CN109847772B - Special catalyst for preparing parachlorobenzonitrile by ammoxidation method, preparation method and application - Google Patents
Special catalyst for preparing parachlorobenzonitrile by ammoxidation method, preparation method and application Download PDFInfo
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Abstract
The invention discloses a special catalyst for preparing p-chlorobenzonitrile by an ammonia oxidation method, wherein a carrier of the catalyst is silica gel modified by organic silicon, a main catalyst is vanadium and phosphorus components, a cocatalyst is at least one of a component G and a component D and a component E, and active components are represented as follows: VPbGcDdEeOx(ii) a G is molybdenum, chromium, titanium, nickel or bismuth, D is boron, manganese, iron, cobalt, copper, zinc or tin, and E is potassium, lithium, sodium, cesium, magnesium or calcium. The invention also discloses a preparation method and application of the catalyst. The electron-donating groups on the organic silicon and the inorganic elements are used for carrying out the Lewis acid-base reaction, so that the effect of the inorganic oxide and the carrier is enhanced; meanwhile, the inorganic oxide is dispersed more uniformly, the loss of catalyst components is less, the catalytic activity is high, the selectivity is good, and the service life of the industrial catalyst is prolonged from one year to more than two years. The catalyst has simple preparation method, low cost, good thermal stability and mechanical strength, and can be used in fixed bed and fluidized bed reactors.
Description
Technical Field
The invention relates to a special catalyst for preparing p-chlorobenzonitrile 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
Para-chlorobenzonitrile is an important organic intermediate. Starting from p-chlorobenzonitrile, p-chlorobenzoic acid, p-chlorobenzamide, p-fluorobenzonitrile, p-fluorobenzoic acid, p-fluoroaniline and the like can be prepared, and the method is widely applied to industries such as dye, medicine, pesticide, photosensitive materials and the like. A novel high-performance pigment C.I. pigment red 254[1, 4-diketone-3, 6-di (4-chlorophenyl) pyrrolopyrrole ] which is researched and proposed by Ciba-Geigy company for 25 years is produced by taking p-chlorobenzonitrile as a raw material, so that the p-chlorobenzonitrile attracts more attention of people.
The classical preparation method of p-chlorobenzonitrile is obtained by the reaction of corresponding aldehyde, aldoxime or acid, and the methods have high raw material price, long reaction route and serious environmental pollution. The method for preparing the aromatic nitrile by the ammoxidation method has the advantages of simple and direct process, continuous operation, simple operation, strong production capacity, remarkable economic benefit, environmental friendliness and the like. Para-chlorotoluene (PCT) is a basic chemical raw material with low price, and the ammoxidation of the PCT is the best method for preparing the parachlorobenzonitrile. At present, the research of preparing p-chlorobenzonitrile internationally by an ammoxidation method reaches a higher level, wherein Martin and the like use unsupported vanadium-phosphorus oxide as a catalyst, and the yield of the p-chlorobenzonitrile reaches 92.6 percent; however, the unsupported catalyst has small specific surface area and poor mechanical strength, and is not suitable for the large-scale preparation of the parachlorobenzonitrile by the fluidized bed in industry. The inventor of the invention develops a silica gel supported multi-component composite oxide catalyst, the metal oxide loading capacity is 10%, the molar yield can reach more than 90%, the silica gel supported catalyst takes silica gel as a carrier, not only provides a large specific surface area, reduces the catalyst cost, but also improves the high-temperature sintering resistance, the mechanical strength and the wear resistance of the catalyst; therefore, the device is suitable for a fixed bed and a fluidized bed; however, the catalytic activity of the silica gel supported catalyst begins to decrease after half a year to one year of use in the industrial production process, and the activity decreases seriously after one or two years, so that the silica gel supported catalyst needs to be replaced, which causes resource waste and product cost increase. The main reason for the analytical activity decrease is the loss of active components on the surface of the catalyst; the silica gel supported catalyst is prepared by a silica gel impregnation method, namely, the silica gel is prepared by high-temperature calcination and activation after adsorbing a mixed metal salt solution; the composite metal oxide is attached to the surface of the silica gel mainly through physical adsorption, the acting force of the metal oxide and the silica gel carrier is weak, catalyst microspheres in a fluidized bed reactor collide and rub with each other, the metal oxide is easy to fall off, and in addition, partial components in the composite metal oxide volatilize under a high temperature for a long time, so that the loss of active components of the catalyst and the change of the proportion are caused, the activity of the catalyst is reduced after a certain degree, and the service life of the catalyst is influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a special catalyst for preparing parachlorobenzonitrile by an ammoxidation method.
The invention also aims to provide a preparation method of the special catalyst.
The third technical problem to be solved by the invention is to provide the application of the special catalyst.
In order to solve the first technical problem, the invention provides a special catalyst for preparing p-chlorobenzonitrile by an ammoxidation method.
The special catalyst is an organosilicon modified silica gel loaded composite inorganic oxide catalyst, the carrier is organosilicon modified silica gel, the main catalyst is vanadium and phosphorus components, the cocatalyst is at least one of D and E components and G component, and the composition of active components of the catalyst is as follows: VPbGcDdEeOx(when the amount of a cocatalyst is zero, it means that the cocatalyst is not contained); the active component is uniformly loaded on the organosilicon modified silica gel carrier; the weight percentage content of the active component in the catalyst is 5-50%, preferably 5-20%. The organosilicon being SiXnY4-nWherein X is one or more of halogen, alkyl or alkoxy, the halogen comprises chlorine, bromine and iodine, and the alkyl or alkoxy comprises C1-C10 alkyl or alkoxy; y is a group with a lone pair of electrons; n is 1, 2 or 3. The dosage of the organic silicon is 1-10% of the weight of the silica gel (the silica gel before modification, the same below). The silica gel is in a microsphere shape of 20-200 meshes. Wherein G is molybdenum, chromium, titanium, nickel or bismuth; d is boron, manganese, iron, cobalt, copper, zinc or tin; e isPotassium, lithium, sodium, cesium, magnesium or calcium; b is 0.3-3; c is 0.01 to 1.0; d is 0-0.8; e is 0-0.5; x is determined according to the content of each element according to the valence equilibrium.
Preferably, Y is a group containing a nitrogen, oxygen, sulfur or phosphorus atom, including-NH2、-NHR、-NR2、-CmNH2、-CmNHR、-CmNR2、-OH、-OR、-CmOH、-CmOR、-SH、-SR、-CmSH、-CmSR、-PH2、-PHR、-PR2、-PR2、-CmPH2、-CmPHR、-CmPR2Etc. wherein CmThe compound represents an organic group having m carbon atoms, wherein m is 1 to 20, and R represents an alkyl group or an aryl group.
Preferably, G is chromium, nickel; d is iron and cobalt; e is potassium or sodium; b is 0.7 to 1.0; c is 0.5-0.8; d is 0.10 to 0.20; e is 0.05 to 0.10.
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 of oxide and carrier silica gel needs to be strengthened, and the inventor prepares a new generation of high-activity silica gel loaded composite inorganic oxide catalyst by modifying organic silicon; electron-donating groups on the organic silicon and inorganic elements (mainly metal) are utilized to carry out Lewis acid-base reaction, so that the functions of inorganic oxides and carriers are enhanced; meanwhile, the inorganic oxide is dispersed more uniformly, the loss of catalyst components is reduced, and the service life of the industrial catalyst is prolonged from one year to more than two years while the higher activity and selectivity of the catalyst are maintained.
The catalyst is prepared by adopting an impregnation method, and the method comprises the following specific steps: conversion to form the catalyst active component VPbGcDdEeOxDissolving and mixing the precursors to obtain mixed precursor solution,adding a certain amount of organic silicon into the mixed precursor solution, uniformly mixing, then soaking and fully stirring with silica gel, standing and aging for 3-12 hours, drying at the temperature of 373-473K, and then activating for a certain time at a proper temperature to obtain the special catalyst. The activation temperature is usually between 673K and 923K, and the optimum temperature range is 723K to 873K. The activation time is generally 2 to 20 hours, and the optimum activation time range is 3 to 10 hours. The precursors refer to compounds containing at least V, P, G, D, E, and the ratio of the sum of the substances of V, the sum of the substances of P, the sum of the substances of G, the sum of the substances of D and the sum of the substances of E in each precursor is 1: b: c: d: e; when D is zero, any precursor does not contain D element; when E is zero, any precursor does not contain E element.
When the catalyst is prepared, the carrier silica gel can be modified by organic silicon, and then the active component is adsorbed, and the method comprises the following specific steps: dissolving a certain amount of organic silicon in a solvent, adding carrier silica gel, stirring for 1-24 hours, filtering or directly distilling under reduced pressure to remove the solvent, and performing vacuum drying to obtain an organic silicon modified silica gel carrier; conversion to form the catalyst active component VPbGcDdEeOxDissolving and mixing the precursors to obtain a mixed precursor solution, soaking and adsorbing the mixed precursor solution by using an organic silicon modified silica gel carrier, and then aging, drying, activating and the like to obtain the catalyst.
The solvent for dissolving the organic silicon in the preparation of the catalyst is distilled water or C1-C20 alkane, C1-C20 cycloalkane, aromatic hydrocarbon or alcohol compound, acetone, diethyl ether, dichloromethane, ethyl acetate, petroleum ether, N-dimethylformamide and other organic solvents. Preferably, the alcohol compound is methanol or ethanol; the alkane of C1-C20 is hexane; the cycloalkane of C1-C20 is cyclohexane; the aromatic hydrocarbon is benzene or toluene.
When preparing the catalyst, any precursor can be oxide, salt, acid or alkali containing at least V, P, G, D, E. For example, V can be used2O5Or NH4VO3Etc.; phosphorus can be replaced by H3PO4、(NH4)3PO4、(NH4)2HPO4、(NH4)H2PO4Or P2O5Etc.; boron can be replaced by H3BO3、B2O3Etc.; the molybdenum can be MoO3、(NH4)6Mo7O24Etc.; the chromium may be Cr (NO)3)3·9H2O、Cr2O3、CrO3Or (NH)4)2Cr2O7Etc.; titanium can be TiCl4、TiCl3Or TiO2Etc.; the nickel can be NiCl2·6H2O or Ni (NO)3)2·6H2O, etc.; 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 copper can be CuCl2Or Cu (NO)3)2Etc.; 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.; li may be used as Li2O、LiCl、LiNO3Or Li2CO3Etc.; the sodium can be Na2CO3、NaHCO3、NaOH、NaCl、NaNO3Or 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.
In order to solve the third technical problem, the special catalyst provided by the invention is used for preparing p-chlorobenzonitrile by the ammoxidation of p-chlorotoluene.
Taking p-chlorotoluene as a raw material, and carrying out an ammoxidation reaction with ammonia gas and oxygen under the action of a catalyst to obtain p-chlorobenzonitrile; the reaction yield is 70-98%. The optimum process condition range for preparing the parachlorobenzonitrile by catalyzing the ammoxidation of the parachlorotoluidine by using the catalyst is as follows: the reaction temperature is 633-693K, the molar ratio of air to p-chlorotoluene is 8-50, the molar ratio of ammonia to p-chlorotoluene 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 p-chlorotoluene can be higher than 98 percent, and the molar yield of p-chlorobenzonitrile can reach more than 90 percent.
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. The prepared catalyst has better thermal stability and mechanical strength, can be used on both fixed bed and fluidized bed reactors, and greatly prolongs the service life from one year to more than two years. The catalyst is used for preparing p-chlorobenzonitrile by ammoxidation and has higher selectivity and activity.
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
9.33 g of H2C2O4·2H2O in 100mL of 80 ℃ distilled water, 4.49 g of V was added2O5After complete reaction, slowly adding 5.69 g of 85% phosphoric acid, 7.89g of chromium nitrate nonahydrate, 0.77 g of boric acid and 0.13 g of sodium carbonate, after forming a uniform solution, adding 10g of aminopropyltrimethoxysilane, fully mixing, adding 90 g of 60-120 mesh silica gel, stirring uniformly, and aging for 1Drying at 110 deg.C in muffle furnace for 2 hr, gradually heating to 550 deg.C, and holding for 6 hr. Naturally cooling, and standing by. The catalyst comprises the following components: VPCr0.4B0.25Na0.05O6/m-SiO2。
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: p-chlorotoluene NH3Air is 1:5:40, the reaction temperature is 673 + -1K, and the catalyst loading is 100g/(kgcat h). After 8 hours of reaction time, the conversion of p-chlorotoluene was 98.6% and the molar yield of p-chlorobenzonitrile was 92.3%.
Examples 2 to 7
The catalyst formulation was varied, the reaction conditions were the same as in example 1, and the results are given in the following table:
example 8
Dissolving 5g of thienyl trimethoxy silane in 50ml of ethanol, adding 80g of silica gel, uniformly stirring, standing for 12 hours, evaporating to remove the solvent, and drying at 60 ℃ in vacuum for later use. 13.93 g of H2C2O4·2H2O was dissolved in 80mL of distilled water at 85 ℃ and then 6.71 g of V was added2O511.89 g of phosphoric acid, 4.38 g of nickel chloride and 2.15 g of cobalt nitrate hexahydrate, after a homogeneous solution had formed, 80g of the above silica gel treated with thienyltrimethoxysilane were slowly added. After being stirred evenly, the mixture is kept stand for 12 hours, dried in a muffle furnace at 120 ℃, gradually heated to 500 ℃ and kept warm for 12 hours. And naturally cooling, and storing for later use. The catalyst comprises the following components: VP1.4Ni0.25Co0.1O6.4。
15g of catalyst is loaded into a quartz tube fixed bed reactor with the inner diameter of 30mm, and raw material mixed gas passes through a catalyst bed layer to react. The composition of the raw material mixed gas is as follows: p-chlorotoluene, ammonia gas and air in a ratio of 1:3: 30. The reaction temperature was 658. + -.1K, and the catalyst loading was 80g/(kgcat h). After 8 hours of reaction time, the conversion of p-chlorotoluene was 98.7%, the molar yield of p-chlorobenzonitrile was 94.3%, and the selectivity was 95.5%.
Examples 9 to 11
The catalyst formulation was varied and the process conditions were the same as in example 8, with the results as given in the following table:
the catalyst of the present invention comprising other promoter components can be prepared by the above method, wherein oxides, salts, acids or bases of the other promoter components can be used for the corresponding precursors. During preparation, the required catalyst can be obtained by correspondingly replacing the corresponding precursor substances according to the proportion by referring to the above embodiment.
Claims (10)
1. A special catalyst for preparing p-chlorobenzonitrile by an ammoxidation method is characterized in that:
the special catalyst is an organosilicon modified silica gel loaded composite inorganic oxide catalyst, the carrier of the special catalyst is organosilicon modified silica gel, the main catalyst is a V component and a P component, the cocatalyst is at least one of a G component and a D component and an E component, and the composition of the active components is as follows: VPbGcDdEeOx(ii) a The active component is uniformly loaded on the organosilicon modified silica gel carrier; the weight percentage content of active components in the catalyst is 5-50%; the organic silicon is SiXnY4-nWherein X is one or more of halogen, alkyl or alkoxy; y is a group with a lone electron pair; n is 1, 2 or 3; the silica gel is in a microspheric shape with 20-120 meshes; g is molybdenum, chromium, titanium, nickel or bismuth, D is boron, manganese, iron, cobalt, copper, zinc or tin, E is potassium, lithium, sodium, cesium, magnesium or calcium, b is 0.5-3, c is 0.05-1.0, D is 0-0.8, and E is 0-0.5; x is determined according to the content of V, P, G, D and E in the active component according to the valence state balance.
2. The specialized catalyst of claim 1, wherein: the weight percentage content of active components in the catalyst is 5-20%.
3. The dedicated catalyst according to claim 1 or 2, characterized in that:
the organosilicon SiXnY4-nWherein Y is a group containing nitrogen, oxygen, sulfur, phosphorus atoms, including-NH2、-NHR、-NR2、-CmNH2、-CmNHR、-CmNR2、-OH、-OR、-CmOH、-CmOR、-SH、-SR、-CmSH、-CmSR、-PH2、-PHR、-PR2、-CmPH2、-CmPHR、-CmPR2Wherein C ismThe compound represents an organic group having m carbon atoms, wherein m is 1 to 20, and R represents an alkyl group or an aryl group.
4. The dedicated catalyst according to claim 1 or 2, characterized in that:
the active component VP of the catalystbGcDdEeOxIn the formula, G is chromium or nickel; d is iron or cobalt; e is potassium or sodium; b is 0.7 to 1.0; c is 0.5-0.8; d is 0.10 to 0.20; e is 0.05 to 0.10.
5. The process for the preparation of the specialized catalyst of any of claims 1 to 4, characterized in that: the method comprises the following steps:
1) conversion to form the catalyst active component VPbGcDdEeOxDissolving and mixing the precursors to obtain a mixed precursor solution;
2) adding a certain amount of organic silicon into the mixed precursor solution, uniformly mixing, then soaking and fully stirring with silica gel, standing and aging for 3-12 hours, and drying at the temperature of 373-473K;
3) activating at high temperature to obtain the special catalyst;
the precursors refer to compounds containing at least V, P, G, D, E, and the ratio of the sum of the substances of V, the sum of the substances of P, the sum of the substances of G, the sum of the substances of D and the sum of the substances of E in each precursor is 1: b: c: d: e; when D is zero, any precursor does not contain D element; when E is zero, any precursor does not contain E element;
the high-temperature activation temperature is 673-923K, and the activation time is 2-20 hours.
6. The process for the preparation of the specialized catalyst of any of claims 1 to 4, characterized in that: the method comprises the following steps:
1) dissolving organic silicon in a solvent, adding carrier silica gel, stirring for 1-24 hours, removing the solvent, and drying to obtain an organic silicon modified silica gel carrier;
2) conversion to form the catalyst active component VPbGcDdEeOxDissolving and mixing the precursors to obtain a mixed precursor solution;
3) dipping and adsorbing the mixed precursor solution by using an organic silicon modified silica gel carrier, standing and aging for 3-12 hours, and drying at the temperature of 373-473K;
4) activating at high temperature to obtain the special catalyst;
the precursors refer to compounds containing at least V, P, G, D, E, and the ratio of the sum of the substances of V, the sum of the substances of P, the sum of the substances of G, the sum of the substances of D and the sum of the substances of E in each precursor is 1: b: c: d: e; when D is zero, any precursor does not contain D element; when E is zero, any precursor does not contain E element;
the high-temperature activation temperature is 673-923K, and the activation time is 2-20 hours.
7. The method for preparing the dedicated catalyst according to claim 5 or 6, characterized in that: the high-temperature activation temperature is 673-873K, and the activation time is 3-10 hours.
8. The method for preparing the special catalyst according to claim 6, wherein the method comprises the following steps: the solvent is distilled water, methanol, ethanol, acetone, diethyl ether, dichloromethane, ethyl acetate, petroleum ether, N-dimethylformamide, benzene, toluene, cyclohexane or hexane.
9. The method for preparing the dedicated catalyst according to claim 5 or 6, characterized in that: the precursor is an oxide, a salt, an acid or an alkali at least containing V, P, G, D, E; including but not limited to V2O5、NH4VO3、H3PO4、(NH4)3PO4、(NH4)2HPO4、(NH4)H2PO4、P2O5、H3BO3、B2O3、MoO3、(NH4)6Mo7O24、Cr(NO3)3·9H2O、Cr2O3、CrO3、(NH4)2Cr2O7、TiCl4、TiCl3、TiO2、NiCl2·6H2O、Ni(NO3)2·6H2O、MnO2、MnCl2、Mn(NO3)2、FeCl3、Fe2O3、Fe3O4、Fe(NO3)3·9H2O、Fe(OAc)2、FeC2O4·2H2O、Fe2(C2O4)3·6H2O、Co(OAc)2、Co(NO3)2·6H2O、Co3O4、CoCl2、CuCl2、Cu(NO3)2、ZnO、ZnCl2、Zn(NO3)2、Zn(OAc)2·2H2O、SnCl2、SnCl4、KOH、KCl、KNO3、K2CO3、K2C2O4、Li2O、LiCl、LiNO3、Li2CO3、Na2CO3、NaHCO3、NaOH、NaCl、NaNO3、Na2C2O4、MgO、MgCl2、Mg(NO3)2·6H2O、CaCl2·6H2O、Ca(OH)2Or Ca (NO)3)2。
10. Use of the specialized catalyst of any of claims 1 to 4, characterized in that: the special catalyst is used for preparing p-chlorobenzonitrile by the ammoxidation of p-chlorotoluene.
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