CN111821919A - Continuous catalytic hydrogenation equipment and continuous catalytic hydrogenation method for pyridine compounds - Google Patents
Continuous catalytic hydrogenation equipment and continuous catalytic hydrogenation method for pyridine compounds Download PDFInfo
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- CN111821919A CN111821919A CN202010664303.9A CN202010664303A CN111821919A CN 111821919 A CN111821919 A CN 111821919A CN 202010664303 A CN202010664303 A CN 202010664303A CN 111821919 A CN111821919 A CN 111821919A
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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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/12—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with only hydrogen atoms attached to the ring nitrogen atom
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
Abstract
The invention provides continuous catalytic hydrogenation equipment and a continuous catalytic hydrogenation method for pyridine compounds. A continuous catalytic hydrogenation apparatus comprising: a liquid raw material supply unit; a hydrogen gas supply unit; at least three stages of fixed bed reactors connected in series in sequence, wherein each fixed bed reactor is provided with a feed inlet at the bottom and a product outlet at the top, a liquid raw material supply unit and a hydrogen supply unit are connected with the feed inlet of the first stage of fixed bed reactor, a partition plate is arranged in each fixed bed reactor and used for bearing a catalyst and a filler, and a sampling port is arranged on a connecting pipeline between each stage of fixed bed reactor; the heat exchange jackets are arranged in one-to-one correspondence with the fixed bed reactor, and are sleeved on the outer wall of the fixed bed reactor in one-to-one correspondence; and the gas-liquid separator is connected with the product outlet of the last stage of fixed bed reactor. The equipment is beneficial to the filling and replacement of the catalyst of each fixed bed reactor and the effective control of the catalytic effect.
Description
Technical Field
The invention relates to the technical field of catalytic hydrogenation of pyridine compounds, and particularly relates to continuous catalytic hydrogenation equipment and a continuous catalytic hydrogenation method for the pyridine compounds.
Background
Piperidine and derivatives thereof are heterocyclic compounds with wide physiological and pharmacological activities, have high research value and application prospect in the aspects of cancer resistance, inflammation diminishing, sedation, hypnosis and the like, and can be widely applied to organic synthesis as chiral reagents. Piperidine and derivatives thereof are generally prepared from corresponding pyridine and derivatives thereof by catalytic hydrogenation, and the synthesis method has high reaction yield and simple product post-treatment, and is widely applied in industry.
The catalytic hydrogenation reduction reaction industrial production mainly uses a high-pressure reaction kettle as a reaction container, solid catalyst and raw material solution are added into the high-pressure kettle, hydrogen is filled into the high-pressure kettle to be added to a certain pressure, and the gas-liquid-solid three-phase mixed reaction is carried out by utilizing the strong stirring of the reaction kettle. This reaction requires sufficient space for hydrogen, which results in a large reaction vessel and reduced safety under high pressure conditions. In addition, extra equipment is needed for separating the catalyst, and the reaction effect is poor due to catalyst poisoning or other uncontrollable factors in the reaction process, so that the reaction period is prolonged, and the selectivity is poor.
Compared with the traditional batch hydrogenation process, the continuous catalytic hydrogenation process has incomparable advantages. The method has the advantages of lower equipment investment cost, smaller occupied area, higher safety, easier realization of process automation and more excellent reaction kinetics. However, how to realize the amplification of the gas-liquid-solid three-phase continuous hydrogenation process has always plagued chemists and engineers in the fields of fine chemistry and medicinal chemistry. Fixed bed technology can only be applied to laboratory scale experiments, and safety issues such as heat release control will increase dramatically as the fixed bed size increases. The proposal proposed in patent application with publication number CN107089961 adopts a three-stage split-tube type fixed bed reactor connected in series, and the heat exchange medium introduced in the shell side can effectively control the reaction temperature of the materials in the tubes, but the operation of changing the catalyst, reinstalling the equipment and the like becomes complicated because a plurality of fixed tubes are connected in parallel in the same cylindrical container, and the catalytic effect of the catalyst in a single fixed tube cannot be tracked.
Disclosure of Invention
The invention mainly aims to provide continuous catalytic hydrogenation equipment and a continuous catalytic hydrogenation method for pyridine compounds, and aims to solve the problem that in the prior art, gas-liquid-solid three-phase continuous reaction equipment is difficult to effectively control the catalytic effect in each reactor.
In order to achieve the above object, according to one aspect of the present invention, there is provided a continuous catalytic hydrogenation apparatus for pyridine compounds, comprising: a liquid raw material supply unit; a hydrogen gas supply unit; at least three stages of fixed bed reactors connected in series in sequence, wherein each fixed bed reactor is provided with a feed inlet at the bottom and a product outlet at the top, a liquid raw material supply unit and a hydrogen supply unit are connected with the feed inlet of the first stage of fixed bed reactor, a partition plate is arranged in each fixed bed reactor and used for bearing a catalyst and a filler, and a sampling port is arranged on a connecting pipeline between each stage of fixed bed reactor; the heat exchange jackets are arranged in one-to-one correspondence with the fixed bed reactor, and are sleeved on the outer wall of the fixed bed reactor in one-to-one correspondence; and the gas-liquid separator is connected with the product outlet of the last stage of fixed bed reactor.
Furthermore, the heat exchange jackets are arranged in parallel.
Further, the length-diameter ratio of each fixed bed reactor is 40-200: 1, preferably 60 to 120: 1.
further, the catalyst is spherical particle or columnar particle catalyst with the particle size of 0.5-5 mm.
According to another aspect of the present invention, a continuous catalytic hydrogenation method for pyridine compounds is provided, the continuous catalytic hydrogenation method comprises performing continuous catalyst hydrogenation on pyridine compounds by using any one of the continuous catalytic hydrogenation apparatuses, and sampling by using a sampling port to detect the composition of catalytic hydrogenation products of each fixed bed reactor.
Further, the pyridine compound hasGeneral formula (VII)
Wherein R is C1～C10Any one of the alkyl group, the halogeno group and the amine group of (a), is preferably-CH3、-C2H5-Cl, -Br or-NH2。
Further, the catalyst is selected from palladium-carbon, rhodium-carbon, ruthenium-carbon, palladium-alumina, rhodium-alumina and ruthenium-alumina catalysts, the total amount of the catalyst in the fixed bed reactor is 1% -15% of the equivalent of the pyridine compound, and the loading amount of the active ingredients in the catalyst is 5%.
Further, the temperature of the continuous hydrogenation reaction of each fixed bed reactor of the continuous catalytic hydrogenation equipment is 40-150 ℃, preferably 50-130 ℃, more preferably 80-120 ℃, the pressure of the continuous hydrogenation reaction is preferably 1-8 MPa, more preferably 2-6 MPa, more preferably 3-5 MPa, and the total effective retention time in the fixed bed reactor is 5-120 min, preferably 30-80 min.
Further, in the continuous catalytic hydrogenation reaction, the hydrogen equivalent is 3 to 20 equivalents, preferably 5 to 18 equivalents, and more preferably 10 to 15 equivalents.
Further, the pyridine compounds are sent into the first-stage fixed bed reactor through a liquid raw material supply unit in a solution mode, and the solvent of the solution is methanol, ethanol, isopropanol or tert-butanol.
By applying the technical scheme of the invention, the multistage fixed bed reactors are connected in series, so that the continuous catalyst hydrogenation of the pyridine compounds is realized, and the filling and the replacement of the catalyst of each fixed bed reactor are facilitated. The sampling ports are arranged on connecting pipelines of all levels of fixed bed reactors, the catalytic hydrogenation reaction products of all levels of fixed bed reactors are sampled by the sampling ports, the composition of the samples is detected, then the catalytic effect of all fixed bed reactors can be obtained, and the feeding speed, the reaction temperature and/or the reaction pressure of all reaction materials are adjusted according to the catalytic effect so as to optimize the catalytic effect. The fixed bed reactors adopt a heat exchange jacket for controlling the temperature, and the reaction temperature of each fixed bed reactor is adjusted by adjusting the temperature and the speed of a heat exchange medium entering the heat exchange jacket.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic diagram of a continuous catalytic hydrogenation apparatus for pyridine compounds according to an embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a liquid raw material supply unit; 20. a hydrogen gas supply unit; 30. a fixed bed reactor; 31. a sampling port; 40. a heat exchange jacket; 50. a gas-liquid separator.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background of the present application, the gas-liquid-solid three-phase continuous reaction equipment in the prior art employs tubular fixed bed reactors, and thus it is difficult to effectively control the catalytic effect in each tubular of each reactor. In order to solve the problem, the application provides a continuous catalytic hydrogenation device and a continuous catalytic hydrogenation method for pyridine compounds.
In a typical embodiment of the present application, a continuous catalytic hydrogenation apparatus for pyridine compounds is provided, as shown in fig. 1, the continuous catalytic hydrogenation apparatus includes a liquid raw material supply unit 10, a hydrogen supply unit 20, at least three stages of fixed bed reactors 30 connected in series in sequence, heat exchange jackets 40 and gas-liquid separators 50 disposed in one-to-one correspondence to the fixed bed reactors 30, each fixed bed reactor 30 having a feed inlet at the bottom and a product outlet at the top, the liquid raw material supply unit 10 and the hydrogen supply unit 20 being connected to the feed inlet of the first stage fixed bed reactor 30, each fixed bed reactor 30 having a partition plate therein for supporting a catalyst and a filler, and a sampling port 31 being disposed on a connection line between each stage of fixed bed reactors 30; the heat exchange jackets 40 are sleeved on the outer wall of the fixed bed reactor 30 in a one-to-one correspondence manner; the gas-liquid separator 50 is connected to the product outlet of the last fixed-bed reactor 30.
No tubes are provided in the fixed bed reactor 30 of the present application.
The continuous catalytic hydrogenation equipment of the application connects the multistage fixed bed reactors 30 in series, realizes the continuous catalyst hydrogenation of pyridine compounds, and is favorable for the filling and replacement of the catalyst of each fixed bed reactor 30. The sampling ports 31 are arranged on the connecting pipelines of all stages of fixed bed reactors 30, the sampling ports 31 are utilized to sample catalytic hydrogenation reaction products of all stages of fixed bed reactors 30, the composition of the samples is detected, then the catalytic effect of all fixed bed reactors 30 can be obtained, and the feeding speed, the reaction temperature and/or the reaction pressure of all reaction materials are adjusted according to the catalytic effect, so that the catalytic effect is optimized. The fixed bed reactors 30 are controlled in temperature by using heat exchange jackets 40, and the reaction temperature of each fixed bed reactor 30 is adjusted by adjusting the temperature and speed of a heat exchange medium entering the heat exchange jackets 40.
In order to further flexibly and pertinently adjust the temperature of each fixed bed reactor 30, it is preferable that the heat exchange jackets 40 are connected in parallel, and the temperature of each fixed bed reactor 30 is independently adjusted by adjusting the temperature and the speed of the heat exchange medium introduced into each heat exchange jacket 40. The heat exchange jacket 40 has a heat exchange medium inlet and a heat exchange medium outlet, and preferably, the heat exchange medium inlet is located at the bottom of the heat exchange jacket 40, and the heat exchange medium outlet is located at the top of the heat exchange jacket 40, so as to achieve more sufficient heat exchange.
The fixed bed reactor 30 used in the present application may adopt a fixed bed reactor 30 commonly used in the prior art, and in order to further realize uniformity of catalytic hydrogenation reaction temperature in the whole fixed bed reactor 30, preferably, the aspect ratio of each fixed bed reactor 30 is 40 to 200: 1, preferably 60 to 120: 1.
the catalyst setting mode of the fixed bed reactor 30 of the present application is the same as the prior art, namely, the catalyst is arranged on the partition plate, and the filler is further arranged above the catalyst, so that the catalyst is prevented from flowing out along with the gas. In order to ensure that the catalyst has a large contact area with hydrogen and pyridine compounds and reduce the loss of the catalyst as much as possible, the catalyst is preferably a spherical particle or columnar particle catalyst with the particle size of 0.5-5 mm.
In another exemplary embodiment of the present application, a continuous catalytic hydrogenation method of pyridine compounds is provided, which comprises performing continuous catalytic hydrogenation of pyridine compounds by using any one of the continuous catalytic hydrogenation apparatuses, and sampling by using a sampling port 31 to detect the composition of catalytic hydrogenation products of each fixed bed reactor 30.
The liquid raw material supply unit 10 and the hydrogen supply unit 20 of the continuous catalytic hydrogenation equipment are utilized to respectively and continuously supply the pyridine compound and the hydrogen to the fixed bed reactor 30, the pyridine compound and the hydrogen are catalyzed in the fixed bed reactor 30 under the action of the hydrogenation catalyst to react to form corresponding products, the fixed bed reactors 30 are connected in series to enable the reaction to be continuously carried out, the continuous catalytic hydrogenation reaction of the pyridine compound is realized, and the filling and the replacement of the catalyst of each fixed bed reactor 30 are facilitated. The sampling ports 31 are arranged on the connecting pipelines of all stages of fixed bed reactors 30, the sampling ports 31 are utilized to sample catalytic hydrogenation reaction products of all stages of fixed bed reactors 30, the composition of the samples is detected, then the catalytic effect of all fixed bed reactors 30 can be obtained, and the feeding speed, the reaction temperature and/or the reaction pressure of all reaction materials are adjusted according to the catalytic effect, so that the catalytic effect is optimized. The fixed bed reactors 30 are controlled in temperature by using heat exchange jackets 40, and the reaction temperature of each fixed bed reactor 30 is adjusted by adjusting the temperature and speed of a heat exchange medium entering the heat exchange jackets 40.
The pyridines used in the continuous catalytic hydrogenation apparatus of the present application are preferably pyridine compounds whose hydrogenation products are stable, such as pyridines having the general formula
Wherein R is C1～C10Any one of the alkyl group, the halogeno group and the amine group of (a), is preferably-CH3、-C2H5-Cl, -Br or-NH2。
The catalyst can adopt the catalyst commonly used in the prior art for catalytic hydrogenation of pyridine compounds, preferably the catalyst is selected from palladium-carbon, rhodium-carbon, ruthenium-carbon, palladium-alumina, rhodium-alumina and ruthenium-alumina catalysts, the catalytic effect of each catalyst is prominent, the total amount of the catalyst in the fixed bed reactor is 1-15% of the equivalent of the pyridine compound, and the loading amount of active ingredients in the catalyst is 5%. The loaded catalyst can be repeatedly used for more than 8 times, and the catalytic activity is not obviously reduced.
Because the continuous catalytic hydrogenation process is adopted, the heat of each fixed bed reactor 30 can be taken away in time under the action of the heat exchange jacket 40, and the reaction heat is taken out of the reactor at any time along with the flowing of the material, so that the continuous catalytic hydrogenation reaction can be carried out at a higher temperature, preferably, the temperature of the continuous hydrogenation reaction of each fixed bed reactor 30 of the continuous catalytic hydrogenation equipment is 40-150 ℃, preferably 50-130 ℃, more preferably 80-120 ℃, and the higher hydrogenation efficiency is realized at the temperature.
Because the continuous reaction reactor is smaller, compared with batch reaction, the unit usage amount of hydrogen is reduced, the materials are dispersed more uniformly among catalyst bed layers, the reaction pressure is adjusted in a wider range, and the pressure of the continuous hydrogenation reaction is preferably 1-8 MPa, preferably 2-6 MPa, and more preferably 3-5 MPa. The total effective retention time in the fixed bed reactor 30 is 5min to 120min, preferably 10 min to 80min, more preferably 30 min to 80min, the reaction effect in each reactor is judged by sampling through a sampling port, and the optimal retention time is determined within the range.
Preferably, in order to improve the hydrogen utilization rate, in the continuous catalyst hydrogenation reaction, the hydrogen equivalent is 3 to 20 equivalents, preferably 5 to 18 equivalents, and more preferably 10 to 15 equivalents.
The pyridine compounds of the present application are preferably fed into the first-stage fixed-bed reactor 30 through the liquid raw material supply unit 10 in the form of a solution of methanol, ethanol, isopropanol, or tert-butanol as a solvent. The solvent has wide source, low cost and stability.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of the starting material 2-methylpyridine was dissolved in 800g of methanol for use and pumped into the first stage fixed bed reactor 30 by means of a feed pump. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 100 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 3-4 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 98.3 percent, and the yield of the product is 95.1 percent.
Example 2
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 100 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 7-8 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 99.0 percent, and the yield of the product is 93.8 percent.
Example 3
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 100 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 4-5 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 98.5 percent, and the yield of the product is 95 percent.
Example 4
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the external bath temperature of the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 100 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 5.5-6.5 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 98.8 percent, and the yield of the product is 95.2 percent.
Example 5
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 100 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 1-2 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 95.8 percent, and the yield of the product is 92.5 percent.
Example 6
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the external bath temperature of the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 40 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 3-4 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through the 4-stage fixed bed reactor 30, the conversion rate of the raw material is 43.5 percent, and the yield of the product is 42.7 percent.
Example 7
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical particle alumina is laid above and below the catalyst to serve as a filler, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 50 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 3-4 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 63.3 percent, and the yield of the product is 63.0 percent.
Example 8
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 80 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 3-4 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 93.1 percent, and the yield of the product is 93.0 percent.
Example 9
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 120 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 3-4 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 98.9 percent, and the yield of the product is 94.0 percent.
Example 10
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the bath temperature outside the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 130 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 3-4 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 99.2 percent, and the yield of the product is 94.2 percent.
Example 11
The structure of the continuous catalytic hydrogenation equipment is shown in figure 1, wherein 4 stages of fixed bed reactors 30 are used in series, and materials are fed in from bottom to top. 200g of 2-methylpyridine was dissolved in 800g of methanol for use. The length-diameter ratio of each fixed bed reactor 30 is 80, 5g of 5% loading spherical rhodium-carbon with the particle size of 3mm is filled into the fixed bed reactors 30 to serve as a catalyst, 3mm spherical alumina particles are paved above and below the catalyst to serve as fillers, nitrogen is used for purging the fixed bed reactors 30 connected in series for 0.5h, the external bath temperature of the heat exchange jacket 40 of each fixed bed reactor 30 is set to be 150 ℃, the heat exchange medium of the heat exchange jacket 40 is heat conduction oil, and feeding is carried out from bottom to top. In the temperature rise process, the fixed bed reactor 30 apparatus was purged with hydrogen. After the temperature rise is finished, the pressure of the fixed bed reactor 30 connected in series is adjusted to 3-4 MPa by the outlet valve, and the hydrogen flow rate is adjusted to 0.9-1.0L/min (9-10 equivalent). Feeding the raw materials into the fixed bed reactor 30 at a rate of 2g/min through a feeding pump, allowing the raw materials to flow through the 4-stage fixed bed reactor 30, allowing the total retention time of the fixed bed reactor 30 to be 50min, allowing the raw materials to pass through a gas-liquid separator 50, collecting liquid, and concentrating to obtain the product. After passing through a 4-stage fixed bed reactor 30, the conversion rate of the raw material is 99.7 percent, and the yield of the product is 92.2 percent.
Example 12
The difference from the example 1 is that the length-diameter ratio of each stage of fixed bed reactor 30 is 120, the conversion rate of raw materials is 96.2% and the yield of products is 95.3% after passing through the 4 stages of fixed bed reactors 30.
Example 13
The difference from the example 1 is that the length-diameter ratio of each stage of fixed bed reactor 30 is 40, and the conversion rate of the raw material is 93.5% and the yield of the product is 92.8% after passing through the 4 stages of fixed bed reactors 30.
Example 14
The difference from the example 1 is that the length-diameter ratio of each stage of fixed bed reactor 30 is 20, and the conversion rate of raw materials is 56.7% and the yield of products is 55.2% after passing through the 4 stages of fixed bed reactors 30.
Example 15
The difference from example 1 is that the total retention time of the fixed bed reactor 30 was adjusted to 5min by adjusting the feed rate through the 4-stage fixed bed reactor 30, the conversion of the raw material was 54.7%, and the yield of the product was 54.2%.
Example 16
The difference from example 1 is that the total retention time of the fixed bed reactor 30 is adjusted to 120min by adjusting the feeding rate through the 4-stage fixed bed reactor 30, the conversion rate of the raw material is 98.7%, and the yield of the product is 95.2%.
Example 17
The difference from example 1 is that 2-chloropyridine is used to replace 2-methylpyridine, and the raw material conversion rate is 96.7% and the product yield is 95.2% after passing through a 4-stage fixed bed reactor 30.
Example 18
The difference from example 1 is that 2-aminopyridine is used to replace 2-methylpyridine, and the raw material conversion rate is 98.4% and the product yield is 94.5% after passing through a 4-stage fixed bed reactor 30.
Example 19
The difference from example 1 is that 2-nitropyridine is used to replace 2-methylpyridine, and the raw material conversion rate is 92.5% and the product yield is 61.4% after passing through a 4-stage fixed bed reactor 30.
Example 20
The difference from the example 1 is that 2-picoline is replaced by 2-aldehyde pyridine, and the raw material conversion rate is 52.1 percent and the product yield is 48.8 percent after passing through a 4-stage fixed bed reactor 30.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the continuous catalytic hydrogenation equipment provided by the application is used for serially connecting the multistage fixed bed reactors, so that the continuous catalyst hydrogenation of the pyridine compounds is realized, and the filling and the replacement of the catalyst of each fixed bed reactor are facilitated. The sampling ports are arranged on connecting pipelines of all levels of fixed bed reactors, the catalytic hydrogenation reaction products of all levels of fixed bed reactors are sampled by the sampling ports, the composition of the samples is detected, then the catalytic effect of all fixed bed reactors can be obtained, and the feeding speed, the reaction temperature and/or the reaction pressure of all reaction materials are adjusted according to the catalytic effect so as to optimize the catalytic effect. The fixed bed reactors adopt a heat exchange jacket for controlling the temperature, and the reaction temperature of each fixed bed reactor is adjusted by adjusting the temperature and the speed of a heat exchange medium entering the heat exchange jacket.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A continuous catalytic hydrogenation equipment of pyridine compounds is characterized by comprising:
a liquid raw material supply unit (10);
a hydrogen supply unit (20);
at least three stages of fixed bed reactors (30) connected in series in sequence, wherein each fixed bed reactor (30) is provided with a feed inlet at the bottom and a product outlet at the top, the liquid raw material supply unit (10) and the hydrogen supply unit (20) are connected with the feed inlet of the first stage of fixed bed reactor (30), a partition plate is arranged in each fixed bed reactor (30) and used for bearing a catalyst and a filler, and a sampling port (31) is arranged on a connecting pipeline between each stage of fixed bed reactors (30);
the heat exchange jackets (40) are arranged in one-to-one correspondence to the fixed bed reactors (30), and the heat exchange jackets (40) are sleeved on the outer walls of the fixed bed reactors (30) in one-to-one correspondence; and
and the gas-liquid separator (50) is connected with the product outlet of the fixed bed reactor (30) at the last stage.
2. The continuous catalytic hydrogenation apparatus according to claim 1, wherein each of the heat exchange jackets (40) is arranged in parallel.
3. The continuous catalytic hydrogenation apparatus according to claim 1, wherein the aspect ratio of each fixed bed reactor (30) is 40 to 200: 1, preferably 60 to 120: 1.
4. the continuous catalytic hydrogenation apparatus according to claim 1, wherein the catalyst is a spherical particle or columnar particle catalyst having a particle size of 0.5 to 5 mm.
5. A continuous catalytic hydrogenation method for pyridine compounds, characterized in that the continuous catalytic hydrogenation method comprises the steps of carrying out continuous catalyst hydrogenation on the pyridine compounds by using the continuous catalytic hydrogenation equipment of any one of claims 1 to 4, and sampling by using the sampling port (31) to detect the composition of catalytic hydrogenation products of each fixed bed reactor (30).
6. The continuous catalytic hydrogenation process of claim 5, wherein the pyridine compound has the general formula
Wherein R is C1～C10Any one of the alkyl group, the halogeno group and the amine group of (a), is preferably-CH3、-C2H5-Cl, -Br or-NH2。
7. The continuous catalytic hydrogenation process according to claim 5, wherein the catalyst is selected from palladium-carbon, rhodium-carbon, ruthenium-carbon, palladium-alumina, rhodium-alumina, ruthenium-alumina catalysts, the total amount of the catalyst in the fixed bed reactor is 1% to 15% relative to the equivalent of the pyridine compound, and the loading amount of the active ingredient in the catalyst is 5%.
8. The continuous catalytic hydrogenation method according to claim 5, wherein the temperature of the continuous hydrogenation reaction in each fixed bed reactor (30) of the continuous catalytic hydrogenation equipment is 40-150 ℃, preferably 50-130 ℃, more preferably 80-120 ℃, preferably the pressure of the continuous hydrogenation reaction is 1-8 MPa, more preferably 2-6 MPa, more preferably 3-5 MPa, and the total effective retention time in the fixed bed reactor (30) is 5-120 min, preferably 30-80 min.
9. The continuous catalytic hydrogenation method according to claim 5, wherein the hydrogen equivalent in the continuous catalytic hydrogenation reaction is 3 to 20 equivalents, preferably 5 to 18 equivalents, and more preferably 10 to 15 equivalents.
10. The continuous catalytic hydrogenation method according to claim 5, wherein the pyridine compound is fed into the first stage fixed bed reactor (30) through the liquid feedstock supply unit (10) in the form of a solution, and the solvent of the solution is methanol, ethanol, isopropanol or tert-butanol.
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| WO2022006869A1 (en) * | 2020-07-10 | 2022-01-13 | 吉林凯莱英制药有限公司 | Continuous catalytic hydrogenation apparatus and method for pyridine compounds |
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