CN110302796A - A kind of Mn-Fe-Cu/ γ-Al of hypergravity fluidisation spray-stain method preparation2O3Catalyst and its application - Google Patents
A kind of Mn-Fe-Cu/ γ-Al of hypergravity fluidisation spray-stain method preparation2O3Catalyst and its application Download PDFInfo
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention belongs to loaded catalyst preparation and technical field of waste water processing, the problems such as generally existing active component dispersion degree of loaded catalyst is not high, load is uneven, load capacity is low, the production cycle is long is prepared for current infusion process, a kind of hypergravity fluidisation spray-stain method preparation Mn-Fe-Cu/ γ-Al is provided2O3Catalyst and its application.γ-Al2O3Carrier is filler, and manganese, iron, copper metal salt make maceration extract, and hypergravity makes maceration extract contact dipping with carrier from inside to outside with Sprayable, and reverse air blast makes carrier granular be near fluidization, and active component is in carrier surface uniform adsorption.The high loaded catalyst of active component dispersion degree height, even particle size, activity is prepared in roasting.Make filler with the catalyst, make reactor so that hypergravity adverse current is rotary packed bed, high-gravity technology, heterogeneous catalysis and ozone oxidation synergistic effect improve nitrobenzene degradation rate and ozone utilization rate, shorten process cycle, is suitble to the nitrobenzene waste water that processing is of large quantities, processing task is heavy.
Description
Technical field
The invention belongs to loaded catalyst preparation and technical field of waste water processing, and in particular to a kind of hypergravity fluidisation spray
Mn-Fe-Cu/ γ-the Al of stain method preparation2O3Catalyst, and heterogeneous catalysis ozone oxidation degrading nitrobenzene is coupled for hypergravity
Waste water.
Background technique
Heterogeneous catalysis ozone Oxidation Treatment organic wastewater using the absorption of catalyst, is urged by introducing solid catalyst
Change characteristic, catalysis ozone, which decomposes, generates more OH free radicals, and causes a series of radical chain reaction, to thoroughly drop
Solve the persistent organic pollutants in waste water.Heterogeneous catalysis has high catalytic activity, mineralization of organic material rate height, without secondary dirt
It contaminates, be easily recycled the advantages of processing, thus receive significant attention.It focuses primarily upon metal composite oxide at present and support type is urged
The development of the solid catalysts such as agent, modified mineral.
Loaded catalyst includes the (CN 102091619 such as aluminium oxide, molecular sieve, ceramics, active carbon with porous material
B, 2012.10.24；CN 101811049 B, 2013.03.27；CN 106311270 B, 2018.09.11；CN 103586026
A ,2014.02.19；CN 105289585 B, 2018.04.03) it is carrier, by Determination of multiple metal elements or metal oxide supported
Thereon, in conjunction with the interaction of carrier and active component, the dissolution of metal ion is avoided, enhances its catalytic activity, and have both
The good advantage of carrier large specific surface area itself, high mechanical strength and thermal stability.Metal member currently used for heterogeneous catalysis
Element mainly has noble metal, transition metal and rare-earth metal series.Wherein transition metal price is relatively cheap, raw material is easy to get, is catalyzed
Activity is high and is concerned.And its catalytic activity of manganese catalyst series is the most prominent, is most widely used, but its anti-SO2With it is anti-
H2The ability of O is poor, needs to adulterate other components to improve its catalytic activity.Common carrying method have infusion process, the precipitation method,
Mixing method, ion-exchange etc., wherein infusion process principle is when active component solution is contacted with porous carrier in capillary pressure
It is penetrated into inside support voids under effect, the process with absorption is diffused in inner surface of the carrier.This method is simple, raw material is sharp
It is low with rate height, economic cost, it is easy to industrial application.The patent of invention of 106311270 B of Publication No. CN with grain active carbon or
Y type molecular sieve prepares ozone oxidation catalyst as active component as carrier, using the oxide of iron, molybdenum, tantalum, potassium, manganese, is used for
Catalytic ozonation degradation coking wastewater and agricultural chemicals waste water, COD removal rate reach 90% or more.105289585 B of publication number CN
Patent of invention using active carbon as carrier, iron and manganese oxides are as active component, and sodium hydroxide is as precipitating reagent, using leaching
The stain precipitation method prepare loaded catalyst, handle dyeing waste water for O3 catalytic oxidation, can reach Treatment of Industrial Water discharge
Standard.
But in above-mentioned preparation process, solute is limited by diffusion absorption and is easy in catalyst drying process migration,
Lead to the problem of active component poor dispersion, load are uneven, active site is reduced.For equi-volume impregnating, activity
Component dispersion degree is very poor, and granular size is different；Excessive infusion process, immersion period is long, the bad control of load capacity；And dipper precipitation
Method, sedimentation cycle is long, easily formation egg-shell catalyst.Moreover, being related to gas-liquid-solid three for heterogeneous catalysis ozone oxidation system
Phase, using conventional reactor, generally existing Ozone Gas Mass Transfer Efficiency is low, and ozone utilization rate is not high and filling of catalyst is fixed
Problem.Therefore it provides a kind of active component dispersion degree height, Load Balanced, large specific surface area, activity are high, with short production cycle negative
Supported catalyst preparation method can strengthen ozone mass transfer in combination with one kind, increase the reaction of gas, liquid, solid three-phase contact area
Equipment is of great significance for the research of heterogeneous catalysis ozone oxidation.
High-gravity technology (High Gravity Technology, Higee) is strengthened as a kind of novel chemical process
Technology generates super gravity field by the high speed rotation of packed bed, make air-liquid under Elevated Gravity porous media or duct in
Liquid shear is very thin liquid film and small liquid mist, drop by flowing, huge shearing force, increases phase boundary specific surface area,
Phase interface renewal rate is accelerated, to greatly improve mass transfer rate, the microcosmic mixing alternate for two has traditional reactor
Incomparable advantage can be widely applied to the chemical processes such as absorption, rectifying, extraction, absorption.
Summary of the invention
Prepare that the generally existing active component dispersion degree of loaded catalyst is not high, load is uneven for current infusion process
Even, the problems such as load capacity is low, the production cycle is long, the present invention provides a kind of Mn-Fe-Cu/ of hypergravity fluidisation spray-stain method preparation
γ-Al2O3Catalyst and its application, the catalyst activity component dispersion degree height, Load Balanced, activity are high, with short production cycle, together
When combination can strengthen ozone mass transfer, increase the hypergravity equipment of gas, liquid, solid three-phase contact area, which is used for hypergravity
Heterogeneous catalysis ozone oxidation nitrobenzene waste water in.
Hypergravity equipment of the present invention is the rotary packed bed (CN of hypergravity adverse current having disclosed
201510093434.5), packing layer is the mixing filled layer of wire packing and carrier or loaded catalyst.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of Mn- of hypergravity fluidisation spray-stain method preparation
Fe-Cu/γ-Al2O3Catalyst, the Mn-Fe-Cu/ γ-Al2O3Catalyst is with γ-Al2O3Carrier as filler, Mn, Fe,
Cu metal salt is maceration extract, rotary packed bed using hypergravity adverse current, adjusts air mass flow, and carrier granular is made to be in nearly fluidisation shape
State makes maceration extract and air in rotary packed bed middle counter current contacting under hypergravity centrifugal action, after carrier is sufficiently impregnated, uses
Hot-air stripping moisture, fixes active component, catalyst precursor is then taken out 300-700 DEG C of high-temperature roasting, i.e.,
For Mn-Fe-Cu/ γ-Al2O3Loaded catalyst.
Mn, Fe, Cu metal salt is the mixed solution of copper nitrate, ferric nitrate and manganese acetate, concentration of metal ions proportion
For 1:1-4:1-4；In terms of Cu concentration of metal ions, the concentration of salt solution is 0.01-0.05 mol/L.
The preparation Mn-Fe-Cu/ γ-Al2O3The method of catalyst, the specific steps are as follows:
(1) impregnation: γ-Al2O3Filling even enters cross_flow rotating packed bed after Vehicle element；Mn, Fe, Cu metal salt
Mixed impregnant liquor is placed in reservoir, is pumped into cross_flow rotating packed bed inner cavity through circulation, maceration extract is equal via liquid distribution trough
It is even to be sprayed at carrier bed inner edge, under the effect of high speed centrifugation power, leaching is radially contacted with carrier from inside to outside with Sprayable
Stain, while air is sent into through blower by bed exocoel, under inside and outside differential pressure effect, ecto-entad connects with maceration extract and carrier adverse current
Touching, by adjusting gas velocity, makes carrier granular be in nearly fluidized state, with the revolution and rotation of particle, makes carrier granular and leaching
Stain liquid comes into full contact with, and the liquid after dipping returns to reservoir and carries out circulation dipping；
(2) high-temperature roasting: after the completion of dipping, carrying out stripping to bed using hot-air, remove catalyst surface moisture, fixed to live
Property component, take out catalyst precursor after 300-700 DEG C of high-temperature roasting.
γ-the Al2O3Carrier is the spherical gamma-Al of partial size 1-2 mm2O3, loading is 50 g/L.
γ-Al2O3Vehicle element method are as follows: 2 h are impregnated with 0.1 mol/L dust technology, deionized water is cleaned to neutrality,
12 h are dried at 105 DEG C, roast 4 h at 300 DEG C.
The rotary packed bed revolving speed is 600-1200 rpm, and fluid flow is 40-120 L/h, air mass flow 4-
10 m3/ h, circulation dip time are 30 ~ 90 min.
The air stripping method is 120 DEG C of 60 min of hot-air stripping, and tolerance is 4 m3/h。
Calcining time is 3-6 h.
Mn-Fe-Cu/ γ-the Al2O3Catalyst heterogeneous catalysis ozone oxidation nitrobenzene waste water in super gravity field
In application, concrete application method are as follows: by Mn-Fe-Cu/ γ-Al2O3For catalyst as filler, filling even enters adverse current rotary filling
Expect that bed, loading are 100 g；The 2 L nitrobenzene waste waters of 200 mg/L are added to reservoir, are pumped into rotary filling material through circulation
Bed inner cavity, ozone are sent into rotary packed bed through rotary packed bed gas access, and controlling rotary packed bed revolving speed is 1000 rpm,
Fluid flow is 85L/h, and gas flow 60L/h, gas phase ozone concentration is 60mg/L, and nitrobenzene waste water is under hypergravity along diameter
It is thrown away to from rotary packed bed bed inner edge, the ozone gas counter current contacting of rotary packed bed bed, liquid is passed through with ecto-entad
Body is then thrown to outer wall vertical and falls, and returns to reservoir, nitrobenzene waste water and ozone gas in rotation filler from liquid outlet
Counter current contacting carries out circular response in bed.
Treated, and nitrobenzene waste water is analyzed from thief hatch direct sample, is gone according to the degradation rate of nitrobenzene waste water and TOC
Except rate evaluates the catalytic activity of the catalyst.
The present invention utilizes high-gravity technology, and rotary packed bed as hypergravity equipment using adverse current, catalyst carrier is used as and fills out
Material, maceration extract aerosol dispersion is made under super gravity field, is sprayed in high-speed rotating carrier surface, simultaneously with liquid mist, drop state
Reverse air blast makes carrier granular be near fluidization, promotes the revolution rotation of particle, on the one hand extends the dipping residence time, improves
The load capacity of active component, while promoting active component in the uniform adsorption of carrier surface, reduce dipping yin-yang face phenomenon.This
Outside, is further shortened the production cycle, most using the quick stripping of hot-air for the drying process of shaping carrier in super gravity field
By roasting, active component dispersion degree height, even particle size, activity height, loaded catalyst with short production cycle are prepared.
Rotary packed bed as reactor using adverse current later, above-mentioned catalyst makes nitro under super gravity field as filler
Benzene waste water with ozone gas react by the counter current contacting in catalyst bed, joint high-gravity technology, heterogeneous catalysis and ozone oxygen
The synergistic effect for changing three, improves the degradation rate of nitrobenzene and the utilization rate of ozone.
The present invention utilizes high-gravity technology, with carrier γ-Al2O3As filler, make maceration extract aerosol dispersion, with liquid mist, liquid
Drop-wise state is sprayed in high-speed rotating carrier surface, while reverse air blast makes carrier granular be near fluidization, promotes particle
Revolution rotation, on the one hand extends the dipping residence time, improves the load capacity of Mn, Fe, Cu active component, while promoting active component
In the uniform adsorption of carrier surface, dipping yin-yang face phenomenon is reduced.
Life is further shortened using 120 DEG C of hot-air quick strippings for the drying process of shaping carrier in super gravity field
The period is produced, while with mm grades of spherical gamma-Al2O3As carrier, the forming process in catalyst later period is eliminated, the catalysis prepared
Agent have with rotary packed bed matching, active component is uniformly dispersed, large specific surface area, catalytic activity are high, with short production cycle excellent
Point.
It is rotary packed bed as gas-liquid-solid phase reaction device, Mn-Fe-Cu/ γ-Al using adverse current2O3Catalyst as filler,
Joint high-gravity technology, heterogeneous catalysis and ozone oxidation three synergistic effect, accelerate mass transfer and the decomposition of ozone, promote to produce
Raw more OH free radicals, effectively improve the degradation rate of nitrobenzene and the utilization rate of ozone, shorten process cycle, are suitble to place
Manage the nitrobenzene waste water of processing task weight of large quantities.
Detailed description of the invention
Fig. 1 is that the present invention prepares the Mn-Fe-Cu/ γ-Al2O3The process flow chart of catalyst；In figure: 1- ozone occurs
Device；2- valve；3- flowmeter；4- blower；5- preheater；6- shell；7- motor；8- carrier；9- reservoir；10- pump；11- tail
Aspiration receiving apparatus；
Fig. 2 is that hypergravity fluidizes spray-stain method preparation Mn-Fe-Cu/ γ-Al2O3The device master of catalyst and treatment of Nitrobenzene waste water
Body figure；In figure: 6.1- liquid outlet；6.2- silk screen；6.3- gas vent；6.4- liquid inlet；6.5- liquid distribution trough；6.6-
Gas access；
Fig. 3 is Mn-Fe-Cu/γ-Al in embodiment 12O3The outside drawing for roasting front and back, in figure: A is outside drawing before roasting；B
For outside drawing after roasting；
Fig. 4 is Mn-Fe-Cu/γ-Al in embodiment 12O3The SEM of catalyst and carrier figure；
Fig. 5 is Mn-Fe-Cu/γ-Al in embodiment 12O3Catalyst Catalytic Ozonation nitrobenzene in super gravity field
Waste water nitrobenzene degradation rate with catalyst access times trend chart.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and detailed description.But the content of present invention not by
Following embodiments are limited to.
Embodiment 1: using process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, with the dilute nitre of 0.1 mol/L
2 h of acid soak, deionized water are cleaned to neutrality, dry 12 h at 105 DEG C, roast 4 h at 300 DEG C, filling even enters after cooling
Rotary packed bed, loading is 50 g/L.Molar ratio 1:1:4 nitric acid is prepared by 0.05 mol/L (in terms of Cu concentration of metal ions)
Copper, ferric nitrate, manganese acetate metal mixed salt solution, adjusting pH is 5.0, is placed in reservoir.By maceration extract through circulation be pumped into it is super
Gravity is rotary packed bed, and fluid flow is 40 L/h, and air mass flow is 6 m3/ h, revolving speed are set as 800 rpm, make itself and carrier
Dipping is come into full contact with, circulation dip time is 90 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make to live
Property component is fixed.It takes out catalyst and roasts the Cu01- that 4 h are 13% to get metallic element load capacity at 500 DEG C
Fe01-Mn04/γ-Al2O3Catalyst.
Prepared catalyst is through electron microscope scanning, as a result as shown in figure 4, Mn-Fe-Cu/γ-Al2O3Catalyst
SEM figure it can be seen that load after carrier surface become coarse, metal oxide is with lesser even particulate dispersion in carrier
Surface, active site is more, and catalytic activity is high.In combination with outside drawing 3, it can be seen that catalyst surface color is uniform, is not present
Apparent yin-yang face phenomenon, shows that active component reaches uniform load in carrier surface, keeps good exterior appearance.
Embodiment 2: the process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, with 0.1 mol/L dust technology
2h is impregnated, deionized water is cleaned to neutrality, dry 12 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotation after cooling
Packed bed, loading are 50 g/L.By 0.05 mol/L (in terms of Cu concentration of metal ions) prepare molar ratio 1:1:4 copper nitrate,
Ferric nitrate, manganese acetate metal mixed salt solution, adjusting pH is 5.0, is placed in reservoir.Maceration extract is pumped into hypergravity through circulation
Rotary packed bed, fluid flow is 40 L/h, and air mass flow is 4 m3/ h, revolving speed are set as 600 rpm, fill it with carrier
Tap touching dipping, circulation dip time are 30 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make activity
Component is fixed.It takes out catalyst and roasts the Cu01-Fe01- that 2 h are 10% to get metallic element load capacity at 500 DEG C
Mn04/γ-Al2O3Catalyst.
Embodiment 3: the process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, with 0.1 mol/L dust technology
2h is impregnated, deionized water is cleaned to neutrality, dry 12 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotation after cooling
Packed bed, loading are 75 g/L.Molar ratio 1:2:2 copper nitrate, nitre are prepared by 0.03mol/L (in terms of Cu concentration of metal ions)
Sour iron, manganese acetate metal mixed salt solution, adjusting pH is 5.0, is placed in reservoir.Maceration extract is pumped into hypergravity rotation through circulation
Turn packed bed, fluid flow is 120 L/h, and air mass flow is 10 m3/ h, revolving speed are set as 800 rpm, keep it abundant with carrier
Contact dipping, circulation dip time are 60 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make active group
Divide and is fixed.It takes out catalyst and roasts the Cu01-Fe02- that 6 h are 9% to get metallic element load capacity at 300 DEG C
Mn02/γ-Al2O3Catalyst.
Embodiment 4: the process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, with 0.1mol/L dust technology
2h is impregnated, deionized water is cleaned to neutrality, dry 12 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotation after cooling
Packed bed, loading are 100 g/L.By 0.05mol/L (in terms of Cu concentration of metal ions) prepare molar ratio 1:1:4 copper nitrate,
Ferric nitrate, manganese acetate metal mixed salt solution, adjusting pH is 5.0, is placed in reservoir.Maceration extract is pumped into hypergravity through circulation
Rotary packed bed, fluid flow is 80 L/h, and air mass flow is 8 m3/ h, revolving speed are set as 1200 rpm, fill it with carrier
Tap touching dipping, circulation dip time are 90 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make activity
Component is fixed.It takes out catalyst and roasts the Cu01-Fe01- that 4 h are 16% to get metallic element load capacity at 500 DEG C
Mn04/γ-Al2O3Catalyst.
Embodiment 5: the process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, with 0.1 mol/L dust technology
2h is impregnated, deionized water is cleaned to neutrality, dry 12 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotation after cooling
Packed bed, loading are 50 g/L.Molar ratio 1:4:2 copper nitrate, nitre are prepared by 0.05mol/L (in terms of Cu concentration of metal ions)
Sour iron, manganese acetate metal mixed salt solution, adjusting pH is 5.0, is placed in reservoir.Maceration extract is pumped into hypergravity rotation through circulation
Turn packed bed, fluid flow is 120 L/h, and air mass flow is 10 m3/ h, revolving speed are set as 1200 rpm, fill it with carrier
Tap touching dipping, circulation dip time are 30 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make activity
Component is fixed.It takes out catalyst and roasts the Cu01-Fe04- that 4 h are 17% to get metallic element load capacity at 700 DEG C
Mn02/γ-Al2O3Catalyst.
Embodiment 6: using Mn-Fe-Cu/ γ-Al made from example 12O3Catalyst, O3 catalytic oxidation treatment of Nitrobenzene
Waste water.Using process flow shown in Fig. 1, by Mn-Fe-Cu/ γ-Al2O3Filling even enters rotary packed bed, loading 100
g.The 2 L nitrobenzene solutions that initial concentration is 200 mg/L are prepared, adjusting pH is 6.9, is placed in reservoir.Adjust ozone generator
Outlet gas phase ozone concentration be 60 mg/L, gas flow be 60 L/h, pumping fluid flow be 85 L/h, rotary packed bed turn
The rpm of fast N=1000, gas-liquid two-phase counter current contacting in catalyst bed are reacted.
Mn-Fe-Cu/γ-Al2O3Catalyst catalytic ozonation degradation nitrobenzene waste water nitre in super gravity field
As shown in figure 5, treated, nitrobenzene waste water is straight from thief hatch with the trend charts of catalyst access times for base benzene degradation rate
Connect sampling analysis, the degradation rate of nitrobenzene up to 100%, TOC removal rate up to 87%, ozone utilization rate reaches 78%.Catalyst
20 h are used continuously, catalytic performance is without the trend that is decreased obviously, and metal ion does not occur dissolution phenomenon.
Prepared catalyst catalytic performance repeats experimental result as shown in figure 5, according to experiment is repeated as can be seen that catalysis
Agent is with good stability, this is related with the more active site of catalyst surface Load Balanced, holding.
Mn-Fe-Cu/γ-Al prepared by embodiment 1- embodiment 52O3Catalyst ozonisation results of property is shown in Table
1.As can be seen from Table 1 using Mn-Fe-Cu/γ-Al of hypergravity fluidisation spray-stain method preparation2O3Catalyst loadings are high, for
The degradation rate and TOC removal rate of nitrobenzene respectively reach 95%, 70% or more；Ozone utilization rate reaches 65% or more.Show this method
The catalyst significant effect of preparation, while high-gravity technology, heterogeneous catalysis and ozone oxidation three being coupled, utilize association
Same effect can accelerate mass transfer and the decomposition of ozone, promote to generate more OH free radicals, effectively improve the mineralization rate of nitrobenzene
With the utilization rate of ozone, it is suitble to the nitrobenzene waste water that processing is of large quantities, processing task is heavy.
Table 1 is Mn-Fe-Cu/γ-Al under different preparation conditions2O3Catalyst ozonizes results of property table
Claims (9)
1. a kind of Mn-Fe-Cu/ γ-Al of hypergravity fluidisation spray-stain method preparation2O3Catalyst, it is characterised in that: the Mn-Fe-
Cu/γ-Al2O3Catalyst is in hypergravity adverse current is rotary packed bed, with γ-Al2O3Carrier is filler, Mn, Fe, Cu metal
Salt is maceration extract, and adjusting air mass flow makes carrier granular be in nearly fluidized state, while under hypergravity centrifugal action, making to impregnate
Liquid and the air counter current contacting in carrier bed, after carrier is sufficiently impregnated, using hot-air stripping moisture, are subject to active component
It is fixed, then 300-700 DEG C of high-temperature roasting, as Mn-Fe-Cu/ γ-Al are taken out from bed2O3Loaded catalyst.
2. a kind of Mn-Fe-Cu/ γ-Al of hypergravity fluidisation spray-stain method preparation according to claim 12O3Catalyst,
Be characterized in that: Mn, Fe, Cu metal salt is the mixed solution of copper nitrate, ferric nitrate and manganese acetate, concentration of metal ions proportion
For 1:1-4:1-4；In terms of Cu concentration of metal ions, the concentration of salt solution is 0.01-0.05 mol/L.
3. preparing Mn-Fe-Cu/ γ-Al of any of claims 1 or 22O3The method of catalyst, it is characterised in that: specific steps
It is as follows:
(1) impregnation: γ-Al2O3Filling even enters cross_flow rotating packed bed after Vehicle element；Mn, Fe, Cu metal salt
Mixed impregnant liquor is placed in reservoir, is pumped into cross_flow rotating packed bed inner cavity through circulation, maceration extract is equal via liquid distribution trough
It is even to be sprayed at carrier bed inner edge, under the effect of high speed centrifugation power, leaching is radially contacted with carrier from inside to outside with Sprayable
Stain, while air is sent into through blower by bed exocoel, under inside and outside differential pressure effect, ecto-entad connects with maceration extract and carrier adverse current
Touching, by adjusting gas velocity, makes carrier granular be in nearly fluidized state, with the revolution and rotation of particle, makes carrier granular and leaching
Stain liquid comes into full contact with, and the liquid after dipping returns to reservoir and carries out circulation dipping；
(2) high-temperature roasting: after the completion of dipping, carrying out stripping to bed using hot-air, remove catalyst surface moisture, fixed to live
Property component, take out catalyst precursor after 300-700 DEG C of high-temperature roasting.
4. preparation Mn-Fe-Cu/ γ-Al according to claim 32O3The method of catalyst, it is characterised in that: the γ-
Al2O3Carrier is the spherical gamma-Al of partial size 1-2 mm2O3, loading is 50 g/L.
5. preparation Mn-Fe-Cu/ γ-Al according to claim 32O3The method of catalyst, it is characterised in that: γ-Al2O3
Vehicle element method are as follows: 2 h are impregnated with 0.1 mol/L dust technology, deionized water is cleaned to neutrality, dry 12 h at 105 DEG C,
4 h are roasted at 300 DEG C.
6. preparation Mn-Fe-Cu/ γ-Al according to claim 32O3The method of catalyst, it is characterised in that: the rotation
The revolving speed of packed bed is 600-1200 rpm, and fluid flow is 40-120 L/h, and air mass flow is 4-10 m3/ h, circulation dipping
Time is 30 ~ 90 min.
7. preparation Mn-Fe-Cu/ γ-Al according to claim 32O3The method of catalyst, it is characterised in that: the heat is empty
Air-blowing desorption method is 120 DEG C of 60 min of hot-air stripping, and tolerance is 4 m3/h。
8. preparation Mn-Fe-Cu/ γ-Al according to claim 32O3The method of catalyst, it is characterised in that: calcining time
For 3-6 h.
9. Mn-Fe-Cu/ γ-Al of any of claims 1 or 22O3Catalyst O3 catalytic oxidation nitrobenzene in super gravity field
Application in waste water, application is it is characterized by: concrete application method are as follows: by Mn-Fe-Cu/ γ-Al2O3Catalyst as filler,
It is rotary packed bed that filling even enters adverse current type, loading 100g；The 2 L nitrobenzene waste waters of 200 mg/L are added to liquid storage
Slot is pumped into rotary packed bed inner cavity through circulation, and ozone is sent into rotary packed bed through rotary packed bed gas access, control rotation
Turning packed bed revolving speed is 1000rpm, fluid flow 85L/h, gas flow 60L/h, and gas phase ozone concentration is 60mg/L, nitre
Base benzene waste water is radially thrown away from rotary packed bed bed inner edge under hypergravity, passes through rotary packed bed bed with ecto-entad
Ozone gas counter current contacting, liquid is then thrown to outer wall vertical and falls, and returns to reservoir, nitrobenzene waste water from liquid outlet
Circular response is carried out in rotary packed bed middle counter current contacting with ozone gas.
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