CN107628987A - A kind of method of membrane reactor production 2,2` bipyridyls - Google Patents
A kind of method of membrane reactor production 2,2` bipyridyls Download PDFInfo
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- CN107628987A CN107628987A CN201710851253.3A CN201710851253A CN107628987A CN 107628987 A CN107628987 A CN 107628987A CN 201710851253 A CN201710851253 A CN 201710851253A CN 107628987 A CN107628987 A CN 107628987A
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Abstract
The invention discloses a kind of method that membrane reactor produces 2,2 ' bipyridyls, including：The preheated gasification of pyridine, reactor is passed through in gaseous state, and by beds, 2,2 ' bipyridyls of reaction generation, 2,2 ' bipyridyls are condensed through gas-liquid separator with the unreacted pyridine in part and produced under dehydrogenation effect；The hydrogen and most of unreacted pyridine for reacting generation enter in membrane tube with 2 through inserting the film porous material pipe of beds, and 2 ' bipyridyls realize separation, and nitrogen is introduced from membrane tube bottom, purge gaseous state pyridine and hydrogen, and gaseous mixture is from the discharge of membrane tube top.The method that inventive film reactor produces 2,2 ' bipyridyls, pyridine high conversion rate, can separate unreacted raw material and product immediately, extend the life-span of catalyst.
Description
Technical field
The invention belongs to fine chemistry industry and organic synthesis field, and in particular to a kind of membrane reactor prepares 2,2 '-bipyridyl
Method.
Background technology
2,2 '-bipyridyl is the important intermediate of chemical industry and pharmaceutical synthesis, due to the chelation with uniqueness, Ke Yizuo
For the part of metallic catalyst, sensitising agent, the indicator etc. for detecting metal ion.
Be adapted to preparation of industrialization 2, the method for 2 '-bipyridyl mainly has two kinds, one kind be Ullmann methods (M.Tiecco etc.,
Communications, 1984,736-738), using 2- haloperidids as raw material, coupling reaction occurs under catalyst action, it is raw
It is high conversion rate the advantages of this method, reaction condition is gentle, and shortcoming is that quantity of three wastes is big, is gradually washed in a pan into 2,2 '-bipyridyl
Eliminate.Another method is using pyridine as raw material, generates 2 under nickel-base catalyst effect, 2 '-bipyridyl.The advantages of this method
It is atom utilization height, it is environmentally friendly, but single transformation rate is relatively low, patent GB897473 uses Raney's nickel normal in cable-styled reactor
Pressure, 100-120 DEG C of preparation 2,2 '-bipyridyl, maximum conversion is less than 1%；US5416217 is using nickel-loaded in fixed bed reaction
2,2 '-bipyridyl is prepared in device, temperature is 175-240 DEG C, pressure 0.9-1.5Mpa, although this method catalyst life reaches
500h, but conversion ratio is still less than 1%.Low-conversion causes product 2, and the separation of 2 '-bipyridyl and raw material pyridine becomes cumbersome,
For example being separated by the way of rectifying needs to consume big energy, and the difficulty of separation also constrains the industrialization of this method.
Therefore, it is necessary to which a kind of high conversion rate, separating energy consumption is low, and the 2 of catalyst life length, 2 '-bipyridyl producer
Method.
The content of the invention
The purpose of the present invention is to provide a kind of high conversion rate for above-mentioned problem, and separating energy consumption is low, and is catalyzed
The 2 of agent long lifespan, the production method of 2 '-bipyridyl, this method is simple to operate, and pyridine conversion ratio is up to 25-50%.
The purpose of the present invention is achieved through the following technical solutions：
A kind of membrane reactor production 2, the method for 2 '-bipyridyl, including：The preheated gasification of pyridine, reaction is passed through in gaseous state
Device, by beds, the reaction generation 2 under dehydrogenation effect, 2 '-bipyridyl, 2,2 '-bipyridyl and part be not anti-
The pyridine answered is condensed through gas-liquid separator and produced；The hydrogen generated and most of unreacted pyridine are reacted through inserting catalyst bed
The film porous material pipe of layer enters in membrane tube with 2, and 2 '-bipyridyl realizes separation, introduces nitrogen from membrane tube bottom, purges gaseous state pyrrole
Pyridine and hydrogen, gaseous mixture are discharged from membrane tube top.
Described reaction temperature is 300-600 DEG C, pressure 0.1-0.2Mpa.
Preferably, described reaction temperature is 500-600 DEG C, pressure 0.1-0.2Mpa.
The flow velocity of described gaseous state pyridine is 0.02-0.06Lmin-1G catalyst-1。
Described dehydrogenation is Raney's nickel or nickel-loaded.
The nickel content of described nickel-loaded is more than 20%, and carrier is aluminum oxide, specific surface area 120m2/ more than g, it is excellent
Elect 120-250m as2/ g, pore volume 0.6m3/ more than g, preferably 0.6-0.8m3/g。
Described film porous material pipe is made up of the perforate of membrane tube bottom and cover layer porous material；Described film porous material
Aperture be 4-10nm；Film porous material is alumino-silicate.In the reactor, 2,2 '-bipyridyl and pyridine are gas, due to
The size of membrane aperture, gaseous state pyridine can enter membrane tube by film, and bipyridyl cannot be introduced into, so most of pyridine passes through film
With 2, the separation of 2 '-bipyridyl, the unreacted pyridine in part and 2,2 '-bipyridyl enters gas-liquid separator, in gas-liquid separator
Reach vapor liquid equilibrium, liquid is released from bottom, and gas is in liquid upper.The purpose that the present invention sets gas-liquid separator is to ensure
Reactor pressure is stable and sampling is convenient.Pressure in described gas-liquid separator is about 0.78Mpa；Gas-liquid separator it is cold
Solidifying temperature is 70-80 DEG C.Pressure in described membrane tube is less than the pressure 1-10Kpa in gas-liquid separator.
It is a further object to provide one kind production 2, the membrane reactor of 2 '-bipyridyl, the device includes reaction
Device, gas-liquid separator；Reactor includes cylinder, and heater is externally provided with cylinder；Catalysis dehydrogenation dosage form is filled with cylinder
Into beds；More equally distributed feed pipes are provided with the middle part of reactor, gas flowmeter is provided with every feed pipe；
Membrane tube is axially inserted into reactor, the upper/lower terminal closing of membrane tube, simultaneously cover layer is porous in described membrane tube bottom perforate
Material forms film porous material pipe, and film porous material pipe is inserted in beds；Air inlet pipe is provided with described membrane tube；
Membrane tube top is provided with gas outlet；Reactor connects through the charging aperture of bottom discharging opening and gas-liquid separator；Described gas-liquid separation
Device outer cover is provided with chuck, leads to 70-80 DEG C of hot water in chuck, gas-liquid separator bottom is provided with discharge nozzle；Described gas-liquid separation
Device is provided with nitrogen balance supplement tracheae and counterbalance valve.
Described reactor shell is stainless steel cylinder.
Described membrane tube is stainless steel tube.
Described air inlet pipe stainless steel tube.The inlet-end manifold of described air inlet pipe stretches out membrane tube top, the outlet of air inlet pipe
Hold close to membrane tube bottom.
Described feed pipe arranges that the radical of feed pipe is at least 3, preferably 3-8 roots in divergent shape.
Described gas outlet is higher than membrane tube reactor.
Described reactor is provided with first pressure table and is used to measure reaction pressure, and second pressure gauge is provided with membrane tube and is measured
Film overpressure；Thermocouple is provided with reactor to be used to measure reaction bed temperature；Described gas-liquid separator is provided with the
Three pressure gauges.
Occur that film overpressure is higher than the situation of pressure in gas-liquid separator in actual mechanical process, therefore in gas-liquid
Separator top supplements tracheae by nitrogen balance and supplements nitrogen to keep pressure in gas-liquid separator to be higher than pressure in membrane tube.
Described counterbalance valve is used for the pressure and reactor pressure for controlling gas-liquid separator.
Beneficial effects of the present invention：
The present invention method of 2 '-bipyridyl, pyridine high conversion rate, can separate unreacted immediately using membrane reactor production 2
Raw material and product, extend life-span of catalyst.
Brief description of the drawings
Fig. 1 is the schematic diagram of the membrane reactor of 2,2 '-bipyridyl of production；
Fig. 2 is that reactor feed pipe arranges schematic diagram；
In figure, 1- reactors, 2- gas-liquid separators, 3- feed pipes, 4- gas flowmeters, 5- membrane tubes, 6- air inlet pipe, 7- urges
Agent bed, 8- gas outlets, 9- first pressure tables, 10- second pressure gauges, 11- thermocouples, 12- discharge nozzles, 13- nitrogen balances
Supplement tracheae, the pressure gauges of 14- the 3rd, 15- counterbalance valves.
Embodiment
With reference to embodiment, the present invention will be further described, but protection scope of the present invention not limited to this.
As shown in Figure 1, 2, it is a kind of to be used for production 2, the membrane reactor of 2 '-bipyridyl, including reactor 1, gas-liquid separator
2；Reactor 1 includes stainless steel cylinder, and heater is externally provided with cylinder；In cylinder catalysis is formed filled with dehydrogenation
Agent bed 7；8 feed pipes 3 are connected in the middle part of reactor, gas flowmeter 4 is provided with every feed pipe 3；In the interior edge of reactor 1
Membrane tube 5 is axially inserted into, the upper/lower terminal closing of membrane tube 5, is formed in the described bottom perforate of membrane tube 5 and cover layer porous material
Film porous material pipe, film porous material pipe are inserted in beds 7；Stainless steel air inlet pipe 6 is provided with membrane tube 5, air inlet pipe 6
Inlet-end manifold stretches out membrane tube 5 top, and the outlet side of air inlet pipe 6 is close to the bottom of membrane tube 5；Gas outlet 8 is provided with the top of membrane tube 5, is gone out
Gas port 8 is higher than reactor upper end；Described reactor 1 is provided with first pressure table 9 and is used to measure reaction pressure, is set in membrane tube 5
There is second pressure gauge 10 to be used to measure pressure in membrane tube 5；Thermocouple 11 is provided with reactor 1 to be used to measure beds temperature
Degree；Described reactor 1 is connected through bottom discharging opening with the charging aperture of gas-liquid separator 2；The outer cover of gas-liquid separator 2 is provided with folder
Cover, 70-80 DEG C of hot water is led in chuck, the bottom of gas-liquid separator 2 is provided with discharge nozzle 12；The described top of gas-liquid separator 2 is provided with
Nitrogen balance supplement tracheae 13, the 3rd pressure gauge 14 and counterbalance valve 15.
Described membrane tube 4 is stainless steel tube.
Described film porous material is covered in the bottom outer wall of membrane tube 5 and forms film porous material pipe, the aperture of film porous material
For 4- 10nm.
Based on above-mentioned membrane reactor generation 2, the method for 2 '-bipyridyl, gaseous state pyridine enters reactor, by gas flowmeter
2 measurement gas flows, gaseous state pyridine pass through beds 7, the reaction generation 2 under dehydrogenation effect, 2 '-bipyridyl,
Most of unreacted pyridine and the hydrogen of generation enter membrane tube through membrane separation, and the air inlet pipe 6 in membrane tube is passed through nitrogen and purged
Gas in membrane tube, N2/H2Gaseous mixture is discharged on membrane tube top through gas outlet 3, product 2, the unreacted original of 2 '-bipyridyl and part
Expect mixture by gas-liquid separator condensation discharging.
Embodiment 1-6
Load 60g Raney's nickels in above-mentioned production 2, the reactor of the device of 2 '-bipyridyl, gaseous state pyridine is with certain flow rate
It is 300-600 DEG C in temperature by beds by beds into reactor, under raney ni catalysis, reaction
Generation 2,2 '-bipyridyl, reaction solution produce by gas-liquid separator；Gas caused by reaction enters membrane tube, is passed through from air inlet pipe
Overflowed in nitrogen to membrane tube from membrane tube bottom, purge gas in membrane tube, gaseous mixture is discharged from membrane tube top.
Embodiment 7-12
Load 60g nickel-loadeds in above-mentioned production 2, the reactor of the device of 2 '-bipyridyl, wherein, the nickel of nickel-loaded contains
Measure as 20%, carrier is aluminum oxide, specific surface area 120-250m2/ g, pore volume 0.6m3/g.Gaseous state pyridine is with certain flow rate
Into reactor, by beds, under nickel-loaded catalysis, reaction generation 2,2 '-bipyridyl, reaction solution is by gas-liquid point
Produced from device；Gas caused by reaction enters membrane tube, is passed through in nitrogen to membrane tube from membrane tube bottom and overflows from air inlet pipe, purges film
Gas in pipe, gaseous mixture are discharged from membrane tube top.
Table 1 is the conversion ratio of different catalysts pyridine under different temperatures, pressure, flow velocity, reaction time.
Table 1
Claims (10)
1. a kind of membrane reactor production 2, the method for 2 '-bipyridyl, it is characterised in that gaseous state pyridine is passed through membrane reactor, passed through
Beds, the reaction generation 2 under dehydrogenation effect, 2 '-bipyridyl, 2,2 '-bipyridyl and the unreacted pyrrole in part
Pyridine is condensed through gas-liquid separator and produced；React the hydrogen of generation and most of film of the unreacted pyridine through insertion beds
Porous material pipe enters in membrane tube with 2, and 2 '-bipyridyl realizes separation, introduces nitrogen from membrane tube bottom, purges gaseous state pyridine and hydrogen
Gas, gaseous mixture are discharged from membrane tube top.
2. according to the method for claim 1, it is characterised in that reaction temperature is 300-600 DEG C, pressure 0.1-0.2Mpa.
3. according to the method for claim 2, it is characterised in that described reaction temperature is 500-600 DEG C, pressure 0.1-
0.2Mpa。
4. according to the method for claim 1, it is characterised in that the flow velocity of described gaseous state pyridine is 0.02-0.06Lmin-1G catalyst-1。
5. according to the method for claim 1, it is characterised in that described dehydrogenation is Raney's nickel or nickel-loaded.
6. according to the method for claim 5, it is characterised in that the nickel content of described nickel-loaded is more than 20%, and carrier is
Aluminum oxide, specific surface area 120m2/ more than g, pore volume 0.6m3/ more than g.
7. according to the method for claim 1, it is characterised in that described film porous material pipe by the perforate of membrane tube bottom and covers
Epiphragma porous material is made；The aperture of described film porous material is 4-10nm.
8. according to the method for claim 1, it is characterised in that the pressure in described gas-liquid separator is 0.78Mpa, gas
The condensation temperature of liquid/gas separator is 70-80 DEG C；Pressure in described membrane tube is less than the pressure 1-10Kpa in gas-liquid separator.
9. one kind is used for the membrane reactor of claim 1 production 2,2'- bipyridyls, it is characterised in that including reactor, gas-liquid point
From device；Reactor includes cylinder, and heater is externally provided with cylinder；In cylinder catalyst bed is formed filled with dehydrogenation
Layer；More equally distributed feed pipes are provided with the middle part of reactor, gas flowmeter is provided with every feed pipe；In reactor
Membrane tube is axially inserted into, the upper/lower terminal closing of membrane tube, film is formed in described membrane tube bottom perforate and cover layer porous material
Porous material pipe, film porous material pipe are inserted in beds；Air inlet pipe is provided with membrane tube；Outlet is provided with membrane tube top
Mouthful；Reactor connects through the charging aperture of bottom discharging opening and gas-liquid separator；Described gas-liquid separator outer cover is provided with chuck,
Bottom is provided with discharge nozzle；Described gas-liquid separator is provided with nitrogen balance supplement tracheae and counterbalance valve.
10. the membrane reactor of production 2,2'- bipyridyls according to claim 9, it is characterised in that described reactor is set
There is first pressure table, second pressure gauge is provided with membrane tube；Thermocouple is provided with reactor；Described gas-liquid separator is provided with
3rd pressure gauge.
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Cited By (5)
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| CN108440392A (en) * | 2018-04-19 | 2018-08-24 | 合肥工业大学 | The continuous production device and production method of a kind of 2,2 '-bipyridyls of synthesis |
| CN109589874A (en) * | 2018-11-19 | 2019-04-09 | 湖北三里枫香科技有限公司 | A kind of methanol oxidator in novel silver formaldehyde device |
| CN109603687A (en) * | 2018-11-19 | 2019-04-12 | 湖北三里枫香科技有限公司 | A kind of methanol oxidator in efficient silver-colored formaldehyde device |
| CN110279830A (en) * | 2019-07-01 | 2019-09-27 | 张颖 | A kind of manufacture craft of health perfume (or spice) board |
| CN117723873A (en) * | 2024-02-07 | 2024-03-19 | 广东卡沃罗氢科技有限公司 | Electrolytic cell testing system and electrolytic cell testing method |
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Cited By (7)
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| CN109589874A (en) * | 2018-11-19 | 2019-04-09 | 湖北三里枫香科技有限公司 | A kind of methanol oxidator in novel silver formaldehyde device |
| CN109603687A (en) * | 2018-11-19 | 2019-04-12 | 湖北三里枫香科技有限公司 | A kind of methanol oxidator in efficient silver-colored formaldehyde device |
| CN109603687B (en) * | 2018-11-19 | 2021-08-24 | 江苏玖鸿化工技术有限公司 | Methanol oxidizer in efficient silver-process formaldehyde device |
| CN110279830A (en) * | 2019-07-01 | 2019-09-27 | 张颖 | A kind of manufacture craft of health perfume (or spice) board |
| CN117723873A (en) * | 2024-02-07 | 2024-03-19 | 广东卡沃罗氢科技有限公司 | Electrolytic cell testing system and electrolytic cell testing method |
| CN117723873B (en) * | 2024-02-07 | 2024-06-04 | 广东卡沃罗氢科技有限公司 | Electrolytic cell testing system and electrolytic cell testing method |
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Effective date of registration: 20180517 Address after: 210047 No. 168 aromatics South Road, Nanjing chemical industry park, Jiangsu Applicant after: Nanjing Red Sun Biological Chemical Co., Ltd. Applicant after: Nanjing Redsun Co., Ltd. Address before: 210047 No. 168 aromatics South Road, Nanjing chemical industry park, Jiangsu Applicant before: Nanjing Red Sun Biological Chemical Co., Ltd. |
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