CN109096184B - Preparation method of picolinic acid compound - Google Patents
Preparation method of picolinic acid compound Download PDFInfo
- Publication number
- CN109096184B CN109096184B CN201811016586.5A CN201811016586A CN109096184B CN 109096184 B CN109096184 B CN 109096184B CN 201811016586 A CN201811016586 A CN 201811016586A CN 109096184 B CN109096184 B CN 109096184B
- Authority
- CN
- China
- Prior art keywords
- picolinic acid
- reaction
- acid compounds
- catalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- C07D213/60—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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
- C07D213/807—Processes of preparation by oxidation of pyridines or condensed pyridines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a preparation method of a picolinic acid compound, which comprises the following steps: (1) pretreating raw materials, namely respectively pressurizing and heating a picoline compound, a gas oxidant and protective gas to a reaction temperature and a reaction pressure; (2) carrying out catalytic oxidation reaction, namely respectively sending the raw materials pretreated in the step (1) into a slurry bed oxidation reaction system filled with a catalyst for catalytic oxidation reaction to generate reaction liquid of the picolinic acid compounds; (3) and (3) membrane separation, namely separating the reaction liquid of the picolinic acid compound obtained in the step (2) by an inorganic membrane to obtain a filtrate of the picolinic acid compound. The preparation method has the advantages of mild technological process conditions, simple operation, high efficiency, low raw material price, high yield, low energy consumption, no generation of harmful waste gas and waste liquid in the preparation process and the like, can be widely applied to the industrial production of the picolinic acid compounds, and has good economic and social benefits.
Description
Technical Field
The invention relates to a preparation method of an organic matter, and particularly relates to a preparation method of a picolinic acid compound.
Background
2-picolinic acid, nicotinic acid (3-picolinic acid) or isonicotinic acid (4-picolinic acid) are all important organic synthesis intermediates. The 2-picolinic acid can be used for preparing carbocaine drugs and nervous drugs, is widely applied to nerve inhibition and local anesthesia, and can also be used for synthesizing 2-picolinate, herbicides and the like; nicotinic acid is an indispensable vitamin B in human body3Nicotinic acid is used as an intermediate for producing dozens of medicines, and is also used for synthesizing nicotinamide, nicobrake, nicotinic acid triazine, herbicide, pesticide and the like; the isonicotinic acid is mainly used for preparing isoniazid which is an antituberculotic medicament, and is also used for synthesizing derivatives such as amide, hydrazide, esters and the like.
At present, the synthesis method of the picolinic acid compounds mainly comprises the following steps: chemical reagent oxidation, ammonia oxidation, gas phase catalytic oxidation, and electrochemical oxidation.
The chemical reagent oxidation method is the earliest method for synthesizing picolinic acid, and takes potassium permanganate, nitric acid, ozone and the like as oxidants to directly oxidize picolinic acid, ethylpyridine and the like to synthesize picolinic acid. The method has the advantages of large oxidant consumption, high cost, large amount of waste liquid generated in the production process, serious environmental pollution and no compliance with the requirements of green chemistry and clean production.
The ammoxidation method is one of important industrial production methods of the picolinic acid, and comprises the steps of firstly converting alkyl pyridine into steam at 300-450 ℃, then mixing the steam with ammonia gas, water vapor, air or oxygen, generating nitrile pyridine through catalytic oxidation, and then hydrolyzing to obtain the picolinamide and the picolinic acid. The method has the advantages of high reaction temperature, high energy consumption, difficult control of reaction and high requirement of the catalyst on the purity of the raw materials.
The gas-phase catalytic oxidation method takes air or oxygen-enriched air as an oxidant, and under the action of a catalyst, picoline is oxidized into picolinic acid. Compared with the ammonia oxidation method, the method has the advantages of low reaction temperature, low energy consumption and convenient control, but the catalyst has high requirement on the purity of raw materials and is easy to generate tar and toxic gas.
The electrochemical oxidation method is a new technology which takes electrons as a reagent and realizes the synthesis of organic compounds through the gain and loss of the electrons on electrodes by reactants. The method has the problems of high technical difficulty, strict production control, high cost, low yield and the like, so the method still stays in the test stage at present.
The analysis proves that the existing synthesis process of the picolinic acid is complex, harsh in conditions, high in cost, low in energy production and large in pollutant discharge amount. With the increasing use amount of the picolinic acid compound in medicine, chemical industry, food and production life, it is necessary to research a synthetic method of the picolinic acid compound which is low in cost, high in yield, green and environment-friendly.
Disclosure of Invention
The invention aims to provide a preparation method of a picolinic acid compound, which aims to solve the problems of complex process, high cost and great pollution of the existing preparation method.
The purpose of the invention is realized as follows:
a preparation method of picolinic acid compounds comprises the following steps:
(1) pretreating raw materials, namely respectively pressurizing and heating a picoline compound, a gas oxidant and protective gas to a reaction temperature and a reaction pressure;
(2) carrying out catalytic oxidation reaction, namely respectively sending the raw materials pretreated in the step (1) into a slurry bed oxidation reaction system filled with a catalyst for catalytic oxidation reaction to generate reaction liquid of the picolinic acid compounds;
(3) membrane separation, namely separating the reaction liquid of the picolinic acid compounds obtained in the step (2) by an inorganic membrane to obtain a filtrate of the picolinic acid compounds, and performing aftertreatment to obtain the picolinic acid compounds; the catalyst is trapped by the inorganic membrane in the slurry bed oxidation reaction system to continue to participate in subsequent reactions.
The picolines compound is 2-picoline, 3-picoline or 4-picoline, and the prepared picolinic acid product is 2-picolinic acid, nicotinic acid or isonicotinic acid correspondingly.
The gas oxidant is one or more of pure oxygen, ozone or prepared air, and when the gas oxidant is prepared air, the mass content of oxygen in the prepared air is 5-90%, preferably 10-50%.
The protective gas is nitrogen or circulating tail gas, and the circulating tail gas is tail gas (mostly nitrogen and containing a little amount of prepared air) discharged from the slurry bed oxidation reactor after the reaction is carried out for a period of time.
In the catalytic oxidation reaction process in the step (2), the molar ratio of the picolines compound to the component playing the role of oxidation in the gas oxidant is controlled to be 1: 0.05-5, the mass concentration of the catalyst is 1% -8%, the reaction temperature is 150-330 ℃, the reaction pressure is 1.0-3.0 MPa, and the retention time is 15-90 min. Preferably, in the step (2), the molar ratio of the picolines to the component having an oxidizing effect in the gaseous oxidizing agent is 1: 0.1 to 2; the mass concentration of the catalyst is 3% -5%; the reaction temperature is 160-280 ℃, the reaction pressure is 1.5-2.5 MPa, and the residence time is 15-60 min.
And (3) arranging the inorganic membrane in the step (3) in a slurry bed oxidation reactor and/or on an external circulation pipeline outside the slurry bed oxidation reactor, wherein the inorganic membrane is a metal membrane or a ceramic membrane.
As shown in figure 2, the slurry bed oxidation reaction system used in the invention comprises a slurry bed oxidation reactor and an external circulation pipeline, wherein the top of the reactor is provided with a picoline compound inlet, a protective gas inlet and a tail gas outlet, a material distributor, a stirrer and an internal membrane filter are arranged in the reactor, the material outlet at the bottom end of the reactor is sequentially connected with a circulating pump, a first condenser, an external membrane filter, a static mixer, a pre-reactor and a second condenser through pipelines, and the discharge port of the second condenser is connected with the circulation material inlet at the top of the reactor through a pipeline. Each section of pipeline, the circulating pump, the first condenser, the external membrane filter, the static mixer, the pre-reactor and the second condenser jointly form an external circulating pipeline. The internal membrane filter in the reactor and the external membrane filter on the external circulation pipeline can be arranged at the same time or alternatively.
When only the built-in membrane filter is arranged, adding a catalyst, a picoline compound and protective gas into the reactor, starting a stirrer and a circulating pump to establish circulation, introducing a gas oxidant into the static mixer, oxidizing the picoline compound by the gas oxidant in the presence of the catalyst in the pre-reactor, and finishing the reaction in the upper half part of the reactor to obtain a picolinic acid compound reaction solution. In the lower half part of the reactor, the reaction liquid of the picolinic acid compound is separated by a built-in membrane filter, the exuded filtrate of the picolinic acid compound is discharged, the catalyst is retained in the reactor, is mixed with the gas oxidant continuously introduced into the static mixer through a circulating material outlet at the bottom of the reactor, a circulating pump and a first condenser, and then is returned to the reactor through a pre-reactor, a second condenser and a pipeline to realize the continuous operation of the circulating reaction and the separation.
When only the external membrane filter is arranged, the picolinic acid compound reaction liquid enters the external membrane filter for filtration and separation after passing through a circulating material outlet, a circulating pump and a first condenser at the bottom of the reactor, the exuded picolinic acid compound filtrate is discharged, the catalyst slurry is intercepted and enters a static mixer in a circulating material flow mode to be mixed with a gas oxidant, and then the catalyst slurry returns to the reactor through a pre-reactor, a second condenser and a pipeline to realize continuous circulation reaction and separation.
When the built-in membrane filter and the external membrane filter are arranged at the same time, the reaction liquid of the picolinic acid compound obtained in the reactor is divided into two parts which respectively pass through the built-in membrane filter and the external membrane filter to realize the circulating reaction and separation.
The preparation method of picolinic acid compounds provided by the invention specifically comprises the steps of taking picolinic acid compounds and a gas oxidant as raw materials, adopting a slurry bed process, carrying out one-step catalytic oxidation on the picolinic acid compounds in the presence of a catalyst to prepare the picolinic acid compounds, carrying out separation on reaction liquid by a membrane separation technology, and intercepting the catalyst in a reaction system to continuously participate in an oxidation reaction, wherein the process flow schematic diagram of the invention is shown in figure 1.
Compared with the prior art, the method has the advantages of easily available raw materials, low cost, high yield, simple operation, short process flow, continuity, environmental protection and the like, and has good practical significance and economic and social benefits. The invention avoids the use of strong corrosive oxidant, and is beneficial to clean production; the invention adopts a slurry bed reactor, the contact area of reactants and a catalyst is large, the reactants and the catalyst are uniformly mixed, the reaction temperature is low, the temperature of a reaction system is uniform, the reaction hot point is eliminated, and the occurrence of high-temperature side reaction is reduced; the invention couples the reaction process with the separation process, and immediately separates after the reaction is finished, thereby greatly improving the production efficiency.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
FIG. 2 is a schematic diagram of a slurry bed oxidation reaction system.
In the figure, the device comprises a material distributor 1, a stirrer 2, a stirrer 3, a reactor 4, an internal membrane filter 5, a circulating pump 6, a first condenser 7, an external membrane filter 8, a static mixer 9, a pre-reactor 10 and a second condenser.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
The preparation method of the picolinic acid compound provided by the invention comprises the following steps:
adding a catalyst and a picoline compound into a slurry bed reactor, introducing protective gas, starting a stirrer and a circulating pump to establish circulation, introducing a gas oxidant into static mixed gas, oxidizing the picoline compound by the gas oxidant in a pre-reactor in the presence of the catalyst, and finishing the reaction in the reactor to obtain a picolinic acid compound reaction solution. The method comprises the following steps of pretreating a picolinic compound, a protective gas and a gas oxidant to obtain raw materials at a reaction temperature and a reaction pressure, wherein the molar ratio of the picolinic compound to components playing an oxidizing role in the gas oxidant is 1: 0.05-5, a catalyst can catalyze and oxidize the picolinic compound to generate the picolinic acid compound, the mass concentration of the catalyst is 1% -8%, the reaction temperature in a reactor is 150-330 ℃, the reaction pressure is 1.0-3.0 MPa, and the retention time is 15-90 min.
Filtering and separating the obtained reaction liquid of the picolinic acid compound by a built-in membrane filter in the reactor, intercepting the catalyst in the reactor, and obtaining filtrate of the picolinic acid compound at the permeation side;
or the obtained reaction liquid of the picolinic acid compounds is sent into an external membrane filter outside the reactor through a circulating pump for filtration and separation, catalyst slurry is intercepted and participates in the reaction of the subsequent addition raw materials in a circulating material flow mode, and the filtrate of the picolinic acid compounds is obtained at the permeation side;
the membrane in the membrane filter is a metal membrane or a ceramic membrane, and the separation mode is dead-end filtration or cross-flow filtration.
And concentrating and purifying the filtrate of the picolinic acid compound to obtain the picolinic acid compound.
Example 1
(1) Pretreatment of raw materials
Heating and pressurizing 2-methylpyridine to the temperature of 160 ℃ and the pressure of 1.5 MPa;
preparing air into prepared air with the oxygen mass content of 20%, filtering, compressing to the pressure of 1.5MPa, and preheating to 160 ℃;
nitrogen was compressed to a pressure of 1.5MPa and then preheated to a temperature of 160 ℃.
(2) Oxidation reaction
Continuously feeding the pretreated 2-picoline, prepared air and nitrogen in the step (1) into a slurry bed oxidation reaction system filled with a catalyst respectively to perform catalytic oxidation reaction to generate a reaction liquid of the 2-picolinic acid. In the reaction process, the reaction temperature is controlled at 160 ℃, the pressure is 1.5MPa, the residence time is 30 min, the molar ratio of the 2-methylpyridine to oxygen molecules in the prepared air is 1: 0.5, and the mass concentration of the catalyst is 3% (the catalyst is required to be supplemented into the reaction kettle at proper time according to the unit consumption of the catalyst).
(3) Membrane separation
And (3) carrying out dead-end filtration and separation on the reaction liquid of the 2-picolinic acid obtained in the step (2) through a metal membrane arranged in a slurry bed oxidation reactor to obtain 2-picolinic acid filtrate, and intercepting the catalyst in a reaction system to continue participating in the subsequent catalytic oxidation reaction.
And carrying out post-treatment processes such as concentration, purification and the like on the obtained filtrate to finally obtain the 2-picolinic acid, wherein the conversion rate of the 2-picoline reaches 95%, and the selectivity of the product 2-picolinic acid reaches 97%.
Example 2
(1) Pretreatment of raw materials
Heating and pressurizing 3-methylpyridine to 170 ℃ and 1.6 MPa;
preparing air into prepared air with the oxygen mass content of 30%, filtering, compressing to the pressure of 1.6MPa, and preheating to 170 ℃;
the nitrogen or the recycled tail gas is compressed to a pressure of 1.6MPa and then preheated to a temperature of 170 ℃. Nitrogen is used as protective gas at the beginning of the reaction, after the reaction is carried out for a period of time, tail gas (most of nitrogen and containing a little amount of prepared air) discharged from the slurry bed oxidation reactor is recycled, namely, the recycled tail gas is heated and pressurized to the reaction temperature and pressure.
(2) Oxidation reaction
Continuously feeding the pretreated 3-methylpyridine, prepared air and nitrogen (or circulating tail gas) in the step (1) into a slurry bed oxidation reaction system filled with a catalyst respectively to perform catalytic oxidation reaction to generate a reaction solution of nicotinic acid. In the reaction process, the reaction temperature is controlled at 170 ℃, the pressure is 1.6MPa, the residence time is 45 min, the molar ratio of the 3-methylpyridine to oxygen molecules in the prepared air is 1: 0.5, and the mass concentration of the catalyst is 3% (the catalyst is required to be supplemented into the reaction kettle at proper time according to the unit consumption of the catalyst).
(3) Membrane separation
And (3) carrying out cross-flow filtration separation on the reaction liquid of the nicotinic acid obtained in the step (2) through a metal membrane arranged on an external circulation pipeline of the slurry bed oxidation reactor to obtain a nicotinic acid filtrate, and intercepting a catalyst in a reaction system to continuously participate in the subsequent catalytic oxidation reaction.
The obtained filtrate is subjected to post-treatment procedures such as concentration, purification and the like to obtain the nicotinic acid, the conversion rate of the 3-methylpyridine reaches 96 percent, and the selectivity of the product nicotinic acid reaches 98 percent.
Example 3
(1) Pretreatment of raw materials
Heating and pressurizing 4-methylpyridine to the temperature of 180 ℃ and the pressure of 1.8 MPa;
preparing air into prepared air with the oxygen mass content of 25%, filtering, compressing until the pressure is 1.8MPa, and then preheating to 180 ℃;
nitrogen was compressed to a pressure of 1.8MPa and then preheated to a temperature of 180 ℃.
(2) Oxidation reaction
Continuously feeding the 4-methylpyridine pretreated in the step (1), prepared air and nitrogen into a slurry bed oxidation reaction system filled with a catalyst respectively to perform catalytic oxidation reaction to generate isonicotinic acid reaction liquid. In the reaction process, the reaction temperature is controlled at 180 ℃, the pressure is 1.8MPa, the residence time is 50 min, the molar ratio of the 4-methylpyridine to oxygen molecules in the prepared air is 1: 0.6, and the mass concentration of the catalyst is 3% (the catalyst is required to be supplemented into the reaction kettle in due time according to the unit consumption of the catalyst).
(3) Membrane separation
And (3) carrying out cross-flow filtration separation on one part of the isonicotinic acid reaction liquid obtained in the step (2) through a metal membrane arranged outside the slurry bed oxidation reactor, carrying out dead-end filtration on the other part of the isonicotinic acid reaction liquid through the metal membrane arranged inside the slurry bed oxidation reactor to obtain isonicotinic acid filtrate, and intercepting the catalyst in a reaction system to continuously participate in the subsequent catalytic oxidation reaction.
The obtained filtrate is subjected to post-treatment procedures such as concentration, purification and the like to obtain the isonicotinic acid, wherein the conversion rate of 4-methylpyridine reaches 95 percent, and the selectivity to the product isonicotinic acid reaches 97 percent.
Example 4
The raw material is 3-methylpyridine, the reaction temperature is 160 ℃, the reaction pressure is 1.5MPa, the residence time is 45 min, the molar ratio of the 3-methylpyridine to oxygen molecules in the prepared air is 1: 0.1, the mass concentration of the catalyst is 3 percent, and other conditions and operations are the same as those of the example 2.
The conversion rate of the 3-methylpyridine reaches 97 percent, and the selectivity of the product nicotinic acid reaches 97 percent.
Example 5
The raw material is 3-methylpyridine, the reaction temperature is 280 ℃, the reaction pressure is 2.5MPa, the residence time is 15 min, the molar ratio of the 3-methylpyridine to oxygen molecules in the prepared air is 1: 2, the mass concentration of the catalyst is 3 percent, and other conditions and operations are the same as those in the example 2.
The conversion rate of the 3-methylpyridine reaches 96 percent, and the selectivity of the product nicotinic acid reaches 98 percent.
Claims (10)
1. A preparation method of picolinic acid compounds is characterized by comprising the following steps:
(1) pretreating raw materials, namely respectively pressurizing and heating a picoline compound, a gas oxidant and protective gas to a reaction temperature and a reaction pressure, wherein the reaction temperature is 150-330 ℃, and the reaction pressure is 1.0-3.0 MPa;
(2) carrying out catalytic oxidation reaction, namely respectively sending the raw materials pretreated in the step (1) into a slurry bed oxidation reaction system filled with a catalyst for catalytic oxidation reaction to generate reaction liquid of the picolinic acid compounds;
(3) membrane separation, namely separating the reaction liquid of the picolinic acid compounds obtained in the step (2) by an inorganic membrane to obtain filtrate of the picolinic acid compounds, and performing aftertreatment to obtain the picolinic acid compounds; the catalyst is trapped by the inorganic membrane in the slurry bed oxidation reaction system to continue to participate in subsequent reactions.
2. The preparation method of picolinic acid compounds according to claim 1, wherein the gaseous oxidant is one or more of pure oxygen, ozone or prepared air, and the mass content of oxygen in the prepared air is 5-90%.
3. The preparation method of picolinic acid compounds according to claim 2, wherein the mass fraction of oxygen in the prepared air is 10-50%.
4. The method for preparing picolinic acid based compounds of claim 1, wherein the shielding gas is nitrogen or a recycled tail gas generated from a catalytic oxidation reaction process.
5. The preparation method of picolinic acid compounds according to claim 1, wherein in the catalytic oxidation reaction process of step (2), the molar ratio of picolinic acid compounds to the component having an oxidizing effect in the gaseous oxidant is controlled to be 1: 0.05-5, the mass concentration of the catalyst is 1% -8%, and the retention time is 15-90 min.
6. The method according to claim 5, wherein the molar ratio of the picolinic acid compound to the component having an oxidizing action in the gaseous oxidizing agent in step (2) is 1: 0.1-2.
7. The preparation method of picolinic acid compounds according to claim 5, wherein the mass concentration of the catalyst in step (2) is 3% to 5%.
8. The method for preparing picolinic acid compounds according to claim 5, wherein in the step (2), the reaction temperature is 160-280 ℃, the reaction pressure is 1.5-2.5 MPa, and the retention time is 15-60 min.
9. The method for preparing picolinic acid based compounds according to claim 1, wherein the inorganic membrane in step (3) is disposed in the slurry bed oxidation reactor and/or disposed on an external circulation line outside the slurry bed oxidation reactor, and the inorganic membrane is a metal membrane or a ceramic membrane.
10. The method of claim 1, wherein the picolinic acid compound is 2-picoline, 3-picoline, or 4-picoline, and the picolinic acid compound is 2-picolinic acid, nicotinic acid, or isonicotinic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811016586.5A CN109096184B (en) | 2018-09-03 | 2018-09-03 | Preparation method of picolinic acid compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811016586.5A CN109096184B (en) | 2018-09-03 | 2018-09-03 | Preparation method of picolinic acid compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109096184A CN109096184A (en) | 2018-12-28 |
| CN109096184B true CN109096184B (en) | 2020-07-10 |
Family
ID=64864747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811016586.5A Active CN109096184B (en) | 2018-09-03 | 2018-09-03 | Preparation method of picolinic acid compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109096184B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247190A (en) * | 1998-09-01 | 2000-03-15 | 底古萨－胡尔斯股份公司 | Method for preparing nicotinic acid |
| CN101623648A (en) * | 2009-08-14 | 2010-01-13 | 中国科学院山西煤炭化学研究所 | Catalyst of picolinic acid synthesized by selectively oxygenizing picoline as well as preparation method and application thereof |
| CN102399183A (en) * | 2010-09-13 | 2012-04-04 | 朱比兰特生命科学有限公司 | A kind of method for preparing pyridine carboxylic acid |
| CN104109116A (en) * | 2014-06-11 | 2014-10-22 | 浙江工业大学 | Process and device for one-step air catalytic oxidation synthesis of picolinic acid type compounds |
| CN104311513A (en) * | 2014-10-16 | 2015-01-28 | 河北美邦工程科技有限公司 | Method of preparing propylene epoxide |
| CN206253115U (en) * | 2016-11-28 | 2017-06-16 | 河北美邦工程科技股份有限公司 | A kind of heterogeneous catalytic reaction is combined the unit with UF membrane |
-
2018
- 2018-09-03 CN CN201811016586.5A patent/CN109096184B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247190A (en) * | 1998-09-01 | 2000-03-15 | 底古萨－胡尔斯股份公司 | Method for preparing nicotinic acid |
| CN101623648A (en) * | 2009-08-14 | 2010-01-13 | 中国科学院山西煤炭化学研究所 | Catalyst of picolinic acid synthesized by selectively oxygenizing picoline as well as preparation method and application thereof |
| CN102399183A (en) * | 2010-09-13 | 2012-04-04 | 朱比兰特生命科学有限公司 | A kind of method for preparing pyridine carboxylic acid |
| CN104109116A (en) * | 2014-06-11 | 2014-10-22 | 浙江工业大学 | Process and device for one-step air catalytic oxidation synthesis of picolinic acid type compounds |
| CN104311513A (en) * | 2014-10-16 | 2015-01-28 | 河北美邦工程科技有限公司 | Method of preparing propylene epoxide |
| CN206253115U (en) * | 2016-11-28 | 2017-06-16 | 河北美邦工程科技股份有限公司 | A kind of heterogeneous catalytic reaction is combined the unit with UF membrane |
Non-Patent Citations (3)
| Title |
|---|
| Continuous flow metal-free oxidation of picolines using air;Masaya Hamano，等;《Chem. Commun.》;20120104;2086–2088 * |
| 异烟酸合成研究进展;张姝，等;《化学试剂》;20101231;第32卷(第3期);219-222 * |
| 环己酮氨肟化浆态床反应器的改进及实践;金作宏，等;《河北工业科技》;20160331;第33卷(第2期);158-163 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109096184A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106148448A (en) | A kind of method utilizing pseudomonas putida to prepare nicotinic acid | |
| CN104109116B (en) | Method and the device thereof of one step air catalytic oxidation pyridine synthesis formic acid compounds | |
| CN109096184B (en) | Preparation method of picolinic acid compound | |
| US3929811A (en) | Production of pyridine nitriles and carboxylic acids | |
| CN108610226B (en) | Method for preparing amide compound by using manganese oxide to catalyze amine oxidation | |
| CN1046504C (en) | The preparation method of niacin | |
| CN101623648A (en) | Catalyst of picolinic acid synthesized by selectively oxygenizing picoline as well as preparation method and application thereof | |
| CN101623628B (en) | Catalyst for synthesizing picolinic acid, preparation method and application | |
| CN107266361A (en) | The synthetic method of the picoline of 2 amino 5 | |
| US3970659A (en) | Preparation of cyanopyridines | |
| US3970657A (en) | Preparation of cyanopyridines | |
| CN106928135B (en) | A kind of continuous preparation method of N- pyridine-N-oxide | |
| EP2049492B1 (en) | Method of making cyanopyridines | |
| CN110963964B (en) | Continuous synthesis method of piroctone | |
| US3981879A (en) | Preparation of cyanopyridines | |
| Cislak | Pyridine-N-Oxide | |
| JP4161119B2 (en) | Oxidative ammonolysis of alkylpyridines. | |
| US3689491A (en) | Method of producing pyridine | |
| US3335144A (en) | Method of producing pyridine and 2-picoline by decarboxylation | |
| Suvorov et al. | The vapor phase oxidation of 3-picoline on tin and titanium vanadates | |
| CN100484925C (en) | Preparation process of intermediate 2-cyanpyrazine of pyrazinamide drug | |
| JPS61251663A (en) | Production of aminomethylpyridine | |
| CN101035763B (en) | Process for producing heteroaromatic carboxylic acids | |
| CN101648910B (en) | Method for preparing 3,5-dimethylpyridine-N-oxide | |
| SU311914A1 (en) | METHOD OF OBTAINING 3-CYANPYRIDINE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |