CN104402789A - Method and reactor for catalyzing cumene oxidation by utilizing structured carbon nano-tube catalyst - Google Patents
Method and reactor for catalyzing cumene oxidation by utilizing structured carbon nano-tube catalyst Download PDFInfo
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Abstract
The invention provides a method and a reactor for catalyzing cumene oxidation by utilizing a structured carbon nano-tube catalyst. The method comprises the following steps: (1) mounting the structured carbon nano-tube catalyst on the stirring shaft of a tank reactor, adding cumene used as a reactant into the reactor for heating to 60-100 DEG C, filling the reactor with oxygen till the pressure reaches 0.2-0.8 Mpa, and stirring the mixture for 2-10 hours' reaction, wherein the structured carbon nano-tube catalyst is obtained through in-situ growth of carbon nano-tubes on the surface of foam metal by utilizing chemical vapor deposition and the foam metal is coated with aluminum oxide sol; (2) after the reaction is finished, conducting separation and purification on the liquid mixture to obtain a product, namely cumene hydroperoxide. Through adoption of the reactor, the process for recovering the carbon nano-tube catalyst is simplified, and both mass transfer and heat transfer are enhanced. The structured carbon nano-tube catalyst is good in activity, high in selectivity of cumene hydroperoxide and excellent in stability.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of carbon nanotube structure catalyzer for liquid phase hydrocarbon oxidation and load the rotation foam stirring rake reactor of this catalyzer, be specially adapted to cumene oxidation hydrogen phosphide cumene.
Background technology
Phenol is a kind of important petrochemical intermediates, and its main production method has cumene method, benzene direct oxidation method, toluol-benzene formic acid method etc.Because production cost is low, product purity is high, cumene method is the main method of producing phenol in current world wide, and its throughput accounts for more than 90% of Phenol at Home throughput.
Cumene method is produced phenol and is comprised three reactions: (1) benzene and propylene addition synthesizing iso-propylbenzene; (2), under oxygen effect, isopropyl benzene peroxidation generates isopropyl benzene hydroperoxide; (3) isopropyl benzene hydroperoxide (CHP) decomposes in acid condition and obtains phenol and acetone.Wherein, isopropyl benzene peroxidation efficiency is minimum, is a step very important in isopropyl benzene legal system phenol process.Traditional processing technology needs to add alkaline additive as (NaOH, Na
2cO
3) organic acid in neutralization reaction, temperature of reaction is 110 ~ 115 DEG C.This method service temperature is higher, causes CHP acutely to decompose, and careless manipulation may be explosion caused, and alkali lye corrosive equipment.In order to eliminate the impact of alkaline matter, US6956136-BZ patent a certain proportion of ammonium salt and ammonia water mixture replace alkali lye, and can obtain good selectivity, but temperature of reaction is still very high, liquid waste disposal is more complicated also.Therefore, the high-performance catalyst finding a kind of reaction conditions gentleness is the study hotspot reacted about cumene oxidation always.
Transition metal can promote the oxidation of isopropyl benzene, and shortening decomposition induction time, is a class catalyzer of most study.But transition metal promotes that CHP decomposes, and can produce a large amount of by product 2-phenyl-2-propyl alcohol, reduce the selectivity of CHP.In order to improve the selectivity of CHP, in the patent of CN101235007 and CN1948365, transition metal being prepared into the form of organic complex, individually disclosing the method for metal leaf beautiful jade and polymer xifualkali phthalocyanin bimetal compound catalysis cumene oxidation.This method can improve the selectivity of CHP; But catalyst preparing is complicated, expensive, and organic coordination compound is poisonous, is not suitable for industrial application.
In the patent of WO200174767-A, employ a kind of non-metallic catalyst.It is using nitrogenous substances (as HP) as the catalyzer of isopropyl benzene peroxidation, and CHP selectivity is close to 100%, and transformation efficiency is also higher.But this catalyzer is expensive, be difficult to reclaim and recycle, simultaneously residual catalyzer also can affect subsequent technique.
In recent years, carbon nanotube because technology of preparing is simple, price is relatively cheap, environmental friendliness and there is catalytic oxidation activity, by extensive concern.Use carbon nanotube as the catalyzer of ethylbenzene oxidation methyl phenyl ketone in patent CN102675072A, there is reaction preference high, cost is low, efficiency advantages of higher.In patent CN102911096, disclose the oxidation of carbon nanotube as catalyst isopropyl benzene, temperature of reaction is lower, functional.In addition, carbon nanotube can also be used for the liquid phase catalytic oxidation process of hexanaphthene, tetrahydrobenzene etc., disclose a kind of method of carbon nanometer pipe catalytic oxidizing ethyle alkyl direct production hexanodioic acid in patent CN101337878A, avoid the pollution of use to environment and the corrosion of equipment of nitric acid in hexanodioic acid production process.But in these processes, carbon nanotube generally participates in reaction using the form of powder as catalyzer, cause catalyzer and reactants separate difficulty, catalyst abrasion is serious with loss, is unfavorable for suitability for industrialized production.Propose in patent CN102040504B and utilize the magnetic carbon nanomaterial of tool as catalyzer, greatly can improve liquid-solid separation efficiency, but magnetic carbon nano-tube preparation is more difficult.
Summary of the invention
The object of the invention is to overcome conventional powder shape carbon nano-tube catalyst separation difficulty in isopropyl benzene liquid-phase catalytic oxidation system, the shortcomings such as mass-transfer efficiency is low, provide a kind of method of structurizing carbon nano-tube catalyst catalysis cumene oxidation.
The present invention takes following technical scheme to be achieved:
A kind of reactor for catalysis cumene oxidation, the stir shaft of reactor is provided with structurizing carbon nanocatalyst, described reactor is using carbon nanotube/foamed metal structures catalyzer simultaneously as whipping appts and catalyzer, forms and rotates foam stirred reactor.
A method for structurizing carbon nano-tube catalyst catalysis cumene oxidation, comprises the following steps:
(1) structurizing carbon nanocatalyst is installed on the stir shaft of (autoclave) reactor, again reactant isopropyl benzene is added in reactor, isopropyl benzene is heated to 60 DEG C-100 DEG C, being filled with oxygen to pressure is 0.2-0.8Mpa, stirring velocity is 100r/min-1000r/min, reaction 2-10h; In described structurizing carbon nanocatalyst, the quality of carbon nanotube and the mass ratio of isopropyl benzene are 0.002 ~ 0.01:1; Described structurizing carbon nano-tube catalyst is obtained by the foamed metal surface chemistry vapour deposition in-situ growing carbon nano tube scribbling alumina sol on surface;
(2) after question response terminates, by liquid mixture separating-purifying, product hydrogen peroxide isopropyl benzene is obtained.
The porosity of described foamed metal is 20-100ppi, and carbon nanotube mass accounts for 4.5% ~ 27.0% of structurizing carbon nanocatalyst.The porosity of foamed metal is preferably 40-100ppi.Be liquefied petroleum gas (LPG) for the carbon compound of carbon nano-tube in the present invention, use other raw materials or different processing parameter carbon nano-tubes also can, should not regard as limitation of the present invention.
The material that described foamed metal is foam Ni, foam Fe, foam Co, foam Fe-Cr alloy, foam Ni-Fe alloy, foam Fe-Co alloy/C or stainless steel foam etc. have catalysis carbon containing hydrocarbon compound chemical vapour deposition reaction carbon nano-tube is formed.
The concrete preparation method of described structurizing carbon nano-tube catalyst is: first cleaned up by foamed metal and drying, then adopt pickling process at foamed metal surface-coated one deck alumina sol, calcine 2h, obtain the foamed metal of surface modification at 600 DEG C; Pass into argon gas and do carrier gas, after furnace temperature rises to 650 DEG C, pass into hydrogen reducing 30min; Be warming up to 750 DEG C and pass into liquefied petroleum gas (LPG) again, at the foamed metal surface growth carbon nanotube through surface modification, wherein the flow of argon gas, hydrogen, liquefied petroleum gas (LPG) is respectively 480ml/min, 140ml/min, 60ml/min, and growth time is 5-10min.
The cleaning of described foamed metal is that it is put into acetone, ethanolic soln respectively, each ultrasonic cleaning 30min; Put into deionized water again to clean; Dry condition is dry 24h at 100 DEG C.
In described structurizing carbon nanocatalyst, the mass ratio of carbon nanotube and isopropyl benzene is 0.008 ~ 0.01:1.
The temperature of described reaction is 80 DEG C-90 DEG C, and the speed of described stirring is 200r/min-500r/min, the time 8-10h of described reaction.
Also add hydrogen phosphide cumene in described reactor as initiator, the volume ratio of described isopropyl benzene and initiator is (50 ~ 60): 1.
The charge capacity of described foamed metal surface alumina oxide is 3.0-31.4wt%.
The present invention compared with prior art, has the following advantages:
1, the invention provides a kind of structurizing carbon nano-tube catalyst of entirety that uses simultaneously as catalyzer and whipping appts, and use it in the oxidizing reaction of isopropyl benzene, overcome the wearing and tearing of conventional powder shape catalyzer and the problem of solid-liquid mix products separation difficulty.
2, carbon nanotube/foamed metal structures catalyzer that the present invention is used installation and removal are in the reactor convenient, save man-hour.
3, the present invention adopts foamed metal to form the matrix of structural catalyst, reduces pressure drop, improves the heat and mass transfer efficiency of chemical reaction.
4, carbon nanotube/foamed metal structures catalyzer that the present invention is used is good to Liquid-Phase Oxidation of Cumene catalytic activity, and reaction efficiency is high, and catalyst stability is good.
Accompanying drawing explanation
Fig. 1 is the gas chromatogram of embodiment 9 cumene oxidation product;
Fig. 2 is for rotating foam stirring rake still reactor assembly figure;
Fig. 3 is the SEM figure of carbon nanotube of the present invention/foamed metal structures catalyzer;
Fig. 4 is the SEM figure of carbon nanotube on carbon nanotube of the present invention/foamed metal structures catalyzer;
Fig. 5 is the TEM figure of carbon nanotube on carbon nanotube of the present invention/foamed metal structures catalyzer.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited thereto, for the processing parameter do not indicated especially, can refer to routine techniques and carry out.
The preparation of carbon nanotube/foam Ni structural catalyst: foamed metal is successively put into acetone, ethanolic soln, each ultrasonic cleaning 30min respectively; Put into deionized water again to clean, then dry 24h at 100 DEG C; Adopt pickling process at foamed metal surface-coated one deck alumina sol again, calcine 2h at 600 DEG C, realize foamed metal surface modification treatment; Pass into argon gas and do carrier gas, after furnace temperature rises to 650 DEG C, pass into hydrogen reducing 30min; Be warming up to 750 DEG C and pass into liquefied petroleum gas (LPG) again, the foamed metal surface growth carbon nanotube of process is being gone out through surface modification, wherein the flow of argon gas, hydrogen, liquefied petroleum gas (LPG) is respectively 480ml/min, 140ml/min, 60ml/min, and growth time is 5-10min.
Embodiment 1 ~ 5
Catalyzer adopts carbon nanotube/foam Ni structural catalyst, and content of carbon nanotubes 5.5 ~ 6.7wt% on it, the charge capacity of aluminum oxide is 5.6 ~ 6.9wt%.The diameter of foam Ni is the right cylinder of 45mm, thickness 10 ~ 30mm, porosity 40ppi.
By 160ml isopropyl benzene and 3ml hydrogen phosphide cumene (initiator) supersound process, to be mixedly evenly join in the rotation foam stirring rake still reactor of loading carbon nanotube/foam Ni structural catalyst 1 (as shown in Figure 2), then arranging stir speed (S.S.) is 500r/min, passing into oxygen to pressure after being heated to 80 DEG C is 0.4Mpa, reaction 8h.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get product carry out gas chromatographic analysis and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).Comparative example 1,2,3,4,5 can find out that carbon nanotube/foam Ni structural catalyst has higher activity to cumene oxidation reaction, its reaction effect is significantly better than the situation (embodiment 1) of carbon-free nanoscale pipe on structured catalyst, and the transformation efficiency of reaction and CHP output all increase with carbon nanotube consumption and improves.
The impact that table 1 carbon nanotube amount is reacted cumene oxidation
Embodiment | 1 | 2 | 3 | 4 | 5 |
The charge capacity (%) of CNTs | 0 | 5.5 | 5.5 | 5.5 | 6.7 |
Catalyst thickness (mm) | 30 | 10 | 20 | 30 | 30 |
Carbon nanotube and isopropyl benzene mass ratio | 0 | 0.002 | 0.005 | 0.008 | 0.01 |
Cumene rate (%) | 2.09 | 9.3 | 12.6 | 17.6 | 22.6 |
CHP yield (%) | 2.04 | 8.8 | 10.7 | 11.8 | 16.1 |
Embodiment 6 ~ 13
Catalyzer adopts carbon nanotube/foam Ni structural catalyst, and content of carbon nanotubes 5.6wt% on it, the charge capacity of aluminum oxide is 4.8wt%.The diameter of foam Ni is 45mm, thickness 30mm, porosity 40ppi.
By 160ml isopropyl benzene with 3ml hydrogen phosphide cumene (initiator) supersound process is to be mixed evenly joins in the rotation foam stirring rake still reactor of loading carbon nanotube/foam Ni structural catalyst, the mass ratio of carbon nanotube and isopropyl benzene is 0.007:1, mixing speed is set to preset value (as table 2), oxygen is passed into after being heated to 80 DEG C, pressure is 0.4Mpa, reaction 8h.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get product and carry out gas chromatographic analysis, and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).Comparative example 5-12 can find out the increase along with rotating speed, the transformation efficiency first increases and then decreases of isopropyl benzene, and rotating speed is that 200r/min-500r/min is more excellent.
The impact that table 2 rotating speed reacts cumene oxidation
Embodiment | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
Rotating speed (r/min) | 100 | 200 | 300 | 400 | 500 | 600 | 800 | 1000 |
Transformation efficiency (%) | 13.6 | 19.1 | 22.0 | 18.1 | 14.9 | 13.4 | 12.8 | 11.3 |
CHP yield (%) | 12.3 | 14.1 | 14.9 | 13.6 | 12.0 | 10.6 | 9.3 | 8.5 |
Embodiment 14 ~ 18
Catalyzer adopts carbon nanotube/foam Ni structural catalyst, and content of carbon nanotubes 6.7wt% on it, the charge capacity of aluminum oxide is 6.9wt%.The diameter of foam Ni is 45mm, thickness 30mm, porosity 40ppi.
By 160ml isopropyl benzene and 3ml hydrogen phosphide cumene (initiator) supersound process, to be mixedly evenly join in the rotation foam stirring rake still reactor of loading carbon nanotube/foam Ni structural catalyst, the mass ratio of carbon nanotube and isopropyl benzene is 0.01:1, mixing speed 400r/min, oxygen is passed into after being heated to 80 DEG C, pressure is 0.4Mpa, and the reaction times is as table 3.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get product and carry out gas chromatographic analysis, and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).Comparative example 14-18 can find out along with time lengthening, and the transformation efficiency of isopropyl benzene and the yield of CHP increase thereupon, but after 8h, rate of increase reduces, so optimal time should at 8h-10h.
The impact that table 3 time reacts cumene oxidation
Embodiment | 14 | 15 | 16 | 17 | 18 |
Time (h) | 2 | 4 | 6 | 8 | 10 |
Cumene rate (%) | 9.4 | 15.9 | 18.8 | 25.1 | 26.4 |
CHP yield (%) | 5.5 | 8.9 | 11.8 | 15.8 | 18.1 |
Embodiment 19 ~ 22
Catalyzer adopts carbon nanotube/foam Ni structural catalyst, and wherein content of carbon nanotubes 6.7wt%, the charge capacity of aluminum oxide is 6.9wt%.The diameter of foam Ni is 45mm, thickness 30mm, porosity 40ppi.
By 160ml isopropyl benzene and 3ml hydrogen phosphide cumene (initiator) supersound process, to be mixedly evenly join in the rotation foam stirring rake still reactor of loading carbon nanotube/foam Ni structural catalyst, the mass ratio of carbon nanotube and isopropyl benzene is 0.01:1, mixing speed 400r/min, oxygen is passed into after being heated to design temperature (as table 4), pressure is 0.4Mpa, reaction 2h.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get product and carry out gas chromatographic analysis, and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).Comparative example 14,19-22 can find out that the transformation efficiency of isopropyl benzene and the yield of CHP raise with temperature and increase, but after 90 DEG C, hydrogen phosphide cumene decomposes serious, and yield declines, so Optimal Temperature should be 80 DEG C-90 DEG C.
The impact that table 4 temperature is reacted cumene oxidation
Embodiment | 19 | 20 | 14 | 21 | 22 |
Temperature (DEG C) | 60 | 70 | 80 | 90 | 100 |
Cumene rate (%) | 5.4 | 8.2 | 9.4 | 13.7 | 20.6 |
CHP yield (%) | 3.4 | 4.3 | 5.5 | 7.4 | 4.1 |
Embodiment 23 ~ 24
Catalyzer adopts carbon nanotube/foam Ni structural catalyst, and wherein content of carbon nanotubes 5.6-27wt%, the charge capacity of aluminum oxide is 4.8-31.4wt%.The diameter of foam Ni is 45mm, and thickness 7-30mm, the porosity of foamed metal is as shown in table 5.
By 160ml isopropyl benzene and 3ml hydrogen phosphide cumene (initiator) supersound process, to be mixedly evenly join in the rotation foam stirring rake still reactor of loading carbon nanotube/foam Ni structural catalyst, mixing speed 400r/min, be heated to 80 DEG C, after pass into oxygen, pressure is 0.4Mpa, reaction 8h.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get product and carry out gas chromatographic analysis, and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).Comparative example 9,23,24 can find out that the transformation efficiency of the isopropyl benzene when the aperture of foamed metal is greater than 40ppi is tending towards constant, so optimum aperture is 40ppi-100ppi.
The impact that table 5 foamed metal aperture is reacted cumene oxidation
Embodiment | 23 | 9 | 24 |
CNTs charge capacity (%) | 6.5 | 5.6 | 27 |
Thickness (mm) | 30 | 30 | 7 |
Carbon nanotube and isopropyl benzene mass ratio | 0.0072:1 | 0.0074:1 | 0.0068:1 |
Aperture (PPI) | 20 | 40 | 100 |
Cumene rate (%) | 12.9 | 18.1 | 18.7 |
CHP yield (%) | 11.8 | 13.6 | 15.2 |
Embodiment 25 ~ 26
Catalyzer adopts carbon nanotube/foam Ni structural catalyst, and carbon nanotube loaded amount 6.7wt%, the charge capacity of adhesive agent aluminum oxide is 6.9wt%, and wherein the diameter of foamed metal is 45mm, thickness 30mm, foamed metal porosity 40ppi.
By 160ml isopropyl benzene with 3ml hydrogen phosphide cumene (initiator) supersound process is to be mixed evenly joins in the rotation foam stirring rake still reactor of loading carbon nanotube/foam Ni structural catalyst, the mass ratio of carbon nanotube and isopropyl benzene is 0.01:1, mixing speed 400r/min, be heated to 80 DEG C, after pass into oxygen, pressure is as shown in table 6, reaction 8h.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get quantitative product carry out analyzing and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).Comparative example 17,25,26 can find out that oxygen pressure is little on the impact of cumene rate.
The impact that table 6 pressure reacts cumene oxidation
Embodiment | 25 | 17 | 26 |
Pressure (Mpa) | 0.2 | 0.4 | 0.8 |
Cumene rate (%) | 23.8 | 25.1 | 26.0 |
CHP yield (%) | 14.2 | 15.8 | 15.7 |
Embodiment 27
Catalyzer adopts carbon nanotube/foamed metal structures catalyzer, and carbon nanotube loaded amount 6.7wt%, the charge capacity of adhesive agent aluminum oxide is 6.9wt%, and wherein the diameter of foamed metal is 45mm, thickness 30mm, foamed metal porosity 40ppi.
By 160ml isopropyl benzene (density 8.4g/ml) with 3ml hydrogen phosphide cumene (initiator) supersound process is to be mixed evenly joins in the rotation foam stirring rake still reactor of loading carbon nanotube/foamed metal structures catalyzer, the mass ratio of carbon nanotube and isopropyl benzene is 0.01:1, mixing speed 400r/min, be heated to 80 DEG C, after pass into oxygen, pressure 0.4MPa, reaction 8h.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get quantitative product carry out analyzing and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).The structurizing carbon nanometer pipe catalytic cumene oxidation that it is substrate that comparative example 17,27 can be found out with nickel foam and stainless steel foam all shows good activity and performance difference is little, shows that the method that the present invention proposes has certain ubiquity.
The impact that table 7 foam substrate material reacts cumene oxidation
Embodiment | 17 | 27 |
Foam substrate material | Ni | Fe-Cr alloy |
Cumene rate (%) | 25.1 | 23.3 |
CHP yield (%) | 15.8 | 15.1 |
Embodiment 28 ~ 31
Catalyzer adopts carbon nanotube/foam Ni structural catalyst, and content of carbon nanotubes 5.5wt% on it, the charge capacity of aluminum oxide is 5.6wt%.The diameter of foam Ni is the right cylinder of 45mm, thickness 30mm, porosity 40ppi.
By 160ml isopropyl benzene and 3ml hydrogen phosphide cumene (initiator) supersound process, to be mixedly evenly join in the rotation foam stirring rake still reactor of loading carbon nanotube/foam Ni structural catalyst 1 (as shown in Figure 2), then arranging stir speed (S.S.) is 500r/min, passing into oxygen to pressure after being heated to 80 DEG C is 0.4Mpa, reaction 8h.After question response terminates, by liquid mixture separating-purifying, obtain product hydrogen peroxide isopropyl benzene.Get product carry out gas chromatographic analysis and calculate the transformation efficiency of isopropyl benzene and the yield of hydrogen phosphide cumene (CHP).Comparative example 4,28,29,30,31 can find out that carbon nanotube/foam Ni structural catalyst is after recycling 5 times, the transformation efficiency of isopropyl benzene and the yield of CHP remain unchanged substantially, so the carbon nanotube structure catalyzer of preparation has satisfactory stability.
Table 8 carbon nanotube structure catalyst stability is tested
Embodiment | 4 | 28 | 29 | 30 | 31 |
Multiplicity | 1 | 2 | 3 | 4 | 5 |
Cumene rate (%) | 17.6 | 17.7 | 17.3 | 17.1 | 17.0 |
CHP yield (%) | 11.8 | 11.6 | 11.6 | 10.8 | 11.8 |
Claims (10)
1. a method for structurizing carbon nano-tube catalyst catalysis cumene oxidation, is characterized in that, comprise the following steps:
(1) structurizing carbon nanocatalyst is installed on the stir shaft of reactor, add in reactor by reactant isopropyl benzene again, isopropyl benzene is heated to 60 DEG C-100 DEG C, being filled with oxygen to pressure is 0.2-0.8Mpa, stirring velocity is 100r/min-1000r/min, reaction 2-10h; In described structurizing carbon nanocatalyst, the quality of carbon nanotube and the mass ratio of isopropyl benzene are 0.002 ~ 0.01:1; Described structurizing carbon nano-tube catalyst is obtained by the foamed metal surface chemistry vapour deposition in-situ growing carbon nano tube scribbling alumina sol on surface;
(2) after question response terminates, by liquid mixture separating-purifying, product hydrogen peroxide isopropyl benzene is obtained.
2. method according to claim 1, is characterized in that, the porosity of described foamed metal is 20-100ppi, and carbon nanotube mass accounts for 4.5% ~ 27.0% of structurizing carbon nanocatalyst.
3. method according to claim 2, is characterized in that, described foamed metal is foam Ni, foam Fe, foam Co, foam Fe-Cr alloy, foam Ni-Fe alloy, foam Fe-Co alloy/C or stainless steel foam.
4. the method according to claim 1 or 2 or 3, it is characterized in that, the concrete preparation method of described structurizing carbon nano-tube catalyst is: first cleaned up by foamed metal and drying, adopt pickling process at foamed metal surface-coated one deck alumina sol again, calcine 2h at 600 DEG C, obtain the foamed metal of surface modification; Pass into argon gas and do carrier gas, after furnace temperature rises to 650 DEG C, pass into hydrogen reducing 30min; Be warming up to 750 DEG C and pass into liquefied petroleum gas (LPG) again, at the foamed metal surface growth carbon nanotube through surface modification, wherein the flow of argon gas, hydrogen, liquefied petroleum gas (LPG) is respectively 480ml/min, 140ml/min, 60ml/min, and growth time is 5-10min.
5. method according to claim 4, is characterized in that, the cleaning of described foamed metal is that it is put into acetone, ethanolic soln respectively, each ultrasonic cleaning 30min; Put into deionized water again to clean; Dry condition is dry 24h at 100 DEG C.
6. the method according to claim 1 or 2 or 3, is characterized in that, in described structurizing carbon nanocatalyst, the mass ratio of carbon nanotube and isopropyl benzene is 0.008 ~ 0.01:1.
7. the method according to claim 1 or 2 or 3, is characterized in that, the charge capacity of described foamed metal surface alumina oxide is 3.0-31.4wt%.
8. the method according to claim 1 or 2 or 3, is characterized in that, the temperature of described reaction is 80 DEG C-90 DEG C, and the speed of described stirring is 200r/min-500r/min, the time 8-10h of described reaction.
9. the method according to claim 1 or 2 or 3, is characterized in that, also adds hydrogen phosphide cumene as initiator in described reactor, and the volume ratio of described isopropyl benzene and initiator is (50 ~ 60): 1.
10. for a reactor for catalysis cumene oxidation, it is characterized in that, the stir shaft of reactor is provided with the structurizing carbon nanocatalyst described in any one of claim 1 ~ 7 method.
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