CN105536795B - Preparation method, product and the application of iron copper aluminum oxide composite catalyst - Google Patents
Preparation method, product and the application of iron copper aluminum oxide composite catalyst Download PDFInfo
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- CN105536795B CN105536795B CN201510939912.XA CN201510939912A CN105536795B CN 105536795 B CN105536795 B CN 105536795B CN 201510939912 A CN201510939912 A CN 201510939912A CN 105536795 B CN105536795 B CN 105536795B
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- C02F1/722—Oxidation by peroxides
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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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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of preparation method of iron copper aluminum oxide composite catalyst, including：(1) aluminium salt is added in the cushioning liquid of formic acid/ammonium formate, after aluminium salt is completely dissolved, adds mesoporous SBA 15, after the completion of absorption, drying, roasting obtains the samples of SBA 15 of aluminium load；(2) samples of SBA 15 that aluminium loads are placed in containing in iron ion and copper ion solution, after the completion of dipping, drying is selectable to be calcined, and obtains iron copper aluminum oxide composite catalyst.The catalyst and the application process of the catalyst being prepared invention additionally discloses above-mentioned preparation method.The present invention is modified mesoporous material SBA 15 by Al, obtains good Al2O3Nanometer layer, after continuing supported bi-metallic component Fe and Cu, active component continues to keep the nanometer layer of high degree of dispersion, and in neutral conditions, catalyst has good degraded to remove, and shows the high catalytic activity of catalyst.
Description
Technical field
The invention belongs to catalyst preparation technical field, and it is compound to be specifically related to a kind of property of high score three iron/copper-aluminum oxide
Preparation method, product and the application of catalyst.
Background technology
In traditional Fenton catalysis, the applicable of catalyst is confined to acid range, especially left in pH=3.Although class
Fenton catalyst employs solid form, and avtive spot also switchs to solid state surface from homogeneous ionic state, but catalyst can only
The essence for showing high catalytic activity in acid condition does not become.
In fact, a large amount of actual waste water pH are in neutral or alkaline range, it is both needed to adjust using a large amount of soda acids before and after the processing
Save the needs of pH is to meet Fenton's reaction and subsequent treatment so that whole processing procedure operation is loaded down with trivial details, and it is big to consume sour alkali consumption.Mesh
Before, some new ferrum-based catalysts have been able to be reacted under conditions of neutral or close neutrality, but require to compare
It is harsh or need to be additionally provided other reaction conditions, for example, catalyst amountses are too high, reaction when need heating, dioxygen water conservancy
It is low with rate.Therefore, explore exploitation and be capable of the class fenton catalyst of efficient catalytic in neutral conditions as advanced oxidation research
The common objective of worker.
Enable catalyst efficient catalytic Fenton's reaction in neutral conditions, it is necessary to build the acyclic acidic of a local
Border, i.e. acidic micro-environment, this needs the metal component decentralized environment for building high degree of dispersion.According to the literature with research experience table
It is bright, it is difficult to obtain the catalyst under pH neutrallty conditions with high activity by iron one-component.Hacgyu Lim were once reported in
Fe2O3Under existence condition, active Al2O3Middle Al attracts Fe as the second metal in the form of lewis acidic2O3On electron density,
So that Fe (III) can revert to Fe (II) rapidly, accelerate ferrikinetics, so as to accelerate Fenton catalytic reaction so that reaction energy
Enough degradation of phenol under conditions of pH=4.0.But the metal nanoparticle for preparing of conventional metal ion solution infusion process compared with
Greatly, it is difficult to the nano active component of activity high degree of dispersion.
The content of the invention
The invention provides a kind of preparation method of iron/copper-aluminum oxide composite catalyst, this method is simple to operate, together
When process costs it is low, substantial amounts of waste water etc. will not be produced in preparation process, it is easy to accomplish industrialization.
Invention also provides the iron/copper being prepared by the above method-aluminum oxide composite catalyst, the catalyst
Activity is high in neutral conditions, high to the degradation efficiency of organic pollution, and usage amount is few, and use cost is low.
Present invention also offers a kind of above-mentioned using organic in above-mentioned iron/copper-aluminum oxide composite catalyst degrading waste water
The application process of pollutant, its step are simple.
A kind of preparation method of iron/copper-aluminum oxide composite catalyst, including：
(1) aluminium salt is added in the cushioning liquid of formic acid/ammonium formate, after aluminium salt is completely dissolved, adds mesoporous SBA-15,
After the completion of absorption, drying, roasting obtains the SBA-15 samples of aluminium load；
(2) the SBA-15 samples that aluminium loads are placed in containing in iron ion and copper ion solution, after the completion of dipping, dried,
It is selectable to be calcined, obtain iron/copper-aluminum oxide composite catalyst.
In step (1), one or more of the aluminium salt in aluminum sulfate, aluminum nitrate, aluminium chloride etc.；More preferably sulphur
Sour aluminium.Al plays lewis acidic effect in the present invention, can provide acidic micro-environment in neutral reaction for catalyst.
When Al content increases, catalyst also improves therewith to the class Fenton removal efficiency of organic pollution, shows repairing for Al
Decorations improve catalyst lewis acidity, and more Lewis-acid sites are provided in catalyst surface.In step (1), add
Aluminium salt total amount, with the Mass Calculation of aluminium atom, aluminium atom is 0.5~5 with mesoporous SBA-15 mass ratio:1, further preferably
For：Aluminium atom is 0.9~3.4 with mesoporous SBA-15 mass ratio:1；Still more preferably it is：Aluminium atom and mesoporous SBA-15 quality
Than for 2.0~3.0:1.
In step (1), after adding mesoporous SBA-15, it may be selected to use 10~30min of ultrasonic vibration；Then in a water bath,
60~80 DEG C are heated and are stirred vigorously 1~3h.After solution cooling, vacuum filtration, and washed repeatedly with ultra-pure water and absolute ethyl alcohol
Wash；Then gained solid is dried overnight removing ethanol for 60~100 DEG C in an oven, is finally placed in Muffle furnace 400~500 DEG C
It is calcined 1~3h.
Traditional Al modifications use alkaline sedimentation method, and the nano particle of acquisition is larger, and in formic acid/ammonium formate cushioning liquid
It is middle to use Al (OH)3Homogeneous precipitation rule can form uniform thin layer, rather than the nano-particle of convex, so as to contribute to
Catalyst obtains higher catalytic activity.The present invention uses the SBA-15 that Al is modified as carrier, using Fe as catalyst activity component
Central metal, while loaded Cu, the class fenton catalyst of efficient catalytic in neutral conditions is prepared.
Traditional Al modifications use alkaline sedimentation method, and the nano particle of acquisition is larger, and in formic acid/ammonium formate cushioning liquid
It is middle to use Al (OH)3Homogeneous precipitation rule can form uniform thin layer, rather than the nano-particle of convex, so as to contribute to
Catalyst obtains higher catalytic activity.The present invention uses the SBA-15 that Al is modified as carrier, using Fe as catalyst activity component
Central metal, while loaded Cu, the class fenton catalyst of efficient catalytic in neutral conditions is prepared.Preferably, institute
The pH value for stating cushioning liquid is 4~5, and further preferred pH value is 4.4~4.5.
Iron ion and copper ion solution are selected from the aqueous solution containing water miscible molysite and mantoquita, the iron in step (2)
One or more of the salt in ferric nitrate, iron chloride, ferric sulfate；The mantoquita is in copper nitrate, copper chloride, copper sulphate
It is one or more.
In addition to Al, Ni metal can also play certain lewis acid in catalyst, and Cu sheets are as Fenton activity
Metal, H can be catalyzed2O2Decompose and produce OH degradation of contaminant.Because Fe also has a Fenton catalytic activity in itself, thus Fe and
Cu shows significantly to act synergistically in degraded.But both influences each to reaction are not quite similar.In step (2), make
To be preferred, in the iron ion and copper ion solution, the mol ratio between iron ion and copper ion is (10~1):(1~10)；
More preferably (2~1):(1~10)；More one progress is preferably 1:3.Experiment shows, when Fe content reduces, Cu content
During rise, the clearance of dyestuff significantly improves therewith.In Fe：Cu is 9：When 1,3h is reacted, the clearance of rhodamine B is only
66.3%, and work as Fe：Cu is reduced to 1：When 1, the clearance of rhodamine B is up to 95.4%.But with Fe:Cu ratios continue to subtract
Small, Cu content persistently raises, and dyestuff clearance no longer increases, and shows an optimum proportioning between Fe and Cu be present.This be because
It is Fenton active metal for Fe and Cu, but the two catalytic activity difference under the conditions of same pH is larger, in acid condition
(pH=3 or so), Fe have stronger Fenton catalysis characteristics, and when the ph is increased, Fe components easily form metal hydroxides
And metal oxide, catalytic activity reduces even loses catalytic activity completely, and Cu in neutral conditions can be more efficient
Produce oxidative species, fast degradation organic matter.
In step (2), being calculated with mesoporous SBA-15 gross mass, the mass percent that copper and iron add is generally below 10%,
Preferably 6~10%.
In step (3), the temperature of roasting is preferably 200~450 DEG C.Experiment shows that, when reduction temperature raises, gained is urged
Catalytic degradation behavior of the agent to dyestuff is not quite similar, but is not especially big with the difference of raw catalyst, and this is probably
The active component that catalyst is formed under different reduction temperatures checks and balance, shifting, not metal (the oxygen of jljl phase and valence state
Compound) mixed phase has higher class Fenton catalytic degradation effect to dyestuff.
The present invention also provides iron/copper-alumina that a kind of preparation method as described in any of the above-described technical scheme is prepared
Thing composite catalyst.
Invention also provides one kind to utilize organic dirt in above-mentioned iron/copper-aluminum oxide composite catalyst degrading waste water
Contaminate the application process of thing.
Using in above-mentioned iron/copper-aluminum oxide composite catalyst, directly putting into catalyst needs waste water to be processed
In, you can, operation is very simple.
Preferably, described waste water is waste water from dyestuff, hydrogen peroxide is added in processing procedure；Experiment shows, is adding H2O2Bar
Under part, catalyst has high catalytic elimination effect to dyestuff contaminant, and more than 90% is reached in 4h.As further excellent
Choosing, the waste water is the organic wastewater containing rhodamine B or acid red 73.
Preferably, in the waste water, the concentration of organic pollution is 10~200mg/L；Further preferred concentration is
30~60mg/L.
Preferably, in application process, the usage amount of the catalyst is 0.4~1g/L, more preferably 0.5~
0.8g/L。
Preferably, the molar concentration of the hydrogen peroxide is 0.5~1.5mol/L；More preferably 0.8~1.2mol/
L。
The mechanism with high catalyzing activation may be as follows in neutral conditions for the catalyst of the present invention：
From catalyst surface pattern, active component has highly uniform distribution in catalyst surface, rather than with
Bulky grain nano-particle at random is present, and this distribution, which is likely to become catalyst, has one of the reason for high activity.First, when with
Al is (with Al after annealing2O3Form presence) modification SBA-15, because modification passes through cushioning liquid control pH, Al (OH)3Molten
In liquid slowly, be uniformly dispersed in carrier surface, so as to form finely dispersed Al2O3Thin layer.It is growing in advance, dispersed good
Good tetrahedron Al2O3Surface carries positive charge, as a large amount of H of absorption+There is stronger ion exchange afterwards, and when continuation
When impregnating Fe and Cu active component, Fe3+And Cu2+With H+Generation exchange interaction, so as to be evenly distributed on Al2O3With SBA-15 tables
Face, play a part of behind in the growth course of iron species and copper species " seed ", so as to be formed uniformly in catalyst surface
Tiny nanometer layer.The nanometer layer of these high degree of dispersion has more avtive spots, therefore has bigger catalytic activity.
Understood in removal experiment of the catalyst to dyestuff acid red 73 and rhodamine B, in neutral conditions, catalyst pair
The dye of positive ion and anionic dye suffer from excellent class Fenton degradation effect.Only difference is that catalyst is to acid red 73
Absorption it is very strong, approach, and rhodamine B almost do not adsorbed with class Fenton degraded removal effect in a short time, contaminate
The removal of material is attributed to the fact that class Fenton is degraded completely.The reason for causing this species diversity is likely to two kinds of dye structure differences, type
Difference, the electrically charged difference of institute in same pH solution, therefore it is also different with the active force of catalyst surface electric charge.In order to confirm this
Kind infer, we determine catalyst Al (Fe+Cu)-SBA surface charge and acid red 73 and rhodamine B in pH=7
Zeta current potentials.As seen from Figure 11, catalyst is all positively charged in the range of pH=3-7, and dye, rhodamine B and acidity
Red 73 is all negatively charged, but electrically charged very low, the only -5.4mV of rhodamine B, and acid red 73 is then -24.2mV.It is aobvious
And be clear to, the active force between catalyst and rhodamine B is smaller, and the electrostatic attraction between acid red 73 is stronger, because
This has strong suction-operated to acid red 73.
To the efficient degradation of dyestuff except dispersed active component, the synergy also between each component has catalyst
Close.Centered on the iron in the class Fenton catalysis of element, an important reaction, i.e. Fe (III)+H be present2O2→Fe(II)+·
HO2+H+.This reaction is a rate-limiting reaction, and Fe (III) is oxidized to Fe to Fe (II) conversion rate far below Fe (II)
(III) speed, therefore as a poorly efficient major reason of conventional class fenton catalyst.And work as and pass through Al2O3SBA-15 is entered
After row modification, the Al in octahedral structure plays lewis acidic effect, can attract the electron density on surrounding Fe (III),
Fe (II) is converted into so as to promote Fe (III) to be easier.In addition, copper species have lewis acid and class Fenton special in itself
Property, OH can be produced in neutral conditions, and redox cycle can be formed between iron species, acceleration Fe (III)/
Fe (II) conversion and cycle, so as to accelerate the progress of class Fenton's reaction.Therefore exactly Al and Cu double action, it is not only reaction
An acidic micro-environment is provided, and accelerates ferrikinetics so that catalyst being capable of efficient degradation dyestuff in neutral conditions.
The chemical reaction occurred in course of reaction can represent as follows：
Fe(III)+H2O2→Fe(II)+·HO2+H+ (1)
Fe(II)+H2O2→Fe(III)+·OH+OH- (2)
Cu(II)+H2O2→Cu(I)+·HO2+H+ (3)
Cu(I)+H2O2→Cu(II)+·OH+OH- (4)
Fe(III)+Cu(I)→Fe(II)+Cu(II) (5)
dye+·OH→CO2+H2O (6)
Analysis on Mechanism shows that the synergy between the various active component in catalyst accelerates entering for class Fenton degraded
OK.Al lewis acid effect can attract Fe (III) electron density, promote ferrikinetics.Copper species are not only able to autocatalysis
Class Fenton is degraded, additionally it is possible to redox reaction occurs between iron species, further speeds up Fe (III)/Fe (II) circulations, makes
Catalyst can efficient catalytic degradation of dye in neutral conditions, there is great practical value.
Mesoporous material SBA-15 is modified by Al in the present invention, obtains good Al2O3Nanometer layer, it is double to continue load
After metal component Fe and Cu, active component continues to keep the nanometer layer of high degree of dispersion, therefore is not observed on section TEM
The presence of bulky grain nano-particle, also occur on XRD without corresponding peak, and SEM-EDS observation and XPS spectrum figure confirm
The presence of metallic element and high degree of dispersion.
Can to the class Fenton degradation experiment of dye of positive ion rhodamine B and anionic dye acid red 73 by catalyst
Know, in neutral conditions, the catalyst of present invention gained suffers from good degraded for the dyestuff of both types and removed, and shows
The high catalytic activity of catalyst is shown.
Brief description of the drawings
Fig. 1 is that sample Al (the Fe+Cu)-SBA that embodiment is prepared (load with SBA-15, Al-SBA on SBA-15
Al), (Fe+Cu)-SBA (Fe+Cu is loaded on SBA-15) section TEM figures；
Fig. 2 is the SEM figures and sample distribution diagram of element that Al modifies SBA-15；
The SEM figures and sample distribution diagram of element that Fig. 3 is Al (Fe+Cu)-SBA that embodiment is prepared；
Fig. 4 is original SBA-15 and Metal Supported sample Al (Fe+Cu)-SBA XRD spectrum；
The XPS that Fig. 5 is (Fe+Cu)-SBA that embodiment is prepared is composed entirely and Al, Fe and Cu open score；
Degradation results figures of the Fig. 6 for the catalyst that embodiment is prepared to rhodamine B；
Degradation results figures of the Fig. 7 for the catalyst that embodiment is prepared to acid red 73；
Fig. 8 is the influence that different Al contents are degraded to rhodamine B in embodiment；
Fig. 9 is the influence that different Fe and Cu ratios are degraded to rhodamine B in embodiment；
Figure 10 is the influence that different reduction temperatures are degraded to rhodamine B in embodiment；
Figure 11 is the zeta potential diagrams that catalyst sample Al (Fe+Cu)-SBA and dyestuff are prepared in embodiment.
Embodiment
With reference to embodiment, the invention will be further described：
The raw material that embodiment uses：
SBA-15(SiO2/Al2O3>=500, aperture 6-8nm, BET:400-600m2g-1) it is purchased from Nanjing Xian Feng nano materials
Science and Technology Ltd., using preceding 80 DEG C of dry 3h in vacuum drying chamber, to remove the organic matter of adsorption.Aluminum sulfate (Al2
(SO4)3·18H2O), ferric nitrate (Fe (NO3)3·9H2O), copper nitrate (Cu (NO3)2·3H2O), anhydrous formic acid (>98%), first
Sour ammonium and hydrogen peroxide (GR, 30wt%) are that analysis is pure, are purchased from Shanghai traditional Chinese medicines chemical reagent Co., Ltd.Acid red 73 is bought
In Chengdu West Asia chemical reagent Co., Ltd.Experimental water is ultra-pure water (electrical conductivity：18.23MΩ·cm).
Embodiment 1~17
SBA-15 is modified with Al：According to the data of table 1 by a certain amount of aluminum sulfate (with aluminium atom Mass Calculation, aluminium atom
With mesoporous SBA-15 mass ratio) it is added in 500mL round-bottomed flasks, then add 250mL pH=4.40 formic acid/ammonium formate
Cushioning liquid, vibration are completely dissolved aluminum sulfate.Then 0.5g mesoporous SBA-15 samples, sonic oscillation 15min are added.By flask
It is placed in water-bath, 70 DEG C are heated and are stirred vigorously 2h.After solution cooling, vacuum filtration, and it is anti-with ultra-pure water and absolute ethyl alcohol
After backwashing is washed.Gained solid is dried overnight removing ethanol for 80 DEG C in an oven, is placed in 450 DEG C of roasting 2h in Muffle furnace.
Sample after roasting (is thrown with the mixed aqueous solution of ferric nitrate and copper nitrate according to the mol ratio and copper and iron total amount of table 1
Material) incipient impregnation is carried out, dry at room temperature, removing residual moisture is dried for 105 DEG C in an oven, according to the reduction temperature of table 1
Required catalyst is produced in Muffle kiln roasting 2h, Al (Fe+Cu)-SBA is temporarily named as in the procatalyst not characterized.In order to just
In the performance for comparing and assessing catalyst, the catalyst being prepared under different Al contents, Fe and Cu ratios and different reduction temperatures.
Table 1
| Embodiment | Al：SBA-15 | Iron：Copper | Iron copper total amount, % | Reduction temperature, DEG C |
| 1 | 0.9:1 | 1:3 | 6% | 450 |
| 2 | 1.5:1 | 1:3 | 8% | 450 |
| 3 | 2.1:1 | 1:3 | 9% | 450 |
| 4 | 3.0:1 | 1:3 | 10% | 450 |
| 5 | 3.0:1 | 9:1 | 10% | 450 |
| 6 | 3.0:1 | 3:1 | 10% | 450 |
| 7 | 3.0:1 | 2:1 | 10% | 450 |
| 8 | 3.0:1 | 1:1 | 10% | 450 |
| 9 | 3.0:1 | 1:2 | 10% | 450 |
| 10 | 3.0:1 | 1:3 | 10% | 450 |
| 11 | 3.0:1 | 1:9 | 10% | 450 |
| 12 | 3.0:1 | 1:3 | 10% | 200 |
| 13 | 3.0:1 | 1:3 | 10% | 250 |
| 14 | 3.0:1 | 1:3 | 10% | 300 |
| 15 | 3.0:1 | 1:3 | 10% | 350 |
| 16 | 3.0:1 | 1:3 | 10% | 400 |
| 17 | 3.0:1 | 1:3 | 10% | 450 |
The sign of catalyst：
(1) high dispersive Fe2O3-CuO/Al2O3The formation of nanometer layer
In our current research, Al modifies SBA-15 and uses Al (OH) in formic acid/ammonium formate cushioning liquid3Sluggish precipitation, this
Al made from method2O3Uniform thin layer, rather than the nano-particle of convex will be formed on SBA-15 surfaces, so as to help to urge
Agent obtains higher catalytic activity.We use N first2The result of adsorption-desorption experiment confirms metal active constituent
Success loads.As can be seen from Table 2, with modifications of the Al to SBA-15, specific surface area is by the 558m before loading2g-1Fall below negative
336m after load2g-1, per unit pore volume is also by 0.94cm3/ g falls below 0.43cm3/ g, aperture are also retracted to by 5.75nm
3.84nm, it was confirmed that mesopore orbit due to Metal Supported and duct volume is occupied so that specific surface area, pore volume and aperture contracting
It is small.When continuing to load Fe and Cu active components, specific surface area and pore volume continue significantly to reduce.SBA-15 pore structure parameters
Explanation active component is significantly changed successfully to be supported on SBA-15.
The structural parameters of the SBA-15 load samples of table 2
Continue the SBA- after being modified using section TEM the Al obtained among SBA-15 samples, embodiment 4 or embodiment 10
The surface of Al (Fe+Cu)-SBA catalyst that 15 samples, embodiment 4, embodiment 10 or embodiment 17 are prepared is observed,
As a result it is as shown in Figure 1.From figure 1 it appears that SBA-15 contains obvious mesopore orbit (in Fig. 1 (a)) in itself, repaiied when with Al
After decorations (Fig. 1 (b)), obvious Al is not found2O3Nano-particle, show Al2O3It is uniformly dispersed in SBA-15 surfaces.
When continuing to load Fe and Cu (Fig. 1 (c)) on the SBA-15 modified in Al, also without discovery Al2O3And Fe and Cu active component shapes
Into the trace of nano-particle, but Fe and Cu (Fig. 1 (d)) is loaded on the SBA-15 modified without Al can then be clearly visible and receive
The presence of rice corpuscles, huge difference show that Al modification can be such that metal active constituent disperses in SBA-15 apparent heights,
Even distribution.
Because the nano-particle of metal active constituent formation is not observed directly in TEM, in order to confirm Al, Fe, Cu
Three kinds of metallic elements have successfully been loaded on SBA-15, and we are entered by SEM-EDX to the SBA-15 samples that Al is modified first
Go and observed and analyze.Figure it is seen that the same panel region selected at random on a catalyst has been detected simultaneously by Al, Si
With tri- kinds of elements of O, and three kinds of elements are uniformly distributed.Due to the basic element that Si and O is SBA-15, therefore Al detection shows
It has successfully been loaded on SBA-15, and is distributed highly uniform.On this basis, we continue through SEM-EDX pairs
Al (Fe+Cu)-SBA samples are observed and analyzed.From figure 3, it can be seen that in the same panel region of catalyst, except carrying
Outside body SBA-15 basic element Si and O, tri- kinds of metals of Al, Fe and Cu are also detected, and these three elements are in SBA-15
Surface is uniformly distributed.Result above has absolutely proved that tri- kinds of elements of Al, Fe and Cu have successfully been loaded on SBA-15, and
And be evenly distributed, generated without larger nano particle.
On this basis, we carry out XRD signs (Fig. 4) to sample, as a result find Al (Fe+Cu)-SBA spectrogram and original
Beginning SBA-15 spectrogram is very alike, and 22 ° nearby have a very wide diffraction maximum on the diagram, and this is amorphous silicon typical case on carrier
Characteristic peak.In addition, without the diffraction maximum of other obvious metal active constituents, this shows metal active constituent with without fixed
Form and very small nanometer crystalline form are present, and this is consistent with TEM result, and the state of this high dispersive is exactly to come from
In Al contribution.
Due to active component high degree of dispersion, XRD can not obtain the chemical composition of metal component, it is therefore desirable to pass through XPS pairs
The element composition and chemical state of catalyst surface are studied, as shown in Figure 5.From Al (Fe+Cu)-SBA full spectrogram (Fig. 5 of XPS
(a)) as can be seen that except carrier S BA-15 in itself had Si, O absworption peak and pollution C absworption peak, the metal of load
Al, Fe and Cu are detected, it was confirmed that the successful load of three kinds of metal active constituents, and deposited in the form of high degree of dispersion
.The absworption peak that Al 2p open scores can be seen that at 74.4eV in Fig. 5 (b) correspond to Al2O3In Al3+, it was confirmed that Al
The SBA-15 surfaces of modification form Al2O3.And in Fig. 5 (c) in Fe 2p open scores, with reference to can be in the Fe at 711.5eV
2p3/2Absworption peak, with reference to can be in the Fe 2p at 724.3eV1/2Absworption peak, and the corresponding satellites at 719eV are common
Show that Fe elements mainly exist in the form of Fe (III), and be primarily present in α-Fe2O3Xiang Zhong.It is similar, shown in Fig. 5 (d)
In Cu 2p open scores, with reference to can be located at 933.3eV at Cu 2p3/2Cu 2p at absworption peak and 953.1eV1/2Absworption peak and both
Between obvious satellites collectively showed that Cu elements exist in the form of CuO.So far, we can draw, prepared by this research
Active component on catalyst is with Fe2O3-CuO/Al2O3The form of mixed oxide is present.
Catalyst performance is tested
Catalysis degeneration experiment is carried out in 100mL conical flasks, is positioned over after reaction solution sealing in constant temperature vibration case, 25
Reacted at DEG C with 150rpm velocity fluctuation.Typical reaction system includes catalyst 0.6g/L, model pollutant rhodamine B (or
Acid red 73), volume 50mL, concentration 50mg/L, pH=7, and 50mmol H2O2.After intervals, reaction is taken out
Mixture removes catalyst by 0.22 μm of membrane filtration, is measured immediately with ultraviolet-uisible spectrophotometer.
(1) rhodamine B degradation experiment
Because common class fenton catalyst suffers from good catalytic degradation effect for most of organic matter, and to sieve
The difficult degradation type dye effects such as red bright B, methylene blue are poor, therefore in order to assess the catalyst activity of this research preparation, we
Dye of positive ion rhodamine B is selected as model pollutant, the catalysis prepared using embodiment 4, embodiment 10 or embodiment 17
Agent carries out degradation experiment (sampling interval 0min, 20min, 40min, 60min, 120min, 180min and 240min) respectively.From
Fig. 6, which can be seen that, is adding H2O2Under the conditions of, catalyst has high catalytic elimination effect to rhodamine B, reaches in 4h
More than 90%, and the absorption under the same terms can almost be ignored completely, the removal for showing rhodamine B is entirely to be dropped by class Fenton
Solution causes.
(2) degradation experiment of acid red 73
Acid red 73 is a kind of common anionic dye, has important use in the industry such as printing and dyeing, weaving, this is previous
The directly model pollutant as this laboratory.Therefore, the present invention is process object with acid red 73, and further research loads
Al (1.5)-(Fe+Cu) that SBA-15 catalyst that FeCu SBA-15 catalyst, Fe is individually loaded, embodiment 2 are prepared
Catalyst in neutral conditions class Fenton catalytic degradation ability (sampling interval 0min, 10min, 30min, 60min,
120min).As shown in fig. 7, when carrying out the degraded of class Fenton to acid red 73 in neutral conditions, it can be seen that only load
Removal of Fe, Cu catalyst in pH=7 to dyestuff nearly reaches 50%, and the SBA-15 catalyst that Fe is individually loaded is in
Property under the conditions of almost without absorption and degraded, show that the load of the second Ni metal enhances the catalytic activity of catalyst.Further
FeCu is loaded on the SBA-15 of Al modifications, it is found that the activity of catalyst greatly improves, the removal to acid red in 2h is reachable
To 80%, show that Al modification enhances the lewis acidity of catalyst really.
(3) influence of the tenor to catalyst activity
Because the SBA-15 catalyst individually loaded with Fe in itself does not have any class Fenton catalytic activity in neutral conditions.
Therefore, SBA-15 modified metals Al and common carried metal Cu have a significant impact to the activity of catalyst.Al rises in the present invention
Lewis acidic effect, acidic micro-environment can be provided in neutral reaction for catalyst, therefore Al content needs to examine first
Consider.The present invention is utilized respectively Al (0.9)-(Fe+Cu) catalyst, Al (1.5)-(Fe+Cu) catalysis that embodiment 1-4 is prepared
Agent, Al (2.1)-(Fe+Cu) catalyst, Al (3.0)-(Fe+Cu) catalyst carry out degradation experiment (sampling interval to rhodamine B
For 0min, 20min, 40min, 60min, 120min, 360min), as a result see Fig. 8.As seen from Figure 8, when Al content increases
When catalyst to rhodamine B Fenton remove also improve therewith, showing Al modification improves catalyst lewis acidity, is urging
Agent surface provides more Lewis-acid sites.
In addition to Al, Ni metal can also play certain lewis acid, and Cu sheets are as Fenton active metal, can
It is catalyzed H2O2Decompose and produce OH degradation of contaminant.Because Fe also has Fenton catalytic activity in itself, therefore Fe and Cu are in degraded
Show significantly to act synergistically.But both influences each to reaction are not quite similar, the poly-metal deoxide of formation or
Influence of the mixed metal oxide catalyst to reaction also greatly differs from each other, therefore keeps the total load capacity of metal constant, investigates Fe
The influence degraded with Cu ratio to dyestuff has great importance.The present invention is utilized respectively what embodiment 5-11 was prepared
Al- (Fe+Cu) catalyst to rhodamine B carry out degradation experiment (sampling interval 0min, 20min, 40min, 60min, 80min,
100min, 120min, 180min), as a result see Fig. 9.As shown in Figure 9, when the total load quality of metal is original SBA-15's
When 10%, change the ratio of metal, Fe and the respective load capacity of Cu change therewith, to the removal effect of rhodamine B also phase not to the utmost
Together.When Fe content reduces, Cu content raises, the clearance of dyestuff significantly improves therewith.In Fe：Cu is 9：When 1, reaction
3h, the clearance of rhodamine B is only 66.3%, and works as Fe：Cu is reduced to 3：When 1, the clearance of rhodamine B is up to 95.4%.
But with Fe:Cu ratios continue reduction, Cu content persistently raises, and dyestuff clearance no longer increases, and shows between Fe and Cu
In the presence of an optimum proportioning.Because Fe and Cu are Fenton active metal, but the two is catalyzed work under the conditions of same pH
Property difference it is larger, in acid condition (pH=3 or so), Fe has stronger Fenton catalysis characteristics, and when the ph is increased, Fe groups
Partial volume easily forms metal hydroxides and metal oxide, and catalytic activity reduces even loses catalytic activity completely, and Cu exists
Generation oxidative species that can be more efficient under neutrallty condition, fast degradation organic matter.
(4) influence of the reduction temperature to catalyst activity
Whether H is carried out in catalyst preparation process2Reduce has important influence to the activity of catalyst, because catalyst
On active component always played a role in the form of specific thing phase and in the presence of chemical state, and H2Reduction, which can have influence on, urges
The chemical state of agent, and then have influence on the activity of catalyst.According to Figure 10 as can be seen that when reduction temperature raises, gained is urged
Catalytic degradation behavior of the agent to dyestuff is not quite similar, but is not especially big with the difference of raw catalyst, and this is probably
The active component that catalyst is formed under different reduction temperatures checks and balance, shifting, not metal (the oxygen of jljl phase and valence state
Compound) mixed phase has higher class Fenton catalytic degradation effect to dyestuff.
Claims (9)
- A kind of 1. preparation method of iron/copper-aluminum oxide composite catalyst, it is characterised in that including：(1) aluminium salt is added in the cushioning liquid of formic acid/ammonium formate, after aluminium salt is completely dissolved, adds mesoporous SBA-15, absorption After the completion of, drying, roasting obtains the SBA-15 samples of aluminium load；(2) the SBA-15 samples that aluminium loads are placed in containing in iron ion and copper ion solution, the iron ion and copper ion Mol ratio is (10~1)：(1~10), after the completion of dipping, dry, roasting, obtain iron/copper-aluminum oxide composite catalyst.
- 2. the preparation method of iron/copper according to claim 1-aluminum oxide composite catalyst, it is characterised in that step (1) in, the total amount of the aluminium salt of addition, with the Mass Calculation of aluminium atom, aluminium atom is 0.5~5 with mesoporous SBA-15 mass ratio:1.
- 3. the preparation method of iron/copper according to claim 1-aluminum oxide composite catalyst, it is characterised in that with mesoporous SBA-15 gross masses calculate, and the mass percent sum that copper and iron add is less than or equal to 10%.
- 4. the preparation method of iron/copper according to claim 1-aluminum oxide composite catalyst, it is characterised in that step (2) in, the temperature of roasting is 200~450 DEG C.
- 5. a kind of iron/copper-aluminum oxide composite catalyst, it is characterised in that as described in claim 1-4 any claims The preparation method of iron/copper-aluminum oxide composite catalyst is prepared.
- 6. a kind of application process using organic pollution in iron/copper-aluminum oxide composite catalyst degrading waste water, its feature exists In the iron/copper-aluminum oxide composite catalyst is as iron/copper-aluminum oxide described in claim 1-4 any claims The preparation method of composite catalyst is prepared.
- 7. it is according to claim 6 using in iron/copper-aluminum oxide composite catalyst degrading waste water organic pollution should With method, it is characterised in that the pH value of the waste water is 6~8.
- 8. it is according to claim 6 using in iron/copper-aluminum oxide composite catalyst degrading waste water organic pollution should With method, it is characterised in that described waste water is waste water from dyestuff, and hydrogen peroxide is added in processing procedure.
- 9. it is according to claim 6 using in iron/copper-aluminum oxide composite catalyst degrading waste water organic pollution should With method, it is characterised in that in the waste water, the concentration of organic pollution is 10~200mg/L；Iron/copper-the aluminum oxide The usage amount of composite catalyst is 0.4~1g/L.
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