CN107382745A - A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline - Google Patents
A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline Download PDFInfo
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- CN107382745A CN107382745A CN201710803255.5A CN201710803255A CN107382745A CN 107382745 A CN107382745 A CN 107382745A CN 201710803255 A CN201710803255 A CN 201710803255A CN 107382745 A CN107382745 A CN 107382745A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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Abstract
A kind of method that the present invention synthesizes aniline for nitrobenzene continuous liquid phase hydrogenation.This method comprises the following steps：After reactor of the nitrogen displacement equipped with active metal/metal packing catalyst 8~12 minutes, reactor is warming up to 60~200oC, then 40~120 will be preheating to respectivelyoC nitrobenzene and hydrogen is continuously added to be reacted in reactor, 0.01~3h of liquid air speed of nitrobenzene‑1, the gas air speed of hydrogen is 100~2000h‑1, the pressure in reactor is 0.3~2.0MPa；After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen is back to reactor, and liquid phase obtains reaction product aniline.Catalyst activity metal of the present invention utilizes high with rate, and activity is good, and heat and mass surface area is big, and resistance is small, and course of reaction is without effect of intraparticle diffusion, and reaction speed is fast, equipment and simple production process, and production efficiency is high, and catalyst can maintain a long-term stability operation.
Description
Technical field
The invention belongs to field of catalytic reactions, more particularly to using metal packing as carrier prepare carried-type active metal/
Metal packing catalyst, the method that nitrobenzene continuous liquid phase hydrogenation synthesis aniline is then carried out using the catalyst.
Background technology
Aniline is a kind of important organic chemical industry's intermediate, is widely used in urethane raw diphenylmethane diisocyanate
The production of ester (MDI), fuel, medicine, rubber chemicals, agricultural chemicals and fine-chemical intermediate, market potential are larger.Aniline is given birth at present
The process route of production is most with the application of nitrobenzene (NB) catalytic hydrogenation method, accounts for the 85% of aniline total productive capacity.Industrial nitre
Base benzene catalytic hydrogenation method has fixed-bed catalytic hydrogenation, fluidized bed catalytic hydrogenation and three kinds of techniques of liquid-phase hydrogenatin.Fixed Bed Gas Phase adds
Hydrogen aniline uses Ni systems or Cu series catalysts, 150~300 DEG C of reaction temperature, 200~1500kPa of pressure more.The technique has
Technology maturation, reaction temperature are low, equipment and it is simple to operate, maintenance cost is low, good product quality the advantages that, weak point be reaction
Pressure is high, and hot-spot easily occurs and causes side reaction and catalyst inactivation.Fluidized-bed hydrogenation technique can avoid the office of fixed bed
Frequent parking caused by portion's overheat and more catalyst changeout, can keep continuous run in long period.Such as BASF AG's fluidized-bed hydrogenation
Technology is fed using nitrobenzene, hydrogen mixed atomizing, and hydrogenation reaction is carried out under 250~300 DEG C, 400~1000kPa of pressure,
Technique and operation are relative complex.Nitrobenzene liquid-phase hydrogenatin industrial installation generally use high activity noble metal catalyst.The U.S.
Patent US2293879 discloses a kind of liquid phase continuous catalytic hydrogenation technique, and using aniline as solvent, hydrogenation temperature boils close to solvent
Point, reaction pressure are less than 10kPa, and reaction heat is partly or entirely absorbed by product evaporation, and a large amount of aniline pass back into reactor, with
Keep the stabilization of operating condition.Liquid-phase hydrogenatin has that reaction temperature is low, side reaction is few, catalyst loading is high, equipment capacity
Advantage, the weak points such as greatly, gross investment is low are that reactant must be separated with catalyst, reactant with solvent, the behaviour of equipment
It is higher to make maintenance cost.
The present inventor discloses one kind and prepares active reaction component in the immobilized active component of reactor component surface, utilizes work
Property reactive means carry out the method (CN201410526666.0) of synthesizing amino benzene by hydrogenation of nitrobenzene, methods described is included gold-supported
Load type metal catalyst, aqueous solvent and the accelerator of category active component are put into the reactor with hardware, are being stirred
With handled 1~10 hour under certain temperature in hydrogen atmosphere, supported catalyst is then recovered by filtration.Repeat said process 3-4
Secondary, reactor component surface forms high activity reaction center.Nitrobenzene is added into the reactor equipped with active reaction component to enter
Row reaction, under the conditions of 120 DEG C of reaction temperature, Hydrogen Vapor Pressure 1.0MPa, 3h is reacted, nitrobenzene conversion rate and aniline yield rate are
99.5%.Although the above method may be implemented in direct supported active metals on metal material surface and use it for nitrobenzene liquid phase
Hydrogenation synthesis aniline reaction, but catalyst preparation need to be completed by loaded catalyst, processing procedure needs to be separated by filtration to urge
Agent, not only complex operation, and need solution to use the recovery and utilization of loaded catalyst active metal after handling
Problem, while also have considerable restraint to handled hardware structure, it is only applicable to reactor metal wall, agitating paddle, heat
Thermowell, cooling coil and a small amount of component pattern of metal plate washer, metal tube, the woven wire that can add, reacted
The surface area that the available hardware of journey contacts with reaction solution is small, and reaction needs intermittently to carry out in reactor, production efficiency
It is low.
The content of the invention
The technical problems to be solved by the invention are：For the deficiency of existing liquid-phase hydrogenatin production aniline process, there is provided a kind of
Metal supported catalyst directly is prepared on Large ratio surface metal packing surface, it is continuous then to carry out nitrobenzene in the catalyst surface
The method that liquid-phase hydrogenatin synthesizes aniline.Described catalyst preparation process is carried out in the pole dilute aqueous solution of metal salt, by metal
In extremely dilute metal salt solution, now its concentration, which is in, is advantageous to the monatomic existing state of metal for the formation control of particle,
The kinetic energy provided by stirring and treatment temperature forms metallic atom insert material surface stable activated centre, processing procedure
It is special to any type of metal material in the absence of the separation problem of solid catalyst in CN201410526666.0 and processing material
It is not that bigger serface metal packing can be completed to load, preparation method is simple.Catalyst activity metal of the present invention utilizes
Rate is high, and activity is good, and heat and mass surface area is big, and resistance is small, and course of reaction is without effect of intraparticle diffusion, and reaction speed is fast, equipment and life
Production. art is simple, and production efficiency is high, and catalyst can maintain a long-term stability operation.
The technical scheme is that：
A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline, comprises the following steps：
After reactor of the nitrogen displacement equipped with active metal/metal packing catalyst 8~12 minutes, reactor is heated up
To 60~200 DEG C, then the nitrobenzene and hydrogen that are preheating to 40~120 DEG C respectively are continuously added to be reacted in reactor,
0.01~3h of liquid air speed of nitrobenzene-1, the gas air speed of hydrogen is 100~2000h-1, pressure in reactor for 0.3~
2.0MPa；After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen is back to reactor, and liquid phase obtains reaction production
Thing aniline；
Described reactor is preferably tubular fixed-bed reactor or trickle bed reactor；
The liquid air speed of described nitrobenzene feed is preferably 0.2~1.2h-1, the gas air speed of hydrogen is preferably 160~900h-1；
Described active metal/metal packing catalyst, is prepared by following methods, comprises the following steps：
The first step, metal packing is fitted into reactor, the admission space of filler is the 80%~90% of reactor volume；
Then nitrogen displacement processing unit and pipe-line system are used；Final reactor is warming up to 80~200 DEG C；
Second step, the treatment fluid in solution reservoir is squeezed into preheater with pump, then into the reactor of the first step,
0.15~2.0MPa of reactor pressure；It is vented after the gas condensation ejected by reactor, the liquid of discharge is collected into described
In solution reservoir, processing is continued to participate in as treatment fluid；After 1~2h of reactor continuous processing, active metal/metal packing is obtained
Catalyst；
Wherein, the temperature of described preheater is 80~200 DEG C, and described treatment fluid enters the mode of the first stage reactor
To enter directly into the reactor of the first step, or enter after being mixed with nitrogen hydrogen mixeding gas in the reactor of the first step；Nitrogen
The air speed of hydrogen gaseous mixture is 500~800h-1, nitrogen hydrogen ratio is 10:0.01~1；
Described treatment fluid is the mixed liquor that the metal salt of active component and water are hybridly prepared into, the gold in terms of active component
The concentration for belonging to salt is 0.1~10ppm；The metal salt of described active component is the salt of platinum, palladium, rhodium, ruthenium, gold or nickel；
Described metal packing is stainless steel, zirconium or filler made of alloy, the specific surface area of filler for 200~
5000m2/m3。
The metal salt of described active component is preferably chloroplatinic acid, palladium bichloride, ruthenium trichloride or radium chloride.
Metal packing in the described first step is preferably that specific surface area is 501~3700m2/m3θ ring fillers or ripple
Filler.
In described second step, metal salt solution liquid air speed is preferably 50~100h-1。
In described second step, nitrogen hydrogen ratio preferably 10 in nitrogen hydrogen mixeding gas:1；
In described second step, the concentration of the metal salt of active component meter is preferably 0.5~3ppm in treatment fluid.
The beneficial effects of the invention are as follows:
(1) present invention provide one kind is used for nitrobenzene continuous liquid phase hydrogenation active metal/metal packing catalyst, by
In the solution of extremely dilute metal salt, metal salt is converted into metallic atom using hydrogenating reduction or thermal decomposition and reduction, then molten
Metallic atom is quickly embedded in metal packing surface under the circulation collision effect of liquid and forms metal supported catalyst.Preparation method letter
It is single easy, it can be loaded in bigger serface metal packing, to form of bio-carrier, structure without specifically limited requirement.(2) originally
Invention provides one kind and is used for nitrobenzene continuous liquid phase hydrogenation active metal/metal packing catalyst, catalyst activity Metal Supported
Measure low, but utilization rate is high, and activity is good, and the nitrobenzene transformation frequency in terms of active metal reaches 9.69 X 104gNB·(g·h)-1,
Far above the activity level of current commercial catalyst.(3) present invention provides a kind of for nitrobenzene continuous liquid phase hydrogenation activity gold
Category/metal packing catalyst, reaction directly can be carried out continuously on filler surface, and resistance to mass tranfer is small, and heat transfer coefficient is high, reacts
Journey is without effect of intraparticle diffusion, it is not necessary to which plus solvent, equipment and simple production process, production efficiency are high.(4) present invention provides a kind of
It is not catalyzed for nitrobenzene continuous liquid phase hydrogenation active metal/metal packing catalyst, catalyst performance stabilised, course of reaction
Agent is lost and inactivation regeneration issues, can remain stable over operation.
Embodiment
Embodiment 1
The first step, the stainless steel θ ring filler fillers that 4L specifications are 3 × 3mm are put into a diameter of 100mm, a height of 600mm's
In tubular fixed-bed reactor, packing specific area 2800m2/m3, heap density is 460kg/m3；
Second step, with nitrogen displacement processing unit and pipe-line system 8~12 minutes；
3rd step, chloroplatinic acid and water are hybridly prepared into platinum acid chloride solution of the 150L platinum concentrations for 0.8ppm as treatment fluid
It is put into solution reservoir；
4th step, with pump by the treatment fluid in the 3rd step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Spend for 80 DEG C, be then 500h with air speed-1, nitrogen hydrogen ratio be 10:Enter the reactor of the first step after 1 nitrogen hydrogen mixeding gas mixing
In and act on filler surface, the temperature of reactor is 80 DEG C, pressure 0.15MPa, after the gas condensation come out by reactor
Emptying；The solution reservoir that the liquid of discharge returns to the 3rd step continues continuously to participate in the processing procedure of this step as treatment fluid；Reaction
Device obtains Pt/ metal packing catalyst after the continuous circular treatment 1 hour for the treatment of fluid and nitrogen and hydrogen mixture.Utilize inductance coupling
Close plasma emission spectrometer and Pt constituent content analysis is carried out to catalyst, Pt load capacity is 32.1mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Pt/ metal packing catalyst of the 4th step
Road system, after 8~12 minutes, reactor is warming up to 150 DEG C.Raw material nitrobenzene is squeezed into preheating by 1.6L/h of flow with pump
100 DEG C are preheated in device, then (i.e. now liquid air speed is 0.4h into reactor for autoreactor bottom-1).To equally it be warming up to
Hydrogen (the i.e. gas air speed 300h that 100 DEG C of flows are 1200L/h-1) gas-liquid distributor of reacted device bed bottom is dispersed to raw material
In liquid, gas-liquid mixture carries out catalytic reaction in filler catalyst surface, nitrobenzene is converted into aniline.Reaction pressure is
0.8MPa.After the gas-liquid mixture condensed device condensation come out from reactor, hydrogen recycles, and liquid phase is reaction product, nitre
Base benzene conversion ratio is 100%, and the yield of aniline is 99.8%, and the equivalent nitrobenzene transformation frequency counted using unit mass Pt is 3.25
ⅹ104gNB·(gPt·h)-1。
Embodiment 2
The first step, the stainless steel θ ring fillers that 4L specifications are 2 × 2mm are put into a diameter of 100mm, a height of 600mm tubular type
In fixed bed reactors, packing specific area 3700m2/m3, heap density is 576kg/m3；
Second step, with nitrogen displacement processing unit and pipe-line system 8~12 minutes；
3rd step, chloroplatinic acid and water are hybridly prepared into platinum acid chloride solution of the 150L platinum concentrations for 1.0ppm as treatment fluid
It is put into solution reservoir；
4th step, with pump by the treatment fluid in the 3rd step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Spend for 80 DEG C, be then 800h with air speed-1, nitrogen hydrogen ratio be 10:Enter the reactor of the first step after 1 nitrogen hydrogen mixeding gas mixing
In, the temperature of reactor is 80 DEG C, pressure 0.15MPa, is vented after the gas condensation come out by reactor；The liquid of discharge returns
Solution reservoir to the 3rd step continues as treatment fluid continuously to participate in the processing procedure of this step；Reactor passes through treatment fluid and nitrogen hydrogen
The continuous circular treatment of gaseous mixture obtains Pt/ metal packing catalyst after 2 hours.Launch light using inductively coupled plasma
Spectrometer carries out Pt constituent content analysis to catalyst, and Pt load capacity is 42.1mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Pt/ metal packing catalyst of the 4th step
Road system, after 8~12 minutes, reactor is warming up to reaction temperature, reaction temperature is 180 DEG C.With pump by raw material nitrobenzene with
Flow is squeezed into preheater for 4.8L/h and is preheated to 120 DEG C, and then into reactor, (i.e. now liquid air speed is for autoreactor bottom
1.2h-1).It is 3600L/h (i.e. gas air speed 900h that 120 DEG C of flows, which will be equally warming up to,-1) hydrogen reacted device bed bottom
Gas-liquid distributor is dispersed in material liquid, and gas-liquid mixture carries out catalytic reaction in filler catalyst surface, converts nitrobenzene
For aniline.Reaction pressure is 1.2MPa.After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen recycles,
Liquid phase is reaction product, and nitrobenzene conversion rate 100%, the yield of aniline is 99.7%, converts into the nitre in terms of unit mass Pt
Base benzene transformation frequency is 5.94 X 104gNB·(gPt·h)-1。
Embodiment 3
The first step, 4L zirconium material perforated plate corrugated fillers are put into a diameter of 100mm, a height of 600mm tubular fixed-bed reaction
In device, packing specific area 501m2/m3, heap density is 325kg/m3；
Second step, with nitrogen displacement processing unit and pipe-line system 8~12 minutes；
3rd step, chloroplatinic acid and water are hybridly prepared into platinum acid chloride solution of the 150L platinum concentrations for 0.5ppm as treatment fluid
It is put into solution reservoir；
4th step, with pump by the treatment fluid in the 3rd step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Spend for 150 DEG C, be then 800h with air speed-1, nitrogen hydrogen ratio be 10:Enter the anti-of the first step after 1 nitrogen hydrogen mixeding gas mixing
Answer in device and act on filler surface, the temperature of reactor is 150 DEG C, pressure 0.8MPa, and gas condensation is come out by reactor
After be vented；The solution reservoir that the liquid of discharge returns to the 3rd step continues continuously to participate in the processing procedure of this step as treatment fluid；Instead
Device is answered to obtain Pt/ metal packing catalyst after the continuous circular treatment 2 hours for the treatment of fluid and nitrogen and hydrogen mixture.Utilize electricity
Feel coupled plasma optical emission spectrometer and Pt constituent content analysis is carried out to catalyst, Pt load capacity is 38.1mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Pt/ metal packing catalyst of the 4th step
Road system, after 8~12 minutes, reactor is warming up to reaction temperature, reaction temperature is 200 DEG C.With pump by raw material nitrobenzene with
4L/h, which is squeezed into preheater, is preheated to 120 DEG C, and then into reactor, (i.e. now liquid air speed is 1.0h for autoreactor bottom-1)。
It is 2800L/h (i.e. gas air speed 700h that 120 DEG C of flows, which will be equally warming up to,-1) H2The gas-liquid distributor of reacted device bed bottom
It is dispersed in material liquid, gas-liquid mixture carries out catalytic reaction in filler catalyst surface, nitrobenzene is converted into aniline.Reaction
Pressure is 1.2MPa.After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen is recycled, and liquid phase is produced for reaction
Thing, nitrobenzene conversion rate 100%, the yield of aniline is 99.7%, converts into the nitrobenzene transformation frequency in terms of unit mass Pt
For 9.69 X 104gNB·(gPt·h)-1。
Embodiment 4
The first step, 4L materials are put into a diameter of 100mm, a height of 600mm drip for the screen waviness packings of stainless steel
In bed reactor, packing specific area 700m2/m3, heap density is 415kg/m3；
Second step, with nitrogen displacement processing unit 8~12 minutes；
3rd step, palladium bichloride and water are hybridly prepared into the palladium chloride solution that 80L palladiums concentration is 2ppm and put as treatment fluid
Enter solution reservoir；
4th step, with the treatment fluid in the step solution reservoir of pump the 3rd with air speed 50h-1Squeeze into preheater, the temperature of preheater
For 150 DEG C, subsequently into the reactor of the first step and filler surface is acted on, the temperature of reactor is 150 DEG C, and pressure is
0.3MPa；The solution reservoir that the liquid ejected by reactor returns to the 3rd step continues continuously to participate in this step as treatment fluid
Reason process；Reactor obtains Pd/ filler catalyst after the continuous circular treatment for the treatment of fluid 2 hours.Using inductive etc. from
Daughter emission spectrometer carries out Pd constituent content analysis to catalyst, and Pd load capacity is 29.1mgkg-1；
5th step, uses N2Replace the trickle bed reactor and its pipe-line system equipped with Pd/ filler catalyst of the 4th step, 8
After~12 minutes, reactor is warming up to reaction temperature, reaction temperature is 60 DEG C.With pump by raw material nitrobenzene with 0.8L/h (i.e.
Liquid air speed 0.2h-1) squeeze into preheater and be preheated to 40 DEG C, it is 640L/h (i.e. gas air speeds then and to be equally warming up to 40 DEG C of flows
160h-1) H2Enter reactor at the top of mixing autoreactor.Gas-liquid mixture carries out catalytic reaction in filler catalyst surface,
Nitrobenzene is set to be converted into aniline.Reaction pressure is 2.0MPa.After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen
Gas recycles, and liquid phase is reaction product, and nitrobenzene conversion rate 95.0%, the yield of aniline is 99.9%, is converted into unit
The nitrobenzene transformation frequency of quality Pd meters is 1.89 X 104gNB·(gPd·h)-1。
Embodiment 5
The first step, it is 100mm that the net corrugated filling that 4L materials are monel metal, which is put into a diameter of, a height of 600mm
Tubular fixed-bed reactor in, packing specific area 643m2/m3, heap density is 508kg/m3；
Second step, with nitrogen displacement processing unit and pipe-line system 8~12 minutes；
3rd step, rhodium chloride and water are hybridly prepared into rhodium chloride solution of the 100L concentration for 1.5ppm as processing
Liquid is put into solution reservoir；
4th step, with pump by the treatment fluid in the 3rd step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Spend for 200 DEG C, be then 800h with air speed-1, nitrogen hydrogen ratio be 10:Enter the reaction of the first step after 1 nitrogen hydrogen mixeding gas mixing
In device and filler surface is acted on, the temperature of reactor is 200 DEG C, pressure 2.0MPa, and the gas come out by reactor condenses
After be vented；The solution reservoir that the liquid of discharge returns to the 3rd step continues continuously to participate in the processing procedure of this step as treatment fluid；Instead
Device is answered to obtain Rh/ metal packing catalyst after the continuous circular treatment 1 hour for the treatment of fluid and nitrogen and hydrogen mixture.Utilize electricity
Feel coupled plasma optical emission spectrometer and Rh constituent content analysis is carried out to catalyst, Rh load capacity is 31.5mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Rh/ metal packing catalyst of the 4th step
Road system, after 8~12 minutes, reactor is warming up to reaction temperature, reaction temperature is 150 DEG C.With pump by raw material nitrobenzene with
3.2L/h, which is squeezed into preheater, is preheated to 100 DEG C, and then autoreactor bottom enters reactor (i.e. now liquid air speed 0.8h-1)。
It is 2500L/h (i.e. gas air speed 625h that 100 DEG C of flows, which will be equally warming up to,-1) H2The gas-liquid distributor of reacted device bed bottom
It is dispersed in material liquid, gas-liquid mixture carries out catalytic reaction in filler catalyst surface, nitrobenzene is converted into aniline.Reaction
Pressure is 1.0MPa.After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen is recycled, and liquid phase is produced for reaction
Thing, nitrobenzene conversion rate 100%, the yield of aniline is 99.7%, converts into the nitrobenzene transformation frequency in terms of unit mass Rh
For 6.0 X 104gNB·(gRh·h)-1。
Embodiment 6
The first step, the stainless steel θ ring fillers that 4L specifications are 3 × 3mm are put into a diameter of 100mm, a height of 600mm tubular type
In fixed bed reactors, packing specific area 2800m2/m3, heap density is 460kg/m3；；
Second step, with nitrogen displacement processing unit and pipe-line system 8~12 minutes；
3rd step, ruthenium trichloride and water are hybridly prepared into solution of ruthenium trichloride of the 100L concentration for 1.5ppm as processing
Liquid is put into solution reservoir；
4th step, with pump by the treatment fluid in the 3rd step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
Spend for 100 DEG C, be then 800h with air speed-1, nitrogen hydrogen ratio be 10:Enter the reaction of the first step after 1 nitrogen hydrogen mixeding gas mixing
In device and filler surface is acted on, the temperature of reactor is 100 DEG C, pressure 0.3MPa, and the gas come out by reactor condenses
After be vented；The solution reservoir that the liquid of discharge returns to the 3rd step continues continuously to participate in the processing procedure of this step as treatment fluid；Instead
Device is answered to obtain Ru/ metal packing catalyst after 1 hour by the continuous circular treatment for the treatment of fluid and nitrogen and hydrogen mixture.Utilize inductance
Coupled plasma optical emission spectrometer carries out Ru constituent content analysis to catalyst, and Ru load capacity is 51.3mgkg-1；
5th step, uses N2Replace the tubular fixed-bed reactor and its pipe equipped with Ru/ metal packing catalyst of the 4th step
Road system, after 8~12 minutes, reactor is warming up to reaction temperature, reaction temperature is 120 DEG C.With pump by raw material nitrobenzene with
1L/h, which is squeezed into preheater, is preheated to 80 DEG C, and then autoreactor bottom enters reactor (i.e. now liquid air speed 0.25h-1).Will
It is 800L/h (i.e. gas air speed 200h to be equally warming up to 80 DEG C of flows-1) H2The vapor-liquid distributor of reacted device bed bottom disperses
Into material liquid, gas-liquid mixture carries out catalytic reaction in filler catalyst surface, nitrobenzene is converted into aniline.Reaction pressure
For 0.3MPa.After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen recycles, and liquid phase is reaction product,
The yield of nitrobenzene conversion rate and aniline is 100%, is converted into using the nitrobenzene transformation frequency that unit mass Ru is counted as 1.28 X
104gNB·(gRu·h)-1。
Embodiment 7
The course of reaction of embodiment 2 is continuously run and remained at 1000h, nitrobenzene conversion rate and aniline yield rate
100% and 99.7%, the metal/metal filler catalyst performance stabilised invented.Launch light using inductively coupled plasma
Spectrometer carries out Pt constituent content analysis to the catalyst after operating 1000h, and Pt load capacity is 42.1mgkg-1, it is and new before reaction
For fresh catalyst compared to not changing, the loss problem of active metal is not present in course of reaction.
Unaccomplished matter of the present invention is known technology.
Claims (6)
- A kind of 1. method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline, it is characterized in that this method comprises the following steps：After reactor of the nitrogen displacement equipped with active metal/metal packing catalyst 8~12 minutes, reactor is warming up to 60~200oC, then 40~120 will be preheating to respectivelyoC nitrobenzene and hydrogen is continuously added to be reacted in reactor, nitro 0.01~3h of liquid air speed of benzene-1, the gas air speed of hydrogen is 100~2000 h-1, the pressure in reactor is 0.3~2.0MPa； After the condensed device condensation of gas-liquid mixture come out from reactor, hydrogen is returned instead to reactor, and liquid phase obtains reaction product benzene Amine；Described reactor is tubular fixed-bed reactor or trickle bed reactor；The liquid air speed of described nitrobenzene feed is preferably 0.2~1.2h-1, the gas air speed of hydrogen is preferably 160~900 h-1；Described active metal/metal packing catalyst, is prepared by following methods, comprises the following steps：The first step, metal packing is fitted into reactor, the admission space of filler is the 80%~90% of reactor volume；Then use Nitrogen displacement processing unit and pipe-line system；Final reactor is warming up to 80~200oC ；Second step, the treatment fluid in solution reservoir is squeezed into preheater with pump, then into the reactor of the first step, reacted 0.15~2.0MPa of device pressure；It is vented after the gas condensation ejected by reactor, the liquid of discharge is collected into described solution In storage tank, processing is continued to participate in as treatment fluid；After the h of reactor continuous processing 1~2, obtain active metal/metal packing and urge Agent；Wherein, the temperature of described preheater is 80~200oC, the mode that described treatment fluid enters the first stage reactor are In the reactor for entering directly into the first step, or enter after being mixed with nitrogen hydrogen mixeding gas in the reactor of the first step；Nitrogen hydrogen The air speed of gaseous mixture is 500~800h-1, nitrogen hydrogen ratio is 10:0.01~1；Described treatment fluid is the mixed liquor that the metal salt of active component and water are hybridly prepared into, the metal salt in terms of active component Concentration be 0.1~10ppm；The metal salt of described active component is the salt of platinum, palladium, rhodium, ruthenium, gold or nickel；Described metal packing is stainless steel, zirconium or filler made of alloy, and the specific surface area of filler is 200~5000m2/m3。
- 2. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as claimed in claim 1, it is characterized in that described activearm The metal salt divided is preferably chloroplatinic acid, palladium bichloride, ruthenium trichloride or radium chloride.
- 3. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as claimed in claim 1, it is characterized in that the described first step In metal packing be preferably that specific surface area is 501~3700 m2/m3θ ring fillers or ripple packing.
- 4. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as claimed in claim 1, it is characterized in that described second step In, metal salt solution liquid air speed is preferably 50~100 h-1。
- 5. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as claimed in claim 1, it is characterized in that described second step In, nitrogen hydrogen ratio preferably 10 in nitrogen hydrogen mixeding gas:1.
- 6. the method for nitrobenzene continuous liquid phase hydrogenation synthesis aniline as claimed in claim 1, it is characterized in that described second step In, the concentration of the metal salt in treatment fluid in terms of active component is preferably 0.5~3ppm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107721804A (en) * | 2017-10-16 | 2018-02-23 | 绍兴贝斯美化工股份有限公司 | A kind of method for preparing ortho-xylene through 3 nitro ortho-xylenes |
| CN110721646A (en) * | 2019-12-02 | 2020-01-24 | 河北工业大学 | Active micro-reactor |
| CN113429295A (en) * | 2021-07-12 | 2021-09-24 | 浙江迪邦化工有限公司 | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor |
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| CN103769164A (en) * | 2014-01-10 | 2014-05-07 | 浙江工业大学 | Stainless steel wire gauze platinum-loaded catalyst and application thereof |
| CN104311433A (en) * | 2014-10-09 | 2015-01-28 | 河北工业大学 | Process for synthesizing aniline by nitrobenzene hydrogenation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103769164A (en) * | 2014-01-10 | 2014-05-07 | 浙江工业大学 | Stainless steel wire gauze platinum-loaded catalyst and application thereof |
| CN104311433A (en) * | 2014-10-09 | 2015-01-28 | 河北工业大学 | Process for synthesizing aniline by nitrobenzene hydrogenation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107721804A (en) * | 2017-10-16 | 2018-02-23 | 绍兴贝斯美化工股份有限公司 | A kind of method for preparing ortho-xylene through 3 nitro ortho-xylenes |
| CN107721804B (en) * | 2017-10-16 | 2020-09-18 | 绍兴贝斯美化工股份有限公司 | Method for preparing o-xylene through 3-nitro-o-xylene |
| CN110721646A (en) * | 2019-12-02 | 2020-01-24 | 河北工业大学 | Active micro-reactor |
| CN113429295A (en) * | 2021-07-12 | 2021-09-24 | 浙江迪邦化工有限公司 | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor |
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