greater than 50 mm, and more preferably 200 to 500 mm.

[0053] According to a preferred embodiment of the present invention, a baffle 30 is provided in the fluidization unit region 14, the baffle 30 having a structure with holes and / or slits, and the vertical angle between the baffle 30 and the primary hot water drain pipe 13 is 5 to 45°. By adopting the aforementioned technical solution, the particle fluidization quality in the fluidization unit region 14 is enhanced, thereby improving the gas-solid mass transfer efficiency and making the internal temperature distribution more uniform.

[0054] According to the present invention, the present invention provides an application of the apparatus described herein in oxidation reactions, particularly in ammonia oxidation reactions.

[0055] According to a preferred embodiment of the present invention, the ratio of the vertical distance between the supplementary nozzle 21 and the first distributor 4 to the vertical distance between the first distributor 4 and the second distributor 7 is 0.2 to 0.7.

[0056] This invention provides a fluidized bed reaction method, which is carried out in the apparatus and includes the following steps:

[0057] a. A stream of air participating in the reaction enters the fluidized unit region 14 within the dual distributor area of ​​the fluidized bed reactor 2 through the second distributor. It reacts with the raw material and ammonia from the first distributor 4 under the action of the catalyst in the fluidized unit region 14 to generate product gas 12.

[0058] b. Another stream of air enters the lattice oxygen replenishment unit region 15 within the dual distributor region of the fluidized bed reactor 2 from the second distributor 7, and comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction from the fluidized unit region 14, replenishing lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit region 14 to continue the reaction.

[0059] According to a preferred embodiment of the present invention, in the fluidized bed reactor 2, the raw material is a hydrocarbon and / or a hydrocarbon derivative, preferably a C2-C6 alkane or olefin, a C7-C8 aromatic hydrocarbon and / or a C7-C8 aromatic hydrocarbon derivative, more preferably the molar ratio of raw material, ammonia and air is 1:(1-9):(10-40), and even more preferably the reaction temperature is 320-450°C, the pressure is 0.01-0.11 MPa, and the apparent gas linear velocity is 0.2-1.2 m / s.

[0060] According to a preferred embodiment of the present invention, the volume ratio of the total air flow rate from the supplementary nozzle (21) to the total air flow rate from the fluidizing nozzle (20) is 0.05 to 0.8.

[0061] This invention forms a dual-distributor region by setting up a first distributor and a second distributor. An isolation unit is provided within the dual-distributor region, dividing it into a fluidization unit region and a lattice oxygen replenishment unit region. By combining and coupling the fluidization unit region and the lattice oxygen replenishment unit region, the system's thermal balance can be maintained efficiently and stably, thereby improving product distribution, increasing the yield of the target product, and extending the duration of long-cycle operation. Furthermore, when applied to ammonia oxidation reactions, it effectively avoids the excessive supply of air and ammonia, as is common in existing technologies, significantly improving economic efficiency.

[0062] According to a preferred embodiment of the present invention, the isolation unit preferably includes a plurality of isolation components, the center of which coincides with the center of the primary hot water discharge pipe. The isolation components surround and enclose the hot water discharge pipe. Due to the adhesion effect, the primary hot water discharge pipe is conducive to the fluidization of particles. At the same time, the local temperature difference around the primary hot water discharge pipe is small, which is conducive to the reaction.

[0063] The technical solution of this invention is applied to the ammonia oxidation reaction. While ensuring that the local ammonia ratio and air ratio meet the process requirements, it improves the fluidization quality and heat exchange level of the fluidized bed, effectively reduces the total ammonia ratio and total air ratio, improves the utilization rate of raw materials, achieves the purpose of energy saving, consumption reduction and emission reduction, improves product yield, and achieves good technical results.

[0064] In this invention, apart from the components required by the aforementioned device, other components can be conventionally configured and will not be described in detail in this invention.

[0065] The following examples demonstrate the use of... Figure 1-3 The present invention is described in detail with respect to the apparatus, which includes a gas collection chamber, a fluidized bed reactor, a first distributor, a second distributor, an air feed pipe, an isolation component, a cyclone separator, a primary heat dissipation pipe, a fluidized unit region, a lattice oxygen replenishment unit region, a fluidized nozzle, a replenishment nozzle, and a baffle.

[0066] The gas collection chamber is located at the top of the fluidized bed reactor and is connected to the cyclone separator for collecting product gas;

[0067] The fluidized bed reactor has a dual distributor region formed by the first and second distributors arranged vertically in the middle. An isolation unit is set in the dual distributor region. The isolation unit includes multiple isolation components. The isolation components are cylindrical structures, so that a fluidized unit region is formed inside the cylindrical structure. The region formed by the dual distributor region and the outside of the cylindrical structure is a lattice oxygen replenishment unit region. By combining the circulation and coupling of the fluidized unit region and the lattice oxygen replenishment unit region, the thermal balance of the system is maintained efficiently and stably, and the yield of the target product is improved.

[0068] The fluidized bed unit region is connected to the lattice oxygen replenishment unit region. The fluidized bed unit region is connected to the second distributor through the fluidized nozzle. The lattice oxygen replenishment unit region is connected to the second distributor through the replenishment nozzle. The second distributor is connected to the outside through the air feed pipe. The first distributor is connected to the outside through the feed pipe. This facilitates the control of the raw material feed rate, effectively avoids the excessive supply of air and other raw materials such as ammonia, and realizes the recycling of the catalyst.

[0069] The isolation component surrounds and encloses the primary hot water pipe, and coincides with the vertical center of the primary hot water pipe, which helps to control small local temperature differences and facilitates the reaction.

[0070] The fluidization unit region is provided with the baffle, which is a flow baffle with holes / slits.

[0071] The product gas recovery rate is recorded in Table 1.

[0072] Example 1

[0073] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0074] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0075] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0076] The side opening ratio of the isolation component is 2%;

[0077] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0078] The ratio of the vertical distance between the upper and lower surfaces of the isolation member to the vertical distance between the first distributor and the second distributor is 0.5, and the same applies to other embodiments;

[0079] The distance between the isolation components is 300mm;

[0080] The angle between the baffle and the first-stage hot water pipe is 15°.

[0081] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0082] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.3:23, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0083] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the isophthalonitrile yield is 81.9%.

[0084] Example 2

[0085] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0086] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0087] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.01.

[0088] The side opening ratio of the isolation component is 2%;

[0089] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0090] The distance between the isolation components is 300mm;

[0091] The angle between the baffle and the first-stage hot water pipe is 15°.

[0092] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0093] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.4:23, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0094] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the isophthalonitrile yield is 81.2%.

[0095] Example 3

[0096] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0097] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0098] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.5.

[0099] The side opening ratio of the isolation component is 2%;

[0100] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0101] The distance between the isolation components is 300mm;

[0102] The angle between the baffle and the first-stage hot water pipe is 15°.

[0103] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0104] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.4:22.8, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0105] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the isophthalonitrile yield is 81.4%.

[0106] Example 4

[0107] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0108] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0109] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0110] The side opening rate of the isolation component is 0%;

[0111] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.1;

[0112] The distance between the isolation components is 300mm;

[0113] The angle between the baffle and the first-stage hot water pipe is 15°.

[0114] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0115] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.1:24.4, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0116] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the isophthalonitrile yield is 81.1%.

[0117] Example 5

[0118] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0119] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0120] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0121] The side opening ratio of the isolation component is 15%;

[0122] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.03.

[0123] The distance between the isolation components is 300mm;

[0124] The angle between the baffle and the first-stage hot water pipe is 15°.

[0125] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0126] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.5:21.3, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0127] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the isophthalonitrile yield is 81.3%.

[0128] Example 6

[0129] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0130] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0131] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0132] The side opening ratio of the isolation component is 2%;

[0133] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0134] The distance between the isolation components is 200mm;

[0135] The angle between the baffle and the first-stage hot water pipe is 5°.

[0136] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0137] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.2:23.7, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0138] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the isophthalonitrile yield is 82.1%.

[0139] Example 7

[0140] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0141] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0142] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0143] The side opening ratio of the isolation component is 2%;

[0144] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0145] The distance between the isolation components is 500mm;

[0146] The angle between the baffle and the first-stage hot water pipe is 45°.

[0147] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0148] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.4:23.3, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0149] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the isophthalonitrile yield is 81.5%.

[0150] Example 8

[0151] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0152] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0153] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0154] The side opening ratio of the isolation component is 2%;

[0155] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0156] The distance between the isolation components is 300mm;

[0157] The angle between the baffle and the first-stage hot water pipe is 15°.

[0158] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.7;

[0159] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.8:23.2, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0160] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.05, and the isophthalonitrile yield is 81.3%.

[0161] Example 9

[0162] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with the m-xylene and ammonia from the first distributor 4 under the action of the catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0163] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0164] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0165] The side opening ratio of the isolation component is 2%;

[0166] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0167] The distance between the isolation components is 300mm;

[0168] The angle between the baffle and the first-stage hot water pipe is 15°.

[0169] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.2;

[0170] The reaction mixture consisted of m-xylene, ammonia, and air in a molar ratio of 1:5.6:24.8, at a temperature of 420℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0171] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.8, and the isophthalonitrile yield is 81.4%.

[0172] Example 10

[0173] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with toluene and ammonia from the first distributor 4 under the action of a catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0174] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0175] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0176] The side opening ratio of the isolation component is 2%;

[0177] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0178] The distance between the isolation components is 300mm;

[0179] The angle between the baffle and the first-stage hot water pipe is 15°.

[0180] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0181] Toluene, ammonia, and air were reacted in a molar ratio of 1:3.1:12.6 at a temperature of 400°C and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.5 m / s.

[0182] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the benzonitrile yield is 83.6%.

[0183] Example 11

[0184] A stream of air from the raw material feed pipe is ejected from the fluidization nozzle of the second distributor and enters the fluidization unit region within the dual distributor area of ​​the fluidized bed reactor. It reacts with o-chlorotoluene and ammonia from the first distributor 4 under the action of a catalyst in the fluidization unit region. The generated product gas is collected through a cyclone separator and a gas collection chamber.

[0185] Another stream of air is ejected from the supplement nozzle of the second distributor and enters the lattice oxygen supplementation unit area within the dual distributor region of the fluidized bed reactor. It comes into full contact with the catalyst that has lost lattice oxygen after participating in the reaction in the fluidized unit area, replenishing sufficient lattice oxygen. The catalyst after replenishing lattice oxygen returns to the fluidized unit area to continue the reaction.

[0186] The ratio of the cross-sectional area of ​​the primary hot water pipe to the cross-sectional area of ​​the isolation component is 0.3.

[0187] The side opening ratio of the isolation component is 2%;

[0188] The ratio of the vertical distance between the first distributor and the second distributor to the vertical height of the fluidized bed reactor is 0.06.

[0189] The distance between the isolation components is 300mm;

[0190] The angle between the baffle and the first-stage hot water pipe is 15°.

[0191] The ratio of the vertical distance between the supplementary nozzle and the first distributor to the vertical distance between the first distributor and the second distributor is 0.35;

[0192] The reaction mixture consisted of o-chlorotoluene, ammonia, and air in a molar ratio of 1:3.9:38.6, at a temperature of 425℃ and a pressure of 0.05 MPa, with an apparent gas linear velocity of 0.2 m / s.

[0193] The ratio of the total airflow from the supplementary nozzle to the total airflow from the fluidizing nozzle is 0.25, and the yield of o-chlorobenzonitrile is 94.4%.

[0194] Comparative Example 1

[0195] Using a fluidized bed reactor with existing technology, m-xylene and ammonia are vaporized and then introduced into the dense phase zone of the fluidized bed reactor via a gas distribution chamber, where they undergo an aromatic hydrocarbon ammoxidation reaction under the action of a catalyst. The reactants in the dense phase zone of the fluidized bed reactor are m-xylene, ammonia, and air, with a molar ratio of 1:5.1:24.4. The reaction temperature is 420℃, the pressure is 0.05 MPa, the apparent gas linear velocity is 0.5 m / s, and the yield of isophthalonitrile is 77.2%.

[0196] Comparative Example 2

[0197] Using a fluidized bed reactor with existing technology, o-chlorotoluene and ammonia are vaporized and then mixed with air, entering the dense phase zone of the fluidized bed reactor through the gas distribution chamber. There, under the action of a catalyst, the ammoxidation reaction of halogenated aromatic hydrocarbons takes place. The reactants in the dense phase zone of the fluidized bed reactor are o-chlorotoluene, ammonia, and air, with a molar ratio of 1:3.9:38.6. The reaction temperature is 425℃, the pressure is 0.05 MPa, the apparent gas linear velocity is 0.2 m / s, and the yield of o-chlorobenzonitrile is 92.1%.

[0198] The results above show that the technical solution of this invention significantly improves product yield and significantly reduces ammonia and oxygen consumption in both aromatic hydrocarbon ammonia oxidation and halogenated aromatic hydrocarbon ammonia oxidation processes, demonstrating significantly better performance compared to existing technologies.

[0199] 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 inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An aromatic hydrocarbon ammoxidation fluidized bed reaction apparatus comprising a fluidized bed reactor, characterized by, The fluidized bed reactor (2) is provided with a first distributor (4) and a second distributor (7), a double-distributor area is formed between the first distributor (4) and the second distributor (7), and a separation unit is arranged in the double-distributor area, the separation unit comprises a plurality of separation members (10) in a cylindrical structure, the inside of the cylindrical structure forms a fluidization unit area (14), and the area formed outside the cylindrical structure in the double-distributor area is a lattice oxygen supplement unit area (15); the fluidization unit area (14) is used for the contact and mixing of reactants and catalyst particles and for reaction; The lattice oxygen supplement unit area (15) is used for supplementing the lattice oxygen of the catalyst particles; The fluidized bed reactor (2) is provided with a first distributor (4) and a second distributor (7), a double-distributor area is formed between the first distributor (4) and the second distributor (7), and a separation unit is arranged in the double-distributor area, the separation unit comprises a plurality of separation members (10) in a cylindrical structure, the inside of the cylindrical structure forms a fluidization unit area (14), and the area formed outside the cylindrical structure in the double-distributor area is a lattice oxygen supplement unit area (15); the fluidization unit area (14) is used for the contact and mixing of reactants and catalyst particles and for reaction; The baffle (30) is provided with holes and / or slits on the baffle (30); The second distributor (7) is provided with a fluidization nozzle (20) and a supplement nozzle (21), the upper end of the fluidization nozzle (20) is in communication with the fluidization unit area (14), the upper end of the supplement nozzle (21) is in communication with the lattice oxygen supplement unit area (15), and the fluidization unit area (14) is in communication with the lattice oxygen supplement unit area (15).

2. The apparatus of claim 1, wherein, The ratio of the vertical distance between the supplement nozzle (21) and the first distributor (4) to the vertical distance between the first distributor (4) and the second distributor (7) is 0.2-0.

7.

3. The apparatus of claim 1, wherein, The ratio of the cross-sectional area of the first-level heat removal water pipe (13) to the cross-sectional area of the separation member (10) is 0.01-0.

5.

4. The apparatus of claim 1, wherein, The side opening rate of the separation member (10) is 0-15%.

5. The apparatus of claim 1, wherein, The ratio of the vertical distance between the first distributor (4) and the second distributor (7) to the vertical height of the fluidized bed reactor (2) is 0.03-0.

1.

6. The apparatus of claim 1, wherein, The ratio of the vertical distance between the upper bottom surface and the lower bottom surface of the separation member (10) to the vertical distance between the first distributor (4) and the second distributor (7) is 0.4-0.

9.

7. The apparatus of claim 1, wherein, The separation unit comprises a plurality of separation members (10) arranged uniformly along the horizontal direction.

8. The apparatus of claim 7, wherein, The distance between two adjacent separation members (10) is greater than 50 mm.

9. The apparatus of claim 7, wherein, The distance between two adjacent separation members (10) is 200-500 mm.

10. The apparatus of any of claims 1-9, wherein, The vertical included angle between the baffle (30) and the first-level heat removal water pipe (13) is 5-45°.

11. The device according to any one of claims 1-10 is used in an oxidation reaction.

12. Use according to claim 11, wherein, The oxidation reaction is an ammonia oxidation reaction.

13. A fluidized bed process for the ammoxidation of an aromatic hydrocarbon, characterized in that, The method is carried out in the device according to any one of claims 1-10, and comprises the following steps: (a) One of the air participating in the reaction enters the fluidized unit area (14) in the double-distributor area of the fluidized bed reactor (2) from the second distributor (7), and reacts with the raw material and ammonia from the first distributor (4) in the fluidized unit area (14) under the action of the catalyst to generate product gas (12); (b) Another air enters the lattice oxygen supplement unit area (15) in the double-distributor area of the fluidized bed reactor (2) from the second distributor (7), and fully contacts with the catalyst losing lattice oxygen after participating in the reaction from the fluidized unit area (14) to supplement lattice oxygen, and the catalyst after supplementing lattice oxygen returns to the fluidized unit area (14) to continue the reaction.

14. The method of claim 13, wherein, In the fluidized bed reactor (2), the raw material is hydrocarbon and / or hydrocarbon derivative, the molar ratio of the raw material, ammonia and air is 1:(1-9):(10-40), the reaction temperature is 320-450℃, the pressure is 0.01-0.11MPa, and the gas superficial linear velocity is 0.2-1.2m / s.

15. The method of claim 14, wherein, The raw material is C2-C6 alkene, C7-C8 aromatic hydrocarbon and / or C7-C8 aromatic hydrocarbon derivative.

16. The method of claim 13, wherein, One of the air participating in the reaction enters from the fluidizing nozzle (20) of the second distributor (7), and another air enters from the supplement nozzle (21) of the second distributor (7), wherein the volume ratio of the total air flow from the supplement nozzle (21) to the total air flow from the fluidizing nozzle (20) is 0.05-0.8.

Images