CN1230537A - Preparation process of 2,6-dichloro benzonitrile - Google Patents
Preparation process of 2,6-dichloro benzonitrile Download PDFInfo
- Publication number
- CN1230537A CN1230537A CN 98110745 CN98110745A CN1230537A CN 1230537 A CN1230537 A CN 1230537A CN 98110745 CN98110745 CN 98110745 CN 98110745 A CN98110745 A CN 98110745A CN 1230537 A CN1230537 A CN 1230537A
- Authority
- CN
- China
- Prior art keywords
- bromine
- dichlorobenzonitrile
- technology
- catalyzer
- prepare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
During the preparation process, 2,6-dichloro methylbenzene, ammonia and oxygen are used as raw material, V-P-Na system composite is used as catalyst and bromine and/or bromide is added in the course of reaction. The preparation process has the features of high yield of 2,6-dichloro benzonitrile product, capacity of overcoming the amplification effect, heat transferring and other problems in the reactor. It may be used in industrial production.
Description
The present invention relates to be used to prepare 2, the technology of 6-dichlorobenzonitrile particularly about being catalyzer with the V, the P system that contain sodium, is added the technology of bromine and/or bromine-containing compound in the reaction process.
2,6-dichlorobenzonitrile (being called for short DBN) is a kind of good weedicide.It has special damping effect to annual and perennial weeds; Very low to mammalian toxicity, it is the important intermediate of agricultural chemicals and organic synthesis raw material simultaneously, is widely used in producing 2,6-difluorobenzonitrile, 2, agricultural chemicals such as 6-difluoroaniline, chlorothiamid, diflubenzuron, flufenoxuron.
DBN is typical fine chemical product, and its production technology route can be divided into organic synthesis method and gas phase oxidation proceses of ammonia.The gas phase ammonoxidation method is with 2, and 6-toluene dichloride, oxygen and ammonia are that raw material carries out gas phase catalytic reaction acquisition product 2,6-dichlorobenzonitrile.
Because the chlorine in the toluene dichloride is active group, and the methyl on the toluene is had activation, but two replacement chlorine can cause serious space steric effect at the ortho position of methyl, cause oxidative ammonolysis to be difficult to carry out.Only use the V catalyzer to carry out oxidative ammonolysis for this material, all can cause coming off of halogen, the increase of by product.Such catalysts and reaction conditions are the keys of influence reaction.
Early stage 2,6-toluene dichloride ammonia oxidation technology generally all uses simple vanadium component or vanadium component to be furnished with the catalyzer of a small amount of other component, and its general reaction yield is lower.From recent 2,6-toluene dichloride ammoxidation catalyst component mainly contains V-P, Sb-Fe, the catalyzer of three kinds of compositions of V-Cr.It is body of catalyst that the clear 43-5386 of document JP, the clear 43-10623 of JP etc. disclose with V, and gama-alumina is the catalyzer of carrier, 2, and the highest yield of 6-dichlorobenzonitrile only is 70%.This technology is owing to use single-component V to be catalyzer, and ammonia decomposition and dehalogenation atomic reaction are serious, so yield is lower.A kind of preparation 2 is disclosed among the document Japanese Patent JP flat 344362, the catalyzer of 6-dichlorobenzonitrile, this catalyzer is a catalyst component by V, P, Mo, Cr element, with γ-Al
2O
3Be carrier, owing to, therefore be only applicable to fixed bed reaction by immersion process for preparing.Though its product D BN yield reaches 85.0%, because oxidative ammonolysis is the reaction of strong heat release, there are serious problems in the heat of moving of fixed bed reaction on engineering, cause industrial application to be restricted.Disclose preparation 2 in the document US 4530797, the technology of 6-dichlorobenzonitrile, this technology are to be catalyst component with V, P, by add the method for bromine or bromine compounds in reaction system, improve product 2, the purpose of 6-dichlorobenzonitrile yield to reach.The levels of catalysts of its use is lower, and when not adding bromine or bromine compounds, product yield is the highest by only 58.4%.
The objective of the invention is to exist engineering to amplify, move the defective of problem such as heat in order to overcome the on the low side or industrial reactor of the product D BN yield that exists in the above-mentioned document, a kind of new preparation 2 is provided, the technology of 6-dichlorobenzonitrile, this technology has can effectively overcome the reactor scale effect, move problems such as heat, and have 2, the characteristics that 6-dichlorobenzonitrile yield is high.
The objective of the invention is to realize: a kind ofly be used to prepare 2 by following technical scheme, the technology of 6-dichlorobenzonitrile, with 2,6-toluene dichloride, ammonia and molecular oxygen are raw material, add bromine and/or bromine-containing compound in reaction process, the catalyzer that uses in reaction process contains silica supports and the following composition of chemical formula:
V
1.0P
bNa
cA
dB
eO
xA is at least a lithium, potassium, rubidium or the caesium of being selected from the formula;
B is at least a magnesium, calcium, barium, chromium, manganese, iron, cobalt, nickel or the tin of being selected from; Wherein b is 0.3～4.0; C is 0.01～0.7; D is 0.05～1.0; E is 0～2.0; X is the summation that satisfies other element valence requisite oxygen atomicity; The content of carrier silicon-dioxide is 50～80% by weight percentage in the catalyzer.
The preferable range of b is 0.5～3.0 in the technique scheme; The preferable range of c is 0.1～0.4; The preferable range of d is 0.05～0.50; The preferable range of e is 0.05～1.5.
Among the present invention because to adopt silicon-dioxide be carrier, and the fluid catalyst technology that adopts spraying to be shaped, thereby overcome the reactor engineering scale effect that exists on the engineering effectively, move problem such as heat.By V, P catalyzer being carried out discovering extensively and profoundly, the physicals of catalyzer can be significantly improved after in two yuan of components of V, P, adding basic metal and/or alkaline-earth metal, and the selectivity and the product yield of oxidative ammonolysis can be improved, reduce by-product NH
4Cl, CO
2, CO, HCN growing amount.Interpolation bromine and/or bromine-containing compound can improve product 2 effectively in the technology, and the yield of 6-dichlorobenzonitrile has been obtained good effect.
Catalyzer of the present invention can not only be applicable to fluidized-bed, and is applicable to fixed bed, and good catalytic activity is all arranged.
V
2O
5, P
2O
5, alkalimetal oxide or alkaline earth metal oxide be the starting raw material of catalyzer, other compound that also can select to make by suitable processing is made raw material.Example:
Vanadium raw materials: ammonium meta-vanadate, Vanadosulfuric acid, organic acid vanadium such as vanadium oxalate, tartrate vanadium;
Cr materials: chromic acid, chromic salt;
Phosphorus raw material: phosphoric acid, ammonium phosphate.
Category-A raw material: available nitrate or vitriol;
B raw material: the salt of nitrate or other solubility;
Silicon raw material: use silicon sol, silica gel and silicon-dioxide carrier as catalyzer.
Preparation of catalysts makes by the method for being familiar with: with ammonium metavanadate solution and phosphoric acid, basic metal or alkaline earth salt aqueous solution, add silicon sol, concentrated suspended nitride mixture is for good dissolving more can add some oxalic acid.After the fluid catalyst slurry is spray-dried, roasting.Fixed bed catalyst slurry evaporation after drying, roasting.400～700 ℃ of maturing temperatures are preferably 450～650 ℃, and the time is 2～10 hours.
Oxide content is with V in the catalyzer
2O
5, P
2O
5, alkalimetal oxide or alkaline earth metal oxide and other metal oxide weight percent meter.
Chlorotoluene can be: 2, and 6-toluene dichloride, 2,4, derivatives such as 6-trichlorotoluene zotrichloride.
When being O with the air
2During the source, the concentration of toluene dichloride gas phase mixture is 0.2～10% (Vol), and preferable range is 0.5～7.0% (Vol).
The ammonia usage quantity is greater than theoretical amount at least, a high proportion of NH
3To reaction is favourable, but vast scale excessive N H
3There is the problem that reclaims.The NH of this technology
3Amount is about 2～15 times of theoretical amount, and preferable range is 3～10 times.
O
2At least be 1.5 times of theoretical amount, more suitable scope is 2～10 times.Usually air is as O
2The source, N
2, CO
2, water vapour can be used as the thinner of rare gas element.
If 2,6-toluene dichloride amount is 1mol, NH so
3Be 3～10 times (mol), the O of theoretical amount
2Be 2～10 times (mol) of theoretical amount, meeting NH
3/ O
2When being 1.1～1.7 conditions, the reaction result that can obtain.
Bromine compounds is selected from hydrogen bromide, a monobromethane, methylene bromide, methenyl bromide, tetrabromomethane, 1-monobromethane, 1 in bromine that this technology is used and/or the bromine compounds, 2-ethylene dibromide, 1-bromine n-propane, 2-N-PROPYLE BROMIDE, 1-n-butyl bromide, tert-bromo butane, isopentyl bromination alkane, cyclohexyl bromoalkane, bromobenzene or bromine ethylbenzene or their mixture, be added in the reaction system with the gas phase form, add-on is 2,0.1～10% of 6-toluene dichloride weight, preferable range are 0.5～7.0%.
This technological reaction temperature is 300～500 ℃, and preferable range is 330～450 ℃.Temperature is lower than 300 ℃, and reaction conversion ratio is low; Be higher than 500 ℃, dechlorination atom and oxidizing reaction are serious, CO
2, NH
4Cl, HCN content obviously increase, and fragrant nitrile yield descends.The optimum temps of this reaction depends on concentration, the duration of contact of the position of chlorine atom in the chlorotoluene and number, initiator, the factors such as roasting condition of catalyzer.Thereby suitable reaction temperature is that variation with above-mentioned condition changes.
Bigger mobility scale is arranged duration of contact of the present invention, and generally at 0.2～30 second, more suitable scope is 0.5～20 second.
The present invention reacts under normal pressure usually, but also can depress reaction adding.
Catalyzer of the present invention is formed and technology both can be used for fixed bed, can be used for moving-bed and fluidized-bed again.Because oxidative ammonolysis reaction heat is big, although fixed bed reaction has better performance, owing to move heat problem, the control of reaction heat can become difficult point, and the higher meeting of temperature causes the reaction of dechlorination atomic pair, and yield descends.Use fluidized-bed and moving-bed to removing reaction heat and preventing local superheating, very big benefit is arranged.
The investigation condition of catalyzer of the present invention is to carry out in φ 38mm * 1800mm stainless steel fluidized-bed reactor.The add-on of catalyzer is 550g, and reaction pressure is 0.01MPa, and the monobromethane addition is 2,2.0% of 6-toluene dichloride (DCT) weight, and be added in the reaction system with the gas phase form.
The invention will be further elaborated below by embodiment.[embodiment 1]
Preparation of Catalyst
186.1g NH
4VO
3Be dissolved in the 2800ml water, with 85%H
3PO
4220g, 400ml water mixes, and adds 20%NaNO
3202.5g, 20%LiNO
3109.7g, mix the back and add 40%SiO
21750g stirs, and heating evaporation is to solid content 38%.
Slurry is through spray shaping, 250 ℃ of gas feed temperature, and 130 ℃ of gas outlet temperatures, the catalyzer of moulding is dry 2hr under 130 ℃ of air conditionses, and then at 400 ℃ of preroasting 0.5hr, at last at 580 ℃ of roasting 3hr.Get the composition of catalyzer: V at last
1P
1.2Na
0.3Li
0.2O
6.75/ 70%SiO
2, oxide concentration 30%.Heap compares 0.98g/cm
3
Evaluating catalyst I:
Feed 2,6-toluene dichloride (DCT) 1.16g/min, NH
30.67 l/min, air (Air) 2.28 l/min, DCT: NH
3: Air=1: 4.2: 14.3 (mol/mol), 360 ℃ of temperature of reaction, the result is as follows:
2,6-toluene dichloride transformation efficiency 86.9%
2,6-dichlorobenzonitrile yield 74.1%
2,6-dichlorobenzonitrile selectivity 85.2%
Evaluating catalyst II:
Feed 2,6-toluene dichloride (DCT) 1.16g/min, NH
30.67 l/min, air (Air) 2.28 l/min, DCT: NH
3: Air=1: 4.2: 14.3 (mol/mol), 360 ℃ of temperature of reaction, monobromethane 0.023g/min, the result is as follows:
2,6-toluene dichloride transformation efficiency 98.0%
2,6-dichlorobenzonitrile yield 88.7%
2,6-dichlorobenzonitrile selectivity 90.5%[embodiment 2～10]
Method for preparing catalyst is with embodiment 1, changes the proportioning or the composition of catalyzer, and the results are shown in Table 1 to press among the embodiment 1 evaluating catalyst I condition evaluating, and the results are shown in Table 2 to press among the embodiment 1 evaluating catalyst II condition evaluating.
Table 1
| Embodiment | Catalyzer | The DCT transformation efficiency, % | The DBN yield, % | The DBN selectivity, % |
| ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 | V 1P 1.2Na 0.3Li 0.3O 5.8(SiO 270％) V 1P 1.2Na 0.4Li 0.2O 5.8(SiO 270％) V 1P 1.2Na 0.4Li 0.3O 5.8(SiO 270％) V 1P 0.9Na 0.3Li 0.1O 4.95(SiO 270％) V 1P 1.0Na 0.3K 0.2O 5.75(SiO 270％) V 1P 1.3Na 0.3Ba 0.1O 6.0(SiO 270％) V 1P 1.2Na 0.3Li 0.15K 0.1O 5.78(SiO 270％) V 1P 1.2Na 0.3K 0.15Cs 0.075O 5.76(SiO 270％) V 1P 1.4Na 0.2K 0.1Ba 0.1O 6.25(SiO 270％) | ????86.8 ????85.5 ????83.8 ????83.7 ????83.3 ????83.8 ????87.1 ????87.2 ????83.8 | ????73.9 ????72.3 ????71.1 ????70.3 ????70.6 ????71.0 ????74.0 ????74.0 ????71.1 | ????85.1 ????84.6 ????84.8 ????84.0 ????84.7 ????84.7 ????85.0 ????84.9 ????84.8 |
Table 2
[embodiment 11～13]
| Embodiment | Catalyzer | The DCT transformation efficiency, % | The DBN yield, % | The DBN selectivity, % |
| ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 | V 1P 1.2Na 0.3Li 0.3O 5.8(SiO 270％) V 1P 1.2Na 0.4Li 0.2O 5.8(SiO 270％) V 1P 1.2Na 0.4Li 0.3O 5.8(SiO 270％) V 1P 0.9Na 0.3Li 0.1O 4.95(SiO 270％) V 1P 1.0Na 0.3K 0.2O 5.75(SiO 270％) V 1P 1.3Na 0.3Ba 0.1O 6.0(SiO 270％) V 1P 1.2Na 0.3Li 0.15K 0.1O 5.78(SiO 270％) V 1P 1.2Na 0.3K 0.15Cs 0.075O 4.76(SiO 270％) V 1P 1.4Na 0.2K 0.1Ba 0.1O 6.25(SiO 270％) | ??97.0 ??96.7 ??94.9 ??95.3 ??94.9 ??95.6 ??98.1 ??97.2 ??95.0 | ??88.2 ??86.2 ??85.4 ??84.4 ??84.9 ??85.3 ??88.5 ??88.4 ??85.4 | ??91.0 ??89.1 ??90.0 ??88.6 ??89.4 ??89.3 ??90.2 ??90.9 ??89.9 |
The composition of catalyzer and preparation method change the add-on of monobromethane with embodiment 1, and add-on is 2,0.5～3% of 6-toluene dichloride weight, and its evaluating data is listed in the table 3.
Table 3
[embodiment 14～16]
| Embodiment | The monobromethane add-on, % | The DCT transformation efficiency, % | The DBN yield, % | The DBN selectivity, % |
| ????11 ????12 ????13 | ????0.5 ????1.0 ????3.0 | ????89.9 ????96.8 ????99.6 | ????76.0 ????83.5 ????90.4 | ????84.5 ????86.3 ????90.8 |
The add-on of the composition of catalyzer and preparation method and bromine and/or bromine compounds changes the adding kind of bromine and/or bromine compounds with embodiment 1, and its evaluating data is listed in the table 4.
Table 4
[comparative example 1～6]
| Embodiment | Add kind | The DCT transformation efficiency, % | The DBN yield, % | The DBN selectivity, % |
| ????14 ????15 ????16 | Bromine hydrogen bromide 1-bromine n-propane | ????89.3 ????92.3 ????96.3 | ????74.6 ????76.7 ????86.2 | ????83.5 ????83.1 ????89.5 |
Method for preparing catalyst is made the catalyzer of following different proportionings with embodiment 1, and the results are shown in Table 5 to press among the embodiment 1 evaluating catalyst I condition evaluating, and the results are shown in Table 6 to press among the embodiment 1 evaluating catalyst II condition evaluating.
Table 5
| Comparative example | Catalyzer | The DCT transformation efficiency, % | The DBN yield, % | The DBN selectivity, % |
| ????1 ????2 ????3 ????4 ????5 ????6 | V 1P 1.2Cr 0.3O 6.4(SiO 270％) V 1P 1.2Mn 0.3O 6.55(SiO 270％) V 1P 1.2Fe 0.3O 6.1(SiO 270％) V 1P 1.2Sn 0.3O 6.1(SiO 270％) V 1P 1.2Co 0.3O 6.1(SiO 270％) V 1P 1.2O 5.5(SiO 270％) | ????70.0 ????72.8 ????67.9 ????66.3 ????71.6 ????70.7 | ????55.4 ????58.4 ????50.7 ????51.5 ????57.8 ????56.9 | ????79.1 ????80.2 ????74.7 ????77.7 ????80.7 ????80.5 |
Table 6
| Comparative example | Catalyzer | The DCT transformation efficiency, % | The DBN yield, % | The DBN selectivity, % |
| ????1 ????2 ????3 ????4 ????5 ????6 | V 1P 1.2Cr 0.3O 6.4(SiO 270％) V 1P 1.2Mn 0.3O 6.55(SiO 270％) V 1P 1.2Fe 0.3O 6.1(SiO 270％) V 1P 1.2Sn 0.3O 6.1(SiO 270％) V 1P 1.2Co 0.3O 6.1(SiO 270％) V 1P 1.2O 5.5(SiO 270％) | ????95.0 ????98.0 ????96.7 ????94.5 ????97.4 ????98.0 | ????81.4 ????86.1 ????83.4 ????80.3 ????85.5 ????84.8 | ????85.2 ????87.8 ????86.2 ????85.0 ????87.8 ????86.5 |
Claims (5)
1, a kind ofly be used to prepare 2,6-dichlorobenzonitrile technology is with 2,6-toluene dichloride, ammonia and molecular oxygen are raw material, in reaction process, add bromine and/or bromine-containing compound, it is characterized in that the catalyzer that uses contains silica supports, and have the composition of following chemical formula:
V
1.0P
bNa
cA
dB
eO
x
A is at least a lithium, potassium, rubidium or the caesium of being selected from the formula;
B is at least a magnesium, calcium, barium, chromium, manganese, iron, cobalt, nickel or the tin of being selected from;
Wherein b is 0.3～4.0;
C is 0.01～0.7;
D is 0.05～1.0;
E is 0～2.0;
X is the summation that satisfies other element valence requisite oxygen atomicity;
The content of carrier silicon-dioxide is 50～80% by weight percentage in the catalyzer.
2, be used to prepare 2 according to claim 1 is described, 6-dichlorobenzonitrile technology, the preferable range that it is characterized in that b is 0.5～3.0; The preferable range of c is 0.1～0.4; The preferable range of d is 0.05～0.5; The preferable range of e is 0.05～1.5.
3, be used to prepare 2 according to claim 1 is described, 6-dichlorobenzonitrile technology, it is characterized in that bromine-containing compound is hydrogen bromide, a monobromethane, methylene bromide, methenyl bromide, tetrabromomethane, 1-monobromethane, 1,2-monobromethane, 1-bromine n-propane, 2-N-PROPYLE BROMIDE, 1-n-butyl bromide, tert-bromo butane, isopentyl bromination alkane, cyclohexyl bromoalkane, bromobenzene or bromine ethylbenzene and composition thereof.
4, be used to prepare 2 according to claim 1 is described, 6-dichlorobenzonitrile technology is characterized in that bromine and/or bromine-containing compound are to join in the reaction system in the gas phase mode, and add-on is 2,0.1～10% of 6-toluene dichloride weight.
5, be used to prepare 2 according to claim 4 is described, 6-dichlorobenzonitrile technology is characterized in that bromine and/or bromine-containing compound add-on are 2,0.5～7.0% of 6-toluene dichloride weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110745A CN1069634C (en) | 1998-03-30 | 1998-03-30 | Preparation process of 2,6-dichloro benzonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110745A CN1069634C (en) | 1998-03-30 | 1998-03-30 | Preparation process of 2,6-dichloro benzonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1230537A true CN1230537A (en) | 1999-10-06 |
| CN1069634C CN1069634C (en) | 2001-08-15 |
Family
ID=5220768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110745A Expired - Lifetime CN1069634C (en) | 1998-03-30 | 1998-03-30 | Preparation process of 2,6-dichloro benzonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1069634C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909043A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Catalyst for preparing 2,6-dichlorobenzonitrile and compositing method and application of catalyst |
| CN101759596B (en) * | 2010-01-25 | 2013-02-13 | 南通泰禾化工有限公司 | Method for preparing 3,4-dichloro-cyanobenzene |
| CN103382166A (en) * | 2013-07-26 | 2013-11-06 | 扬州天辰精细化工有限公司 | Method for preparing 2, 6-dichlorobenzonitrile |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530797A (en) * | 1984-09-10 | 1985-07-23 | Nippon Kayaku Kabushiki Kaisha | Process for producing polychlorobenzonitrile |
-
1998
- 1998-03-30 CN CN98110745A patent/CN1069634C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759596B (en) * | 2010-01-25 | 2013-02-13 | 南通泰禾化工有限公司 | Method for preparing 3,4-dichloro-cyanobenzene |
| CN102909043A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Catalyst for preparing 2,6-dichlorobenzonitrile and compositing method and application of catalyst |
| 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 |
| CN103382166A (en) * | 2013-07-26 | 2013-11-06 | 扬州天辰精细化工有限公司 | Method for preparing 2, 6-dichlorobenzonitrile |
| CN103382166B (en) * | 2013-07-26 | 2015-04-08 | 扬州天辰精细化工有限公司 | Method for preparing 2, 6-dichlorobenzonitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1069634C (en) | 2001-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5297450B2 (en) | Catalyst for production of acrolein and acrylic acid by dehydration reaction of glycerin and production method thereof | |
| KR100786051B1 (en) | Improved catalyst for the manufacture of acrylonitrile | |
| US6924387B1 (en) | Solid catalyst with core-shell catalytic phase and a method of preparation thereof | |
| KR20080109437A (en) | Method for preparing heteropoly acid catalyst | |
| CN1300238A (en) | Method for regenerating molybdenum-containing oxide fluidized-bed catalyst | |
| EP3650120A1 (en) | Fluidized-bed catalyst applicable to haloarylnitrile production, and preparation and application thereof | |
| KR101419052B1 (en) | Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid | |
| CN101759596A (en) | Method for preparing 3,4-dichloro-cyanobenzene | |
| CN1069634C (en) | Preparation process of 2,6-dichloro benzonitrile | |
| JP3465350B2 (en) | Method for producing catalyst for methacrylic acid production | |
| JPH05138028A (en) | Method for oxidation of gas phase oxidation catalyst,propylene, isobutylene or t-butanol and oxydehydrogenation method for isobutyric acid or its lower ester | |
| CN1092540C (en) | Fluidized bed catalyst for ammoxidation of propylene | |
| CN1074308C (en) | Fluid and catalyst for the preparation of aromatic nitrile halide | |
| KR100516342B1 (en) | Process for production of prussic acid | |
| WO2005056185A1 (en) | Process for producing composite oxide catalyst | |
| CN1086154C (en) | Propylene ammonoxidating catalyst | |
| CN1074309C (en) | Fluid bed catalyst for the preparation of aromatic nitrile halide | |
| CN103664696A (en) | Method for preparing cyanobenzene | |
| CN102219710A (en) | Method for preparing cyanobenzene | |
| CN1193009C (en) | Method for producing o-chlorobenzonitrile | |
| CN1187320C (en) | Fluidized bed catalyst for preparing o-chlorobenzonitrile | |
| CN1123385C (en) | Fluidized-bed catalyst for preparing isophthalonitrile | |
| CN1751791A (en) | Fluidized bed catalyst for preparing acetonitrile | |
| CN1506352A (en) | Prepn process of o-chlorobenzonitrile | |
| CN111620760B (en) | Method for preparing 2,3,5, 6-tetrachlorobenzonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20010815 |
|
| CX01 | Expiry of patent term |