CN109174168B - Catalyst for preparing 2-methylpyridine by pyridine alkylation, preparation method and application - Google Patents
Catalyst for preparing 2-methylpyridine by pyridine alkylation, preparation method and application Download PDFInfo
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- CN109174168B CN109174168B CN201811258682.0A CN201811258682A CN109174168B CN 109174168 B CN109174168 B CN 109174168B CN 201811258682 A CN201811258682 A CN 201811258682A CN 109174168 B CN109174168 B CN 109174168B
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Abstract
The invention discloses a catalyst for preparing 2-methylpyridine by pyridine alkylation, which comprises a matrix, a first auxiliary agent and a second auxiliary agent; the matrix is a sodium molecular sieve, the first auxiliary agent is one or more of Ba, Mg, Ni, Ca and Fe, and is beneficial to improving the conversion rate of pyridine, and the second auxiliary agent is one or more of Co, Bi, Cu and Zn, and is beneficial to improving the selectivity of 2-methylpyridine; and introducing the first auxiliary agent and the second auxiliary agent onto the matrix by adopting an ion exchange method or an impregnation method. The invention also discloses a method for preparing 2-methylpyridine by catalyzing pyridine alkylation by using the catalyst, wherein methanol and pyridine are used as reaction raw materials, nitrogen is used as carrier gas, and products such as 2-methylpyridine and the like are obtained by reaction. The first auxiliary agent in the catalyst is beneficial to improving the conversion rate of pyridine, the second auxiliary agent can improve the selectivity of 2-methylpyridine, the 2-methylpyridine can be prepared from methanol and pyridine with high selectivity, and the catalyst has good regeneration performance.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing 2-methylpyridine by pyridine alkylation, and a preparation method and application thereof.
Background
2-methylpyridine is an important chemical intermediate and has wide application in the field of fine chemical engineering. 2-methylpyridine can be used for preparing 2-vinylpyridine, and butadiene styrene-pyridine latex prepared by copolymerizing 2-vinylpyridine with butadiene and styrene is an important raw material in the rubber industry; the 2-methylpyridine is also used in pharmaceutical industry for preparing pyriminoxidil, additives of long-acting sulfonamides, anti-silicosis drugs, laxatives and film sensitizers, dye intermediates, rubber accelerators, etc. At present, the production process routes of 2-methylpyridine at home and abroad mainly comprise: (1) acetaldehyde and ammonia gas phase method produce 2-methylpyridine and 4-methylpyridine, but its product is complicated, 2-methylpyridine mole yield is lower; (2) the boiling point of the product is close to that of the 2-methylpyridine prepared from ethylene or acetylene and ammonia, and the separation is difficult; (3) the process for producing the 2-methylpyridine by using the acetone and the acrylonitrile as raw materials has two steps of reaction and more side reactions.
At present, the process for preparing 2-methylpyridine is mostly improved and optimized on the basis of the traditional process route. Chinese patent application CN1869023A discloses a method for synthesizing 2-methylpyridine by acetylene acetonitrile, which is to prepare a crude product containing more than 90% of 2-methylpyridine by catalyzing acetylene and acetonitrile at the temperature of 130-. The method needs to react under the anhydrous and anaerobic conditions, needs to carry out non-oxidation treatment on raw materials of acetonitrile and an organic cobalt catalyst, has a complex process and can not carry out continuous production. Chinese patent CN105384683A discloses a method for producing 2-methylpyridine and 4-methylpyridine, which uses aniline as raw material, and makes it pass through a fixed bed reactor filled with molecular sieve to produce the mixture of diphenylamine, 2-methylpyridine, 4-methylpyridine, acridine and 4-aminobiphenyl, etc. Because the product has complex types and can be separated only by multistage rectification, the post-treatment cost is higher. Chinese patent CN1886195A discloses a method for synthesizing 2-methylpyridine and 4-methylpyridine, which uses acetaldehyde and ammonia gas as raw materials, and uses a base material carrying heteropoly acid as a catalyst to prepare 2-methylpyridine and 4-methylpyridine, but the conversion rate of acetaldehyde to methylpyridine in the given examples is only 70% at most, and the specific composition of methylpyridine is not given. No report on the preparation of 2-methylpyridine by alkylation of pyridine with methanol is available at present.
Disclosure of Invention
Aiming at the problems of more side reactions and difficult separation of products in the existing 2-methylpyridine production process, the invention provides a catalyst for preparing 2-methylpyridine by directly alkylating pyridine, and the catalyst is used for preparing 2-methylpyridine by alkylating pyridine, so that high-selectivity preparation of 2-methylpyridine can be realized, and a new thought is provided for industrial production.
The purpose of the invention is realized by the following technical scheme:
a catalyst for preparing 2-methylpyridine by pyridine alkylation comprises a substrate, a first auxiliary agent and a second auxiliary agent; the matrix is a sodium type molecular sieve; the first auxiliary agent is one or more of Ba, Mg, Ni, Ca and Fe; the second auxiliary agent is one or more of Co, Bi, Cu and Zn.
The sodium type molecular sieve is one or more of a NaX molecular sieve, a NaY molecular sieve and a Nabeta molecular sieve, and preferably one or more of a NaX molecular sieve and a NaY molecular sieve;
the catalyst is prepared by taking a sodium type molecular sieve as a matrix and respectively introducing a first auxiliary agent and a second auxiliary agent by an impregnation method or an ion exchange method.
Preferably, the catalyst is prepared by taking a sodium type molecular sieve as a matrix and respectively introducing a first auxiliary agent by an ion exchange method and a second auxiliary agent by an impregnation method.
The ion exchange degree in the ion exchange method for introducing the first auxiliary agent is 10-100%, preferably 50-100%; the loading amount of the second auxiliary agent is 1-20%, preferably 1-10% of the molecular sieve matrix.
The invention also aims to provide a preparation method of the catalyst for preparing 2-methylpyridine by pyridine alkylation, which comprises the following steps:
step (1), preparing a molecular sieve precursor containing a first auxiliary agent: carrying out ion exchange on the sodium type molecular sieve and a nitrate solution of a first auxiliary agent, washing, drying and roasting to prepare a molecular sieve precursor containing the first auxiliary agent;
step (2), introducing a second auxiliary agent by an impregnation method: and (2) dipping the molecular sieve precursor obtained in the step (1) and a nitrate solution of a second auxiliary agent, drying and roasting to obtain the required catalyst.
In the step (1), the mass fraction of the nitrate of the first auxiliary agent is 1.5-15%; the mass ratio of the sodium type molecular sieve to the nitrate solution of the first auxiliary agent is 1: 5-20.
The conditions of ion exchange were: exchanging for 1-3 times at 40-90 deg.C, and each time for 5-24 hr to reach the desired ion exchange degree.
The washing solvent is one or more of deionized water, methanol, ethanol and acetone.
The drying conditions are as follows: drying at 60-120 deg.C for 2-24 hr.
The roasting conditions are as follows: roasting at the temperature of 350-700 ℃ for 2-6 h.
In the step (2), the dipping treatment comprises the following steps: dissolving nitrate of a second auxiliary agent into water with the saturated water absorption amount of 1-2 times of that of a sodium type molecular sieve or a molecular sieve precursor containing the first auxiliary agent to prepare a nitrate solution of the second auxiliary agent; mixing and pulping a molecular sieve precursor containing a first auxiliary agent and a nitrate solution of a second auxiliary agent, and soaking for 5-24h at the temperature of 30-80 ℃.
The drying conditions are as follows: drying at 60-120 deg.C for 2-24 hr.
The roasting conditions are as follows: roasting at the temperature of 350-700 ℃ for 2-6 h.
In the invention, an inductively coupled plasma emission spectrometer (ICP-OES) is adopted to measure the ion exchange degree.
Another object of the present invention is to provide a method for preparing 2-methylpyridine by pyridine alkylation by using the catalyst, which comprises: the mixture of pyridine and methanol is used as a raw material, nitrogen is used as a carrier gas, and the mixture of pyridine and methanol and nitrogen are mixed in a preheater and then pass through a fixed bed reactor filled with the catalyst to react at the temperature of 300 ℃ and 500 ℃ and under the pressure of 0.1-1MPa to obtain 2-methylpyridine; wherein the molar ratio of the methanol to the pyridine is 1-10:1, and the proper excess of the methanol can promote the reaction to be carried out in the forward direction, so the molar ratio of the methanol to the pyridine is preferably 2-10: 1; the weight hourly space velocity of the mixture of pyridine and methanol is 1-10h-1(ii) a The volume space velocity of the nitrogen is 100-1200h-1。
The invention has the beneficial effects that:
according to the invention, a first auxiliary agent and a second auxiliary agent are introduced into a sodium type molecular sieve for modification, the prepared catalyst can be used for preparing 2-methylpyridine by pyridine alkylation, the first auxiliary agent is beneficial to improving the conversion rate of pyridine, and the second auxiliary agent can improve the selectivity of 2-methylpyridine. Compared with the traditional method, the catalyst has the advantages of simple operation, high selectivity, good catalyst regeneration performance and the like when used for catalyzing methanol and pyridine to prepare the 2-methylpyridine, and provides a new idea for the production of the 2-methylpyridine.
Detailed Description
The technical scheme of the invention is described in detail by combining the following embodiments:
example 1
Step (1), weighing 5.1282g Mg (NO)3)2·6H2Adding water into O to prepare 100g of solution, exchanging 10g of NaX molecular sieve with the magnesium nitrate solution at 40 ℃ for 5 hours, filtering after the exchange is finished, and washing the obtained solid with 100mL of deionized water for three times; drying the obtained solid at 110 ℃ for 2h, roasting at 550 ℃ for 4h to obtain a precursor A, and measuring the ion exchange degree of the precursor A by ICP-OES to be 52%;
step (2), weighing 1.9009g of Cu (NO)3)2·3H2Dissolving O to prepare 15mL of aqueous solution (the saturated water absorption of the precursor A needs to be measured before preparation, and the specific method is that 10g of the precursor A is taken, deionized water is dropwise added into the precursor A and continuously stirred, when 8.5mL of deionized water is dropwise added and no dry powder exists, the precursor A is saturated in water absorption, and the water absorption rate of the precursor A is 0.85 mL/g). Dropwise adding a copper nitrate solution into the precursor A under the heating of a water bath at 50 ℃, stirring and pulping, and keeping at 50 ℃ for 5 hours; the obtained slurry-like substance is dried for 10h at the temperature of 80 ℃ and roasted for 4h at the temperature of 550 ℃ to obtain the required catalyst.
Example 2
Step (1), weighing 1.4539g of Ni (NO)3)2·6H2Adding water to O to prepare 50g of solution, exchanging 10g of NaY molecular sieve with the nickel nitrate solution at 80 ℃ for 15h, filtering after the exchange is finished, and using 100mWashing the obtained solid with L ethanol for three times, and repeatedly exchanging once according to the same operation conditions; drying the obtained solid at 120 ℃ for 10h, roasting the solid at 350 ℃ for 3h to obtain a precursor B, and measuring the ion exchange degree of the precursor B by ICP-OES to be 79%;
step (2), weighing 0.4939gCo (NO)3)2·6H2Preparing 9.5mL of water solution from O (the water absorption of the precursor B is 0.95mL/g), dropwise adding the cobalt nitrate solution into the precursor B under the heating of water bath at 60 ℃, stirring and pulping, and keeping the temperature at 60 ℃ for 20 hours; the obtained slurry-like substance is dried for 24 hours at 120 ℃ and roasted for 3 hours at 350 ℃ to obtain the required catalyst.
Example 3
Step (1), weighing 29.134g Ba (NO)3)2Adding water to prepare 200g of solution, exchanging 10g of NaY molecular sieve with the barium nitrate solution at 70 ℃ for 10 hours, filtering after the exchange is finished, washing the obtained solid with 100mL of methanol for three times, and repeatedly exchanging twice according to the same operation condition; drying the obtained solid at 60 ℃ for 12h, roasting at 700 ℃ for 2h to obtain a precursor C, and measuring the ion exchange degree of the precursor C by ICP-OES to be 99%;
step (2), weighing 2.2744g Zn (NO)3)2·6H2Preparing 16mL of water solution from O (the water absorption of the precursor C is 0.8mL/g), dropwise adding the zinc nitrate solution into the precursor C under the heating of water bath at 30 ℃, stirring and pulping, and keeping the temperature at 30 ℃ for 24 hours; the obtained slurry-like substance is dried for 20h at 60 ℃ and roasted for 6h at 600 ℃ to obtain the required catalyst.
Example 4
Step (1), weighing 16.16g Fe (NO)3)3·9H2Adding water into O to prepare 200g of solution, exchanging 10g of Nabeta molecular sieve with ferric nitrate solution at 90 ℃ for 24h, filtering after the exchange is finished, washing the obtained solid with 100mL of acetone for three times, and repeating the exchange twice according to the same operation condition; drying the obtained solid at 80 ℃ for 20h, roasting at 600 ℃ for 6h to obtain a precursor D, and measuring the ion exchange degree of the precursor D by ICP-OES to be 95%;
step (2), weighing 0.2321g Bi (NO)3)3·5H2O is prepared into 10mL of aqueous solution (the water absorption of the precursor D is 0.85mL/g), and the bismuth nitrate solution is dropwise added into the precursor under the heating of water bath at 70 DEG CStirring and pulping in the body D, and keeping the temperature at 70 ℃ for 20 hours; the obtained slurry-like substance is dried for 10h at 110 ℃, and is roasted for 10h at 550 ℃ to obtain the required catalyst.
Example 5
Step (1), weighing 3.1423g Ca (NO)3)2·4H2Adding water into O to prepare 150g of solution, exchanging 10g of NaX molecular sieve with calcium nitrate solution at 90 ℃ for 20h, filtering after the exchange is finished, washing the obtained solid with 100mL of water for three times, and repeatedly exchanging once according to the same operation condition; drying the obtained solid at 120 ℃ for 24h, roasting at 550 ℃ for 6h to obtain a precursor E, and measuring the ion exchange degree of the precursor E by ICP-OES to be 66%;
step (2), weighing 4.9386gCo (NO3)2·6H2Preparing 15mL of water solution from O (the water absorption of the precursor E is 0.9mL/g), dropwise adding the cobalt nitrate solution into the precursor E under the heating of water bath at 80 ℃, stirring and pulping, and keeping the temperature at 80 ℃ for 15 hours; the obtained slurry-like substance is dried for 2h at 120 ℃ and roasted for 4h at 700 ℃ to obtain the required catalyst.
Example 6
Step (1), weighing 29.134g Ba (NO)3)2Adding water to prepare 200g of solution, exchanging 10g of NaX molecular sieve with the barium nitrate solution at 70 ℃ for 10 hours, filtering after the exchange is finished, washing the obtained solid with 100mL of methanol for three times, and repeatedly exchanging twice according to the same operation condition; drying the obtained solid at 60 ℃ for 12h, roasting at 700 ℃ for 2h to obtain a precursor F, and measuring the ion exchange degree by ICP-OES to be 98%;
step (2), weighing 2.2744g Zn (NO)3)2·6H2Preparing 16mL of water solution from O (the water absorption of the precursor F is 0.8mL/g), dropwise adding the zinc nitrate solution into the precursor F under the heating of water bath at 30 ℃, stirring and pulping, and keeping the temperature at 30 ℃ for 24 hours; the obtained slurry-like substance is dried for 20h at 60 ℃ and roasted for 6h at 600 ℃ to obtain the required catalyst.
Example 7
Step (1), weighing 29.134g Ba (NO)3)2Adding water to prepare 200g of solution, exchanging 10g of Nabeta molecular sieve with barium nitrate solution at 70 ℃ for 10h, filtering after the exchange is finished, washing the obtained solid with 100mL of methanol for three times, and adding water to prepare the solutionRepeatedly exchanging twice according to the same operating conditions; drying the obtained solid at 60 ℃ for 12h, roasting at 700 ℃ for 2h to obtain a precursor G, and measuring the ion exchange degree of the precursor G by ICP-OES to be 99%;
step (2), weighing 2.2744g Zn (NO)3)2·6H2Preparing 16mL of water solution from O (the water absorption of the precursor G is 0.85mL/G), dropwise adding the zinc nitrate solution into the precursor G under the heating of water bath at 30 ℃, stirring and pulping, and keeping the temperature at 30 ℃ for 24 hours; the obtained slurry-like substance is dried for 20h at 60 ℃ and roasted for 6h at 600 ℃ to obtain the required catalyst.
Comparative example 1
Weighing 2.2744g Zn (NO) by taking 10g NaY molecular sieve3)2·6H2Preparing 16mL of water solution from O, dropwise adding the zinc nitrate solution into the NaY molecular sieve under the heating of water bath at 30 ℃, stirring and pulping, and keeping the temperature at 30 ℃ for 24 hours; the obtained slurry-like substance is dried for 20h at 60 ℃ and roasted for 6h at 600 ℃ to obtain the required catalyst.
Comparative example 2
Weighing 29.134g Ba (NO)3)2Adding water to prepare 200g of solution, exchanging 10g of NaY molecular sieve with the barium nitrate solution at 70 ℃ for 10 hours, filtering after the exchange is finished, washing the obtained solid with 100mL of methanol for three times, and repeatedly exchanging twice according to the same operation condition; drying the obtained solid at 60 ℃ for 12h, roasting the solid at 700 ℃ for 2h to obtain the required catalyst, and measuring the ion exchange degree by ICP-OES to be 98%.
Comparative example 3
Roasting the NaY molecular sieve at 700 ℃ for 2h to obtain the required catalyst.
Performance evaluation of the catalyst
The catalytic performance of the catalyst was evaluated using a fixed bed reactor.
The specific method comprises the following steps: 5g of 20-40 mesh catalyst is filled in a constant temperature section of a fixed bed reactor, and the reactor adopts a reaction tube with the inner diameter of 19mm and the tube length of 700 mm. Before the reaction, nitrogen is adopted to activate the catalyst, and the space velocity of the nitrogen is 1000h-1Activation time is 3h at 550 ℃. Cooling to reaction temperature after activation, reducing nitrogen flow rate to required flow rate, introducing mixture of methanol and pyridine by using a metering pump,and uniformly mixing the mixture of pyridine and methanol with nitrogen in a preheater, allowing the mixture to pass through a fixed bed reactor, reacting for 5h, keeping the temperature through a pipeline to a gas chromatography six-way valve, and performing online sample injection analysis by chromatography.
Table 1 catalyst performance investigation
Note: the catalyst of example 3 stops feeding when the pyridine conversion rate is less than 30%, air is introduced, charking is carried out at 500 ℃ for 3h for regeneration, then feeding is carried out again, and the reaction is carried out again under the same conditions after three times of regeneration.
Claims (8)
1. A catalyst for preparing 2-methylpyridine by pyridine alkylation is characterized in that the catalyst is prepared by taking a sodium type molecular sieve as a matrix, and respectively introducing a first auxiliary agent by an ion exchange method and a second auxiliary agent by an impregnation method; the matrix is a sodium type molecular sieve, and the sodium type molecular sieve is one or more of a NaX molecular sieve, a NaY molecular sieve and a Nabeta molecular sieve; the first auxiliary agent is one or more of Ba, Mg, Ni, Ca and Fe, and the ion exchange degree of the first auxiliary agent is 10-100%; the second auxiliary agent is one or more of Co, Bi, Cu and Zn, and the loading amount of the second auxiliary agent is 1-20% of the mass of the molecular sieve matrix.
2. The catalyst of claim 1, wherein the sodium type molecular sieve is one or more of NaX molecular sieve and NaY molecular sieve.
3. The catalyst according to claim 1, characterized in that the first auxiliary agent has an ion exchange degree of 50-100%; the loading amount of the second auxiliary agent is 1-10% of the molecular sieve matrix weight.
4. The method for preparing the catalyst for pyridine alkylation to prepare 2-methylpyridine according to claim 1, comprising:
step (1), preparing a molecular sieve precursor containing a first auxiliary agent: carrying out ion exchange on the sodium type molecular sieve and a nitrate solution of a first auxiliary agent, washing, drying and roasting to prepare a molecular sieve precursor containing the first auxiliary agent;
step (2), introducing a second auxiliary agent by an impregnation method: and (2) dipping the molecular sieve precursor obtained in the step (1) and a nitrate solution of a second auxiliary agent, drying and roasting to obtain the required catalyst.
5. The method for preparing the catalyst according to claim 4, wherein in the step (1), the mass fraction of the nitrate of the first auxiliary agent is 1.5-15%; the mass ratio of the sodium type molecular sieve to the nitrate solution of the first auxiliary agent is 1: 5-20; the conditions of ion exchange were: exchanging for 1-3 times at 40-90 deg.C, each time for 5-24 hr.
6. The method for preparing a catalyst according to claim 4, wherein in the step (2), the impregnation treatment is: taking a sodium type molecular sieve or deionized water with the amount which is 1-2 times of the saturated water absorption capacity of a molecular sieve precursor containing a first auxiliary agent, and dissolving nitrate of a second auxiliary agent to prepare a nitrate solution of the second auxiliary agent; mixing and pulping a molecular sieve precursor containing a first auxiliary agent and a nitrate solution of a second auxiliary agent, and soaking for 5-24h at the temperature of 30-80 ℃.
7. A process for preparing 2-methylpyridine by alkylation of pyridine with the catalyst of claim 1, which comprises: taking a mixture of pyridine and methanol as a raw material, taking nitrogen as a carrier gas, mixing the mixture of pyridine and methanol with the nitrogen, and then reacting the mixture with the nitrogen through a fixed bed reactor filled with the catalyst in the claim 1 at the temperature of 300 ℃ and 500 ℃ and under the pressure of 0.1-1MPa to obtain 2-methylpyridine; wherein the molar ratio of the methanol to the pyridine is 1-10: 1; the weight hourly space velocity of the mixture of pyridine and methanol is 1-10h-1(ii) a The volume space velocity of the nitrogen is 100-1200h-1。
8. The process according to claim 7, wherein the molar ratio of methanol to pyridine is 2-10: 1.
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