CN113877487A - Fluidized bed device and method for ammonia oxidation of m-xylene - Google Patents
Fluidized bed device and method for ammonia oxidation of m-xylene Download PDFInfo
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- CN113877487A CN113877487A CN202111341229.8A CN202111341229A CN113877487A CN 113877487 A CN113877487 A CN 113877487A CN 202111341229 A CN202111341229 A CN 202111341229A CN 113877487 A CN113877487 A CN 113877487A
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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 178
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 67
- 229910021529 ammonia Inorganic materials 0.000 title claims description 33
- 238000000034 method Methods 0.000 title description 6
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 77
- BOHCMQZJWOGWTA-UHFFFAOYSA-N 3-methylbenzonitrile Chemical compound CC1=CC=CC(C#N)=C1 BOHCMQZJWOGWTA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000012856 packing Methods 0.000 claims abstract description 20
- 238000011049 filling Methods 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 57
- 238000000926 separation method Methods 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 34
- 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
- 239000012530 fluid Substances 0.000 claims 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006900 dealkylation reaction Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- IMLNVYRZWZFRLH-UHFFFAOYSA-N azane;1,3-xylene Chemical compound N.CC1=CC=CC(C)=C1 IMLNVYRZWZFRLH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 68
- 239000006227 byproduct Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 5
- 229920006391 phthalonitrile polymer Polymers 0.000 description 5
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000006200 vaporizer Substances 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
- 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000020335 dealkylation Effects 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
- 239000000203 mixture Substances 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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 oxidizing m-xylene ammonia, wherein a porous distribution plate is arranged in the fluidized bed device and divides the fluidized bed device into two filler sections; a first reaction packing section and a second reaction packing section are arranged from bottom to top in sequence; a first material inlet is formed in the upper part of the first reaction filling section and 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; and a second material distribution component is arranged at the bottom of the second reaction filling section, and a second heat exchange component is arranged above the porous distribution plate. According to the invention, the material distribution component of the m-methyl benzonitrile is arranged, so that the generation of the m-methyl benzonitrile in the reaction is reduced, the separated m-methyl benzonitrile can be reacted again, the m-xylene segmented feeding is arranged, the m-xylene dealkylation reaction is inhibited, the content of the benzonitrile is reduced, and the yield of the m-methyl benzonitrile 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 method for oxidizing m-xylene ammonia.
Background
Isophthalonitrile (IPN) is an important organic synthetic raw material, is a key intermediate for preparing chlorothalonil (tetrachlorodicyanobenzene, a broad-spectrum, low-toxicity and efficient herbicide), and can also be used as a raw material for products such as plastics, synthetic fibers, epoxy resin curing agents and the like.
The conventional method for synthesizing m-phthalonitrile is to carry out ammoxidation reaction on m-xylene with ammonia and oxygen under the action of a catalyst, wherein the principle is that a metal oxide type catalyst is adopted to react with the m-xylene, air and ammonia at the temperature of 400-450 ℃, the air is an oxidizing medium, the m-xylene and the ammonia have reducibility and need to be respectively introduced, and the reaction is carried out after the m-xylene and the ammonia are adsorbed on the catalyst. Since the reaction is a strongly exothermic reaction, a fluidized bed reactor is generally used to control the reaction temperature. However, because air reacts violently with ammonia and the like, a large amount of meta-xylene and ammonia are converted into CO and CO in the reaction2Resulting in a yield of the target product (isophthalonitrile) of less than 78%; meanwhile, gas-solid back mixing in the fluidized bed and incomplete conversion of intermediate products cause part of intermediate products to directly escape from the reactor, and the part of impurities increases the difficulty of product separation and also reduces the yield of target products.
CN204434527U discloses a production device for improving yield of m-phthalonitrile, the device includes liquid ammonia jar, evaporimeter, primary vaporizer, ammonia buffer tank, metaxylene elevated tank, vaporizer, static mixer, fluidized bed and condenser, its increase a static mixer between vaporizer and fluidized bed reactor, make the ammonia and metaxylene after the vaporization mix each other in advance in static mixer, improve the dwell time and the area of contact of material reaction in the fluidized bed, and then improved the yield of m-phthalonitrile.
However, the reaction is strongly exothermic and high in temperature, and the oxidation state of the catalyst is dominant in an oxygen-containing atmosphere, so that m-xylene has dealkylation behavior in the reaction process, a benzonitrile byproduct is generated, and the separation difficulty and the separation cost are increased.
Therefore, there is a need to develop a new fluidized bed apparatus and method for ammoxidation of m-xylene, which can solve the above problems and simultaneously increase the conversion rate of m-xylene and reduce the production cost.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a fluidized bed device and a method for the ammoxidation of m-xylene, wherein the fluidized bed device is provided with a material distribution component of a byproduct, namely m-methylbenzonitrile, so that the byproduct is fully converted; through the arrangement of the m-xylene sectional feeding, the raw material distribution of the second reaction packing section is changed, the reducibility of the catalyst is increased, the excessive oxidation of the catalyst under the conditions of high temperature and high oxygen content is inhibited, the dealkylation reaction of the m-xylene is further inhibited, and the generation of a byproduct, namely benzonitrile is reduced.
In order to achieve the technical effect, the invention adopts the following technical scheme:
in a first aspect, the invention provides a fluidized bed device for ammoxidation of m-xylene, wherein a porous distribution plate is arranged in the fluidized bed device and divides the fluidized bed device into two filler sections; a first reaction packing section and a second reaction packing section are arranged from bottom to top in sequence;
a gas inlet is arranged at the bottom of the fluidized bed device, and a gas distribution assembly is arranged above the gas inlet;
a first material inlet is formed in the upper part of the first reaction filling section and 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 packing section is provided with a second material distribution component, and the second material distribution component is provided with a second material inlet;
the side wall of the second reaction packing 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;
and a gas-solid separation component is arranged at the top of the second reaction packing section and is connected with a gas outlet arranged at the top of the fluidized bed device.
The device can reduce the gas back mixing in the fluidized bed, and the two heat exchange assemblies can more flexibly control the activity of the catalyst.
The fluidized bed device is divided into two filling sections, and by arranging the material distribution component of the m-methyl benzonitrile, the generation of a by-product (m-methyl benzonitrile) in the reaction can be reduced, and the separated m-methyl benzonitrile can be re-reacted, so that the yield of a target product is improved; by arranging the m-xylene sectional feeding, the raw material distribution of the second reaction packing section is changed, the m-xylene dealkylation reaction is inhibited, the content of the by-product (benzonitrile) is reduced, and the yield of the target product is improved.
In a preferred embodiment of the present invention, the distance between the upper end of the gas distribution member and the lower end of the first material distribution member is 2 to 9% of the diameter of the fluidized bed apparatus, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, but is not limited to the values listed above, and other values not listed above in the range of values are also applicable.
In a preferred embodiment of the present invention, the distance between the lower end of the second material distribution module and the adjacent porous distribution plate below the second material distribution module is 2-9% of the diameter of the fluidized bed apparatus, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also 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%, but not limited to the values listed above, and other values not listed in the numerical ranges may be similarly applied.
In a preferred embodiment of the present invention, the heat exchange area ratio of the first heat exchange means to the second heat exchange means is 5 to 20, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, but is not limited to the values listed above, and other values not listed above in the numerical range are also applicable.
In a second aspect, the present invention provides a use of a fluidized 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 from a second material inlet, bringing part of the catalyst onto the porous distribution plate by using the airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature by using the second heat exchange component, and discharging and separating the obtained reaction product through the gas-solid separation component and the gas outlet.
As a preferred technical scheme of the invention, the application also comprises that the gas flow generated by the reaction in the step (2) carries part of the catalyst to the top of the fluidized bed, and the gas flow is returned to the gas distribution assembly through the gas-solid separation assembly and reused in the step (2).
In the invention, after the obtained reaction product is separated, a byproduct, namely the m-methylbenzonitrile, obtained by separation is taken as a reaction raw material and is introduced from a second material inlet for reaction.
As a preferred technical scheme of the invention, the gas in the step (1) comprises air.
Preferably, the reaction temperature in step (2) is controlled to be 410-450 ℃, such as 410 ℃, 420 ℃, 430 ℃, 440 ℃ or 450 ℃, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the molar ratio of m-xylene to ammonia in step (2) is 1: (3-10) may be, for example, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the volume ratio of ammonia to gas in step (2) is 1: (3-12) may be, for example, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11 or 1:12, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the meta-xylene is loaded at 0.01 to 0.3kg/kgcat h, such as 0.01kg/kgcat h, 0.05kg/kgcat h, 0.1kg/kgcat h, 0.15kg/kgcat h, 0.2kg/kgcat h, 0.25kg/kgcat h or 0.3kg/kgcat h, but not limited to the values listed, and other values not listed within the range of values are equally applicable.
As a preferred embodiment of the present invention, the reaction temperature in step (3) is controlled to 410-420 ℃, for example, 410 ℃, 412 ℃, 414 ℃, 416 ℃, 418 ℃ or 420 ℃, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
As a preferable technical scheme of the invention, the mass ratio of the m-xylene in the step (2) to the m-xylene in the step (3) is (10-20): for example, 1 is 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) the device can reduce the back mixing of gas in the fluidized bed, increase the conversion rate of the m-xylene, and more flexibly control the activity of the catalyst by the two heat exchange assemblies;
(2) the device is provided with the material distribution component of the m-methyl benzonitrile, so that the generation of the m-methyl benzonitrile in the reaction can be reduced, the separated m-methyl benzonitrile can be reacted again, and the yield of the m-methyl benzonitrile is improved;
(3) the device provided by the invention is provided with m-xylene sectional feeding, so that the m-xylene dealkylation reaction is inhibited, the content of cyanobenzene is reduced, and the yield of the m-cyanobenzene is further improved;
(4) the yield of the m-phthalonitrile prepared by the application of the method is higher than 80%, the product purity is high, and the content of byproducts is low.
Drawings
FIG. 1 is a schematic view of a fluidized bed apparatus for ammoxidation of metaxylene provided by the present invention.
Wherein: 1-a fluidized bed; 2-a 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-a porous distribution plate; 9-a second heat exchange assembly; 10-catalyst inlet; 11-gas-solid separation component; 12-gas outlet.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
In this embodiment, as shown in fig. 1, a porous distribution plate 8 is disposed in the fluidized bed 1, and the porous distribution plate 8 divides the fluidized bed 1 into two sections of packing; the first reaction packing section and the second reaction packing section are arranged from bottom to top in sequence.
A gas inlet 2 is arranged at the bottom of the fluidized bed 1 device, and a gas distribution assembly 3 is arranged above the gas inlet 2; a first material inlet 4 is formed in the upper part of the first reaction filling section, 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 component 7 is arranged at the bottom of the second reaction packing section, and a second material inlet is formed in the second material distribution component 7; the side wall of the second reaction packing 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; and a gas-solid separation component 11 is arranged at the top of the second reaction packing section, and the gas-solid separation component 11 is connected with a gas outlet 12 arranged at the top of the fluidized bed 1.
The distance between the upper end of the gas distribution component 3 and the lower end of the first material distribution component 5 is 2 percent of the diameter of the fluidized bed 1.
The distance between the lower end of the second material distribution component 7 and the adjacent porous distribution plate 8 below the lower end is 9 percent of the diameter of the device of the fluidized bed 1.
The distance between the lowest end of the gas-solid separation component 11 and the upper end of the gas distribution component 3 is 0.01 percent of the diameter 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 5.
Example 2
The difference between the embodiment and the embodiment 1 is only 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 component 7 and the adjacent porous distribution plate 8 below the second material distribution component is 2 percent of the diameter of the device of the fluidized bed 1; the distance between the lowest end of the gas-solid separation component 11 and the upper end of the gas distribution component 3 is 0.03 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 20, and other conditions are the same as those in embodiment 1.
Example 3
The difference between the embodiment and the embodiment 1 is only 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 component 7 and the adjacent porous distribution plate 8 below the second material distribution component is 4 percent of the diameter of the fluidized bed 1; the distance between the lowest end of the gas-solid separation component 11 and the upper end of the gas distribution component 3 is 0.02 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 12, and other conditions are the same as those in embodiment 1.
Example 4
The difference between the embodiment and the embodiment 1 is only 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 component 7 and the adjacent porous distribution plate 8 below the second material distribution component is 6 percent of the diameter of the fluidized bed 1; the distance between the lowest end of the gas-solid separation component 11 and the upper end of the gas distribution component 3 is 0.015 percent of the diameter 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 in embodiment 1.
Example 5
The difference between the embodiment and the embodiment 1 is only 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 percent of the diameter of the fluidized bed 1; the distance between the lower end of the second material distribution component 7 and the adjacent porous distribution plate 8 below the second material distribution component 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 component 11 and the upper end of the gas distribution component 3 is 0.025 percent of the diameter 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 in embodiment 1.
Application example 1
This application example uses the fluidized bed apparatus provided in application example 1 to perform 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 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;
(3) introducing m-xylene and m-tolunitrile from a second material inlet, bringing part of the catalyst to the porous distribution plate 8 by using the airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-tolunitrile, controlling the reaction temperature to be 412 ℃ by using the second heat exchange component 9, discharging and separating the obtained reaction product through the gas-solid separation component 11 and the 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;
(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, returns to the gas distribution component 3 through the gas-solid separation component 11 and is reused in the step (2);
(5) and (3) separating the reaction products obtained in the step (2) and the step (3), and introducing a separated byproduct, namely m-methylbenzonitrile, as a reaction raw material from a second material inlet for reaction.
Application example 2
The difference between the application example and the application example 1 is only that the load of the m-xylene in the step (2) is 0.3kg/kgcat h, the reaction temperature of the first heat exchange component in the step (2) is controlled to be 450 ℃, and the molar ratio of the m-xylene to ammonia in the step (2) is 1:10, the volume ratio of the ammonia to the air in the step (2) is 1:3, the mass ratio of the m-xylene in the step (2) to the m-xylene in the step (3) is 10:1, the other conditions were the same as in application example 1.
Application example 3
This application example uses the fluidized bed apparatus provided in example 2 for the ammoxidation of meta-xylene, the 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 component 6, discharging and separating the obtained reaction product through a gas-solid separation component 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;
(3) introducing m-xylene and m-tolunitrile from a second material inlet, bringing 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-tolunitrile, controlling the reaction temperature to be 410 ℃ by a second heat exchange component 9, discharging and separating an obtained reaction product through a gas-solid separation component 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;
(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, returns to the gas distribution component 3 through the gas-solid separation component 11 and is reused in the step (2);
(5) and (3) separating the reaction products obtained in the step (2) and the step (3), and introducing a separated byproduct, namely m-methylbenzonitrile, as a reaction raw material from a second material inlet for reaction.
Application example 4
This application example uses the fluidized bed apparatus provided in application example 3 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;
(3) introducing m-xylene and m-tolunitrile from a second material inlet, bringing 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-tolunitrile, controlling the reaction temperature to be 420 ℃ by a second heat exchange assembly 9, discharging and separating an 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;
(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, returns to the gas distribution component 3 through the gas-solid separation component 11 and is reused in the step (2);
(5) and (3) separating the reaction products obtained in the step (2) and the step (3), and introducing a separated byproduct, namely m-methylbenzonitrile, as a reaction raw material from a second material inlet for reaction.
Application example 5
This application example uses the fluidized bed apparatus provided in application example 4 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 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 component 6, discharging and separating the obtained reaction product through a gas-solid separation component 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-tolunitrile from a second material inlet, bringing 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-tolunitrile, controlling the reaction temperature to be 418 ℃ by a second heat exchange assembly 9, discharging and separating an 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;
(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, returns to the gas distribution component 3 through the gas-solid separation component 11 and is reused in the step (2);
(5) and (3) separating the reaction products obtained in the step (2) and the step (3), and introducing a separated byproduct, namely m-methylbenzonitrile, as a reaction raw material from a second material inlet for reaction.
Application example 6
This application example uses the fluidized bed apparatus provided in application example 5 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;
(3) introducing m-xylene and m-tolunitrile from a second material inlet, bringing 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-tolunitrile, controlling the reaction temperature to be 415 ℃ by a second heat exchange component 9, discharging and separating the obtained reaction product through a gas-solid separation component 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;
(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, returns to the gas distribution component 3 through the gas-solid separation component 11 and is reused in the step (2);
(5) and (3) separating the reaction products obtained in the step (2) and the step (3), using the separated by-product m-methylbenzonitrile as a reaction raw material, and introducing the reaction raw material from a second material inlet to participate in the reaction.
The reaction product of the above application examples includes isophthalonitrile, methylbenzonitrile, benzonitrile, water and CO2The molar yields of the reaction products (based on m-xylene) result 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 the ammoxidation of m-xylene, 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 the isophthalonitrile, reduce the generation of a byproduct, namely the m-methylbenzonitrile in the reaction and inhibit the dealkylation reaction of the m-xylene when being applied to the conversion of the m-xylene ammoxidation.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A fluidized bed device for the ammoxidation of m-xylene is characterized in that a porous distribution plate is arranged in the fluidized bed device, and the fluidized bed device is divided into two filler sections by the porous distribution plate; a first reaction packing section and a second reaction packing section are arranged from bottom to top in sequence;
a gas inlet is arranged at the bottom of the fluidized bed device, and a gas distribution assembly is arranged above the gas inlet;
a first material inlet is formed in the upper part of the first reaction filling section and 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 packing section is provided with a second material distribution component, and the second material distribution component is provided with a second material inlet;
the side wall of the second reaction packing 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;
and a gas-solid separation component is arranged at the top of the second reaction packing section and is connected with a gas outlet arranged at the top of the fluidized bed device.
2. The fluidized bed apparatus according to claim 1, wherein the upper end of the gas distribution assembly is spaced from the lower end of the first material distribution assembly by a distance of 2-9% of the diameter of the fluidized bed apparatus.
3. The fluid bed apparatus according to claim 1 or 2, wherein the distance between the lower end of the second material distribution member and the porous distribution plate adjacent therebelow is 2-9% of the diameter of the fluid bed apparatus.
4. The fluidized bed apparatus according to any one of claims 1 to 3, wherein 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.
5. The fluid bed apparatus according to any of the claims 1 to 4, wherein the heat exchange area ratio of the first heat exchange assembly to the second heat exchange assembly is 5 to 20.
6. Use of a fluidized bed apparatus according to any one of claims 1 to 5 for the ammoxidation of meta-xylene, 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 from a second material inlet, bringing part of the catalyst onto the porous distribution plate by using the airflow generated by the reaction in the step (2), catalyzing the reaction of the m-xylene and the m-methylbenzonitrile, controlling the reaction temperature by using the second heat exchange component, and discharging and separating the obtained reaction product through the gas-solid separation component and the gas outlet.
7. The use of claim 6, wherein the use further comprises step (2) wherein the gas stream produced by the reaction brings a portion of the catalyst to the top of the fluidized bed, and is returned to the gas distribution assembly through the gas-solid separation assembly for reuse in step (2).
8. The use of claim 6 or 7, wherein the gas of step (1) comprises air;
preferably, the reaction temperature in the step (2) is controlled to be 410-450 ℃;
preferably, the molar ratio of m-xylene to ammonia in step (2) is 1: (3-10);
preferably, the volume ratio of ammonia to gas in step (2) is 1: (3-12);
preferably, the meta-xylene load is from 0.01 to 0.3kg/kgcat h.
9. The use according to any one of claims 6-8, wherein the reaction temperature in step (3) is controlled to be 410-420 ℃.
10. Use according to any one of claims 6 to 9, wherein the mass ratio of the meta-xylene of step (2) to the meta-xylene of step (3) is (10-20): 1.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309569A (en) * | 1999-04-28 | 2000-11-07 | Asahi Chem Ind Co Ltd | PRODUCTION OF alpha,beta-UNSATURATED NITRILE |
| CN101954264A (en) * | 2010-04-20 | 2011-01-26 | 南通泰禾化工有限公司 | Novel fluidized bed reactor for synthetizing m-phthalonitrile |
| CN102513037A (en) * | 2011-11-29 | 2012-06-27 | 清华大学 | Fluidized bed reactor for preparing methanol by synthesis gas and method |
| KR20150034420A (en) * | 2013-09-26 | 2015-04-03 | 코오롱인더스트리 주식회사 | Method for Producing Phthalonitriles |
| CN106622044A (en) * | 2017-01-22 | 2017-05-10 | 清华大学 | Ammonia oxidation reactor and preparation method of nitrile compounds |
| CN111111563A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Fluidized bed reaction device for preparing aromatic nitrile by ammoxidation of aromatic hydrocarbon and reaction method thereof |
| CN112707844A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for producing aromatic nitrile by ammoxidation of aromatic hydrocarbon |
| CN112717839A (en) * | 2020-12-25 | 2021-04-30 | 江苏新河农用化工有限公司 | Fluidized reaction device and method for oxidizing m-xylene by using same |
-
2021
- 2021-11-12 CN CN202111341229.8A patent/CN113877487B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309569A (en) * | 1999-04-28 | 2000-11-07 | Asahi Chem Ind Co Ltd | PRODUCTION OF alpha,beta-UNSATURATED NITRILE |
| CN101954264A (en) * | 2010-04-20 | 2011-01-26 | 南通泰禾化工有限公司 | Novel fluidized bed reactor for synthetizing m-phthalonitrile |
| CN102513037A (en) * | 2011-11-29 | 2012-06-27 | 清华大学 | Fluidized bed reactor for preparing methanol by synthesis gas and method |
| KR20150034420A (en) * | 2013-09-26 | 2015-04-03 | 코오롱인더스트리 주식회사 | Method for Producing Phthalonitriles |
| CN106622044A (en) * | 2017-01-22 | 2017-05-10 | 清华大学 | Ammonia oxidation reactor and preparation method of nitrile compounds |
| CN111111563A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Fluidized bed reaction device for preparing aromatic nitrile by ammoxidation of aromatic hydrocarbon and reaction method thereof |
| CN112707844A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for producing aromatic nitrile by ammoxidation of aromatic hydrocarbon |
| CN112717839A (en) * | 2020-12-25 | 2021-04-30 | 江苏新河农用化工有限公司 | Fluidized reaction device and method for oxidizing m-xylene by using same |
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