CN115368298B - Method for preparing 3-methylpyridine - Google Patents
Method for preparing 3-methylpyridine Download PDFInfo
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- CN115368298B CN115368298B CN202211146035.7A CN202211146035A CN115368298B CN 115368298 B CN115368298 B CN 115368298B CN 202211146035 A CN202211146035 A CN 202211146035A CN 115368298 B CN115368298 B CN 115368298B
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- pyridine
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- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011973 solid acid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- WFERVLWLPNZDOV-UHFFFAOYSA-N O[Si](O)(O)OP(=O)=O Chemical compound O[Si](O)(O)OP(=O)=O WFERVLWLPNZDOV-UHFFFAOYSA-N 0.000 claims abstract description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- -1 so that on one hand Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 6
- 229960000892 attapulgite Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052625 palygorskite Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- DMGGLIWGZFZLIY-UHFFFAOYSA-N 3-methyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=C[N+]([O-])=C1 DMGGLIWGZFZLIY-UHFFFAOYSA-N 0.000 description 1
- 239000005875 Acetamiprid Substances 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
-
- 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
Abstract
The invention relates to a method for preparing 3-methylpyridine, which belongs to the technical field of chemical synthesis and comprises the following specific steps: pyridine and methanol are used as raw materials, and react in a fluidized bed reactor under the action of a supported heteropolyacid catalyst, and after the reaction is finished, the product is subjected to aftertreatment to obtain a 3-methylpyridine product and a recycled catalyst; according to the invention, pyridine and methanol are used as raw materials, one or more of solid acids such as phosphotungstic acid, phosphosilicic acid and phosphomolybdic acid are adopted to be loaded on active carbon or MCM-41 molecular sieve to prepare the supported heteropolyacid catalyst, so that on one hand, raw materials and catalyst ingredients are easy to obtain, the cost is low, continuous production can be realized, the supported heteropolyacid catalyst is prepared by adopting an isovolumetric impregnation method, heteropolyacid is effectively loaded on a carrier, the surface area of the heteropolyacid catalyst can be greatly increased, the stability and the service life of the heteropolyacid catalyst can be improved, the catalyst has high catalytic activity and selectivity, and the obtained product is easy to separate.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing 3-methylpyridine.
Background
Picoline, also known as beta-picoline, 3-Pi Kaolin, is an organic synthetic intermediate and solvent, is a colorless oily liquid, and has an unpleasant odor. Mixing with water, ethanol, and diethyl ether. The oxidant is inflammable when exposed to fire and high temperature; and the toxic nitrogen oxide gas is generated by heating. The intermediate is used as an intermediate of pesticides imidacloprid and acetamiprid in pesticide, is used for synthesizing a next-step intermediate 3-methylpyridine-N-oxide, and can also be used as a medical intermediate, a dye intermediate, a resin intermediate and the like.
Chinese patent CN201711019936.9 discloses a method for producing nano attapulgite composite catalyst for preparing 3-picoline, which comprises the following steps: adding the nano attapulgite crude ore into hydrochloric acid aqueous solution for separation and washing, then washing with silver nitrate solution, then heating and boiling with distilled water, and centrifugally washing to obtain acid modified nano attapulgite; mixing with zeolite molecular sieve, drying, grinding, calcining at high temperature to obtain nano attapulgite composite carrier; and adding the composite carrier into the silica sol for full adsorption, and drying and grinding to obtain the nano attapulgite composite catalyst. The method has the advantages of complex process flow, high cost consumption and inapplicability to industrial production.
Disclosure of Invention
The invention provides a method for preparing 3-methylpyridine, which aims to solve the problems of low yield, more byproducts and high cost in the existing method for synthesizing 3-methylpyridine.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing 3-methylpyridine, which comprises the following specific steps:
pyridine and methanol are used as raw materials, the reaction is carried out in a fluidized bed reactor under the conditions of the temperature of 200-400 ℃ and the pressure of 4-8MPa under the action of a supported heteropolyacid catalyst, and after the reaction is finished, the product is subjected to post-treatment to obtain a 3-methylpyridine product and a recycled catalyst.
Preferably, the molar ratio of pyridine to methanol is 1:2-4, more preferably, the molar ratio of pyridine to methanol is 1:2.5.
preferably, the supported heteropolyacid catalyst is used in an amount of 1 to 8% of the sum of the mass of pyridine and methanol.
Preferably, the material is held in the fluidized bed reactor for a period of time of from 10 to 60 minutes.
Wherein the supported heteropolyacid catalyst is obtained by supporting a solid acid solution on a carrier by an isovolumetric impregnation method, and the solid acid loading is 1-50wt%, more preferably 20-40%.
Preferably, the solid acid comprises one or more of phosphotungstic acid, phosphosilicic acid and phosphomolybdic acid which are mixed according to any proportion, and the carrier is active carbon or MCM-41 molecular sieve.
Preferably, the supported heteropolyacid catalyst is prepared as follows:
adding the solid acid aqueous solution and the carrier into a stirrer, uniformly mixing, standing for 10 hours, drying, and roasting at 350 ℃ for 6 hours to obtain the supported heteropolyacid catalyst, wherein the volume of the solid acid aqueous solution is the same as the pore volume of the carrier, and the mass of the solid acid aqueous solution is 30-40%.
The invention has the beneficial effects that:
according to the invention, pyridine and methanol are used as raw materials, one or more of solid acids such as phosphotungstic acid, phosphosilicic acid and phosphomolybdic acid are adopted and loaded on active carbon or MCM-41 molecular sieve to prepare a supported heteropolyacid catalyst, the supported heteropolyacid catalyst is reacted in a fluidized bed reactor, and the supported heteropolyacid catalyst is used for continuous production, so that on one hand, raw materials and catalyst ingredients are easily obtained, the cost is lower, meanwhile, continuous production can be realized, and the supported heteropolyacid catalyst is prepared by adopting an isovolumetric impregnation method, and heteropolyacid is effectively loaded on a carrier, so that the surface area of the supported heteropolyacid catalyst can be greatly increased, the stability and the service life of the supported heteropolyacid catalyst can be improved, the supported heteropolyacid catalyst has high catalytic activity and selectivity, the obtained product is easy to separate, and the yield of the target product 3-methylpyridine prepared by the method is up to more than 80%.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The supported heteropolyacid catalyst is prepared by adopting different carriers and solid acid:
A、35％H 3 PW 12 O 40 activated carbon is prepared by the following steps:
using 35% phosphotungstic acid aqueous solution by mass fraction, using active carbon as carrier, the volume of impregnating solution is the same as the pore volume of active carbon, stirring them uniformly, standing for 10h, drying, roasting at 350 deg.C for 6h to obtain 35% H 3 PW 12 O 40 Activated carbon.
B、35％H 3 PW 12 O 40 MCM-41 preparation method is the same as 35% H 3 PW 12 O 40 Activated carbon, only the carrier activated carbon is replaced by MCM-41 molecular sieve.
C、35％H 4 SiW 12 O 40 Preparation method of activated carbon and 35% H 3 PW 12 O 40 Activated carbon, wherein the mass fraction of the activated carbon is 35% of the mass fraction of the aqueous solution of phosphotungstic acid is replaced by 35% of H 4 SiW 12 O 40 An aqueous solution.
D、35％H 4 SiW 12 O 40 MCM-41 preparation method is the same as 35% H 4 SiW 12 O 40 Activated carbon, only the carrier is replaced by MCM-41 molecular sieve.
E、35％H 4 PMo 12 O 40 Preparation method of activated carbon and 35% H 3 PW 12 O 40 Preparation method of activated carbon comprises replacing 35% by mass of water solution of phosphotungstic acid with 35% by mass of H 4 PMo 12 O 40 An aqueous solution.
F、35％H 4 PMo 12 O 40 MCM-41 preparation method is the same as 35% H 4 PMo 12 O 40 Activated carbon, only the carrier is replaced by MCM-41 molecular sieve.
Taking A, B, C, D, E, F group of obtained products as a catalyst, and firstly, according to the molar ratio of pyridine to methanol of 1:2.5 preparation of 79.1g pyridine, 80.1g methanol mixture, 6g catalyst was packed in the catalyst layer. Opening a heating jacket on the outer layer of the fluidized bed reactor, opening a nitrogen pipe valve to introduce nitrogen so as to fluidize the supported catalyst, opening a pyridine and methanol feed inlet valve to introduce mixed liquid so as to enable pyridine and methanol to react with the catalyst layer in the fluidized bed reactor, setting a program to start heating, and discharging the generated product through a discharge hole, condensing and collecting the product, wherein the reaction temperature is 380 ℃, the pressure is 5MPa, and the reaction time is 40 min. The results are shown in Table 1.
TABLE 1 Effect of different supported heteropolyacid catalysts on 3-methylpyridine yield
| Catalyst | 3-methylpyridine yield/% |
| 35％H 3 PW 12 O 40 Activated carbon | 82.5 |
| 35％H 3 PW 12 O 40 /MCM-41 | 79.4 |
| 35％H 4 SiW 12 O 40 Activated carbon | 77.5 |
| 35％H 4 SiW 12 O 40 /MCM-41 | 79.3 |
| 35％H 4 PMo 12 O 40 Activated carbon | 80.4 |
| 35％H 4 PMo 12 O 40 /MCM-41 | 81.4 |
From the data in Table 1, it is understood that the molar ratio of pyridine to methanol as the reaction raw materials was 1:2.5 ratio reaction for 40min, different supported heteropolyacid catalysts having different effects on 3-methylpyridine yield, wherein the supported type is 35% H 3 PW 12 O 40 The highest selectivity of activated carbon to 3-methylpyridine was 82.5%.
Example 2
A mixture of 79.1g of pyridine and 80.1g of methanol was prepared at a molar ratio of 1:2.5, and the catalyst layers were filled with catalysts of different masses. Opening a heating jacket on the outer layer of the fluidized bed reactor, opening a nitrogen pipe valve to introduce nitrogen so as to fluidize the supported catalyst, opening a pyridine and methanol feed inlet valve to introduce mixed liquid so as to enable pyridine and methanol to react with the catalyst layer in the fluidized bed reactor, setting a program to start heating, and discharging the generated product through a discharge hole, condensing and collecting the product, wherein the reaction temperature is 380 ℃, the pressure is 5MPa, and the reaction time is 40 min.
The mass of the catalyst is respectively verified to be 3g, 6g, 9g and 12g, and the yields of the 3-methylpyridine after the reaction are respectively 72.6%, 80.5%, 79.3% and 75.4%. It can be seen that the catalyst mass is increased when the molar ratio of pyridine to methanol is 1:2.5 at 380 ℃ and 5MPa for 40min, the yield of the target product is increased and then reduced, and the 3-methylpyridine yield is up to 80.5% when the catalyst mass is 7.5% of pyridine, so that the catalytic effect can be controlled by controlling the addition amount of the catalyst.
Example 3
The molar ratios of pyridine and methanol were verified to be 1:2.5, 1:5, 1:7.5, 1:10, respectively, mixed solutions, and 6g of the self-made supported catalyst was packed in the catalyst layer in the fluidized bed reactor. And opening a heating jacket on the outer layer of the fluidized bed reactor, opening a nitrogen pipe valve to introduce nitrogen so as to fluidize the supported catalyst, opening a pyridine and methanol feed inlet valve to introduce mixed liquid so as to enable pyridine and methanol to react with the catalyst layer in the fluidized bed reactor, setting a program to start heating, controlling the reaction temperature to 380 ℃, controlling the pressure to 5MPa, controlling the reaction time to 40min, discharging the generated product through a discharge hole, condensing and collecting the product, and the result is shown in Table 2.
TABLE 2 influence of different molar ratios of starting materials on the yield of 3-methylpyridine
| Molar ratio of raw materials | 3-methylpyridine yield/% |
| 1:2.5 | 79.5 |
| 1:5 | 77.4 |
| 1:7.5 | 75.1 |
| 1:10 | 73.9 |
As can be seen from Table 2, the higher the methanol content in the raw material, the lower the yield of 3-methylpyridine after 40 minutes of reaction at 380℃and 5MPa, and the yield of 3-methylpyridine can be improved by properly reducing the molar ratio of pyridine to methanol.
Example 4
79.1g of pyridine and 80.1g of methanol mixed solution are prepared according to the molar ratio of pyridine to methanol of 1:2.5, and 6g of self-made 35wt% H is filled in 3 PW 12 O 40 Catalyst layer of activated carbon in fluidized bed reactor. Opening a heating jacket at the outer layer of the fluidized bed reactor, opening a nitrogen pipe valve to introduce nitrogen so as to fluidize the supported catalyst, and opening a pyridine and methanol feed inlet valve to introduce mixed liquid so as to ensure that the pyridine and the methanol are mixed with each other in the fluidized bed reactorThe catalyst layer is reacted, the temperature is programmed to rise, the reaction temperature is 380 ℃, the pressure is 5MPa, the catalyst layer stays for different times, the generated product is discharged through a discharge hole, and then is condensed and collected, and the result is shown in a table 3.
TABLE 3 influence of different reaction times on the yield of 3-methylpyridine
| Reaction time (min) | Yield of 3-methylpyridine% |
| 20 | 78.3 |
| 30 | 79.6 |
| 40 | 81.6 |
| 50 | 80.5 |
| 60 | 77.6 |
As can be seen from Table 3, when 35wt% H is used 3 PW 12 O 40 When activated carbon is used as a catalyst, and the molar ratio of pyridine to methanol in the raw materials is 1:2.5 at 380 ℃ and 5MPa, the reaction time is long, the generation of 3-methylpyridine is facilitated, and the selectivity of 3-methylpyridine reaches 81.6% after 40min of reaction.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (4)
1. A method for preparing 3-methylpyridine, which is characterized by comprising the following specific steps:
pyridine and methanol are used as raw materials, under the action of a supported heteropolyacid catalyst, the reaction is carried out in a fluidized bed reactor at the temperature of 200-400 ℃ and the pressure of 4-8MPa, and after the reaction is finished, the product is subjected to post-treatment to obtain a 3-methylpyridine product and a recycled catalyst;
the preparation method of the supported heteropolyacid catalyst comprises the following steps:
adding the solid acid aqueous solution and the carrier into a stirrer, mixing, standing for 10 hours, drying, and roasting at 350 ℃ for 6 hours to obtain a supported heteropolyacid catalyst, wherein the volume of the solid acid solution is the same as the pore volume of the carrier, and the mass fraction of the solid acid aqueous solution is 30-40%;
the solid acid is formed by mixing one or more of phosphotungstic acid, phosphosilicic acid and phosphomolybdic acid according to any proportion;
the carrier is active carbon or MCM-41 molecular sieve.
2. A process for the preparation of 3-methylpyridine according to claim 1, wherein the molar ratio of pyridine to methanol is 1:2-4.
3. A process for the preparation of 3-methylpyridine as claimed in claim 1, wherein the supported heteropolyacid catalyst is used in an amount of 1 to 8% based on the sum of pyridine and methanol.
4. A process for the preparation of 3-methylpyridine as claimed in claim 1, wherein the residence time of the material in the fluidised bed reactor is from 10 to 60 minutes.
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| CN102249989A (en) * | 2011-06-03 | 2011-11-23 | 北京华地博源生化科技有限公司 | Method for preparing 3-methylpyridine by utilizing acrolein |
| CN105622365A (en) * | 2016-03-04 | 2016-06-01 | 沈阳化工大学 | Method for preparing diethoxymethane by supported heteropolyacid catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249989A (en) * | 2011-06-03 | 2011-11-23 | 北京华地博源生化科技有限公司 | Method for preparing 3-methylpyridine by utilizing acrolein |
| CN105622365A (en) * | 2016-03-04 | 2016-06-01 | 沈阳化工大学 | Method for preparing diethoxymethane by supported heteropolyacid catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 3-甲基吡啶合成工艺的研究进展;罗才武等;《化学工业与工程》;第35卷(第4期);第1.3.2节 * |
| 3-甲基吡啶合成工艺路线进展;姜枫等;《化工时刊》;第23卷(第10期);第2.5节 * |
| Selective synthesis of 3-picoline via the vapor-phase methylation of pyridine with methanol over Ni1-xCoxFe2O4(x=0,0.2,0.5,0.8 and 1.0) type ferrites;K.Sreekumar等;《Catalysis Letters》;第65卷;摘要、第102-104页 * |
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