CN1055028C - New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process - Google Patents
New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process Download PDFInfo
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- CN1055028C CN1055028C CN97109006A CN97109006A CN1055028C CN 1055028 C CN1055028 C CN 1055028C CN 97109006 A CN97109006 A CN 97109006A CN 97109006 A CN97109006 A CN 97109006A CN 1055028 C CN1055028 C CN 1055028C
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- catalyzer
- ammonia
- dichlorobenzonitrile
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- nitrile
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Abstract
The present invention discloses a novel catalyst for preparing 2, 6-dichlorobenzonitrile by an ammoxidation method, which is in a chemical structure of Va Ti<b> Pc Cr<d> Ox. The catalyst containing four components uses vanadium and titanium as main catalysts and uses phosphorus and chromium as cocatalysts. The present invention has the advantages of high activity, good selectivity, high product yield, high product purity, long service life and simple manufacturing process under optimum processing conditions. The mole yield, the selectivity and the purity of the product are respectively and correspondingly as 85.8%, 88.3% and greater than 99.0%. The present invention has outstanding social and economic benefits.
Description
The present invention relates to a kind of ammonia oxidation legal system 2, the new catalyst of 6-dichlorobenzonitrile, it belongs to technical field of organic chemistry, also belongs to organic chemistry industrial technology field.
2, the 6-dichlorobenzonitrile itself is a kind of weedicide.2, the 6-dichlorobenzonitrile is through the derivative of fluoridizing, hydrolysis obtains 2, and the 6-difluorobenzamide is the intermediate of ultra-high efficiency agricultural chemicals process for preparation of benzoylurea compounds of high physiologically active, the low residue of the emphasis development of a series of current developed countries.From 2, the 6-dichlorobenzonitrile sets out, and can produce multiple agrochemicals such as " chlorothiamid ", " UC 62644 ", " its worm grand ", " Teflubenzuron ", " diflubenzuron ", " flufenoxuron ", " fluorine bell urea ", " flucycloxuron ".These effective usage quantitys that are called the ultra-high efficiency agricultural chemicals only are the tens of grams in per hectare farmland, belong to the hormones sterilant, promptly by interference insect chitin deposition, thereby destroy the formation of new epidermis, make normally molt metamorphosis and death has so just overcome big, the residual high weakness of contact pesticide consumption of insect.Transnational companys such as some mechanisms of states such as the U.S., Japan, Holland and Shell pass through the research in year surplus in the of ten, screen above-mentioned valuable agrochemicals from a large amount of compounds, and they all are with 2, the intermediate of 6-dichlorobenzonitrile for producing.
As monomer 2,6-dichlorobenzonitrile and diphenols polycondensation can obtain so far special engineering plastics-polyphenylene oxide nitrile that use properties is the best in the world.Polyphenylene oxide nitrile HD 300 has high heat resistance, is the best kind of thermotolerance in the thermoplasticity crystal type resin, and the life-time service temperature is 230 ℃, and after strengthening with glass fibre or carbon fiber, heat-drawn wire is up to 330 ℃.It has splendid mechanical property and fabulous oil resistant, wear-resistant, corrosion-resistant, flame retardant properties and good electric property, regenerability, and it also has the moulding flowability and advantage such as composite performance is good, production technique is simple relatively.
Data-searching shows: 2, and some derived product of 6-dichlorobenzonitrile as " diflubenzuron ", has begun to enter China market.Prediction 2, the market outlook of 6-dichlorobenzonitrile are very optimistic.
Ammoxidation of aromatic hydrocarbon is a new and high technology.The ammonia oxidation technology is under the effect of catalyzer, utilizes cheap ammonia and air, and the labile methyl group of a step with organic molecule changes into cyano group.After the ammoxidating propylene to produce acrylonitrile industrialization, developed country falls over each other to carry out the research that ammoxidation of aromatic hydrocarbon prepares fragrant nitrile in succession, to replace the classical methods of producing fragrant nitrile such as diazotization that route is long, energy consumption is high, environmental pollution is serious.
Oxidation proceses of ammonia preparation 2, the yield of 6-dichlorobenzonitrile is significantly less than in a very long time-6-chlorophenyl nitrile always, is the oxidation proceses of ammonia preparation 2 of international the seventies level of representative with English Patent UK1317064, and the molar yield of 6-dichlorobenzonitrile only is 53.3%.Dr.Manfred Baerns and U.S. Pat 4530797 etc. are summed up as 2 with its reason, and 6-toluene dichloride sterically hindered big is than the ammonia oxidation difficulty of monochlorotoluene or other toluene dichloride.
In order to improve yield, the employing special measure is competitively studied by developed countries such as the U.S., Japan, obtains many effects over past ten years.For example: U.S. Pat 4530797 is used vanadium, phosphorus catalyst (VP1.2O5.5), claims and add haloalkane in reaction raw materials, can be with 2, and the molar yield of 6-dichlorobenzonitrile brings up to 86.7% from 58.4%.The European patent EP of Japanese publication-0273317 adopts iron, antimony-based catalyst (Fe
10Sb
20V
1.7Cr
2.2O
54.4) claim that to adopt the series connection of two towers to reclaim unreacted 2, the 6-toluene dichloride, thus molar yield is brought up to 81%.The flat 3-44362 of Japanese Patent JP then claims and charge into nitrogen in reaction raw materials, adopts vanadium series catalyst (VMo
0.2CrP
0.7)), can make 2, the yarn yield that rubs of 6-dichlorobenzonitrile reaches 85%.But these measures make the production technique relative complex more, and investment increases severely; Or cause problems such as equipment corrosion, product purity be low.
At present, domestic still do not have 2, and oxidation proceses of ammonia is not more adopted in the large-scale production of 6-dichlorobenzonitrile.Classical through steps such as nitrated, reduction, diazotization preparation 2, the method for 6-dichlorobenzonitrile, operational path is long, energy consumption is high, of poor quality, environmental pollution is serious, can't form scale.
At the beginning of 1996, " chemical science and technology development guides " the magazine No.1 phase that the petrochemical industry Room, Jiangsu Province science and technology department sponsors is released a kind of from 2, the 6-dichlorobenzonitrile is through four step synthetic methods of chlorination, one-tenth aldehyde, one-tenth oxime, one-tenth nitrile, and route is: 2, and 6-dichlorobenzonitrile sulfuric acid oxammonium hydrochloride acetic acid aceticanhydride
↓ ↓ ↓ ↓ chlorine → chlorination → one-tenth aldehyde → one-tenth oxime → be dehydrated into nitrile → Crystallization Separation →
↓????↓????????↓????????↓
Hydrogenchloride spent acid spent acid dilute acetic acid aceticanhydride → recrystallization → centrifugation → drying → finished product packing
Hope replaces restore nitrification method old technology with this.But long because of route, total recovery is low, and has a difficult problem that reclaims a large amount of spent acid, diluted acid.
Ammoxidation of aromatic hydrocarbon seminar of department of chemistry of Wuhan University has aimed at the forward position of international ammonia oxidation research since the eighties, be devoted to study the ammoxidation of aromatic hydrocarbon reaction, obtains many achievements.Wherein, the catalyzer " Chinese patent: ZL89101565.5 " of ortho-chlorotolu'ene oxidation proceses of ammonia production o-chloro benzonitrile reaches the leading level in the world.Relevant achievement obtains multinomial awards such as the Ministry of Chemical Industry's scientific-technical progress first prize in 1986,87 years national science and technology progress second prizes and State Education Commission, the Hubei Province State Scientific and Technological Commission progress prize in science and technology.Nineteen ninety-five, free problem was developed oxidation proceses of ammonia preparation 2 at home first on original working foundation, and the variation route of 6-dichlorobenzonitrile utilizes cheap ammonia and air, one-step synthesis 2, and the 6-dichlorobenzonitrile, its synthetic route is:
2,6-toluene dichloride → ammonia oxidation → capture → centrifugation → drying → finished product packing
Obviously, oxidation proceses of ammonia technology is simple and direct, and therefore, equipment and investment in fixed assets reduce significantly; Raw materials used kind reduces, and the decline of main raw material unit consumption, and therefore, process cost and production cost descend; Reaction is carried out continuously, easily realizes operation automation, is convenient to management; The equipment used production intensity is big, the product purity height, and economic and technical norms advanced person, remarkable in economical benefits, and the problem that does not exist spent acid to handle are beneficial to environment protection.
The objective of the invention is: because complicated process of preparation, the route of existing classics is long, energy consumption is high, poor product quality, environmental pollution are serious, the present invention proposes a kind of raw catalyst of a kind of employing only needs a step to get final product, with 2, the ammonia oxidation of 6-toluene dichloride makes 2, the 6-dichlorobenzonitrile, and it should have active high, good, the long service life of selectivity, product yield height, product purity is also high, does not have environmental pollution.Be the technical measures that realize that the object of the invention is taked: 2, the main reaction formula of 6-toluene dichloride ammonia oxidation:
Be strong exothermal reaction.Reaction heat is estimated as 517KJ/mol.
Main side reaction is perfect combustion and generates ammonium chloride:
Reaction heat is estimated as 3568KJ/mol.
We have at first carried out the preliminary comparation and assessment and the screening of the catalyzer of a large amount of different systems on " little inverse spectrum " combined apparatus, in Φ 30 silica tubes, further carry out the test of industry simulation continuous production then, determine the relevant performance of catalyzer and the processing condition of reaction.
The concrete grammar of experiment is: filling 15-25ml solid catalyst in reactor, will be through air, the ammonia, 2 of metering, and pass through beds after mixing of 6-toluene dichloride and the preheating.Temperature of reaction is kept by outer heating, and controls and regulate with accurate temperature controller.The high-temperature gas that breaks away from reactor, by the chilling condenser, with generate 2, the condensation of 6-dichlorobenzonitrile, be deposited in the trap.Tail gas is through offgas duct emptying.Trap is changed in per tour (8 hours), and sampling, processing, analysis, weighing also calculate productive rate.According to the productive rate, product color, purity etc. of operation in several eight hours, the performance quality and the processing condition of all catalyzer of comprehensive evaluation.
By a large amount of tests, finding with vanadium, titanium at last is Primary Catalysts, and phosphorus, chromium are four component catalysts of promotor, and its effective ingredient consists of:
V
aTi
bP
cCr
dO
x
A=1 wherein; B=1～2.5; C=0.1～1.5; D=0.1～0.5; X then decides according to the content of each element.
Each element can make with oxide compound or oxysalt and other soluble salts etc. of a series of these elements in the composition catalyzer.Vanadium for example, available V
2O
5, NH
4CO
3Deng; Phosphorus can be used P
2O
5Z, H
3PO
4Titanium can be used TiCl
4, Ti
2(C
2O
4)
3Chromium can be used Cr
2O
3, Cr (NO
3)
3Deng.
Preparation of catalysts adopts pickling process; The active princlple of catalyzer is dissolved mixing respectively, mix with carrier silica gel again, still aging, 〉=400 to 600 ℃ of activation 12 hours.
The optimum reaction conditions of experiment gained is as follows:
Temperature of reaction: 360～410 ℃; Reaction pressure: normal pressure; Water ratio: zero; Best ammonia ratio: 1: 3～10; Optimum air ratio: 1: 8～40; Catalyst loading: 50～100 gram/kilogram catalyzer hour.Under the aforementioned stable reaction conditions, molar yield reaches 85.8%; Transformation efficiency is 97.2%, and selectivity is 88.3%, and product purity reaches more than 99%.
Compared with the prior art, the technique effect that reached of the present invention:
The catalyst performance that the present invention develops is good, and its highest molar yield can reach 85.8%, and transformation efficiency is 97.2%, and product purity is higher than 99%, reaches international the nineties advanced level.When using this catalyzer, need not in reaction raw materials, to add other composition; Also need not to reclaim unreacted 2, the 6-toluene dichloride, this simple and reliable technology and the method for corresponding production unit taked, its enforcement will not only have the important social benefit, and appreciable economic benefit is also arranged.
2,6-toluene dichloride oxidation proceses of ammonia preparation 2, finishing and the further suitability for industrialized production that realizes of 6-dichlorobenzonitrile research, not only will help the become more meticulous raising of degree of China's Chemicals, change present China and still need import 2, the situation of 6-dichlorobenzonitrile for new and effective agricultural chemicals such as China's development process for preparation of benzoylurea compounds provide solid reliable intermediate guarantee, and can prove absolutely that research occupies important one seat in the ammoxidation of aromatic hydrocarbon forward position in China.
Below in conjunction with embodiment, the technology of the present invention is described in further detail.
Embodiment:
Carefully 3.21 gram Vanadium Pentoxide in FLAKESs and 1.62 grams are contained 85% phosphoric acid respectively and be dissolved in 50 milliliters of aqueous solution that contain 6.68 gram oxalic acid, the cooling back adds 0.53 gram chromium trioxide.Above-mentioned solution and 30.05 grams, 40% titanium tetrachloride aqueous solution are mixed back impouring 50 restrain that to be preheating to 110 ℃, granularity be in the 40-60 purpose silica gel.Stir, placement is spent the night.In High Temperature Furnaces Heating Apparatus, progressively rise to 580 ℃ then, be incubated 12 hours.After treating naturally cooling, it is standby to bottle.This catalyzer has following composition:
V
1Ti
1.8P
0.1Cr
0.15O
7.3
15 gram catalyzer are packed in the quartz reactor of Φ 30, and in the material mixed gas 2,6-toluene dichloride: ammonia: air=1: 3: 20, temperature of reaction are 370 ℃, react result such as following table after 12 hours:
Catalyzer is formed V
1Ti
1.8P
0.1Cr
0.15O
7.3
370 ℃ of temperature of reaction
Yield (%) 85.8
Selectivity (%) 88.3
Above-mentioned catalyst reaction 12 hours is compared as follows table with the result of reaction after 1000 hours, illustrates that this activity of such catalysts and selectivity are constant substantially: (table is seen the literary composition back)
Catalyst reaction 12 hours and the as a result catalyst reaction time response temperature yield selectivity of reaction after 1000 hours
(time) (℃) be (%) V (%)
1Ti
1.8P
0.4Cr
0.15O
7.312 370 85.8 88.3V
1Ti
1.8P
0.4Cr
0.15O
7.31,000 370 85.4 88.0
Claims (3)
1. ammonia oxidation legal system 2, the catalyzer of 6-dichlorobenzonitrile is characterized in that: this catalyzer is to be Primary Catalysts with vanadium, titanium, and phosphorus, chromium are that four components of promotor are formed, and its composition is:
V
aTi
bP
cCr
dO
x
A=1 wherein, b is 〉=1 to 2.5; C is 〉=0.1 to 1.5; D is 〉=0.1 to 0.5; X then decides according to the content of each element.
2. the described Preparation of catalysts method of claim 1 is characterized in that: will comprise V
2O
5, NH
4CO
3, P
2O
5, H
3PO
4, TiCl
4, Ti
2(C
2O
4)
3, Cr
2O
3, Cr (NO
3)
3The oxide compound of each vanadium, phosphorus, titanium, chromium or the active principle of the catalyzer of oxysalt and soluble salt dissolve mixing respectively, mix with carrier silica gel again, still aging, 〉=400 to 600 ℃ of activation 12 hours.
3. the described catalyzer of claim 1 is used for oxidation proceses of ammonia preparation 2,6-two benzonitrile nitriles, and its processing condition are: temperature of reaction is 〉=360 to 410 ℃; Reaction pressure is a normal pressure; The water ratio is 0; Best ammonia ratio is 1: 〉=3 to 10; The optimum air ratio is 1: 〉=8 to 40; Catalyst loading is 〉=50 to 100 gram/kilogram catalyzer hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109006A CN1055028C (en) | 1997-01-13 | 1997-01-13 | New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109006A CN1055028C (en) | 1997-01-13 | 1997-01-13 | New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1166378A CN1166378A (en) | 1997-12-03 |
| CN1055028C true CN1055028C (en) | 2000-08-02 |
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ID=5170833
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97109006A Expired - Fee Related CN1055028C (en) | 1997-01-13 | 1997-01-13 | New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1515946A2 (en) * | 2002-06-04 | 2005-03-23 | Tessenderlo Chemie S.A. | Method for the preparation of halogenated benzonitriles |
| 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 |
| CN102924328A (en) * | 2012-11-14 | 2013-02-13 | 连云港阳方催化科技有限公司 | Synthesis method of 2, 6-dichlorobenzonitrile |
| CN103041838A (en) * | 2012-12-28 | 2013-04-17 | 武汉今福科技有限公司 | Catalyst for preparing 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene by means of ammoxidation |
| CN104326940A (en) * | 2014-11-24 | 2015-02-04 | 苏州乔纳森新材料科技有限公司 | Method for synthesizing 2,6-dichlorobenzonitrile by ammoxidation |
| CN109046454B (en) * | 2018-08-23 | 2022-11-18 | 常州新日催化剂股份有限公司 | Catalyst for synthesizing 2, 6-dichlorobenzonitrile and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2711332A1 (en) * | 1977-01-14 | 1978-07-20 | Nippon Kayaku Kk | PROCESS FOR PRODUCING AROMATIC NITRILE |
| EP0141228A1 (en) * | 1983-09-24 | 1985-05-15 | Nippon Kayaku Kabushiki Kaisha | A process for producing polychlorobenzonitrile |
| EP0273317A1 (en) * | 1986-12-19 | 1988-07-06 | Nitto Chemical Industry Co., Ltd. | Process for producing 2,6-dichlorobenzonitrile |
| CN1045532A (en) * | 1989-03-17 | 1990-09-26 | 武汉大学 | The new catalyst of ortho-chlorotolu'ene prepared by ammoxidation o-chloro benzonitrile |
| CN1106314A (en) * | 1994-06-23 | 1995-08-09 | 化学工业部北京化工研究院 | Catalyst for preparing cyanopyridine by ammoxidation of alkyl-pyridine and its application |
-
1997
- 1997-01-13 CN CN97109006A patent/CN1055028C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2711332A1 (en) * | 1977-01-14 | 1978-07-20 | Nippon Kayaku Kk | PROCESS FOR PRODUCING AROMATIC NITRILE |
| EP0141228A1 (en) * | 1983-09-24 | 1985-05-15 | Nippon Kayaku Kabushiki Kaisha | A process for producing polychlorobenzonitrile |
| EP0273317A1 (en) * | 1986-12-19 | 1988-07-06 | Nitto Chemical Industry Co., Ltd. | Process for producing 2,6-dichlorobenzonitrile |
| CN1045532A (en) * | 1989-03-17 | 1990-09-26 | 武汉大学 | The new catalyst of ortho-chlorotolu'ene prepared by ammoxidation o-chloro benzonitrile |
| CN1106314A (en) * | 1994-06-23 | 1995-08-09 | 化学工业部北京化工研究院 | Catalyst for preparing cyanopyridine by ammoxidation of alkyl-pyridine and its application |
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| Publication number | Publication date |
|---|---|
| CN1166378A (en) | 1997-12-03 |
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