CN107628987B - Method for producing 2,2' -bipyridine by using membrane reactor - Google Patents
Method for producing 2,2' -bipyridine by using membrane reactor Download PDFInfo
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Abstract
The invention discloses a method for producing 2,2' -bipyridine by using a membrane reactor, which comprises the following steps: preheating and gasifying pyridine, introducing the gasified pyridine into a reactor in a gaseous state, passing through a catalyst bed layer, reacting under the action of a dehydrogenation catalyst to generate 2,2 '-bipyridine, and condensing and extracting the 2,2' -bipyridine and part of unreacted pyridine through a gas-liquid separator; hydrogen generated by the reaction and most of unreacted pyridine enter the membrane tube through the membrane porous material tube inserted into the catalyst bed layer to be separated from the 2,2' -bipyridine, nitrogen is introduced from the bottom of the membrane tube to purge gaseous pyridine and hydrogen, and mixed gas is discharged from the upper part of the membrane tube. The method for producing 2,2' -bipyridine by using the membrane reactor has high pyridine conversion rate, can immediately separate unreacted raw materials and products, and prolongs the service life of the catalyst.
Description
Technical Field
The invention belongs to the field of fine chemical engineering and organic synthesis, and particularly relates to a method for preparing 2,2' -bipyridine by using a membrane reactor.
Background
The 2,2' -dipyridyl is an important intermediate for chemical engineering and drug synthesis, and can be used as a ligand of a metal catalyst, a photosensitizer, an indicator for detecting metal ions and the like due to the unique chelation.
Two methods are mainly suitable for the industrial preparation of 2,2 '-bipyridyl, one is an Ullmann method (M.Tiecco et al, Communications,1984,736-738), and 2-halopyridine is used as a raw material to perform a coupling reaction under the action of a catalyst to generate the 2,2' -bipyridyl. In the other method, pyridine is used as a raw material, and 2,2' -bipyridine is generated under the action of a nickel-based catalyst. The method has the advantages of high atom utilization rate and environmental protection, but the single conversion rate is low, and the 2,2' -bipyridyl is prepared by Raney nickel in a Soxhlet reactor at normal pressure and at the temperature of 100 ℃ and 120 ℃ with the highest conversion rate being less than 1 percent; US5416217 uses supported nickel to prepare 2,2' -bipyridine in a fixed bed reactor at 175-240 deg.C and 0.9-1.5MPa, and although the catalyst life reaches 500h, the conversion rate is still lower than 1%. The low conversion rate causes the separation of the product 2,2' -bipyridyl and the raw material pyridine to become complicated, for example, the separation by adopting a rectification mode needs a large amount of energy, and the industrialization of the method is restricted by the difficulty of the separation.
Therefore, there is a need for a process for producing 2,2' -bipyridine with high conversion, low energy consumption for separation, and long catalyst life.
Disclosure of Invention
The invention aims to provide a method for producing 2,2' -bipyridyl with high conversion rate, low separation energy consumption and long catalyst life aiming at the existing problems, the method is simple to operate, and the conversion rate of pyridine can reach 25-50%.
The purpose of the invention is realized by the following technical scheme:
a process for producing 2,2' -bipyridine in a membrane reactor comprising: preheating and gasifying pyridine, introducing the gasified pyridine into a reactor in a gaseous state, passing through a catalyst bed layer, reacting under the action of a dehydrogenation catalyst to generate 2,2 '-bipyridine, and condensing and extracting the 2,2' -bipyridine and part of unreacted pyridine through a gas-liquid separator; hydrogen generated by the reaction and most of unreacted pyridine enter the membrane tube through the membrane porous material tube inserted into the catalyst bed layer to be separated from the 2,2' -bipyridine, nitrogen is introduced from the bottom of the membrane tube to purge gaseous pyridine and hydrogen, and mixed gas is discharged from the upper part of the membrane tube.
The reaction temperature is 300-600 ℃, and the pressure is 0.1-0.2 Mpa.
Preferably, the reaction temperature is 500-.
The flow rate of the gaseous pyridine is 0.02-0.06 L.min-1G catalyst-1。
The dehydrogenation catalyst is Raney nickel or supported nickel.
The nickel content of the supported nickel is more than 20 percent, the carrier is alumina, and the specific surface area is 120m2More than/g, preferably 120-250m2Per g, pore volume of 0.6m3A ratio of at least one of 0.6 to 0.8 m/g, preferably3/g。
The membrane porous material pipe is made by opening a hole at the lower part of the membrane pipe and covering the membrane porous material; the pore diameter of the membrane porous material is 4-10 nm; the membrane porous material is aluminosilicate. In the reactor, 2,2' -bipyridyl and pyridine are both gas, gaseous pyridine can enter a membrane pipe through the membrane due to the size of the pore diameter of the membrane, and bipyridyl cannot enter the membrane pipe, so most of pyridine is separated from 2,2' -bipyridyl through the membrane, part of unreacted pyridine and 2,2' -bipyridyl enter a gas-liquid separator, gas-liquid balance is achieved in the gas-liquid separator, liquid is discharged from the lower part, and gas is in the upper part of the liquid. The invention is provided with the gas-liquid separator to ensure the stable pressure in the reactor and convenient sampling. The pressure in the gas-liquid separator is about 0.78 Mpa; the condensation temperature of the gas-liquid separator is 70-80 ℃. The pressure in the membrane pipe is 1-10Kpa lower than the pressure in the gas-liquid separator.
Another object of the present invention is to provide a membrane reactor for producing 2,2' -bipyridine, which comprises a reactor, a gas-liquid separator; the reactor comprises a cylinder body, and a heating device is arranged outside the cylinder body; a dehydrogenation catalyst is filled in the cylinder to form a catalyst bed layer; a plurality of uniformly distributed feeding pipes are arranged in the middle of the reactor, and each feeding pipe is provided with a gas flowmeter; inserting a membrane tube into the reactor along the axial direction, wherein the upper end and the lower end of the membrane tube are closed, the lower part of the membrane tube is provided with a hole and covered with a membrane porous material to form a membrane porous material tube, and the membrane porous material tube is inserted into a catalyst bed layer; an air inlet pipe is arranged in the membrane pipe; the upper part of the membrane tube is provided with an air outlet; the reactor is connected with a feed inlet of the gas-liquid separator through a discharge hole at the lower part; the outer part of the gas-liquid separator is sleeved with a jacket, hot water at the temperature of 70-80 ℃ is introduced into the jacket, and the bottom of the gas-liquid separator is provided with a discharge pipe; the gas-liquid separator is provided with a nitrogen balance gas supplementing pipe and a back pressure valve.
The reactor cylinder is a stainless steel cylinder.
The membrane tube is a stainless steel tube.
The air inlet pipe is a stainless steel pipe. The air inlet end pipe of the air inlet pipe extends out of the top end of the membrane pipe, and the air outlet end of the air inlet pipe is close to the bottom of the membrane pipe.
The feeding pipes are arranged in a divergent mode, the number of the feeding pipes is at least 3, and the feeding pipes are preferably 3-8.
The air outlet is higher than the membrane tube reactor.
The reactor is provided with a first pressure gauge for measuring reaction pressure, and a second pressure gauge for measuring the pressure in the membrane tube is arranged in the membrane tube; a thermocouple is arranged in the reactor and used for measuring the temperature of the catalyst bed layer; the gas-liquid separator is provided with a third pressure gauge.
In actual operation, the pressure in the membrane tube is higher than that in the gas-liquid separator, so that the pressure in the gas-liquid separator is maintained higher than that in the membrane tube by supplementing nitrogen through a nitrogen balance make-up gas tube in the upper part of the gas-liquid separator.
The back pressure valve is used for controlling the pressure of the gas-liquid separator and the pressure in the reactor.
The invention has the beneficial effects that:
the method for producing the 2,2' -bipyridine by adopting the membrane reactor has high pyridine conversion rate, can immediately separate unreacted raw materials and products, and prolongs the service life of the catalyst.
Drawings
FIG. 1 is a schematic diagram of a membrane reactor for the production of 2,2' -bipyridine;
FIG. 2 is a schematic view of a reactor feed tube arrangement;
in the figure, 1-a reactor, 2-a gas-liquid separator, 3-a feeding pipe, 4-a gas flowmeter, 5-a membrane pipe, 6-a feeding pipe, 7-a catalyst bed layer, 8-a gas outlet, 9-a first pressure gauge, 10-a second pressure gauge, 11-a thermocouple, 12-a discharging pipe, 13-a nitrogen balance supplement gas pipe, 14-a third pressure gauge and 15-a back pressure valve.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
As shown in fig. 1 and 2, a membrane reactor for producing 2,2' -bipyridine comprises a reactor 1, a gas-liquid separator 2; the reactor 1 comprises a stainless steel cylinder, and a heating device is arranged outside the cylinder; a dehydrogenation catalyst is filled in the cylinder to form a catalyst bed layer 7; the middle part of the reactor is connected with 8 feed pipes 3, and each feed pipe 3 is provided with a gas flowmeter 4; inserting a membrane tube 5 into the reactor 1 along the axial direction, sealing the upper end and the lower end of the membrane tube 5, opening a hole at the lower part of the membrane tube 5 and covering a membrane porous material to form a membrane porous material tube, and inserting the membrane porous material tube into a catalyst bed layer 7; a stainless steel air inlet pipe 6 is arranged in the membrane pipe 5, an air inlet end pipe of the air inlet pipe 6 extends out of the top end of the membrane pipe 5, and an air outlet end of the air inlet pipe 6 is close to the bottom of the membrane pipe 5; the upper part of the membrane tube 5 is provided with an air outlet 8, and the air outlet 8 is higher than the upper end of the reactor; the reactor 1 is provided with a first pressure gauge 9 for measuring reaction pressure, and a second pressure gauge 10 for measuring pressure in the membrane tube 5 is arranged in the membrane tube 5; a thermocouple 11 is arranged in the reactor 1 and is used for measuring the temperature of the catalyst bed layer; the reactor 1 is connected with a feed inlet of the gas-liquid separator 2 through a discharge hole at the lower part; a jacket is sleeved outside the gas-liquid separator 2, hot water with the temperature of 70-80 ℃ is introduced into the jacket, and a discharge pipe 12 is arranged at the bottom of the gas-liquid separator 2; and the upper part of the gas-liquid separator 2 is provided with a nitrogen balance gas supplementing pipe 13, a third pressure gauge 14 and a back pressure valve 15.
The membrane tube 4 is a stainless steel tube.
The membrane porous material covers the outer wall of the lower part of the membrane tube 5 to form a membrane porous material tube, and the aperture of the membrane porous material is 4-10 nm.
Production of 2,2' -bis based on the above membrane reactorThe pyridine gas is fed into reactor, gas flow rate is measured by gas flowmeter 2, the gas pyridine is passed through catalyst bed layer 7, and reacted under the action of dehydrogenation catalyst to produce 2,2' -dipyridyl, most of unreacted pyridine and produced hydrogen gas are passed through membrane separation and fed into membrane tube, and the gas in the membrane tube is purged by introducing nitrogen gas into gas inlet pipe 6 in the membrane tube, and N is2/H2The mixed gas is discharged from the upper part of the membrane tube through a gas outlet 3, and the product 2,2' -bipyridyl and part of the unreacted raw material mixture are condensed and discharged through a gas-liquid separator.
Examples 1 to 6
60g of Raney nickel is filled in a reactor of the device for producing the 2,2 '-bipyridyl, the gaseous pyridine enters the reactor at a certain flow rate, passes through a catalyst bed layer and a catalyst bed layer, reacts to generate the 2,2' -bipyridyl under the catalysis of the Raney nickel at the temperature of 300-; and gas generated by reaction enters the membrane tube, nitrogen is introduced into the membrane tube from the air inlet tube and overflows from the lower part of the membrane tube, gas in the membrane tube is purged, and mixed gas is discharged from the upper part of the membrane tube.
Examples 7 to 12
60g of supported nickel is filled in a reactor of the device for producing the 2,2' -bipyridyl, wherein the supported nickel has the nickel content of 20 percent, the carrier is alumina, and the specific surface area is 120-250m2Per g, pore volume of 0.6m3(ii) in terms of/g. Gaseous pyridine enters a reactor at a certain flow rate, passes through a catalyst bed layer, reacts under the catalysis of loaded nickel to generate 2,2' -bipyridine, and reaction liquid is extracted through a gas-liquid separator; and gas generated by reaction enters the membrane tube, nitrogen is introduced into the membrane tube from the air inlet tube and overflows from the lower part of the membrane tube, gas in the membrane tube is purged, and mixed gas is discharged from the upper part of the membrane tube.
Table 1 shows the pyridine conversion for different catalysts at different temperatures, pressures, flow rates, and reaction times.
TABLE 1
Claims (9)
1. A method for producing 2,2' -bipyridine by a membrane reactor is characterized in that gaseous pyridine is introduced into the membrane reactor, passes through a catalyst bed layer and reacts under the action of a dehydrogenation catalyst to generate 2,2' -bipyridine, and the 2,2' -bipyridine and part of unreacted pyridine are condensed and extracted by a gas-liquid separator; hydrogen generated by the reaction and most of unreacted pyridine enter a membrane tube through a membrane porous material tube inserted into a catalyst bed layer to be separated from 2,2' -bipyridyl, nitrogen is introduced from the bottom of the membrane tube to purge gaseous pyridine and hydrogen, and mixed gas is discharged from the upper part of the membrane tube; wherein the reaction temperature is 300-600 ℃, and the pressure is 0.1-0.2 Mpa.
2. The method according to claim 1, wherein the reaction temperature is 500-600 ℃ and the pressure is 0.1-0.2 MPa.
3. The method of claim 1, wherein the gaseous pyridine has a flow rate of 0.02 to 0.06L-min-1G catalyst-1。
4. The process of claim 1 wherein the dehydrogenation catalyst is raney nickel or supported nickel.
5. The method according to claim 4, wherein the nickel content of the supported nickel is 20% or more, the carrier is alumina, and the specific surface area is 120m2More than g, pore volume of 0.6m3More than g.
6. The method of claim 1, wherein the membrane porous material tube is made of a membrane porous material with an open lower portion; the pore diameter of the membrane porous material is 4-10 nm.
7. The method according to claim 1, characterized in that the pressure in the gas-liquid separator is 0.78Mpa, and the condensation temperature of the gas-liquid separator is 70-80 ℃; the pressure in the membrane pipe is 1-10Kpa lower than the pressure in the gas-liquid separator.
8. A membrane reactor for the production of 2,2' -bipyridine according to claim 1, characterized by comprising a reactor, a gas-liquid separator; the reactor comprises a cylinder body, and a heating device is arranged outside the cylinder body; a dehydrogenation catalyst is filled in the cylinder to form a catalyst bed layer; a plurality of uniformly distributed feeding pipes are arranged in the middle of the reactor, and each feeding pipe is provided with a gas flowmeter; inserting a membrane tube into the reactor along the axial direction, wherein the upper end and the lower end of the membrane tube are closed, the lower part of the membrane tube is provided with a hole and covered with a membrane porous material to form a membrane porous material tube, and the membrane porous material tube is inserted into a catalyst bed layer; an air inlet pipe is arranged in the membrane pipe; the upper part of the membrane tube is provided with an air outlet; the reactor is connected with a feed inlet of the gas-liquid separator through a discharge hole at the lower part; the outer part of the gas-liquid separator is sleeved with a jacket, and the bottom of the gas-liquid separator is provided with a discharge pipe; the gas-liquid separator is provided with a nitrogen balance gas supplementing pipe and a back pressure valve.
9. The membrane reactor of claim 8 wherein the reactor is provided with a first pressure gauge and a second pressure gauge is provided in the membrane tube; a thermocouple is arranged in the reactor; the gas-liquid separator is provided with a third pressure gauge.
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| CN108440392B (en) * | 2018-04-19 | 2020-09-25 | 合肥工业大学 | Continuous production device and production method for synthesizing 2, 2' -bipyridyl |
| CN109589874B (en) * | 2018-11-19 | 2021-08-24 | 江苏玖鸿化工技术有限公司 | Methanol oxidizer in silver method formaldehyde device |
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| CN105461620A (en) * | 2015-11-23 | 2016-04-06 | 安徽千和新材料科技发展有限公司 | Raney nickel catalytic preparation method of 2,2'-bipyridine |
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| CN105461620A (en) * | 2015-11-23 | 2016-04-06 | 安徽千和新材料科技发展有限公司 | Raney nickel catalytic preparation method of 2,2'-bipyridine |
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