CN107570146A - A kind of catalyst of supported active metals direct in metal packing - Google Patents
A kind of catalyst of supported active metals direct in metal packing Download PDFInfo
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Abstract
A kind of catalyst of supported active metals direct in metal packing, the catalyst are made for following methods, and described method 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；Second step, the treatment fluid in solution reservoir is squeezed into preheater with pump, then into the reactor of the first step；It is vented after the gas condensation ejected by reactor, the liquid of discharge is collected into described solution reservoir, and processing is continued to participate in as treatment fluid；After the h of reactor continuous processing 1~2, active metal/metal packing catalyst is obtained.The active metal utilization rate for the catalyst that the present invention obtains is high, and heat and mass surface area is big, and resistance is small, and course of reaction is without effect of intraparticle diffusion.
Description
Technical field
The invention belongs to field of catalytic reactions, the catalysis of specially a kind of supported active metals direct in metal packing
Agent.
Background technology
Metal supported catalyst is a kind of important industrial catalyst, is widely used in many important anti-in chemical industry
Answer process.It is generally using the porous oxide of high-specific surface area as carrier.Porous oxide carrier interior is diffused through due to existing
Journey, heterogeneous catalytic reaction rate reduction, selectivity can be made to be deteriorated.Generally use reduces catalyst particle size, increase catalyst
Pore volume and aperture improve intraparticle diffusion efficiency factor, reduce in diffusion influence, but can bring beds pressure drop increase,
The problem of mechanical strength reduces, influence catalytic efficiency more other than surface reduction etc..On the other hand, porous oxide carrier is due to leading
Hot property is poor, makes the more difficult control of temperature of reaction system, produces temperature runaway phenomenon sometimes, causes sintering of catalyst to inactivate, even
Generation security incident.Comparatively speaking, metallic carrier has good heat conductivity, high mechanical strength, diffusion and the spies such as resistance to mass tranfer is small
Point, the catalyst that excellent performance is prepared on metallic carrier are always a focus of concern.Due to metal surface light
Sliding, active component is not easy to load, and metal supported catalyst is required for carrying out metal greatly on the metallic carrier of document report at present
Surface roughening treatment, be allowed to be formed can load active component porous oxide film layer.Such as have been reported that using anodic oxidation skill
Art stainless steel wire it is online it is spontaneous grown the fine and close anodic oxide film (thickness is about 2.5-10 μm) of a Rotating fields, then adopt
Having prepared loaded catalyst with infusion process, (such as Chen Min, Ma Ying, Song Cui is catalyzed journal, 2009,30 (7)：649-653)；Appoint
Human relations etc. of spreading out are prepared for Al using pre-coated and second coat two-step method2O3/ 316L integrated catalyst carriers (Ren Yanlun, Liu Jing
The Chemical Engineerings such as thunder a, jasmine, 2014,42 (4)：54-58)；Molecular sieve catalyst is covered in stainless steel surfaces by single will equality,
The ZSM-5/ stainless steel θ ring catalytic distillation elements for catalytic distillation are prepared for, preparation process is except requiring that molecular sieve has one
Outside fixed mechanical strength, also require that crystal grain is tiny, while intercrystalline has larger space, to reduce (single flat of will points of resistance to mass tranfer
Research prepared by sub- sieve/stainless steel catalytic distillation element:[academic dissertation], Beijing:Research Institute of Petro-Chemical Engineering, 1994.).
Above-mentioned document report, oxide carrier category is still fallen within principle.Although strong compared with pure-oxide carrier heat conductivility and machinery
Degree improves, but because the presence of film layer can decline stainless steel heat conductivility.And it is complicated, interior to also create preparation technology
The new problems such as surface area reduces, film layer is peeled off.
The present inventor discloses one kind by means of conventional supported catalyst, is reduced using in-situ metal in reactor component
Surface produces chain carrier, forms the method (CN201410526689.1) of the catalytic reaction component of high activity, the side
Method includes the load type metal catalyst of carried metal active component, aqueous solvent and accelerator being put into the anti-of hardware
Answer in device, stirring and handled 1~10 hour under certain temperature in hydrogen atmosphere, supported catalyst is then recovered by filtration.Weight
Said process 3~4 times again, reactor component surface form high activity reaction center.Although the above method may be implemented in metal material
Expect supported active metals, but this process need to be completed by loaded catalyst directly on a surface, processing procedure needs to filter
Separating catalyst, not only complex operation, and have considerable restraint to handled hardware structure, is only applicable to reactor metal
Wall, agitating paddle, thermocouple sheath, cooling coil and a small amount of structure of metal plate washer, metal tube, the woven wire that can add
Part pattern, but also need to solve recovery and Utilizing question that loaded catalyst active metal is used after handling.
The content of the invention
The present invention is directed to the deficiency of current techniques, there is provided a kind of catalysis of supported active metals direct in metal packing
Agent, the catalyst are made by the following method：Carried out in the pole dilute aqueous solution of metal salt, the formation control of metallic is existed
In extremely dilute metal salt solution, now its concentration, which is in, is advantageous to the monatomic existing state of metal, by stirring and processing temperature
The kinetic energy provided is provided metallic atom insert material surface is formed to stable activated centre.Processing procedure is not present
The separation problem of solid catalyst and processing material in CN201410526689.1, can be complete to any type of metal material
It is simple into load, preparation method.Compared with conventional load metallic catalyst, the active metal for the catalyst that the present invention obtains utilizes
Rate is high, and heat and mass surface area is big, and resistance is small, and course of reaction is applied in basic organic synthesis reaction, tool without effect of intraparticle diffusion
There is technique simple, reaction speed is fast, the advantages of loss in the absence of catalyst and deactivation prob.
The technical scheme is that:
A kind of catalyst of supported active metals direct in metal packing, the catalyst is made for following methods, described
Method comprise 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 one or more active components and water are hybridly prepared into, with activity
The concentration of the metal salt of component meter is 0.1~10ppm；The metal salt of described active component is platinum, palladium, rhodium, ruthenium, gold or nickel
Salt；
It is described metal packing be stainless steel, filler made of zirconium or 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, radium chloride or nickel nitrate.
Metal packing in the described first step is preferably that specific surface area is 501~3500m2/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 provides a kind of active metal/metal packing catalyst, by the solution of extremely dilute metal salt,
Metal salt is converted into metallic atom using hydrogenating reduction or thermal decomposition and reduction, then by gold under the circulation collision effect of solution
Belong to atom and be quickly embedded in metal packing surface formation metal supported catalyst.Preparation method is simple and easy, to form of bio-carrier, structure
Without specifically limited requirement, can need to select according to reaction.(2) present invention provides a kind of active metal/metal packing catalyst,
Catalyst is used for Continuous Liquid Phase catalytic reaction process, compared with conventional load metallic catalyst, reaction can be directly in metal
Filler surface is carried out, and no film layer comes off problem, and resistance to mass tranfer is small, and heat transfer coefficient is high, and course of reaction, can be extensive without effect of intraparticle diffusion
For various heterogeneous reaction processes；(3) a kind of active metal/metal packing catalyst provided by the invention, active metal profit
It is high with rate, catalyst performance stabilised, operation can be remained stable over.The active metal of preparation/metal packing catalyst is used
In the course of reaction of nitrobenzene continuous liquid phase hydrogenation generation aniline, technique is simple, and reaction speed is fast, the nitro in terms of active metal
Benzene transformation frequency reaches 9.69 X 104gNB·(g·h)-1, far above the activity level of current commercial catalyst.Catalyst is continuous
800h is operated, activity keeps stable, does not find that active metal loses.
Embodiment
Embodiment 1
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, 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
Coupled plasma optical emission spectrometer carries out Pt constituent content analysis to catalyst, and Pt load capacity is 32.1mgkg-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 types are consolidated
In fixed bed reactor, packing specific area 3700m2/m3, heap density is 576kg/m3；
Second step, with nitrogen displacement processing unit 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 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, 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。
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 reactors
In, packing specific area 501m2/m3, heap density is 325kg/m3；
Second step, with nitrogen displacement processing unit 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 500h 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 150 DEG C, pressure 0.8MPa, after coming out gas condensation 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 2 hours for the treatment of fluid and nitrogen and hydrogen mixture.Utilize inductance
Coupled plasma optical emission spectrometer carries out Pt constituent content analysis to catalyst, and Pt load capacity is 38.1mgkg-1。
Embodiment 4
The first step, 4L materials are put into a diameter of 100mm, a height of 600mm trickle beds for the screen waviness packings of stainless steel
In 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 pump by the treatment fluid in the 3rd step solution reservoir with air speed 50h-1Squeeze into preheater, the temperature of preheater
Spend 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/ metal packing catalyst after the continuous circular treatment for the treatment of fluid 2 hours.Utilize inductive
Plasma emission spectrometer carries out Pd constituent content analysis to catalyst, and Pd load capacity is 29.1mgkg-1。
Embodiment 5
The first step, 4L materials are put into a diameter of 100mm, a height of 600mm pipes for the net corrugated filling of monel metal
In formula fixed bed reactors, packing specific area 643m2/m3, heap density is 508kg/m3；
Second step, with nitrogen displacement processing unit 8~12 minutes；
3rd step, rhodium chloride and water are hybridly prepared into rhodium chloride solution of the 100L rhodium concentrations for 1.5ppm as place
Reason liquid is put into solution reservoir；
4th step, with pump by treatment fluid in the 3rd step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
It is then 800h with air speed for 200 DEG C-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 200 DEG C, pressure 2.0MPa, 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 Rh/ metal packing catalyst after the continuous circular treatment 1 hour for the treatment of fluid and nitrogen and hydrogen mixture.Utilize inductance
Coupled plasma optical emission spectrometer carries out Rh constituent content analysis to catalyst, and Rh load capacity is 31.5mgkg-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 types are consolidated
In fixed bed reactor, packing specific area 2800m2/m3, heap density is 460kg/m3；
Second step, with nitrogen displacement processing unit 8~12 minutes；
3rd step, ruthenium trichloride and water are hybridly prepared into solution of ruthenium trichloride of the 100L rutheniums concentration for 1.5ppm as place
Reason 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 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 Ru constituent content analysis is carried out to catalyst, Ru load capacity is 51.3mgkg-1。
Embodiment 7
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 types are consolidated
In fixed bed reactor, packing specific area 2800m2/m3, heap density is 460kg/m3；
Second step, with nitrogen displacement processing unit 8~12 minutes；
3rd step, gold chloride and water are hybridly prepared into chlorauric acid solution of the 100L gold concentrations for 1.5ppm as treatment fluid
It is put into solution reservoir；
4th step, with pump by treatment fluid in the 3rd step solution reservoir with air speed 100h-1Squeeze into preheater, the temperature of preheater
It is then 800h with air speed for 100 DEG C-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 100 DEG C, pressure 0.3MPa, after the gas condensation come out by reactor
Emptying；The liquid of discharge is returned in the solution reservoir of the 3rd step, continues to participate in processing procedure as treatment fluid, continuous processing 1 is small
When after obtain Au/ metal packing catalyst.Au elements are carried out using inductive coupling plasma emission spectrograph to catalyst to contain
Amount analysis, Au load capacity is 46.1mgkg-1。
Embodiment 8
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 types are consolidated
In fixed bed reactor, packing specific area 2800m2/m3, heap density is 460kg/m3；
Second step, with nitrogen displacement processing unit 8~12 minutes；
3rd step, nickel nitrate and water are hybridly prepared into the nickel nitrate solution that 80L nickel concentrations are 3ppm and put as treatment fluid
Enter 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 Ni/ 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 Ni constituent content analysis is carried out to catalyst, Ni load capacity is 46.5mgkg-1。
Embodiment 9
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 types are consolidated
In fixed bed reactor, packing specific area 2800m2/m3, heap density is 460kg/m3；；
Second step, with nitrogen displacement processing unit 8~12 minutes；
3rd step, by chloroplatinic acid, palladium bichloride and water be hybridly prepared into 150L platinum concentrations be 0.5ppm, palladium concentration be 1ppm's
Chloroplatinic acid and palladium bichloride mixed solution are put into solution reservoir as treatment fluid；
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 Pt-Pd/ metal packing catalyst after the continuous circular treatment 2 hours for the treatment of fluid and nitrogen and hydrogen mixture.Utilize
Inductive coupling plasma emission spectrograph carries out Pt and Pd constituent content analysis to catalyst, and Pt, Pd load capacity are respectively
16.5mg·kg-1And 29.6mgkg-1。
Embodiment 10~16 is a kind of application process of metal/metal filler catalyst
Embodiment 10
Use N2The tubular fixed-bed reactor and its pipe for the Pt/ metal packing catalyst that displacement is prepared equipped with 4L embodiments 1
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
1.6L/h, which is squeezed into preheater, is preheated to 100 DEG C, and then autoreactor bottom enters reactor.100 DEG C of streams will be equally warming up to
The gas-liquid distributor for measuring the reacted device bed bottom of hydrogen for 1200L/h is dispersed in material liquid, and gas-liquid mixture is in filler
Catalyst surface carries out catalytic reaction, nitrobenzene is converted into aniline.Reaction pressure is 0.8MPa.The gas-liquid come out from reactor
After the condensation of mixture condensed device, hydrogen recycles, and liquid phase is reaction product, nitrobenzene conversion rate 100%, the receipts of aniline
Rate is 99.8%, is converted into using the nitrobenzene transformation frequency that unit mass Pt is counted as 3.25 X 104gNB·(gPt·h)-1。
Embodiment 11
Use N2The tubular fixed-bed reactor and its pipe for the Pt/ metal packing catalyst that displacement is prepared equipped with 4L embodiments 2
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 autoreactor bottom enters reactor.To equally it be warming up to
The gas-liquid distributor for the reacted device bed bottom of hydrogen that 120 DEG C of flows are 3600L/h is dispersed in material liquid, gas-liquid mixture
Catalytic reaction is carried out in filler catalyst surface, nitrobenzene is converted into aniline.Reaction pressure is 1.2MPa.Come out from reactor
The condensation of liquid-vapor mixture condensed device after, hydrogen recycles, and liquid phase is reaction product, nitrobenzene conversion rate 100%, benzene
The yield of amine is 99.7%, is converted into using the nitrobenzene transformation frequency that unit mass Pt is counted as 5.94 X 104gNB·(gPt·h)-1。
Embodiment 12
Use N2The tubular fixed-bed reactor and its pipe for the Pt/ metal packing catalyst that displacement is prepared equipped with 4L embodiments 3
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 autoreactor bottom enters reactor.120 DEG C of flows will be equally warming up to
For 2800L/h H2The gas-liquid distributor of reacted device bed bottom is dispersed in material liquid, and gas-liquid mixture is catalyzed in filler
Agent surface carries out catalytic reaction, nitrobenzene is converted into aniline.Reaction pressure is 1.0MPa.The gas-liquid mixed come out from reactor
After the condensation of thing condensed device, hydrogen recycles, and liquid phase is reaction product, nitrobenzene conversion rate 100%, and the yield of aniline is
99.7%, convert into using the nitrobenzene transformation frequency that unit mass Pt is counted as 9.69 X 104gNB·(gPt·h)-1。
Embodiment 13
Use N2The trickle bed reactor for the Pd/ metal packing catalyst that displacement is prepared equipped with 4L embodiments 4 and its pipeline system
System, after 8~12 minutes, reactor is warming up to reaction temperature, reaction temperature is 60 DEG C.With pump by raw material nitrobenzene with 0.8L/h
Squeeze into preheater and be preheated to 40 DEG C, then and be equally warming up to the H that 40 DEG C of flows are 640L/h2Enter at the top of mixing autoreactor
Enter reactor.Gas-liquid mixture carries out catalytic reaction in filler catalyst surface, nitrobenzene is converted into aniline.Reaction pressure is
2.0MPa.After the liquid-vapor mixture condensed device condensation come out from reactor, hydrogen recycles, and liquid phase is reaction product, nitre
Base benzene conversion ratio is 95.0%, and the yield of aniline is 99.9%, and the equivalent nitrobenzene transformation frequency in terms of unit mass Pd is
1.89ⅹ104gNB·(gPd·h)-1。。
Embodiment 14
Use N2The tubular fixed-bed reactor and its pipe for the Rh/ metal packing catalyst that displacement is prepared equipped with 4L embodiments 5
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.100 DEG C of streams will be equally warming up to
Measure the H for 2500L/h2The vapor-liquid distributor of reacted device bed bottom is dispersed in material liquid, and liquid-vapor mixture is urged in filler
Agent surface carries out catalytic reaction, nitrobenzene is converted into aniline.Reaction pressure is 1.0MPa.The vapour-liquid come out from reactor is mixed
After the condensation of compound condensed device, hydrogen recycles, and liquid phase is reaction product, nitrobenzene conversion rate 100%, the yield of aniline
For 99.7%, convert into using the nitrobenzene transformation frequency that unit mass Rh is counted as 6.0 X 104gNB·(gRh·h)-1。
Embodiment 15
Use N2The tubular fixed-bed reactor and its pipe for the Ru/ metal packing catalyst that displacement is prepared equipped with 4L embodiments 6
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.80 DEG C of flows, which will be equally warming up to, is
800L/h H2The gas-liquid distributor of reacted device bed bottom is dispersed in material liquid, and gas-liquid mixture is in filler catalyst table
Face carries out catalytic reaction, nitrobenzene is converted into aniline.Reaction pressure is 0.3MPa.The liquid-vapor mixture warp come out from reactor
After condenser condensation, hydrogen recycles, and liquid phase is reaction product, and 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 16
The course of reaction of embodiment 11 is continuously run and remained at 1000h, nitrobenzene conversion rate and aniline yield rate
In 100% and 99.7%, the metal/metal filler catalyst performance stabilised invented.Launched 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, 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. catalyst of supported active metals direct in metal packing, it is characterized in that the catalyst is following methods system , described method 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, active metal/filler catalyst is obtained；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 one or more active components and water are hybridly prepared into, with active component The concentration of the metal salt of meter 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, and the specific surface area of filler is 200~5000m2/m3。
- 2. as claimed in claim 1 in metal packing direct supported active metals catalyst, it is characterized in that described work The metal salt of property component is preferably chloroplatinic acid, palladium bichloride, ruthenium trichloride, radium chloride or nickel nitrate.
- 3. as claimed in claim 1 in metal packing direct supported active metals catalyst, it is characterized in that described Metal packing in one step is preferably that specific surface area is 501~3700 m2/m3θ ring fillers or ripple packing.
- 4. as claimed in claim 1 in metal packing direct supported active metals catalyst, it is characterized in that described In two steps, metal salt solution liquid air speed is preferably 50~100 h-1。
- 5. as claimed in claim 1 in metal packing direct supported active metals catalyst, it is characterized in that described In two steps, nitrogen hydrogen ratio preferably 10 in nitrogen hydrogen mixeding gas:1.
- 6. as claimed in claim 1 in metal packing direct supported active metals catalyst, it is characterized in that described In two steps, the concentration of the metal salt of active component meter is preferably 0.5~3ppm in treatment fluid.
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| CN112156653A (en) * | 2020-10-10 | 2021-01-01 | 湖北楚儒同位素科技有限公司 | Low-temperature separation and concentration device and process for stable isotopes |
| CN112619656A (en) * | 2020-12-17 | 2021-04-09 | 湖北楚儒同位素科技有限公司 | Carbon monoxide conversion catalyst using copper wire mesh corrugated packing as carrier |
| CN112973587A (en) * | 2019-12-02 | 2021-06-18 | 河北工业大学 | High-efficient catalytic reactor based on metal sintering membrane |
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