Fluidized bed reaction device for preparing organic amine

Abstract

The utility model provides a fluidized bed reaction device for preparing amine compounds, which is characterized in that an air inlet nozzle and a central flow guide pipe are further arranged in a reaction cavity, a reaction area is divided into an annular area and a central area, and a catalyst circularly flows between the annular area and the central area in a fluidized state; reaction raw materials in different reaction atmospheres of the two regions are rapidly reduced and aminated on the surface of the catalyst to form target organic amine. The fluidized bed device has the characteristics of simple structure, high conversion rate, few byproducts and the like. The reaction process is gas-phase catalytic conversion, and compared with liquid-phase reductive amination, the gas-phase catalytic conversion has higher reaction temperature and reaction activity, and the conversion rate and the selectivity are greatly improved; and meanwhile, the problems of generation of nitrides, carbides and the like on the surface of the catalyst, adsorption of organic amines, easy generation of secondary amines, tertiary amines and the like are effectively reduced.

Description

Technical Field

[0001] The utility model relates to the technical field of multiphase catalytic reaction, in particular to a fluidized bed reaction device for producing organic amine compounds. Background Art

[0002] Amines are very important organic compounds. They are key precursors and main intermediates for the synthesis of advanced chemicals, life science molecules, dyes and polymers. They are widely used in dyes, medicines, pesticides, surfactants and materials science. Among them, fatty amines play an especially important role. For example, hexamethylenediamine can be used to produce nylon 66, and meta-phenylenediamine can be used to produce epoxy resin curing agents and nylon products. With the advancement of industrial technology, the production of fatty amines such as ethylenediamine and hexamethylenediamine has reached hundreds of thousands of tons. Fine chemicals represented by amines have a wide range of uses and a broad market, and demand is still growing.

[0003] Reductive amination to synthesize organic amines generally uses metal hydrogenation / dehydrogenation catalysts, and the reaction is usually an exothermic reaction, usually a gas-liquid-solid three-phase intermittent kettle process or a tubular continuous fixed bed process, such as: CN116217525A biomass-based aldehydes and ketones are reacted in a methanol solution, and ammonia is introduced into a high-pressure reactor to prepare organic amines. CN117398925A provides an internal heat pipe fixed bed reactor, which combines a heat pipe heat exchanger with a fixed reactor, adjusts the height ratio of the upper and lower parts of the catalyst bed, reduces the hot spot temperature of the bed, and preheats the inlet mixed gas to achieve a uniform temperature distribution of the catalyst bed, reducing the probability of side reactions. In addition, CN201520683124.4 provides a fixed bed reactor with a shell-side loaded catalyst and an internal heat extraction tube bundle. CN2020010564060.1 discloses a fixed bed reactor, in which a liquid inlet adjustment member is designed in a feed distribution device to achieve targeted diversion of raw materials, thereby controlling the raw materials according to the temperature distribution of each area in the reactor, playing the role of reaction temperature regulation. In short, the reduction amination fixed bed design used in the prior art mainly focuses on solving the problem of strong heat release of the reaction.

[0004] However, other problems in the reductive amination process, such as excessive hydrogenation, lead to low yields of primary amines and imines, difficult separation, and increased costs. In the corrosive reaction environment of reductive amination, the stability of metal-based catalysts is relatively poor; organic amines in reactants and products tend to be strongly adsorbed on the surface of metal-based catalysts, resulting in reduced catalyst hydrogenation capacity. These cannot be well solved in fixed bed reactors. In addition, during the recycling of the catalyst, the active sites of the metal-based catalyst will sinter, lose, oxidize, and carbonize, resulting in catalyst deactivation.

[0005] Therefore, while improving and developing catalysts with higher and more stable activities, there is an urgent need to develop reactors dedicated to the reductive amination process, and to strengthen the binding of raw materials on the catalyst surface and the migration process of products by optimizing the transfer properties, so as to ultimately achieve the purpose of improving the catalyst's reaction capacity and reducing catalyst deactivation. Utility Model Content

[0006] In view of the problems existing in the prior art, the utility model provides a fluidized bed reaction device for preparing amine compounds. The device further arranges an air inlet nozzle and a central flow guide pipe in the reaction chamber to divide the reaction zone into an annular zone and a central zone. The catalyst circulates between the annular zone and the central zone in a fluidized state. The reaction raw materials in different reaction atmospheres in the two zones are rapidly reduced and aminated on the catalyst surface to form the target organic amine. The fluidized bed device has the characteristics of simple structure, high conversion rate, and few by-products.

[0007] The technical solution according to the utility model is as follows:

[0008] A fluidized bed reaction device for preparing organic amines, the reactor body of the device is a three-section tower structure; the upper part is a cylindrical structure as an expansion section, the middle part is an inverted cone structure, and the lower part is a cylindrical structure as a reaction zone, wherein a central guide pipe and an air inlet nozzle are arranged along the central axis inside the lower reaction section.

[0009] Preferably, the diameter of the upper cylindrical structure is greater than that of the lower cylindrical structure, and is an enlarged section; the upper and lower diameter ratio is 1.1:1 to 4:1, and is connected to form a whole through the middle inverted cone structure, and the angle between the cone surface of the middle inverted cone structure and the vertical direction is 15°-45°.

[0010] Preferably, a gas outlet is provided at the top of the upper cylindrical structure for discharging a gaseous mixture containing products after the reaction, and a feed port is provided on the side wall of the upper cylindrical structure, through which the feeder is connected to an external feed unit.

[0011] Preferably, a collector is provided inside the upper cylindrical structure near the gas outlet for intercepting and capturing catalyst fine powder entrained into the upper cylindrical structure to reduce the solid content in the gas phase mixture containing the product.

[0012] Preferably, an air inlet and an air inlet nozzle are provided at the bottom end of the lower cylindrical structure, the air inlet is used to introduce ammonia-rich reaction gas into the lower cylindrical structure, and the air inlet nozzle is used to introduce hydrogen-rich reaction gas into the lower cylindrical structure.

[0013] Preferably, a distribution plate is provided at the inner lower end of the lower cylindrical structure, and the distribution plate is located above the air inlet. A catalyst is filled above the distribution plate, and the mixed gas of ammonia and hydrogen input from the air inlet passes through the distribution plate and then reaches the catalyst layer, thereby evenly fluidizing the catalyst and causing heat and mass transfer.

[0014] Preferably, the air inlet nozzle is sleeved in the air inlet, penetrates into the interior of the lower cylindrical structure, and the nozzle of the air inlet nozzle passes through the distribution plate to spray high-speed airflow.

[0015] Preferably, the central flow guide pipe is arranged inside the lower cylindrical structure along the central axis, and the central flow guide pipe is arranged directly above the air intake nozzle. A contracted throat structure is provided at the lower end of the central flow guide pipe, and an annular gap is left between the edge of the lower end of the throat and the nozzle of the air intake nozzle; the central flow guide pipe divides the interior of the lower cylindrical structure into two parts, namely a central area and an annular area.

[0016] Preferably, the diameter of the central flow guide pipe is 1 / 6-1 / 3 of the diameter of the lower cylindrical structure, and the upper end of the central flow guide pipe is not higher than the height of the lower cylindrical structure.

[0017] Preferably, the feeder is connected to an external feed pump outlet pipeline, and the feeder may include but is not limited to an atomizing nozzle, a liquid phase distribution plate, and the like.

[0018] Preferably, the collector includes but is not limited to a cyclone plate, a cyclone separator, a filter screen, etc. and a combination thereof.

[0019] Preferably, the distribution plate may be a horizontal distribution plate or an inverted cone distribution plate, and the angle between the cone surface and the horizontal plane is 10-50°, preferably 15-40°.

[0020] Preferably, the distribution plate includes but is not limited to a sieve plate, a sintered plate, and a bubble cap plate.

[0021] Preferably, an auxiliary heat exchanger may be provided on the outer wall of the reaction zone of the lower cylindrical structure of the fluidized bed reaction device, and the auxiliary heat exchanger includes but is not limited to a heating belt, a heat exchange coil, a heat exchange jacket, and a ceramic heating plate.

[0022] Beneficial Effects

[0023] The reaction device of the utility model is aimed at the reaction process of alcohol (aldehyde, ketone) reduction amination. Through the internal structure design of the core reactor, the movement process of the catalyst particles is controlled, so that the central area is conducive to catalytic dehydrogenation and desorption of organic amines, and the annular area is conducive to the generation of imines and hydrogenation to amines. The reaction process of the utility model is a gas-phase catalytic conversion. Compared with liquid-phase reduction amination, it has a higher reaction temperature and reaction activity, and the conversion rate and selectivity are greatly improved; at the same time, it effectively reduces the generation of nitrides, carbides, etc. on the catalyst surface, as well as the adsorption of organic amines, and the problem of easy generation of secondary amines and tertiary amines. This method does not use any organic solvents, so there are few three wastes, it is safe and reliable, and it is a continuous and efficient green reaction device. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the specific implementation methods of the utility model or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the utility model. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 A schematic structural diagram of a fluidized bed reaction device for preparing organic amines according to the utility model;

[0026] In the figure: 1-reactor body, 2-feeder, 3-collector, 4-gas outlet, 5-gas inlet, 6-distribution plate, 7-gas inlet nozzle, 8-central conduit; DETAILED DESCRIPTION

[0027] The present invention will be described in detail below. Before the description is made, it should be understood that the terms used in this specification and the appended claims should not be interpreted as limited to the general meaning and dictionary meaning, but should be interpreted according to the meaning and concept corresponding to the technical aspects of the present invention on the basis of the principle that the utility model is allowed to appropriately define the terms for the best interpretation. Therefore, the descriptions presented here are only preferred examples for illustrative purposes and are not intended to limit the scope of the present invention, so that it should be understood that other equivalents or improvements can be obtained therefrom without departing from the spirit and scope of the present invention.

[0028] The following examples are only listed as examples of the embodiments of the present invention and do not constitute any limitation to the present invention. It can be understood by those skilled in the art that modifications within the scope of the essence and concept of the present invention fall within the protection scope of the present invention. Unless otherwise specified, the reagents and instruments used in the following examples are commercially available products.

[0029] Hereinafter, the preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the terms used in the specification and the appended claims should not be interpreted as limited to the general and dictionary meanings, but should be interpreted based on the principle of allowing the utility model to appropriately define the terms for the best interpretation, based on the meaning and concept corresponding to the technical level of the utility model. Therefore, the description herein is only a preferred example for illustrative purposes, and is not intended to limit the scope of the utility model, so it should be understood that other equivalent implementations and modifications can be made without departing from the spirit and scope of the utility model.

[0030] In this document, the terms "include", "including", "have", "contain" or any other similar terms are open conjunctions, which are intended to cover non-exclusive inclusions. For example, a composition or product containing multiple elements is not limited to the elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or product. In addition, unless otherwise explicitly stated, the term "or" refers to an inclusive "or" rather than an exclusive "or". For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and A and B are both true (or exist). In addition, in this document, the interpretation of the terms "include", "including", "have", and "contain" should be considered to have been specifically disclosed and simultaneously cover closed or semi-closed conjunctions such as "consisting of" and "consisting essentially of".

[0031] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges are only for brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have covered and specifically disclosed all possible secondary ranges and individual values ​​within the range, especially integer values. For example, the range description of "1 to 8" should be deemed to have specifically disclosed all secondary ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., especially secondary ranges defined by all integer values, and should be deemed to have specifically disclosed individual values ​​within the range such as 1, 2, 3, 4, 5, 6, 7, 8, etc. Unless otherwise specified, the above interpretation method applies to all contents of the entire text of the utility model, regardless of whether the scope is broad or not.

[0032] If the quantity or other numerical value or parameter is expressed as a range, a preferred range or a series of upper and lower limits, it should be understood that all ranges consisting of any upper limit or preferred value of the range and the lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, if a numerical range is mentioned herein, unless otherwise specified, the range should include its endpoints and all integers and fractions within the range.

[0033] In this document, under the premise of achieving the purpose of the utility model, the numerical value should be understood to have the accuracy of the significant digits of the numerical value. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0034] In order to clarify the present invention, parts irrelevant to the description are omitted in the drawings, and the same or similar components are denoted by the same reference numerals throughout the specification.

[0035] In addition, the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of explanation, and thus the present invention is not necessarily limited to those shown in the drawings.

[0036] Throughout the specification, when it is mentioned that a certain element is “connected” to another element, it includes not only “direct connection” but also “indirect connection” between other components. In addition, when it is mentioned that a certain element “includes” a certain component, it means that the element may further include other components rather than excluding other components, unless explicitly described to the contrary.

[0037] The terms “first”, “second” and the like used herein are used to explain various constituent elements, and they are used merely for the purpose of distinguishing one constituent element from another constituent element.

[0038] Furthermore, the terms used herein are only used to explain exemplary embodiments and are not intended to limit the present invention. Singular expressions also include plural expressions thereof, unless otherwise clearly indicated in the context. Terms such as "comprising", "equipped with" or "having" used herein are used to specify the existence of practical characteristics, numbers, steps, constituent elements, or combinations thereof, and should be understood as not excluding the possibility of adding or existing one or more other characteristics, numbers, steps, constituent elements, or combinations thereof.

[0039] Also, if a layer or an element is referred to as being formed “on” or “over” a “layer” or “element,” this means that each layer or element is formed directly on the layer or element, or other layers or elements may be formed between layers, bodies, or substrates.

[0040] Reference below Figure 1 Specifically describe the structure of the utility model device:

[0041] The reactor body 1 of a fluidized bed reaction device for preparing organic amines is a three-stage tower structure; the upper part is a cylindrical structure as an expansion section, the middle part is an inverted cone structure, and the lower part is a cylindrical structure as a reaction zone, wherein an air inlet nozzle 7 and a central guide pipe 8 are arranged along the central axis inside the lower reaction section.

[0042] Among them, the reactor body 1 is a tower fluidized bed, the upper part is a cylindrical structure, the middle part is an inverted cone structure, and the lower part is a cylindrical structure. The diameter of the upper cylindrical structure is greater than the diameter of the lower cylindrical structure, which is an expanded section. The upper and lower diameter ratio is 1.1:1-4:1, and the middle inverted cone structure is connected to form a whole. The angle between the cone surface of the middle inverted cone structure and the vertical direction is 15°-45°. The lower cylindrical structure is the main reaction zone. In a smaller space, the reactants and catalysts are fully contacted to achieve reaction conditions by controlling process conditions such as gas distribution, wind speed, and heat exchange, and then react quickly. The main purpose of the upper cylindrical structure is: first, to reduce the gas velocity to separate the gas and solid phases; second, to provide sufficient space for setting auxiliary components such as feeding or exhaust devices. The middle inverted cone structure plays a role in connecting the upper and lower structures and promoting the reflux of materials or catalysts into the lower reaction zone of the fluidized bed, which is specifically controlled by the cone angle, fluidizing gas velocity, catalyst particle size, etc.

[0043] Preferably, a gas outlet 4 is provided at the top of the upper cylindrical structure for conducting out a gaseous mixture containing products after the reaction (main components are organic amines, ammonia, hydrogen, a small amount of secondary amines, tertiary amines, etc.), and a feed port is provided on the side wall of the upper cylindrical structure, through which the feeder 2 is connected to an external feed unit for inputting and dispersing the reaction raw materials; the substrates for reductive amination are alcohols, aldehydes, and ketones, which are mostly in liquid phase, so the feeder 2 needs to evenly disperse the raw materials while introducing them to ensure sufficient contact with the catalyst in the fluidized bed, and to carry out mass transfer and heat transfer.

[0044] Preferably, a collector 3 is provided inside the upper cylindrical structure near the gas outlet 4 to intercept and capture catalyst fine powder entrained into the upper cylindrical structure, thereby reducing the solid content in the gas phase mixture containing the product.

[0045] Preferably, the bottom end of the lower cylindrical structure is provided with an air inlet 5 and an air inlet nozzle 7, wherein the air inlet 5 is used to introduce ammonia-rich reaction gas into the lower cylindrical structure, and the air inlet nozzle 7 is used to introduce hydrogen-rich reaction gas into the lower cylindrical structure. The mixed gas of ammonia and hydrogen introduced through the air inlet 5 is both the reaction gas and the fluidizing air of the fluidized bed.

[0046] Preferably, a distribution plate 6 is provided at the inner lower end of the lower cylindrical structure, and the distribution plate 6 is located above the air inlet 5. A catalyst is filled above the distribution plate 6. The mixed gas of ammonia and hydrogen input from the air inlet 5 passes through the distribution plate 6 and then reaches the catalyst layer, so that the catalyst is evenly fluidized and heat and mass transfer occurs.

[0047] Preferably, the air inlet nozzle 7 is sleeved in the air inlet 5, penetrates into the interior of the lower cylindrical structure, and the nozzle of the air inlet nozzle 7 passes through the distribution plate 6, for ejecting high-speed airflow.

[0048] Preferably, the central guide pipe 8 is arranged along the central axis inside the lower cylindrical structure, and the central guide pipe 8 is arranged just above the air inlet nozzle 7. The lower end of the central guide pipe 8 is provided with a contracted throat structure, and an annular gap is left between the edge of the lower end of the throat and the nozzle of the air inlet nozzle 7; the central guide pipe 8 divides the interior of the lower cylindrical structure into two parts: a central area and an annular area. When the air inlet nozzle 7 ejects a high-speed jet, the catalyst fluidized at the surrounding distribution plate 6 is violently disturbed, and then sucked into the central guide pipe 8 from the annular gap, and moves upward through the throat with the jet until it is ejected from the top of the central guide pipe 8. The ejected catalyst scatters around and continues to fluidize in the annular area outside the central guide pipe 8, and returns to the vicinity of the distribution plate 6, so the catalyst circulates continuously in the central area and the annular area in a fluidized state.

[0049] Preferably, the diameter of the central flow guide tube 8 is 1 / 6-1 / 3 of the diameter of the lower cylindrical structure, and the upper end of the central flow guide tube 8 is not higher than the height of the lower cylindrical structure.

[0050] Preferably, the feeder 2 is connected to an external feed pump outlet pipeline.

[0051] Preferably, the feeder 2 may include but is not limited to an atomizing nozzle, a liquid phase distribution plate, and the like.

[0052] Preferably, the collector 3 includes but is not limited to a cyclone plate, a cyclone separator, a filter screen, etc. and a combination thereof.

[0053] Preferably, the distribution plate 6 can be a horizontal distribution plate or an inverted cone distribution plate, and the angle between the cone surface and the horizontal plane is 10-50°, preferably 15-40°.

[0054] Preferably, the distribution plate 6 includes but is not limited to a sieve plate, a sintered plate, and a bubble cap plate.

[0055] Preferably, the diameter of the central flow guide tube 8 is 1 / 6-1 / 3 of the diameter of the lower cylindrical structure, and the upper end of the central flow guide tube 8 is not higher than the height of the lower cylindrical structure.

[0056] Preferably, an auxiliary heat exchanger may be provided on the outer wall of the reaction zone of the lower cylindrical structure of the fluidized bed reaction device, and the auxiliary heat exchanger includes but is not limited to a heating belt, a heat exchange coil, a heat exchange jacket, and a ceramic heating plate.

[0057] Preferably, the gas in the air inlet 5 and the air inlet nozzle 7 is mainly hydrogen and ammonia, the ammonia-hydrogen molar ratio in the ammonia-rich reaction gas of the air inlet 5 is 3-30:1, and the ammonia-hydrogen molar ratio in the hydrogen-rich reaction gas of the air inlet nozzle 7 is 1:3-20; the gas flow rate of the air inlet 5 and the air inlet nozzle 7 is 3-50:1. Therefore, the annular area above the distribution plate is a high-ammonia and low-hydrogen reaction atmosphere, while the central area is a high-hydrogen and low-ammonia reaction atmosphere; the annular area is conducive to the generation of imines and hydrogenation to amines, while the central area is conducive to catalytic dehydrogenation and desorption of organic amines, thereby effectively reducing the generation of metal nitrides, metal carbides and active component oxides on the catalyst surface, as well as organic amine adsorption, and the problem of easy generation of secondary amines and tertiary amines.

[0058] Preferably, the reaction raw materials for the reductive amination suitable for the fluidized bed reaction device of the utility model are selected from the following structures:

[0059]

[0060] Wherein R1 is selected from C1-C10 alkyl, halogen-substituted C1-10 alkyl, hydroxyl-substituted C1-10 alkyl, amine-substituted C1-6 alkyl, or R1 and R2 can be connected to form an unsaturated C5-C8 cycloalkyl, a C6-C14 aryl, a 5-15 membered heterocyclic group containing 1-3 heteroatoms selected from N, O and S, or a 5-15 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0061] R2 is selected from hydrogen, C1-C10 alkyl, halogen-substituted C1-10 alkyl, hydroxyl-substituted C1-10 alkyl, amine-substituted C1-6 alkyl, or R1 and R2 can be connected to form an unsaturated C5-C8 cycloalkyl, a C6-C14 aryl, a 5-15 membered heterocyclic group containing 1-3 heteroatoms selected from N, O and S, or a 5-15 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0062] Wherein R3 is selected from C1-C10 alkyl, halogen-substituted C1-10 alkyl, hydroxyl-substituted C1-10 alkyl, amine-substituted C1-6 alkyl, or R3 and R4 can be connected to form an unsaturated C5-C8 cycloalkyl, a C6-C14 aryl, a 5-15 membered heterocyclic group containing 1-3 heteroatoms selected from N, O and S, or a 5-15 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0063] R4 is selected from hydrogen, C1-C10 alkyl, halogen-substituted C1-10 alkyl, hydroxyl-substituted C1-10 alkyl, amine-substituted C1-6 alkyl, or R3 and R4 can be connected to form an unsaturated C5-C8 cycloalkyl, a C6-C14 aryl, a 5-15 membered heterocyclic group containing 1-3 heteroatoms selected from N, O and S, or a 5-15 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0064] Preferably, the reaction temperature of the fluidized bed reaction device is 80-350° C., and the reaction pressure is 0.1-5 MPa.

[0065] Preferably, the catalyst for the reductive amination is a noble metal catalyst such as Ni, Co, Cu, Ru, Pd, Pt, Rh, Ir and Re, and may also be a metal oxide or a supported catalyst.

[0066] Embodiment 1:

[0067] refer to Figure 1 The structure of the fluidized bed is selected with the following dimensions: reaction section Φ40mm, horizontal distribution plate, upper expansion section Φ100mm, total length of about 400mm, and loading of about 360g of supported Cu-Co catalyst.

[0068] 1) After the system is replaced with nitrogen, preheated nitrogen is introduced into the reactor body 1 through the air inlet 5 of the fluidized bed reactor, and the flow meter controls the flow rate to be about 5 L / min, so that the catalyst in the reactor body 1 is fluidized and preheated to about 200° C.;

[0069] 2) When the temperature of the catalyst bed reaches the set temperature, the air inlet 5 is gradually switched to a preheated ammonia and hydrogen mixed atmosphere to fluidize the catalyst until the temperature of the reaction zone is stabilized at 230-250°C and the pressure is 0.2-1.5MPa;

[0070] 3) Open the air inlet nozzle 7 to start air intake, and gradually control the air intake volume to reach 1 / 5 to 1 / 3 of the total amount, and the molar ratio of ammonia to hydrogen in the air is 1:3 to 5; observe that the catalyst in the reaction zone fluidizes smoothly, and at the same time, the catalyst forms a stable circulation in the central area and the annular area inside and outside the central guide tube 8;

[0071] 4) The raw material is n-pentanol, the feeder 2 is turned on, and the feed rate is gradually adjusted to feed the reaction raw material into the reactor 1 and evenly disperse it;

[0072] 5) When n-pentanol falls into the reaction zone of the reactor body 1, it is quickly mixed with the catalyst to transfer heat and mass, and the n-pentanol is quickly gasified and undergoes a reduction amination reaction with ammonia on the catalyst surface. The catalyst is sucked into the central flow guide 8 by the jet roll of the air inlet nozzle 7. Under the action of the hydrogen-rich gas flow in the central zone, the n-pentanol is more likely to undergo catalytic dehydrogenation, and the product n-pentylamine is more likely to desorb from the catalyst, thereby reducing the possibility of continuing to generate secondary amines. At the same time, the hydrogen-rich atmosphere effectively inhibits the generation and adhesion of catalyst deactivating substances such as metal carbides, metal nitrides and oxides; after the catalyst is ejected from the central zone with the gas flow, it falls into the ammonia-rich annular zone, and the dehydrogenated n-valeraldehyde quickly forms imines and is catalytically hydrogenated to form n-pentylamine products;

[0073] 6) As the catalyst circulates continuously in the central zone and the annular zone, the reductive amination of n-pentanol continues, and the product n-pentylamine desorbs from the catalyst and continues to rise with the gas flow to the expansion section of the reactor body 1;

[0074] 7) The gas phase products such as n-pentylamine obtained in step 6) reach the collector 3 at the top of the reactor body 1 along with the excess ammonia and hydrogen, and finally flow out of the reactor body 1 from the gas outlet 4 after separating the catalyst fine powder entrained in the gas phase;

[0075] 8) Adjust the feed rate of the feeder 1, the reaction pressure, the air flow rate, composition, temperature of the air inlet 5, the flow rate, composition of the air inlet nozzle 7 and other process conditions respectively to control and optimize the conversion rate, selectivity and by-product generation of the raw alcohol.

[0076] When the reaction temperature is 150-250°C, the pressure is 0.2-2.0MPa, the ammonia-alcohol molar ratio is 3-12:1, the hydrogen-alcohol molar ratio is 2-12:1; the results are as follows:

[0077]

[0078] The above is only a specific implementation of the utility model, but the protection scope of the utility model is not limited thereto. Any technician familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed by the utility model, which should be included in the protection scope of the utility model. Therefore, the protection scope of the utility model should be based on the protection scope of the claims.

Claims

1. A fluidized bed reaction device for preparing organic amines, wherein the reactor body of the device is a three-stage tower structure, characterized in that: The upper part is a cylindrical structure which is an expansion section, the middle part is an inverted cone structure, and the lower part is a cylindrical structure which is a reaction zone, wherein a central guide pipe and an air inlet nozzle are arranged along the central axis inside the lower reaction section.

2. The fluidized bed reaction device for preparing organic amines according to claim 1, characterized in that: The diameter of the upper cylindrical structure is greater than that of the lower cylindrical structure, and is an enlarged section; the upper and lower diameter ratio is 1.1:1 to 4:1, and is connected to form a whole through the middle inverted cone structure, and the angle between the cone surface of the middle inverted cone structure and the vertical direction is 15°-45°.

3. The fluidized bed reaction device for preparing organic amines according to claim 1, characterized in that: The top of the upper cylindrical structure is provided with a gas outlet for conducting out the gaseous mixture containing the product after the reaction. The side wall of the upper cylindrical structure is provided with a feed port, and the feeder is connected to the external feed unit through the feed port.

4. The fluidized bed reaction device for preparing organic amines according to claim 3, characterized in that: A collector is provided inside the upper cylindrical structure near the gas outlet for intercepting and capturing catalyst fine powder entrained into the upper cylindrical structure, thereby reducing the solid content in the gas phase mixture containing the product.

5. The fluidized bed reaction device for preparing organic amines according to claim 1, characterized in that: An air inlet and an air inlet nozzle are provided at the bottom end of the lower cylindrical structure. The air inlet is used to introduce ammonia-rich reaction gas into the lower cylindrical structure, and the air inlet nozzle is used to introduce hydrogen-rich reaction gas into the lower cylindrical structure.

6. The fluidized bed reaction device for preparing organic amines according to claim 5, characterized in that: A distribution plate is provided at the lower end of the lower cylindrical structure, and the distribution plate is located above the air inlet. A catalyst is filled above the distribution plate. The mixed gas of ammonia and hydrogen input from the air inlet passes through the distribution plate and then reaches the catalyst layer, thereby evenly fluidizing the catalyst and causing heat and mass transfer.

7. The fluidized bed reaction device for preparing organic amines according to claim 6, characterized in that: The air inlet nozzle is sleeved in the air inlet, penetrates into the interior of the lower cylindrical structure, and the nozzle of the air inlet nozzle passes through the distribution plate, so as to spray high-speed airflow.

8. The fluidized bed reaction device for preparing organic amines according to claim 1, characterized in that: The central flow guide pipe is arranged inside the lower cylindrical structure along the central axis, and the central flow guide pipe is arranged directly above the air intake nozzle. A contracted throat structure is provided at the lower end of the central flow guide pipe, and an annular gap is left between the edge of the lower end of the throat and the nozzle of the air intake nozzle; the central flow guide pipe divides the interior of the lower cylindrical structure into two parts: a central area and an annular area.

9. The fluidized bed reaction device for preparing organic amines according to claim 1, characterized in that: The diameter of the central flow guide pipe is 1 / 6-1 / 3 of the diameter of the lower cylindrical structure, and the upper end of the central flow guide pipe is not higher than the height of the lower cylindrical structure.

10. The fluidized bed reaction device for preparing organic amines according to claim 3, characterized in that: The feeder is connected to an external feed pump outlet pipeline, and the feeder comprises an atomizing nozzle and a liquid phase distribution plate.

11. The fluidized bed reaction device for preparing organic amines according to claim 4, characterized in that: The collector includes a cyclone plate, a cyclone separator, a filter or a combination thereof.

12. The fluidized bed reaction device for preparing organic amines according to claim 6 or 7, characterized in that: The distribution plate is a horizontal distribution plate, or an inverted cone distribution plate, and the angle between the cone surface and the horizontal plane is 10-50 degrees.

13. The fluidized bed reaction device for preparing organic amines according to claim 12, characterized in that: The distribution plate is an inverted cone-shaped distribution plate, and the angle between the cone surface and the horizontal plane is 15-40 degrees.

14. The fluidized bed reaction device for preparing organic amines according to claim 6 or 7, characterized in that: The distribution plate includes a sieve plate, a sintered plate and a bubble cap plate.

15. The fluidized bed reaction device for preparing organic amines according to claim 1, characterized in that: An auxiliary heat exchanger is arranged on the outer wall of the reaction zone of the lower cylindrical structure of the fluidized bed reaction device, and the auxiliary heat exchanger comprises a heating belt, a heat exchange coil, a heat exchange jacket, and a ceramic heating plate.

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