CN109046454B - Catalyst for synthesizing 2, 6-dichlorobenzonitrile and preparation method thereof - Google Patents
Catalyst for synthesizing 2, 6-dichlorobenzonitrile and preparation method thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention provides a catalyst for preparing 2, 6-dichlorobenzonitrile by an ammonia oxidation method and a preparation method thereof. The catalyst can be used for catalyzing the reaction of preparing 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene and also can be used for catalyzing the reaction of preparing 2, 6-dichlorobenzonitrile from 2, 6-dichlorobenzyl chloride. The catalyst can reduce the over-oxidation reaction of 2, 6-dichlorobenzyl chloride, ensure that the product has very high selectivity and yield, greatly reduce the industrial production cost and meet the requirement of large-scale industrial production.
Description
The technical field is as follows:
the invention belongs to the technical field of catalysis, and particularly relates to a catalyst for preparing 2, 6-dichlorobenzonitrile by an ammoxidation method and a preparation method thereof.
The background art comprises the following steps:
2, 6-dichlorobenzonitrile, also known as dichlobenil, is an important chemical intermediate and is widely applied to the fields of herbicides, insecticides, medicines, dyes, high molecular materials and the like.
The method for synthesizing 2, 6-dichlorobenzonitrile is mainly divided into an organic synthesis method and a gas-phase ammoxidation method. The gas phase ammoxidation method is to perform ammoxidation reaction on reactants, ammonia gas and oxygen gas under the action of a catalyst to generate the 2, 6-dichlorobenzonitrile. Compared with the organic synthesis method, the gas phase ammoxidation method has the advantages of simple process, low energy consumption, little pollution and high product yield and purity, and is an ideal method for industrialization.
So far, the related patents of the catalyst for preparing 2, 6-dichlorobenzonitrile by using an ammoxidation method at home and abroad all adopt 2, 6-dichlorotoluene as a raw material. Chinese patent CN98110745.1 uses silicon dioxide as carrier, and the composition of active components conforms to general formula V 1.0 P b Na c A d B e O x The catalyst is used for catalyzing the reaction of preparing 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene through ammoxidation, wherein the conversion rate of the 2, 6-dichlorotoluene can reach 98%, the selectivity of the 2, 6-dichlorobenzonitrile can reach 90%, and the yield can reach more than 88%. Chinese patent CN201110222993 is a catalyst for preparing 2, 6-dichlorobenzonitrile, which takes silicon dioxide as a carrier, and the active ingredient of the catalyst conforms to a general formula V 1.0 P a Cr b Co c X d O m The catalyst is prepared by adopting a coprecipitation method and takes V-Cr-P-Co as a main active component, and is applied to the technical process of preparing 2, 6-dichlorobenzonitrile by carrying out ammoxidation on 2, 6-dichlorotoluene, the conversion rate of the 2, 6-dichlorotoluene can reach 99.5 percent, the selectivity of the 2, 6-dichlorobenzonitrile can reach 90 percent, and the yield can reach 90 percent.
The catalysts for preparing 2, 6-dichlorobenzonitrile described above are all catalysts in which 2, 6-dichlorotoluene is used as a reactant. The price of the 2, 6-dichlorotoluene is high, the 2, 6-dichlorobenzonitrile produced by using the 2, 6-dichlorotoluene as a reactant is expensive, the price of the 2, 6-dichlorobenzyl chloride is less than half of that of the 2, 6-dichlorotoluene, the 2, 6-dichlorobenzonitrile produced by using the 2, 6-dichlorotoluene as a reactant is very cheap, and the method is very suitable for large-scale industrial production.
Because the chemical property of the 2, 6-dichlorobenzyl chloride is more active, the over-oxidation reaction is more easily generated, and a large amount of CO is generated 2 The selectivity and yield of the product 2, 6-dichlorobenzonitrile are low, and therefore the presently disclosed catalysts are not suitable for use with 2, 6-dichlorobenzyl chloride as a starting materialA preparation process of the material. If the catalyst which is suitable for preparing the 2, 6-dichlorobenzonitrile by using the 2, 6-dichlorobenzyl chloride as the raw material and has good selectivity and high yield of the product 2, 6-dichlorobenzonitrile can be invented, the industrial production cost can be greatly reduced.
The invention content is as follows:
the invention discloses a catalyst for preparing 2, 6-dichlorobenzonitrile by an ammonia oxidation method and a preparation method thereof. The catalyst can be used for catalyzing the reaction for preparing 2, 6-dichlorobenzonitrile by using 2, 6-dichlorotoluene as a raw material, and can also be used for catalyzing the reaction for preparing 2, 6-dichlorobenzonitrile by using 2, 6-dichlorobenzyl chloride as a raw material. The catalyst can reduce the over-oxidation reaction of 2, 6-dichlorobenzyl chloride, so that the 2, 6-dichlorobenzyl chloride is smoothly converted into the 2, 6-dichlorobenzonitrile through the ammoxidation reaction, the product has very high selectivity and yield, the industrial production cost is greatly reduced, and the requirement of large-scale industrial production is met.
The reaction equation for preparing 2, 6-dichlorobenzonitrile by ammoxidation of 2, 6-dichlorobenzyl chloride is as follows:
C 7 H 5 Cl 3 +2NH 3 +O 2 ＝C 7 H 3 Cl 2 N+NH 4 Cl+2H 2 O
the main side reaction is over oxidation reaction, and the reaction equation is as follows:
2C 7 H 5 Cl 3 +6NH 3 +15O 2 ＝6NH 4 Cl+14CO 2 +2H 2 O
the invention discloses a catalyst for synthesizing 2, 6-dichlorobenzonitrile, which has an atomic composition conforming to the following general formula:
V 1.0 P a Mo b X c O d /YO e
wherein X is selected from one or two of cobalt and chromium, Y is selected from one of silicon, aluminum and titanium,
a is 0.2 to 1.5
b is 0.1 to 1.0
c is 0.05 to 0.8
d is the total number of oxygen atoms required by the valence of V, P, mo, X and other elements.
In the above catalyst, an oxide containing X is used as an auxiliary and an oxide containing Y is used as a carrier.
The invention also discloses a preparation method of the catalyst, which comprises the following three steps:
1. preparation of reactive precursors
Adding an organic solvent into a reaction kettle with a stirring, heating and condensing reflux device, adding a vanadium compound, a phosphorus compound and a molybdenum compound, stirring to prepare a suspension, heating to raise the temperature, reacting at 80-160 ℃ and 0-40 kPa for 4-6 h, cooling, filtering, drying a filter cake at 100-160 ℃ for 24h, and roasting at 280-400 ℃ for 4-8 h to obtain an active precursor.
Wherein the organic solvent is one or more of n-hexanol, isobutanol and benzyl alcohol; the vanadium compound can be vanadium pentoxide, ammonium metavanadate, vanadium oxalate and the like, and preferably vanadium pentoxide and ammonium metavanadate; the phosphorus compound can be phosphoric acid, ammonium phosphate, sodium phosphate, phosphorus pentoxide and the like, and phosphoric acid and phosphorus pentoxide are preferred; the molybdenum compound may be ammonium heptamolybdate, ammonium tetramolybdate, molybdenum trioxide, etc., and ammonium heptamolybdate and ammonium tetramolybdate are preferred. The reaction temperature is 80-160 ℃, preferably 90-140 ℃.
2. Preparation of semifinished products
And (3) uniformly mixing the active precursor obtained in the step (1) with a carrier and an auxiliary agent to obtain a mixed material, and then forming the mixed material to prepare a semi-finished product.
Wherein, the carrier can be alumina, silica and titanium oxide; the assistant can be cobalt and/or a chromium compound, wherein the cobalt compound can be cobalt nitrate, cobalt phosphate, cobalt sulfate, cobalt oxide and the like, and cobalt nitrate and cobalt phosphate are preferred; the chromium compound may be chromium nitrate, chromium carbonate, chromium sulfate, chromium oxide, etc., preferably chromium nitrate, chromium carbonate.
Any one of the conventional methods can be selected for forming, and some usable formed shapes and forming methods thereof are listed:
(1) Strip-shaped: adding 30-80% of water, 1-15% of pore-forming agent (such as sesbania powder) and 1-5% of lubricant (such as carboxymethyl cellulose) into the mixed material according to the weight, kneading uniformly in a kneading machine until the mixed material is suitable for extruding strips, extruding the mixed material into strips with the diameter of 4-8 mm by using an extruding machine, drying the strips for 6-24 h at the temperature of 100-140 ℃, and crushing the strips into strip-shaped particles with the length of 4-8 mm to obtain strip-shaped semi-finished products.
(2) Spherical: extruding the mixture into strips with the diameter of 4-6 mm according to the method in the step (1), preparing the strips into spheres with the diameter of 4-6 mm by a sphere cutting machine, and drying the spheres at 100-140 ℃ for 6-24 h to obtain spherical semi-finished products.
(3) Cylinder or hollow cylinder: wet granulation may be used: adding water accounting for 20-50% of the weight of the mixed material, kneading uniformly, then granulating into particles of 10-40 meshes by a granulator, drying, and mixing with lubricants such as graphite or stearic acid to obtain particles suitable for tabletting; or adopting dry granulation: the mixed material is mixed with lubricants such as graphite or stearic acid, and the mixture is directly made into particles with 10 meshes to 40 meshes by a dry granulating machine. Then pressing the particles into a cylinder or a hollow cylinder with the diameter of 4-7 mm by a tablet machine.
3. Activation of
And (4) putting the semi-finished product into a muffle furnace, and activating in an oxygen-deficient air atmosphere.
Controlling the oxygen content in the activated atmosphere by adding a proper amount of nitrogen into the air, wherein the volume content of the oxygen in the oxygen-deficient air is 3-15%, preferably 6-12%; the activation temperature is 400-600 ℃, preferably 450-550 ℃; the activation time is 2h to 10h, preferably 4h to 8h.
When the catalyst is used, the catalyst can be filled in a fixed bed reactor with the diameter of 25mm and the length of 4 meters, and the filling height of the catalyst is 3.5m. 2, 6-dichlorobenzyl chloride, ammonia gas and oxygen-deficient air are taken as raw materials, and the raw materials are subjected to ammoxidation reaction at the temperature of 300-500 ℃ and the pressure of 10-100 kPa to generate 2, 6-dichlorobenzonitrile. When the reaction temperature is controlled to ensure that the conversion rate of the 2, 6-dichlorobenzyl chloride is more than 99 percent, the selectivity and the yield of the product 2, 6-dichlorobenzonitrile can reach more than 80 percent.
Vanadium is the main active component for ammoxidation, and the valence of vanadium is rightIts activity and selectivity are important. When vanadium exists mainly in a valence of +5, the activity of the catalyst is high, excessive oxidation reaction is easy to occur, and useless CO is generated 2 Thus, the selectivity of the target product is poor; when vanadium is mainly present in a valence of +4, the activity of the catalyst is very low, resulting in good selectivity but low product yield. In some patents introduced in the background of the invention, the valence state of vanadium is between + 4.9- +5.0, very close to +5, and thus its activity is too high, when 2, 6-dichlorobenzyl chloride, which is more active than 2, 6-dichlorotoluene in chemical property, is used as reactant, peroxidation is more likely to occur, and a large amount of CO is generated 2 Resulting in low selectivity and yield of the target product. The vanadium in the catalyst can synthesize VOHPO with a stable structure in an alcohol solvent 4 The method has the advantages of good product selectivity and high yield, so the method is an excellent catalyst for preparing 2, 6-dichlorobenzonitrile by using 2, 6-dichlorobenzyl chloride as a raw material, helps to realize a process for preparing the 2, 6-dichlorobenzonitrile by using the low-cost 2, 6-dichlorobenzyl chloride instead of the high-cost 2, 6-dichlorotoluene as the raw material, can be suitable for large-scale industrial production, and greatly reduces the industrial production cost.
Meanwhile, by using the catalyst of the invention, the same reactor can be used, the same conditions are controlled, 2, 6-dichlorotoluene is used as a raw material for carrying out ammoxidation reaction to prepare the 2, 6-dichlorobenzonitrile, and when the reaction temperature is controlled to ensure that the conversion rate of the 2, 6-dichlorotoluene is more than 99%, the selectivity and the yield of the product 2, 6-dichlorobenzonitrile can both reach more than 90%, and the catalytic effect is also good.
The invention discloses a catalyst for preparing 2, 6-dichlorobenzonitrile by an ammoxidation reaction and a preparation method thereof. The catalyst can be used for catalyzing the reaction for preparing 2, 6-dichlorobenzonitrile by using 2, 6-dichlorotoluene as a raw material, and can also be used for catalyzing the reaction for preparing 2, 6-dichlorobenzonitrile by using 2, 6-dichlorobenzyl chloride as a raw material. The catalyst can reduce the over-oxidation reaction of 2, 6-dichlorobenzyl chloride, so that the 2, 6-dichlorobenzyl chloride is smoothly converted into the 2, 6-dichlorobenzonitrile through the ammoxidation reaction, the product has very high selectivity and yield, the industrial production cost is greatly reduced, and the requirement of large-scale industrial production is met.
The specific implementation mode is as follows:
the invention is further described below by way of examples.
The first embodiment is as follows:
5000g of n-hexanol and 1000g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, 636g of vanadium pentoxide, 396g of phosphoric acid and 120g of ammonium heptamolybdate are sequentially added, the temperature is controlled to be 90-100 ℃, 30-40 kPa are reacted, evaporated organic solvent is condensed by a water condenser and then flows back into the reaction kettle, and the reaction is stopped after 6 hours. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 120-140 ℃ for 18h, and then roasting at 300-320 ℃ for 8h to obtain the active precursor.
Adding an active precursor into a kneader, then adding 1524g of alumina, 206g of cobalt nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the materials are suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the diameter of 5mm, then the strips are cut into balls with the diameter of 5mm by a grain cutting machine, the spherical particles are dried for 24 hours at the temperature of 110-120 ℃, and are roasted for 8 hours at the temperature of 480-500 ℃ in the atmosphere with the oxygen content of 9-11 percent to obtain the catalyst A1.
The second embodiment:
5000g of n-hexanol and 1000g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, then 829g of ammonium metavanadate, 178g of phosphoric acid and 186g of ammonium heptamolybdate are sequentially added, the temperature is controlled to be 90-100 ℃, and 30-40 kPa are carried out for reaction, evaporated organic solvent is condensed by a water condenser and then reflows into the reaction kettle, and the reaction is stopped after 6 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 120-140 ℃ for 18h, and then roasting at 300-320 ℃ for 8h to obtain the active precursor.
Adding the active precursor into a dry granulating machine, then adding 1524g of alumina and 196g of cobalt nitrate, and uniformly mixing to obtain particles of 12-20 meshes. The particles are pressed into a cylinder with the diameter of 5mm and the height of 5mm by a tablet press, and then are roasted for 8 hours at 480-500 ℃ in the atmosphere with the oxygen content of 9-11 percent to obtain the catalyst A2.
Example three:
5500g of n-hexanol and 1100g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, 636g of vanadium pentoxide, 122g of phosphorus pentoxide and 120g of ammonium heptamolybdate are sequentially added, the temperature is controlled at 90-100 ℃, 30-40 kPa are reacted, evaporated organic solvent is condensed by a water condenser and then flows back into the reaction kettle, and the reaction is stopped after 6 hours. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at the temperature of 120-140 ℃ for 18 hours, and roasting at the temperature of 300-320 ℃ for 8 hours to obtain the active precursor.
Adding an active precursor into a kneader, then adding 1524g of alumina, 206g of cobalt nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the materials are suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the diameter of 5mm, then the strips are cut into balls with the diameter of 5mm by a grain cutting machine, the spherical particles are dried for 24 hours at the temperature of 110-120 ℃, and are roasted for 8 hours at the temperature of 480-500 ℃ in the atmosphere with the oxygen content of 9-11 percent to obtain the catalyst A3.
Example four:
5500g of n-hexanol and 1100g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, then 736g of vanadium pentoxide, 343g of phosphorus pentoxide and 216g of ammonium heptamolybdate are sequentially added, the temperature is controlled at 100-110 ℃, 20 kPa-30 kPa for reaction, evaporated organic solvent is condensed by a water condenser and then flows back into the reaction kettle, and the reaction is stopped after 5 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 110-130 ℃ for 24h, and roasting at 300-320 ℃ for 8h to obtain the active precursor.
Adding an active precursor into a kneader, then adding 1524g of alumina, 358g of chromium nitrate, 110g of cobalt nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the material is suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the diameter of 5mm, then a granulator is used for cutting the strips into balls with the diameter of 5mm, the spherical particles are dried for 24h at the temperature of 110-120 ℃, and are roasted for 8h at the temperature of 480-500 ℃ in the atmosphere with the oxygen content of 9-11 percent to obtain the catalyst A4.
Example five:
5000g of n-hexanol and 1000g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, then 829g of ammonium metavanadate, 198g of phosphoric acid and 130g of ammonium heptamolybdate are sequentially added, the temperature is controlled at 100-110 ℃, 20 kPa-30 kPa are carried out for reaction, evaporated organic solvent is condensed by a water condenser and then refluxed into the reaction kettle, and the reaction is stopped after 5 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 110-130 ℃ for 24h, and then roasting at 320-340 ℃ for 6h to obtain the active precursor.
Adding an active precursor into a kneader, then adding 1524g of alumina, 206g of cobalt nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the materials are suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the thickness of 6mm, then the strips are dried for 24 hours at the temperature of 110-120 ℃ and are crushed into strips with the thickness of 4-7 mm, and the strips are roasted for 6 hours at the temperature of 500-520 ℃ in the atmosphere with the oxygen content of 8-9 percent to obtain the catalyst A5.
Example six:
5500g of n-hexanol and 1100g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, then 778g of ammonium metavanadate, 138g of phosphoric acid, 115g of ammonium tetramolybdate and 50g of calcium oxide are sequentially added, the temperature is controlled at 120-130 ℃, 10-20 kPa are carried out for reaction, evaporated organic solvent is condensed by a water condenser and then flows back into the reaction kettle, and the reaction is stopped after 4 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 120-140 ℃ for 18h, and then roasting at 320-340 ℃ for 6h to obtain the active precursor.
Adding the active precursor into a kneader, then adding 1265g of titanium dioxide, 327g of chromium nitrate, 110g of cobalt nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the materials are suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the diameter of 6mm, then the strips are cut into balls with the diameter of 6mm by a grain cutting machine, the spherical particles are dried for 24 hours at the temperature of 110-120 ℃, and are roasted for 8 hours at the temperature of 500-520 ℃ in the atmosphere with the oxygen content of 8-9 percent to obtain the catalyst A6.
Example seven:
5500g of n-hexanol and 1100g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, then 778g of ammonium metavanadate, 456g of phosphoric acid and 234g of ammonium heptamolybdate are sequentially added, the temperature is controlled at 120-130 ℃, 10-20 kPa are carried out for reaction, evaporated organic solvent is condensed by a water condenser and then flows back into the reaction kettle, and the reaction is stopped after 4 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 120-140 ℃ for 18h, and then roasting at 320-340 ℃ for 6h to obtain the active precursor.
Adding the active precursor into a dry granulating machine, then adding 1578g of alumina and 206g of cobalt nitrate, and uniformly mixing to obtain particles of 14-24 meshes. The particles are pressed into a hollow cylinder with the outer diameter of 5.5mm, the height of 5.5mm and the center hole of 2mm by a tablet press, and then the hollow cylinder is roasted for 6 hours at the temperature of 500-520 ℃ in the atmosphere with the oxygen content of 8-9 percent to obtain the catalyst A7.
Example eight:
5500g of n-hexanol and 1100g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, then 736g of vanadium pentoxide, 289g of phosphorus pentoxide and 140g of ammonium heptamolybdate are sequentially added, the temperature is controlled at 120-130 ℃, 10-20 kPa is carried out for reaction, evaporated organic solvent is condensed by a water condenser and then flows back into the reaction kettle, and the reaction is stopped after 4 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 130-150 ℃ for 14h, and then roasting at 340-360 ℃ for 5h to obtain the active precursor.
Adding the active precursor into a kneader, then adding 1578g of alumina, 403g of chromium nitrate, 110g of cobalt nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the materials are suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the thickness of 4mm, then the strips are dried for 24 hours at the temperature of 110-120 ℃ and are crushed into strips with the thickness of 4-6 mm, and the strips are roasted for 6 hours at the temperature of 500-520 ℃ in the atmosphere with the oxygen content of 8-9 percent to obtain the catalyst A8.
Example nine:
5500g of n-hexanol and 1100g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, 636g of vanadium pentoxide, 150g of phosphorus pentoxide and 120g of ammonium heptamolybdate are sequentially added, the temperature is controlled at 130-140 ℃ and 0-10 kPa for reaction, evaporated organic solvent is condensed by a water condenser and then flows back into the reaction kettle, and the reaction is stopped after 4 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 130-150 ℃ for 14h, and then roasting at 340-360 ℃ for 5h to obtain the active precursor.
Adding the active precursor into a kneader, then adding 1578g of alumina, 527g of chromium nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the materials are suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the diameter of 4mm, then the strips are cut into balls with the diameter of 4mm by a grain cutting machine, the spherical particles are dried for 24 hours at the temperature of 110-120 ℃, and are roasted for 4 hours at the temperature of 520-540 ℃ in the atmosphere with the oxygen content of 6-8 percent to obtain the catalyst A9.
Example ten:
5500g of n-hexanol and 1100g of benzyl alcohol are added into a reaction kettle with a stirring, heating and condensing reflux device under stirring, 829g of ammonium metavanadate, 402g of phosphorus pentoxide and 130g of ammonium heptamolybdate are sequentially added, the temperature is controlled at 130-140 ℃ and 0-10 kPa for reaction, the evaporated organic solvent is condensed by a water condenser and then refluxed into the reaction kettle, and the reaction is stopped after 4 hours of reaction. And carrying out solid-liquid separation on the obtained slurry to obtain a filter cake, drying the filter cake at 130-150 ℃ for 14h, and then roasting at 340-360 ℃ for 5h to obtain the active precursor.
Adding the active precursor into a kneader, then adding 1278g of silicon dioxide, 513g of chromium nitrate, 100g of sesbania powder and 50g of carboxymethyl cellulose, uniformly mixing, and then adding a proper amount of water under continuous kneading until the material is suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the diameter of 4mm, then the strips are cut into balls with the diameter of 4mm by a granulator, the spherical particles are dried for 24h at the temperature of 110-120 ℃, and are roasted for 4h at the temperature of 520-540 ℃ in the atmosphere with the oxygen content of 6-8 percent to obtain the catalyst A10.
Comparative example one (see patent CN 98110745.1):
186.1g of ammonium metavanadate was added to 2800mL of water, mixed with 85% phosphoric acid 220g,400mL of water, and 20% NaNO was added 3 202.5g，20％LiNO 3 109.7g, siO was added after mixing 2 175g, stirring, heating and evaporating until the solid content is 38%, spray-drying the slurry to obtain particles, and pre-roasting the particles at 400 ℃ for 0.5h to obtain the precursor.
Adding the precursor into a kneader, adding 50g of sesbania powder and 30g of carboxymethyl cellulose, uniformly mixing, and adding a proper amount of water under continuous kneading until the material is suitable for extruding strips. The kneaded material is transferred into a strip extruding machine to be extruded into strips with the diameter of 4mm, then the strips are cut into balls with the diameter of 4mm by a grain cutting machine, the spherical particles are dried for 24 hours at the temperature of 110-120 ℃, and are roasted for 4 hours at the temperature of 520-540 ℃ in the atmosphere with the oxygen content of 6-8 percent to obtain the catalyst B1.
Comparative example two (see patent CN 201110222993):
262g of V 2 O 5 Adding the solution into a solution which consists of 4000ml of water and 500g of oxalic acid and has the temperature of 80-90 ℃, fully stirring, and reacting to obtain a vanadium oxalate solution.
Mixing 40% (wt) SiO 2 1450g of silica sol was slowly added to the above solution under stirring, and 690g of Cr (NO) was added thereto, respectively 3 ) 3 ·9H 2 Solution of O and 90ml of water, 84gCo (NO) 3 ) 2 ·6H 2 O and 30ml water, 1.6mol phosphoric acid solution, and finally 29g KNO 3 And 100ml of water, stirring and mixing, and heating and evaporating until the solid content is 38% (wt) to obtain viscous slurry. Spray-forming the slurry, granulating the formed particles by dry method, drying at 120 deg.C for 12h, calcining at 500 deg.C for 6h, and tabletting to obtain cylindrical body with diameter of 5mm and height of 5mmTo obtain the catalyst B2.
The catalysts A1-A10, B1 and B2 are respectively filled in a fixed bed reactor with the diameter of 25mm and the length of 4 meters, and the filling height of the catalyst is 3.5m. Taking 2, 6-dichlorobenzyl chloride, ammonia gas and air as raw materials, and controlling the reaction conditions of the 2, 6-dichlorobenzyl chloride: ammonia gas: the volume ratio of air is 1:5: performing ammoxidation at a reaction temperature of 350 to 450 ℃ and a pressure of 10 to 100kPa, controlling the reaction temperature so that the conversion of 2, 6-dichlorobenzyl chloride is >99%, collecting and analyzing the content of 2, 6-dichlorobenzonitrile in the product, and calculating the selectivity and yield of 2, 6-dichlorobenzonitrile, wherein the measurement results are shown in Table 1, wherein the selectivity and yield of 2, 6-dichlorobenzonitrile are defined as follows:
the selectivity of 2, 6-dichlorobenzonitrile was:
molar amount of produced 2, 6-dichlorobenzonitrile/molar amount of reacted 2, 6-dichlorobenzyl chloride. Times.100%
The yield of 2, 6-dichlorobenzonitrile was:
the molar amount of the generated 2, 6-dichlorobenzonitrile per the molar amount of the starting 2, 6-dichlorobenzyl chloride is multiplied by 100%.
TABLE 1
As can be seen from the data in Table 1, the catalyst disclosed in the invention can be used for catalyzing the reaction for preparing 2, 6-dichlorobenzonitrile by using 2, 6-dichlorobenzyl chloride as a raw material, and the product has very high selectivity and yield.
Catalysts A1 to A10, B1 and B2 were respectively loaded in a fixed bed reactor having a diameter of 25mm and a length of 4m, the catalyst loading height was 3.5m, 2, 6-dichlorotoluene, ammonia gas and air were used as raw materials, and the reaction conditions of 2, 6-dichlorotoluene: ammonia gas: the volume ratio of air is 1:5: and 15, carrying out ammoxidation at the reaction temperature of 350-450 ℃ and under the pressure of 10-100 kPa, controlling the reaction temperature so that the conversion rate of the 2, 6-dichlorotoluene is greater than 99%, collecting and analyzing the content of the 2, 6-dichlorobenzonitrile in the product, and calculating the selectivity and yield of the 2, 6-dichlorobenzonitrile, wherein the measurement results are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, the catalyst disclosed in the invention can also be used for catalyzing the reaction for preparing 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene, and the product has very high selectivity and yield.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention.
Claims (5)
1. A preparation method of a catalyst for synthesizing 2, 6-dichlorobenzonitrile is characterized in that: the method comprises the following steps:
1) Preparation of reactive precursors
Adding a vanadium compound, a phosphorus compound and a molybdenum compound into an alcohol solvent, stirring to prepare a suspension, heating to raise the temperature, reacting at the reaction temperature of 80-160 ℃ and the reaction pressure of 0-40 kPa for 4-6 h, cooling, filtering, drying a filter cake at the temperature of 100-160 ℃ for 24h, and roasting at the temperature of 280-400 ℃ for 4-8h; wherein the alcohol solvent is one or more of n-hexanol, isobutanol and benzyl alcohol;
2) Preparation of semifinished products
Uniformly mixing the active precursor obtained in the step 1) with a carrier and an auxiliary agent to obtain a mixed material, and then molding the mixed material; wherein the carrier is one of alumina, silicon oxide and titanium oxide; the auxiliary agent is a cobalt compound and/or a chromium compound;
3) Activation of
Activating the semi-finished product obtained in the step 2) in an oxygen-deficient air atmosphere with the oxygen content ranging from 3% to 15%, wherein the activation temperature is 400 ℃ to 600 ℃, and the activation time is 2h to 10h;
the catalyst synthesized by the method comprises the following elements in molar ratio:
V 1.0 P a Mo b X c O d /YO e
wherein X is selected from one or two of cobalt and chromium, Y is selected from one of silicon, aluminum and titanium, a ranges from 0.2 to 1.5, b ranges from 0.1 to 1.0, c ranges from 0.05 to 0.8, d is the total oxygen atom number required by the valence of other elements;
the vanadium compound is one or more of vanadium pentoxide, ammonium metavanadate and vanadium oxalate;
the phosphorus compound is one or more of phosphoric acid, ammonium phosphate, sodium phosphate and phosphorus pentoxide;
the molybdenum compound is one or more of ammonium heptamolybdate, ammonium tetramolybdate and molybdenum trioxide.
2. The method for preparing a catalyst according to claim 1, characterized in that: the reaction temperature is 90-140 ℃.
3. The method for preparing a catalyst according to claim 1, characterized in that: the cobalt compound is one or more of cobalt nitrate, cobalt phosphate, cobalt sulfate and cobalt oxide; the chromium compound is one or more of chromium nitrate, chromium carbonate, chromium sulfate and chromium oxide.
4. The method for preparing a catalyst according to claim 1, characterized in that: activating the semi-finished product obtained in the step 2) in an oxygen-poor air atmosphere with the oxygen content ranging from 6% to 12%, wherein the activation temperature is 450 ℃ to 550 ℃, and the activation time is 4h to 8h.
5. Use of the catalyst prepared by the method for synthesizing 2, 6-dichlorobenzonitrile according to any of claims 1 to 4 in the preparation of 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene or 2, 6-dichlorobenzyl by an ammoxidation method using 2, 6-dichlorotoluene or 2, 6-dichlorobenzyl as a reaction raw material.
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| CN1230465A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Fluid bed catalyst for the preparation of aromatic nitrile halide |
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| CN103041838A (en) * | 2012-12-28 | 2013-04-17 | 武汉今福科技有限公司 | Catalyst for preparing 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene by means of ammoxidation |
| CN104326940A (en) * | 2014-11-24 | 2015-02-04 | 苏州乔纳森新材料科技有限公司 | Method for synthesizing 2,6-dichlorobenzonitrile by ammoxidation |
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| GB1005066A (en) * | 1961-12-14 | 1965-09-22 | Shell Int Research | Preparation of polychlorobenzonitriles |
| CN1166378A (en) * | 1997-01-13 | 1997-12-03 | 武汉大学 | New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process |
| CN1230465A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Fluid bed catalyst for the preparation of aromatic nitrile halide |
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