CN1443754A - Method for producing o-chlorobenzonitrile - Google Patents
Method for producing o-chlorobenzonitrile Download PDFInfo
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- CN1443754A CN1443754A CN 02111021 CN02111021A CN1443754A CN 1443754 A CN1443754 A CN 1443754A CN 02111021 CN02111021 CN 02111021 CN 02111021 A CN02111021 A CN 02111021A CN 1443754 A CN1443754 A CN 1443754A
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Abstract
The present invention relates to a method for producing o-chlorobenzonitrile, and is characterized by that it adopts the fluidized bed catalyst process using vanadium-chromium-born as main active components, its operation conditions are as follows: reaction temp. is 300-500 deg.C, reaction process is normal pressure to 0.05 MPa, residence time is 0.2-20 sec. and the role ratio of reaction raw materials is: tolylchloride: ammonia: air=1:2-13:10-50.
Description
Technical Field
The present invention relates to a process for producing o-chlorobenzonitrile.
Background
The o-chlorobenzonitrile is an important intermediate of dye, medicine, pesticide and perfume. For example, the important intermediate 2-cyano-4-nitroaniline of the multipurpose azo disperse dye can be prepared by carrying out nitration and ammonolysis reaction on o-chlorobenzonitrile; the biphenyl compound synthesized with halogenated benzene is used for preparing non-peptide angiotensin and various anti-inflammatory and antibacterial drugs.
The simplest and most advanced method for preparing o-chlorobenzonitrile is an o-chlorotoluene direct ammoxidation process developed and matured in nearly thirty years, and the method has the advantages of short process flow, simplicity and convenience in operation, good product quality and high yield, and is developed rapidly in recent years.
The main reaction formula is as follows:
since this reaction is carried out at a high temperature, dechlorination atoms, deep oxidation, and ammoxidation decomposition side reactions are likely to occur.
These major and minor reactions are accompanied by the evolution of large amounts of heat. Meanwhile, since halogen-substituted toluene has high reactivity, the above-mentioned side reaction is likely to occur due to the high activity of the catalyst when the o-chlorotoluene is subjected to ammoxidation using a common toluene or xylene ammoxidation catalyst. So that the reaction selectivity is reduced, or the conversion rate is not high, and a high-yield and high-purity product cannot be obtained. Thus, the choice of the active components and the form of the catalyst and the choice of the corresponding reactor are of great importance.
In the ammoxidation technology of halogenated aromatic hydrocarbon, early literature reports that the V-system catalyst is the most common and effective catalytic system, such as V-P, V-Cr and Sb-Fe systems, which are usually carried by alumina, silicon carbide and silicon oxide and are examined by adopting a fixed bed or coarse particle baffle fluidized bed process. JP 57-26394 discloses a V-Cr-W-Bi/Al2O3The catalyst reacts at 390 ℃, and the yield of the o-chlorobenzonitrile is 78%. JPShowa 57-26594 discloses a V-Cr-Ni/α -Al alloy2O3Is used as the ammoxidation process of the catalyst, reacts at the temperature of 420 ℃, and has the yield of the o-chlorobenzonitrile of 77 percent. CN1045532 discloses a V-P-Li-K-SiO2The yield of the catalyst, o-chlorobenzonitrile, reaches 93.6 percent. CN1047226 discloses V-P-Fe-Li/SiO2Catalyst, product yield 81.5%. JP 63-190646 discloses a Sb-Fe-Cr-V-Mo/SiO2The catalyst reacts at 350 ℃, and the yield of the product o-chlorobenzonitrile is 79.8%. JP56-77250 discloses a V-P-Li catalyst with an o-chlorobenzonitrile product yield of 90.3%. The above data are the results of fixed bed investigation and do not represent the reactivity in the fluidized bed.
All the processes reported in the literature have not very high product yield, and in order to solve the problems of reaction heat removal and catalyst stability, obtain good reaction results, and be limited by the safe concentration of the reaction feed, prevent the blockage of the ammonium chloride at the outlet of the reactor, without adding a large amount of inert diluent, such as N, in the reaction process2Water, etc. However, these problems, such as the enlargement of the reactor, inevitably cause difficulties in heat removal of the reaction, decrease in product yield and quality, decrease in the effective load of the reactor, and shortening of the catalyst life, are not fundamentally solved. Therefore, in industrial production, it is difficult to develop their technical level. And the existence of process water causes inconvenience to the product post-treatment and also causes severe corrosion to equipment.
Disclosure of Invention
The invention aims to solve the technical problems of the prior method for producing the o-chlorobenzonitrile, such as the amplification effect of a reactor, difficult reaction heat removal and the like caused by the use of a fixed bed, and the problem of load reduction of the reactor caused by the addition of water in the process, and provides a novel method for producing the o-chlorobenzonitrile. The method has the characteristics of effectively solving the amplification effect of reaction engineering and reaction heat removal, improving reaction load and keeping higher product yield.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for producing o-chlorobenzonitrile uses o-chlorotoluene, ammonia gas and oxygen as reaction raw materials, in the presence of a fluidized bed catalyst, the reaction raw materials react in a fluidized bed reactor under the conditions that the reaction temperature is 300-500 ℃, the reaction pressure is normal pressure to 0.05MPa, the retention time is 0.2-20 seconds, and the molar ratio of the reaction raw materials is o-chlorotoluene, ammonia and air is 1: 2-13: 10-50 to generate the o-chlorobenzonitrile, wherein the fluidized bed catalyst uses silicon dioxide as a carrier, and active components comprise the following general formula components in terms of atomic ratio:
V1.0CraBbXcYdZeOm
wherein X is selected from at least one of oxides of phosphorus or arsenic;
y is at least one of alkali metal or alkaline earth metal oxide;
z is at least one of metal oxides of Ni, Co, Pb, Fe, Mo or W;
the value range of a is 0.5-2.0;
the value range of b is 0.1-1.0;
the value range of c is 0.1-2.0;
the value range of d is 0.01-0.1;
the value range of e is 0.1-0.5;
m is the number of oxygen atoms required to satisfy the valence of the element;
the content of the catalyst carrier silicon dioxide is 30-80% by weight.
In the technical scheme, the preferable range of the reaction temperature is 380-430 ℃, the preferable range of the residence time is 1-10 seconds, and the preferable scheme of the molar ratio of the reaction raw materials is that o-chlorotoluene, ammonia and air are 1: 3-6: 15-30. The alkali metal is preferably selected from sodium or potassium and mixtures thereof and the alkaline earth metal is preferably barium. The preferable range of the value of a is 0.7-1.3, the preferable range of the value of b is 0.4-0.8, the preferable range of the value of c is 0.1-0.6, and the preferable range of the value of e is 0.1-0.3.
The catalyst composition is suitable for fluidized bed reaction and fixed bed reaction, and has good catalytic activity.
V2O5、Cr2O3And the corresponding oxides of the elements of formula X, Y, Z are the starting materials for the catalyst of the present invention, and other compounds prepared by suitable methods may also be selected as the starting materials for the catalyst components of the present invention. Example (c):
vanadium raw materials: ammonium metavanadate, vanadium sulfate, organic acid vanadium such as vanadium oxalate or vanadium tartrate;
chromium raw material: chromic acid, chromate (ammonium), chromic anhydride, chromic nitrate, or organochromium: chromium oxalate, chromium tartrate;
raw material X: acid or ammonium salts corresponding to elemental oxides;
y raw material: a nitrate or a soluble salt;
raw material Z: a nitrate or a soluble salt;
silicon raw material: silica sol, silica gel or silica is used as a carrier of the catalyst.
The preparation of the catalyst was prepared by the familiar method: adding soluble X, Y, Z solution to V2O5、Cr2O3And boric acid in oxalic acid solution to obtain suspension mixture, and adding glycol if auxiliary solvent is needed. The fluidized bed catalyst slurry is roasted after being sprayed, formed and dried. The fixed bed catalyst is dried by evaporation of slurry, and then dried and roasted.
The roasting of the catalyst can be divided into two stages of decomposition of each element salt in the catalyst and high-temperature roasting. The roasting temperature is 450-800 ℃, the preferable range is 450-650 ℃, and the time is 2-15 hours. The decomposition and the high-temperature roasting can be carried out in two roasting furnaces, can also be carried out in one roasting furnace, or can be carried out in a continuous rotary roasting furnace.
The oxide content in the catalyst is V2O5、Cr2O3Acidic oxide, basic oxide and divalentThe weight percentage of the highest valence oxide of the upper metal.
The starting halotoluene of the present invention may be: o-chlorotoluene, p-chlorotoluene, dichlorotoluene, fluorotoluene, bromotoluene, iodotoluene and the like. The invention is carried out with ortho-chlorotoluene.
The oxygen consumption of the invention is at least 1.5 times of the theoretical amount, and the proper range is 2-10 times. Air is generally used as the oxygen source, and nitrogen, carbon dioxide, water vapor may be used as the inert diluent.
When air is used as an oxygen source, the concentration of the mixture of the halogenated toluene is 0.1-10% (volume), preferably 0.2-5.0% (volume).
The ammonia amount of the invention is at least several times of the theoretical amount, the high proportion of ammonia is beneficial to the reaction, and the ammonia amount of the process is 2-13 times of the theoretical amount, and the preferable range is 3-10 times.
The reaction temperature of the process is 300-500 ℃, and the preferable range is 330-480 ℃; when the temperature is lower than 300 ℃, the reaction conversion rate is low, and when the temperature is higher than 500 ℃, the deep oxidation reaction is serious, and CO is byproduct2CO, HCN and NH4The Cl content is obviously increased, and the yield of the o-chlorobenzonitrile product is reduced. The optimum temperature for this reaction depends on the number, position, starting material concentration, active composition of the catalyst, calcination conditions of the catalyst, reaction contact time and loading factors.
The contact time of the present invention varies widely, generally from 0.2 to 20 seconds, and preferably from 1 to 10 seconds.
The catalyst is prepared into the fluidizing agent catalyst suitable for the operation of the fluidized bed reactor, and the average grain diameter of the finished catalyst is 200 meshes, so that the problems of amplification effect of reaction engineering and reaction heat removal are effectively solved. In addition, because no water or other diluents are needed in the process, the reaction load of the reactor is effectively increased. By modulating the catalyst components, for example, adding Y-type elements, the selectivity is improved on one hand, and the abrasion resistance of the catalyst is improved on the other hand, so that the catalyst is suitable for the operation of a fluidized bed. By adopting the technical scheme, the method is used for fluidized bed reaction operation, the highest yield of the o-chlorobenzonitrile can reach 92.4%, and a better effect is achieved.
The reaction of the present invention is usually carried out under normal pressure, and may be carried out under pressure.
The conversion rate of the catalyst of the invention to o-chlorotoluene, the selectivity of o-chlorobenzonitrile and the once-through yield of o-chlorobenzonitrile are defined as follows:
the catalyst example of the invention is examined in a stainless steel fluidized bed reactor with the diameter of 38 mm multiplied by 1800 mm, the adding amount of the catalyst is 550 g, and the pressure of the reaction system is 0.01 MPa.
The invention is further illustrated by the following examples.
Detailed description of the preferred embodimentsa specific embodiment [ example 1]
Preparing a catalyst:
224 g of V2O5Adding the solution into a solution which consists of 490 ml of 468 g of oxalic acid in water and has the temperature of 80-90 ℃, fully stirring, and reacting to obtain a vanadium oxalate solution.
SiO with the weight percentage concentration of 40 percent21250 g of silica sol was slowly added to the above solution under stirring, and 864 g of Cr (NO) was added thereto3)3·9H2O, 12.4 g KNO371.6 g Co (NO)3)·6H2Solution of O and 500 ml of water, 76.4 g of H3BO385.1 g of 85% phosphoric acid and 500 ml of water, and 43.5 g (NH)4)6Mo7O24·4H2O and 100 ml of water, stirring, and heating to evaporate to a solid content of 40% by weight to obtain a viscous slurry.
Spray drying the slurry in a spray dryer for forming, pre-roasting the formed catalyst precursor at 300 ℃ for 2 hours, and then roasting at 650 ℃ for 4.5 hours to obtain the catalyst which comprises the following components in atomic ratio:
V1.00Cr0.9B0.50P0.30Mo0.10Co0.1K0.05/SiO2the catalyst had a main loading weight ratio of 50/50 and an average particle diameter of 200 mesh.
Evaluation of catalyst Performance:
the process comprises the following steps: o-chlorotoluene, ammonia and air in a ratio of 1: 4: 20 (mol)
Load 50 g/kg catalyst.h
The reaction temperature was 425 deg.C
The reaction pressure is normal pressure
As a result: the conversion rate of o-chlorotoluene is 98.9 percent
O-chlorobenzonitrile selectivity 93.1%
Yield of o-chlorobenzonitrile 92.1% [ examples 2 to 10]
The catalyst preparation method was the same as in example 1, the catalyst composition in Table 1 was obtained by changing the catalyst ratio or composition, and the evaluation was made by the catalyst evaluation method in example 1. The results are listed in Table 1.
TABLE 1
[ comparison]Example 1
| Examples | Catalyst for the preparation of a catalyst | O-chlorotoluene Conversion rate% | O-chlorobenzonitrile Selectivity% | O-chlorobenzonitrile Yield% |
| 2 | V1.0Cr0.9B0.50P0.30Co0.2 | 99.5 | 89.8 | 89.4 |
| 3 | V1.0Cr0.9B0.50P0.30Ba0.05 | 99.6 | 88.4 | 88.1 |
| 4 | V1.0Cr0.9B0.50P0.30Co0.2K0.03Ba0.03 | 97.5 | 92.5 | 90.2 |
| 5 | V1.0Cr1.0B0.50P0.10W0.10Fe0.10Na0.05 | 95.0 | 81.7 | 77.6 |
| 6 | V1.0Cr1.0B0.50P0.30Ni0.1Na0.05 | 97.0 | 91.2 | 88.5 |
| 7 | V1.0Cr1.0B0.40P0.20Mo0.05W0.05Na0.05 | 97.2 | 89.2 | 86.7 |
| 8 | V1.0Cr0.7B0.10P0.10K0.05 | 99.7 | 78.6 | 78.4 |
| 9 | V1.0Cr0.7B0.50P0.30W0.10Co0.1 | 96.0 | 92.0 | 88.3 |
| 10 | V1.0Cr0.70B0.60P0.40Fe0.10 | 97.6 | 87.2 | 85.1 |
The fixed bed investigation evaluation was carried out according to the catalyst composition and process conditions of example 1, and the evaluation results were as follows:
the conversion rate of o-chlorotoluene is 99.5 percent
Selectivity to o-chlorobenzonitrile is 94.4%
O-chlorobenzonitrile yield 94.0% [ example 11]
3.0 tons of industrial catalyst is produced according to the preparation method and the composition of the catalyst in the example 1, the catalyst is filled in the o-chlorobenzonitrile fluidized bed reactor of 1000 tons/year at one time, the industrial production is carried out according to the process evaluation conditions in the example 1, and the catalyst is calibrated by industrial operation in half a year, which shows that the catalyst has good activity and stability. The results are shown in Table 2 below:
TABLE 2
[ examples 12 to 14]
| Item | Two weeks after driving | Bearing after half a year of operation |
| Percent conversion of o-chlorotoluene% | 99.2 | 99.3 |
| Selectivity to o-chlorobenzonitrile% | 94.2 | 93.8 |
| Yield of o-chlorobenzonitrile% | 93.4 | 93.2 |
The catalyst preparation method, composition and conditions were as in example 1 except that the process evaluation conditions of example 1 were changed, and the evaluation results are shown in Table 3.
TABLE 3[ COMPARATIVE EXAMPLE 2]
Following the same catalyst and examination of the basic process conditions of example 1, the process water was added to the feed only, with the results being that:
the conversion rate of o-chlorotoluene is 99.4 percent
O-chlorobenzonitrile selectivity 93.0%
The yield of the o-chlorobenzonitrile is 92.4 percent
Claims (8)
1. A method for producing o-chlorobenzonitrile uses o-chlorotoluene, ammonia gas and oxygen as reaction raw materials, in the presence of a fluidized bed catalyst, the reaction raw materials react in a fluidized bed reactor under the conditions that the reaction temperature is 300-500 ℃, the reaction pressure is normal pressure to 0.05MPa, the retention time is 0.2-20 seconds, and the molar ratio of the reaction raw materials is o-chlorotoluene, ammonia and air is 1: 2-13: 10-50 to generate the o-chlorobenzonitrile, wherein the fluidized bed catalyst uses silicon dioxide as a carrier, and active components comprise the following general formula components in terms of atomic ratio:
V1.0CraBbXcYdZeOm
wherein X is selected from at least one of oxides of phosphorus or arsenic;
y is at least one of alkali metal or alkaline earth metal oxide;
z is at least one of metal oxides of Ni, Co, Pb, Fe, Mo or W;
the value range of a is 0.5-2.0;
the value range of b is 0.1-1.0;
the value range of c is 0.1-2.0;
the value range of d is 0.01-0.1;
the value range of e is 0.1-0.5;
m is the number of oxygen atoms required to satisfy the valence of the element;
the content of the catalyst carrier silicon dioxide is 30-80% by weight.
2. The method for producing o-chlorobenzonitrile according to claim 1, wherein the reaction temperature is 380 to 430 ℃, the residence time is 1 to 10 seconds, and the molar ratio of the raw materials is 1: 3 to 6: 15 to 30.
3. The process for producing o-chlorobenzonitrile according to claim 1, wherein the alkali metal is selected from the group consisting of sodium or potassium and mixtures thereof.
4. The process for producing o-chlorobenzonitrile according to claim 1, wherein the alkaline earth metal is selected from barium.
5. The method for producing o-chlorobenzonitrile according to claim 1, wherein a is in the range of 0.7 to 1.3.
6. The method for producing o-chlorobenzonitrile according to claim 1, wherein b is selected from the range of 0.4 to 0.8.
7. The method for producing o-chlorobenzonitrile according to claim 1, wherein c is selected from the range of 0.1 to 0.6.
8. The method for producing o-chlorobenzonitrile according to claim 1, wherein e is selected from the range of 0.1 to 0.3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531958A (en) * | 2011-11-18 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing aromatic nitrile by using fluidized bed reactor |
| CN103539701A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing o-chlorobenzonitrile through ammoxidation |
| CN106083651A (en) * | 2016-06-03 | 2016-11-09 | 安徽广信农化股份有限公司 | The new technique for synthesizing of salicylonitrile |
| CN113563226A (en) * | 2021-08-07 | 2021-10-29 | 江西永芳科技有限公司 | High-yield production method of o-chlorobenzonitrile |
-
2002
- 2002-03-13 CN CNB021110212A patent/CN1193009C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531958A (en) * | 2011-11-18 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing aromatic nitrile by using fluidized bed reactor |
| CN102531958B (en) * | 2011-11-18 | 2014-07-02 | 中国石油化工股份有限公司 | Method for producing aromatic nitrile by using fluidized bed reactor |
| CN103539701A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing o-chlorobenzonitrile through ammoxidation |
| CN103539701B (en) * | 2012-07-12 | 2015-12-16 | 中国石油化工股份有限公司 | For the method for prepared by ammoxidation for o-Cyanochlorobenzene |
| CN106083651A (en) * | 2016-06-03 | 2016-11-09 | 安徽广信农化股份有限公司 | The new technique for synthesizing of salicylonitrile |
| CN106083651B (en) * | 2016-06-03 | 2017-11-21 | 安徽广信农化股份有限公司 | The synthesis technique of salicylonitrile |
| CN113563226A (en) * | 2021-08-07 | 2021-10-29 | 江西永芳科技有限公司 | High-yield production method of o-chlorobenzonitrile |
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