CN101768107A - Method for preparing polychlorinated pyridine - Google Patents
Method for preparing polychlorinated pyridine Download PDFInfo
- Publication number
- CN101768107A CN101768107A CN201010034066A CN201010034066A CN101768107A CN 101768107 A CN101768107 A CN 101768107A CN 201010034066 A CN201010034066 A CN 201010034066A CN 201010034066 A CN201010034066 A CN 201010034066A CN 101768107 A CN101768107 A CN 101768107A
- Authority
- CN
- China
- Prior art keywords
- pyridine
- weight
- loaded catalyst
- content
- chlorine
- 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
Images
Abstract
The invention provides a method for preparing polychlorinated pyridine. The method comprises the following step of: in the presence of a supported catalyst, contacting pyridine in gaseous state with chlorine, wherein the supported catalyst comprises a carrier and an active component carried on the carrier; the carrier is silicon dioxide; and the active component is at least one of the chloride of a transition metal and the chloride of an alkaline-earth metal. The supported catalyst used in the method of the invention is difficult to be inactive, has a long service life, can regenerate after being inactive and has a higher catalytic activity, so as to greatly promote the efficiency for preparing polychlorinated pyridine and lower the cost of production.
Description
Technical field
The present invention relates to a kind of preparation method of polychlorinated pyridine.
Background technology
4 chloro pyridine is a kind of important organic compound and important synthesis intermediates, can be used for synthetic herbicide, sterilant, sterilant, plant-growth regulator and medical pharmacy etc.Perchloropyridine has higher biological activity; the synthetic intermediate that can be used as agricultural chemicals, medicine and dyestuff; and have characteristics such as wide spectrum, efficient and low toxicity by a series of agricultural chemicals of Perchloropyridine synthetic, and agricultural development and ecological protection are had great importance, market potential is very wide.
The method of existing preparation 4 chloro pyridine or Perchloropyridine mainly contains pyridine liquid phase chlorination and pyridine gas-solid catalysis chlorination process etc.Wherein flow process is simple because of having, yield is high has application prospect most for the gas-solid catalysis chlorination process.The pyridine gas-solid catalysis chlorination catalyst of having reported is with muriatic loaded catalysts such as activated carbon loaded cobalt as active ingredient, lanthanums, yet, carbon distribution in use easily takes place and causes the inactivation of catalyzer in this catalyzer, and, can not regenerate behind this catalyst deactivation.
Summary of the invention
The objective of the invention is the easy inactivation of catalyzer in order to be adopted in the method that overcomes existing preparation polychlorinated pyridine such as 4 chloro pyridine or Perchloropyridine, can not regenerate behind the inactivation, and the not high shortcoming of catalytic activity, a kind of new method for preparing polychlorinated pyridine is provided, the loaded catalyst that is adopted in this method is difficult for inactivation, and work-ing life is longer, can regenerate behind the inactivation, and catalytic activity is very high, thereby has improved the efficient of preparation polychlorinated pyridine greatly and reduced production cost.
The invention provides a kind of preparation method of polychlorinated pyridine, this method is included under the existence of loaded catalyst, pyridine is contacted with chlorine with gaseous form, described loaded catalyst comprises carrier and the active ingredient that loads on the described carrier, described carrier is a silicon-dioxide, and described active ingredient is at least a in the muriate of the muriate of transition metal and alkaline-earth metal.
In the described method for preparing polychlorinated pyridine provided by the invention, described loaded catalyst is owing to use silicon-dioxide to substitute existing activated carbon as carrier, thereby obviously improved the catalytic activity and the stability of described loaded catalyst; And in the process of preparation polychlorinated pyridine, be difficult for producing carbon distribution, and therefore being not easy inactivation, work-ing life is longer; In addition, this loaded catalyst can be handled by aerating oxygen at high temperature after inactivation, activates by feeding chlorine then, thereby is regenerated, and therefore, has improved the utilization ratio of catalyzer greatly and has reduced the production cost of polychlorinated pyridine.
Description of drawings
Fig. 1 represents to be used to implement the synoptic diagram of the system of described preparation polychlorinated pyridine provided by the invention.
Embodiment
Be included under the existence of loaded catalyst according to the described method for preparing polychlorinated pyridine provided by the invention, pyridine is contacted with chlorine with gaseous form, described loaded catalyst comprises carrier and the active ingredient that loads on the described carrier, described carrier is a silicon-dioxide, and described active ingredient is at least a in the muriate of the muriate of transition metal and alkaline-earth metal.
In described loaded catalyst, be benchmark with the gross weight of described loaded catalyst, the content of described active ingredient can be 5-20 weight %, is preferably 7-15 weight %, the content of described carrier can be 80-95 weight %, is preferably 85-93 weight %.Content by making described active ingredient preferably in 7-15 weight %, can guarantee that the catalytic activity of described loaded catalyst is higher on the one hand at 5-20 weight %, thereby guarantees fully to react by the raw material of described loaded catalyst; Can also overcome the higher defective of catalyzer cost that causes because of described active component content is excessive on the other hand.Therefore, take all factors into consideration the catalytic activity of economic factors and loaded catalyst, the content of the preferred described activity of such catalysts composition of the present invention is in above-mentioned scope.
In described catalyzer, the transition metal that described active ingredient can be used for the method preparing polychlorinated pyridine of various routines or the muriate of alkaline-earth metal, yet, in order further to improve the catalytic activity of described loaded catalyst, and then improving catalytic efficiency in the process of preparation polychlorinated pyridine, described active ingredient is preferably at least a in the muriate of cobalt, lanthanum, barium, iron, copper and zinc.
In a kind of preferred implementation of the present invention, active ingredient in the described loaded catalyst comprises cobalt chloride and Lanthanum trichloride at least, under this preferable case, can significantly improve the catalytic activity of described loaded catalyst, particularly, the catalytic efficiency at loaded catalyst described in the process of preparation polychlorinated pyridine has improved widely.Further under the preferable case, in described loaded catalyst, be benchmark with the gross weight of described loaded catalyst, the content of described cobalt chloride can be 2-9 weight %, 3-8 weight % more preferably, the content of described Lanthanum trichloride is 2-12 weight %, more preferably 2.5-10 weight %.
In the present invention, the pore volume of described loaded catalyst can be 0.3-0.4 milliliter/gram catalyzer, is preferably 0.35-0.4 milliliter/gram catalyzer.Described loaded catalyst in above-mentioned pore volume scope has better catalytic activity, and the life-span of longer use.
In the present invention, described loaded catalyst preferably prepares by the method that may further comprise the steps:
(1) at least a aqueous solution in transition metal salt and the alkaline earth salt is mixed with silicon sol, then the gained mixture is carried out drying and roasting, thereby make catalyst precursor;
(2) described catalyst precursor is contacted with chlorine, the condition of described contact makes in the products therefrom of contact back to described transition metal of small part and alkaline-earth metal and exists with its chloride form.
In step (1), the concentration of described solution is different and different with the kind of described transition metal salt and alkaline earth salt, and generally, the concentration of described solution can be the 0.01-0.15 grams per milliliter.
In step (1), what described transition metal salt and alkaline earth salt can be in nitrate, carbonate, oxalate and the muriates is at least a.
In step (1), what the metallic element in described transition metal salt and the alkaline earth salt can be in cobalt, lanthanum, barium, iron, copper and the zinc is at least a.
In the preferred case, the metallic element in described transition metal salt and the alkaline earth salt comprises cobalt and lanthanum at least.Under this preferable case, can significantly improve the catalytic activity of the loaded catalyst that finally makes, particularly, improved widely at the catalytic efficiency of loaded catalyst described in the process of preparation polychlorinated pyridine.
In step (1), there is no particular limitation for concentration of silicon dioxide in the described silicon sol, and for the loaded catalyst that guarantees finally to make has advantages of high catalytic activity, concentration of silicon dioxide is preferably 15-30 weight % in the described silicon sol.
In step (1), at least a aqueous solution in transition metal salt and the alkaline earth salt and silicon sol blended method can be comprised: under 15-40 ℃ temperature, under at the uniform velocity stirring, making the described solution that makes in described silicon sol and the step (1) is 1 with weight ratio: 0.1-1.5 mixes, and keep and stirred 1-7 hour, thereby make abundant dispersive mixing solutions.
In step (1), described exsiccant method preferably includes described mixing solutions is heated to 80-95 ℃, and under this temperature, make moisture evaporation in the described mixture, water-content in mixture is 0.1-15 weight %, be preferably 2-13 weight %, the mixture that obtains was descended dry 12-72 hour at 105-130 ℃.In the present invention, be divided into two stages by drying process with described mixing solutions, be lesser temps drying stage (80-95 ℃) and comparatively high temps drying stage (105-130 ℃), thereby can improve the specific surface area of the loaded catalyst that finally makes, and then guarantee that the loaded catalyst that finally makes has advantages of high catalytic activity.
In step (1), there is no particular limitation for the condition of described roasting, can suitably select in the roasting condition of routine, and under the preferable case, the condition of described roasting can comprise: temperature is 300-500 ℃, and the time is 5-9 hour.
In step (2), the condition that described catalyst precursor contacts with chlorine can comprise: temperature is 300-400 ℃, is preferably 320-380 ℃, and the time is 2-5 hour, is preferably 2.5-4 hour.
In step (2), described catalyst precursor contacts with chlorine preferably and carries out in the presence of shielding gas, and the volume of chlorine accounts for the 30-90% of cumulative volume of the mixed gas of chlorine and described shielding gas.In the present invention, described shielding gas is meant the gas that can not react with chlorine and described catalyst precursor, and common described shielding gas can be a periodic table of elements neutral element gas for nitrogen and conventional rare gas element.
In described method provided by the invention, the mol ratio of the consumption of described pyridine and chlorine can be 1: 4-20.
There is no particular limitation for the temperature that described pyridine contacts with chlorine with gaseous state, is preferably 250-500 ℃, more preferably 300-450 ℃.
In the present invention; described pyridine contacts with chlorine preferably with gaseous state and carries out in the presence of shielding gas; and described shielding gas accounts for the 5-95% of cumulative volume of the mixed gas of described gasiform pyridine, chlorine and described shielding gas, and the volume space velocity of mixed gas is 60-150h
-1Described shielding gas is meant the gas that can not react with pyridine and chlorine, and common described shielding gas can be a periodic table of elements neutral element gas for nitrogen and conventional rare gas element.
In a kind of preferred implementation of the present invention, the described method for preparing polychlorinated pyridine provided by the invention can adopt system as shown in Figure 1 to implement.In Fig. 1, pyridine supplies in the vaporizer by a feed device, simultaneously shielding gas is fed in the described vaporizer, and pyridine is vaporized in the presence of shielding gas; In addition, chlorine is injected preheater be preheated to predetermined temperature, preferably be preheated to the temperature close with the pyridine of described vaporization; Then, the pyridine of vaporization and the chlorine of preheating are injected the reactor that is filled with described loaded catalyst, the pyridine of described vaporization and the chlorine of described preheating are reacted in the presence of described loaded catalyst, generate polychlorinated pyridine, described reactor can be fixed bed reaction and/or fluidized-bed reactor; Collect the polychlorinated pyridine that produces by trap through the product that obtains behind the described reactor reaction; and the mixed gas that makes unreacted pyridine, chlorine and shielding gas by compressor cycle in the shielding gas supply line, along with described shielding gas supplies in the described vaporizer.
The present invention is further detailed explanation by the following examples.
Embodiment 1
Present embodiment is used to illustrate the described method for preparing polychlorinated pyridine provided by the invention.
The Xiao Suangus of 104.2 grams and the lanthanum nitrates of 35.7 grams are dissolved in 2000 milliliters the deionized water, after treating fully dissolving, under room temperature and stirring condition, progressively be added drop-wise in 3.5 kilograms the silicon sol of 27 weight %, thereby continuing after dripping to stir obtained abundant dispersive mixing solutions in 6 hours again.Then, under agitation described mixed solution is warmed up to 90 ℃, and under this temperature, make moisture evaporation in the described mixing solutions, become pasty state (water-content is 10 weight %) up to mixture, then the mixture of this pasty state is placed in the loft drier 120 ℃ dry 48 hours down.Afterwards, dried mixture is placed in the process furnace,, thereby obtains catalyst precursor 450 ℃ of following roastings 8 hours.This catalyst precursor is packed in the fixed-bed reactor, and the internal diameter of the cylinder of described fixed-bed reactor is 32 millimeters, and length is 1200 millimeters.Make described reactor be warming up to 350 ℃ by heating, begin in described reactor to feed the mixed gas (volume of chlorine account for described mixed gas cumulative volume 60%) of chlorine and nitrogen then, described mixed gas fed 4 hours with the flow of 1000 ml/min, thereby made loaded catalyst according to the present invention.CoCl in the described loaded catalyst
2Content be about 7.4 weight %, LaCl
3Content be about 2.7 weight %, and the weight of described loaded catalyst is about 1 kilogram; The pore volume that records described loaded catalyst by nitrogen adsorption desorption method is 0.36 a milliliter/gram catalyzer.
With nitrogen is carrier, pyridine is vaporized, simultaneously chlorine is preheated to the temperature identical with pyridine, make then described pyridine and chlorine with 1: 10 volume ratio in premixed device, mix (volume of nitrogen account for described pyridine, chlorine and nitrogen mixed gas cumulative volume 60%); With the temperature regulation to 330 of the above-mentioned described fixed-bed reactor that described loaded catalyst is housed ℃, and make from the mixed gas in the described premixed device with 110h
-1Air speed feed in the described fixed-bed reactor.Feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Embodiment 2
Present embodiment is used to illustrate the described method for preparing polychlorinated pyridine provided by the invention.
The Xiao Suangus of 104.2 grams, the lanthanum nitrates of 35.7 grams and the bariumchlorides of 30 grams are dissolved in 2000 milliliters the deionized water, after treating fully dissolving, under room temperature and stirring condition, progressively be added drop-wise in 3.5 kilograms the silicon sol of 27 weight %, thereby continuing after dripping to stir obtained abundant dispersive mixing solutions in 6 hours again.Then, under agitation described mixed solution is warmed up to 95 ℃, and under this temperature, make moisture evaporation in the described mixing solutions, become pasty state (water-content is 5 weight %) up to mixture, then the mixture of this pasty state is placed in the loft drier 135 ℃ dry 24 hours down.Afterwards, dried mixture is placed in the process furnace,, thereby obtains catalyst precursor 500 ℃ of following roastings 5 hours.This catalyst precursor is packed in the fixed-bed reactor, and the internal diameter of the cylinder of described fixed-bed reactor is 32 millimeters, and length is 1200 millimeters.Make described reactor be warming up to 400 ℃ by heating, begin in described reactor to feed the mixed gas (volume of chlorine account for described mixed gas cumulative volume 60%) of chlorine and nitrogen then, described mixed gas fed 4 hours with the flow of 1000 ml/min, thereby made loaded catalyst according to the present invention.CoCl in the described loaded catalyst
2Content be about 7.4 weight %, LaCl
3Content be about 2.7 weight %, BaCl
2Content be about 0.3 weight %, and the weight of described loaded catalyst is about 1 kilogram; The pore volume that records described loaded catalyst by nitrogen adsorption desorption method is 0.37 a milliliter/gram catalyzer.
With nitrogen is carrier, pyridine is vaporized, simultaneously chlorine is preheated to the temperature identical with pyridine, make then described pyridine and chlorine with 1: 8 volume ratio in premixed device, mix (volume of nitrogen account for described pyridine, chlorine and nitrogen mixed gas cumulative volume 60%); With the temperature regulation to 450 of the above-mentioned described fixed-bed reactor that described catalyzer is housed ℃, and make from the mixed gas in the described premixed device with 130h
-1Air speed feed in the described fixed-bed reactor.Feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Embodiment 3
Present embodiment is used to illustrate the described method for preparing polychlorinated pyridine provided by the invention.
The Xiao Suangus of 35.2 grams, the lanthanum nitrates of 26.5 grams, the nitrate of baryta of 59 grams and the zinc nitrates of 19 grams are dissolved in 2000 milliliters the deionized water, after treating fully dissolving, under room temperature and stirring condition, progressively be added drop-wise in 3.5 kilograms the silicon sol of 27 weight %, thereby continuing after dripping to stir obtained abundant dispersive mixing solutions in 6 hours again.Then, under agitation described mixed solution is warmed up to 80 ℃, and under this temperature, make moisture evaporation in the described mixing solutions, become pasty state (water-content is 13 weight %) up to mixture, then the mixture of this pasty state is placed in the loft drier 110 ℃ dry 72 hours down.Afterwards, dried mixture is placed in the process furnace,, thereby obtains catalyst precursor 300 ℃ of following roastings 9 hours.This catalyst precursor is packed in the fixed-bed reactor, and the internal diameter of the cylinder of described fixed-bed reactor is 32 millimeters, and length is 1200 millimeters.Make described reactor be warming up to 300 ℃ by heating, begin in described reactor to feed the mixed gas (volume of chlorine account for described mixed gas cumulative volume 60%) of chlorine and nitrogen then, described mixed gas fed 4 hours with the flow of 1000 ml/min, thereby made loaded catalyst according to the present invention.CoCl in the described loaded catalyst
2Content be about 2.5 weight %, LaCl
3Content be about 2.0 weight %, BaCl
2Content be about 5.9 weight %, ZnCl
2Content be about 1.9 weight %, and the weight of described loaded catalyst is about 1 kilogram; The pore volume that records described loaded catalyst by nitrogen adsorption desorption method is 0.39 a milliliter/gram catalyzer.
With nitrogen is carrier, pyridine is vaporized, simultaneously chlorine is preheated to the temperature identical with pyridine, make then described pyridine and chlorine with 1: 5 volume ratio in premixed device, mix (volume of nitrogen account for described pyridine, chlorine and nitrogen mixed gas cumulative volume 60%); With the temperature regulation to 300 of the above-mentioned described fixed-bed reactor that described catalyzer is housed ℃, and make from the mixed gas in the described premixed device with 80h
-1Air speed feed in the described fixed-bed reactor.Feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Embodiment 4
Present embodiment is used to illustrate the described method for preparing polychlorinated pyridine provided by the invention.
Method according to embodiment 1 prepares described loaded catalyst and pyridine and chlorine is reacted, different is, in the process of the described loaded catalyst of preparation, replace the Xiao Suangu of 104.2 grams with the ironic oxalate of 145.7 grams, thereby contain the FeCl of the 7.4 weight % that have an appointment in the loaded catalyst that makes
3LaCl with about 2.7 weight %
3In addition, feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Embodiment 5
Present embodiment is used to illustrate the described method for preparing polychlorinated pyridine provided by the invention.
Method according to embodiment 1 prepares described loaded catalyst and pyridine and chlorine is reacted, different is, in the process of the described loaded catalyst of preparation, the consumption of Xiao Suangu is 21.1 grams, the consumption of lanthanum nitrate is 35.7 grams, thereby contains the CoCl of the 1.5 weight % that have an appointment in the loaded catalyst that makes
2LaCl with about 2.7 weight %
3In addition, feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Embodiment 6
Present embodiment is used to illustrate the described method for preparing polychlorinated pyridine provided by the invention.
Method according to embodiment 1 prepares described loaded catalyst and pyridine and chlorine is reacted, different is, by maturing temperature being controlled to be 380 ℃, roasting time is controlled to be 4.5 hours, is 0.45 milliliter/gram catalyzer thereby make the pore volume of the loaded catalyst that finally makes.In addition, feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Embodiment 7
Present embodiment is used to illustrate the described method for preparing polychlorinated pyridine provided by the invention.
Method according to embodiment 3 prepares described loaded catalyst and pyridine and chlorine is reacted, different is, in the process of the described loaded catalyst of preparation, do not use zinc nitrate, and the consumption of Xiao Suangu is 35.2 grams, the consumption of lanthanum nitrate is 21.2 grams, and the consumption of nitrate of baryta is 74.0 grams, thereby contains the CoCl of the 2.5 weight % that have an appointment in the loaded catalyst that makes
2, about 1.6 weight % LaCl
3BaCl with about 5.9 weight %
2In addition, feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Comparative Examples 1
Preparation contains 74 gram CoCl
2With 27 gram LaCl
3Mixing solutions, the activated carbon that under agitation with 899 average particulate diameters that restrain is 0.7 millimeter then is added in the described mixing solutions, after all being added in the described mixing solutions, continues again activated carbon to stir 4 hours, descend dry 24 hours at 85 ℃ then, thereby obtain 1 kilogram loaded catalyst.
This catalyzer is filled in the fixed-bed reactor, and the internal diameter of the cylinder of described fixed-bed reactor is 32 millimeters, and length is 1200 millimeters.
Then, the method according to embodiment 1 reacts pyridine and chlorine.Feed in the described fixed-bed reactor after 24 hours, 100 hours and 500 hours at described mixed gas respectively, the product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and Perchloropyridine is as shown in table 1 in the transformation efficiency of pyridine and the product.
Table 1
As can be seen from Table 1, in the described method for preparing polychlorinated pyridine provided by the invention, the work-ing life of described loaded catalyst is longer, has very high catalytic activity, and can generate 4 chloro pyridine and/or Perchloropyridine with higher selectivity catalysis pyridine and chlorine reaction.In addition, in described loaded catalyst, contain cobalt chloride and Lanthanum trichloride at least, and the content of cobalt chloride is 2-9 weight %, when the content of Lanthanum trichloride is 2-12 weight %, make that the content of 4 chloro pyridine in the product that pyridine and chlorine reaction generate and/or Perchloropyridine is relative higher, thereby show better catalytic activity.
Claims (10)
1. the preparation method of a polychlorinated pyridine, it is characterized in that, this method is included under the existence of loaded catalyst, pyridine is contacted with chlorine with gaseous form, described loaded catalyst comprises carrier and the active ingredient that loads on the described carrier, described carrier is a silicon-dioxide, and described active ingredient is at least a in the muriate of the muriate of transition metal and alkaline-earth metal.
2. method according to claim 1 wherein, in described loaded catalyst, is a benchmark with the gross weight of described loaded catalyst, and the content of described active ingredient is 5-20 weight %, and the content of described carrier is 80-95 weight %.
3. method according to claim 2 wherein, in described loaded catalyst, is a benchmark with the gross weight of described loaded catalyst, and the content of described active ingredient is 7-15 weight %, and the content of described carrier is 85-93 weight %.
4. method according to claim 1, wherein, described active ingredient is at least a in the muriate of cobalt, lanthanum, barium, iron, copper and zinc.
5. according to any described method among the claim 1-4, wherein, at least comprise cobalt chloride and Lanthanum trichloride in the described active ingredient, and in described loaded catalyst, gross weight with described loaded catalyst is a benchmark, the content of described cobalt chloride is 2-9 weight %, and the content of described Lanthanum trichloride is 2-12 weight %.
6. method according to claim 5, wherein, the content of described cobalt chloride is 3-8 weight %, the content of described Lanthanum trichloride is 2.5-10 weight %.
7. according to any described method among the claim 1-3, wherein, the pore volume of described loaded catalyst is 0.3-0.4 milliliter/gram catalyzer.
8. method according to claim 1, wherein, the mol ratio of described pyridine and chlorine is 1: 4-20.
9. according to claim 1 or 8 described methods, wherein, the temperature that described pyridine contacts with chlorine with gaseous state is 250-500 ℃.
10. method according to claim 9; wherein; described pyridine contacts in the presence of shielding gas with chlorine with gaseous state and carries out; and described shielding gas accounts for the 5-95% of cumulative volume of the mixed gas of described gasiform pyridine, chlorine and described shielding gas, and the volume space velocity of mixed gas is 60-150h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010034066A CN101768107A (en) | 2010-01-13 | 2010-01-13 | Method for preparing polychlorinated pyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010034066A CN101768107A (en) | 2010-01-13 | 2010-01-13 | Method for preparing polychlorinated pyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101768107A true CN101768107A (en) | 2010-07-07 |
Family
ID=42501230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010034066A Pending CN101768107A (en) | 2010-01-13 | 2010-01-13 | Method for preparing polychlorinated pyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101768107A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127011A (en) * | 2011-01-11 | 2011-07-20 | 湘潭大学 | Method and equipment for synthesizing polychloropyridine and derivatives thereof by chlorination catalyzed by active carbon |
| CN103739543A (en) * | 2014-01-08 | 2014-04-23 | 盐城恒盛化工有限公司 | Preparation method of tetrachlorpyridine |
| CN104888491A (en) * | 2015-06-04 | 2015-09-09 | 宜昌恒友化工有限公司 | Condensation trapping device for pentachloropyridine |
| CN108409644A (en) * | 2018-05-10 | 2018-08-17 | 四川福思达生物技术开发有限责任公司 | A kind of preparation method of penta chloropyridine |
| CN110746347A (en) * | 2019-11-08 | 2020-02-04 | 湖南比德生化科技股份有限公司 | Method for recovering and recycling tetrachloropyridine rectification residual liquid |
-
2010
- 2010-01-13 CN CN201010034066A patent/CN101768107A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127011A (en) * | 2011-01-11 | 2011-07-20 | 湘潭大学 | Method and equipment for synthesizing polychloropyridine and derivatives thereof by chlorination catalyzed by active carbon |
| CN102127011B (en) * | 2011-01-11 | 2012-10-03 | 湘潭大学 | Method and equipment for synthesizing polychloropyridine and derivatives thereof by chlorination catalyzed by active carbon |
| CN103739543A (en) * | 2014-01-08 | 2014-04-23 | 盐城恒盛化工有限公司 | Preparation method of tetrachlorpyridine |
| CN104888491A (en) * | 2015-06-04 | 2015-09-09 | 宜昌恒友化工有限公司 | Condensation trapping device for pentachloropyridine |
| CN108409644A (en) * | 2018-05-10 | 2018-08-17 | 四川福思达生物技术开发有限责任公司 | A kind of preparation method of penta chloropyridine |
| CN108409644B (en) * | 2018-05-10 | 2021-03-05 | 四川福思达生物技术开发有限责任公司 | Preparation method of pentachloropyridine |
| CN110746347A (en) * | 2019-11-08 | 2020-02-04 | 湖南比德生化科技股份有限公司 | Method for recovering and recycling tetrachloropyridine rectification residual liquid |
| CN110746347B (en) * | 2019-11-08 | 2023-02-14 | 湖南比德生化科技股份有限公司 | Method for recovering and recycling tetrachloropyridine rectification residual liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101433836A (en) | Catalyst for producing 3-cyano pyridine as well as preparation method and use thereof | |
| CN101768107A (en) | Method for preparing polychlorinated pyridine | |
| CN101632932B (en) | Dimethyl carbonate supported catalyst directly synthesized by methanol and carbon dioxide | |
| CN102989490B (en) | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof | |
| CN102188981B (en) | The preparation method of acrylonitrile fluidized-bed catalyst | |
| CN104710325B (en) | The method of Supported Manganese oxygen compound catalysis alkohol and amine one-step synthesis imines | |
| CN101695657A (en) | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin | |
| CN103102287A (en) | Production process for preparing chlorobenzonitrile through ammoxidation | |
| CN101773842B (en) | Supported catalyst and preparation method thereof | |
| CN101147867B (en) | Fluidized bed catalyst for oxidation of propene ammonia | |
| CN103894209B (en) | A kind of catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation and preparation and application | |
| CN108409644A (en) | A kind of preparation method of penta chloropyridine | |
| CN108772074A (en) | A kind of catalyst and preparation method thereof of ethylenediamine Hydrogenation diethylenetriamine | |
| CN102295581A (en) | Method for preparing 3,4-dichlorobenzonitrile by ammonia oxidation | |
| CN112441922B (en) | Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof | |
| CN100408172C (en) | Acrylonitrile fluid bed catalyst | |
| CN101767014B (en) | Fluidized bed catalyst for producing acrylonitrile by propylene ammoxidation | |
| CN100384531C (en) | Fluid-bed catalyst for ammoxidation to prepare acrylonitrile | |
| CN103664696A (en) | Method for preparing cyanobenzene | |
| CN102219710A (en) | Method for preparing cyanobenzene | |
| CN103418403A (en) | Low-temperature high-load catalyst for olefin ammoxidation reaction | |
| CN1072029C (en) | Catalyst containing Ni-P non-crystalline-state alloy, preparation method and application thereof | |
| CN101306372B (en) | Fluid bed catalyst for acrylonitrile production | |
| CN103894203B (en) | High-load catalyst for olefin ammoxidation reactions | |
| CN100566828C (en) | The fluid catalyst of preparation acrylonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: BEIJING NUTRICHEM INTERNATIONAL CO., LTD. Free format text: FORMER OWNER: BEIJING YINGTAI JIAHE SCIENCE AND TECHNOLOGY CO., LTD. Effective date: 20100928 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20100928 Address after: 100192 Beijing, Haidian District West Road, No. 66, building D-1 Applicant after: Nutrichem International Co., Ltd. Address before: 100192, D-1 building, North Territory, Dongsheng Science Park, No. 66 Xiao Dong Road, Beijing, Haidian District, Zhongguancun Applicant before: Nutrichem Laboratory Co., Ltd. |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100707 |