CN105536795A - Iron-copper-aluminum oxide composite catalyst and its preparation method and use - Google Patents
Iron-copper-aluminum oxide composite catalyst and its preparation method and use Download PDFInfo
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- CN105536795A CN105536795A CN201510939912.XA CN201510939912A CN105536795A CN 105536795 A CN105536795 A CN 105536795A CN 201510939912 A CN201510939912 A CN 201510939912A CN 105536795 A CN105536795 A CN 105536795A
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- 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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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a preparation method of an iron-copper-aluminum oxide composite catalyst. The preparation method comprises 1, adding an aluminum salt into a formic acid/ammonium formate buffer solution, after the aluminum salt is completely dissolved, adding mesoporous SBA-15 into the solution and after adsorption, carrying out drying and roasting to obtain an aluminum-loaded SBA-15 sample, and 2, immersing the aluminum-loaded SBA-15 sample into the solution containing iron and copper ions and then carrying out drying and optionally, carrying out roasting to obtain the iron-copper-aluminum oxide composite catalyst. The invention also discloses the iron-copper-aluminum oxide composite catalyst obtained through the preparation method and a use of the iron-copper-aluminum oxide composite catalyst. The mesoporous SBA-15 material is modified through Al so that a good Al2O3 nanometer coating is obtained. After two metal ingredients Fe and Cu are loaded, the active ingredients are highly dispersed in the nanometer coating. Under neutral conditions, the iron-copper-aluminum oxide composite catalyst has good degradation and removal effects and has very high catalyst catalytic activity.
Description
Technical field
The invention belongs to catalyst preparation technical field, specifically relate to a kind of preparation method of high score three property iron/copper-aluminum oxide composite catalyst, product and application.
Background technology
In traditional Fenton catalysis, the applicable of catalyst is confined to acid range, especially left at pH=3.Although class fenton catalyst have employed solid form, avtive spot also transfers solid state surface to from the ionic state of homogeneous phase, but the essence that catalyst can only show high catalytic activity in acid condition does not become.
In fact, a large amount of actual waste water pH is in neutrality or alkaline range, all needs to use a large amount of acid-base accommodation pH to meet the demand of Fenton's reaction and subsequent treatment before and after process, whole processing procedure is operated loaded down with trivial details, consumes sour alkali consumption large.At present, some novel ferrum-based catalysts can react under neutral or close neutral condition, but require harsher or need additionally to provide other reaction condition, such as catalyst amounts is too high, reaction time need heating, hydrogen peroxide utilization rate low.Therefore, explore exploitation and the class fenton catalyst of efficient catalytic can become the common objective of advanced oxidation research worker in neutral conditions.
Make catalyst can efficient catalytic Fenton's reaction in neutral conditions, must build the sour environment of a local, i.e. acidic micro-environment, this needs the metal component decentralized environment building high degree of dispersion.Show according to bibliographical information and research experience, dependence iron one-component is difficult to obtain has highly active catalyst under pH neutrallty condition.HacgyuLim was once reported in Fe
2o
3under existence condition, active A l
2o
3middle Al attracts Fe as the second metal with lewis acidic form
2o
3on electron density, thus make Fe (III) that Fe (II) can be reverted to rapidly, accelerate ferrikinetics, thus accelerate Fenton catalytic reaction, make reaction can under the condition of pH=4.0 degradation of phenol.But metal nanoparticle prepared by the metal ion solution infusion process of routine is comparatively large, is difficult to the nano active component of activity high degree of dispersion.
Summary of the invention
The invention provides the preparation method of a kind of iron/copper-aluminum oxide composite catalyst, the method is simple to operate, and process costs is low simultaneously, can not produce a large amount of waste water etc., be easy to realize industrialization in preparation process.
Invention also provides the iron/copper-aluminum oxide composite catalyst prepared by said method, this catalyst is active high in neutral conditions, high to the degradation efficiency of organic pollution, and use amount is few, and use cost is low.
Present invention also offers a kind of above-mentioned application process utilizing organic pollution in above-mentioned iron/copper-aluminum oxide composite catalyst degrading waste water, its step is simple.
A preparation method for iron/copper-aluminum oxide composite catalyst, comprising:
(1) joined by aluminium salt in the cushioning liquid of formic acid/ammonium formate, after aluminium salt dissolves completely, add mesoporous SBA-15, after having adsorbed, dry, roasting obtains the SBA-15 sample of aluminium load;
(2) the SBA-15 sample of aluminium load is placed in containing iron ion and copper ion solution, after having flooded, dries, selectablely carry out roasting, obtain iron/copper-aluminum oxide composite catalyst.
In step (1), aluminium salt be selected from aluminum sulfate, aluminum nitrate, aluminium chloride etc. one or more; More preferably aluminum sulfate.Al plays lewis acidic effect in the present invention, can provide acidic micro-environment for catalyst in neutral reaction.
When Al content increases, the class Fenton removal efficiency of catalyst to organic pollution also improves thereupon, shows that the modification of Al improves catalyst lewis acidity, provides more Lewis-acid sites at catalyst surface.In step (1), the total amount of the aluminium salt added, with the Mass Calculation of aluminium atom, aluminium atom and mesoporous SBA-15 mass ratio are 0.5 ~ 5:1, more preferably: aluminium atom and mesoporous SBA-15 mass ratio are 0.9 ~ 3.4:1; Further be preferably: aluminium atom and mesoporous SBA-15 mass ratio are 2.0 ~ 3.0:1.
In step (1), after adding mesoporous SBA-15, can select to adopt ultrasonic vibration 10 ~ 30min; Then in a water bath, 60 ~ 80 DEG C of heating also vigorous stirring 1 ~ 3h.After solution cooling, vacuum filtration, and with ultra-pure water and absolute ethyl alcohol cyclic washing; Then by gained solid 60 ~ 100 DEG C of dried overnight removing ethanol in an oven, Muffle furnace 400 ~ 500 DEG C of roasting 1 ~ 3h are finally placed in.
Traditional Al modifies and adopts alkaline sedimentation method, and the nano particle of acquisition is comparatively large, and adopts Al (OH) in formic acid/ammonium formate cushioning liquid
3homogeneous precipitation rule can form uniform thin layer, instead of the nano particle of convex, thus contributes to the higher catalytic activity of catalyst acquisition.The SBA-15 that the present invention adopts Al to modify is carrier, take Fe as the central metal of catalyst activity component, and loaded Cu, prepares the class fenton catalyst of efficient catalytic in neutral conditions simultaneously.
Traditional Al modifies and adopts alkaline sedimentation method, and the nano particle of acquisition is comparatively large, and adopts Al (OH) in formic acid/ammonium formate cushioning liquid
3homogeneous precipitation rule can form uniform thin layer, instead of the nano particle of convex, thus contributes to the higher catalytic activity of catalyst acquisition.The SBA-15 that the present invention adopts Al to modify is carrier, take Fe as the central metal of catalyst activity component, and loaded Cu, prepares the class fenton catalyst of efficient catalytic in neutral conditions simultaneously.As preferably, the pH value of described cushioning liquid is 4 ~ 5, and preferred pH value is 4.4 ~ 4.5 further.
Iron ion and copper ion solution are selected from the aqueous solution containing water miscible molysite and mantoquita in step (2), described molysite be selected from ferric nitrate, iron chloride, ferric sulfate one or more; Described mantoquita be selected from copper nitrate, copper chloride, copper sulphate one or more.
Except Al, in catalyst, Ni metal also can play certain lewis acid effect, and Cu is originally as Fenton active metal, can catalysis H
2o
2decompose and produce OH degradation of contaminant.Because Fe itself also has Fenton catalytic activity, therefore Fe and Cu shows obvious synergy in degraded.But both are not quite similar on the impact of reaction separately.In step (2), as preferably, in described 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 progressive preferably 1:3.Experiment shows, when the content of Fe reduce, the content of Cu raise time, the clearance of dyestuff significantly improves thereupon.When Fe:Cu is 9:1, reaction 3h, the clearance of rhodamine B is only 66.3%, and when Fe:Cu is reduced to 1:1, the clearance of rhodamine B is up to 95.4%.But along with Fe:Cu ratio continues the lasting rising of content of reduction, Cu, dyestuff clearance no longer increases, and shows to there is an optimum proportioning between Fe and Cu.This is because Fe and Cu is Fenton active metal, but the two catalytic activity difference under same pH condition is larger, in acid condition (about pH=3), Fe has stronger Fenton catalysis characteristics, and when the ph is increased, Fe component easily forms metal hydroxides and metal oxide, catalytic activity reduction loses catalytic activity even completely, and Cu can produce oxidative species in neutral conditions more efficiently, fast degradation organic matter.
In step (2), calculate with mesoporous SBA-15 gross mass, the mass percent that copper and iron add, generally lower than 10%, is preferably 6 ~ 10%.
In step (3), the temperature of roasting is preferably 200 ~ 450 DEG C.Experiment shows, when reduction temperature raises, the catalytic degradation behavior of gained catalyst to dyestuff is not quite similar, but not large especially with the difference of raw catalyst, this active component that may be catalyst is formed under different reduction temperature checks and balance, shifting, metal (oxide) mixed phase of jljl phase and valence state does not all have higher class Fenton catalytic degradation effect to dyestuff.
The present invention also provides a kind of iron/copper-aluminum oxide composite catalyst prepared by preparation method described in above-mentioned arbitrary technical scheme.
Invention also provides a kind of application process utilizing organic pollution in above-mentioned iron/copper-aluminum oxide composite catalyst degrading waste water.
Use in above-mentioned iron/copper-aluminum oxide composite catalyst, directly catalyst put into and need in waste water to be processed, operate very simple.
As preferably, described waste water is waste water from dyestuff, adds hydrogen peroxide in processing procedure; Experiment shows, is adding H
2o
2under condition, catalyst has high catalytic elimination effect to dyestuff contaminant, in 4h, reach more than 90%.As preferred further, described waste water is the organic wastewater containing rhodamine B or acid red 73.
As preferably, in described waste water, the concentration of organic pollution is 10 ~ 200mg/L; Preferred concentration is 30 ~ 60mg/L further.
As preferably, in application process, the use amount of described catalyst is 0.4 ~ 1g/L, more preferably 0.5 ~ 0.8g/L.
As preferably, the molar concentration of described hydrogen peroxide is 0.5 ~ 1.5mol/L; More preferably 0.8 ~ 1.2mol/L.
The mechanism possibility that catalyst of the present invention has high catalyzing activation is in neutral conditions as follows:
From catalyst surface pattern, active component has at catalyst surface and distributes very uniformly, instead of exists with bulky grain nano particle at random, and this distribution may become catalyst and have one of highly active reason.First, when with Al (with Al after annealing
2o
3form exists) modify SBA-15, because modification is by cushioning liquid control pH, Al (OH)
3slowly, be uniformly dispersed in carrier surface in the solution, thus form finely dispersed Al
2o
3thin layer.Leading growth, the tetrahedron Al of favorable dispersibility
2o
3surperficial with positive charge, as a large amount of H of absorption
+there is stronger ion exchange afterwards, and when continuing the active component of dipping Fe and Cu, Fe
3+and Cu
2+with H
+there is exchange interaction, thus be evenly distributed on Al
2o
3with SBA-15 surface, in the growth course of iron species and copper species thereafter, play the effect of " seed ", thus form evenly tiny nanometer layer at catalyst surface.The nanometer layer of these high degree of dispersion has more avtive spot, therefore has larger catalytic activity.
Known in the removal experiment of catalyst to dyestuff acid red 73 and rhodamine B, in neutral conditions, catalyst has excellent class Fenton degradation effect to the dye of positive ion and anionic dye.Unique difference is that catalyst is very strong to the absorption of acid red 73, close with class Fenton degraded removal effect at short notice, and does not almost adsorb rhodamine B, and the degraded of class Fenton is given the credit in the removal of dyestuff completely.Cause the reason of this species diversity to be likely two kinds of dye structure differences, type is different, and electrically charged difference in same pH solution is therefore also different with the active force of catalyst surface electric charge.In order to confirm this deduction, we determine the surface charge of catalyst A l (Fe+Cu)-SBA and acid red 73 and the zeta current potential of rhodamine B when pH=7.As seen from Figure 11, catalyst is all positively charged within the scope of pH=3-7, and dye, rhodamine B and acid red 73 all electronegative, but rhodamine B institute electrically charged very low, only have-5.4mV, acid red 73 is then-24.2mV.Obviously, the active force between catalyst and rhodamine B is smaller, and stronger with the electrostatic attraction between acid red 73, therefore has strong suction-operated to acid red 73.
Catalyst except homodisperse active component, is gone back relevant with the synergy between each component to the efficient degradation of dyestuff.Centered by iron element the catalysis of class Fenton in, there is an important reaction, i.e. Fe (III)+H
2o
2→ Fe (II)+HO
2+ H
+.This reaction is a rate-limiting reaction, Fe (III) is oxidized to the speed of Fe (III) far below Fe (II) to the conversion rate of Fe (II), therefore become a major reason of conventional class fenton catalyst poor efficiency.And when passing through Al
2o
3after modifying SBA-15, the Al in octahedral structure plays lewis acidic effect, can attract the electron density on around Fe (III), thus impel Fe (III) to be more easily converted into Fe (II).In addition, copper species itself have lewis acid and class Fenton characteristic, can produce OH in neutral conditions, and can and iron species between form redox cycle, accelerate Fe (III)/Fe (II) conversion and cycle, thus accelerate the carrying out of class Fenton's reaction.Therefore the double action of Al and Cu just, not only for reaction provides an acidic micro-environment, and accelerates ferrikinetics, makes catalyst can efficient degradation dyestuff in neutral conditions.The chemical reaction occurred in course of reaction can be expressed as follows:
Fe(III)+H
2O
2→Fe(II)+·HO
2+H
+(1)
Fe(II)+H
2O
2→Fe(III)+·OH+OH
-(2)
Cu(II)+H
2O
2→Cu(I)+·HO
2+H
+(3)
Cu(I)+H
2O
2→Cu(II)+·OH+OH
-(4)
Fe(III)+Cu(I)→Fe(II)+Cu(II)(5)
dye+·OH→CO
2+H
2O(6)
Analysis on Mechanism shows, the synergy between the various active component in catalyst accelerates the carrying out of class Fenton degraded.The lewis acid effect of Al can attract Fe (III) electron density, promotes ferrikinetics.Copper species not only can be degraded by autocatalysis class Fenton, can also and iron species between there is redox reaction, the circulation of further quickening Fe (III)/Fe (II), makes catalyst can efficient catalytic degradation of dye in neutral conditions, has great practical value.
By Al, mesoporous material SBA-15 is modified in the present invention, obtain good Al
2o
3nanometer layer, after continuing supported bi-metallic component Fe and Cu, active component continues the nanometer layer keeping high degree of dispersion, therefore on section TEM, bulky grain nano particle is not observed, XRD does not have yet corresponding peak occur, and the observation of SEM-EDS and XPS spectrum figure confirm existence and the high degree of dispersion of metallic element.
Known by the class Fenton degradation experiment of catalyst to dye of positive ion rhodamine B and anionic dye acid red 73, in neutral conditions, the catalyst of gained of the present invention has good degraded to remove for the dyestuff of this two type, demonstrates the catalytic activity that catalyst is high.
Accompanying drawing explanation
Fig. 1 is that sample Al (the Fe+Cu)-SBA that embodiment prepares schemes with the section TEM of SBA-15, Al-SBA (SBA-15 upper load Al), (Fe+Cu)-SBA (the upper load Fe+Cu of SBA-15);
Fig. 2 is SEM figure and the sample distribution diagram of element that Al modifies SBA-15;
Fig. 3 is SEM figure and the sample distribution diagram of element of Al (the Fe+Cu)-SBA that embodiment prepares;
Fig. 4 is the XRD collection of illustrative plates of original SBA-15 and Metal Supported sample Al (Fe+Cu)-SBA;
Fig. 5 is that the XPS of (Fe+Cu)-SBA that embodiment prepares composes the open score with Al, Fe and Cu entirely;
Fig. 6 is that the catalyst for preparing of embodiment is to the degradation results figure of rhodamine B;
Fig. 7 is that the catalyst for preparing of embodiment is to the degradation results figure of acid red 73;
Fig. 8 is the impact that in embodiment, different al content is degraded on rhodamine B;
Fig. 9 is the impact that in embodiment, different Fe and Cu ratio is degraded on rhodamine B;
Figure 10 is the impact that in embodiment, different reduction temperature is degraded on rhodamine B;
Figure 11 is the zeta potential diagram preparing catalyst sample Al (Fe+Cu)-SBA and dyestuff in embodiment.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
The raw material that embodiment adopts:
SBA-15 (SiO
2/ Al
2o
3>=500, aperture 6-8nm, BET:400-600m
2g
-1) be purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., use before in vacuum drying chamber 80 DEG C of dry 3h, to remove the organic matter of adsorption.Aluminum sulfate (Al
2(SO
4)
318H
2o), ferric nitrate (Fe (NO
3)
39H
2o), copper nitrate (Cu (NO
3)
23H
2o), anhydrous formic acid (>98%), ammonium formate and hydrogen peroxide (GR, 30wt%) be analyze pure, be purchased from Shanghai traditional Chinese medicines chemical reagent Co., Ltd.Acid red 73 is bought in West Asia, Chengdu chemical reagent Co., Ltd.Experimental water is ultra-pure water (electrical conductivity: 18.23M Ω cm).
Embodiment 1 ~ 17
With Al, SBA-15 is modified: according to table 1 data, a certain amount of aluminum sulfate (is calculated with aluminium atomic mass, aluminium atom and mesoporous SBA-15 mass ratio) join in 500mL round-bottomed flask, then add the cushioning liquid of 250mLpH=4.40 formic acid/ammonium formate, vibration makes aluminum sulfate dissolve completely.Then 0.5g mesoporous SBA-15 sample is added, sonic oscillation 15min.Flask is placed in water-bath, 70 DEG C of heating also vigorous stirring 2h.After solution cooling, vacuum filtration, and with ultra-pure water and absolute ethyl alcohol cyclic washing.By gained solid 80 DEG C of dried overnight removing ethanol in an oven, be placed in Muffle furnace 450 DEG C of roasting 2h.
The mixed aqueous solution of the sample after roasting and ferric nitrate and copper nitrate (feeding intake according to the mol ratio of table 1 and copper iron total amount) carries out incipient impregnation, dry under room temperature, 105 DEG C of dry removing residual moistures in an oven, namely required catalyst is obtained, at the temporary called after Al (Fe+Cu) of the procatalyst do not characterized-SBA according to reduction temperature roasting 2h in Muffle furnace of table 1.For the ease of comparing and assess the performance of catalyst, prepare the catalyst under different al content, Fe and Cu ratio and different reduction temperature.
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 Fe
2o
3-CuO/Al
2o
3the formation of nanometer layer
In this research, Al modifies SBA-15 and adopts Al (OH) in formic acid/ammonium formate cushioning liquid
3sluggish precipitation, the Al that this method is obtained
2o
3uniform thin layer will be formed on SBA-15 surface, instead of the nano particle of convex, thus contribute to the higher catalytic activity of catalyst acquisition.First we adopt N
2the result of adsorption-desorption experiment confirms the successful load of metal active constituent.As can be seen from Table 2, along with Al is to the modification of SBA-15, specific area is by the 558m before load
2g
-1drop to the 336m after load
2g
-1, per unit pore volume is also by 0.94cm
3/ g has dropped to 0.43cm
3/ g, aperture has also been retracted to 3.84nm by 5.75nm, confirms that duct volume is occupied specific area, pore volume and aperture are reduced mesopore orbit due to Metal Supported.When continuation load Fe and Cu active component, specific area and pore volume continue significantly to reduce.The remarkable change of SBA-15 pore structure parameter illustrates that active component success load is on SBA-15.
The structural parameters of table 2SBA-15 load sample
Continue to adopt the surface of section TEM to Al (the Fe+Cu)-SBA catalyst that SBA-15 sample, embodiment 4, embodiment 10 or the embodiment 17 after the Al modification obtained in the middle of SBA-15 sample, embodiment 4 or embodiment 10 prepares to observe, result as shown in Figure 1.As can be seen from Figure 1, SBA-15 itself, containing obvious mesopore orbit (in Fig. 1 (a)), after modifying with Al (Fig. 1 (b)), does not find obvious Al
2o
3nano particle, shows Al
2o
3be dispersed in SBA-15 surface uniformly.When the SBA-15 modified at Al continuing load Fe and Cu (Fig. 1 (c)), also do not find Al
2o
3and Fe and Cu active component forms the trace of nano particle, but load Fe and Cu (Fig. 1 (d)) then obviously can see the existence of nano particle on the SBA-15 modified without Al, huge difference shows that the modification of Al can make metal active constituent in the dispersion of SBA-15 apparent height, is uniformly distributed.
Because do not observe directly the nano particle that metal active constituent is formed in TEM, in order to confirm that Al, Fe, Cu tri-kinds of metallic elements have successfully loaded on SBA-15, first we carried out observation and analysis by SEM-EDX to the SBA-15 sample that Al modifies.As can be seen from Figure 2, random selected same panel region detects Al, Si and O tri-kinds of elements simultaneously on a catalyst, and three kinds of elements are uniformly distributed.Because Si and O is the basic element of SBA-15, therefore detecting of Al shows that it has successfully been loaded on SBA-15, and distribution is very even.On this basis, we continue through SEM-EDX and have carried out observation and analysis to Al (Fe+Cu)-SBA sample.As can be seen from Figure 3, in the same panel region of catalyst, except basic element Si and O of carrier S BA-15, also detect Al, Fe and Cu tri-kinds of metals, and these three kinds of elements distribute at SBA-15 surface uniform.Above result has absolutely proved that Al, Fe and Cu tri-kinds of elements have successfully been loaded on SBA-15, and is evenly distributed, and does not have larger nano particle to generate.
On this basis, we carry out XRD sign (Fig. 4) to sample, found that the spectrogram of the spectrogram of Al (Fe+Cu)-SBA and original SBA-15 is very alike, figure has near 22 ° the diffraction maximum that very wide, and this is the typical characteristic peak of amorphous silicon on carrier.In addition, do not have the diffraction maximum of other obvious metal active constituent, this shows that metal active constituent exists with amorphous state and very little nanocrystalline form, and this is consistent with the result of TEM, and the state of this high dispersive comes from the contribution of Al just.
Due to active component high degree of dispersion, XRD cannot obtain the chemical composition of metal component, therefore needs to be studied the element composition of catalyst surface and chemical state by XPS, as shown in Figure 5.As can be seen from the full spectrogram of XPS (Fig. 5 (a)) of Al (Fe+Cu)-SBA, except carrier S BA-15 itself there is the absworption peak of Si, O and pollute the absworption peak of C, metal A l, Fe and Cu of load are detected, confirm the successful load of three kinds of metal active constituents, and exist with the form of high degree of dispersion.In Fig. 5 (b), the 2p open score of Al can be found out, correspond to Al at the absworption peak at 74.4eV place
2o
3in Al
3+, confirm that the SBA-15 surface that Al modifies defines Al
2o
3.And in Fig. 5 (c) Fe 2p open score in, in conjunction with can at the Fe2p at 711.5eV place
3/2absworption peak, combine can at the Fe2p at 724.3eV place
1/2absworption peak, and the satellites being positioned at 719eV place accordingly shows that Fe element mainly exists with Fe (III) form jointly, and be mainly present in α-Fe
2o
3xiang Zhong.Similar, Fig. 5 (d) Suo Shi Cu 2p open score in, in conjunction with being positioned at 933.3eV place Cu2p
3/2absworption peak and 953.1eV place Cu2p
1/2absworption peak and between the two obvious satellites indicate Cu element together to be existed with CuO form.So far, we can draw, the active component on the catalyst of this research preparation is with Fe
2o
3-CuO/Al
2o
3the form of mixed oxide exists.
Catalyst performance is tested
Catalysis degeneration experiment carries out in 100mL conical flask, is positioned in constant temperature vibration case, reacts at 25 DEG C with the velocity fluctuation of 150rpm after reaction solution sealing.Typical reaction system comprises catalyst 0.6g/L, model pollutant rhodamine B (or acid red 73), and volume is 50mL, and concentration is 50mg/L, pH=7, and the H of 50mmol
2o
2.Behind certain hour interval, take out reactant mixture and remove catalyst by 0.22 μm of membrane filtration, measure with ultraviolet-uisible spectrophotometer immediately.
(1) rhodamine B degradation experiment
Because common class fenton catalyst has good catalytic degradation effect for most of organic matter, and it is poor to the difficult degradation such as rhodamine B, methylene blue type dye effect, therefore in order to assess the catalyst activity of this research preparation, we select dye of positive ion rhodamine B as model pollutant, and the catalyst utilizing embodiment 4, embodiment 10 or embodiment 17 to prepare carries out degradation experiment (sampling interval is 0min, 20min, 40min, 60min, 120min, 180min and 240min) respectively.As can be seen from Figure 6, H is being added
2o
2under condition, catalyst has high catalytic elimination effect to rhodamine B, reach more than 90%, and the absorption under the same terms almost can be ignored completely in 4h, shows that the removal of rhodamine B is degraded by class Fenton to cause completely.
(2) acid red 73 degradation experiment
Acid red 73 is a kind of common anionic dyes, in the industry such as printing and dyeing, weaving, have important use, before this always as the model pollutant in this laboratory.Therefore, the present invention for handling object, studies Al (1.5)-(Fe+Cu) catalyst class Fenton catalytic degradation ability (sampling interval is 0min, 10min, 30min, 60min, 120min) in neutral conditions that load the SBA-15 catalyst of FeCu, the SBA-15 catalyst of the independent load of Fe, embodiment 2 prepare with acid red 73 further.As shown in Figure 7, when carrying out the degraded of class Fenton to acid red 73 in neutral conditions, can see that the catalyst of only load Fe, Cu almost reaches 50% when pH=7 to the removal of dyestuff, and the SBA-15 catalyst of the independent load of Fe does not almost adsorb in neutral conditions and degrades, show that the load of the second Ni metal enhances the catalytic activity of catalyst.Load FeCu on the SBA-15 of Al modification further, finds that the activity of catalyst improves greatly, can reach 80%, show that the modification of Al enhances the lewis acidity of catalyst really in 2h to the removal of acid red.
(3) tenor is on the impact of catalyst activity
Because the catalyst of SBA-15 itself and the independent load of Fe is in neutral conditions without any class Fenton catalytic activity.Therefore, SBA-15 modified metal Al and the common activity of carried metal Cu to catalyst have a significant impact.Al plays lewis acidic effect in the present invention, can provide acidic micro-environment for catalyst in neutral reaction, and therefore the content of Al needs first to consider.The Al (0.9) that the present invention utilizes embodiment 1-4 to prepare respectively-(Fe+Cu) catalyst, Al (1.5)-(Fe+Cu) catalyst, Al (2.1)-(Fe+Cu) catalyst, Al (3.0)-(Fe+Cu) catalyst carries out degradation experiment (sampling interval is 0min, 20min, 40min, 60min, 120min, 360min) to rhodamine B, the results are shown in Figure 8.As seen from Figure 8, when Al content increases, catalyst is removed rhodamine B Fenton and is also improved thereupon, shows that the modification of Al improves catalyst lewis acidity, provides more Lewis-acid sites at catalyst surface.
Except Al, Ni metal also can play certain lewis acid effect, and Cu is originally as Fenton active metal, can catalysis H
2o
2decompose and produce OH degradation of contaminant.Because Fe itself also has Fenton catalytic activity, therefore Fe and Cu shows obvious synergy in degraded.But both are not quite similar on the impact of reaction separately, the poly-metal deoxide formed or the impact of mixed metal oxide catalyst on reaction also greatly differ from each other, therefore the load capacity keeping metal total is constant, and the impact of ratio on dye degrades investigating Fe and Cu has great importance.Al-(Fe+Cu) catalyst that the present invention utilizes embodiment 5-11 to prepare respectively carries out degradation experiment (sampling interval is 0min, 20min, 40min, 60min, 80min, 100min, 120min, 180min) to rhodamine B, the results are shown in Figure 9.As shown in Figure 9, when the load quality that metal is total is 10% of original SBA-15, change the ratio of metal, Fe and Cu load capacity separately changes thereupon, is also not quite similar to the removal effect of rhodamine B.When the content of Fe reduce, the content of Cu raise time, the clearance of dyestuff significantly improves thereupon.When Fe:Cu is 9:1, reaction 3h, the clearance of rhodamine B is only 66.3%, and when Fe:Cu is reduced to 3:1, the clearance of rhodamine B is up to 95.4%.But along with Fe:Cu ratio continues the lasting rising of content of reduction, Cu, dyestuff clearance no longer increases, and shows to there is an optimum proportioning between Fe and Cu.This is because Fe and Cu is Fenton active metal, but the two catalytic activity difference under same pH condition is larger, in acid condition (about pH=3), Fe has stronger Fenton catalysis characteristics, and when the ph is increased, Fe component easily forms metal hydroxides and metal oxide, catalytic activity reduction loses catalytic activity even completely, and Cu can produce oxidative species in neutral conditions more efficiently, fast degradation organic matter.
(4) reduction temperature is on the impact of catalyst activity
Whether H is carried out in catalyst preparation process
2reduction has important impact to the activity of catalyst, because play a role when the active component on catalyst always exists with specific thing phase form and chemical state, and H
2reduction can have influence on the chemical state of catalyst, and then has influence on the activity of catalyst.Can find out according to Figure 10, when reduction temperature raises, the catalytic degradation behavior of gained catalyst to dyestuff is not quite similar, but not large especially with the difference of raw catalyst, this active component that may be catalyst is formed under different reduction temperature checks and balance, shifting, metal (oxide) mixed phase of jljl phase and valence state does not all have higher class Fenton catalytic degradation effect to dyestuff.
Claims (10)
1. a preparation method for iron/copper-aluminum oxide composite catalyst, is characterized in that, comprising:
(1) joined by aluminium salt in the cushioning liquid of formic acid/ammonium formate, after aluminium salt dissolves completely, add mesoporous SBA-15, after having adsorbed, dry, roasting obtains the SBA-15 sample of aluminium load;
(2) the SBA-15 sample of aluminium load is placed in containing iron ion and copper ion solution, after having flooded, dries, selectablely carry out roasting, obtain iron/copper-aluminum oxide composite catalyst.
2. the preparation method of iron/copper according to claim 1-aluminum oxide composite catalyst, is characterized in that, in step (1), the total amount of the aluminium salt added, with the Mass Calculation of aluminium atom, aluminium atom and mesoporous SBA-15 mass ratio are 0.5 ~ 5:1.
3. the preparation method of iron/copper according to claim 1-aluminum oxide composite catalyst, is characterized in that, the mol ratio of described iron ion and copper ion is (10 ~ 1): (1 ~ 10).
4. the preparation method of iron/copper according to claim 1-aluminum oxide composite catalyst, is characterized in that, calculate with mesoporous SBA-15 gross mass, the mass percent that copper and iron add is less than or equal to 10%.
5. the preparation method of iron/copper according to claim 1-aluminum oxide composite catalyst, is characterized in that, in step (2), the temperature of roasting is 200 ~ 450 DEG C.
6. iron/copper-aluminum oxide composite catalyst, is characterized in that, is prepared by the preparation method of the iron/copper-aluminum oxide composite catalyst described in the arbitrary claim of claim 1-5.
7. one kind utilizes the application process of organic pollution in iron/copper-aluminum oxide composite catalyst degrading waste water, it is characterized in that, described iron/copper-aluminum oxide composite catalyst is prepared by the preparation method of the iron/copper-aluminum oxide composite catalyst described in the arbitrary claim of claim 1-5.
8. the application process utilizing organic pollution in iron/copper-aluminum oxide composite catalyst degrading waste water according to claim 7, is characterized in that, the pH value of described waste water is 6 ~ 8.
9. the application process utilizing organic pollution in iron/copper-aluminum oxide composite catalyst degrading waste water according to claim 7, it is characterized in that, described waste water is waste water from dyestuff, adds hydrogen peroxide in processing procedure.
10. the application process utilizing organic pollution in iron/copper-aluminum oxide composite catalyst degrading waste water according to claim 7, is characterized in that, in described waste water, the concentration of organic pollution is 10 ~ 200mg/L; The use amount of described iron/copper-aluminum oxide composite catalyst is 0.4 ~ 1g/L.
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| CN109718771A (en) * | 2019-01-25 | 2019-05-07 | 东南大学 | A kind of bimetal-doped type alumina aerogels and its preparation and application |
| CN110116019A (en) * | 2019-04-28 | 2019-08-13 | 太原理工大学 | A kind of nano-cobaltic-cobaltous oxide/aluminium oxide@carried catalyst and its preparation method and application |
| CZ307971B6 (en) * | 2018-10-15 | 2019-09-18 | Ústav Chemických Procesů Av Čr, V. V. I. | Process for preparing an alumina-based material with a layer of ferrous spinels |
| CN112958090A (en) * | 2021-02-05 | 2021-06-15 | 长春工业大学 | Efficient and stable iron-copper montmorillonite heterogeneous Fenton catalyst and preparation method and application thereof |
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| CZ307971B6 (en) * | 2018-10-15 | 2019-09-18 | Ústav Chemických Procesů Av Čr, V. V. I. | Process for preparing an alumina-based material with a layer of ferrous spinels |
| CN109718771A (en) * | 2019-01-25 | 2019-05-07 | 东南大学 | A kind of bimetal-doped type alumina aerogels and its preparation and application |
| CN109718771B (en) * | 2019-01-25 | 2022-04-12 | 东南大学 | Bimetal doped alumina aerogel and preparation and use methods thereof |
| CN110116019A (en) * | 2019-04-28 | 2019-08-13 | 太原理工大学 | A kind of nano-cobaltic-cobaltous oxide/aluminium oxide@carried catalyst and its preparation method and application |
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| CN112958090A (en) * | 2021-02-05 | 2021-06-15 | 长春工业大学 | Efficient and stable iron-copper montmorillonite heterogeneous Fenton catalyst and preparation method and application thereof |
| CN112958090B (en) * | 2021-02-05 | 2023-05-12 | 长春工业大学 | Efficient and stable iron-copper montmorillonite heterogeneous Fenton catalyst and preparation method and application thereof |
| CN115212884A (en) * | 2022-07-29 | 2022-10-21 | 广西科学院 | Preparation method and application of catalyst based on metal ion reinforced free radical leading |
| CN115212884B (en) * | 2022-07-29 | 2023-09-26 | 广西科学院 | Preparation method and application of catalyst based on metal ion reinforced free radical domination |
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