CN1045532A - The new catalyst of ortho-chlorotolu'ene prepared by ammoxidation o-chloro benzonitrile - Google Patents
The new catalyst of ortho-chlorotolu'ene prepared by ammoxidation o-chloro benzonitrile Download PDFInfo
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- CN1045532A CN1045532A CN 89101565 CN89101565A CN1045532A CN 1045532 A CN1045532 A CN 1045532A CN 89101565 CN89101565 CN 89101565 CN 89101565 A CN89101565 A CN 89101565A CN 1045532 A CN1045532 A CN 1045532A
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- chlorotolu
- ene
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Abstract
A kind of efficient catalyst that is used for ortho-chlorotolu'ene prepared by ammoxidation o-chloro benzonitrile, it has following composition:
V
aP
bLi
cA
dO
eA is Mo or K in the formula
Evaluate catalysts has adopted " little anti--chromatogram-microcomputer " combined apparatus.This catalyzer is by lab scale and pilot scale, and is applied to produce per year the industrial production of 100 tons of o-chloro benzonitriles.Test-results shows, this catalyzer have active high, selectivity is good, catalyst life is long, manufacturing process is simple and advantage such as low price.
Description
The method that alkene, aromatic hydrocarbons and derivative thereof are made nitrile compounds through oxidation proceses of ammonia is a kind of new technology that is developed over nearly more than 20 years, oxidation proceses of ammonia only needs alkene, aromatic hydrocarbons and derivative thereof mixed with ammonia, oxygen (or air) by corresponding catalyzer and can be easy to formation-CN base in the N atom introducing organic molecule, and the nitrile compound of gained such as prussic acid, vinyl cyanide, cyanobenzene, benzene dicarbonitrile etc. are the important source material of chemical industry such as organic synthesis, plastics, fiber, agricultural chemicals and dyestuff.
Ortho-chlorotolu'ene can be produced o-chloro benzonitrile by ammonia oxidation, and the latter is the intermediate of dyestuff, medicine, perfume industry, for example, o-chloro benzonitrile through nitrated, ammonia separate two the step then can obtain 2 cyano 4 nitro aniline, the latter is the important intermediate of dispersed dye.The purpose of our research work is exactly the reaction mechanism according to the ortho-chlorotolu'ene ammonia oxidation, changes the composition and the proportioning of catalyzer, to obtain the catalyzer of excellent performances such as high reactivity and highly selective.For evaluate catalysts, set up cover " miniature reactor-gas-chromatography-microcomputer " combined apparatus.
The reaction that the ortho-chlorotolu'ene ammonia oxidation generates o-chloro benzonitrile is:
Because there is active chlorine in the ortho position of methyl, therefore when the ortho-chlorotolu'ene ammonia oxidation, often be accompanied by deep oxidation and take place that phenyl ring decomposes or side reactions such as dechlorination, as:
Adopted most of catalyzer of past all seem too strong to the activity of ortho-chlorotolu'ene ammonia oxidation, cause deep oxidation easily and make product purity and yield all not ideal enough.According to United States Patent (USP) (U.S.Pat.4124631) report in 1978, the catalyzer that consists of vanadium-phosphorus-chromium carried out the result of lab scale with fixed bed, and the highest molar yield of o-chloro benzonitrile is 84.0%.Japanese Patent in 1981 (day special public clear 56-77250) report consists of the catalyzer of vanadium-phosphorus-lithium, and the molar yield of o-chloro benzonitrile reaches 90.1%.At home, the research to ortho-chlorotolu'ene ammonia oxidation process and catalyzer thereof is that early eighties begins.The ammoxidation catalyst of Xiangtan Designing Inst. of Chemical Industry's development is tested on the ebullated bed of φ 32, and the molar yield of o-chloro benzonitrile is 62.4%.Six component catalysts of the common development of department of chemistry of Wuhan University in 1984 and Xiang Tan chemical research designing institute, its molar yield brings up to 82%, and this yield still has one section not small distance with the highest yield of report in the world.Therefore, develop the ammoxidation catalyst of a kind of high reactivity and highly selective, o-chloro benzonitrile is produced in exploitation ortho-chlorotolu'ene ammonia oxidation just seemed very important.For activity and the selectivity that improves the ortho-chlorotolu'ene ammoxidation catalyst, prolong the work-ing life of catalyzer, we have carried out more deep research to ammoxidation catalyst since the second half year in 1985.
According to the analysis to reaction mechanism, the ortho-chlorotolu'ene ammonia oxidation is actually steps such as a series of dehydrogenations, confession (oxygen), nitrilation and forms.Thereby good catalyzer must be adapted to it by the group that the dehydrogenation center with suitable activity and number, confession (oxygen) center and nitrilation center are formed.According to the requirement of reaction mechanism, can design numerous prescriptions differences, the different catalyzer of preparation technology.But important problem is how to choose appropriate catalyst from numerous catalyzer fast, and by after industry simulation lab scale and the pilot scale checking performance, just can be used for actual production.For this purpose, we have set up cover " miniature reactor-gas-chromatography " combined apparatus, then again with this device and microcomputer coupling, the speed of evaluate catalysts performance and reliability are improved greatly.
Through successively multiple formulations being studied, according to " little anti--chromatogram " combined apparatus comparation and assessment result, adjust component, proportioning and preparation technology, filter out better several catalyzer and in simulator, carry out lab scale, the molar yield of o-chloro benzonitrile can reach more than 92%, has surpassed the optimum value of present foreign literature report, much larger than the domestic molar yield index of having reported.The catalyzer of choosing has been applied to the production equipment that 100 tons of o-chloro benzonitriles are produced in Wuhan University-Huang Po chemical plant per year after pilot scale.
This catalyzer is made up of the oxide compound of following metallic element:
V
aP
bLi
cA
dO
e
A is Mo or K in the formula, and wherein the scope of each atoms of elements ratio is as follows:
a∶b∶c∶d＝1∶0.1～3∶0.05～2.5∶0.01～2
The content of oxygen is then decided according to the content of other elements than e.
Each metallic element can make with oxide compound or oxysalt and other soluble salts etc. of a series of these metals in the composition catalyzer.Vanadium for example, available V
2O
5, NH
4VO
3Deng compound; The then available P of phosphorus
2O
5, H
3PO
4; Lithium can be used Li
2CO
3, LiNO
3; Molybdenum can be used (NH
4)
6Mo
7O
244H
2O; Potassium can be used K
2SO
4, K
2CO
3Deng.
Preparation of catalysts adopts pickling process, its preparation technology is undertaken by general known step: the fine particle silica gel of certain particle size is joined in the metal compound solution for preparing, still aging certain hour heats up behind the evaporate to dryness more gradually, activates 12 hours down at 400～600 ℃ at last.
This catalyzer can react in fixed bed or fluidized-bed reactor.
In reaction mixture gas, can add the water vapour of some amount, can reduce side reaction like this and be convenient to controlled temperature.Ortho-chlorotolu'ene in the reactor feed gas: ammonia: air: water vapour=1: 1.1～10: 8～50: 5～35.Be reflected under the normal pressure and carry out, 350～550 ℃ of temperature of reaction, be 0.1～15 second the duration of contact of reactant gases and catalyzer.
Example 1
With ammonium meta-vanadate NH
4VO
37.7 gram, oxalic acid H
2C
2O
412.4 gram, ammonium molybdate (NH
4)
6Mo
7O
244H
2The O7.0 gram adds in the entry, adds 85%H again
3PO
49.8 about gram, low-grade fever to 50 ℃, slowly add Quilonum Retard Li then
2CO
31.2 gram.Solution colour is black-and-blue by the xanthochromia palm fibre at last, has a large amount of bubbles to emit.When bubble reduces, with SiO
240 grams are poured into and are stirred.At room temperature still aging 8 hours, be evaporated to driedly then, be warming up to 550 ℃ gradually, after 12 hours, naturally cool to room temperature in this temperature-activated, this catalyzer has following composition:
V
1P
1.3Li
0.5Mo
0.6Oe
The 30ml catalyzer is packed in φ 32 quartz tube reactors into ortho-chlorotolu'ene in the material mixed gas: ammonia: air: water vapour (mol ratio)=1: 3: 20: 10, temperature of reaction is 430 ℃, be 4 seconds duration of contact.React result such as table 1 after 6 hours.
Example 2
With ammonium meta-vanadate 10.3 grams, oxalic acid 16.6 grams, ammonium molybdate 3.1 grams add in the entry, add 85% phosphatase 11,3.2 grams again.Low-grade fever adds Quilonum Retard 1.6 grams then.Stir,, pour hydrothermal solution into SiO to emitting bubble when rare
2In, stirring, ageing, evaporate to dryness then.Be warming up to 550 ℃ gradually, this temperature-activated 14 hours, this catalyzer had following composition:
V
1P
1.3Li
0.5Mo
0.2Oe
This catalyzer reacts by example 1 condition, the results are shown in Table 1.
Table 1
| Routine number | Catalyzer is formed | Temperature of reaction (℃) | Duration of contact (second) | Yield (%) | Selectivity (%) |
| 1 | V 1P 1.3Li 0.5Mo 0.6Oe | 430 | 4 | 92.6 | 94.5 |
| 2 | V 1P 1.3Li 0.5Mo 0.2Oe | 440 | 4 | 93.4 | 94.9 |
Example 3-5
Press the method preparation catalyzer of example 1, only difference is to change ammonium molybdate into K
2SO
4, change formula rate.Catalyzer is formed and reaction result sees Table 2.
Table 2
| Routine number | Catalyzer is formed | Temperature of reaction (℃) | Duration of contact (second) | Yield (%) | Selectivity (%) |
| 3 | V 1P 1.1Li 0.2K 0.02Oe | 420 | 4 | 93.6 | 95.5 |
| 4 | V 1P 1.1Li 0.2K 0.05Oe | 420 | 4 | 93.1 | 95.0 |
| 5 | V 1P 1.1Li 0.2K 0.08Oe | 420 | 4 | 92.5 | 94.6 |
Example 6
Example 3 reaction 6 hours and the result comparison of reaction after 1000 hours illustrate that as table 3 this activity of such catalysts and selectivity are constant substantially.
Table 3
| Routine number | Catalyzer is formed | Reaction times (hour) | Temperature of reaction (℃) | Duration of contact (second) | Yield (%) | Selectivity (%) |
| 3 | V 1P 1.1Li 0.2K 0.02Oe | 6 | 420 | 4 | 93.6 | 95.5 |
| 3 | V 1P 1.1Li 0.2K 0.02Oe | 1000 | 420 | 4 | 93.4 | 95.3 |
Claims (5)
1, a kind of efficient catalyst that is used for ortho-chlorotolu'ene prepared by ammoxidation o-chloro benzonitrile.Its characteristics are: the catalyzer by general known immersion process for preparing becomes is used for fixing bed or fluidized-bed ortho-chlorotolu'ene ammonia oxidation legal system o-chloro benzonitrile.This catalyzer can be used for industrial production, has active high, advantages such as selectivity is good, preparation technology is simple, low price.
2, by the described catalyzer of claim 1, its characteristics are: this catalyzer is that the oxide compound by metallic element is constituted, and it consists of V
aP
bLi
cA
dO
e: V is a vanadium in the composition, and P is a phosphorus, and Li is a lithium, and A is Mo or K.The scope of each atoms of elements ratio is a: b: c: d=1: 0.1～3.0: 0.05～2.5: 0.01～2.0, and the content of oxygen is then decided according to the content of other element than e.Each metallic element can make with other soluble salt with the oxide compound or the oxysalt of a series of these metals in the catalyzer.
3, by claim 1 and 2 described catalyzer, its characteristics are: when catalyzer was estimated, the molar yield of its ammonia oxidation can reach 92.5～93.6%, and selectivity can reach 94.5～95.5%.
4, by the described catalyzer of claim 1, its characteristics are: with the active principle dissolving of catalyzer, low-grade fever to 50 ℃, solution colour becomes black-and-blue by the xanthochromia palm fibre at last, when the bubble that produces reduces gradually, mix mutually with carrier silica gel, at room temperature still aging 8 hours, be evaporated to dried then, activation is 12-14 hour under 400～600 ℃ of temperature, thereby obtains the effective catalyst of high reactivity, highly selective.
5, by claim 1,2 and 4 described catalyzer, its characteristics are: in the reaction of ortho-chlorotolu'ene prepared by ammoxidation o-chloro benzonitrile, ortho-chlorotolu'ene in the material mixed gas: ammonia: air: the mol ratio of water vapour is 1: 1.1～10: 8～50: 5～35, the oxidative ammonolysis temperature is 350～550 ℃, and reaction contact time is 0.1～15 second.The use of catalyzer can reach 1000 hours at least.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89101565 CN1024633C (en) | 1989-03-17 | 1989-03-17 | Catalyst containing ortho chloro-toluene-ammonia oxidant and ortho chlorobenzoyl cyanide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89101565 CN1024633C (en) | 1989-03-17 | 1989-03-17 | Catalyst containing ortho chloro-toluene-ammonia oxidant and ortho chlorobenzoyl cyanide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1045532A true CN1045532A (en) | 1990-09-26 |
| CN1024633C CN1024633C (en) | 1994-05-25 |
Family
ID=4854337
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89101565 Expired - Fee Related CN1024633C (en) | 1989-03-17 | 1989-03-17 | Catalyst containing ortho chloro-toluene-ammonia oxidant and ortho chlorobenzoyl cyanide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024633C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055028C (en) * | 1997-01-13 | 2000-08-02 | 武汉大学 | Novel catalyst for preparing 2, 6-dichlorobenzonitrile by ammoxidation |
| CN1074309C (en) * | 1998-03-30 | 2001-11-07 | 中国石油化工总公司 | Fluid bed catalyst for the preparation of aromatic nitrile halide |
| CN1074308C (en) * | 1998-03-30 | 2001-11-07 | 中国石油化工总公司 | Fluid and catalyst for the preparation of aromatic nitrile halide |
| CN100435949C (en) * | 2006-03-23 | 2008-11-26 | 浙江工业大学 | Integrated member type methyl aromatic hydrocarbon selective oxidizing catalyst and its preparation and use |
| CN103769184A (en) * | 2014-01-24 | 2014-05-07 | 先尼科化工（上海）有限公司 | Catalyst for producing aromatic nitrile through aromatic ammoxidation, and applications of catalyst |
| CN107497466A (en) * | 2017-09-04 | 2017-12-22 | 南通天泽化工有限公司 | A kind of o-chloro benzonitrile catalyst and preparation method thereof |
| CN109876837A (en) * | 2018-12-17 | 2019-06-14 | 中南民族大学 | The special-purpose catalyst and preparation method and purposes of preparing chlorobenzonitrile by using ammoxidation method |
| 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 |
-
1989
- 1989-03-17 CN CN 89101565 patent/CN1024633C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055028C (en) * | 1997-01-13 | 2000-08-02 | 武汉大学 | Novel catalyst for preparing 2, 6-dichlorobenzonitrile by ammoxidation |
| CN1074309C (en) * | 1998-03-30 | 2001-11-07 | 中国石油化工总公司 | Fluid bed catalyst for the preparation of aromatic nitrile halide |
| CN1074308C (en) * | 1998-03-30 | 2001-11-07 | 中国石油化工总公司 | Fluid and catalyst for the preparation of aromatic nitrile halide |
| CN100435949C (en) * | 2006-03-23 | 2008-11-26 | 浙江工业大学 | Integrated member type methyl aromatic hydrocarbon selective oxidizing catalyst and its preparation and use |
| CN103769184A (en) * | 2014-01-24 | 2014-05-07 | 先尼科化工（上海）有限公司 | Catalyst for producing aromatic nitrile through aromatic ammoxidation, and applications of catalyst |
| CN107497466A (en) * | 2017-09-04 | 2017-12-22 | 南通天泽化工有限公司 | A kind of o-chloro benzonitrile catalyst and preparation method thereof |
| CN109876837A (en) * | 2018-12-17 | 2019-06-14 | 中南民族大学 | The special-purpose catalyst and preparation method and purposes of preparing chlorobenzonitrile by using ammoxidation method |
| CN109876837B (en) * | 2018-12-17 | 2022-02-22 | 中南民族大学 | Special catalyst for preparing o-chlorobenzonitrile by ammoxidation method, preparation method and application thereof |
| 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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| Publication number | Publication date |
|---|---|
| CN1024633C (en) | 1994-05-25 |
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