CN118142443A - Trickle bed reactor and method for preparing benzyl amine by using same - Google Patents
Trickle bed reactor and method for preparing benzyl amine by using same Download PDFInfo
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- CN118142443A CN118142443A CN202410580133.4A CN202410580133A CN118142443A CN 118142443 A CN118142443 A CN 118142443A CN 202410580133 A CN202410580133 A CN 202410580133A CN 118142443 A CN118142443 A CN 118142443A
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- bed reactor
- trickle bed
- liquid
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- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000012856 packing Methods 0.000 claims abstract description 79
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 67
- 239000000835 fiber Substances 0.000 claims abstract description 49
- 239000000945 filler Substances 0.000 claims abstract description 33
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 69
- 239000007789 gas Substances 0.000 claims description 25
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000008602 contraction Effects 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 15
- 239000012071 phase Substances 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000007791 liquid phase Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 4
- 238000011020 pilot scale process Methods 0.000 abstract description 2
- 238000010812 external standard method Methods 0.000 description 16
- 238000004811 liquid chromatography Methods 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010586 diagram Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001154 acute effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 230000010349 pulsation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011172 small scale experimental method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0292—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds with stationary packing material in the bed, e.g. bricks, wire rings, baffles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of production equipment and production. At present, the production equipment of the benzyl amine is a trickle bed reactor, and during a low liquid speed pilot scale experiment, the radial distribution and the temperature distribution of liquid flow are uneven, so that the gas phase and the liquid phase are in a trickle region. The invention provides a trickle bed reactor, which comprises a reactor shell, wherein a liquid distributor, at least one layer of pulse filler and at least one layer of supporting plate are sequentially arranged in the reactor shell at intervals from top to bottom; a three-dimensional combined filler is arranged in the catalyst bed layer; the three-dimensional combined filler is vertically arranged in the catalyst bed layer and comprises a plurality of three-dimensional combined filler units; the three-dimensional combined packing unit comprises a central rope and a ring piece; the central rope is penetrated and fixed in the center of the ring piece along the central shaft of the ring piece; the periphery of the annular sheet is vertically provided with a plurality of fiber bundles which are distributed on the periphery of the annular sheet. Also provided are methods of making benzyl amine using the foregoing trickle bed reactors. The trickle bed reactor and the method using the same can improve the turbulence degree and the mass transfer efficiency of gas and liquid phases in a bed.
Description
Technical Field
The invention belongs to the field of production equipment and production technology, and in particular relates to a trickle bed reactor and a method for preparing benzyl amine by using the trickle bed reactor.
Background
The trickle bed reactor is a typical gas-liquid-solid three-phase reactor, can obtain higher conversion rate, is widely applied to chemical processes such as petroleum refining, petrochemical industry, fine chemical industry and the like, and is mainly applied to reaction types such as hydrogenation, oxidation and the like. Trickle bed reactors, however, also suffer from the following disadvantages: in pilot experiments with low liquid velocities, the radial and temperature distributions of the liquid stream are not uniform, hot spots are formed, the catalyst is deactivated rapidly or the gas-liquid flow state is further affected, which is unfavorable for the trickle bed reactor operation. Therefore, there is a need for an improvement in trickle bed reactors to achieve operation at the boundary of the trickle flow region and the pulse flow region as much as possible, to provide a relatively uniform gas-liquid phase distribution, and to avoid localized overheating.
The benzyl amine is light amber liquid, is dissolved in water and organic solvent, and has obvious application in rubber product, nylon product, lubricant and other fields. At present, the continuous process route of the benzylamine is mainly carried out in a trickle bed reactor, but the gas-liquid two-phase flow rate in a small test is low and is in a trickle zone, so that accurate and valuable data cannot be provided for pilot-scale or industrial reactors. Therefore, aiming at the problems of the existing small-scale continuous test at present, an improved trickle bed reactor is required to be sought so as to improve the turbulence degree of gas-liquid two phases in small-scale test, strengthen mass and heat transfer and provide accurate data for the operation of an industrial reactor.
Disclosure of Invention
A first object of the present invention is to provide a trickle bed reactor having a three-dimensional combined packing and pulse packing, which can improve the turbulence degree and mass transfer efficiency of gas and liquid phases in a bed, and is suitable for the reaction of preparing benzyl amine by catalytic hydrogenation of benzonitrile;
The second object of the present invention is to provide a method for preparing benzyl amine by using the trickle bed reactor, which is simple and easy to operate, strengthens mass transfer and heat transfer between three phases of gas, liquid and solid, and improves the data accuracy of small-scale experiments.
In order to achieve the first object of the present invention, the following technical solutions are adopted:
a trickle bed reactor comprising a reactor shell;
The reactor comprises a reactor shell, a liquid distributor, at least one layer of pulse filler and at least one layer of supporting plate, wherein the reactor shell is internally provided with the liquid distributor, the at least one layer of pulse filler and the at least one layer of supporting plate at intervals from top to bottom, and the reactor shell is internally divided into a gas cavity, at least 2 catalyst beds and a liquid cavity from top to bottom in sequence; the catalyst bed layer is filled with a three-dimensional combined filler;
The top of the reactor shell is provided with a gas phase inlet, the bottom of the reactor shell is provided with a liquid outlet, the side wall of the reactor shell is provided with a liquid inlet corresponding to the liquid distributor, and the side wall of the reactor shell is provided with a gas outlet corresponding to the liquid cavity;
The three-dimensional combined packing is vertically arranged in the catalyst bed and comprises a plurality of vertically, parallel and dispersedly arranged three-dimensional combined packing units, and a vertical third liquid channel is formed between every two adjacent three-dimensional combined packing units;
The three-dimensional combined packing unit comprises a central rope and a ring piece; the center rope is fixedly arranged in the center of the ring piece in a penetrating way along the center shaft of the ring piece; the circumference of the ring piece is vertically provided with a plurality of fiber bundles, and the fiber bundles are arranged on the circumference of the ring piece in a dispersing way.
In the trickle bed reactor of the present invention, preferably, in the three-dimensional combined packing unit, the plurality of ring pieces are arranged at intervals along the central rope.
The trickle bed reactor of the present invention, preferably, the central cord has a diameter of 10-15 mm a.
The trickle bed reactor of the present invention, preferably, the ring pieces have an outer diameter of 100-200 mm and an inner diameter of 60-120 mm.
The trickle bed reactor of the present invention, preferably, the length of the fiber bundles is 20-80 mm.
The trickle bed reactor of the present invention, preferably, the fiber bundle comprises 20-50 filaments.
In the trickle bed reactor of the present invention, preferably, the spacing length between adjacent fiber bundles on the annular sheet along the circumferential direction thereof is 10-50 mm.
In the trickle bed reactor of the present invention, preferably, in the three-dimensional combined packing, a plurality of the three-dimensional combined packing units are arranged in a square grid within the catalyst bed.
In the trickle bed reactor of the present invention, preferably, the interval distance between every two adjacent 2 three-dimensional combined packing units along the square grid is L 01, the outer diameter of the ring sheet is L 02, the length of the fiber bundle is L 03, and then L 02+2L03≤L01≤4L02.
In the trickle bed reactor of the present invention, preferably, the pulse packing comprises a plurality of pulse tubes which are vertically, parallelly and dispersedly arranged, wherein the pulse tubes are provided with vertical first liquid channels, and vertical second liquid channels are formed between adjacent pulse tubes.
In the trickle bed reactor of the present invention, preferably, the pulse tube comprises a contraction section and an expansion section alternately arranged along a length direction thereof, and adjacent contraction section and expansion section form 1 pulse unit; the pulse tube comprises at least 1 of the pulse units.
In the trickle bed reactor of the present invention, preferably, in the pulse packing, the pulse tubes are arranged between adjacent 2 catalyst beds in the following manner: adjacent 3 pulse tubes are arranged in a regular triangle to form a minimum arrangement unit.
The trickle bed reactor of the present invention, preferably, has an aspect ratio of 3-8.
To achieve the second object of the present invention, there is also provided a method for preparing benzyl amine using the foregoing trickle bed reactor, the method comprising:
(1) Introducing hydrogen into the trickle bed reactor from the gas phase inlet to activate the catalyst filled in the catalyst bed;
(2) Introducing a composite solvent dissolved with benzonitrile into the trickle bed reactor from the liquid inlet, carrying out catalytic hydrogenation reaction on the catalyst bed layer and the introduced hydrogen to prepare benzyl amine, and outputting from the liquid outlet.
In the method, in the catalytic hydrogenation reaction, the molar ratio of the benzonitrile to the hydrogen to the composite solvent is preferably 1 (1-5): 1-20.
In the process of the present invention, preferably, in the catalytic hydrogenation reaction, the reaction pressure is 7 to 15 MPa, and/or the reaction temperature is 50 to 150 ℃.
The method of the present invention, preferably, the complex solvent comprises any two or more of tetrahydrofuran, methanol, toluene, cyclohexane, liquid ammonia, and N-methylpyrrolidone.
In the method of the present invention, preferably, the catalyst packed in the catalyst bed is a nickel-based catalyst.
The invention has the beneficial effects that:
(1) According to the trickle bed reactor, the three-dimensional combined filler is filled in the catalyst bed layer in a penetrating manner, so that the gas-liquid distribution is uniform due to the characteristic of the specific high specific surface, the gas-liquid is fully contacted, and the mass transfer efficiency of the gas-liquid is improved;
(2) The trickle bed reactor of the invention is provided with the pulse filler layer between two adjacent catalyst beds, and the special pulse characteristic can greatly improve the wetting degree of the catalyst, so that 'pulsation' is generated in the beds, and the turbulence degree and mass transfer efficiency of gas and liquid phases in the beds can be improved;
(3) The trickle bed reactor can strengthen heat transfer and mass transfer among gas, liquid and solid under the combined action of the three-dimensional combined filler and the pulse filler, so that the flow pattern in the bed layer is close to the adjacent areas of trickle flow and pulse flow, the flow pattern is more stable, and the phenomenon of uneven temperature and concentration distribution can be avoided; the catalyst is suitable for catalytic hydrogenation reaction;
(4) The method for preparing the benzyl amine by utilizing the trickle bed reactor is simple and easy to operate, and the catalytic hydrogenation reaction of the benzyl cyanide catalytic hydrogenation to prepare the benzyl amine is carried out under the combined action of the three-dimensional combined filler and the pulse filler, so that the wetting degree of the catalyst is greatly improved, the flow pattern in the bed is close to the adjacent areas of trickle flow and pulse flow, the flow pattern is more stable, the phenomenon of uneven temperature and concentration distribution is avoided, the airspeed of a small test device can be improved, the data accuracy of a small test experiment is improved, and more accurate data is provided for an industrialized device; and simultaneously, the process operation condition is reduced.
Drawings
FIG. 1 is a schematic diagram of the trickle bed reactor of the present invention in one embodiment;
FIG. 2 is a schematic diagram of the structure of a three-dimensional combined packing unit of the three-dimensional combined packing in a trickle bed reactor of the present invention in one embodiment;
FIG. 3 is a schematic diagram of the arrangement of the stereoscopic combination packing elements (also schematic diagram of the cross-sectional structure) of the stereoscopic combination packing in the trickle bed reactor of the present invention in one embodiment;
FIG. 4 is a schematic diagram of the pulsing unit of the pulsing packing in the trickle bed reactor of the present invention in one embodiment;
FIG. 5 is a schematic diagram of the arrangement of pulse tubes of pulse fillers in one embodiment (also a schematic diagram of the cross-sectional structure) of a trickle bed reactor of the present invention;
Wherein 1 is a gas phase inlet, 2 is a liquid distributor, 3 is a liquid inlet, 4 is a catalyst bed layer, 5 is a three-dimensional combined packing, 51 is a three-dimensional combined packing unit, 511 is a central rope, 512 is a ring sheet, 513 is a fiber bundle, 514 is a fixed seat, 515 is a fixed rod, 6 is a pulse packing, 61 is a pulse tube, 611 is a contraction section, 612 is an expansion section, 7 is a support plate, 8 is a gas outlet, 9 is a liquid outlet, and 10 is a reactor shell.
Detailed Description
The technical scheme and effects of the present invention are further described below with reference to the detailed description/examples and the accompanying drawings. The following embodiments/examples are only for illustrating the contents of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention using the inventive concept are within the scope of the invention as claimed.
The present invention provides a trickle bed reactor, as shown in FIGS. 1-5, comprising a reactor housing 10;
The reactor shell 10 is internally provided with a liquid distributor 2, at least one layer of pulse packing 6 and at least one layer of supporting plate 7 at intervals from top to bottom in sequence, and the reactor shell 10 is internally divided into a gas cavity, at least 2 catalyst beds 4 and a liquid cavity from top to bottom in sequence; the catalyst bed layer 4 is filled with a three-dimensional combined filler 5;
The top of the reactor shell 10 is provided with a gas phase inlet 1, the bottom is provided with a liquid outlet 9, the side wall of the reactor shell is provided with a liquid inlet 3 corresponding to the liquid distributor 2, and the side wall of the reactor shell is provided with a gas outlet 8 corresponding to the liquid cavity;
The three-dimensional combined packing 5 is vertically arranged in the catalyst bed 4 and comprises a plurality of vertically, parallel and dispersedly arranged three-dimensional combined packing units 51, and a vertical third liquid channel is formed between every two adjacent 2 three-dimensional combined packing units 51;
The three-dimensional combined packing unit 51 includes a central string 511 and a ring 512; the central rope 511 is fixed to the center of the ring 512 along the central axis of the ring 512; the fiber bundles 513 are provided around the circumference of the ring 512, and the plurality of fiber bundles 513 are provided around the circumference of the ring 512 in a dispersed manner.
According to the trickle bed reactor, the three-dimensional combined filler is filled in the catalyst bed layer in a penetrating manner, so that the gas-liquid distribution is uniform due to the characteristic of the specific high specific surface, the gas-liquid is fully contacted, and the mass transfer efficiency of the gas-liquid is improved; the pulse filler layers are arranged between two adjacent catalyst beds, and the special pulse characteristics can greatly improve the wetting degree of the catalyst, so that 'pulsation' is generated in the beds, and the turbulence degree and mass transfer efficiency of gas and liquid phases in the beds can be improved; under the combined action of the three-dimensional combined filler and the pulse filler, the heat transfer and mass transfer between the gas phase, the liquid phase and the solid phase can be enhanced, so that the flow pattern in the bed layer is close to the adjacent areas of the trickle flow and the pulse flow, the flow pattern is more stable, and the phenomenon of uneven temperature and concentration distribution can be avoided; is suitable for catalytic hydrogenation reaction.
Those skilled in the art will appreciate that there are many ways of fixing the ring 512 to the central string 511 in the three-dimensional packing unit 51, and correspondingly, many fixing structures. In one embodiment, the fixing member is disposed at the inner circumference of the ring 512, and the fixing member includes a fixing seat 514 and a fixing rod 515; the fixing seat 514 is concentrically arranged at the center of the ring 512, and a fixing hole for the central rope 511 to pass through is arranged along the center thereof; the fixing rods 515 are multiple and are radially disposed between the ring 512 and the fixing base 514, one end of each fixing rod is fixed to the outer periphery of the fixing base 514, and the other end of each fixing rod is fixed to the inner periphery of the ring 512.
In one embodiment, in the three-dimensional combined packing unit 51, a plurality of the ring pieces 512 are provided at intervals along the central string 511; preferably, on the central cord 511, the sheet spacing between two adjacent loop sheets 512 is 100-150 mm, such as 105-mm, 110-mm, 115-mm, 120-mm, 125-mm, 130-mm, 135-mm, 140-mm and 145-mm.
It will be understood by those skilled in the art that, in the three-dimensional combined packing unit 51, the central rope 511 and the fixing seat 514 are fixedly arranged, and the fixing between the central rope 511 and the fixing seat can be achieved by tightening, tying or other manners, so that in the three-dimensional combined packing unit 51, a plurality of ring pieces 512 are fixedly arranged on the central rope 511 at intervals. The details are not described in detail.
In one embodiment, the central cord 511 has a diameter of 10-15 mm, such as 11-mm, 12-mm, 13-mm, and 14-mm.
In one embodiment, the ring 512 has an outer diameter (denoted as L 02) of 100-200 mm, such as 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, and 190 mm; the inner diameters are 60-120 mm, such as 70 mm, 80 mm, 90 mm, 100 mm and 110 mm.
In one embodiment, the length of the fiber bundles 513 (denoted as L 03) is 20-80 mm, such as 30 mm, 40 mm, 50mm, 60 mm, and 70 mm.
In one embodiment, the fiber bundle 513 comprises 20-50 fibers, such as 20, 25, 30, 35, 40, 45, and 50; preferably the filaments have a diameter of 0.35-0.55 mm, such as 0.4 mm, 0.45 mm and 0.5 mm.
In one embodiment, the fiber bundles 513 are adjacent to the ring 512 at intervals of 10-50 mm, such as 20-mm, 30-mm, and 40-mm, along the circumference.
In the present invention, the interval length of the adjacent fiber bundles 513 in the circumferential direction thereof means the arc-shaped length of the adjacent 2 fiber bundles 513 in the circumferential direction thereof.
In one embodiment, in the three-dimensional combined packing 5, a plurality of the three-dimensional combined packing units 51 are arranged in a square grid within the catalyst bed 4.
In a preferred embodiment, the spacing distance between two adjacent three-dimensional combined packing units 51 along a square grid is denoted as L 01, the outer diameter of the ring segments 512 is denoted as L 02, and the length of the fiber bundles 513 is denoted as L 03, then, for example, L 01 is any length within this range.
Those skilled in the art will understand that in the present invention, in the adjacent 2 three-dimensional combined packing units 51, the fiber bundles 513 may be transversely stretched on the ring sheet 512 along the radial direction thereof in the related process, and if L 01 is too small, the adjacent fiber bundles 513 may be entangled and knotted to damage when stretched; if L 01 is too large, the three-dimensional composite filler unit 51 is small, and the dispersion effect cannot be effectively achieved. The invention can effectively avoid the former situation by limiting the L 02+2L03≤L01≤4L02.
In one embodiment, the pulse packing 6 includes a plurality of pulse tubes 61 arranged vertically, in parallel, and in a dispersed manner, the pulse tubes 61 having a first liquid passage vertically and a second liquid passage vertically formed between adjacent pulse tubes 61.
In one embodiment, the pulse tube 61 comprises contracted segments 611 and expanded segments 612 alternately disposed along its length, adjacent contracted segments 611 and expanded segments 612 forming 1 pulse unit; the pulse tube 61 includes at least 1 of the pulse units.
In the present invention, the contracted section 611 means a portion in which the cross-sectional area decreases in order from top to bottom, and the expanded section 612 means a portion in which the cross-sectional area increases in order from top to bottom.
In one embodiment, the area of the largest cross-section in the pulse unit is 10-50 mm 2, such as 15mm 2、20 mm2、25 mm2、30 mm2、35 mm2、40 mm2 and 45 mm 2.
In one embodiment, the area ratio of the smallest cross section to the largest cross section in the pulse unit is 0.01-0.25, such as 0.03, 0.05, 0.07, 0.1, 0.13, 0.15, 0.17, 0.2, 0.22, and 0.24, effective to form a pulse.
In one embodiment, the length ratio of the expansion section 612 to the contraction section 611 is 1/3-1, such as 1/3, 3/8, 1/2, 5/8, 2/3, 3/4, 7/8, and 1; preferably less than 1 on this basis.
In the present invention, the lengths of the expansion section 612 and the contraction section 611 refer to the lengths of both along the length of the pulse tube 61.
In the present invention, when the length of the expansion section 612 is smaller, the rate of change of the velocity of the fluid in the expansion section 612 is larger, thereby improving the impulse effect.
In one embodiment, the ratio of the specific surface area of the expanded section 612 to the contracted section 611 is 1-3, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, and 2.9; preferably greater than 1 on this basis, to enable the fluid to change at a faster rate in the expansion section 612, effectively forming a pulse.
In the present invention, the specific surface area of the expansion section 612 means the surface area of the expansion section 612 per unit volume.
Those skilled in the art understand that the volume is inversely proportional to the specific surface area, the larger the volume, the smaller the specific surface area, and conversely, the smaller the volume, the larger the specific surface area. The ratio of the specific surface area of the expansion section 612 to the specific surface area of the contraction section 611 is 1-3, which indicates that the specific surface area of the expansion section 612 is greater than or equal to the specific surface area of the contraction section 611, and correspondingly, the volume of the expansion section 612 is less than or equal to the volume of the contraction section 611, so that the speed change rate of the fluid in the expansion section 612 is greater, and a pulse is effectively formed.
In one embodiment, the length of the constriction 611 is 5-15 mm, such as 6 mm, 7mm, 8mm, 9 mm, 10mm, 11 mm, 12 mm, 13 mm, and 14 mm.
In one embodiment, the contracted section 611 has a specific surface area of 1-5 m 2/m3, such as 1.5 m2/m3、2 m2/m3、2.5 m2/m3、3 m2/m3、3.5 m2/m3、4 m2/m3 and 4.5 m 2/m3.
The cross section of the pulse unit can be in any form, so as to improve the pulse effect and further improve the heat transfer and mass transfer between the gas phase, the liquid phase and the solid phase, and in one embodiment, the cross section of the pulse unit is polygonal, preferably triangular, and further preferably acute triangular.
In one embodiment, the three included angles of the acute triangle are 40-60 °, such as 45 °, 50 ° and 55 °, respectively; 50-70 °, such as 55 °, 60 °, and 65 °;60-90, such as 65 °, 70 °, 75 °, 80 °, and 85 °.
In one embodiment, the pulse tubes 61 are arranged between adjacent 2 of the catalyst beds 4 in the pulse packing 6 as follows: adjacent 3 of the pulse tubes 61 are arranged in a regular triangle, forming a minimum arrangement unit.
In one embodiment, the smallest placement unit, the placement directions of adjacent 2 of the pulse tubes 61 differ by 120 °.
The arrangement directions of the adjacent 2 pulse tubes 61 differ by 120 ° means that, in a minimum arrangement unit arranged in a regular triangle, a point where a first angle on 1 of the cross sections of a first one of the pulse tubes 61 is a, a point where a second angle adjacent thereto is B, and the directions of a to B are 0 ° directions (also 360 ° directions), and then the directions corresponding to a to B are 120 ° directions (or-120 ° directions) in a second one of the pulse tubes 61 adjacent to the first one of the pulse tubes 61; similarly, in a third one of the pulse tubes 61 adjacent to a second one of the pulse tubes 61, the corresponding a to B direction is 240 ° direction (or-240 ° direction). Corresponding to the smallest arrangement unit in a regular triangle arrangement, in which the second one of the pulse tubes 61 is rotated 120 deg. clockwise/counterclockwise about its own vertical central axis and the third one of the pulse tubes 61 is rotated 2 times 120 deg. clockwise/counterclockwise about its own vertical central axis, compared to the arrangement direction of the first one of the pulse tubes 61. The arrangement directions between every two are different by 120 degrees.
In one embodiment, the distance between adjacent 2 of the pulse tubes 61 is L 1, measured as the distance between the vertical central axes of the two, and the length of the longest side of the largest cross-section in the pulse unit is L 2, then L 1/L2 =0.5-5, such as 1, 1.5, 2, 2.5, 3, 3.5, 4, and 4.5.
In one embodiment, the material of the pulse filler 6 is any one or a combination of a plurality of plastics, metals, ceramics or glass.
In one embodiment, the aspect ratio of the catalyst bed 4 is 3 to 8, such as 4,5, 6, and 7.
The present invention also provides a method for preparing benzyl amine using the trickle bed reactor described above, the method comprising:
(1) Introducing hydrogen into the trickle bed reactor from the gas phase inlet 1 to activate the catalyst filled in the catalyst bed 4;
(2) Introducing a composite solvent dissolved with benzonitrile into the trickle bed reactor from the liquid inlet 3, carrying out catalytic hydrogenation reaction on the catalyst bed 4 and the introduced hydrogen to prepare benzyl amine, and outputting from the liquid outlet 9.
In one embodiment, the catalyst packed in the catalyst bed 4 is a nickel-based catalyst.
In a preferred embodiment, the nickel-based catalyst is a skeletal-type catalyst or a supported catalyst, and has a nickel content of 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt% and 11 wt% or more.
In one embodiment, the complex solvent comprises a combination of any two or more of tetrahydrofuran, methanol, toluene, cyclohexane, liquid ammonia, N-methylpyrrolidone.
In one embodiment, the molar ratio of benzonitrile, hydrogen, and complex solvent in the catalytic hydrogenation reaction is 1 (1-5, such as 1.5, 2, 2.5, 3, 3.5, 4, and 4.5): 1-20, such as 3, 5, 7, 11, 13, 15, 17, and 19.
In one embodiment, the catalytic hydrogenation reaction is carried out at a reaction pressure of 7 to 15 MPa, such as 8 MPa, 10 MPa, 12 MPa and 14 MPa; and/or the reaction temperature is 50-150 ℃, such as 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, 110 ℃, 120 ℃, 130 ℃ and 140 ℃.
The method for preparing the benzyl amine by utilizing the trickle bed reactor is simple and easy to operate, and the catalytic hydrogenation reaction of the benzyl cyanide catalytic hydrogenation to prepare the benzyl amine is carried out under the combined action of the three-dimensional combined filler and the pulse filler, so that the wetting degree of the catalyst is greatly improved, the flow pattern in the bed is close to the adjacent areas of trickle flow and pulse flow, the flow pattern is more stable, the phenomenon of uneven temperature and concentration distribution is avoided, the airspeed of a small test device can be improved, the data accuracy of a small test experiment is improved, and more accurate data is provided for an industrialized device; and simultaneously, the process operation condition is reduced.
Raw material sources of raw materials used in the following examples/comparative examples:
benzonitrile, > 99.99%, TCI reagent limited;
Tetrahydrofuran, > 99.99%, available from the chemical industry, inc., of Wellling;
liquid ammonia, > 99.999%, liquefied air (Shanghai) compressed gas Co., ltd;
hydrogen, 99.999%, new energy for smokestack torches limited;
Catalyst, 10% Ni/supported Al 2O3 catalyst, quick Kai catalyst.
Test methods/criteria:
The conversion rate of the benzonitrile is analyzed by adopting a liquid chromatography external standard method; wherein,
Conversion of benzonitrile= (molar amount of benzonitrile converted)/(molar amount of benzonitrile charged) ×100%;
molar yield of the benzylamine is analyzed by adopting a liquid chromatography external standard method; wherein,
Molar yield of benzylamine= (molar amount of benzylamine obtained)/(molar amount of benzonitrile charged) ×100%.
Example 1 (S1)
As shown in fig. 1-5, a trickle bed reactor A1 includes a reactor housing 10;
The reactor shell 10 is internally provided with a liquid distributor 2, at least one layer of pulse filler 6 and at least one layer of supporting plate 7 at intervals from top to bottom in sequence, and the reactor shell is internally divided into a gas cavity, at least 2 catalyst beds 4 and a liquid cavity from top to bottom in sequence; the catalyst bed layer 4 is filled with a three-dimensional combined filler 5;
The top of the reactor shell 10 is provided with a gas phase inlet 1, the bottom is provided with a liquid outlet 9, the side wall of the reactor shell is provided with a liquid inlet 3 corresponding to the liquid distributor 2, and the side wall of the reactor shell is provided with a gas outlet 8 corresponding to the liquid cavity;
The three-dimensional combined packing 5 is vertically arranged in the catalyst bed 4 and comprises a plurality of vertically, parallel and dispersedly arranged three-dimensional combined packing units 51, and a vertical third liquid channel is formed between every two adjacent 2 three-dimensional combined packing units 51;
The three-dimensional combined packing unit 51 includes a central string 511 and a ring 512; the central rope 511 is fixed to the center of the ring 512 along the central axis of the ring 512; the fiber bundles 513 are vertically arranged around the ring 512, and the plurality of fiber bundles 513 are distributed around the ring 512;
In the three-dimensional combined packing unit 51, 3 ring pieces 512 are arranged at intervals along the central rope 511; the spacing between two adjacent ring plates 512 on the central rope 511 is 120 mm;
The diameter of the central rope 511 is 12 mm;
the ring 512 has an outer diameter of 150 mm and an inner diameter of 90 mm;
the length of the fiber bundles 513 is 50 mm;
The fiber bundle 513 comprises 30 filaments having a diameter of 0.45 mm;
The spacing length of adjacent fiber bundles 513 in the circumferential direction of the ring 512 is 20 mm;
In the three-dimensional combined packing 5, a plurality of three-dimensional combined packing units 51 are arranged in a square grid in the catalyst bed layer 4;
The spacing distance between every two adjacent 2 three-dimensional combined packing units 51 along the square grid is marked as L 01 according to the distance between the vertical central axes of the two three-dimensional combined packing units, the outer diameter of the annular sheet 512 is marked as L 02, the length of the fiber bundle 513 is marked as L 03, and then L 01= L02+2L03;
Wherein the pulse packing 6 comprises a plurality of pulse tubes 61 which are vertically, parallelly and dispersedly arranged, the pulse tubes 61 are provided with vertical first liquid channels, and vertical second liquid channels are formed between adjacent pulse tubes 61;
The pulse tube 61 includes a contraction section 611 and an expansion section 612 alternately arranged along a length direction thereof, and adjacent contraction section 611 and expansion section 612 form 1 pulse unit; the pulse tube 61 includes 1 of the pulse units;
The area of the maximum cross section in the pulse unit is 25 mm 2;
The area ratio of the minimum cross section to the maximum cross section in the pulse unit is 0.09;
the length ratio of the expansion section 612 to the contraction section 611 is 2/3;
the ratio of the specific surface area of the expansion section 612 to the contraction section 611 is 1.1;
the length of the constriction 611 is 9 mm;
the specific surface area of the constriction 611 is 1.6 m 2/m3;
The cross section of the pulse unit is in a regular triangle;
In the pulse packing 6, the pulse tubes 61 are arranged between adjacent 2 of the catalyst beds 4 in the following manner: adjacent 3 pulse tubes 61 are arranged in a regular triangle, forming a minimum arrangement unit;
the pulse filler 6 is made of stainless steel;
The height-to-diameter ratio of the catalyst bed 4 is 5, and the diameter is 400 mm.
The preparation of benzyl amine B1 using the trickle bed reactor A1 described above comprises:
(1) Introducing hydrogen into the trickle bed reactor from the gas phase inlet 1 to activate the catalyst filled in the catalyst bed 4;
(2) Introducing a composite solvent dissolved with benzonitrile into the trickle bed reactor from the liquid inlet 3, carrying out catalytic hydrogenation reaction on the catalyst bed 4 and the introduced hydrogen to prepare benzyl amine B1, and outputting from the liquid outlet 9;
wherein the catalyst filled in the catalyst bed layer 4 is 10% Ni/supported Al 2O3 catalyst;
The composite solvent is a composite solvent of tetrahydrofuran and liquid ammonia, and the mass ratio of the tetrahydrofuran to the liquid ammonia is 2:1;
In the catalytic hydrogenation reaction, the molar ratio of the benzonitrile to the hydrogen to the composite solvent is 1:3:10;
In the catalytic hydrogenation reaction, the reaction pressure is 7 MPa, and the reaction temperature is 70 ℃.
The benzylamine B1 from the liquid outlet 9 was analyzed by the liquid chromatography external standard method, and the analysis results are shown in table 1.
Example 2 (S2)
A trickle bed reactor A2 which differs from the trickle bed reactor A1 described in example 1 only in that:
In the three-dimensional combined packing 5,
The spacing between two adjacent ring plates 512 on the central rope 511 is 100 mm;
the diameter of the central rope 511 is 10 mm;
the ring 512 has an outer diameter of 100 mm and an inner diameter of 60 mm;
the length of the fiber bundles 513 is 20 mm;
The fiber bundle 513 comprises 20 filaments having a diameter of 0.35 mm;
the spacing length of the adjacent fiber bundles 513 in the circumferential direction thereof on the ring 512 is 10 mm;
In the pulse filler 6 of the present invention,
The area ratio of the minimum cross section to the maximum cross section in the pulse unit is 0.01;
The length ratio of the expansion section 612 to the contraction section 611 is 1/3;
The ratio of the specific surface area of the expanded section 612 to the contracted section 611 is 1.4.
Benzyl amine B2 was prepared as in example 1 using the trickle bed reactor A2 described above.
The obtained benzylamine B2 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 3 (S3)
A trickle bed reactor A3 which differs from the trickle bed reactor A1 described in example 1 only in that:
In the three-dimensional combined packing 5,
The spacing between two adjacent ring plates 512 on the central rope 511 is 150 mm;
The diameter of the central rope 511 is 15 mm;
the ring 512 has an outer diameter of 200 mm and an inner diameter of 120 mm;
The length of the fiber bundles 513 is 80 mm;
the fiber bundle 513 comprises 50 fibers having a diameter of 0.55 mm;
The spacing length of adjacent fiber bundles 513 in the circumferential direction of the ring 512 is 50 mm;
In the pulse filler 6 of the present invention,
The area ratio of the minimum cross section to the maximum cross section in the pulse unit is 0.25;
the length ratio of the expansion section 612 to the contraction section 611 is 1;
The ratio of the specific surface area of the expansion section 612 to the contraction section 611 is 1.
Benzyl amine B3 was prepared as in example 1 using the trickle bed reactor A3 described above; and differs from embodiment 1 only in that:
The obtained benzylamine B3 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 4 (S4)
A trickle bed reactor A4 which differs from the trickle bed reactor A1 described in example 1 only in that:
In the three-dimensional combined packing 5,
The spacing between two adjacent ring plates 512 on the central rope 511 is 80 mm;
the diameter of the central rope 511 is 8 mm;
the ring 512 has an outer diameter of 80 mm and an inner diameter of 50 mm;
the length of the fiber bundles 513 is 15 mm;
the fiber bundle 513 comprises 7 filaments having a diameter of 0.3 mm;
The spacing length of the adjacent fiber bundles 513 in the circumferential direction thereof on the ring 512 is 8 mm;
In the pulse filler 6 of the present invention,
The area ratio of the minimum cross section to the maximum cross section in the pulse unit is 0.008;
The length ratio of the expansion section 612 to the contraction section 611 is 1/4;
The ratio of the specific surface area of the expanded section 612 to the contracted section 611 is 0.9.
Benzyl amine B4 was prepared as in example 1 using the trickle bed reactor A4 described above.
The obtained benzylamine B4 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 5 (S5)
A trickle bed reactor A5 differing from the trickle bed reactor A1 described in example 1 only in that:
In the three-dimensional combined packing 5,
The spacing between two adjacent ring plates 512 on the central rope 511 is 160 mm;
the diameter of the central rope 511 is 18 mm;
The ring 512 has an outer diameter of 220 mm and an inner diameter of 140 mm;
the length of the fiber bundles 513 is 90 mm;
the fiber bundle 513 comprises 50 fibers having a diameter of 0.6 mm;
the spacing length of adjacent fiber bundles 513 in the circumferential direction of the ring 512 is 60 mm;
In the pulse filler 6 of the present invention,
The area ratio of the minimum cross section to the maximum cross section in the pulse unit is 0.3;
The length ratio of the expanded section 612 to the contracted section 611 is 1.2;
the ratio of the specific surface area of the expanded section 612 to the contracted section 611 is 3.2.
Benzyl amine B5 was prepared as in example 1 using the trickle bed reactor A5 described above; and differs from embodiment 1 only in that:
the obtained benzylamine B5 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 6 (S6)
A trickle bed reactor A6 which differs from the trickle bed reactor A1 described in example 1 only in that:
The cross section of the pulse unit is square.
Benzyl amine B6 was prepared as in example 1 using the trickle bed reactor A6 described above.
The obtained benzylamine B6 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 7 (S7)
Benzyl amine B7 was prepared as in example 1 using the trickle bed reactor A1 described above; and differs from embodiment 1 only in that:
in the catalytic hydrogenation reaction, the reaction pressure is 8 MPa, and the reaction temperature is 80 ℃.
The obtained benzylamine B7 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 8 (S8)
A trickle bed reactor A8 differing from the trickle bed reactor A1 described in example 1 only in that:
The cross section of the pulse unit is a right triangle, and the angles of the three included angles are 30 degrees, 60 degrees and 90 degrees respectively.
Benzyl amine B8 was prepared as in example 1 using the trickle bed reactor A8 described above.
The obtained benzylamine B8 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 9 (S9)
A trickle bed reactor A9 which differs from the trickle bed reactor A1 described in example 1 only in that:
In the three-dimensional combined packing 5,
The spacing between two adjacent ring plates 512 on the central rope 511 is 150 mm;
the spacing length of adjacent fiber bundles 513 in the circumferential direction of the ring 512 is 30 mm;
In the three-dimensional combined packing 5, a plurality of three-dimensional combined packing units 51 are arranged in a square grid in the catalyst bed layer 4;
the spacing distance between every two adjacent 2 three-dimensional combined packing units 51 along the square grid is L 01, the outer diameter of the ring sheet 512 is L 02, and the length of the fiber bundle 513 is L 03, then L 01=4L02.
Benzyl amine B9 was prepared as in example 1 using the trickle bed reactor A9 described above.
The obtained benzylamine B9 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Example 10 (S10)
A trickle bed reactor a10 differing from the trickle bed reactor A1 described in example 1 only in that:
In the three-dimensional combined packing 5, a plurality of three-dimensional combined packing units 51 are arranged in a triangular grid in the catalyst bed 4;
The spacing distance between every two adjacent 2 three-dimensional combined packing units 51 along the triangular mesh is L 01, the outer diameter of the ring sheet 512 is L 02, and the length of the fiber bundle 513 is L 03, then L 01=3L02.
The trickle bed reactor A10 was used as described above in the method of example 1; and (3) preparing the phenylmethylamine B10.
The obtained benzylamine B10 was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Comparative example 1 (D1)
A trickle bed reactor A1', which differs from the trickle bed reactor A1 described in example 1 only in that:
the catalyst bed layer 4 is not filled with the three-dimensional combined packing 5.
Benzyl amine B1 'was prepared in the same manner as in example 1 using the trickle bed reactor A1'.
The obtained benzylamine B1' was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Comparative example 2 (D2)
A trickle bed reactor A2' which differs from the trickle bed reactor A1 described in example 1 only in that:
the pulse packing 6 is not arranged between 2 adjacent catalyst beds 4 in the reactor shell 10.
Benzyl amine B2 'was prepared as in example 1 using the trickle bed reactor A2' described above.
The obtained benzylamine B2' was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
Comparative example 3 (D3)
Trickle bed reactor A3', which differs from trickle bed reactor A1 described in example 1 only in that:
the catalyst bed layer 4 is not filled with the three-dimensional combined packing 5;
the pulse packing 6 is not arranged between 2 adjacent catalyst beds 4 in the reactor shell 10.
Benzyl amine B3 'was prepared as in example 1 using the trickle bed reactor A3' described above.
The obtained benzylamine B3' was analyzed by a liquid chromatography external standard method, and the analysis results are shown in Table 1.
In examples 1 to 10 and comparative examples 1 to 3, the liquid phase material from the liquid outlet 9 was analyzed by a liquid chromatography external standard method in the catalytic hydrogenation reaction, respectively, and the analysis results are shown in Table 1.
Analytical results of the catalytic hydrogenation reactions described in Table 1
As can be seen from the comparison of examples 1-10 and comparative examples 1-3 and the data in Table 1, when using the trickle bed reactor according to the present invention and preparing benzylamine according to the method of the present invention, the conversion rate of benzonitrile and the molar yield of benzylamine are both high;
As can be seen from a comparison of example 1 and comparative example 1, when the trickle bed reactor of the present invention is used and the catalyst bed 4 is filled with the three-dimensional combined packing 5, the conversion rate of benzonitrile and the molar yield of benzyl amine are significantly improved;
As can be seen from a comparison of example 1 and comparative example 2, when the trickle bed reactor according to the present invention is used and the pulse packing 6 is not disposed between the adjacent 2 catalyst beds 4 in the reactor shell 10, the conversion rate of benzonitrile and the molar yield of benzyl amine are significantly improved;
As can be seen from a comparison of example 1 and comparative example 3, the trickle bed reactor according to the present invention was used, and the three-dimensional combined packing 5 and the pulse packing 6 in the trickle bed reactor were used together, and both the conversion rate of benzonitrile and the molar yield of benzonitrile were significantly improved when the benzonitrile was prepared according to the method of the present invention;
As can be seen from the comparison of example 1 with comparative examples 1-2 and comparative example 3, if only one of the three-dimensional combined packing 5 and the pulse packing 6 is used in the trickle bed reactor, but the other is not used in combination with the trickle bed reactor, the conversion rate of the benzonitrile and the molar yield of the benzyl amine are obviously reduced; if neither the trickle bed reactor solid combined packing 5 nor the pulse packing 6 is provided, the conversion rate of benzonitrile and the molar yield of benzyl amine are significantly reduced.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not intended to limit the invention. Those skilled in the art will appreciate that many modifications and adaptations of the invention are possible and can be made with the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (10)
1. Trickle bed reactor, characterized in that it comprises a reactor shell (10);
a liquid distributor (2), at least one layer of pulse filler (6) and at least one layer of supporting plate (7) are sequentially arranged in the reactor shell (10) at intervals from top to bottom, and the reactor shell (10) is sequentially divided into a gas cavity, at least 2 catalyst beds (4) and a liquid cavity from top to bottom; the catalyst bed (4) is filled with a three-dimensional combined filler (5);
The top of the reactor shell (10) is provided with a gas phase inlet (1), the bottom is provided with a liquid outlet (9), the side wall of the reactor shell is provided with a liquid inlet (3) corresponding to the liquid distributor (2), and the side wall of the reactor shell is provided with a gas outlet (8) corresponding to the liquid cavity;
the three-dimensional combined packing (5) is vertically arranged in the catalyst bed (4) and comprises a plurality of three-dimensional combined packing units (51) which are vertically, parallelly and dispersedly arranged, and a vertical third liquid channel is formed between every two adjacent three-dimensional combined packing units (51);
the three-dimensional combined packing unit (51) comprises a central rope (511) and a ring piece (512); the center rope (511) is arranged along the center axis of the ring piece (512) in a penetrating way and fixed at the center of the ring piece (512); fiber bundles (513) are vertically arranged on the periphery of the annular sheet (512), and the plurality of fiber bundles (513) are distributed and arranged on the periphery of the annular sheet (512).
2. The trickle bed reactor according to claim 1, wherein,
In the three-dimensional combined packing unit (51), a plurality of ring sheets (512) are arranged at intervals along the central rope (511); and/or the number of the groups of groups,
The diameter of the central rope (511) is 10-15 mm; and/or the number of the groups of groups,
The outer diameter of the ring piece (512) is 100-200 mm, and the inner diameter is 60-120 mm; and/or the number of the groups of groups,
The length of the fiber bundles (513) is 20-80 mm.
3. The trickle bed reactor according to claim 1, wherein,
The fiber bundle (513) comprises 20-50 fibers; and/or the number of the groups of groups,
The spacing length of adjacent fiber bundles (513) on the ring sheet (512) along the circumferential direction is 10-50 mm.
4. Trickle bed reactor according to claim 1, characterized in that in the three-dimensional combined packing (5) a plurality of the three-dimensional combined packing units (51) are arranged in a square grid within the catalyst bed (4).
5. The trickle bed reactor according to claim 4, wherein the spacing distance between adjacent 2 of said three-dimensional combined packing units (51) along a square grid is denoted as L 01, the outer diameter of said ring sheet (512) is denoted as L 02, the length of said fiber bundles (513) is denoted as L 03, then L 02+2L03≤L01≤4L02, in terms of the distance between the vertical central axes of both.
6. Trickle bed reactor according to claim 1, wherein the pulse filler (6) comprises a plurality of pulse tubes (61) arranged vertically, parallel and in a dispersed manner, the pulse tubes (61) having a first vertical liquid channel and a second vertical liquid channel being formed between adjacent pulse tubes (61).
7. The trickle bed reactor according to claim 6, wherein,
The pulse tube (61) comprises contraction sections (611) and expansion sections (612) alternately arranged along the length direction, and the adjacent contraction sections (611) and expansion sections (612) form 1 pulse unit; said pulse tube (61) comprising at least 1 said pulse unit; and/or the number of the groups of groups,
In the pulse packing (6), the pulse tubes (61) are arranged between adjacent 2 of the catalyst beds (4) in the following manner: adjacent 3 pulse tubes (61) are arranged in a regular triangle, forming a minimum arrangement unit.
8. Trickle bed reactor according to claim 1, characterized in that the catalyst bed (4) has an aspect ratio of 3-8.
9. A method of preparing benzyl amine using the trickle bed reactor of any one of claims 1-8, comprising:
(1) Introducing hydrogen gas from the gas phase inlet (1) into the trickle bed reactor to activate the catalyst filled in the catalyst bed (4);
(2) Introducing a composite solvent dissolved with benzonitrile into the trickle bed reactor from the liquid inlet (3), carrying out catalytic hydrogenation reaction on the catalyst bed (4) and the introduced hydrogen to prepare the benzyl amine, and outputting the benzyl amine from the liquid outlet (9).
10. The method of claim 9, wherein the step of providing the first layer comprises,
In the catalytic hydrogenation reaction, the molar ratio of the benzonitrile to the hydrogen to the composite solvent is 1 (1-5) (1-20); and/or the number of the groups of groups,
In the catalytic hydrogenation reaction, the reaction pressure is 7-15 MPa, and/or the reaction temperature is 50-150 ℃; and/or the number of the groups of groups,
The compound solvent comprises any two or more of tetrahydrofuran, methanol, toluene, cyclohexane, liquid ammonia and N-methyl pyrrolidone; and/or the number of the groups of groups,
The catalyst filled in the catalyst bed layer (4) is a nickel catalyst.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3446764A1 (en) * | 2017-08-23 | 2019-02-27 | JULIUS MONTZ GmbH | Material exchange machine |
| CN110818069A (en) * | 2019-11-27 | 2020-02-21 | 徐州百世松岗环保科技发展有限公司 | Environment-friendly combined filler for sewage treatment |
| CN112591879A (en) * | 2020-12-31 | 2021-04-02 | 徐州达娇物资贸易有限公司 | Direction-changing drainage type sewage treatment combined filler |
| CN114471379A (en) * | 2022-02-10 | 2022-05-13 | 万华化学集团股份有限公司 | Trickle bed reactor with elastic filler and method for preparing 1, 3-cyclohexyldimethylamine by using trickle bed reactor |
| CN116637561A (en) * | 2023-05-29 | 2023-08-25 | 万华化学集团股份有限公司 | Trickle bed reactor and method for preparing m-xylylenediamine by using same |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3446764A1 (en) * | 2017-08-23 | 2019-02-27 | JULIUS MONTZ GmbH | Material exchange machine |
| CN110818069A (en) * | 2019-11-27 | 2020-02-21 | 徐州百世松岗环保科技发展有限公司 | Environment-friendly combined filler for sewage treatment |
| CN112591879A (en) * | 2020-12-31 | 2021-04-02 | 徐州达娇物资贸易有限公司 | Direction-changing drainage type sewage treatment combined filler |
| CN114471379A (en) * | 2022-02-10 | 2022-05-13 | 万华化学集团股份有限公司 | Trickle bed reactor with elastic filler and method for preparing 1, 3-cyclohexyldimethylamine by using trickle bed reactor |
| CN116637561A (en) * | 2023-05-29 | 2023-08-25 | 万华化学集团股份有限公司 | Trickle bed reactor and method for preparing m-xylylenediamine by using same |
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