CN113877487B - Fluidized bed device and method for m-xylene ammoxidation - Google Patents
Fluidized bed device and method for m-xylene ammoxidation Download PDFInfo
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- CN113877487B CN113877487B CN202111341229.8A CN202111341229A CN113877487B CN 113877487 B CN113877487 B CN 113877487B CN 202111341229 A CN202111341229 A CN 202111341229A CN 113877487 B CN113877487 B CN 113877487B
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- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 238000000034 method Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000000463 material Substances 0.000 claims abstract description 82
- BOHCMQZJWOGWTA-UHFFFAOYSA-N 3-methylbenzonitrile Chemical compound CC1=CC=CC(C#N)=C1 BOHCMQZJWOGWTA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 62
- 239000003054 catalyst Substances 0.000 claims description 58
- 238000000926 separation method Methods 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 35
- 229910021529 ammonia Inorganic materials 0.000 claims description 30
- 239000007795 chemical reaction product Substances 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 abstract description 19
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006900 dealkylation reaction Methods 0.000 abstract description 6
- 229920006391 phthalonitrile polymer Polymers 0.000 abstract description 5
- 230000020335 dealkylation Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 68
- 239000002994 raw material Substances 0.000 description 10
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- OQHXZZGZASQSOB-UHFFFAOYSA-N 3,4,5,6-tetrachlorobenzene-1,2-dicarbonitrile Chemical compound ClC1=C(Cl)C(Cl)=C(C#N)C(C#N)=C1Cl OQHXZZGZASQSOB-UHFFFAOYSA-N 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
-
- 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
- B01J8/005—Separating solid material from the gas/liquid stream
-
- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1836—Heating and cooling the reactor
-
- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
- B01J8/28—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations the one above the other
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a fluidized bed device for ammoxidation of metaxylene, wherein a porous distribution plate is arranged in the fluidized bed device and divides the fluidized bed device into two filler sections; the first reaction filling section and the second reaction filling section are sequentially arranged from bottom to top; the upper part of the first reaction filling section is provided with a first material inlet which is connected with a first material distribution assembly; a first heat exchange assembly is arranged between the first material inlet and the first material distribution assembly; the bottom of second reaction filler section sets up second material distribution subassembly, the top of porous distribution board sets up second heat transfer subassembly. According to the invention, the material distribution assembly of the m-methylbenzonitrile is arranged, so that the generation of the intermediate methylbenzonitrile in the reaction is reduced, the separated m-methylbenzonitrile can be reacted again, and the meta-xylene is fed in a sectional manner, so that the dealkylation of the meta-xylene is inhibited, the content of the benzonitrile is reduced, and the yield of the m-phthalonitrile is further improved.
Description
Technical Field
The invention belongs to the technical field of chemical process and equipment, and particularly relates to a fluidized bed device and a fluidized bed method for ammoxidation of m-xylene.
Background
Isophthalonitrile (IPN) is an important organic synthesis raw material, is a key intermediate for preparing chlorothalonil (tetrachlorophthalonitrile, a broad-spectrum, low-toxicity and high-efficiency herbicide), and can be used as a raw material of products such as plastics, synthetic fibers, epoxy resin curing agents and the like.
The method for synthesizing isophthalonitrile is that metaxylene is prepared by ammoxidation reaction with ammonia and oxygen under the action of a catalyst, and the principle is that a metal oxide catalyst is adopted to react with metaxylene, air and ammonia at 400-450 ℃, wherein the air is an oxidizing medium, and the metaxylene and the ammonia have reducibility and need to be respectively introduced and adsorbed on the catalyst to react. Since the reaction is a strongly exothermic reaction, a fluidized bed reactor is generally used to control the reaction temperature. However, since the reaction of air with ammonia and the like is severe, a large amount of meta-xylene and ammonia in the reaction are converted into CO, CO 2 Resulting in a yield of the target product (isophthalonitrile) of less than 78%; meanwhile, as the gas-solid back mixing in the fluidized bed and the conversion of the intermediate product are incomplete, part of the intermediate product directly escapes from the reactor, the separation difficulty of the product is increased by the impurity, and the yield of the target product is reduced.
CN204434527U discloses a production device for improving the yield of isophthalonitrile, the device comprises a liquid ammonia tank, an evaporator, a primary evaporator, an ammonia buffer tank, a meta-xylene overhead tank, a vaporizer, a static mixer, a fluidized bed and a condenser, wherein the static mixer is additionally arranged between the vaporizer and the fluidized bed reactor, so that vaporized ammonia gas and meta-xylene are mixed in the static mixer in advance, the residence time and the contact area of the material in the fluidized bed are improved, and the yield of isophthalonitrile is further improved.
However, the reaction is strong in heat release and high in temperature, and the oxidation state of the catalyst is dominant in the oxygen-containing atmosphere, so that meta-xylene has dealkylation behavior in the reaction process, thus generating benzonitrile byproducts, and increasing the separation difficulty and the separation cost.
Therefore, there is a need to develop a new fluidized bed apparatus and method for ammoxidation of meta-xylene, which can solve the above problems, and at the same time, improve the conversion of meta-xylene and reduce the production cost.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a fluidized bed device and a method for ammoxidation of m-xylene, wherein the fluidized bed device is provided with a material distribution assembly of byproduct-m-methylbenzonitrile so as to fully convert the byproduct; by setting the meta-xylene sectional feed, the raw material distribution of the second reaction filler section is changed, the reducibility of the catalyst is increased, the excessive oxidation of the catalyst at high temperature and in a high oxygen content state is inhibited, the dealkylation of the meta-xylene is inhibited, and the generation of byproduct-benzonitrile is reduced.
In order to achieve the technical effects, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a fluidized bed apparatus for ammoxidation of meta-xylene, said fluidized bed apparatus having a porous distribution plate disposed therein, said porous distribution plate dividing the fluidized bed apparatus into two packing segments; the first reaction filling section and the second reaction filling section are sequentially arranged from bottom to top;
the bottom of the fluidized bed device is provided with a gas inlet, and a gas distribution assembly is arranged above the gas inlet;
the upper part of the first reaction filling section is provided with a first material inlet which is connected with a first material distribution assembly, and the first material distribution assembly is arranged above the gas distribution assembly;
a first heat exchange assembly is arranged between the first material inlet and the first material distribution assembly;
a second material distribution assembly is arranged at the bottom of the second reaction filling section, and a second material inlet is formed in the second material distribution assembly;
the side wall of the second reaction filler section is provided with a catalyst inlet;
a second heat exchange assembly is arranged above the porous distribution plate and is positioned below the catalyst inlet;
the top of the second reaction filling section is provided with a gas-solid separation assembly, and the gas-solid separation assembly is connected with a gas outlet arranged at the top of the fluidized bed device.
The device can reduce gas back mixing in the fluidized bed, and the two heat exchange assemblies can control the activity of the catalyst more flexibly.
The fluidized bed device is divided into two filler sections, and by arranging the material distribution assembly of the m-methylbenzonitrile, the generation of byproducts (m-methylbenzonitrile) in the reaction can be reduced, the separated m-methylbenzonitrile can be reacted again, and the yield of target products is improved; by setting the meta-xylene sectional feeding, the raw material distribution of the second reaction filler section is changed, the meta-xylene dealkylation reaction is inhibited, the content of byproducts (benzonitrile) is reduced, and the yield of target products is further improved.
In a preferred embodiment of the present invention, the distance between the upper end of the gas distribution assembly and the lower end of the first material distribution assembly is 2-9% of the diameter of the fluidized bed apparatus, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc., but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In a preferred embodiment of the present invention, the distance between the lower end of the second material distribution element and the adjacent porous distribution plate below the lower end is 2-9% of the diameter of the fluidized bed device, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In a preferred embodiment of the present invention, the distance between the lowermost end of the gas-solid separation module and the upper end of the gas distribution module is 0.01 to 0.03% of the diameter of the fluidized bed apparatus, and may be, for example, 0.01%, 0.014%, 0.018%, 0.022%, 0.026% or 0.03%, etc., but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
As a preferred embodiment of the present invention, the heat exchange area ratio of the first heat exchange component to the second heat exchange component is 5-20, and may be, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, etc., but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In a second aspect, the present invention provides a use of a fluidised bed apparatus as described in the first aspect for the ammoxidation of meta-xylene, said use comprising the steps of:
(1) Loading a catalyst from a catalyst inlet, introducing heated gas from a gas inlet through a gas distribution assembly, and heating the catalyst to 350-400 ℃;
(2) Introducing m-xylene and ammonia from a first material inlet, reacting with the gas and the catalyst in the step (1), controlling the reaction temperature through a first heat exchange assembly, and discharging and separating the obtained reaction product through a gas-solid separation assembly and a gas outlet;
(3) Introducing m-xylene and m-methylbenzonitrile into the reactor from a second material inlet, carrying part of catalyst to a porous distribution plate by the gas flow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature through a second heat exchange assembly, and discharging and separating the obtained reaction product through a gas-solid separation assembly and a gas outlet.
As a preferred technical scheme of the invention, the application further comprises that the gas flow generated by the reaction in the step (2) brings part of the catalyst to the top of the fluidized bed, and the catalyst is returned to the gas distribution assembly through the gas-solid separation assembly and is reused in the step (2).
In the invention, after the obtained reaction product is separated, the byproduct-m-methylbenzonitrile obtained by separation is taken as a reaction raw material, and is introduced into a second material inlet for reaction.
As a preferred embodiment of the present invention, the gas in step (1) includes air.
Preferably, the reaction temperature in the step (2) is controlled to be 410-450 ℃, for example, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃ or the like, but the method is not limited to the listed values, and other non-listed values in the range of values are equally applicable.
Preferably, the molar ratio of meta-xylene to ammonia of step (2) is 1: (3-10), for example, may be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, etc., but are not limited to the recited values, as are other non-recited values within the range of values.
Preferably, the volume ratio of ammonia to gas in step (2) is 1: (3-12), for example, may be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, or 1:12, etc., but are not limited to the recited values, as are other non-recited values within the range of values.
Preferably, the load of meta-xylene is 0.01 to 0.3 kg/kgcat.h, for example, 0.01 kg/kgcat.h, 0.05 kg/kgcat.h, 0.1 kg/kgcat.h, 0.15 kg/kgcat.h, 0.2 kg/kgcat.h, 0.25 kg/kgcat.h or 0.3 kg/kgcat.h, etc., but the values are not limited to the listed values, and other values not listed in the numerical range are equally applicable.
In a preferred embodiment of the present invention, the reaction temperature in the step (3) is controlled to be 410 to 420 ℃, for example, 410 ℃, 412 ℃, 414 ℃, 416 ℃, 418 ℃, 420 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
As a preferable technical scheme of the invention, the mass ratio of the meta-xylene in the step (2) to the meta-xylene in the step (3) is (10-20): 1, for example, may be 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, or 20:1, etc., but are not limited to the recited values, as are other non-recited values within the range of values.
Compared with the prior art, the invention has the following beneficial effects:
(1) The device can reduce gas back mixing in the fluidized bed, increase the conversion rate of m-xylene, and the two heat exchange assemblies can control the activity of the catalyst more flexibly;
(2) The device is provided with the material distribution component of the m-methylbenzonitrile, so that the generation of the intermediate methylbenzonitrile in the reaction can be reduced, the separated m-methylbenzonitrile can be reacted again, and the yield of m-phthalonitrile is improved;
(3) The device provided by the invention is provided with the meta-xylene sectional feed, so that the dealkylation reaction of the meta-xylene is inhibited, the content of the benzonitrile is reduced, and the yield of the meta-phthalonitrile is further improved;
(4) The isophthalonitrile prepared by the method has the advantages of high yield of 80%, high product purity and low byproduct content.
Drawings
FIG. 1 is a schematic diagram of a fluidized bed apparatus for ammoxidation of meta-xylene provided by the present invention.
Wherein: 1-a fluidized bed; 2-gas inlet; 3-a gas distribution assembly; 4-a first material inlet; 5-a first material distribution assembly; 6-a first heat exchange assembly; 7-a second material distribution assembly; 8-porous distribution plate; 9-a second heat exchange assembly; 10-catalyst inlet; 11-a gas-solid separation assembly; 12-gas outlet.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides a fluidized bed device for ammoxidation of metaxylene, as shown in fig. 1, a porous distribution plate 8 is arranged in the fluidized bed 1 device, and the porous distribution plate 8 divides the fluidized bed 1 device into two filler sections; the first reaction filling section and the second reaction filling section are sequentially arranged from bottom to top.
The bottom of the fluidized bed 1 device is provided with a gas inlet 2, and a gas distribution assembly 3 is arranged above the gas inlet 2; the upper part of the first reaction filling section is provided with a first material inlet 4, the first material inlet 4 is connected with a first material distribution assembly 5, and the first material distribution assembly 5 is arranged above the gas distribution assembly 3; a first heat exchange assembly 6 is arranged between the first material inlet 4 and the first material distribution assembly 5; a second material distribution assembly 7 is arranged at the bottom of the second reaction filling section, and a second material inlet is formed in the second material distribution assembly 7; the side wall of the second reaction filler section is provided with a catalyst inlet 10; a second heat exchange assembly 9 is arranged above the porous distribution plate 8, and the second heat exchange assembly 9 is positioned below the catalyst inlet 10; the top of the second reaction filling section is provided with a gas-solid separation assembly 11, and the gas-solid separation assembly 11 is connected with a gas outlet 12 arranged at the top of the fluidized bed 1 device.
The distance between the upper end of the gas distribution assembly 3 and the lower end of the first material distribution assembly 5 is 2% of the diameter of the fluidized bed 1.
The distance between the lower end of the second material distribution element 7 and the adjacent porous distribution plate 8 below the lower end is 9% of the diameter of the device of the fluidized bed 1.
The distance between the lowest end of the gas-solid separation assembly 11 and the upper end of the gas distribution assembly 3 is 0.01% of the diameter of the device of the fluidized bed 1.
The heat exchange area ratio of the first heat exchange component 6 to the second heat exchange component 9 is 5.
Example 2
The difference between this embodiment and embodiment 1 is that the distance between the upper end of the gas distribution assembly 3 and the lower end of the first material distribution assembly 5 is 9% of the diameter of the fluidized bed 1; the distance between the lower end of the second material distribution assembly 7 and the porous distribution plate 8 adjacent to the lower end of the second material distribution assembly is 2% of the diameter of the fluidized bed 1; the distance between the lowest end of the gas-solid separation assembly 11 and the upper end of the gas distribution assembly 3 is 0.03% of the diameter of the device of the fluidized bed 1; the heat exchange area ratio of the first heat exchange assembly 6 to the second heat exchange assembly 9 is 20, and other conditions are the same as those of the embodiment 1.
Example 3
The difference between this embodiment and embodiment 1 is that the distance between the upper end of the gas distribution assembly 3 and the lower end of the first material distribution assembly 5 is 5% of the diameter of the fluidized bed 1; the distance between the lower end of the second material distribution assembly 7 and the porous distribution plate 8 adjacent to the lower end of the second material distribution assembly is 4% of the diameter of the fluidized bed 1; the distance between the lowest end of the gas-solid separation assembly 11 and the upper end of the gas distribution assembly 3 is 0.02% of the diameter of the device of the fluidized bed 1; the heat exchange area ratio of the first heat exchange assembly 6 to the second heat exchange assembly 9 is 12, and other conditions are the same as those of the embodiment 1.
Example 4
The difference between this embodiment and embodiment 1 is that the distance between the upper end of the gas distribution assembly 3 and the lower end of the first material distribution assembly 5 is 3% of the diameter of the fluidized bed 1; the distance between the lower end of the second material distribution assembly 7 and the porous distribution plate 8 adjacent to the lower end of the second material distribution assembly is 6% of the diameter of the fluidized bed 1; the distance between the lowest end of the gas-solid separation assembly 11 and the upper end of the gas distribution assembly 3 is 0.015 percent of the diameter of the device of the fluidized bed 1; the heat exchange area ratio of the first heat exchange assembly 6 to the second heat exchange assembly 9 is 15, and other conditions are the same as those of the embodiment 1.
Example 5
The difference between this embodiment and embodiment 1 is that the distance between the upper end of the gas distribution assembly 3 and the lower end of the first material distribution assembly 5 is 3.5% of the diameter of the fluidized bed 1; the distance between the lower end of the second material distribution assembly 7 and the porous distribution plate 8 adjacent to the lower end of the second material distribution assembly is 4.5 percent of the diameter of the device of the fluidized bed 1; the distance between the lowest end of the gas-solid separation assembly 11 and the upper end of the gas distribution assembly 3 is 0.025% of the diameter of the device of the fluidized bed 1; the heat exchange area ratio of the first heat exchange assembly 6 to the second heat exchange assembly 9 is 17, and other conditions are the same as those of the embodiment 1.
Application example 1
Application example the fluidized bed apparatus provided in example 1 was used for the ammoxidation of meta-xylene, said application comprising the steps of:
(1) Loading the catalyst from a catalyst inlet 10, introducing heated air from a gas inlet through a gas distribution assembly 3, and heating the catalyst to 360 ℃;
(2) Introducing m-xylene and ammonia from a first material inlet 4, controlling the load of the m-xylene to be 0.02kg/kgcat h, reacting with the air and the catalyst in the step (1), controlling the reaction temperature to be 420 ℃ through a first heat exchange assembly 6, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the molar ratio of the m-xylene to the ammonia is 1:5, the volume ratio of ammonia to air is 1:8, 8;
(3) Introducing m-xylene and m-methylbenzonitrile from a second material inlet, carrying part of catalyst to a porous distribution plate 8 by airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature to be 412 ℃ through a second heat exchange assembly 9, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the mass ratio of the m-xylene in the step (2) to the m-xylene in the step (3) is 20:1, a step of;
(4) The gas flow generated by the reaction in the step (2) brings part of the catalyst to the top of the fluidized bed 1, and returns to the gas distribution assembly 3 through the gas-solid separation assembly 11 for reuse in the step (2);
(5) And (3) separating the reaction products obtained in the step (2) and the step (3), and then introducing the separated byproduct-m-methylbenzonitrile serving as a reaction raw material through a second material inlet for reaction.
Application example 2
The present application example differs from application example 1 only in that the load of the meta-xylene in step (2) is 0.3kg/kgcat h, the reaction temperature of the first heat exchange assembly in step (2) is controlled to be 450 ℃, and the molar ratio of the meta-xylene to ammonia in step (2) is 1:10, the volume ratio of ammonia to air in the step (2) is 1:3, the mass ratio of the meta-xylene in the step (2) to the meta-xylene in the step (3) is 10:1, and the other conditions were the same as in application example 1.
Application example 3
Application example the fluidized bed apparatus provided in example 2 was used for the ammoxidation of meta-xylene, said application comprising the steps of:
(1) Loading a catalyst from a catalyst inlet 10, introducing heated air from a gas inlet 2 through a gas distribution assembly 3, and heating the catalyst to 380 ℃;
(2) Introducing m-xylene and ammonia from a first material inlet 4, controlling the load of the m-xylene to be 0.03kg/kgcat h, reacting with the air and the catalyst in the step (1), controlling the reaction temperature to be 410 ℃ through a first heat exchange assembly 6, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the molar ratio of the m-xylene to the ammonia is 1:6, the volume ratio of ammonia to air is 1:6, preparing a base material;
(3) Introducing m-xylene and m-methylbenzonitrile from a second material inlet, carrying part of catalyst to a porous distribution plate 8 by airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature to be 410 ℃ through a second heat exchange assembly 9, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the mass ratio of the m-xylene in the step (2) to the m-xylene in the step (3) is 16:1, a step of;
(4) The gas flow generated by the reaction in the step (2) brings part of the catalyst to the top of the fluidized bed 1, and returns to the gas distribution assembly 3 through the gas-solid separation assembly 11 for reuse in the step (2);
(5) And (3) separating the reaction products obtained in the step (2) and the step (3), and then introducing the separated byproduct-m-methylbenzonitrile serving as a reaction raw material through a second material inlet for reaction.
Application example 4
Application example the fluidized bed apparatus provided in example 3 was used for the ammoxidation of meta-xylene, said application comprising the steps of:
(1) Loading a catalyst from a catalyst inlet 10, introducing heated air from a gas inlet 2 through a gas distribution assembly 3, and heating the catalyst to 390 ℃;
(2) Introducing m-xylene and ammonia from a first material inlet 4, controlling the load of the m-xylene to be 0.05kg/kgcat h, reacting with the air and the catalyst in the step (1), controlling the reaction temperature to be 418 ℃ through a first heat exchange assembly 6, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the molar ratio of the m-xylene to the ammonia is 1:8, the volume ratio of ammonia to air is 1:5, a step of;
(3) Introducing m-xylene and m-methylbenzonitrile from a second material inlet, carrying part of catalyst to a porous distribution plate 8 by airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature to 420 ℃ through a second heat exchange assembly 9, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the mass ratio of the m-xylene in the step (2) to the m-xylene in the step (3) is 12:1, a step of;
(4) The gas flow generated by the reaction in the step (2) brings part of the catalyst to the top of the fluidized bed 1, and returns to the gas distribution assembly 3 through the gas-solid separation assembly 11 for reuse in the step (2);
(5) And (3) separating the reaction products obtained in the step (2) and the step (3), and then introducing the separated byproduct-m-methylbenzonitrile serving as a reaction raw material through a second material inlet for reaction.
Application example 5
Application example the fluidized bed apparatus provided in application example 4 is used for performing m-xylene ammoxidation, and the application comprises the following steps:
(1) Loading the catalyst from a catalyst inlet 10, introducing heated air from a gas inlet 2 through a gas distribution assembly 3, and heating the catalyst to 350 ℃;
(2) Introducing m-xylene and ammonia from a first material inlet 4, controlling the load of the m-xylene to be 0.1kg/kgcat h, reacting with the air and the catalyst in the step (1), controlling the reaction temperature to be 425 ℃ through a first heat exchange assembly 6, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the molar ratio of the m-xylene to the ammonia is 1:5, the volume ratio of ammonia to air is 1:12;
(3) Introducing m-xylene and m-methylbenzonitrile from a second material inlet, carrying part of catalyst to a porous distribution plate 8 by airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature to be 418 ℃ through a second heat exchange assembly 9, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the mass ratio of the m-xylene in the step (2) to the m-xylene in the step (3) is 13:1, a step of;
(4) The gas flow generated by the reaction in the step (2) brings part of the catalyst to the top of the fluidized bed 1, and returns to the gas distribution assembly 3 through the gas-solid separation assembly 11 for reuse in the step (2);
(5) And (3) separating the reaction products obtained in the step (2) and the step (3), and then introducing the separated byproduct-m-methylbenzonitrile serving as a reaction raw material through a second material inlet for reaction.
Application example 6
Application example the fluidized bed apparatus provided in example 5 was used for the ammoxidation of meta-xylene, said application comprising the steps of:
(1) Loading a catalyst from a catalyst inlet 10, introducing heated air from a gas inlet 2 through a gas distribution assembly 3, and heating the catalyst to 400 ℃;
(2) Introducing m-xylene and ammonia from a first material inlet 4, controlling the load of the m-xylene to be 0.01kg/kgcat h, reacting with the air and the catalyst in the step (1), controlling the reaction temperature to be 430 ℃ through a first heat exchange assembly 6, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the molar ratio of the m-xylene to the ammonia is 1:9, the volume ratio of ammonia to air is 1:6, preparing a base material;
(3) Introducing m-xylene and m-methylbenzonitrile from a second material inlet, carrying part of catalyst to a porous distribution plate 8 by airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature to be 415 ℃ through a second heat exchange assembly 9, discharging and separating the obtained reaction product through a gas-solid separation assembly 11 and a gas outlet 12, wherein the mass ratio of the m-xylene in the step (2) to the m-xylene in the step (3) is 18:1, a step of;
(4) The gas flow generated by the reaction in the step (2) brings part of the catalyst to the top of the fluidized bed 1, and returns to the gas distribution assembly 3 through the gas-solid separation assembly 11 for reuse in the step (2);
(5) And (3) separating the reaction products obtained in the step (2) and the step (3), and using the m-methylbenzonitrile as a reaction raw material, which is a byproduct obtained by separation, and introducing the m-methylbenzonitrile through a second material inlet to participate in the reaction.
The reaction products of the above application examples include isophthalonitrile, methylbenzonitrile, benzonitrile, water and CO 2 The molar yield of the reaction product (based on meta-xylene) results are as follows:
TABLE 1
As can be seen from Table 1, when the fluidized bed device provided by the invention is applied to the conversion of m-xylene ammoxidation, the molar yield of m-phthalonitrile is more than or equal to 80%, the molar yield of benzonitrile is less than or equal to 0.02%, and the molar yield of methylbenzonitrile is less than or equal to 0.05%. The fluidized bed device provided by the invention can improve the yield of m-phthalonitrile, reduce the generation of m-methylbenzonitrile as a byproduct in the reaction and inhibit the dealkylation of m-xylene when being applied to the conversion of m-xylene ammoxidation.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (4)
1. The application of the fluidized bed device in the ammoxidation of meta-xylene is characterized in that a porous distribution plate is arranged in the fluidized bed device, and the porous distribution plate divides the fluidized bed device into two filler sections; the first reaction filling section and the second reaction filling section are sequentially arranged from bottom to top;
the bottom of the fluidized bed device is provided with a gas inlet, and a gas distribution assembly is arranged above the gas inlet;
the upper part of the first reaction filling section is provided with a first material inlet, meta-xylene and ammonia are introduced into the first material inlet, the first material inlet is connected with a first material distribution assembly, and the first material distribution assembly is arranged above the gas distribution assembly;
a first heat exchange assembly is arranged between the first material inlet and the first material distribution assembly;
the bottom of the second reaction filling section is provided with a second material distribution assembly, the second material distribution assembly is provided with a second material inlet, and the second material inlet is filled with m-xylene and m-methylbenzonitrile;
the side wall of the second reaction filler section is provided with a catalyst inlet;
a second heat exchange assembly is arranged above the porous distribution plate and is positioned below the catalyst inlet;
the heat exchange area ratio of the first heat exchange component to the second heat exchange component is 5-20;
the top of the second reaction filling section is provided with a gas-solid separation assembly which is connected with a gas outlet arranged at the top of the fluidized bed device;
the distance between the upper end of the gas distribution assembly and the lower end of the first material distribution assembly is 2-9% of the diameter of the fluidized bed device; the distance between the lower end of the second material distribution assembly and the adjacent porous distribution plate below the second material distribution assembly is 2-9% of the diameter of the fluidized bed device; the distance between the lowest end of the gas-solid separation assembly and the upper end of the gas distribution assembly is 0.01-0.03% of the diameter of the fluidized bed device;
the application comprises the following steps:
(1) Loading a catalyst from a catalyst inlet, introducing heated gas from a gas inlet through a gas distribution assembly, and heating the catalyst to 350-400 ℃;
(2) Introducing m-xylene and ammonia from a first material inlet, reacting with the gas and the catalyst in the step (1), controlling the reaction temperature to be 410-450 ℃ through a first heat exchange assembly, and discharging and separating the obtained reaction product through a gas-solid separation assembly and a gas outlet; the load of the meta-xylene in the step (2) is 0.01-0.3kg/kgcat h;
(3) Introducing m-xylene and m-methylbenzonitrile into the reactor from a second material inlet, carrying part of catalyst to a porous distribution plate by the gas flow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature to be 410-420 ℃ through a second heat exchange assembly, and discharging and separating the obtained reaction product through a gas-solid separation assembly and a gas outlet;
the mass ratio of the meta-xylene in the step (2) to the meta-xylene in the step (3) is (10-20): 1, a step of;
the application further comprises that the gas flow generated by the reaction in the step (2) brings part of the catalyst to the top of the fluidized bed, and returns to the gas distribution assembly through the gas-solid separation assembly for reuse in the step (2).
2. The use of claim 1, wherein the gas of step (1) comprises air.
3. The use according to claim 1 wherein the molar ratio of meta-xylene to ammonia in step (2) is 1: (3-10).
4. The use according to claim 1, wherein in step (2) the volume ratio of ammonia to gas is 1: (3-12).
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