CN111569924B - Special catalyst for preparing 2, 6-dichlorobenzonitrile by ammonia oxidation method and preparation method and application thereof - Google Patents

Special catalyst for preparing 2, 6-dichlorobenzonitrile by ammonia oxidation method and preparation method and application thereof Download PDF

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CN111569924B
CN111569924B CN202010323810.6A CN202010323810A CN111569924B CN 111569924 B CN111569924 B CN 111569924B CN 202010323810 A CN202010323810 A CN 202010323810A CN 111569924 B CN111569924 B CN 111569924B
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dichlorobenzonitrile
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carbon nitride
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CN111569924A (en
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谢光勇
丁爽
郑浩
董运召
熊焰
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South Central Minzu University
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
    • B01J35/31—
    • B01J35/40—
    • B01J35/613—
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a special catalyst for preparing 2, 6-dichlorobenzonitrile by an ammoxidation method, which is a multi-component inorganic composite oxide loaded by a silica gel-carbon nitride composite carrier, wherein the composition of active components of the catalyst is expressed as follows: VMo b B c Co d D e O x The method comprises the steps of carrying out a first treatment on the surface of the Wherein D is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium or barium. The invention also discloses a preparation method and application of the catalyst. According to the invention, the nitrogen-containing and carbon-containing organic matters and the silica sol are respectively used as precursors of the carbon nitride and the silica gel, and the mixed calcination is carried out to obtain the silica gel-carbon nitride composite carrier; meanwhile, the carbon nitride can also adjust the acid-base property, the oxidation-reduction capability and the coordination capability with reactants of the catalyst, so that the activity and the selectivity of the catalyst are improved. The catalyst has simple preparation method, good thermal stability and mechanical strength.

Description

Special catalyst for preparing 2, 6-dichlorobenzonitrile by ammonia oxidation method and preparation method and application thereof
Technical Field
The invention relates to a special catalyst for preparing 2, 6-dichlorobenzonitrile by an ammoxidation method, a preparation method and application thereof. It belongs to the technical field of organic chemistry and also belongs to the technical field of organic fine chemicals.
Background
2, 6-dichlorobenzonitrile is also known as 2, 6-dichlorobenzonitrile. The chlorobenzonitrile is used as a fine chemical with high added value, is a key raw material for manufacturing high-efficiency low-toxicity pesticides, novel medicines, high-performance materials, dyes and the like, and is widely applied to various fields of national economy.
2, 6-dichlorobenzonitrile (2, 6-DCBN) is mainly an intermediate which is necessary for an ultra-efficient, pollution-free and low-residual-toxicity benzoyl urea pesticide. Currently, the low-efficiency and high-toxicity pesticides in China are prohibited from being used, sold and produced by law, so that a great deal of efficient and pollution-free pesticide products are urgently needed in China. The 2, 6-dichlorobenzonitrile is a herbicide and is also an intermediate for producing efficient pollution-free pesticide-benzoyl urea pesticide. In recent years, research institutions and across-country companies in developed countries have developed a considerable number of new varieties of benzoylurea pesticides which are efficient and safe to natural enemies and the environment, wherein the well-known commercial products include more than 20 varieties of "diflubenzuron", "chlorfluazuron", "Fuzuron", "hexaflumuron", "flufenoxuron", "chloruron", "lufenuron", and the like, and the annual speed is increased by more than 22%. China also starts to introduce and produce the pesticides. 2,6-DCBN is also an important intermediate of pesticides such as amide insecticides, triazolopyrimidine sulfonamide herbicides, tetrazine insecticides, miticides, diazole and thiadiazoles insecticides, and triazole insecticides.
In addition, 2,6-DCBN is also a monomer of special engineering plastic polyaryl ether nitrile. The poly (arylene ether nitrile) has the advantages of high mechanical strength, chemical corrosion resistance, high temperature resistance, radiation resistance, flame retardance, good high-temperature fluidity, easy processing and forming, excellent electrical property and the like.
The preparation method of 2, 6-dichlorobenzonitrile has more than ten methods, and is generally prepared by taking corresponding aldehyde, aldoxime or acid as raw materials, and the methods have the advantages of high raw material price, long reaction route, low product yield and reaction selectivity and serious environmental pollution. The 2, 6-dichlorobenzonitrile can also be produced by an ammoxidation method, and the method for preparing the 2, 6-dichlorobenzonitrile by the ammoxidation method has the advantages of simple process, continuous operation, simple operation, strong production capacity, obvious economic benefit, environmental protection and the like; the core is the development of industrial catalysts.
Compared with other chlorotoluenes, the 2, 6-dichlorotoluene has lower activity of methyl and is difficult to generate ammoxidation due to the influence of two chlorine atoms with larger steric hindrance and stronger electron withdrawing at the ortho position of the methyl, and the conversion rate of raw materials and the yield of products are lower. The molar yield of 2, 6-dichlorobenzonitrile prepared by the ammoxidation process as reported in UK1317064 was only 53.3%. U.S. patent No. 4530797 uses vanadium phosphorus oxide as an ammoxidation catalyst to increase the yield of 2, 6-dichlorobenzonitrile to over 80%, however, the addition of haloalkanes to the reaction system increases the complexity of the process. European patent EP0271137 uses an iron-antimony catalyst, and the unreacted raw material 2, 6-dichlorotoluene is recovered by a mode of connecting two towers in series, and the molar yield can reach 81 percent. Japanese patent JP-3-44362 requires nitrogen to be charged into the reaction feed. The measures in the above patent lead to complex production process and greatly increase investment; or equipment corrosion and low product purity. The unsupported VPO composite oxide prepared by the sol-gel method, such as Martin, is used as an ammoxidation catalyst to prepare 2, 6-dichlorobenzonitrile, so that the product yield is low, and the requirement of industrial production is difficult to reach; in addition, the catalyst is not mechanically strong and cannot be used in fluidized bed reactors (Journal of Catalysis,2006,240:8-17;Catalysis Today,2009,142:158-164). Preparation of V by silica gel impregnation in Chinese patent CN1055028C a Ti b P c Cr d O x The four-component silica gel supported catalyst catalyzes 2, 6-dichlorotoluene ammoxidation to prepare 2, 6-dichlorobenzonitrile with a yield up to 85%; however, silica gel supported catalysts generally have a short service life in industry. The silicon sol type vanadium-phosphorus composite oxide catalyst is prepared by spray drying in the patent CN101069634C, the product yield can reach more than 85%, however, bromine-containing compounds are needed to be added into raw materials to obtain higher activity. The catalysts used in these patents still have difficulty meeting the industrial requirements for high strength, long life, high loading and high activity and high selectivity of the catalysts.
Disclosure of Invention
The invention aims to provide a special catalyst for preparing 2, 6-dichlorobenzonitrile by using a 2, 6-dichlorotoluene ammoxidation method.
Another technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned special catalyst.
The third technical problem to be solved by the present invention is to provide the use of the above-mentioned special catalyst.
In order to solve the first technical problem, the invention provides a special catalyst for preparing 2, 6-dichlorobenzonitrile by a 2, 6-dichlorotoluene ammoxidation method.
The special catalyst is a multi-component inorganic oxide catalyst loaded by a silica gel-carbon nitride composite carrier, the carrier is a silica gel-carbon nitride composite carrier formed by carbon nitride and silica gel, and the composition of active components is expressed as follows: VMo b B c Co d D e O x The method comprises the steps of carrying out a first treatment on the surface of the Wherein D is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium or barium; b=0.2 to 2.5; c=0.1 to 1.0; d=0 to 1.2; e=0 to 0.5; x is determined by valence balance according to the content of each element. Uniformly mixing the active component with a silica gel-carbon nitride composite carrier to form composite microspheres; the sum of the weight of the active components in the catalyst accounts for 20-80 percent of the total weight of the composite microsphere, and is preferably 40-70 percent. The diameter of the composite microsphere ranges from 30 to 100 mu m, and the average diameter is 45 to 55 mu m. Preferably, b=0.2 to 2.0; c=0.1 to 0.8; d=0 to 1.0; e=0 to 0.2.
The carbon nitride in the catalyst carrier accounts for 0.5-30% of the weight of the carrier. The silica gel in the carrier takes silica sol as a precursor, and the carbon nitride takes organic matters containing nitrogen and carbon as the precursor; adding the organic matters containing nitrogen and carbon into the silica sol, uniformly mixing, and calcining at high temperature to form the silica gel-carbon nitride composite carrier. The silica sol may be an acidic, basic or neutral silica sol. The organic precursors containing nitrogen and carbon include melamine, cyanuric chloride, cyanuric acid, cyanamide, dicyandiamide, urea, ethylenediamine, triethylamine, etc. The preparation method comprises the steps of adding a mixture of a nitrogen-and-carbon-containing organic precursor and silica sol, calcining to obtain a carbon nitride doped silica gel compound serving as a carrier, wherein conjugated pi electrons in the carbon nitride and lone pair electrons on nitrogen can be used as Lewis base to interact with an active center serving as Lewis acid, so that the effect of the active center and the carrier is enhanced, the loss of active components is reduced, the strength and the wear resistance of the catalyst are improved, and the service life of the catalyst is greatly prolonged. Meanwhile, the carrier can also adjust the acid-base property, the oxidation-reduction capability and the coordination capability with reactants of the catalyst through carbon nitride doping, so that the activity and the selectivity of the catalyst are improved.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
in order to reduce the loss of active components of the catalyst and prolong the service life of the catalyst, the interaction between the composite inorganic oxide and a carrier is required to be enhanced, and the new-generation high-activity composite inorganic oxide catalyst is prepared by adding a nitrogen-and-carbon-containing organic precursor and a silica sol mixture, and calcining the mixture to obtain a silica gel-carbon nitride composite serving as the carrier; carbon nitride rich in conjugated pi electrons and lone pair electrons on nitrogen is used as Lewis base to react with a main catalyst and/or a cocatalyst component serving as Lewis acid to carry out Lewis acid-base reaction, so that the effect of inorganic oxide and a carrier is enhanced, and the strength and the wear resistance of the catalyst are improved; meanwhile, inorganic oxides are dispersed more uniformly, so that loss of catalyst components is reduced, and the service life of the catalyst is greatly prolonged; meanwhile, the acidity and alkalinity, oxidation-reduction capability and coordination capability with reactants of the catalyst are regulated by using carbon nitride doped with a carrier, so that the activity and selectivity of the catalyst are improved.
The invention adopts high-speed centrifugal spray drying to prepare a catalyst, which comprises the following specific steps: adding organic precursors containing nitrogen and carbon into silica sol, mixing uniformly, and converting into active component VMo b B c Co d D e O x Dissolving and mixing the precursors of the above-mentioned organic precursor-containing silica sol, uniformly mixing them into suspension or slurry according to a certain proportion; spray-forming by a high-speed centrifugal spray dryer, and then activating at high temperature to obtain the multi-component inorganic oxide microsphere catalyst loaded by the micron-sized silica gel-carbon nitride composite carrier. The activation temperature is generally between 623 and 973K, preferably in the temperature range 673 to 873K. The activation time is generally 2 to 15 hours, and the optimal activation time range is 3 to 8 hours.
The precursor is a compound containing at least one element of V, mo, B, co or D, and the ratio of the sum of the amounts of V, mo, B, co and D in each precursor is 1: b: c: d: e, performing the step of; when d is zero, any precursor does not contain Co element; and when e is zero, any precursor does not contain D element.
In preparing the catalyst, any precursor may be used as an oxide, salt, acid or base containing at least one element of V, mo, B, co or D. For example, vanadium can be used as V 2 O 5 Or NH 4 VO 3 Etc.; molybdenum can be MoO 3 、(NH 4 ) 6 Mo 7 O 24 Etc.; boron can be H 3 BO 3 、B 2 O 3 Etc.; co may be used as Co (OAc) 2 、Co(NO 3 ) 2 ·6H 2 O、Co 3 O 4 Or CoCl 2 Etc.; lithium can be Li 2 O、LiCl、LiNO 3 Or Li (lithium) 2 CO 3 Etc.; na may be Na 2 CO 3 、NaHCO 3 、NaOH、NaCl、NaNO 3 、Na 2 SO 4 NaOAc or Na 2 C 2 O 4 Etc.; potassium can be used as KOH, KCl, KNO 3 、K 2 CO 3 、K 2 SO 4 KOAc or K 2 C 2 O 4 Etc.; rubidium can be RbCl, rbNO 3 、Rb 2 CO 3 、Rb 2 SO 4 RbOAc or Rb 2 C 2 O 4 Etc.; cesium can be CsCl, csNO 3 、Cs 2 CO 3 、Cs 2 SO 4 CsOAc or Cs 2 C 2 O 4 Etc.; the magnesium may be MgO or MgCl 2 Or Mg (NO) 3 ) 2 ·6H 2 O, etc.; the calcium can be CaCl 2 ·6H 2 O、Ca(OH) 2 Or Ca (NO) 3 ) 2 Etc.; barium may be BaCl 2 、Ba(OH) 2 Or Ba (NO) 3 ) 2 Etc. The solutions are prepared by methods commonly known in the art, e.g. V 2 O 5 Equal use H 2 C 2 O 4 Dissolving the aqueous solution to prepare a solution, and KCl and KNO 3 、K 2 CO 3 And the like, directly dissolving with water to prepare a solution.
In order to solve the third technical problem, the special catalyst provided by the invention is used for preparing the 2, 6-dichlorobenzonitrile by a 2, 6-dichlorotoluene ammoxidation method.
2, 6-dichlorobenzene is taken as a raw material, and is subjected to ammoxidation reaction with ammonia and oxygen under the action of a catalyst to obtain 2, 6-dichlorobenzonitrile; the reaction yield is 82-93%. The optimal process conditions for preparing 2, 6-dichlorobenzonitrile by using the catalyst to catalyze the ammoxidation of 2, 6-dichlorotoluene are as follows: the reaction temperature 643-723K, the molar ratio of air to 2, 6-dichlorotoluene is 10-50, the molar ratio of ammonia to 2, 6-dichlorotoluene is 1-10, and the catalyst load is 30-150 g/(kgcat.h). Under the conditions of a quartz tube fixed bed reactor with the inner diameter of 30mm and stable reaction, the conversion rate of the 2, 6-dichlorobenzene can be higher than 98 percent, and the molar yield of the 2, 6-dichlorobenzonitrile can be more than 90 percent.
Compared with other methods, the method has the advantages of low-cost and easily-obtained reaction raw materials, simple and direct process route, environmental friendliness, low cost, high yield and the like, and particularly greatly improves the strength and wear resistance of the catalyst, prolongs the service life and improves the activity of the catalyst and the selectivity of products. The ammoxidation catalyst has higher selectivity and activity; the preparation method is simple, low in cost, good in thermal stability and mechanical strength, and good in application value, and can be used on both fixed bed reactors and fluidized bed reactors.
Detailed Description
The invention will be further understood by the following examples, which are not intended to limit the scope of the invention.
Example 1
4g of melamine is dissolved in 10mL of hot water and evenly mixed with 90mL of silica sol with 30 percent of content; 18.30 g of H 2 C 2 O 4 ·2H 2 O was dissolved in 100mL distilled water at 80℃and 8.80 g V was added 2 O 5 Reaction until no gas was produced, then 20.48 g (NH 4 ) 6 Mo 7 O 24 ·4H 2 O, 3.60 g H 3 BO 3 8.44 g Co (NO) 3 ) 2 ·6H 2 O and 0.36 g Li 2 CO 3 After forming a uniform solution, slowly adding the solution into the mixed solution of the silica sol dissolved with the melamine. After stirring uniformly, concentrating until the solid content is 35%, then carrying out high-speed spray centrifugal drying to obtain a catalyst precursor, drying in a muffle furnace at 110 ℃, then gradually heating to 500 ℃, and preserving heat for 8 hours. And (5) naturally cooling for later use. The active composition of the catalyst is as follows: VMo 1.2 B 0.6 Co 0.3 Li 0.1 O 7.35 The method comprises the steps of carrying out a first treatment on the surface of the The active component content is 50%, and the weight percentage of carbon nitride in the silica gel-carbon nitride composite carrier is about 10%. The average particle size of the catalyst is 55 mu m, the bulk density is 0.99g/ml, and the specific surface area is 52m 2 The abrasion rate per g was 1.7%.
20g of the solid catalyst is filled in a quartz tube fixed bed reactor with the inner diameter of 30mm, and the mol ratio of the reaction raw materials is as follows: 2, 6-Dichlorotoluene NH 3 Air=1:5:30, reaction temperature 683±1K, catalyst loading 50 g/(kgcat h). After 8 hours of reaction, the conversion of 2, 6-dichlorobenzene was 98.3%, and the molar yield of 2, 6-dichlorobenzonitrile was 92.8%.
Example 2
Control example: the catalyst preparation method is the same as in example 1, except that melamine is not added into the silica sol, 100mL of 30% silica sol is used for replacing the mixed solution of the silica sol dissolved with melamine, and the active components of the catalyst are the same. The average particle size of the catalyst tested was 51. Mu.m, the bulk density was 0.92g/ml, and the specific surface area was 63m 2 The abrasion rate per gram is 2.8%, and the abrasion rate is more than 60% higher than that of the example 1; the catalyst of example 1 is thus comparatively denser, stronger and more attrition resistant. The experimental conditions for the ammoxidation of 2, 6-dichlorotoluene were the same as in example 1, and after 8 hours of reaction, the conversion of 2, 6-dichlorotoluene was 99.1%, and the molar yield of 2, 6-dichlorobenzonitrile was 81.6%.
Examples 3 to 7
The catalyst formulation was varied and the reaction conditions were the same as in example 1, with the results shown in the following table:
it is well known to those skilled in the art that catalysts of the present invention comprising other cocatalysts may also be prepared as described above. In the preparation process, the corresponding precursor substances of other cocatalyst components are replaced correspondingly according to the proportion by referring to the embodiment so as to obtain the required catalyst. Wherein the corresponding precursors of the other promoter components may be used as their oxides, salts, acids or bases, etc.

Claims (7)

1. The application of a special catalyst in preparing 2, 6-dichlorobenzonitrile by an ammoxidation method is characterized in that:
the special catalyst is a multi-component inorganic oxide catalyst loaded by a silica gel-carbon nitride composite carrier, the carrier is a silica gel-carbon nitride composite carrier formed by carbon nitride and silica gel, and the composition of active components is expressed as follows: VMo b B c Co d D e O x The method comprises the steps of carrying out a first treatment on the surface of the Wherein D is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium or barium; b=0.2 to 2.5; c=0.1 to 1.0; d=0 to 1.2; e=0 to 0.5; x is determined according to the content of each element and the valence balance;
the active component and the silica gel-carbon nitride composite carrier are uniformly mixed to form composite microspheres; the weight percentage content of active components in the special catalyst is 20-80%; the diameter range of the composite microsphere is 30-100 mu m, and the average diameter is 45-55 mu m;
the special catalyst is prepared by adopting high-speed centrifugal spray drying, and comprises the following specific steps:
1) Adding organic precursors containing nitrogen and carbon into the silica sol and uniformly mixing;
2) Dissolving and mixing all precursors converted into a catalyst active component, and uniformly mixing the precursor with the silica sol containing the organic precursor according to a certain proportion to form suspension or slurry;
3) Spray-forming by a high-speed centrifugal spray dryer;
4) Activating at high temperature to form a multi-component inorganic oxide microsphere catalyst loaded by a micron-sized silica gel-carbon nitride composite carrier; the high-temperature activation temperature is 623-973K, and the activation time is 2-15 hours;
the precursor is a compound containing at least one element of V, mo, B, co or D, and the ratio of the sum of the amounts of V, mo, B, co and D in each precursor is 1: b: c: d: e, performing the step of; when d is zero, any precursor does not contain Co element; and when e is zero, any precursor does not contain D element.
2. Use of a special catalyst according to claim 1 in an ammoxidation process for the preparation of 2, 6-dichlorobenzonitrile, said silica sol being an acidic, basic or neutral silica sol; the organic matter precursor containing nitrogen and carbon comprises melamine, melamine chloride, cyanuric acid, cyanamide, dicyandiamide, urea, ethylenediamine and triethylamine.
3. The use of a special catalyst according to claim 1 or 2 in the preparation of 2, 6-dichlorobenzonitrile by ammoxidation, characterized in that: the carbon nitride in the special catalyst carrier accounts for 0.5-30% of the weight of the carrier.
4. The use of a special catalyst according to claim 1 or 2 in the preparation of 2, 6-dichlorobenzonitrile by ammoxidation, characterized in that: the weight percentage content of active components in the special catalyst is 40-70%.
5. The use of a special catalyst according to claim 1 or 2 in the preparation of 2, 6-dichlorobenzonitrile by ammoxidation, characterized in that: the high-temperature activation temperature is 673-873K, and the activation time is 3-8 hours.
6. The use of a special catalyst according to claim 1 or 2 in the preparation of 2, 6-dichlorobenzonitrile by ammoxidation, characterized in that: the precursor is oxide, salt, acid or alkali containing at least one element of V, mo, B, co or D.
7. The use of the special catalyst according to claim 6 in the preparation of 2, 6-dichlorobenzonitrile by an ammoxidation process, characterized in that: the precursor is V 2 O 5 Or NH 4 VO 3 ；MoO 3 、(NH 4 ) 6 Mo 7 O 24 ；H 3 BO 3 、B 2 O 3 ；Co(OAc) 2 、Co(NO 3 ) 2 ·6H 2 O、Co 3 O 4 Or CoCl 2 ；Li 2 O、LiCl、LiNO 3 Or Li (lithium) 2 CO 3 ；Na 2 CO 3 、NaHCO 3 、NaOH、NaCl、NaNO 3 、Na 2 SO 4 NaOAc or Na 2 C 2 O 4 ；KOH、KCl、KNO 3 、K 2 CO 3 、K 2 SO 4 KOAc or K 2 C 2 O 4 ；RbCl、RbNO 3 、Rb 2 CO 3 、Rb 2 SO 4 RbOAc or Rb 2 C 2 O 4 ；CsCl、CsNO 3 、Cs 2 CO 3 、Cs 2 SO 4 CsOAc or Cs 2 C 2 O 4 ；MgO、MgCl 2 Or Mg (NO) 3 ) 2 ·6H 2 O；CaCl 2 ·6H 2 O、Ca(OH) 2 Or Ca (NO) 3 ) 2 ；BaCl 2 、Ba(OH) 2 Or Ba (NO) 3 ) 2 。
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