CN109046454A - It is a kind of for synthesizing the catalyst and preparation method thereof of 2,6- dichlorobenzonitrile - Google Patents
It is a kind of for synthesizing the catalyst and preparation method thereof of 2,6- dichlorobenzonitrile Download PDFInfo
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- CN109046454A CN109046454A CN201810966666.0A CN201810966666A CN109046454A CN 109046454 A CN109046454 A CN 109046454A CN 201810966666 A CN201810966666 A CN 201810966666A CN 109046454 A CN109046454 A CN 109046454A
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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
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J27/188—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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- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
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Abstract
The present invention provides the catalyst and preparation method thereof that a kind of ammonia oxidation prepares 2,6- dichlorobenzonitrile.The catalyst can be not only used for the reaction that catalysis prepares 2,6- dichlorobenzonitrile using 2,6-DCT as raw material, more can be used for being catalyzed the reaction for preparing 2,6- dichlorobenzonitrile for raw material with 2,6- dichlorobenzyl chloride.The catalyst can reduce the excessive oxidation reaction of 2,6- dichlorobenzyl chloride, and product is made to have very high selectivity and yield, substantially reduce industrial production cost, meet the needs of large-scale industrial production.
Description
Technical field:
The invention belongs to catalysis technical fields, and in particular to a kind of catalyst of ammonia oxidation preparation 2,6- dichlorobenzonitrile
And preparation method thereof.
Background technique:
2,6- dichlorobenzonitriles also known as dichlobenil are a kind of important chemical intermediates, are widely used in herbicide, kill
The fields such as worm agent, medicine, dyestuff, high molecular material.
The method of synthesis 2,6- dichlorobenzonitrile is broadly divided into organic synthesis method and gas phase ammonia oxidation.Gas phase ammonoxidation method
Refer under the effect of the catalyst, reactant and ammonia, oxygen carry out ammoxidation reaction and generates 2,6- dichlorobenzonitrile.Vapor phase ammonia
For oxidizing process compared with organic synthesis method, process is simple, and low energy consumption, pollutes small, product yield and purity is high, is that reason is compared in industrialization
The method thought.
Up to the present, the catalyst related patents of domestic and international application ammonia oxidation preparation 2,6- dichloro-benzenes first eyeball are all adopted
It is raw material with 2,6- dichlorotoleune.Using silica as carrier, active component composition meets logical Chinese patent CN98110745.1
Formula V1.0PbNacAdBeOx, wherein A be it is at least one selected from lithium, potassium, rubidium, caesium element, B be it is at least one selected from magnesium, calcium, barium,
Chromium, manganese, iron, cobalt, nickel, tin element, the catalyst for be catalyzed with 2,6-DCT raw material through ammoxidation prepare 2,6- bis-
The reaction of chlorobenzonitrile, 2,6-DCT conversion ratio can up to 90%, yield up to 98%, 2,6- dichlorobenzonitrile selectivity
Up to 88% or more.Chinese patent CN201110222993 one kind is used to prepare the catalyst of 2,6- dichlorobenzonitrile, catalyst with
Silica is carrier, and active constituent meets general formula V1.0PaCrbCocXdOm, it is to use coprecipitation to prepare with V-Cr-P-Co
For the catalyst of main active component, it is applied to the technique mistake that 2,6-DCT carries out ammoxidation preparation 2,6- dichlorobenzonitrile
Cheng Zhong, 2,6-DCT conversion ratio is up to 99.5%, 2,6- dichlorobenzonitrile selectivity up to 90%, yield up to 90%.
The above-mentioned catalyst for being used to prepare 2,6- dichloro-benzenes first eyeball is all the catalysis using 2,6- dichlorotoleune as reactant
Agent.2,6-DCT price is high, and it is expensive to produce 2,6- dichlorobenzonitrile as reactant to use it, and 2,6- dichloro chlorine
Benzyl price very cheaply uses it as reactant to produce 2,6- dichlorobenzonitrile cost less than the half of 2,6-DCT
It is cheap, it is very suitable to large-scale industrial production.
Since the chemical property of 2,6- dichlorobenzyl chloride is more active, it is easier to excessive oxidation reaction occur, generate a large amount of
CO2, the selectivity of product 2,6- dichlorobenzonitrile is low with yield, therefore presently disclosed catalyst is not appropriate for for 2,6-
Dichlorobenzyl chloride is the preparation process of raw material.If a kind of be suitable for using 2,6- dichlorobenzyl chloride as raw material preparation 2,6- can be invented
Dichlorobenzonitrile, and product 2, the selectivity of 6- dichlorobenzonitrile is good, high income catalyst, then can substantially reduce industrial life
Produce cost.
Summary of the invention:
The invention discloses the catalyst and preparation method thereof that a kind of ammonia oxidation prepares 2,6- dichlorobenzonitrile.The catalysis
Agent can be not only used for the reaction that catalysis prepares 2,6- dichlorobenzonitrile using 2,6-DCT as raw material, more can be used for being catalyzed
The reaction of 2,6- dichlorobenzonitrile is prepared using 2,6- dichlorobenzyl chloride as raw material.The catalyst can reduce the mistake of 2,6- dichlorobenzyl chloride
Oxidation reaction is spent, so that 2,6- dichlorobenzyl chloride is passed through ammoxidation reaction favourable conversions is 2,6- dichlorobenzonitrile, and has product
Very high selectivity and yield substantially reduce industrial production cost, meet the needs of large-scale industrial production.
The reaction equation of 2,6- dichlorobenzyl chloride ammoxidation 2,6- dichlorobenzonitrile are as follows:
C7H5Cl3+2NH3+O2=C7H3Cl2N+NH4Cl+2H2O
Main side reaction is excessive oxidation reaction, reaction equation are as follows:
2C7H5Cl3+6NH3+15O2=6NH4Cl+14CO2+2H2O
The invention discloses a kind of for synthesizing the catalyst of 2,6- dichlorobenzonitrile, and atom composition meets following logical
Formula:
V1.0PaMobXcOd/YOe
Wherein X is selected from one or both of cobalt, chromium, and Y is selected from one of silicon, aluminium, titanium,
A is 0.2~1.5
B is 0.1~1.0
C is 0.05~0.8
D is to meet oxygen atomicity summation required for the element valences such as V, P, Mo, X.
In above-mentioned catalyst, the oxide containing X is as auxiliary agent, and the oxide containing Y is as carrier.
The invention also discloses the preparation methods of above-mentioned catalyst, and there are three steps altogether:
1, the preparation of active presoma
With stirring, heating and condensation reflux unit reaction kettle in, be added organic solvent, add vfanadium compound,
Suspension is made in phosphorus compound, molybdenum compound, stirring, and heat temperature raising is reacted at 80 DEG C~160 DEG C, 0~-40kPa,
React 4h~6h, cooled and filtered, filter cake at 100 DEG C~160 DEG C it is dry for 24 hours, roasted at 280 DEG C~400 DEG C 4h~
8h obtains active presoma.
Wherein, the organic solvent is one or more of n-hexyl alcohol, isobutanol, benzyl alcohol；The vanadium chemical combination
Object can be vanadic anhydride, ammonium metavanadate, vanadium oxalate etc., preferably vanadic anhydride, ammonium metavanadate；The phosphorus compound can
To be phosphoric acid, ammonium phosphate, sodium phosphate, phosphorus pentoxide etc., preferably phosphoric acid, phosphorus pentoxide；The molybdenum compound can be
Ammonium heptamolybdate, ammonium tetramolybdate, molybdenum trioxide etc., preferably ammonium heptamolybdate, ammonium tetramolybdate.The reaction temperature is 80 DEG C~160
DEG C, preferably 90 DEG C~140 DEG C.
2, prepared by semi-finished product
The active presoma that step 1 is obtained is uniformly mixed to obtain mixed material with carrier, auxiliary agent, is then shaped,
Semi-finished product are made.
Wherein, the carrier can be aluminium oxide, silica, titanium oxide；The auxiliary agent can be cobalt and/or chromium
Compound, wherein cobalt compound can be cobalt nitrate, cobalt phosphate, cobaltous sulfate, cobalt oxide etc., preferably cobalt nitrate, cobalt phosphate；Chromium
Compound can be chromic nitrate, chromium carbonate, chromium sulfate, chromium oxide etc., preferably chromic nitrate, chromium carbonate.
The forming of any one conventional method may be selected, enumerate some available shaping forms and its manufacturing process:
(1) bar shaped: 30%~80% water, 1%~15% pore creating material (such as sesbania powder are added by its weight for mixed material
Deng), 1%~5% lubricant (such as carboxymethyl cellulose), mediated in kneader uniformly until suitable extrusion, then
It is squeezed into diameter 4mm~8mm bar by banded extruder, by 6h dry at 100 DEG C~140 DEG C~for 24 hours, then is broken into length
The bar shaped particle of 4mm~8mm, obtains bar shaped semi-finished product.
(2) spherical: to be squeezed into diameter 4~6mm bar by (1) the method, 4~6mm of diameter is made by cut machine
Spherical shape, by 6h dry at 100 DEG C~140 DEG C~obtain spherical semi-finished product for 24 hours.
(3) cylindrical body or hollow cylinder: can use wet granulation: its weight 20%~50% is added in mixed material
Water is mediated uniformly, is then caused 10 mesh~40 mesh particle through pelletizer, is admixed the lubricants such as graphite or stearic acid after dry and obtain
To the particle of appropriate tablet；Or use non-slurry pelletizing: mixed material being admixed into the lubricants such as graphite or stearic acid and is made through dry method
Grain machine directly contributes 10 mesh~40 mesh particle.Particle is pressed into the cylindrical body of diameter 4mm~7mm or hollow through tablet press machine again
Cylindrical body.
3, it activates
Semi-finished product are put into Muffle furnace, are activated under oxygen denuded air atmosphere.
The oxygen content in activation phenomenon is controlled by being incorporated suitable nitrogen in air, oxygen is in oxygen denuded air
Volume content range be 3%~15%, preferably 6%~12%；Activation temperature be 400 DEG C~600 DEG C, preferably 450 DEG C~550
℃；Activation time is 2h~10h, preferably 4h~8h.
It, can be by Catalyst packing in diameter 25mm, the fixed bed reactors that 4 meters of length when using catalyst of the invention
In, catalyst packing height 3.5m.With 2,6- dichlorobenzyl chloride, ammonia, oxygen denuded air be raw material, 300 DEG C~500 DEG C of temperature,
Ammoxidation reaction is carried out under pressure 10kPa~100kPa, reaction generates 2,6- dichlorobenzonitrile.When control reaction temperature makes 2,6-
When the conversion ratio of dichlorobenzyl chloride > 99%, product 2, the selectivity and yield of 6- dichlorobenzonitrile can reach 80% or more.
For ammoxidation reaction, vanadium is main active component, and the valence state of vanadium is critically important to its activity and selectivity.As vanadium master
In the presence of will be with+5 valences, the activity of catalyst can be very high, it is easy to excessive oxidation reaction occur, generate useless CO2, thus mesh
Marking selectivity of product can be very poor；And when vanadium mainly with+4 valences in the presence of, catalyst activity can it is very low, cause its selectivity it is good,
But product yield is low.In some patents that background of invention is introduced, the valence state of vanadium connects very much between+4.9~+5.0
Closely+5 valences, thus its hyperactivity, when use more active than 2,6-DCT chemical property 2,6- dichlorobenzyl chloride conduct
When reactant, it is easier to peroxidization occur, generate a large amount of CO2, cause the selectivity of target product and yield low.And this
Vanadium in invention catalyst can synthesize the VOHPO of rock-steady structure in alcohols solvent4, the selectivity of product is good, and yield is also very
Height, so being a kind of fabulous catalyst, side for being for raw material prepares 2,6- dichlorobenzonitrile with 2,6- dichlorobenzyl chloride
Helping realizes the preparation 2,6- dichloro-benzenes using the high 2,6- dichlorotoleune of 2,6- dichlorobenzyl chloride alternative cost at low cost as raw material
The technique of formonitrile HCN, and it can be applicable in large-scale industrial production, greatly reduce industrial production cost.
Meanwhile using catalyst of the invention, above-mentioned identical reactor can also be used, control identical condition, used
2,6-DCT is that raw material carries out ammoxidation reaction preparation 2,6- dichlorobenzonitrile, when control reaction temperature makes 2,6- dichloromethane
When the conversion ratio of benzene > 99%, product 2, the selectivity and yield of 6- dichlorobenzonitrile can reach 90% or more, catalytic effect
Very well.
The invention discloses the catalyst and preparation method thereof that a kind of ammoxidation reaction prepares 2,6- dichlorobenzonitrile.This is urged
Agent can be not only used for the reaction that catalysis prepares 2,6- dichlorobenzonitrile using 2,6-DCT as raw material, more can be used for urging
Change the reaction that 2,6- dichlorobenzonitrile is prepared using 2,6- dichlorobenzyl chloride as raw material.The catalyst can reduce 2,6- dichlorobenzyl chloride
Excessive oxidation reaction, so that 2,6- dichlorobenzyl chloride is passed through ammoxidation reaction favourable conversions is 2,6- dichlorobenzonitrile, and has product
There are very high selectivity and yield, substantially reduce industrial production cost, meets the needs of large-scale industrial production.
Specific embodiment:
The present invention is further described by the following embodiment.
Embodiment one:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5000g n-hexyl alcohol and 1000g
Then benzyl alcohol sequentially adds vanadic anhydride 636g, phosphoric acid 396g, ammonium heptamolybdate 120g, control temperature 90 DEG C~100
DEG C, reacted under -30kPa~-40kPa, the organic solvent of evaporation is back in reaction kettle after water condenser condenses, instead
Stop reaction after answering 6h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake dries 18h at 120 DEG C~140 DEG C,
Then active presoma is obtained in 300 DEG C~320 DEG C roasting 8h.
Active presoma is added in kneader, aluminium oxide 1524g, cobalt nitrate 206g, sesbania powder 100g, carboxylic is then added
Methylcellulose 50g is uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for extrusion.It mediates
Good material is transferred to the item that 5mm is squeezed into banded extruder, the ball of diameter 5mm is then cut into pelleter, spherical particle is at 110 DEG C
~120 DEG C of dryings for 24 hours, roast 8h at 480 DEG C~500 DEG C under the atmosphere of oxygen content 9%~11% and obtain catalyst A1.
Embodiment two:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5000g n-hexyl alcohol and 1000g
Benzyl alcohol, then sequentially adds ammonium metavanadate 829g, phosphatase 11 78g, ammonium heptamolybdate 186g, control temperature 90 DEG C~100 DEG C ,-
It is reacted under 30kPa~-40kPa, the organic solvent of evaporation is back in reaction kettle after water condenser condenses, and reacts 6h
Stop reaction afterwards.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake dries 18h at 120 DEG C~140 DEG C, then
Active presoma is obtained in 300 DEG C~320 DEG C roasting 8h.
Active presoma is added in dry granulating machine, aluminium oxide 1524g is then added, cobalt nitrate 196g, is uniformly mixed,
Cause 12 mesh~20 mesh particle.Particle is pressed into the cylindrical body of diameter 5mm, height 5mm by tablet press machine, then at 480 DEG C
8h is roasted at~500 DEG C under the atmosphere of oxygen content 9%~11% and obtains catalyst A2.
Embodiment three:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5500g n-hexyl alcohol and 1100g
Then benzyl alcohol sequentially adds vanadic anhydride 636g, phosphorus pentoxide 122g, ammonium heptamolybdate 120g, control temperature at 90 DEG C
~100 DEG C, reacted under -30kPa~-40kPa, the organic solvent of evaporation is back to reaction kettle after water condenser condenses
In, stop reaction after reacting 6h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake is dry at 120 DEG C~140 DEG C
Then 18h obtains active presoma in 300 DEG C~320 DEG C roasting 8h.
Active presoma is added in kneader, aluminium oxide 1524g, cobalt nitrate 206g, sesbania powder 100g, carboxylic is then added
Methylcellulose 50g is uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for extrusion.It mediates
Good material is transferred to the item that 5mm is squeezed into banded extruder, the ball of diameter 5mm is then cut into pelleter, spherical particle is at 110 DEG C
~120 DEG C of dryings for 24 hours, roast 8h at 480 DEG C~500 DEG C under the atmosphere of oxygen content 9%~11% and obtain catalyst A3.
Example IV:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5500g n-hexyl alcohol and 1100g
Then benzyl alcohol sequentially adds vanadic anhydride 736g, phosphorus pentoxide 343g, ammonium heptamolybdate 216g, control temperature at 100 DEG C
~110 DEG C, reacted under -20kPa~-30kPa, the organic solvent of evaporation is back to reaction kettle after water condenser condenses
In, stop reaction after reacting 5h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake is dry at 110 DEG C~130 DEG C
For 24 hours, active presoma then is obtained in 300 DEG C~320 DEG C roasting 8h.
Active presoma is added in kneader, aluminium oxide 1524g, chromic nitrate 358g, cobalt nitrate 110g, field is then added
Cyanines powder 100g, carboxymethyl cellulose 50g are uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for squeezing
Until item.Kneaded material is transferred to the item that 5mm is squeezed into banded extruder, and the ball of diameter 5mm is then cut into pelleter, spherical
Particle 110 DEG C~120 DEG C dryings for 24 hours, at 480 DEG C~500 DEG C under the atmosphere of oxygen content 9%~11% roast 8h obtain
Catalyst A4.
Embodiment five:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5000g n-hexyl alcohol and 1000g
Then benzyl alcohol sequentially adds ammonium metavanadate 829g, phosphatase 11 98g, ammonium heptamolybdate 130g, control temperature 100 DEG C~110
DEG C, reacted under -20kPa~-30kPa, the organic solvent of evaporation is back in reaction kettle after water condenser condenses, instead
Stop reaction after answering 5h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake is dried for 24 hours at 110 DEG C~130 DEG C,
Then active presoma is obtained in 320 DEG C~340 DEG C roasting 6h.
Active presoma is added in kneader, aluminium oxide 1524g, cobalt nitrate 206g, sesbania powder 100g, carboxylic is then added
Methylcellulose 50g is uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for extrusion.It mediates
Good material is transferred to the item that 6mm is squeezed into banded extruder, then 110 DEG C~120 DEG C dryings for 24 hours, be broken into 4mm~7mm item
Shape roasts 6h at 500 DEG C~520 DEG C under the atmosphere of oxygen content 8%~9% and obtains catalyst A5.
Embodiment six:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5500g n-hexyl alcohol and 1100g
Then benzyl alcohol sequentially adds ammonium metavanadate 778g, phosphatase 11 38g, ammonium tetramolybdate 115g, calcium oxide 50g, control temperature 120
DEG C~130 DEG C, reacted under -10kPa~-20kPa, the organic solvent of evaporation is back to reaction after water condenser condenses
In kettle, stop reaction after reacting 4h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake is done at 120 DEG C~140 DEG C
Then dry 18h obtains active presoma in 320 DEG C~340 DEG C roasting 6h.
Will active presoma be added kneader in, then be added titanium dioxide 1265g, chromic nitrate 327g, cobalt nitrate 110g,
Sesbania powder 100g, carboxymethyl cellulose 50g are uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for
Until extrusion.Kneaded material is transferred to the item that 6mm is squeezed into banded extruder, and the ball of diameter 6mm, ball are then cut into pelleter
Shape particle 110 DEG C~120 DEG C dryings for 24 hours, at 500 DEG C~520 DEG C under the atmosphere of oxygen content 8%~9% roast 8h obtain
To catalyst A6.
Embodiment seven:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5500g n-hexyl alcohol and 1100g
Then benzyl alcohol sequentially adds ammonium metavanadate 778g, phosphatase 24 56g, ammonium heptamolybdate 234g, control temperature 120 DEG C~130
DEG C, reacted under -10kPa~-20kPa, the organic solvent of evaporation is back in reaction kettle after water condenser condenses, instead
Stop reaction after answering 4h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake dries 18h at 120 DEG C~140 DEG C,
Then active presoma is obtained in 320 DEG C~340 DEG C roasting 6h.
Active presoma is added in dry granulating machine, aluminium oxide 1578g is then added, cobalt nitrate 206g, is uniformly mixed,
Cause 14 mesh~24 mesh particle.Particle is pressed into outer diameter 5.5mm, height 5.5mm, the sky that centre bore is 2mm by tablet press machine
Then heart cylindrical body roasts 6h under the atmosphere of oxygen content 8%~9% at 500 DEG C~520 DEG C and obtains catalyst A7.
Embodiment eight:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5500g n-hexyl alcohol and 1100g
Then benzyl alcohol sequentially adds vanadic anhydride 736g, phosphorus pentoxide 289g, ammonium heptamolybdate 140g, control temperature at 120 DEG C
~130 DEG C, reacted under -10kPa~-20kPa, the organic solvent of evaporation is back to reaction kettle after water condenser condenses
In, stop reaction after reacting 4h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake is dry at 130 DEG C~150 DEG C
Then 14h obtains active presoma in 340 DEG C~360 DEG C roasting 5h.
Active presoma is added in kneader, aluminium oxide 1578g, chromic nitrate 403g, cobalt nitrate 110g, field is then added
Cyanines powder 100g, carboxymethyl cellulose 50g are uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for squeezing
Until item.Kneaded material is transferred to the item that 4mm is squeezed into banded extruder, then 110 DEG C~120 DEG C dryings for 24 hours, be broken into
4mm~6mm bar shaped roasts 6h at 500 DEG C~520 DEG C under the atmosphere of oxygen content 8%~9% and obtains catalyst A8.
Embodiment nine:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5500g n-hexyl alcohol and 1100g
Then benzyl alcohol sequentially adds vanadic anhydride 636g, phosphorus pentoxide 150g, ammonium heptamolybdate 120g, control temperature at 130 DEG C
~140 DEG C, reacted under 0kPa~-10kPa, the organic solvent of evaporation is back to reaction kettle after water condenser condenses
In, stop reaction after reacting 4h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake is dry at 130 DEG C~150 DEG C
Then 14h obtains active presoma in 340 DEG C~360 DEG C roasting 5h.
Active presoma is added in kneader, aluminium oxide 1578g, chromic nitrate 527g, sesbania powder 100g, carboxylic is then added
Methylcellulose 50g is uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for extrusion.It mediates
Good material is transferred to the item that 4mm is squeezed into banded extruder, the ball of diameter 4mm is then cut into pelleter, spherical particle is at 110 DEG C
~120 DEG C of dryings for 24 hours, roast 4h at 520 DEG C~540 DEG C under the atmosphere of oxygen content 6%~8% and obtain catalyst A9.
Embodiment ten:
In the reaction kettle with stirring, heating and condensation reflux unit, it is added with stirring 5500g n-hexyl alcohol and 1100g
Benzyl alcohol, then sequentially adds ammonium metavanadate 829g, phosphorus pentoxide 402g, ammonium heptamolybdate 130g, control temperature 130 DEG C~
140 DEG C, reacted under 0kPa~-10kPa, the organic solvent of evaporation is back in reaction kettle after water condenser condenses,
Stop reaction after reacting 4h.Obtained slurry is separated by solid-liquid separation to obtain filter cake, filter cake is dry at 130 DEG C~150 DEG C
Then 14h obtains active presoma in 340 DEG C~360 DEG C roasting 5h.
Will active presoma be added kneader in, then be added silica 1 278g, chromic nitrate 513g, sesbania powder 100g,
Carboxymethyl cellulose 50g is uniformly mixed, and suitable water then is added under continuous mediate, until material is suitable for extrusion.It pinches
The material got togather is transferred to the item that 4mm is squeezed into banded extruder, the ball of diameter 4mm is then cut into pelleter, spherical particle is 110
DEG C~120 DEG C of dryings for 24 hours, at 520 DEG C~540 DEG C under the atmosphere of oxygen content 6%~8% roast 4h obtain catalyst A10.
Comparative example one (referring to patent CN98110745.1):
186.1g ammonium metavanadate is added to by 2800mL water, is mixed with 85% phosphoric acid 220g, 400ml water, is added 20%
NaNO3202.5g, 20%LiNO3SiO is added after mixing in 109.7g2175g, stirring, heating evaporation to solid content 38%, slurry
Expect spray-dried at particle, particle obtains presoma in 400 DEG C of preroast 0.5h.
Presoma is added in kneader, sesbania powder 50g, carboxymethyl cellulose 30g is then added, is uniformly mixed, then
Suitable water is added under continuous mediate, until material is suitable for extrusion.Kneaded material, which is transferred in banded extruder, to be squeezed into
The item of 4mm, is then cut into the ball of diameter 4mm with pelleter, spherical particle 110 DEG C~120 DEG C dryings for 24 hours, 520 DEG C~
4h is roasted at 540 DEG C under the atmosphere of oxygen content 6%~8% and obtains catalyst B1.
Comparative example two (referring to patent CN201110222993):
By the V of 262g2O5It is added in the solution for being 80-90 DEG C by the temperature that 4000ml water and 500g oxalic acid form, sufficiently stirs
It mixes, reaction obtains oxalic acid vanadium solution.
By 40% (wt) SiO2Silica solution 1450g be slowly added in above-mentioned solution under stiring, be then respectively adding
By 690gCr (NO3)3·9H2The solution of O and 90ml water composition, 84gCo (NO3)2·6H2The solution of O and 30ml water composition, phosphoric acid
Solution 1.6mol, is eventually adding 29gKNO3It with the solution of 100ml water composition, is stirred, heating evaporation to solid content is 38%
(wt), viscous paste is obtained.Slurry is sprayed forming, the particle after forming passes through non-slurry pelletizing, the dry 12h at 120 DEG C, and 500
6h is roasted at DEG C, and the cylindrical body of diameter 5mm, height 5mm are then pressed by tablet press machine, obtains catalyst B2.
Catalyst A1~A10, B1, B2 are loaded on diameter 25mm respectively, in the fixed bed reactors that 4 meters of length, catalysis
Height 3.5m is loaded in agent.With 2,6- dichlorobenzyl chloride, ammonia, air for raw material, 2,6- dichlorobenzyl chloride: ammonia: the body of air is controlled
Product carries out ammoxidation reaction, control is anti-than being 1:5:15 at 350 DEG C~450 DEG C of reaction temperature, pressure 10kPa~100kPa
Answer temperature so that 2,6- dichlorobenzyl chlorides conversion ratio > 99%, collect and analyze 2,6- dichlorobenzonitrile content in product, calculate 2,
The selectivity and yield of 6- dichlorobenzonitrile, measurement result are listed in table 1, wherein 2,6- dichlorobenzonitriles selectivity and yield definition
It is as follows:
2,6- dichlorobenzonitrile selectivity are as follows:
2,6- dichlorobenzyl chloride mole × 100% for the 2,6- dichlorobenzonitrile mole of generation/reacted
2,6- dichlorobenzonitrile yield are as follows:
The 2,6- dichlorobenzonitrile mole of generation/raw material 2,6- dichlorobenzyl chloride mole × 100%.
Table 1
From the data in table 1, it can be seen that catalyst disclosed in this invention can be used for being catalyzed with 2,6- dichlorobenzyl chloride for raw material system
The reaction of standby 2,6- dichlorobenzonitrile, and make product that there is very high selectivity and yield.
Separately catalyst A1~A10, B1, B2 are loaded on diameter 25mm respectively, in the fixed bed reactors that 4 meters of length, urged
Agent loads height 3.5m, using 2,6-DCT, ammonia, air as raw material, controls 2,6-DCT: ammonia: air
Volume ratio is 1:5:15, carries out ammoxidation reaction at 350 DEG C~450 DEG C of reaction temperature, pressure 10kPa~100kPa, control
Reaction temperature so that 2,6-DCT conversion ratio > 99%, collect and analyze 2,6- dichlorobenzonitrile content in product, calculate
The selectivity and yield of 2,6- dichlorobenzonitriles, measurement result are listed in table 2.
Table 2
From the data in table 2, it can be seen that catalyst disclosed in this invention can be also used for catalysis using 2,6-DCT as raw material
The reaction of 2,6- dichlorobenzonitrile is prepared, and makes product that there is very high selectivity and yield.
The present invention is not limited to the above embodiment the specific technical solution, all technical sides formed using equivalent replacement
Case is the range that the present invention is protected.
Claims (10)
1. one kind is for synthesizing the catalyst of 2,6- dichlorobenzonitrile, element composition and molar ratio computing are as follows:
V1.0PaMobXcOd/YOe
Wherein X is selected from one or both of cobalt, chromium, and Y is selected from one of silicon, aluminium, titanium, and a value range is 0.2~1.5, b
For 0.1~1.0, c be 0.05~0.8, d be meet oxygen atomicity summation required for other elements chemical valence.
2. the preparation method of catalyst of the one kind for synthesizing 2,6- dichlorobenzonitrile, the steps include:
1) preparation of active presoma
Vfanadium compound, phosphorus compound, molybdenum compound are added in alcohols solvent, suspension is made in stirring, and heat temperature raising is reacting
Temperature is 80 DEG C~160 DEG C, reaction pressure is reacted under being 0~-40kPa, react 4h~6h, cooled and filtered, filter cake in
Drying for 24 hours, roasts 4h~8h at 280 DEG C~400 DEG C at 100 DEG C~160 DEG C；Wherein, alcohols solvent is n-hexyl alcohol, isobutyl
One of alcohol, benzyl alcohol are a variety of；
2) prepared by semi-finished product
Be uniformly mixed the resulting active presoma of step 1) to obtain mixed material with carrier, auxiliary agent, then by mixed material at
Shape；Wherein the carrier is one of aluminium oxide, silica, titanium oxide or a variety of；The auxiliary agent be cobalt compound and/
Or chromium compound；
3) it activates
The resulting semi-finished product of step 2) are activated in the case where oxygen content range is 3%~15% oxygen denuded air atmosphere, it is living
Changing temperature is 400 DEG C~600 DEG C, and activation time is 2h~10h.
3. the preparation method of catalyst according to claim 2, it is characterised in that: the vfanadium compound is five oxidations two
One of vanadium, ammonium metavanadate, vanadium oxalate are a variety of.
4. the preparation method of catalyst according to claim 2, it is characterised in that: the phosphorus compound is phosphoric acid, phosphorus
One of sour ammonium, sodium phosphate, phosphorus pentoxide are a variety of.
5. the preparation method of catalyst according to claim 2, it is characterised in that: the molybdenum compound is seven molybdic acids
One of ammonium, ammonium tetramolybdate, molybdenum trioxide are a variety of.
6. the preparation method of catalyst according to claim 2, it is characterised in that: the reaction temperature be 90 DEG C~
140℃。
7. the preparation method of catalyst according to claim 2, it is characterised in that: the cobalt compound be cobalt nitrate,
One of cobalt phosphate, cobaltous sulfate, cobalt oxide are a variety of；The chromium compound is chromic nitrate, chromium carbonate, chromium sulfate, oxidation
One of chromium is a variety of.
8. the preparation method of catalyst according to claim 2, it is characterised in that: by the resulting semi-finished product of step 2) in oxygen
It is activated under the oxygen denuded air atmosphere that Gas content range is 6%~12%, activation temperature is 450 DEG C~550 DEG C, activation time
For 4h~8h.
9. catalyst described in claim 1 is used to pass through ammonia as using 2,6- dichlorotoleune or 2,6- dichlorobenzyl chloride as reaction raw materials
Oxidizing process prepares the catalyst of 2,6- dichlorobenzonitrile.
10. using catalyst prepared by the preparation method of any catalyst of claim 2~8 as with 2,6- dichloro
Toluene or 2,6- dichlorobenzyl chloride are the catalyst that reaction raw materials prepare 2,6- dichlorobenzonitrile by ammonia oxidation.
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| SU194089A1 (en) * | Б. В. Суворов, В. С. Кудинова, Г. Н. Гуцалюк , Т. И. Институт химических наук Казахской ССР | CONTINUOUS SINGLE-STAGE METHOD FOR OBTAINING 2,6-DICHLOROBENZONITRILE | ||
| 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 |
| CN1230464A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Fluid and catalyst for the preparation of aromatic nitrile halide |
| 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 |
| WO2003101939A2 (en) * | 2002-06-04 | 2003-12-11 | Tessenderlo Chemie S.A. | Method for the preparation of halogenated benzonitriles |
| 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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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU194089A1 (en) * | Б. В. Суворов, В. С. Кудинова, Г. Н. Гуцалюк , Т. И. Институт химических наук Казахской ССР | CONTINUOUS SINGLE-STAGE METHOD FOR OBTAINING 2,6-DICHLOROBENZONITRILE | ||
| 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 |
| CN1230464A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Fluid and catalyst for the preparation of aromatic nitrile halide |
| 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 |
| WO2003101939A2 (en) * | 2002-06-04 | 2003-12-11 | Tessenderlo Chemie S.A. | Method for the preparation of halogenated benzonitriles |
| 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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