CN101850264A - Production process for preparing chlorobenzonitrile by using ammoxidation method - Google Patents
Production process for preparing chlorobenzonitrile by using ammoxidation method Download PDFInfo
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- CN101850264A CN101850264A CN201010194755A CN201010194755A CN101850264A CN 101850264 A CN101850264 A CN 101850264A CN 201010194755 A CN201010194755 A CN 201010194755A CN 201010194755 A CN201010194755 A CN 201010194755A CN 101850264 A CN101850264 A CN 101850264A
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Abstract
The invention provides a production process for preparing chlorobenzonitrile by using an ammoxidation method. In the production process, VaPbCecSbdOx is adopted as an active catalyst, wherein a=1, b=0.7-2, c=0.3-1, d=0.31 and x=35-40 percent. In the production process of the invention, the VaPbCecSbdOx is used as the active catalyst which has the characteristics of high activity, high selectivity and the like, thereby the production process of chlorobenzonitrile is improved, and the yield rate of the product is obviously increased.
Description
[technical field]
The present invention relates to chemical technology field, relate in particular to a kind of production technology of utilizing preparing chlorobenzonitrile by using ammoxidation method.
[background technology]
O-chloro benzonitrile is a kind of important organic intermediate, belongs to chemical medicine intermediate field, is the source of correlative technology fields such as medicine.The high speed development of association area such as medicine has promoted the development in chemical raw material, intermediate field in recent years, and the development in chemical raw material and intermediate field promotes or restricting the development of association areas such as medicine again conversely.O-chloro benzonitrile (OCBN) is a white needle-like crystals, and fusing point is 42 ℃, easily distillation.Contain carbon nitrogen three key in the OCBN molecule, much more active than amide compound, hydrolysis, alcoholysis, ammonia can take place separate, many reactions such as reduction, it is a kind of intermediate of synthetic medicine.The report of relevant its application is a lot, for example is used for synthesizing many medicines such as treating angiocardiopathy aspect medical.
The extensive use of OCBN has caused attention both domestic and external.The synthesising process research of relevant OCBN is a lot, but great majority are the laboratory synthetic method, and its main synthetic method has following several:
First kind, synthesize " 1 " by aldoxime:
Second kind, become " 2,3 " entirely by aldehyde:
The third is by ortho-chlorotolu'ene (PCT) ammoxidation synthetic " 4,9 "
The 4th kind, synthesize " 10 " by 0-chloro-benzoic acid:
In the said method, third and fourth kind of method the simplest (step is synthetic), but with raw materials used 0-chloro-benzoic acid price height in the 0-chloro-benzoic acid synthetic method, thereby the economic implications that synthesizes with this method is little.And be the synthetic method that present production cost is minimum, technology is the simplest, environmental pollution is minimum by the method for the synthetic o-chloro benzonitrile of ortho-chlorotolu'ene ammoxidation, in market competition, have very strong competitiveness.
Yet,, except that aforesaid main reaction, also have following main side reaction with synthetic o-chloro benzonitrile of one step of ortho-chlorotolu'ene method for ammoxidation.
From above-mentioned reaction as can be known, when o-chloro benzonitrile is synthesized in the ortho-chlorotolu'ene ammoxidation, side reactions such as deep oxidation may take place, suppress these side reactions, the key that obtains high yield is the catalyst of screening high selectivity and the optimization of technological process, process conditions and equipment, therefore, its development difficulty is again maximum in above-mentioned all methods.
[summary of the invention]
Based on this, be necessary to provide a kind of production technology of preparing chlorobenzonitrile by using ammoxidation method of high yield.
A kind of production technology of preparing chlorobenzonitrile by using ammoxidation method, this production technology adopts V
aP
bCe
cSb
dO
xAs active catalyst, wherein a=1, b=0.7～2, c=0.3～1, x=35%～40%.
Preferably, the reaction temperature of described production technology is 370～380 ℃.
Preferably, described active catalyst adopts the gross porosity microsphere silica gel as carrier.
Preferably, described active catalyst can bring back to life by soaking increase loss composition again.
Production technology of the present invention adopts V
aP
bCe
cSb
dO
xAs active catalyst, this catalyst has characteristics such as active height, selectivity height, has improved the production technology of o-chloro benzonitrile, and product yield obviously improves.
[description of drawings]
Fig. 1 is the equipment schematic of the production technology of preferred embodiment preparing chlorobenzonitrile by using ammoxidation method of the present invention.
Fig. 2 is the technological process of production figure of preferred embodiment preparing chlorobenzonitrile by using ammoxidation method of the present invention.
[specific embodiment]
As can be known described by preamble, choose the production method of ortho-chlorotolu'ene ammonia oxidation as synthetic o-chloro benzonitrile, be the synthetic method that present production cost is minimum, technology is the simplest, environmental pollution is minimum, but there is the side reaction that much influences yield in traditional ortho-chlorotolu'ene ammonia oxidation.
Be the yield in the production technology of improving adjacent preparing chlorobenzonitrile by using ammoxidation method, at the synthetic characteristics of o-chloro benzonitrile, technology of the present invention is improved the technology of preparing chlorobenzonitrile by using ammoxidation method from process conditions such as catalyst, reaction temperature, material proportions.
At first, improve catalyst system.The selection of catalyst system is the key of synthetic o-chloro benzonitrile, by testing repeatedly and screening, finally selects V
aP
bCe
cSb
dO
x(wherein: a=1, b=0.7～2, c=0.3～1, x=35%～40%) is as active catalyst.The making of this catalyst is simple, reaction condition is gentle, long service life, selectivity height, can obviously improve the yield of product.In order to improve the service life of catalyst, under the prerequisite that guarantees catalyst activity, can select gross porosity bastard silica gel to make carrier, and fully activation.Prove that by experiment the optimal activation temperature is 480 ℃.The hot-air (＞450 ℃) that feeds capacity in the process of activating catalyst makes the abundant oxidation of catalyst, prolonged the service life of catalyst greatly, so not only reduced cost but also reduced material loss and the environmental pollution that causes in the frequent replacing process of catalyst.
Secondly, preferred ammoxidation reaction temperature.For the ammoxidation reaction that in heterogeneous catalytic system, carries out, reaction condition preferably very important.Experiment shows that the reaction temperature of ortho-chlorotolu'ene preparing chlorobenzonitrile by using ammoxidation method is comparatively suitable between 370-380 ℃.At this temperature section, the side reaction in the preparation process is few, and reaction temperature is controlled easily and be more stable.
Once more, rationally adjust material ratio.The ortho-chlorotolu'ene ammonia oxidation wants to reach optimum state, accomplish sufficient reacting and be unlikely deep oxidation, consumption of raw materials is reduced to minimum level, adjusts the proportioning of ortho-chlorotolu'ene, air, ammonia and water repeatedly through experiment, has finally reached satisfied effect.After the adjustment, the ammonia consumption is reduced to o-chloro benzonitrile per ton and consumes 0.3 ton of ammonia, takes the closed cycle of ammoniacal liquor refluxed evaporator in order to allow the ammonia consumption reduce us, has so both reduced the ammonia consumption, has reduced production cost, has avoided pollution on the environment again.
By the improvement of above several respects, with V
aP
bCe
cSb
dO
xActive catalyst adopts the ortho-chlorotolu'ene preparing chlorobenzonitrile by using ammoxidation method under 370-380 ℃ of reaction temperature, this selection of catalysts greater than 95%, conversion ratio is higher than 99.3%, the final products yield can reach more than 92%.
In addition, because the o-chloro benzonitrile product is close with the impurity composition fusing point, o-chloro benzonitrile product distillation process difficulty is bigger, and ortho-chlorotolu'ene is difficult with separating of o-chloro benzonitrile.Owing to improved product yield by above-mentioned improvement, thereby reduced the load of rectifying.The first product content that the experiment initial achievements shows production only need just can reach 99.5% through simple rectifying product content greater than 99%.
See also Fig. 1 and Fig. 2, concise and to the point technological process principle of the present invention as shown in fig. 1.At first, air, ammonia, steam and ortho-chlorotolu'ene (PCT) are prepared burden according to material proportion through quantum meter 1-4 respectively.Again with ortho-chlorotolu'ene through 5 vaporizations of PCT vaporizer after, together be transported in the fluidized bed reactor 6 with air, ammonia and steam and react.Reacted product can obtain final products after capturing through trap 7,8 secondaries.
Mainly contain excess of ammonia in the synthetic o-chloro benzonitrile technique waste water of ortho-chlorotolu'ene ammoxidation, take the ammoniacal liquor circulating and evaporating to recycle, our employing of the gas in the tail gas is got the buck cooling and is reclaimed, and the waste water of absorption will be used the comprehensive regulation of ozone oxidation method.Pilot-scale experiment shows that one ton of o-chloro benzonitrile of every production only need be handled 0.2 ton of waste water, so this process environments pollution is little.
This technology is main material with the ortho-chlorotolu'ene, under 370-380 ℃ of reaction temperature, and the V of the synthetic o-chloro benzonitrile of the ammonia oxygen method of selection
aP
bCe
cSb
dO
xCatalyst.Compared to the ammonia oxidation process that adopts other System Catalyst (for example oxide of V, Pb, Fe or amino-oxide), adopt V
aP
bCe
cSb
dO
xThe advantage of the ammonia oxidation process of catalyst is as shown in table one.
Table one technology of the present invention and traditional handicraft contrast
Obviously, have the following advantages according to the technology of the present invention of the data in the table one:
1. catalyst is made simple: catalyst is made to form and is once finished (dissolving-carrier impregnation of making up a prescription-ageing-airing-activation-finished product), has overcome the unstability that most of catalyst is made the multiple operation conditional operation;
2. the catalyst cost of manufacture is cheap: manufacturing cost only is 20% of a catalyst of the same type;
3. the catalyst activity load is high;
4. catalyst is easy to recovery, loss is few: big because the catalyst of body series adopts gross porosity microsphere silica gel (20～120 order) as carrier than other catalyst (＞120 order) particle, and more easily collecting, difficult loss;
5. catalyst life is long: catalyst service life of this technology is more than 3 years and can bring back to life the effect that performance reaches raw catelyst by soaking (increasing loss composition Ce, P etc.) again;
6. reaction temperature gentleness: this catalyst well-defined reaction temp has been avoided the many disadvantages of ammoxidation reaction temperature drift (about 470 ℃) side reaction in the past about 370 ℃, and the ammonia consumption also reduces greatly;
7. catalytic selectivity height;
8. feed stock conversion height:
9. product is collected the rate height;
10. product purity height.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (4)
1. the production technology of a preparing chlorobenzonitrile by using ammoxidation method is characterized in that: this production technology employing V
aP
bCe
cSb
dO
xAs active catalyst, wherein a=1, b=0.7～2, c=0.3～1, x=35%～40%.
2. production technology according to claim 1 is characterized in that: the reaction temperature of described production technology is 370～380 ℃.
3. according to each described production technology in claim 1 or 2, it is characterized in that: described active catalyst adopts the gross porosity microsphere silica gel as carrier.
4. production technology according to claim 3 is characterized in that: described active catalyst can bring back to life by soaking increase loss composition again.
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| CN201010194755A CN101850264A (en) | 2010-06-01 | 2010-06-01 | Production process for preparing chlorobenzonitrile by using ammoxidation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019191A (en) * | 2010-11-15 | 2011-04-20 | 湖北惠通科技有限公司 | Novel catalyst for preparing 4-Iodobenzonitrile |
| CN103102287A (en) * | 2013-01-31 | 2013-05-15 | 湖北郡泰医药化工有限公司 | Production process for preparing chlorobenzonitrile through ammoxidation |
| CN111978210A (en) * | 2020-09-03 | 2020-11-24 | 常州新日催化剂有限公司 | Trapping device and process for production of o-chlorobenzonitrile |
| 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 |
-
2010
- 2010-06-01 CN CN201010194755A patent/CN101850264A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019191A (en) * | 2010-11-15 | 2011-04-20 | 湖北惠通科技有限公司 | Novel catalyst for preparing 4-Iodobenzonitrile |
| CN102019191B (en) * | 2010-11-15 | 2012-09-05 | 应城市澳赛斯化工有限责任公司 | Novel catalyst for preparing 4-Iodobenzonitrile |
| CN103102287A (en) * | 2013-01-31 | 2013-05-15 | 湖北郡泰医药化工有限公司 | Production process for preparing chlorobenzonitrile through ammoxidation |
| CN111978210A (en) * | 2020-09-03 | 2020-11-24 | 常州新日催化剂有限公司 | Trapping device and process for production of o-chlorobenzonitrile |
| CN111978210B (en) * | 2020-09-03 | 2021-03-26 | 常州新日催化剂股份有限公司 | Trapping device and process for production of o-chlorobenzonitrile |
| 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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Application publication date: 20101006 |