CN112778195A - Method for preparing 3-methylpyridine by promoting reaction of acrolein and ammonia gas - Google Patents
Method for preparing 3-methylpyridine by promoting reaction of acrolein and ammonia gas Download PDFInfo
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- CN112778195A CN112778195A CN202110056446.6A CN202110056446A CN112778195A CN 112778195 A CN112778195 A CN 112778195A CN 202110056446 A CN202110056446 A CN 202110056446A CN 112778195 A CN112778195 A CN 112778195A
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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
- C07D213/06—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
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
- C07D213/12—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from unsaturated compounds
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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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
- C07D213/06—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
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
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Abstract
The invention discloses a method for promoting reaction of acrolein and ammonia gas to prepare 3-methylpyridine, and belongs to the field of chemical synthesis. The method is characterized in that under the existence of a catalyst, a certain amount of propylamine is added into a mixed raw material of acrolein and ammonia gas to synthesize the 3-methylpyridine, wherein the catalyst comprises rare earth HZSM-5/ZSM-11 cocrystallized zeolite. Compared with the prior art, the method for promoting the reaction of the acrolein and the ammonia gas to prepare the 3-methylpyridine has the advantages of simple process, high product yield and good popularization and application values.
Description
Technical Field
The invention relates to the field of chemical industry, and particularly provides a method for preparing 3-methylpyridine by promoting the reaction of acrolein and ammonia gas.
Background
3-methylpyridine is an important chemical raw material and is widely applied to the fields of medicines, pesticides, feeds, dyes, spices, rubber, resins, photosensitive materials, liquid crystals and the like.
The most widely used preparation method of 3-methylpyridine in the prior art is to prepare pyridine and 3-methylpyridine by adding a large amount of formaldehyde into raw materials on the basis of synthesizing 2-methylpyridine and 4-methylpyridine by acetaldehyde and ammonia gas phase method. Although the method is simple to operate, the generation of 4-methylpyridine is difficult to completely avoid, so that high-purity 3-methylpyridine is difficult to obtain.
In order to avoid the formation of 4-methylpyridine as much as possible, a process for producing 3-methylpyridine from acrolein as a raw material has been disclosed in the prior art. For example, patent publication No. CN108479847A discloses a "method for preparing a molecular sieve catalyst for the reaction of acrolein, propionaldehyde and ammonia". Although the method can improve the yield of the 3-methylpyridine and the pyridine base by utilizing a specific molecular sieve catalyst, the following defects still exist:
1. propionaldehyde is used as a main raw material, and is particularly activated, a polymerization inhibitor needs to be added in the transportation process, otherwise, explosion is caused by strong heat release of polymerization;
2. no matter how much propionaldehyde is added in the reaction process, a reaction outlet cannot be detected due to the fact that high polymers are generated through polymerization, and propionaldehyde exceeding the reaction amount cannot be reused.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the method for promoting the reaction of the acrolein and the ammonia gas to prepare the 3-methylpyridine, which has simple process and high product yield.
The technical scheme adopted by the invention for solving the technical problems is as follows: a process for preparing 3-methylpyridine by promoting the reaction between acrolein and ammonia gas features that under the existance of catalyst, a certain amount of propylamine is added to the mixture of acrolein and ammonia gas to synthesize 3-methylpyridine, and said catalyst contains HZSM-5/ZSM-11 cocrystallized zeolite.
The reaction scheme for the synthesis of 3-methylpyridine is as follows:
the acrolein carbonium ion reacts with acrolein to generate an intermediate transition state, and the intermediate transition state is cyclized and dehydrogenated with ammonia adsorbed by acid to generate 3-methylpyridine.
Preferably, a predetermined amount of propionaldehyde may be added to the mixed raw material of acrolein and ammonia gas.
Preferably, the propylamine is n-propylamine and/or isopropylamine. When n-propylamine and isopropylamine are used in combination, the molar ratio of n-propylamine to isopropylamine is preferably 1 (0.5 to 1.5), and particularly preferably 1 (0.8 to 1.2).
Preferably, the molar ratio of propylamine to acrolein is (0.1-1): 0.1-1, and particularly preferably (0.1-1): 1.
Preferably, the molar ratio of propionaldehyde to acrolein is (0-1): 1.
Preferably, the catalyst is prepared from rare earth HZSM-5/ZSM-11 cocrystallized zeolite and a binder, wherein the weight percentage of the binder in the mixture of the cocrystallized zeolite and the binder is 15-60%.
The rare earth HZSM-5/ZSM-11 cocrystallized zeolite is synthesized according to the method disclosed by the patent document with the publication number CN1137022, namely: mixing water glass and C2-C8The uniform mixture I consisting of diamine and water and the mixture II consisting of aluminum source, inorganic acid, rare earth element salt and water are mixed into glue under strong stirring, the glue is crystallized for 0.5 to 4 days at the temperature of 200 ℃ under stirring, the glue is rapidly cooled to the room temperature, the water is washed until the pH value is 8 to 9, and the zeolite is obtained after drying.
Preferably, the cocrystallized zeolite is subjected to ammonia exchange, extruded into strips or sprayed into balls with a binder, and roasted to prepare the corresponding catalyst. The sample shape can be particles, strips or microspheres after ball spraying.
Preferably, the binder is silica and/or alumina.
Preferably, the preparation of the 3-methylpyridine of the invention is carried out on a fixed bed or a fluidized bed, and the reaction conditions are preferably as follows: the pressure is 0.05-0.15Mpa, the temperature is 300-600 ℃, and the weight space velocity of acrolein is 0.1-1.5 h-1Particularly preferred are: the pressure is 0.08-0.12MPa, the temperature is 400 ℃ and 500 ℃, and the weight space velocity of acrolein is 0.1-1.0 h-1。
Compared with the prior art, the method for promoting the reaction of the acrolein and the ammonia gas to prepare the 3-methylpyridine has the following outstanding beneficial effects:
the use of propionaldehyde can be avoided, the process is simple and easy to control, and the product yield is high;
secondly, a proper amount of propionaldehyde can be added in the preparation process, so that the product yield is further improved.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Comparative example 1
8.5g of HZSM-5 molecular sieve and 1.5g of silica gel are kneaded, extruded, dried for 4 hours at 120 ℃, roasted for 3 hours at 540 ℃, and crushed into particles of 20-40 meshes to prepare the catalyst, namely Cat-A (the weight ratio of the HZSM-5 in the mixture of the molecular sieve and the silica is 85% w). 2g of the catalyst Cat-A is loaded into a fixed bed reactor for reaction, and the catalyst is N before the reaction2The atmosphere (60ml/min) is raised to 450 ℃, the constant temperature is activated for 2 hours, and then the acrolein weight space velocity is 1.0 hour under the conditions of 0.1MPa, 400 ℃ and-1acrolein/isopropylamine molar ratio of 1/0.5, ammonia: 12-18ml/min, N2Reacting for 5h under the condition of 50-60ml/min, connecting the outlet of the reactor with a condenser, connecting the outlet with a receiving bottle, and absorbing tail gas by three-stage washing. Analysis of the starting material and the product by gas chromatography, normalized by carbon balance, gave a yield of 45.2% for 3-methylpyridine and 15.3% for pyridine.
Example 1
8.5g of LaHZSM-5/ZSM-11 cocrystallized zeolite (La)2O3/Al2O30.12) and 1.5g of silica gel, extruding, drying at 120 ℃ for 4 hours, roasting at 540 ℃ for 3 hours, and crushing into particles of 20-40 meshes to obtain the catalyst which is marked as Cat-B (the weight ratio of the LaHZSM-5/ZSM-11 cocrystallized zeolite in the mixture of the molecular sieve and the silica dioxide is 85% w). The reaction was carried out under the same reaction conditions as in comparative example 1, and the yield of 3-methylpyridine was 65.2% and the yield of pyridine was 10.1%. The experimental results show that the specific co-crystallized zeolite catalyst of the present application has a higher yield of 3-methylpyridine compared to that of the HZSM-5 molecular sieve.
Comparative example 2
A certain amount of LaHZSM-5/ZSM-11 cocrystallized zeolite (La)2O3/Al2O3In a molar ratio of0.12), alumina sol (alumina accounts for 23.0 wt% of the alumina sol, the same as below and will not be described), silica sol (silica accounts for 27.0 wt% of the silica sol, the same as below and will not be described), kaolin and deionized water are uniformly mixed, then spray-molded and dried to obtain the catalyst Cat-C. Wherein the inlet temperature in the spraying condition is 450 ℃, the tail gas temperature is 150 ℃, the spraying pressure is 2.0Mpa, the drying temperature is 500 ℃, and the drying time is 2 hours. The prepared catalyst is marked as Cat-C, wherein the weight contents of LaHZSM-5/ZSM-11 cocrystallized zeolite, alumina and silica are respectively 40%, 24% and 36%. 20g of catalyst in a fixed fluidized bed reaction tube, in N2Heating to 500 ℃ under atmosphere for activation, and then carrying out activation under N2The atmosphere is lowered to the reaction temperature, and the reaction conditions are as follows: 0.1MPa, 460 ℃ and acrolein weight space velocity of 0.5h-1Ammonia gas: 150ml/min, N2100ml/min, each reaction time was 4 hours, and the quantification was carried out by gas chromatography, and the normalization was carried out by carbon balance, whereby the yield of 3-methylpyridine was 30.1% and the yield of pyridine was 3.2%.
Comparative example 3
The catalyst is also Cat-C, and the reaction conditions are as follows: 0.1Mpa, 460 ℃ and acrolein weight space velocity of 0.5h-1Acrolein/propanal molar ratio 1/0.5, ammonia: 150ml/min, N2150ml/min, each reaction time was 4 hours, gas chromatography was used for quantification, normalization was calculated based on carbon balance, and the results showed that the yield of 3-methylpyridine was 35.6% and the yield of pyridine was 4.0%.
Example 2
The catalyst is also Cat-C, and the reaction conditions are as follows: 0.1MPa, 460 ℃ and acrolein weight space velocity of 0.5h-1Acrolein/n-propylamine molar ratio 1/0.5, ammonia: 150ml/min, N2150ml/min, each reaction time is 4 hours, the quantification is carried out by gas chromatography, the normalization is calculated according to carbon balance, and the result shows that the yield of the 3-methylpyridine is 40.0 percent and the yield of the pyridine is 5.6 percent. The experimental results show that the specific co-crystalline zeolite catalyst of the present application has the highest yield of 3-methylpyridine compared to the reaction of acrolein with ammonia, acrolein/propionaldehyde and ammonia.
Example 3
A quantity of a CeHZSM-5/ZSM-11 co-crystallized zeolite(s) (Ce2O3/Al2O3The molar ratio is 0.12), alumina sol, kaolin and deionized water are uniformly mixed, then spray-molded and dried to obtain the catalyst Cat-D. Wherein the inlet temperature in the spraying condition is 450 ℃, the tail gas temperature is 150 ℃, the spraying pressure is 2.0Mpa, the drying temperature is 500 ℃, and the drying time is 2 hours. In the catalyst Cat-D, the weight contents of the CeHZSM-5/ZSM-11 cocrystallized zeolite, the alumina and the silica are respectively 45%, 20% and 35%.
The fixed fluidized bed reaction tube is filled with 40g of catalyst, N2Heating to 450 ℃ under atmosphere for activation, and then activating in N2The atmosphere is lowered to the reaction temperature, and the reaction conditions are as follows: 0.1MPa, 430 ℃ and acrolein weight space velocity of 0.1h-1Acrolein/propanal/n-propylamine molar ratio 1/0.1/1, ammonia: 190ml/min, N2100ml/min, each reaction time was 4 hours, and the quantification was carried out by gas chromatography, and the normalization was carried out by carbon balance, whereby the yield of 3-methylpyridine was 43.4% and the yield of pyridine was 6.0%.
Example 4
A certain amount of LaCeHZSM-5/ZSM-11 cocrystallized zeolite (La)2O3/Al2O3Molar ratio of 0.07, Ce2O3/Al2O3The molar ratio is 0.10), alumina sol, kaolin and deionized water are uniformly mixed, then spray-molded and dried, and the catalyst Cat-E is prepared. Wherein the inlet temperature in the spraying condition is 650 ℃, the tail gas temperature is 200 ℃, the spraying pressure is 0.8Mpa, the drying temperature is 450 ℃, and the drying time is 4 hours. The prepared catalyst Cat-E, wherein the weight contents of the LaCeHZSM-5/ZSM-11 cocrystallized zeolite, the alumina and the silica are respectively 50%, 35% and 15%.
The fixed fluidized bed reaction tube is filled with 40g of catalyst, N2Heating to 450 ℃ under atmosphere for activation, and then activating in N2The atmosphere is lowered to the reaction temperature, and the reaction conditions are as follows: 0.1MPa, 500 ℃ and acrolein weight space velocity of 0.4h-1Acrolein/propanal/n-propylamine/isopropylamine molar ratio 1/1/0.05/0.05, ammonia: 190ml/min, N2120ml/min, each reaction time is 4 hours, the quantification is carried out by gas chromatography, the normalization is calculated according to carbon balance, and the result shows that the yield of the 3-methylpyridineThe yield of pyridine was 48.8% and 5.3%.
The above description is only exemplary of the present application and should not be taken as limiting the scope of the present application, as any modifications, equivalents, improvements and the like that are within the spirit and principle of the present application should be included in the present application.
Claims (10)
1. A method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine is characterized in that: in the presence of a catalyst, a certain amount of propylamine is added into a mixed raw material of acrolein and ammonia gas to synthesize 3-methylpyridine, wherein the catalyst comprises rare earth HZSM-5/ZSM-11 cocrystallized zeolite.
2. The method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine according to claim 1, wherein: a certain amount of propionaldehyde is also added into the mixed raw material of acrolein and ammonia gas.
3. The process for producing 3-methylpyridine by promoting the reaction between acrolein and ammonia according to claim 1 or 2, wherein: the propylamine is n-propylamine and/or isopropylamine.
4. The process for producing 3-methylpyridine by promoting the reaction between acrolein and ammonia according to claim 1 or 2, wherein: the molar ratio of propylamine to acrolein is (0.1-1) to (0.1-1).
5. The method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine according to claim 2, wherein: the molar ratio of propionaldehyde to acrolein is (0-1): 1.
6. The method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine according to claim 1, wherein the catalyst is prepared from rare earth HZSM-5/ZSM-11 cocrystallized zeolite and a binder, and the weight percentage of the binder in the mixture of the cocrystallized zeolite and the binder is 15-60%.
7. The method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine according to claim 6, wherein: the binder is silicon oxide and/or aluminum oxide.
8. The method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine according to claim 6, wherein: after ammonia exchange, the cocrystallized zeolite is extruded or sprayed with adhesive and roasted to obtain the catalyst.
9. The method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine according to claim 1, wherein: the preparation of 3-methylpyridine is carried out on a fixed bed or a fluidized bed.
10. The method for promoting the reaction of acrolein and ammonia gas to prepare 3-methylpyridine according to claim 1, wherein: the reaction pressure is 0.05-0.15Mpa, the temperature is 300--1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115888801A (en) * | 2022-09-28 | 2023-04-04 | 山东明化新材料有限公司 | Modified catalyst for improving yield of 3, 5-dimethylpyridine and production method for improving yield of 3, 5-dimethylpyridine |
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|---|---|---|---|---|
| JPH09124602A (en) * | 1995-10-31 | 1997-05-13 | Mitsubishi Rayon Co Ltd | Production of 3,5-lutidine and 2,3,5-collidine |
| CN108246346A (en) * | 2018-01-26 | 2018-07-06 | 中国科学院大连化学物理研究所 | For methacrylaldehyde, the method for modifying of propionic aldehyde and ammonia reaction ZSM-11 molecular sieve catalysts |
| CN112010802A (en) * | 2020-08-13 | 2020-12-01 | 浙江新和成股份有限公司 | Continuous preparation method of 3-methylpyridine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124602A (en) * | 1995-10-31 | 1997-05-13 | Mitsubishi Rayon Co Ltd | Production of 3,5-lutidine and 2,3,5-collidine |
| CN108246346A (en) * | 2018-01-26 | 2018-07-06 | 中国科学院大连化学物理研究所 | For methacrylaldehyde, the method for modifying of propionic aldehyde and ammonia reaction ZSM-11 molecular sieve catalysts |
| CN112010802A (en) * | 2020-08-13 | 2020-12-01 | 浙江新和成股份有限公司 | Continuous preparation method of 3-methylpyridine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115888801A (en) * | 2022-09-28 | 2023-04-04 | 山东明化新材料有限公司 | Modified catalyst for improving yield of 3, 5-dimethylpyridine and production method for improving yield of 3, 5-dimethylpyridine |
| CN115888801B (en) * | 2022-09-28 | 2024-03-29 | 山东明化新材料有限公司 | Modified catalyst for improving yield of 3, 5-lutidine and production method for improving yield of 3, 5-lutidine |
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