CN101219376B - Catalyst for composite three-dimensional electric field catalysis wet oxidation technique and method for producing the same - Google Patents
Catalyst for composite three-dimensional electric field catalysis wet oxidation technique and method for producing the same Download PDFInfo
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- CN101219376B CN101219376B CN2008100330237A CN200810033023A CN101219376B CN 101219376 B CN101219376 B CN 101219376B CN 2008100330237 A CN2008100330237 A CN 2008100330237A CN 200810033023 A CN200810033023 A CN 200810033023A CN 101219376 B CN101219376 B CN 101219376B
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Abstract
The invention pertains to the field of water treatment technology and environmental functional materials, in particular to a catalyst used in composite three-dimensional electric field catalytic wet oxidation technique and a preparation method thereof. The catalyst takes Gamma-Al2O3 as a carrier, Mn metal oxide and Sn metal oxide as main active compounds and Sb oxide as an addition agent; wherein, the Mn metal oxide accounts for 65wt percent-67wt percent, the Sn metal oxide 32wt percent-34wt percent and the Sb oxide 0.5wt percent-1wt percent. Detail steps are that: the Gamma-Al2O3 carrier is soaked into the distilled water and then is dried for backup; the postprocessed Gamma-Al2O3 carrier is soaked into sol synthesized by Mn(NO3)2, SnCl4, SbCl3, HCl and C2H5, thus obtaining a Mn-Sn-Sb/Gamma-Al2O3 catalyst through dynamic soaking, baking, washing and drying. The invention has relatively good metal dispersivity of composite particles, even and subsequent crystal grains on the electrodesurface of particles, compact and tight crystal structure and relatively large roughness and valid ratio surface area which is larger than 199.6m<2>g; the catalyst is provided with relatively high catalytic activity.
Description
Technical field
The invention belongs to water technology and environment functional material field, be specifically related to a kind of Catalysts and its preparation method that is used for composite three-dimensional electric field catalysis wet oxidation technique.
Background technology
In order to realize organic effective degraded in the water body, arise at the historic moment based on the high-level oxidation technology that produces hydroxyl radical free radical, wherein CWO and electro-catalytic oxidation technology are the focuses of studying at present.Though catalysis wet-type oxidation technology has relaxed the harsh reaction condition of wet oxidation HTHP to a certain extent, seek out desirable treatment effect, its required reaction temperature is still higher.As one with the electronics be catalyst, the catalytic oxidation technology of cleaning comparatively, the electrocatalytic oxidation metallization processes is owing to be subjected to the restriction of its normal temperature and pressure service condition, its treatment effeciency often is not very high.One of key technology of composite three-dimensional electric field catalysis wet oxidation technique is develops the three dimensional particles electrode material that both is fit to catalytic oxidation, this granule electrode is under the effect of high-gradient electric field, induction becomes Bipolar Micro-Electrode, each granule electrode is equivalent to a micro cell, effectively increase electrode surface area, improved current efficiency.This granule electrode can be used as the catalyst of CWO again simultaneously, thereby reaches the Synergistic of composite three-dimensional electric field to CWO.
Three dimensional particles electrode material in the catalytic oxidation need satisfy: the resistance of particle will be beneficial to form high-gradient electric field much smaller than solution resistance, is convenient to the particle polarization; Insulated from each other between the particle.This electrode material should have good electric conductivity, corrosion resistance and electrode reaction is had good electrocatalysis characteristic simultaneously.Catalyst in the CWO should satisfy: catalyst should have preferably activity, chemical stability and mechanical stability.The requirement that also catalyst should satisfy in the catalysis wet-type oxidation technology of composite three-dimensional electric field just of above-mentioned feature.
With reference to active component in CWO and the electro-catalytic oxidation technology, select period 4 transient metal Mn, Fe, Co, Ni, Cu, Zn and rare earth metal Ce and in catalytic oxidation the metal oxide of the most frequently used Sn as active component, respectively with 13X molecular sieve and γ-Al
2O
3Be carrier, investigated stability and the catalytic activity of one pack system oxide catalyst under current field condition.Experimental result shows, though the 13X molecular sieve has higher electrocatalysis characteristic, during take molecular sieve as carrier the active component stripping of catalyst generally more serious, and in roasting process, be prone to crack performance, therefore select γ-Al
2O
3Catalyst carrier for body series.Sn/ γ-Al
2O
3The granule electrode Degradation of Phenol has higher catalytic activity and required tank voltage is lower, Mn/ γ-Al
2O
3Granule electrode then demonstrates higher mineralization ability.
Can reduce the advantage that tank voltage and Mn oxide can improve the phenol mineralization degree in order to give full play to the Sn oxide, on the basis of improving the TOC clearance, further reduce Faradaic current, final selection Mn, Sn metal oxide are active component, take the Sb oxide as auxiliary agent, make SnO
2Lattice dilatation causes defective and energy level splitting takes place, and increases the activity at the center of surface energy and absorption and catalysis, prepares the composite oxide particle electrode catalyst.
Summary of the invention
The object of the present invention is to provide a kind of temperature and pressure that reduces the CWO reaction, improve the Catalysts and its preparation method that is used for composite three-dimensional electric field catalysis wet oxidation technique of total oxidation operation reaction speed.
The catalyst that is used for composite three-dimensional electric field catalysis wet oxidation technique that the present invention proposes, this catalyst is with γ-Al
2O
3Be carrier, Mn metal oxide, Sn metal oxide are that main active component, Sb oxide are auxiliary agent.Calculate by mass percentage, the Mn metal oxide accounts for 65wt%～67wt%, and the Sn metal oxide accounts for 32wt%～34wt%, and the Sb oxide accounts for 0.5wt%～1wt%.
The present invention proposes is used for composite three-dimensional electric field catalysis wet oxidation technique Preparation of catalysts method, and concrete steps are as follows:
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12～14h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly, and the carrier after gained is cleaned is dry 10～12h under 100～110 ℃ of temperature, and the carrier after the oven dry saves backup;
(2) carrier impregnation that step (1) is obtained is in being the Mn (NO of 0.5～0.6mol/L by molar concentration
3)
2, molar concentration is the SnCl of 0.28～0.29mol/L
4, molar concentration is the SbCl of 4.37～4.38mmol/L
3, molar concentration is HCl and the C of 0.4～0.6mol/L
2H
5In the colloidal sol that OH forms, in shaking table, dynamically flood 3～5h with the constant rotational speed of 140～160r/min.Mn (NO wherein
3)
2, SnCl
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: (0.8～1.2): (0.8～1.2): (0.8～1.2): (0.8～1.2);
(3) carrier that step (2) is obtained is dry 1～3h under 80～90 ℃ temperature, its surperficial moisture is evaporated fully, and roasting 2～6h in air atmosphere, 300～600 ℃ Muffle furnace repeats above-mentioned steps 2～3 times then, washing, oven dry obtain Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
Perhaps: being used for composite three-dimensional electric field catalysis wet oxidation technique Preparation of catalysts method can obtain by following method, and concrete steps are as follows:
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12～14h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly, and the carrier after gained is cleaned is dry 10～12h under 100～110 ℃ of temperature, and the carrier after the oven dry saves backup;
(2) it is the SnCl of 0.28～0.29mol/L that the carrier that step (1) is obtained at first impregnated in by molar concentration
4, molar concentration is the SbCl of 4.37～4.38mmol/L
3, molar concentration is HCl and the C of 0.3～0.4mol/L
2H
5In the colloidal sol that OH forms, in shaking table, dynamically flood 3～5h, wherein SnCl with the constant rotational speed of 140～160r/min
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: (0.8～1.2): (0.8～1.2): (0.8～1.2).Soaked carrier is dry 1～3h under 80～90 ℃ temperature, and the moisture of carrier surface is evaporated fully, then roasting 2～6h in air atmosphere, 300～600 ℃ Muffle furnace;
(3) be the Mn (NO of 0.5～0.6mol/L in molar concentration with the carrier impregnation after step (2) processing
3)
2In the solution, the constant rotational speed with 140～160r/min in shaking table is dynamically flooded 3～5h, and the carrier behind the dipping is dry 1～3h under 100～105 ℃ temperature, and the moisture of carrier surface is evaporated fully;
(4) the roasting 2～6h in air atmosphere, 300～600 ℃ Muffle furnace again of the carrier after step (3) is processed, washing, oven dry obtain Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
Perhaps: being used for composite three-dimensional electric field catalysis wet oxidation technique Preparation of catalysts method can obtain by following method, and concrete steps are as follows:
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12～14h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly, and the carrier after gained is cleaned places dry 10～12h under 100～110 ℃ of temperature, and the carrier after the oven dry saves backup;
(2) carrier that step (1) is obtained at first impregnated in the Mn (NO that molar concentration is 0.5～0.6mol/L
3)
2In the solution, constant rotational speed with 140～160r/min in shaking table is dynamically flooded 3～5h, carrier behind the dipping is dry l～3h under 100～105 ℃ of temperature, and the moisture of carrier surface is evaporated fully, then roasting 2～6h in air atmosphere, 300～600 ℃ Muffle furnace;
(3) carrier impregnation after step (2) is processed is in being the SnCl of 0.28～0.29mol/L by molar concentration
4, molar concentration is the SbCl of 4.37～4.38mmol/L
3, molar concentration is HCl and the C of 0.3～0.4mol/L
2H
5In the colloidal sol that OH forms, in shaking table, dynamically flood 3～5h, wherein SnCl with the constant rotational speed of 140～160r/min
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: (0.8～1.2): (0.8～1.2): (0.8～1.2);
(4) with the dry 1～3h under 80～90 ℃ of temperature of the carrier after step (3) processing, the moisture of carrier surface is evaporated fully.Roasting 2～6h in air atmosphere, 300～900 ℃ Muffle furnace then, washing, oven dry obtain Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
Among the present invention, in fixed bed and composite three-dimensional electric field integral continuous CWO reactor, take phenol as object, utilize Mn-Sn-Sb/ γ-Al of the present invention
2O
3Catalyst has carried out the experimental study of composite three-dimensional electric field catalysis wet oxidation degrading high concentration organic wastewater.In addition, to Mn-Sn-Sb/ γ-Al
2O
3Catalyst has carried out respectively the analyses such as scanning electron Electronic Speculum (SEM), X-ray diffraction (XRD) and power spectrum (EDX), chemistry and the phase composition having studied the microstructure of catalyst surface and loaded on the metallic compound on the carrier.Result of study shows that catalyst of the present invention has the following advantages:
(1) the compound particle metal dispersion is better, and the granule electrode surface microstructure is uniform sequential, and crystal structure is tight, firm, and roughness and effective ratio area are all bigger, and its specific area is up to 199.6m
2/ g;
(2) carrier is with γ-Al
2O
3The phase form exists, and the characteristic diffraction peak of Mn, Sn oxide is not obvious, and its phase high degree of dispersion is in γ-Al
2O
3Carrier surface.SEM spectrogram before and after the catalyst reaction is basically identical, and the variation of diffraction peak intensity had not both taken place, and new phase also do not occur, shows that it still has higher catalytic activity after reaction;
(3) catalyst surface is except that containing active component Mn, Sn and Sb element, carrier A l and O element, also contain a spot of C element (conducting resinl that uses during with bonding sample is relevant), and metal M n content, Sn content are higher, Sb content pettiness, consistent with the concentration of active component in the maceration extract, Mn and the Sn distribution on carrier is quite even;
(4) catalyst of the present invention has good CWO activity and electrocatalytic oxidation property, and under the short time of staying (27min) and relatively mild reaction condition (T=130 ℃, P
O2=1.0MPa), can make the clearance of target organic matter phenol reach 94.0%, the TOC clearance reaches 88.4%.
Description of drawings
Fig. 1 is Mn-Sn-Sb/ γ-Al of embodiment 1
2O
3Catalyst electron-microscope scanning figure.
Fig. 2 is Mn-Sn-Sb/ γ-Al of embodiment 1
2O
3The catalyst XRD spectra.
Fig. 3 is Mn-Sn-Sb/ γ-Al of embodiment 1
2O
3Catalyst EDX spectrogram.
The specific embodiment
Give further instruction below by concrete embodiment to technology of the present invention.
Embodiment 1
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 13h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly.Carrier after will cleaning at last is dry 13h under 105 ℃ of temperature;
(2) it is the Mn (NO of 0.57mol/L that the carrier 50g that step (1) is obtained impregnated in by molar concentration
3)
2, molar concentration is the SnCl of 0.285mol/L
4, molar concentration is the SbCl of 4.38mmol/L
3, molar concentration is HCl and the C of 0.5mol/L
2H
5In the colloidal sol that OH forms, amount to 250ml, wherein Mn (NO
3)
2, SnCl
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: 1: 1: 1: 1, dynamically flood 4h with the constant rotational speed of 150r/min in shaking table;
(3) carrier that step (2) is obtained dry 3h under 90 ℃ of temperature evaporates its surperficial moisture fully, roasting 4h in air atmosphere, 550 ℃ Muffle furnace then, and last washing and drying obtains Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
Above-mentioned gained catalyst is used for composite three-dimensional electric field catalysis wet oxidation degradation of phenol waste water, and concrete outcome sees Table 1.
As shown in Figure 1: Mn-Sn-Sb/ γ-Al
2O
3Metal dispersion is better in the catalyst, and the catalyst surface uniform crystal particles is orderly, and crystal structure is tight, firm, and roughness and effective ratio area are all bigger, and its specific area is up to 199.6m
2/ g meets the requirement of catalyst porous.The specific area increase helps the absorption on its surface of oxygen and organic matter on the one hand, and then reacts; Avtive spot is increased, and catalytic performance strengthens.
As shown in Figure 2: the crystal grain of manganese and tin is grown imperfect, and its phase high degree of dispersion is in γ-Al
2O
3Carrier surface is not so detect the oxide characteristic diffraction peak of obvious Mn and Sn.XRD spectra also shows, Mn-Sn-Sb/ γ-Al before and after the reaction
2O
3Spectrogram basically identical, the intensity of XRD diffraction maximum does not almost change, and new phase do not occur, this shows that catalyst still has higher catalytic activity after the reaction of certain hour.
As shown in Figure 3: sample surfaces also contains a spot of C element except that containing active component Mn, Sn and Sb element, carrier A l and O element, and this is relevant with the conducting resinl that uses when the bonding sample.And the metal M n content of sample surfaces is higher, and Sn content is lower, and Sb content is very small, and this is consistent with the concentration of active component in the maceration extract.Get several points and carry out the EDX micro-zone analysis and show that further in identical collection gate time, different microcells all exists Mn, Sn and Sb element, and the strength difference at the Mn that obtains and Sn peak is little by appointing at catalyst surface, this illustrates SnO
2Promoted the dispersion of Mn at catalyst surface with the interaction of Mn, so that Mn and the Sn distribution on carrier is quite even.
Embodiment 2
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly.Carrier after will cleaning at last places dry 12h under 110 ℃ of temperature;
(2) it is the Mn (NO of 0.5mol/L that the carrier 50g that step (1) is obtained impregnated in by molar concentration
3)
2, molar concentration is the SnCl of 0.28mol/L
4, molar concentration is the SbCl of 4.375mmol/L
3, molar concentration is HCl and the C of 0.45mol/L
2H
5In the colloidal sol that OH forms, amount to 230ml, wherein, Mn (NO
3)
2, SnCl
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: 1: 1: 0.8: 0.8.Constant rotational speed with 160r/min is dynamically flooded 5h in shaking table;
(3) carrier that step (2) is obtained under 80 ℃ of temperature dry 3h to its surperficial moisture is evaporated fully, roasting 6h in air atmosphere, 300 ℃ Muffle furnace then, last washing and drying obtains Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
Above-mentioned gained catalyst is used for composite three-dimensional electric field catalysis wet oxidation degradation of phenol waste water, and concrete outcome sees Table 1.
Embodiment 3
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly.At last with peace and quiet carrier dry 12h under 110 ℃ of temperature;
(2) it is the SnCl of 0.285mol/L that the carrier 50g that step (1) is obtained at first impregnated in by molar concentration
4, molar concentration is the SbCl of 4.38mmol/L
3, molar concentration is HCl and the C of 0.5mol/L
2H
5In the colloidal sol that OH forms, amount to 200ml, wherein SnCl
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: 1: 1: 1.With the constant rotational speed of 150r/min dynamic dipping 4h in shaking table, soaked carrier is dry 2h under 90 ℃ temperature, and the moisture of carrier surface is evaporated fully, then roasting 4h in air atmosphere, 550 ℃ Muffle furnace;
(3) be the Mn (NO of 0.57mol/L in the 150ml molar concentration with the carrier impregnation after step (2) processing
3)
2In the solution, with the constant rotational speed of 150r/min dynamic dipping 4h in shaking table, the dry 2h under 105 ℃ of temperature of the carrier behind the dipping evaporates fully to the moisture that makes carrier surface;
(4) the roasting 4h in air atmosphere, 550 ℃ Muffle furnace again of the carrier after step (3) is processed; Last washing and drying obtains Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
Above-mentioned gained catalyst is used for composite three-dimensional electric field catalysis wet oxidation degradation of phenol waste water, and concrete outcome sees Table 1.
Embodiment 4
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly.At last with peace and quiet carrier dry 12h under 110 ℃ of temperature;
(2) the carrier 50g that step (1) is obtained at first impregnated in the Mn (NO that the 200ml molar concentration is 0.57mol/L
3)
2In the solution, with the constant rotational speed of 150r/min dynamic dipping 4h in shaking table, the carrier behind the dipping is dry 2h under 105 ℃ of temperature, and the moisture of carrier surface is evaporated fully, then roasting 2～6h in air atmosphere, 550 ℃ Muffle furnace;
(3) carrier impregnation after step (2) is processed is in being the SnCl of 0.285mol/L by molar concentration
4, molar concentration is the SbCl of 4.38mmol/L
3, molar concentration is HCl and the C of 0.5mol/L
2H
5In the colloidal sol that OH forms, amount to 200ml, wherein SnCl
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: 1: 1: 1.Constant rotational speed with 150r/min is dynamically flooded 4h in shaking table;
(4) with the carrier dry 2h in 90 ℃ baking oven after step (3) processing, the moisture of carrier surface is evaporated fully.Roasting 4h in air atmosphere, 550 ℃ Muffle furnace washs at last, dries then, obtains Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
Above-mentioned gained catalyst is used for composite three-dimensional electric field catalysis wet oxidation degradation of phenol waste water, and concrete outcome sees Table 1.
In fixed bed and the integrated continous way CWO of composite three-dimensional electric field integrated reactor, adopt embodiment 1-embodiment 4 gained catalyst, high concentration hard-degraded organic waste water is experimentized.With phenol is the target organic matter, and initial concentration is 2500mg/L, and temperature is 130 ℃, and partial pressure of oxygen is 1.0MPa, and oxygen flow is 250mL/min, and electric current is 0.5A (when obstructed electric current, thinking independent catalysis wet-type oxidation technology), electrolyte (Na
2SO
4Solution) concentration is 0.05mol/L, and reaction is that the reaction condition of 27min is an example when empty, describes.
Table 1 composite three-dimensional electric field catalysis wet oxidation technique treatment effect
| Composite three-dimensional electric field catalysis wet oxidation technique | ||
| Phenol clearance % | TOC clearance % | |
| Embodiment 1 | 88.2 | 83.4 |
| Embodiment 2 | 86.6 | 81.2 |
| Embodiment 3 | 91.8 | 85.1 |
| Embodiment 4 | 94 | 88.4 |
As can be seen from Table 1, the catalyst that the present invention developed degraded of Pyrogentisinic Acid in composite three-dimensional electric field catalysis wet oxidation technique has goodish effect, and under the short time of staying (27min) and relatively mild reaction condition (T=130 ℃, PO
2=1.0MPa), can make the organic clearance of target reach 94.0%, the TOC clearance also reaches 88.4%.The speed of oxidation reaction is improved, and has reduced the temperature and pressure condition of reacting required, make the material of equipment require to reduce, significantly reduced the cost of operation.
Claims (2)
1. one kind is used for composite three-dimensional electric field catalysis wet oxidation technique Preparation of catalysts method, and described catalyst is with γ-Al
2O
3Be carrier, Mn metal oxide, Sn metal oxide are that main active component, Sb oxide are auxiliary agent; Calculate by mass percentage, the Mn metal oxide accounts for 65wt%～67wt%, and the Sn metal oxide accounts for 32wt%～34wt%, and the Sb oxide accounts for 0.5wt%～1wt%; It is characterized in that its preparation method concrete steps are as follows:
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12～14h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly, and the carrier after gained is cleaned is dry 10～12h under 100～110 ℃ of temperature, and the carrier after the oven dry saves backup;
(2) it is the SnCl of 0.28～0.29mol/L that the carrier that step (1) is obtained at first impregnated in by molar concentration
4, molar concentration is the SbCl of 4.37～4.38mmol/L
3, molar concentration is HCl and the C of 0.3～0.4mol/L
2H
5In the colloidal sol that OH forms, in shaking table, dynamically flood 3～5h, wherein SnCl with the constant rotational speed of 140～160r/min
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: (0.8～1.2): (0.8～1.2): (0.8～1.2); Carrier behind the dipping is dry 1～3h under 80～90 ℃ temperature, and the moisture of carrier surface is evaporated fully, then roasting 2～6h in air atmosphere, 300～600 ℃ Muffle furnace;
(3) be the Mn (NO of 0.5～0.6mol/L in molar concentration with the carrier impregnation after step (2) processing
3)
2In the solution, the constant rotational speed with 140～160r/min in shaking table is dynamically flooded 3～5h, and the carrier behind the dipping is dry 1～3h under 100～105 ℃ temperature, and the moisture of carrier surface is evaporated fully;
(4) the roasting 2～6h in air atmosphere, 300～600 ℃ Muffle furnace again of the carrier after step (3) is processed, washing, oven dry obtain Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
2. one kind is used for composite three-dimensional electric field catalysis wet oxidation technique Preparation of catalysts method, and described catalyst is with γ-Al
2O
3Be carrier, Mn metal oxide, Sn metal oxide are that main active component, Sb oxide are auxiliary agent; Calculate by mass percentage, the Mn metal oxide accounts for 65wt%～67wt%, and the Sn metal oxide accounts for 32wt%～34wt%, and the Sb oxide accounts for 0.5wt%～1wt%; It is characterized in that its preparation method concrete steps are as follows:
(1) with fresh γ-Al
2O
3Carrier also stirs frequently with distilled water immersion 12～14h, the impurity of Dissociative adsorption on carrier, and flushing is to making supernatant limpid repeatedly, and the carrier after gained is cleaned places dry 10～12h under 100～110 ℃ of temperature, and the carrier after the oven dry saves backup;
(2) carrier that step (1) is obtained at first impregnated in the Mn (NO that molar concentration is 0.5～0.6mol/L
3)
2In the solution, constant rotational speed with 140～160r/min in shaking table is dynamically flooded 3～5h, carrier behind the dipping is dry 1～3h under 100～105 ℃ of temperature, and the moisture of carrier surface is evaporated fully, then roasting 2～6h in air atmosphere, 300～600 ℃ Muffle furnace;
(3) carrier impregnation after step (2) is processed is in being the SnCl of 0.28～0.29mol/L by molar concentration
4, molar concentration is the SbCl of 4.37～4.38mmol/L
3, molar concentration is HCl and the C of 0.3～0.4mol/L
2H
5In the colloidal sol that OH forms, in shaking table, dynamically flood 3～5h, wherein SnCl with the constant rotational speed of 140～160r/min
4, SbCl
3, HCl and C
2H
5The OH volume ratio is 1: (0.8～1.2): (0.8～1.2): (0.8～1.2);
(4) with the dry 1～3h under 80～90 ℃ of temperature of the carrier after step (3) processing, the moisture of carrier surface is evaporated fully; Roasting 2～6h in air atmosphere, 300～900 ℃ Muffle furnace then, washing, oven dry obtain Mn-Sn-Sb/ γ-Al
2O
3Catalyst.
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| CN103241807B (en) * | 2013-05-15 | 2014-12-10 | 常州工学院 | Composite particle electrode for bipolar three-dimensional electrode reactor and preparation method of electrode |
| CN103553188B (en) * | 2013-10-30 | 2014-12-10 | 北京师范大学 | Electrocatalytic particle electrode material for treating high-concentration organic wastewater and preparation process thereof |
| CN105110426A (en) * | 2015-09-24 | 2015-12-02 | 南通科技职业学院 | Preparation method of novel filling particle electrode material for treating organic wastewater |
| CN105753503A (en) * | 2016-01-14 | 2016-07-13 | 济南大学 | Electrocatalysis particle electrode for efficiently degrading bisphenol A in wastewater and preparation method of electrocatalysis particle electrode |
| CN107188277A (en) * | 2017-06-27 | 2017-09-22 | 东莞理工学院 | A kind of three-dimensional electrocatalysis oxidation reaction device of multipole and application |
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