CN110038587B - Catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine and preparation method thereof - Google Patents
Catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine and preparation method thereof Download PDFInfo
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- CN110038587B CN110038587B CN201910399684.XA CN201910399684A CN110038587B CN 110038587 B CN110038587 B CN 110038587B CN 201910399684 A CN201910399684 A CN 201910399684A CN 110038587 B CN110038587 B CN 110038587B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine and a preparation method thereof. The preparation of the catalyst adopts a mechanical mixing method, firstly, an aluminum source, an iron source, a manganese source and a cerium source are fully stirred and mixed, then, a granulator is used for granulation, a tablet machine is used for tabletting and molding, and finally, the catalyst is obtained by high-temperature roasting. The catalyst obtained by the invention has the characteristics of simple preparation process and convenient operation, is used for the synthesis reaction of 2, 3-dichloro-5-trifluoromethylpyridine, and has the characteristics of high conversion rate and good stability.
Description
Technical Field
The invention relates to a preparation method of a catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine.
Background
2, 3-dichloro-5-trifluoromethylpyridine (2,3,52DCTF) is an important intermediate in fluoro-nitrogen heterocyclic pesticides. The pesticide synthesized by the herbicide is a herbicide such as fluazifop-butyl, haloxyfop-ethyl, haloxyfop-butyl and the like, and has the characteristics of high pesticide effect, low toxicity, small pollution and the like; the other pesticide, such as benzoylurea insecticides like chlorfluazuron, has unique action mechanism, and has the obvious characteristics of high efficiency, low toxicity, environmental friendliness and the like.
In the prior art, 2, 3-dichloro-5-trifluoromethylpyridine developed by Japan Stone Industrial Co., Ltd is prepared by reacting 3-methylpyridine as a main raw material in the presence of chlorine and a hydrogen fluoride catalyst in a special reactor at 350-450 ℃. The product is only 40 percent, more by-products are produced, more tar is difficult to separate, the product purity is only 95 percent, and the product is difficult to solve by other equipment.
Disclosure of Invention
The invention discloses a preparation method of a catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine from 2-chloro-5-trifluoromethylpyridine and chlorine, which has the characteristics of simple preparation process and convenient operation.
The invention provides a catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine, which consists of 70-80 wt%, 20-30 wt%, 0.1-2 wt%, 0.1-3 wt% of alumina, ferric oxide, manganese dioxide and cerium oxide. The preparation of the catalyst adopts a mechanical mixing method, firstly, an aluminum source, an iron source, a manganese source and a cerium source are fully stirred and mixed, then, a granulator is used for granulation, a tablet machine is used for tabletting and molding, and finally, the catalyst is obtained by high-temperature roasting.
Further, in the above technical solution, the aluminum source is alumina.
Further, in the above technical solution, the iron source is iron oxide.
Further, in the above technical solution, the manganese source is manganese dioxide.
Further, in the above technical solution, the cerium source is cerium oxide.
Further, in the technical scheme, the mesh number of the granulating machine for granulating is 30-40 meshes.
Further, in the technical scheme, the granulating density of the granulator is 0.26-0.3 g/cm 3 In the meantime.
Further, in the technical scheme, the roasting temperature of the catalyst after tabletting and forming by the tablet press is 450-550 ℃, and the roasting time is 4-6 hours.
Further, in the technical scheme, the strength of the calcined catalyst is 120-150N/cm.
The invention adopts a mechanical mixing method to granulate and tablet alumina, ferric oxide, manganese dioxide and cerium oxide according to a certain mass ratio, the catalyst has the characteristics of simple preparation process and convenient operation, and the catalyst obtained by the invention is used for the synthesis reaction of 2, 3-dichloro-5-trifluoromethylpyridine and has the characteristics of high conversion rate and good stability.
The preparation of 2, 3-dichloro-5-trifluoromethylpyridine according to the present invention is further illustrated below with reference to the following specific examples, but the present invention is not limited thereto.
Detailed Description
Example 1
Fully stirring and mixing 300g of aluminum oxide, 80g of ferric oxide, 5g of manganese dioxide and 6g of cerium oxide, and then granulating by using a granulator, wherein the granularity is 30-40 meshes, and the density is 0.26-0.3 g/cm 3 Tabletting and molding the granules, and finally roasting at 550 ℃ for 5 hours to obtain the catalyst CCG-M1.
Example 2
Fully stirring and mixing 300g of aluminum oxide, 90g of ferric oxide, 5g of manganese dioxide and 6g of cerium oxide, and then granulating by using a granulator, wherein the granularity is 30-40 meshes, and the density is 0.26-0.3 g/cm 3 Tabletting and molding the granules, and finally roasting at 550 ℃ for 5 hours to obtain the catalyst CCG-M2.
Example 3
Fully stirring and mixing 300g of aluminum oxide, 80g of ferric oxide, 6g of manganese dioxide and 6g of cerium oxide, and then granulating by using a granulator, wherein the granularity is 30-40 meshes, and the density is 0.26-0.3 g/cm 3 Tabletting and molding the granules, and finally roasting at 550 ℃ for 5 hours to obtain the catalyst CCG-M3.
Example 4
Fully stirring and mixing 300g of aluminum oxide, 80g of ferric oxide, 5g of manganese dioxide and 6g of cerium oxide, and then granulating by using a granulator, wherein the granularity is 30-40 meshes, and the density is 0.26-0.3 g/cm 3 Tabletting and molding the granules, and finally roasting at 550 ℃ for 6 hours to obtain the catalyst CCG-M4.
Application example
The performance of chlorination of 2-chloro-5-trifluoromethylpyridine was evaluated for each of the catalyst samples obtained in comparative example and comparative example.
(1) 4g of 2-chloro-5-trifluoromethylpyridine and 8g of carbon tetrachloride are uniformly mixed for standby; (2) weighing 4g of the ground and sieved 20-40 mesh catalyst, filling the weighed catalyst in the middle part of a reactor, introducing mixed gas of nitrogen and hydrogen at the speed of 20ml/min, heating to 480 ℃ for 4 hours, and activating for 1 hour; (3) closing the hydrogen, continuously introducing nitrogen and cooling to 300 ℃; (4) closing the nitrogen, opening a chlorine regulating valve, and controlling the chlorine introducing speed at 20 ml/min; starting a feeding pump, and controlling the mass space velocity of the raw material 2-chloro-5-trifluoromethylpyridine to be 1 h-1; (5) the material enters a receiver after being condensed by a condenser, and is sampled and analyzed for 0.5h (6) and is sampled and analyzed for 12h after experiment feeding.
The results of the reaction were analyzed by gas chromatography, and the results of evaluating the performance of the catalysts obtained in the comparative examples and examples are shown in Table 1.
TABLE 1
Claims (7)
1. A catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine, which is characterized in that: the catalyst consists of 70-80 wt%, 20-30 wt%, 0.1-2 wt%, 0.1-3 wt% of alumina, ferric oxide, manganese dioxide and cerium oxide; the composition meets the requirement of 100% by mass;
the preparation of the catalyst adopts a mechanical mixing method and comprises the following specific steps:
(1) fully stirring an aluminum source, an iron source, a manganese source and a cerium source, and uniformly mixing;
(2) granulating by a granulator, and tabletting and forming by a tabletting machine;
(3) roasting at high temperature to obtain a catalyst;
the catalyst is used for the reaction of synthesizing 2, 3-dichloro-5-trifluoromethylpyridine from 2-chloro-5-trifluoromethylpyridine and chlorine;
the roasting temperature of the catalyst after tabletting and forming by a tablet press is 450-550 ℃, and the roasting time is 4-6 h;
the strength of the calcined catalyst is 120-150N/cm.
2. The catalyst of claim 1, wherein: the aluminum source is alumina.
3. The catalyst of claim 1, wherein: the iron source is ferric oxide.
4. The catalyst of claim 1, wherein: the manganese source is manganese dioxide.
5. The catalyst of claim 1, wherein: the cerium source is cerium oxide.
6. The catalyst of claim 1, wherein: the mesh number of the granulator is 30-40 meshes.
7. The catalyst of claim 1, wherein: the granulating density of the granulator is between 0.26 and 0.3g/cm for carrying out dry harvest.
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| CN110038587B true CN110038587B (en) | 2022-08-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI629262B (en) * | 2013-06-14 | 2018-07-11 | 科麥農股份有限公司 | A method for producing 2,3-dichloro-5-(trichloromethyl)pyridine |
| CN103288718B (en) * | 2013-06-26 | 2015-07-15 | 辽宁天予化工有限公司 | Preparation method of 2-chloro-5-tirfluoromethylpyridine |
| CN104557683B (en) * | 2013-10-09 | 2016-11-02 | 李波 | The preparation method of 2,3-bis-chloro-5-trifluoromethylpyridines |
| CN105013517B (en) * | 2014-04-16 | 2017-11-10 | 浙江化工院科技有限公司 | A kind of catalyst for being used for the preparation of 3 trifluoromethyl pyridines |
| CN106008330A (en) * | 2016-06-06 | 2016-10-12 | 山东福尔有限公司 | Preparation method for 2,3-dichloro-5-(trifluoromethyl)pyridine |
| CN106397309A (en) * | 2016-08-31 | 2017-02-15 | 南京红太阳生物化学有限责任公司 | Synthetic method of 2,3-dichloro-5-trifluoromethylpyridine |
| CN107759511A (en) * | 2017-10-27 | 2018-03-06 | 苏州盖德精细材料有限公司 | A kind of production method of the trifluoromethyl pyridine of 2 chlorine 5 of high-purity |
| CN107935920A (en) * | 2017-11-30 | 2018-04-20 | 山东汇盟生物科技有限公司 | Preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine |
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