CN111499540A - Method for preparing 2,4,6-trichlorobenzonitrile by ammoxidation method, special catalyst and preparation method - Google Patents

Method for preparing 2,4,6-trichlorobenzonitrile by ammoxidation method, special catalyst and preparation method Download PDF

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CN111499540A
CN111499540A CN202010323817.8A CN202010323817A CN111499540A CN 111499540 A CN111499540 A CN 111499540A CN 202010323817 A CN202010323817 A CN 202010323817A CN 111499540 A CN111499540 A CN 111499540A
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trichlorobenzonitrile
chloride
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谢光勇
郑浩
丁爽
熊焰
周新花
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South Central Minzu University
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Abstract

The invention discloses a method for preparing 2,4,6-trichlorobenzonitrile by an ammoxidation method. The method takes 1,3, 5-trichlorobenzene as a raw material, obtains 2,4, 6-trichlorobenzyl chloride under the action of a special chloromethylation catalyst, and then obtains 2,4,6-trichlorobenzonitrile under the action of a special ammoxidation catalyst. The invention also discloses a special catalyst for preparing the 2,4,6-trichlorobenzonitrile and a preparation method thereof. The special chloromethylation catalyst can better catalyze the reaction of 1,3, 5-trichlorobenzene chloride and formaldehyde or paraformaldehyde and chlorine atom donor to efficiently obtain 2,4, 6-trichlorobenzyl chloride; the special ammoxidation catalyst can better catalyze the 2,4, 6-trichloro-benzyl chloride to react to obtain the 2,4, 6-trichloro-benzonitrile. The special catalyst has the advantages of high activity, high product yield, good selectivity, high product purity, long service life and simple process; the preparation method has the advantages of short reaction route, low reaction temperature, high yield and high selectivity.

Description

Method for preparing 2,4,6-trichlorobenzonitrile by ammoxidation method, special catalyst and preparation method
Technical Field
The invention relates to a method for preparing 2,4,6-trichlorobenzonitrile by an ammoxidation method, a special catalyst and a preparation method thereof. It belongs to the technical field of organic chemistry and also belongs to the technical field of organic fine chemicals.
Background
Trichlorobenzonitrile and derivatives thereof are important fine chemicals and organic intermediates, the downstream products of trichlorobenzoic acid, trichlorobenzamide, trifluorobenzonitrile, trifluorobenzoic acid, trifluoroaniline and the like are relatively easily obtained by taking trichlorobenzonitrile as a raw material, and are widely used in the industries such as pesticides, medicines, dyes, engineering plastics, photosensitive materials and the like, 2,4,6-trichlorobenzonitrile, also known as 2,4,6-trichlorobenzonitrile is an important trichlorobenzonitrile, however, compared with other aromatic nitriles, the preparation method of 2,4,6-trichlorobenzonitrile is very few in J.A. Fanizane takes 2,4,6-trichlorobenzonitrile as a raw material, and 2,4,6-trichlorobenzonitrile (Infrared and rare of 2,4,6-trichlorobenzonitrile, Syndye J.262, Striat, 5, 4, 5, 2-trichlorobenzonitrile, 4,6-trichlorobenzonitrile and the like are prepared by Saneydrafter reaction (the production cost of 2,4,6-trichlorobenzonitrile, 5, 4, 5, 4, 5, 4, 5, 4, 2,4, 2 of the raw materials of the raw material.
The 2,4,6-trichlorobenzonitrile can also be theoretically produced by a gas phase catalytic ammoxidation method by using 2,4, 6-trichlorotoluene as a raw material. Generally speaking, the method for producing chlorobenzonitrile by ammoxidation has the advantages of simple reaction process, environmental protection, few byproducts, high purity of the obtained product, low production cost and the like. However, the methyl ortho-position in the 2,4, 6-trichlorotoluene contains two chlorine atoms with larger steric hindrance, and the chlorine atoms serving as strong electron-withdrawing groups can passivate a benzene ring, so that the ammoxidation reaction is difficult to carry out, and compared with other chlorobenzonitrile, the product yield and selectivity are both obviously reduced; in addition, 2,4, 6-trichlorotoluene is difficult to synthesize and expensive as a starting material. U.S. Pat. No. 4,797,794,797 reports that polychlorinated toluenes (2, 6-dichlorotoluene, 2,4, 6-trichlorotoluene, etc.) containing two ortho-chlorides are prepared by a gas phase ammoxidation method under the action of a vanadium-containing composite oxide catalyst, however, in order to improve the product yield and selectivity, bromine-containing compounds need to be added into the reaction system, which increases the complexity of the process and the product cost.
The present inventors have proposed a selective ammoxidation strategy for the preparation of benzonitrile compounds, for example, using cheap and easily available alkylbenzene as a raw material, obtaining alkylbenzyl chloride by a chloromethylation reaction, and further obtaining alkylbenzene nitrile by a selective ammoxidation reaction with high yield and high selectivity, wherein both alkyl (methyl, ethyl or isopropyl) and chloromethyl in the alkylbenzyl chloride can be subjected to an ammoxidation reaction at a high temperature, but the reaction temperature of chloromethyl is 100 to 200 ℃ lower than that of alkyl, and the selectivity of the ammoxidation reaction at a lower temperature can almost reach 100%.
The 1,3, 5-trichlorobenzene is an organic synthesis intermediate which is cheap and easy to obtain, for example, trichlorobenzonitrile can be obtained by performing chloromethylation reaction on the 1,3, 5-trichlorobenzene, and then the trichlorobenzonitrile can be prepared by performing ammoxidation directly, so that a brand new method is provided for the production and preparation of the 1,3, 5-trichlorobenzonitrile. However, chlorine as a blunting group has a great influence on the reactivity of other groups on a benzene ring, so that a common chlorine atom donor is basically not reacted when trichlorobenzene is subjected to chloromethylation, and a high-efficiency chlorine atom donor needs to be searched; the wangxing of Hunan Tan university uses chlorosulfonic acid as a chlorine atom donor to smoothly realize the chloromethylation reaction of passivated aromatic hydrocarbon, but the reaction conditions are harsh, the reaction time is long, the post-treatment is complex, and particularly, the reaction yield is low and is only 30-50%. On the other hand, the chloromethyl on the polychlorinated benzyl chloride containing a plurality of chlorines on the benzene ring is not easy to generate ammoxidation reaction at a lower temperature.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing 2,4,6-trichlorobenzonitrile by an ammoxidation method, which takes cheap and easily available 1,3, 5-trichlorobenzene as a raw material, firstly performs chloromethylation to obtain a high-selectivity intermediate product 2,4, 6-trichlorobenzyl chloride, and then directly prepares the 2,4,6-trichlorobenzonitrile by the ammoxidation. The reaction formula is as follows:
Figure BDA0002462426470000031
the second technical problem to be solved by the present invention is to provide a dedicated chloromethylation catalyst for preparing 2,4,6-trichlorobenzonitrile, wherein the dedicated chloromethylation catalyst is used for the chloromethylation reaction of 1,3, 5-trichlorobenzene to obtain the intermediate product 2,4, 6-trichlorobenzyl chloride.
The third technical problem to be solved by the invention is to provide a special ammoxidation catalyst for preparing 2,4,6-trichlorobenzonitrile, wherein the special ammoxidation catalyst is used for ammoxidation of 2,4,6-trichlorobenzonitrile to obtain a final product of 2,4, 6-trichlorobenzonitrile.
The fourth technical problem to be solved by the present invention is to provide a preparation method of the above-mentioned special catalyst for ammoxidation of 2,4,6-trichlorobenzonitrile to obtain a final product 2,4, 6-trichlorobenzonitrile.
In order to solve the first technical problem, the technical scheme adopted by the invention comprises the following steps:
1) using cheap and easily available 1,3, 5-trichlorobenzene and formaldehyde or/and paraformaldehyde as raw materials, benzene sulfonyl chloride, p-toluene sulfonyl chloride, p-chlorobenzene sulfonyl chloride, p-trifluoromethyl benzene sulfonyl chloride and m-benzeneDisulfonyl chloride, p-benzenesulfonyl chloride, diphenyl chlorophosphate, etc. as chlorine atom donor, and trifluoromethanesulfonic acid rare earth metal salt L n (CF) is added3SO3)3(abbreviation L n (OTf)3) As a special chloromethylation catalyst, a chloromethylation product 2,4, 6-trichlorobenzyl chloride is obtained through chloromethylation reaction. The specific process of the reaction is as follows: adding 1,3, 5-trichlorobenzene and formaldehyde or/and paraformaldehyde into a reaction device, adding a chlorine atom donor and a catalyst at a certain temperature, reacting for 0.5-100 h under vigorous stirring, washing and drying a product, evaporating redundant 1,3, 5-trichlorobenzene, and distilling under reduced pressure to obtain 2,4, 6-trichlorobenzyl chloride; the mol ratio of the chlorine atom donor to the 1,3, 5-trichlorobenzene is 0.1-3: 1, the molar ratio of the special chloromethylation catalyst to 1,3, 5-trichlorobenzene is 0.01-1: the molar ratio of 1, formaldehyde or/and paraformaldehyde to 1,3, 5-trichlorobenzene is 0.5-10: 1, the reaction temperature is-10-150 ℃. The reaction yield is 50-95%. The selectivity of the monochloromethylation product 2,4, 6-trichlorobenzyl chloride in the product is higher than 95%. Preferably, the mol ratio of the chlorine atom donor to the 1,3, 5-trichlorobenzene is 0.5-2: 1, the molar ratio of the special chloromethylation catalyst to 1,3, 5-trichlorobenzene is 0.01-0.5: 1, the molar ratio of formaldehyde or/and paraformaldehyde to 1,3, 5-trichlorobenzene is 1-5: 1, the reaction temperature is 0-120 ℃.
2) Taking the product 2,4, 6-trichlorobenzyl chloride obtained in the step 1) as a raw material, and carrying out an ammoxidation reaction with ammonia gas and oxygen under the action of a catalyst to obtain 2,4, 6-trichlorobenzonitrile; the reaction yield is 75-98%, and the special ammonia oxidation catalyst comprises the following active components: VTibGcDdEeOxWherein G is at least one element of chromium, phosphorus, molybdenum, boron and bismuth; d is at least one element of manganese, iron, cobalt, nickel, zinc and tin; e is at least one element of potassium, sodium, magnesium and calcium; b is 0.5-2; c is 0.1 to 1.5; d is 0-1.2; e is 0-0.8; x is determined according to the content of each element according to the valence equilibrium. Preferably, b is 0.8-1.2; c is 0.3 to 1.0; d is 0-0.3; e is 0 to 0.2.
In order to solve the second technical problem, the invention provides a special chloromethylation catalyst, wherein the special chloromethylation catalyst is trifluoromethylSulfonic acid rare earth metal salt L n (OTf)3(ii) a The rare earth metals comprise light rare earth lanthanum, cerium, praseodymium, neodymium, promethium and medium rare earth samarium, europium, gadolinium, terbium and dysprosium. The special chloromethylation catalyst is used for the chloromethylation reaction of 1,3, 5-trichlorobenzene and formaldehyde or paraformaldehyde under the participation of a chlorine atom donor to obtain an intermediate product 2,4, 6-trichlorobenzyl chloride; the chlorine atom donor is benzene sulfonyl chloride, p-toluene sulfonyl chloride, p-chlorobenzene sulfonyl chloride, p-trifluoromethyl benzene sulfonyl chloride, m-benzene disulfonyl chloride, p-benzene disulfonyl chloride or diphenyl chlorophosphate. For 1,3, 5-trichlorobenzene containing three strong blunt group chlorine, the chloromethylation reaction is difficult to carry out, common chlorine atom donor is used, the yield of the catalyst is extremely low, the special chloromethylation catalyst provided by the invention can greatly improve the activity of the reaction and the yield of the product, and the reaction selectivity is high.
In order to solve the third technical problem, the invention also provides a special ammoxidation catalyst for preparing the 2,4, 6-trichlorobenzonitrile. The special ammonia oxidation catalyst is a multi-component catalyst which takes nano silica gel as a carrier, vanadium and titanium as main catalysts and G, D, E as a cocatalyst, and comprises the following active components: VTibGcDdEeOxWherein G is at least one of chromium, phosphorus, molybdenum, boron and bismuth; d is at least one of manganese, iron, cobalt, nickel, zinc and tin; e is at least one of potassium, sodium, magnesium and calcium; b is 0.5-2; c is 0.1 to 1.5; d is 0-1.2; e is 0-0.8; x is determined according to the content of each element according to the valence equilibrium. The active component and the nano silica gel carrier form microspheres which are respectively and uniformly distributed in the microspheres; the sum of the atomic weight of each element in the active component accounts for 20-70% of the total weight of the microsphere, and preferably 40-60%. The diameter range of the microspheres is 30-70 mu m.
In order to solve the fourth technical problem, the technical scheme of the invention is as follows:
the catalyst is prepared by high-speed centrifugal spray drying, and active silicon solution is added during the preparation of the catalyst, wherein the active silicon solution can be prepared from inorganic silica sol or amino-free cage type Polysilsesquioxane (POSS) and amino-containing polysilsesquioxaneThe organosilicon containing amino can strengthen the interaction between the active component and the calcined nano silica gel carrier; the organosilicon containing amino groups can be of the formula NH2RnSiX3Is represented by RnIs a C1-C10 hydrocarbon group, X is methoxy, ethoxy, halogen or a mixed group (when the mixed group is used, the total amount of the mixed group in 1mol of the amino-containing organosilicon is 3 mol); the active silicon solution can also be a cage type polysilsesquioxane solution containing amino, and because the amino carried by the active silicon solution has strong interaction with elements in the active component, no organosilicon containing amino is required to be added additionally.
The method comprises the following specific steps: uniformly mixing a solution of each relevant element (namely V, Ti, G, D and E elements) except oxygen in the active component with an active silicon solution to obtain a suspension or slurry; spray-forming by a high-speed centrifugal spray dryer, and then activating at high temperature to obtain micron-sized spherical particles of the vanadium composite oxide. The activation temperature is generally 623-973K, preferably 673-873K. The activation time is generally 2 to 15 hours, and the optimum activation time range is 3 to 8 hours.
In the preparation of the catalyst, the solution of each relevant element may be an oxide, a salt, an acid, a base or the like of the element. For example, V can be used2O5Or NH4VO3Etc.; titanium can be TiCl4、TiCl3Or TiO2Etc.; the chromium may be Cr (NO)3)3·9H2O、Cr2O3、CrO3Or (NH)4)2Cr2O7Etc.; phosphorus can be replaced by H3PO4、(NH4)3PO4、(NH4)2HPO4、(NH4)H2PO4Or P2O5Etc.; the molybdenum can be MoO3、(NH4)6Mo7O24Etc.; boron can be replaced by H3BO3、B2O3Etc.; the bismuth can be Bi (NO)3)3、BiCl3、Bi2O3Etc.; MnO can be used for manganese2、MnCl2、Mn(NO3)2Etc.; FeCl for iron3、Fe2O3、Fe3O4、Fe(NO3)3·9H2O、Fe(OAc)2、FeC2O4·2H2O or Fe2(C2O4)3·6H2O, etc.; the cobalt can be selected from Co (OAc)2、Co(NO3)2·6H2O、Co3O4Or CoCl2Etc.; the nickel can be NiCl2·6H2O or Ni (NO)3)2·6H2O, etc.; the zinc can be ZnO or ZnCl2、Zn(NO3)2Or Zn (OAc)2·2H2O, etc.; the tin can be SnCl2Or SnCl4Etc.; the potassium can be KOH, KCl, KNO3、K2CO3Or K2C2O4Etc.; the sodium can be Na2CO3、NaHCO3、NaOH、NaCl、NaNO3、Na2SO4NaOAc or Na2C2O4Etc.; the magnesium can be MgO or MgCl2Or Mg (NO)3)2·6H2O, etc.; the calcium can be CaCl2·6H2O、Ca(OH)2Or Ca (NO)3)2And the like. The solutions are prepared by conventional methods known in the art, e.g. V2O5And CrO3For equal use of H2C2O4Dissolving in water to prepare solution, and KCl and KNO3、K2CO3And dissolving with water directly to prepare the solution.
The optimal process conditions for preparing 2,4,6-trichlorobenzonitrile by using the catalyst to catalyze the ammoxidation of 2,4, 6-trichlorobenzyl chloride are as follows: the reaction temperature is 603-673K, the molar ratio of air to 2,4, 6-trichlorobenzyl chloride is 10-50, the molar ratio of ammonia to 2,4, 6-trichlorobenzyl chloride is 2-15, and the catalyst load is 40-200 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 2,4, 6-trichlorobenzyl chloride can be higher than 96 percent, and the molar yield of the 2,4,6-trichlorobenzonitrile can reach more than 90 percent; compared with the direct ammoxidation reaction of the chlorotoluene, the reaction stability is reduced by more than 50 ℃, and the reaction selectivity is improved by more than 10%.
The method takes 1,3, 5-trichlorobenzene as raw material, firstly performs chloromethylation reaction to synthesize 2,4, 6-trichlorobenzyl chloride, three hydrogens on the 1,3, 5-trichlorobenzene can be substituted, but the primary substitution product is only one, the chlorine atom donor and the special chloromethylation catalyst used in the method can efficiently obtain the monochloromethylation product 2,4, 6-trichlorobenzyl chloride; and then 2,4,6-trichlorobenzonitrile is prepared by ammoxidation of 2,4, 6-trichlorobenzyl chloride. Compared with other methods, the method has the advantages of cheap and easily-obtained reaction raw materials, simple and direct process route, environmental friendliness, low cost, high yield and the like, and particularly greatly reduces the reaction temperature (which is reduced by 50-100 ℃ compared with the ammoxidation reaction temperature of the chlorotoluene) and obviously improves the selectivity of the product. The ammoxidation catalyst has higher selectivity and activity; the preparation method is simple, has low cost and better thermal stability and mechanical strength, and can be used on both fixed bed reactors and fluidized bed reactors. The method and the used ammonia oxidation catalyst have better application value.
Detailed Description
The following examples will help to further understand the present invention, but are not intended to limit the scope of the present invention.
Example 1
Figure BDA0002462426470000081
Respectively adding 30g of 1,3, 5-trichlorobenzene and 10g of paraformaldehyde into a 100ml three-neck flask, adding 0.5g of lanthanum trifluoromethanesulfonate as a catalyst, installing mechanical stirring, respectively connecting an air condenser pipe with a balloon at the upper end and a constant-pressure dropping funnel with 16ml of terephthaloyl chloride, reacting in an ice-water bath at 0 ℃, slowly dropping the terephthaloyl chloride, starting a stirrer for stirring, and after 2 hours of dropping, heating to 60 ℃ for reacting for 24 hours. After the reaction is finished, adding saturated sodium carbonate solution to completely neutralize unreacted acid liquor, extracting the product by using dichloromethane, separating the liquid of the mixed solution, washing twice by using saturated sodium chloride solution, and drying and removing the obtained organic layer solution by using anhydrous sodium sulfateWater, drying organic solvent by spinning, distilling by oil pump under reduced pressure, separating out raw material and product, condensing into solid, raising the temperature, collecting colorless transparent liquid with pungent odor at 180 deg.C, and obtaining yield of 83%. Product warp1The HNMR and the element analysis verify that,1HNMR (400MHz, Chloroform-d): 7.69(s,2H),4.63(s, 2H); elemental analysis: theoretical value (%): c, 36.57; h, 1.75; test values (%): c, 36.73; h, 1.82.
Example 2
Comparative example: the experimental raw materials and reaction conditions were the same as in example 1 except that no rare earth metal salt catalyst was added, and the final product yield was 36%.
Example 3
28g of 1,3, 5-trichlorobenzene and 10g of formaldehyde solution are respectively added into a 100ml three-neck flask, 1g of samarium trifluoromethanesulfonate is added as a catalyst, 40g of p-trifluoromethylbenzenesulfonyl chloride is slowly dropped at 0 ℃, and the temperature is raised to 80 ℃ for reaction for 56 hours. After the reaction is finished, adding a saturated sodium carbonate solution to completely neutralize the unreacted acid solution, then adding dichloromethane into a flask to extract the product, separating the mixed solution, washing the mixed solution for three times by using a saturated sodium chloride solution to obtain an organic layer solution, drying the organic layer solution by using anhydrous sodium sulfate to remove water, spin-drying the organic solvent, then distilling the organic layer solution by using an oil pump under reduced pressure, collecting oily colorless transparent liquid with pungent smell at 180 ℃, wherein the yield is 81%.
Example 4
Praseodymium trifluoromethanesulfonate is used as a catalyst, p-chlorobenzenesulfonyl chloride is used as a chlorine atom donor, the reaction temperature is 50 ℃, the reaction time is 48 hours, and the product yield is 91%.
Example 5
Europium trifluoromethanesulfonate is used as a catalyst, diphenyl chlorophosphate is used as a chlorine atom donor, the reaction temperature is 30 ℃, the reaction time is 72 hours, and the product yield is 78%.
Example 6
23.4 g of H2C2O4·2H2O was dissolved in 120m L80 ℃ distilled water, 11.3 g of V was added2O5After a homogeneous solution was formed, 8.6 g of 85% phosphoric acid and 7.2 g of Co (B), (C)NO3)2·6H2O, 0.7 g Na2CO3And 28.1 g TiCl4Then slowly adding silica sol with the content of 75m L40%, then adding 5g aminopropyl trimethoxy silane, uniformly stirring, high-speed spray-centrifugally drying to obtain catalyst precursor, drying at 110 deg.C in muffle furnace, gradually heating to 550 deg.C, holding temperature for 6 hr, naturally cooling, and making the catalyst be used1.2P0.6Co0.2Na0.1O6.65The weight content of active components of the catalyst is 50%.
20g of the solid catalyst is filled in a quartz tube fixed bed reactor with the inner diameter of 30mm, and the molar ratio of the reaction raw materials is as follows: 2,4, 6-trichlorobenzyl chloride NH3The Air is 1:3:35, the reaction temperature is 638 +/-1K, and the catalyst load is 100g/(kgcat h). After 8 hours of reaction time, the conversion of 2,4, 6-trichlorobenzyl chloride was 97.2%, and the molar yield of 2,4,6-trichlorobenzonitrile was 86.1%.
Examples 7 to 9
The catalyst formulation was varied, the reaction conditions were the same as in example 6, and the results are given in the following table:
Figure BDA0002462426470000101
the catalysts of the invention comprising further promoters, in which the oxides, salts, acids or bases of the elements, etc., are used for the respective active components, can be prepared in the manner described above. During preparation, the required catalyst can be obtained by correspondingly replacing the corresponding active component substances according to the proportion by referring to the above examples.

Claims (10)

1. A method for preparing 2,4,6-trichlorobenzonitrile by an ammoxidation method is characterized in that: the method comprises the following steps:
1) 1,3, 5-trichlorobenzene and formaldehyde or/and paraformaldehyde are used as raw materials, benzene sulfonyl chloride, p-toluene sulfonyl chloride, p-chlorobenzene sulfonyl chloride, p-trifluoromethyl benzene sulfonyl chloride, m-benzene disulfonyl chloride, p-benzene disulfonyl chloride and diphenyl chlorophosphate are used as chlorine atom donors, and chloromethylation products, namely 2,4, 6-trichlorobenzyl chloride, are obtained through chloromethylation reaction; the specific process of the reaction is as follows: adding 1,3, 5-trichlorobenzene and formaldehyde or/and paraformaldehyde into a reaction device, adding a chlorine atom donor and a special chloromethylation catalyst at a certain temperature, reacting for 0.5-100 h under vigorous stirring, washing and drying a product, evaporating redundant 1,3, 5-trichlorobenzene, and distilling under reduced pressure to obtain 2,4, 6-trichlorobenzyl chloride; the mol ratio of the chlorine atom donor to the 1,3, 5-trichlorobenzene is 0.1-3: 1, the molar ratio of the special chloromethylation catalyst to 1,3, 5-trichlorobenzene is 0.01-1: the molar ratio of 1, formaldehyde or/and paraformaldehyde to 1,3, 5-trichlorobenzene is 0.5-10: 1, the reaction temperature is-10-150 ℃;
2) taking the product 2,4, 6-trichloro-benzyl chloride obtained in the step 1) as a raw material, and carrying out an ammoxidation reaction with ammonia gas and oxygen under the action of a special ammoxidation catalyst to obtain the 2,4, 6-trichlorobenzonitrile.
2. A special chloromethylation catalyst for preparing 2,4,6-trichlorobenzonitrile is characterized in that the special chloromethylation catalyst is trifluoromethanesulfonic acid rare earth metal salt L n (CF)3SO3)3(ii) a The rare earth metals comprise light rare earth lanthanum, cerium, praseodymium, neodymium, promethium and medium rare earth samarium, europium, gadolinium, terbium and dysprosium.
3. A special ammoxidation catalyst for preparing 2,4,6-trichlorobenzonitrile is characterized in that: the special ammonia oxidation catalyst is a multi-component catalyst which takes nano silica gel as a carrier, vanadium and titanium as main catalysts and G, D, E as a cocatalyst, and comprises the following active components: VTibGcDdEeOxWherein G is at least one of chromium, phosphorus, molybdenum, boron and bismuth; d is at least one of manganese, iron, cobalt, nickel, zinc and tin; e is at least one of potassium, sodium, magnesium and calcium; b is 0.5-2; c is 0.1 to 1.5; d is 0-1.2; e is 0-0.8; x is determined according to the content of each element according to valence state balance; the active component and the nano silica gel carrier form microspheres which are respectively and uniformly distributed in the microspheres; the content of each element atom of the active component in the microspheres is 20-70% by weight, and the microspheres are straightThe diameter is 30 to 70 μm.
4. The specialized ammonia oxidation catalyst of claim 3, wherein: the content of each element atom of the active component in the microspheres is 40-60% by weight.
5. The method of claim 3 or 4, wherein the method comprises: the preparation method comprises the following specific steps: uniformly mixing a solution of each relevant element except oxygen in the active component with an active silicon solution to obtain a suspension or slurry; spray-forming by a high-speed centrifugal spray dryer, and then activating at high temperature to obtain micron-sized spherical particles of the vanadium composite oxide, thus obtaining the special ammoxidation catalyst.
6. The method of claim 5, wherein the method comprises: the active silicon solution is a solution consisting of inorganic silica sol or amino-free cage type polysilsesquioxane and amino-containing organic silicon; the general formula of the amino-containing organosilicon is NH2RnSiX3Wherein R isnIs C1-C10 alkyl, and X is methoxyl, ethoxyl, halogen or their mixture.
7. The method of claim 5, wherein the method comprises: the active silicon solution is a cage type polysilsesquioxane solution containing amino.
8. The process for the preparation of the specialized catalyst according to claim 5, 6 or 7, characterized in that: the high-temperature activation temperature is 623-973K, and the activation time is 2-15 hours.
9. The process for the preparation of the specialized catalyst according to claim 5, 6 or 7, characterized in that: when the catalyst is prepared, the solution of each relevant element except oxygen in the active component is the solution prepared by using oxide, salt, acid or alkali of the element.
10. The method for preparing the special catalyst according to claim 9, wherein: solution of each relevant element except oxygen in the active component: v for vanadium2O5Or NH4VO3Preparing; TiCl for titanium4、TiCl3Or TiO2Preparing; cr (NO) for chromium3)3·9H2O、Cr2O3、CrO3Or (NH)4)2Cr2O7Preparing; h for phosphorus3PO4、(NH4)3PO4、(NH4)2HPO4、(NH4)H2PO4Or P2O5Preparing; MoO for molybdenum3、(NH4)6Mo7O24Preparing; h for boron3BO3、B2O3Preparing; MnO for manganese2、MnCl2、Mn(NO3)2Preparing; FeCl for iron3、Fe2O3、Fe3O4、Fe(NO3)3·9H2O、Fe(OAc)2、FeC2O4·2H2O or Fe2(C2O4)3·6H2Preparing O; co for cobalt (OAc)2、Co(NO3)2·6H2O、Co3O4Or CoCl2Preparing; NiCl for nickel2·6H2O or Ni (NO)3)2·6H2Preparing O; ZnO, ZnCl for zinc2、Zn(NO3)2Or Zn (OAc)2·2H2Preparing O; SnCl for tin2Or SnCl4Preparing; KOH, KCl, KNO for potassium3、K2CO3Or K2C2O4Preparing; na for sodium2CO3、NaHCO3、NaOH、NaCl、NaNO3、Na2SO4NaOAc or Na2C2O4Preparing; MgO and MgCl for magnesium2Or Mg (NO)3)2·6H2Preparing O; CaCl for calcium2·6H2O、Ca(OH)2Or Ca (NO)3)2And (4) preparation.
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CN109912453A (en) * 2017-12-13 2019-06-21 中南民族大学 Prepare method and the special-purpose catalyst and preparation method thereof of 2,5- dichlorobenzonitrile

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WO2011132051A2 (en) * 2010-04-19 2011-10-27 Glenmark Pharmaceuticals S.A. Tricycle compounds as phosphodiesterase-10 inhibitors
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