CN102746192A - Method for ammoxidation preparation of 2,4-dichlorobenzonitrile - Google Patents
Method for ammoxidation preparation of 2,4-dichlorobenzonitrile Download PDFInfo
- Publication number
- CN102746192A CN102746192A CN2011100999939A CN201110099993A CN102746192A CN 102746192 A CN102746192 A CN 102746192A CN 2011100999939 A CN2011100999939 A CN 2011100999939A CN 201110099993 A CN201110099993 A CN 201110099993A CN 102746192 A CN102746192 A CN 102746192A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ammonia
- formonitrile hcn
- dichloro benzene
- catalyzer
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for the ammoxidation synthesis of 2,4-dichlorobenzonitrile to mainly solve problems of bad fluidization quality and low yield, or low yield and high production cost after using a fixed bed existing in fluidized bed reactors in present production technologies. The method which adopts 2,4-dichlorotoluene, ammonia and air as raw materials comprises a step that the raw materials contact and react with a catalyst in a fluidized bed under conditions that the raw material ratio of the 2,4-dichlorotoluene to the ammonia to the air is 1:2-10:4-40, the reaction temperature is 300-500DEG C, the reaction pressure is 0.01-0.1Mpa and the catalyst load (WWH) is 0.03-0.1h<-1> to generate the 2,4-dichlorobenzonitrile. The method well solves the problems and can be used for the industrial production of the ammoxidation synthesis of the 2,4-dichlorobenzonitrile.
Description
Technical field
The present invention relates to a kind of method that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN that is used for.
Background technology
The 2,4 dichloro benzene formonitrile HCN (is called for short 2,4-DCN) is broad-spectrum fine-chemical intermediate; Its through fluoridize, synthetic 2,4 difluorobenzene formonitrile HCN, 2,4 dichloro benzene formic acid etc. all are important organic intermediates after the reaction such as hydrolysis, can be widely used as industries such as medicine, agricultural chemicals, pigment, dyestuff and sensitive materials.
In the 2,4 dichloro benzene formonitrile HCN synthetic technology in the past, be chemical synthesis process among the European patent technology EP441004, it is by raw material α, α, and α ,-2, reactions such as 4-toluene pentachloride and ammonia obtain; What the flat 01-96163 of Japanese Patent reported is raw material with the 2,4 dichlorobenzyl chloride, and reaction generates corresponding carboxylic acid, makes with urea reaction again.These chemical synthesis process all have expensive raw materials, the source difficulty, and reaction scheme is long, and impurity in products is many, pollutes greatly shortcomings such as production cost height.
Obviously, simple, the most economic compound method of 2,4 dichloro benzene formonitrile HCN is with 2, and 4-toluene dichloride gas phase oxidative ammonolysis under catalyst action obtains, and its core technology is a catalyzer.
Martin etc. adopt VOHPO
4H
2O carries out with raw material 2 as catalyst precursor, and the oxidative ammonolysis of 4-toluene dichloride and ammonia prepares the 2,4 dichloro benzene formonitrile HCN; Its reaction process condition is 435 ℃ of temperature of reaction, proportioning raw materials 2,4-toluene dichloride: ammonia: oxygen: water=1: 8: 5: 25,2; 4-toluene dichloride transformation efficiency 85%, 2,4 dichloro benzene formonitrile HCN yield 48% (MartinA, Lucke B; WolfG-U et al.Catalysis Letters, 1995,33:349).This method product yield is low, and reaction is added water vapor and made thinner, prolonging its catalyst life, and diluting reaction heat, but has also increased its energy consumption and production cost, and its production level is extremely low; U.S. Pat 4124631 reports carry out oxidative ammonolysis with VPCo/SiO2 as catalyzer, and reaction process is 410 ℃ of temperature of reaction, proportioning raw materials 2,4-toluene dichloride: NH
3: O
2: N
2=1: 4: 3: 12, fixed bed evaluation, 2,4-toluene dichloride transformation efficiency 97.5%, 2,4 dichloro benzene formonitrile HCN yield 80.8%.This technology is used fixed-bed process, and the heat difficulty is removed in reaction, and uses pure oxygen and purity nitrogen, has increased production cost; Chinese patent CN0011464.8 with
The microsphere silica gel of 125-425 μ m is a carrier, is active element with component VaTibPcDdEeOx, adopts the immersion process for preparing catalyzer to carry out oxidative ammonolysis, and its reaction process condition is 400 ℃ of temperature of reaction, proportioning raw materials 2,4 toluene dichloride: NH
3: Air=1: 7: 15,2,4 dichloro benzene formonitrile HCN yield was 82.1%.The wear-resisting poor performance of this technology catalyzer, its reaction result is used the fixed-bed reactor evaluation, and the heat difficulty is removed in reaction during the industrial production design; Scale effect is obvious, in the reaction process condition ammonia than too high, cause or three wastes processing pressure big; Or ammonia recovery energy consumption is high, causes production cost high, and environment is poor.
The reaction that ammonia oxidation is the most generally used is fixed-bed process and fluidized-bed process; Because this reaction is strong exothermal reaction, therefore use fixed-bed process difficulty remove reaction heat and make the reactor drum focus obvious, and wayward temperature of reaction; Cause reaction preference to descend, production cost improves; Fluidized-bed process then can address this problem preferably, makes stable reaction.To be divided into shelf fluidized bed and open fluidized bed, the latter is the most advanced working method of generally using both at home and abroad at present to fluidized-bed process, and can solve reactor drum engineering design scale effect preferably again.
Summary of the invention
Technical problem to be solved by this invention is to exist in the production technology in the fluidized-bed reactor fluidization quality poor in the past, causes yield low; Or it is still low to use fixed bed to estimate yield, and the problem that production cost is high provides a kind of new method that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN that is used for.This method can be improved the fluidization quality in the fluidized-bed reactor effectively, has higher 2,4 dichloro benzene formonitrile HCN yield, and can overcome the advantage of reactor drum engineering scale effect preferably.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind ofly be used for the method that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN; With 2,4-toluene dichloride, ammonia and air are raw material, in the feed molar proportioning: 2; 4-toluene dichloride: ammonia: air=1: 2～10: 4～40; 300～500 ℃ of temperature of reaction, reaction pressure 0.01～0.1Mpa, catalyst weight load WWH is 0.03～0.1 hour
-1Condition under, in fluidized-bed, raw material and catalyzer contact reacts generate the 2,4 dichloro benzene formonitrile HCN, react employed fluid catalyst and with silicon-dioxide be carrier and with the following compsn of atomic ratio measuring chemical formula: V
1.0Cr
aA
bB
cC
dO
x, A is for being selected from lithium, sodium, potassium, rubidium or caesium or its mixture in the formula; B is for being selected from magnesium, calcium, barium, tungsten, titanium, molybdenum, manganese, iron, cobalt, nickel, tin or its mixture; C is for being selected from boron, phosphorus or its mixture; Wherein a is 0.3～2.0; B is 0.01～0.5; C is 0.05～1.0; D is 0.01～2.0; X is the summation that satisfies other element valence requisite oxygen atomicity; The content of carrier silicon-dioxide is 30～90% by weight percentage in the catalyzer.The median size of catalyzer is the 20-100 micron, is shaped as the fine particle sphere.
Above-mentioned catalyzer generates the 2,4 dichloro benzene formonitrile HCN with the raw material contact reacts in the technique scheme in fluidized-bed reactor; Wherein with 2,4-toluene dichloride, ammonia and air are raw material, in the feed molar proportioning: 2; 4-toluene dichloride: ammonia: air=1: 2～10: 4～40; 300～500 ℃ of temperature of reaction, reaction pressure 0.01～0.1Mpa, catalyst weight load (WWH) is 0.03～0.1 hour
-1Condition under carry out oxidative ammonolysis.
The present invention is the several times of theoretical amount in the usage quantity of when reaction ammonia at least, the yield and the selectivity of the favourable raising title product of a high proportion of ammonia, but have the cost recovery and the environmental pollution problems of ammonia.The ammonia amount of this technology is 2～10 times of theoretical amount, and preferable range is 3～8 times.When its consumption surpassed 8 times, the reacting ammonia consumption increased, and the three wastes are handled or the excess ammonia cost recovery increases and production cost is increased; When its consumption is lower than 3 times,, the ammonification ability drop descends owing to making title product 2,4 dichloro benzene formonitrile HCN selectivity and yield.
Air capacity of the present invention is 5 times of theoretical amount at least, and more suitable scope is 4～40 times, and preferable range is 6～20 times.Usually make oxygen source with air, nitrogen, carbonic acid gas, water vapor can be used as inert diluent.When raw material air ratio is too high, deep oxidation can take place generate carbonic acid gas and title product 2,4 dichloro benzene formonitrile HCN selectivity and yield are descended; And cross when low when AIR Proportional, can make raw material 2,4-toluene dichloride transformation efficiency descends and title product 2,4 dichloro benzene formonitrile HCN once through yield is descended.
Bigger mobility scale is arranged the duration of contact of oxidative ammonolysis of the present invention, and generally at 0.2～20 second, preferred range is 0.5～15 second.When duration of contact of oxidative ammonolysis greater than 15 seconds, deep oxidation can take place to be generated carbonic acid gas and make title product 2,4 dichloro benzene formonitrile HCN selectivity and yield decline; When duration of contact of oxidative ammonolysis less than 0.5 second, can make raw material 2,4-toluene dichloride transformation efficiency descends and title product 2,4 dichloro benzene formonitrile HCN once through yield is descended.
The technological reaction temperature that ammonia oxidation of the present invention prepares the 2,4 dichloro benzene formonitrile HCN is 300～500 ℃, and preferable range is 350～450 ℃; When temperature was lower than 350 ℃, reaction conversion ratio was low, caused by-product CO owing to deep oxidation reacts when being higher than 450 ℃
2, CO, HCN growing amount obviously increase, and 2,4 dichloro benzene formonitrile HCN selectivity and yield are descended.When temperature of reaction was lower than 350 ℃, because raw material 2,4-toluene dichloride transformation efficiency descended and title product 2,4 dichloro benzene formonitrile HCN once through yield is descended.The optimum temps of this reaction depends on 2, and the concentration of 4-toluene dichloride, activity of such catalysts are formed, the factors such as roasting condition, reaction contact time and load of catalyzer.When 2, the concentration of 4-toluene dichloride is higher, or the oxidation activity that preparation process condition composite factors such as activity of such catalysts composition, roasting condition cause is higher; Or reaction contact time is longer, or catalyst loading is when low, and the suitable temperature of reaction of ammonia oxidation is lower; Otherwise the oxidative ammonolysis temperature is then higher; Otherwise can cause oxidative ammonolysis or raw material 2,4-toluene dichloride per pass conversion descends, or owing to the deep oxidation product selectivity descends production cost is improved.
The present invention improves the fluidization quality of reaction through using less catalyzer average grain; Improve the abrasive wear resistance of catalyzer, prolong catalyst life; Optimize catalyst elements and form and preparation process condition, select suitable methods such as oxidative ammonolysis processing parameter, make it under the higher per pass conversion prerequisite of raw material; Obtain higher 2; 4-dichlorobenzonitrile yield, production cost descends significantly, has obtained better technical effect.
The present invention's reaction under normal pressure usually also can be depressed reaction adding.
The preferred version of the catalyst A that the present invention selects for use is at least a oxide compound that is selected from lithium, potassium or the sodium; The preferred version of B is to be selected from least a in manganese, tungsten, titanium, cobalt, molybdenum or the nickel.The preferred span of a is 0.8～1.5, and the preferred span of b is 0.05～0.2, and the preferred span of c is 0.1～0.5, and the preferred span of d is 0.3～1.0.In the catalyzer content of carrier silicon-dioxide by weight percentage preferable range be 45～65%.Median size is preferably the 50-80 micron.
V
2O
5, Sb
2O
3And the corresponding oxide compound of each element of general formula A, B, C is the starting raw material of catalyzer, also can select other compound to make raw material.Example:
Vanadium raw materials: ammonium meta-vanadate, Vanadosulfuric acid, organic acid vanadium such as vanadium oxalate or tartrate vanadium;
Cr materials: chromium trioxide, chromic acid, chromic salt (ammonium), chromium nitrate, organic chromium comprises chromium acetate, chromium+oxalic acid;
A raw material: nitrate salt, element oxide or pairing alkali;
B raw material: the muriate of nitrate salt or solubility;
C raw material: the sour ammonium of acid or solubility;
Silicon raw material: use silicon sol, silicon gel or silicon-dioxide carrier as catalyzer.
Preparation of catalysts makes through specific method: A, B, the C solution of solubility are added to V
2O
5, Cr
2O
3Oxalic acid solution in, the material mixture slurry that must suspend adds solvent then spent glycol, oxalic acid etc. like needs.Slurry is after spraying shaping drying during the suspension material mixture pulp preparation fluid catalyst processed, roasting; The slurry of fixed bed catalyst is through evaporation after drying, roasting.
The roasting of catalyzer of the present invention can be divided into each element decomposition of salts and two stages of high-temperature roasting in the catalyzer.The decomposition of salts temperature is 100～200 ℃, and preferable range is 150～180 ℃, and the time is 2～20 hours, and preferable range is 3～15 hours; Maturing temperature is 450～800 ℃, and preferable range is 450～650 ℃, and the time is 2～15 hours, and preferable range is 5～10 hours.Decomposition and high-temperature roasting can be carried out in two stoving ovens, also can in a stoving oven, carry out, or in the continous way rotary roasting furnace, will decompose with high-temperature roasting and carry out simultaneously.
Oxide content is with V in the catalyzer
2O
5, Cr
2O
3, acidic oxide, basic oxide and the above metal of divalence the weight percent meter of maxivalence oxide compound.
Raw material of the present invention uses 2, the 4-toluene dichloride.
The present invention optimizes catalyst elements and forms and preparation process condition through selecting suitable oxidative ammonolysis processing parameter, adopts more fine grain catalyzer to improve fluidization quality; Effectively reduced the appearance of channel and turbulent phenomenon in the fluid mapper process, reduced the formation of bubble, made it under the higher per pass conversion prerequisite of raw material; Obtain higher 2; 4-dichlorobenzonitrile yield, production cost descends significantly, has obtained better technical effect.
The present invention's reaction under normal pressure usually also can be depressed reaction adding.
Among the embodiment of catalyzer of the present invention 2, the transformation efficiency of 4-toluene dichloride, 2,4 dichloro benzene formonitrile HCN selectivity and the definition of 2,4 dichloro benzene formonitrile HCN yield as follows:
It is in
38 millimeters * 1800 millimeters stainless steel fluidized-bed reactors, to carry out that the catalyzer of the embodiment of the invention is investigated; Add-on 550 grams of catalyzer, reacting system pressure is 0.01～0.1MPa.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
Preparation of Catalyst:
201 gram V
2O
5Be added to the temperature of forming by 440 ml waters 420 gram oxalic acid and be in 80～90 ℃ the solution, fully stirring, react vanadium oxalate solution.
With 40% (weight) SiO
2Silicon sol 1250 gram under agitation slowly be added in the above-mentioned solution, add respectively then by 798 gram Cr (NO
3)
39H
2The solution that O and 300 ml waters are formed, 68.6 gram H
3BO
3The solution of forming with 560 ml waters and 39.2 restrains (NH
4)
6Mo
7O
244H
2The solution that O and 50 ml waters are formed, 0.11 mole of phosphoric acid solution adds 9.4 gram Na NO at last
3With the solution that 20 ml waters are formed, add the TiCl of 113.7 grams 30% (weight) again
3Hydrochloric acid soln mixes, and heating evaporation to solid content is 42% (weight), gets viscous paste.
The spraying of above-mentioned slurry is shaped, 250 ℃ of atomizer gas feed temperature, 130 ℃ of temperature outs, the catalyzer after the shaping is in 130 ℃ of dryings 12 hours, 550 ℃ of roastings 8 hours, catalyzer is formed: V
1.0Cr
0.9B
0.5Ti
0.1P
0.05Mo
0.1Na
0.05/ SiO
2, catalyzer master weight-carrying capacity ratio is 50/50, the median size of catalyzer is 200 orders.
The oxidative ammonolysis processing parameter:
Proportioning raw materials (mole): 2,4-toluene dichloride: ammonia: air=1: 3: 15, catalyst weight load 0.060 hour
-1, temperature of reaction: 425 ℃, reaction pressure 0.02MPa.
The result: 2,4-toluene dichloride transformation efficiency 98.5%
2,4 dichloro benzene formonitrile HCN selectivity 85.7%
2,4 dichloro benzene formonitrile HCN yield 84.4%
[embodiment 2～5]
Use embodiment 1 identical catalyst preparation process and oxidative ammonolysis processing parameter, the routine table 1 of catalyzer that obtains and performance thereof.
Table 1 catalyzer is formed the influence to 2,4 dichloro benzene formonitrile HCN yield
[embodiment 6]
Use embodiment 1 identical catalyzer and catalytic amount, identical reaction pressure, reaction load and reaction raw materials ratio change temperature of reaction, press evaluation response processing condition among the embodiment 1, and its evaluation result is listed in the table below 2.
Table 2 temperature is to the influence of reaction
[embodiment 7]
Use embodiment 1 identical catalyzer and catalytic amount, identical temperature of reaction, reaction load and reaction raw materials ratio change reaction pressure, press evaluation response processing condition among the embodiment 1, and its evaluation result is listed in the table below 3.
Table 3 pressure is to the influence of reaction
[embodiment 8]
Use embodiment 1 identical catalyzer and catalytic amount, identical temperature of reaction, reaction pressure and reaction raw materials ratio change the reaction load, press evaluation response processing condition among the embodiment 1, and its evaluation result is listed in the table below 4.
Table 4 load is to the influence of reaction
[embodiment 9]
Use embodiment 1 identical catalyzer and catalytic amount, identical temperature of reaction, reaction load and reaction pressure change reaction raw materials ratio (oxygen ratio and ammonia ratio), press evaluation response processing condition among the embodiment 1, and its evaluation result is listed in the table below 5.
Table 5 proportioning raw materials is to the influence of reaction
Claims (5)
1. one kind is used for the method that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN, with 2; 4-toluene dichloride, ammonia and air are raw material; In the feed molar proportioning: 2,4-toluene dichloride: ammonia: air=1: 2～10: 4～40,300～500 ℃ of temperature of reaction; Reaction pressure 0.01～0.1Mpa, catalyst weight load WWH is 0.03～0.1 hour
-1Condition under, in fluidized-bed, raw material and catalyzer contact reacts generate the 2,4 dichloro benzene formonitrile HCN, react employed fluid catalyst and with silicon-dioxide be carrier and with the following compsn of atomic ratio measuring chemical formula:
V
1.0Cr
aA
bB
cC
dO
x
A is for being selected from lithium, sodium, potassium, rubidium or caesium or its mixture in the formula;
B is for being selected from magnesium, calcium, barium, tungsten, titanium, molybdenum, manganese, iron, cobalt, nickel, tin or its mixture;
C is for being selected from boron, phosphorus or its mixture;
Wherein a is 0.3～2.0;
B is 0.01～0.5;
C is 0.05～1.0;
D is 0.01～2.0;
X is the summation that satisfies other element valence requisite oxygen atomicity;
The content of carrier silicon-dioxide is 30～90% by weight percentage in the catalyzer;
The median size of catalyzer is 20～100 microns, is shaped as the fine particle sphere.
2. be used for the method that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN according to claim 1 is said, it is characterized in that the TR of reacting is 350～450 ℃.
3. be used for the method that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN according to claim 1 is said, it is characterized in that the catalyst weight load is 0.04～0.08 hour
-1
4. be used for the method that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN according to claim 1 is said, it is characterized in that the material molar ratio that reacts is: 2,4-toluene dichloride: ammonia: air=1: 3～8: 6～20.
5. be used for the fluid catalyst that ammonia oxidation prepares the 2,4 dichloro benzene formonitrile HCN according to claim 1 is said, the median size that it is characterized in that catalyzer is 50～80 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100999939A CN102746192A (en) | 2011-04-20 | 2011-04-20 | Method for ammoxidation preparation of 2,4-dichlorobenzonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100999939A CN102746192A (en) | 2011-04-20 | 2011-04-20 | Method for ammoxidation preparation of 2,4-dichlorobenzonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102746192A true CN102746192A (en) | 2012-10-24 |
Family
ID=47026749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100999939A Pending CN102746192A (en) | 2011-04-20 | 2011-04-20 | Method for ammoxidation preparation of 2,4-dichlorobenzonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102746192A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675942A (en) * | 2018-06-19 | 2018-10-19 | 杭州盛漫生物科技有限公司 | A kind of preparation method of aromatic nitrile compounds |
| CN114105818A (en) * | 2021-11-11 | 2022-03-01 | 鞍山七彩化学股份有限公司 | Catalyst for catalyzing butyrolactone to obtain succinonitrile and synthesis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328875A (en) * | 2000-06-20 | 2002-01-02 | 武汉大学 | Method for preparing 3,4-dichlorophenylnitrile by using ammonia oxidation process and its special-purpose catalyst |
| CN1506352A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Prepn process of o-chlorobenzonitrile |
-
2011
- 2011-04-20 CN CN2011100999939A patent/CN102746192A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328875A (en) * | 2000-06-20 | 2002-01-02 | 武汉大学 | Method for preparing 3,4-dichlorophenylnitrile by using ammonia oxidation process and its special-purpose catalyst |
| CN1506352A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Prepn process of o-chlorobenzonitrile |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675942A (en) * | 2018-06-19 | 2018-10-19 | 杭州盛漫生物科技有限公司 | A kind of preparation method of aromatic nitrile compounds |
| CN108675942B (en) * | 2018-06-19 | 2021-01-29 | 杭州盛漫生物科技有限公司 | Preparation method of aromatic nitrile compound |
| CN114105818A (en) * | 2021-11-11 | 2022-03-01 | 鞍山七彩化学股份有限公司 | Catalyst for catalyzing butyrolactone to obtain succinonitrile and synthesis method |
| CN114105818B (en) * | 2021-11-11 | 2023-11-10 | 鞍山七彩化学股份有限公司 | Catalyst for preparing succinonitrile from butyrolactone and synthesis method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5491037B2 (en) | Catalyst for producing acrylonitrile and method for producing acrylonitrile | |
| CN102527419A (en) | Method for preparing m-phthalodinitrile catalyst through ammoxidation | |
| CN103896807B (en) | The method preparing para-Phthalonitrile for ammoxidation | |
| CN106362760B (en) | Ammoxidation of aromatic hydrocarbon catalyst, preparation method and its application method | |
| CN100566829C (en) | Catalyst for preparing acrylonitrile by ammonia oxidizing method | |
| CN102744090B (en) | Catalyst for ammoxidation preparation of 2,4-dichlorobenzonitrile | |
| CN109876794A (en) | Ammoxidation reaction prepares the special-purpose catalyst and preparation method and purposes of m-dicyanobenzene | |
| CN109876837A (en) | The special-purpose catalyst and preparation method and purposes of preparing chlorobenzonitrile by using ammoxidation method | |
| CN102295581A (en) | Method for preparing 3,4-dichlorobenzonitrile by ammonia oxidation | |
| CN1277810C (en) | Fluid-bed catalyst for ammoxidation of aromatic hydrocarbon | |
| CN102746192A (en) | Method for ammoxidation preparation of 2,4-dichlorobenzonitrile | |
| CN102219711A (en) | Method for preparing isophthalodinitrile | |
| KR19980080181A (en) | Hydrocyanic acid production method | |
| CN103664696A (en) | Method for preparing cyanobenzene | |
| CN1225460C (en) | Preparation of 3-cyanopyridine | |
| CN102219710A (en) | Method for preparing cyanobenzene | |
| CN101767014B (en) | Fluidized bed catalyst for producing acrylonitrile by propylene ammoxidation | |
| CN1223579C (en) | Method for preparing p-chloro cyanobenzene | |
| CN100358629C (en) | Fluidized bed catalyst for preparing acetonitrile | |
| CN1204114C (en) | Method for preparing m-phthalonitrile | |
| CN103769129B (en) | Fluid catalyst of prepared by ammoxidation unsaturated nitrile and preparation method thereof | |
| CN1193009C (en) | Method for producing o-chlorobenzonitrile | |
| CN1207278C (en) | Prepn process of o-chlorobenzonitrile | |
| CN101733117B (en) | High-stability fluid catalyst for producing acrylonitrile | |
| CN1187320C (en) | Fluidized bed catalyst for preparing o-chlorobenzonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121024 |