CN110038587A - It is a kind of for synthesizing the catalyst and preparation method thereof of bis- chloro-5-trifluoromethylpyridine of 2,3- - Google Patents

It is a kind of for synthesizing the catalyst and preparation method thereof of bis- chloro-5-trifluoromethylpyridine of 2,3- Download PDF

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CN110038587A
CN110038587A CN201910399684.XA CN201910399684A CN110038587A CN 110038587 A CN110038587 A CN 110038587A CN 201910399684 A CN201910399684 A CN 201910399684A CN 110038587 A CN110038587 A CN 110038587A
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catalyst
source
catalyst according
chloro
trifluoromethylpyridine
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CN110038587B (en
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张旭旺
王志钢
史振宇
李进
王炳春
王贤彬
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Dalian Heterogeneous Catalyst Co Ltd
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Dalian Heterogeneous Catalyst Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention discloses a kind of for synthesizing the catalyst and preparation method thereof of bis- chloro-5-trifluoromethylpyridine of 2,3-.The preparation of catalyst uses mechanical mixing, and silicon source, source of iron, manganese source and cerium source are thoroughly mixed first, are then granulated with pelletizer, then carries out compression molding with tablet press machine, final high temperature roasts to obtain catalyst.Gained catalyst of the invention has the characteristics that preparation process is simple and convenient to operate, and present invention catalyst obtained is used for the synthetic reaction of 2,3-, bis- chloro-5-trifluoromethylpyridine, has the characteristics that high conversion rate, stability are good.

Description

A kind of catalyst and its preparation for synthesizing bis- chloro-5-trifluoromethylpyridine of 2,3- Method
Technical field
The present invention relates to a kind of for synthesizing the preparation method of the catalyst of bis- chloro-5-trifluoromethylpyridine of 2,3-.
Background technique
2,3- bis- chloro-5-trifluoromethylpyridines (2,3,52DCTF) are a kind of centres important in fluoro nitrogen heterocycles pesticide Body.The pesticide synthesized by it, a kind of such as fluazifop, the standing grain spirit of chlorine fluorine second, the herbicides such as haloxyfop, they have drug effect Height, toxicity is low, pollutes the features such as small；Another kind of such as chlorfluazuron process for preparation of benzoylurea compounds, the mechanism of action is unique, has height The distinguishing features such as effect, less toxic, environmentally friendly.
In prior art by Japanese Shi Yuan industry companies develop 2,3-, bis- chloro-5-trifluoromethylpyridine be with 3- methyl pyrrole Pyridine is primary raw material, is reacted simultaneously at 350-450 DEG C in the presence of chlorine, hydrogen fluoride catalyst in a special reactor. Generate the product and there was only 40%, by-product is more, and tar is difficult to separate more, product purity is low only 95% content, another equipment is difficult It solves.
Summary of the invention
The invention discloses one kind for synthesizing the chloro- 5- fluoroform of 2,3- bis- with chlorine by 2- chloro-5-trifluoromethylpyridine The preparation method of the catalyst of yl pyridines, this kind of preparation method have the characteristics that preparation process is simple and convenient to operate, institute of the present invention The catalyst of acquisition is used for the synthetic reaction of 2,3-, bis- chloro-5-trifluoromethylpyridine, with the good spy of high conversion rate, stability Point.
The present invention provides a kind of for synthesizing the catalyst of bis- chloro-5-trifluoromethylpyridine of 2,3-, and the catalyst is by matter Amount score is respectively 70%~80%, 20%~30%, 0.1%~2%, 0.1%~3% aluminium oxide, iron oxide, titanium dioxide Manganese, cerium sesquioxide composition.The preparation of catalyst uses mechanical mixing, and silicon source, source of iron, manganese source and cerium source are sufficiently stirred first Mixing is mixed, is then granulated with pelletizer, then carries out compression molding with tablet press machine, final high temperature roasts to obtain catalyst.
Further, in the above-mentioned technical solutions, the silicon source is aluminium oxide.
Further, in the above-mentioned technical solutions, the source of iron is iron oxide.
Further, in the above-mentioned technical solutions, the manganese source is manganese dioxide.
Further, in the above-mentioned technical solutions, the cerium source is cerium sesquioxide.
Further, in the above-mentioned technical solutions, the mesh number that the pelletizer is granulated is between 30~40 mesh.
Further, in the above-mentioned technical solutions, the density that the pelletizer is granulated is in 0.26~0.3g/cm3Between.
Further, in the above-mentioned technical solutions, the maturing temperature of tabletting machine molding rear catalyst is 450 ~550 DEG C, calcining time is 4~6h.
Further, in the above-mentioned technical solutions, the intensity of the catalyst after the roasting 120~150N/cm it Between.
The present invention uses mechanical mixing, by aluminium oxide, iron oxide, manganese dioxide, cerium sesquioxide according to certain mass Than being granulated, tabletting, catalyst of the invention has the characteristics that preparation process is simple and convenient to operate, and the present invention is obtained Catalyst is used for the synthetic reaction of 2,3-, bis- chloro-5-trifluoromethylpyridine, has the characteristics that high conversion rate, stability are good.
The preparation method of bis- chloro-5-trifluoromethylpyridine of 2,3- of the invention is made combined with specific embodiments below further Illustrate, but content not thereby limiting the invention.
Specific embodiment
Embodiment 1
300g aluminium oxide, 80g iron oxide, 5g manganese dioxide, 6g cerium sesquioxide are thoroughly mixed, then with granulation Machine is granulated, and takes between 30~40 mesh and density is in 0.26~0.3g/cm3Between particle carry out compression molding, last 550 DEG C of high temperature Roasting 5h obtains catalyst CCG-M1.
Embodiment 2
300g aluminium oxide, 90g iron oxide, 5g manganese dioxide, 6g cerium sesquioxide are thoroughly mixed, then with granulation Machine is granulated, and takes between 30~40 mesh and density is in 0.26~0.3g/cm3Between particle carry out compression molding, last 550 DEG C of high temperature Roasting 5h obtains catalyst CCG-M2.
Embodiment 3
300g aluminium oxide, 80g iron oxide, 6g manganese dioxide, 6g cerium sesquioxide are thoroughly mixed, then with granulation Machine is granulated, and takes between 30~40 mesh and density is in 0.26~0.3g/cm3Between particle carry out compression molding, last 550 DEG C of high temperature Roasting 5h obtains catalyst CCG-M3.
Embodiment 4
300g aluminium oxide, 80g iron oxide, 5g manganese dioxide, 6g cerium sesquioxide are thoroughly mixed, then with granulation Machine is granulated, and takes between 30~40 mesh and density is in 0.26~0.3g/cm3Between particle carry out compression molding, last 550 DEG C of high temperature Roasting 6h obtains catalyst CCG-M4.
Application examples
The performance of 2- chloro-5-trifluoromethylpyridine chlorination is carried out to comparative example and the resulting catalyst sample of embodiment respectively Evaluation.
(1) 4g 2- chloro-5-trifluoromethylpyridine is uniformly mixed with 8g carbon tetrachloride, for use；(2) after being ground up, sieved 20-40 mesh catalyst weigh 4g and be filled in position among reactor, the mixed of nitrogen and hydrogen is passed through with the speed of 20ml/min Gas is closed, is warming up within 4 hours 480 DEG C, activates 1h；(3) hydrogen is closed, logical nitrogen is continued and is cooled to 300 DEG C；(4) nitrogen is closed, Chlorine regulating valve is opened, is passed through chlorine speed control in 20ml/min；Restart feed pump, controls the chloro- 5- fluoroform of raw material 2- The mass space velocity of yl pyridines is 1h-1；(5) material enters receiver, 0.5h sampling analysis (6) experiment after condenser condenses 12h sampling analysis after charging.
Reaction result is analyzed using gas-chromatography, the Evaluation results of catalyst obtained by comparative example and embodiment It is listed in Table 1 below.
Table 1

Claims (9)

1. a kind of for synthesizing the catalyst of bis- chloro-5-trifluoromethylpyridine of 2,3-, it is characterised in that: the catalyst is by quality Score is respectively 70%~80%, 20%~30%, 0.1%~2%, 0.1%~3% aluminium oxide, iron oxide, titanium dioxide Manganese, cerium sesquioxide composition；
The preparation of catalyst uses mechanical mixing, the specific steps are as follows:
(1) silicon source, source of iron, manganese source and cerium source are sufficiently stirred, are uniformly mixed；
(2) it is granulated with pelletizer, then carries out compression molding with tablet press machine；
(3) high-temperature roasting obtains catalyst.
2. catalyst according to claim 1, it is characterised in that: silicon source is aluminium oxide.
3. catalyst according to claim 1, it is characterised in that: source of iron is iron oxide.
4. catalyst according to claim 1, it is characterised in that: manganese source is manganese dioxide.
5. catalyst according to claim 1, it is characterised in that: cerium source is cerium sesquioxide.
6. catalyst according to claim 1, it is characterised in that: the mesh number that pelletizer is granulated is between 30~40 mesh.
7. catalyst according to claim 1, it is characterised in that: the density that pelletizer is granulated is in 0.26~0.3g/cm3It Between.
8. catalyst according to claim 1, it is characterised in that: tabletting machine molding rear catalyst maturing temperature be 450~550 DEG C, calcining time is 4~6h.
9. catalyst according to claim 1 or 8, it is characterised in that: the intensity of the catalyst after roasting 120~ Between 150N/cm.
CN201910399684.XA 2019-05-14 2019-05-14 Catalyst for synthesizing 2, 3-dichloro-5-trifluoromethylpyridine and preparation method thereof Active CN110038587B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288718A (en) * 2013-06-26 2013-09-11 联化科技股份有限公司 Preparation method of 2-chloro-5-tirfluoromethylpyridine
CN104557683A (en) * 2013-10-09 2015-04-29 郁建涵 Preparation method of 2,3-dichloro-5-trifluoromethylpyridine
CN105013517A (en) * 2014-04-16 2015-11-04 浙江化工院科技有限公司 Catalyst for preparing 3-trifluoromethyl pyridine
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
US20180057459A1 (en) * 2013-06-14 2018-03-01 Cheminova A/S Method for producing 2,3-dichloro-5-(trichloromethyl)pyridine
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180057459A1 (en) * 2013-06-14 2018-03-01 Cheminova A/S Method for producing 2,3-dichloro-5-(trichloromethyl)pyridine
CN103288718A (en) * 2013-06-26 2013-09-11 联化科技股份有限公司 Preparation method of 2-chloro-5-tirfluoromethylpyridine
CN104557683A (en) * 2013-10-09 2015-04-29 郁建涵 Preparation method of 2,3-dichloro-5-trifluoromethylpyridine
CN105013517A (en) * 2014-04-16 2015-11-04 浙江化工院科技有限公司 Catalyst for preparing 3-trifluoromethyl pyridine
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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