CN103551204A - Multi-stage hierarchical pore structural Fenton-like catalyst and application thereof - Google Patents
Multi-stage hierarchical pore structural Fenton-like catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a multi-stage hierarchical pore structural Fenton-like catalyst and application thereof. The multi-stage hierarchical pore structural Fenton-like catalyst is prepared with sludge as a precursor and can be matched with a hydrogen peroxide aqueous solution to purify organic waste gas. The multi-stage hierarchical pore structural Fenton-like catalyst can be matched with the hydrogen peroxide aqueous solution to treat industrial organic waste gas and effluvial waste gas; the multi-stage hierarchical pore structural catalyst is prepared by using the sludge, thereby realizing the purpose of recycling wastes; less investment brings high environmental benefit; the economic practicality is realized. The multi-stage hierarchical pore structural Fenton-like catalyst belongs to the novel process having a good application prospect on removing the organic waste gas by the wet oxidation process.
Description
Technical field
The invention belongs to environmental improvement field, be specifically related to a kind of Fenton-like catalyst and application thereof of multilevel hierarchy pore structure.
Background technology
Atmosphere pollution is one of at present the most outstanding environmental problem.Extensive use along with organic chemicals, the organic pollution entering in atmosphere increases day by day, mainly low boiling, volatile organic matter (Volatile Organic Compounds, VOCs), as benzene,toluene,xylene, naphthalene, styrene, acetone, n-hexane, methane, propane and some sulphur hydrocarbon, nitrogen hydrocarbon, chlorocarbon etc.Organic exhaust gas is mainly derived from the waste gas discharging in petroleum and chemical industry industry production process, the storage facility of petroleum and chemical industry factory and petroleum chemicals, printing and other industries relevant with petroleum and chemical industry, the occasion and the combustion apparatus that use oil, petrochemicals, the various vehicles that the oil product of take is fuel are all the sources of organic exhaust gas.Organic exhaust gas feature is that quantity is larger, and content of organics fluctuation is large, flammable, have certain toxicity, and what have goes back foul smelling, and environment is had to huge destruction.Some VOCs even has strong carcinogenicity and genotoxicity, brings serious threat to the mankind's life and health.Therefore deal carefully with volatile organic waste gas and become one of focal issue of people's research.
The improvement method of organic exhaust gas mainly contains two classes: a class is absorption method, is mainly for high concentration (> 5000 mg/m
3) or more expensive organic gas.Absorption method is by physical method, under uniform temperature, pressure, by methods such as selective absorbent and permoselective membranes, carrys out separation of VOCs (VOCs), mainly comprises absorption method, pressure-variable adsorption, condensation method and embrane method etc.For intermediate concentration or low concentration (< 1000 mg/m
3) organic exhaust gas adopt another kind of null method.Null method is by chemistry or biological respinse, uses up, heat, catalyst and microbial cleaning method etc. is converted into water and carbon dioxide by organic matter, mainly comprises thermal oxide, catalytic combustion, biological oxidation, plasma decomposes method etc.
The treatment technology of above-mentioned organic exhaust gas respectively has pluses and minuses, for example: it is high that absorption method has removal efficiency, purify thoroughly, energy consumption is low, technical maturity, is easy to the advantage promoted, has good environment and economy benefit, but due to its treatment facility finite capacity, the adsorbent problem such as need to regenerate is restricted application; Thermal oxidation method is specially adapted to low-concentration organic exhaust gas, but owing to often occurring being easy to cause catalyst poisoning by impurity in organic exhaust gas; The major advantage of microbial cleaning method is that flow process and equipment are simpler, but the method exists, reaction unit floor space is large, longer shortcoming of reaction time.
Wet absorption method is as controlling one of important means of atmosphere pollution in environmental project, the absorption cleaning that is not only widely used in inorganic pollution, as wet desulfurizing process be at present in the world application at most, the most ripe desulfur technology, and also can use specific solvent for some organic pollutions, or water absorption is processed.The process that water absorbs VOCs is that pollutant is entered the process of liquid phase by gas phase, and pollutant is not eliminated and is to be only transferred, and the result of processing like this organic exhaust gas is that water body has become the body of marrying again polluting.Therefore being necessary to be degraded or transformed Organic Waste Gas Pollution thing by oxidation technology is nontoxic product, by oxidation technology, can make on the one hand the liquid phase medium after processing recycle, and with saving water resource, reduces pollution control cost.On the other hand, to water-soluble lower organic exhaust gas, by active specy for example hydroxyl radical free radical be oxidized and can change inorganic ions into, thereby reach the object of removing organic exhaust gas.
In numerous high-level oxidation technology (AOPs), Fenton catalytic oxidation can make most of organic matters comprise the advantages such as the oxidation operation of the large and difficult for biological degradation of toxicity and mineralising under gentle condition, has become one of water technology receiving much concern both at home and abroad.The technique of the method has easy to control, easily sets up the advantages such as seal circulation and non-secondary pollution.Yet traditional homogeneous phase Fenton oxidizing process exists insoluble problem: the one, and reaction system requires lower pH value (general 2～3 left and right), and pH is greater than 4-5 can reduce reaction efficiency because of ferric hydroxide precipitate above.The problem existing for overcoming above-mentioned Fenton reaction, over nearly 10 years, people's heterogeneous Fenton-like catalytic oxidation technology (class Fenton catalytic oxidation technology) that begins one's study.At present research more heterogeneous Fenton-like catalyst mainly contain support type magnetic iron ore (Fe
3o
4), bloodstone (α-Fe
2o
3), goethite (alpha-feooh), BiFeO
3deng.Utilize these heterogeneous Fenton-like catalyst treatment organic matters without strict pH value restriction, the loss that has improved greatly iron ion in traditional F enton oxidation reaction, reduces processing cost.But their catalytic activity can't be satisfactory.
Summary of the invention
Goal of the invention of the present invention overcomes deficiency of the prior art, and a kind of Fenton-like catalyst and application thereof of multilevel hierarchy pore structure are provided.
The present invention be take mud and is had multilevel hierarchy pore structure Fenton-like catalyst as presoma preparation, then the purification for organic exhaust gas in conjunction with aqueous hydrogen peroxide solution.Multilevel hierarchy pore structure Fenton-like catalyst of the present invention can be used for processing industrial organic exhaust gas and foul waste gas in conjunction with aqueous hydrogen peroxide solution, by utilizing mud, prepare the object that multilevel hierarchy pore structure catalyst has reached refuse reclamation, can produce with less input very large environmental benefit, having economic and practical, is a novel process very with the wet oxidation process removal organic exhaust gas of application prospect.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A Fenton-like catalyst for pore structure, by following steps, prepared:
S1. prepare precursor solution, described precursor solution is the mixed solution of frerrous chloride and mesopore/macropore pore creating material; Described mesopore/macropore pore creating material is ethylene glycol, hexadecanol or methyl alcohol; The concentration of described frerrous chloride and mesopore/macropore pore creating material is 0.1 ~ 1.0 mol/L;
S2. dewatered sludge is soaked in the precursor solution of step S1 preparation, regulator solution pH is 2.5 ~ 4.5, and 12 ~ 24h vibrates under 20 ~ 40 ℃ of conditions;
S3. the mixed liquor in step S2 is filtered, solid can obtain product through super-dry, calcining, washing, oven dry.
Preferably, in step S2, the solid-liquid weight ratio of dewatered sludge and precursor solution is 1:4-1:10.
Preferably, pore creating material described in step S1 is hexadecanol.
More preferably, in described precursor solution, the concentration of frerrous chloride is 0.25mol/L ~ 1.0mol/L.
Most preferably, in described precursor solution, the concentration of frerrous chloride is 0.5mol/L.
Preferably, in step S3, described dry temperature is 80-105 ℃, and the dry time is 6-12h.
Preferably, in step S3, the temperature of described calcining is 500 ~ 800 ℃, and the time of calcining is 2-6h.
Preferably, in step S3, the temperature of described oven dry is 80-115 ℃, and the time of oven dry is 6-12h.
The present invention is using sewage treatment plant's dewatered sludge as presoma, adopt hexadecanol, ethylene glycol or methyl alcohol as mesopore/macropore pore creating material simultaneously, frerrous chloride is mainly as micropore pore creating material, ferro element is loaded on mud to the multilevel hierarchy pore structure Fenton-like catalyst that is prepared as efficient stable and can repeatedly uses and regenerate by high-temperature calcination.The Fenton-like catalyst preparing has abundant multilevel hierarchy pore structure and larger specific area, by EDS, tests, and result shows that in catalyst, iron content is 3.37 ~ 12.77 wt.%.
Feature of the present invention is frerrous chloride and mesopore/macropore pore creating material to join together, prepare precursor solution, in preparing multilevel hierarchy pore structure Fenton-like catalyst process, mud is dispersed in precursor aqueous solution, and first mud generates the mud colloidal sol with certain space structure through hydrolysis; Then the mesopore/macropore pore creating material being coated in dry run in mud colloidal sol can be overflowed, thereby produces a large amount of mesopore/macropores in Sludge Surface; Finally, in high temperature carbonization processing procedure, the chlorion being adsorbed in Sludge Surface is oxidized, discharges pyrolysis gas and further in Sludge Surface, produces a large amount of micropores.Thereby by the synergy of frerrous chloride and mesopore/macropore pore creating material, form the catalyst of multilevel hierarchy pore structure.
The present invention preparation has in multilevel hierarchy pore structure Fenton-like catalyst process and adopts frerrous chloride to have following features: (1) frerrous chloride can be used as the presoma of preparing multilevel hierarchy pore structure Fenton-like catalyst; (2) frerrous chloride can be used as chemical activating agent and makes the more rich derived from sludge charcoal of microcellular structure.Frerrous chloride has suppressed the formation of carbon containing volatile matter and tar on the one hand, on the other hand, in preparing multilevel hierarchy pore structure Fenton-like catalyst process, chlorion in frerrous chloride is oxidized through high temperature carbonization technique, discharge pyrolysis gas, thereby produce more rich microcellular structure catalyst; (3) frerrous chloride chemical activation method is compared with zinc chloride chemical activation method to overcome the residual drawback that affects finished product purposes of metallic zinc.
The application of the Fenton-like catalyst of multilevel hierarchy pore structure of the present invention in removing organic exhaust gas.
The Fenton-like catalyst of multilevel hierarchy pore structure of the present invention is used for removing organic exhaust gas in conjunction with aqueous hydrogen peroxide solution, sulfate and carbonate that organic exhaust gas generates by heterogeneous Fenton-like reaction oxidation at multilevel hierarchy pore structure catalyst surface are discharged with waste liquid, thereby organic exhaust gas is purified.
Preferably, in described aqueous hydrogen peroxide solution, the concentration of hydrogen peroxide is 2.5 ~ 20 mmol/L.
The process that multilevel hierarchy pore structure catalyst prepared by the present invention is removed organic exhaust gas in conjunction with aqueous hydrogen peroxide solution is: organic exhaust gas enters into reactor from reactor bottom, the Fenton-like catalyst of multilevel hierarchy pore structure and aqueous hydrogen peroxide solution produce hydroxyl radical free radical, organic exhaust gas generates sulfate and carbonate at multilevel hierarchy pore structure catalyst surface and hydroxyl radical reaction, thereby improved the purification efficiency of organic exhaust gas, organic exhaust gas is purified.
By hydrogenperoxide steam generator, can also dissolve the product that remains in catalyst surface in good time, thereby guarantee the continual and steady use of catalyst.The mud of take has multilevel hierarchy pore structure catalyst and can efficiently remove fast organic exhaust gas as prepared by presoma, simultaneously by utilizing mud to prepare the object that multilevel hierarchy pore structure catalyst has reached refuse reclamation.
Preferably, multilevel hierarchy pore structure catalyst carries out at gas/solid/liquid tri-phase system in the reaction of removing organic exhaust gas.Gas/solid/liquid tri-phase system has increased the adsorbance of gas, is conducive to the carrying out of Fenton-like reaction.
Described organic exhaust gas comprises benzene,toluene,xylene, naphthalene, styrene, acetone, n-hexane, methane, propane, CH
3sH etc.
Compared with prior art, the invention solves the technical difficulty running in prior art, there is following beneficial effect:
(1) take the multilevel hierarchy pore structure Fenton-like catalyst that derived from sludge thing is carrier has higher adsorption capacity to gas molecule, thereby has increased the removal efficiency to organic exhaust gas.
(2) multilevel hierarchy pore structure Fenton-like catalyst of the present invention is conducive to organic exhaust gas in conjunction with aqueous hydrogen peroxide solution and generates sulfate and carbonate in Fenton-like catalyst surface reaction (heterogeneous Fenton-like reaction), thereby the purification efficiency that has improved organic exhaust gas is purified organic exhaust gas.
(3) multilevel hierarchy pore structure catalyst carries out at gas/solid/liquid tri-phase system in the reaction of removing organic exhaust gas, has increased the adsorbance of gas, has realized the transfer of gas between gas-liquid two-phase, thereby is conducive to the carrying out of Fenton reaction.
(4) by utilizing mud to prepare the object that multilevel hierarchy pore structure catalyst has reached refuse reclamation, realize the resource of mud, can reach the object of the treatment of wastes with processes of wastes against one another.
(5) multilevel hierarchy pore structure catalyst of the present invention has good stability, and can be a kind of environmental friendliness shaped material by reclaiming and regeneration is reused, multilevel hierarchy pore structure method for preparing catalyst of the present invention is simple simultaneously, cost is low, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the ESEM picture of multilevel hierarchy pore structure Fenton-like catalyst;
Fig. 2 is the graph of pore diameter distribution of multilevel hierarchy pore structure Fenton-like catalyst;
Fig. 3 is the adsorption-desorption thermoisopleth of multilevel hierarchy pore structure Fenton-like catalyst;
Fig. 4 is the reaction unit figure of catalytic wet oxidation gas pollutant;
Fig. 5 is the design sketch that multilevel hierarchy pore structure Fenton-like catalyst is removed toluene;
Fig. 6 is that the multilevel hierarchy pore structure Fenton-like catalyst of different iron load capacity is removed CH
3the design sketch of SH;
Fig. 7 is that variable concentrations hydrogenperoxide steam generator is removed CH to multilevel hierarchy pore structure Fenton-like catalyst
3sH design sketch;
Fig. 8 is that multilevel hierarchy pore structure Fenton-like catalyst-peroxisome ties up to condition of different pH removal CH
3the efficiency chart of SH gas;
Fig. 9 is the design sketch that multilevel hierarchy pore structure Fenton-like catalyst is removed dimethylbenzene;
Figure 10 is that reusable multilevel hierarchy pore structure Fenton-like catalyst is to CH
3the removal efficiency figure of SH gas.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, in embodiment, related reagent, method is the conventional reagent in this area and method.
the preparation of the Fenton-like catalyst of embodiment 1 multilevel hierarchy pore structure
Get the mud that 20 g are dried, be placed in respectively the 0.5 mol/L frerrous chloride-0.5 mol/L ethylene glycol of 200 ml, the 0.5 mol/L frerrous chloride-0.5 mol/L methyl alcohol of the 0.5 mol/L frerrous chloride-0.5 mol/L hexadecanol of 200 ml, 200 ml, the 0.5 mol/L frerrous chloride precursor solution of 200 ml, with sulfuric acid solution and sodium hydroxide solution, adjusting pH is 2.5, in water bath chader in 40 ℃ vibration 24 h, taking-up is filtered dry, in 105 ℃ of electric drying oven with forced convections 12 hours.Then be placed in N
2in the tube furnace of protection atmosphere, with the temperature programming to 800 ℃ of 20 ℃/min speed, calcine 2 h.Cooling rear taking-up is washed 3 times by deionized water, in 105 ℃ of drying boxes, dries and takes out, and the content of load iron is measured by EDS.
Because hexadecanol is insoluble in water, thereby in the present embodiment and subsequent embodiment, 0.5 mol/L frerrous chloride-0.5 mol/L hexadecanol solution is first hexadecanol to be added to the water to adopt 60 ℃ of heating water baths to be dissolved to a small amount of sediment of residue, by dripping a small amount of methyl alcohol to hexadecanol, dissolve completely again, finally add frerrous chloride stirring and dissolving to make.
Result shows: the BET area that the frerrous chloride-hexadecanol of take is prepared gained Fenton-like catalyst as precursor solution is maximum, adopt frerrous chloride-ethylene glycol, frerrous chloride-hexadecanol, frerrous chloride-Methanol to there is macropore, mesoporous and micropore for the heterogeneous Fenton-like catalyst of gained, frerrous chloride-the hexadecanol of wherein take is prepared the heterogeneous Fenton-like catalyst of gained as precursor solution and is contained abundant macropore, mesoporous and micropore (see figure 1), has multilevel hierarchy pore structure.
Fig. 2 is the graph of pore diameter distribution of multilevel hierarchy pore structure Fenton-like catalyst.As can be seen from the figure, adopt frerrous chloride-ethylene glycol, frerrous chloride-hexadecanol, frerrous chloride-methyl alcohol gained catalyst to there is micropore, mesoporous and macropore, and adopt frerrous chloride-hexadecanol to there is more and abundant micropore, mesoporous and macropore compared with frerrous chloride-ethylene glycol, the standby catalyst of frerrous chloride-Methanol.
Fig. 3 is the adsorption-desorption thermoisopleth of multilevel hierarchy pore structure Fenton-like catalyst.Adsorbance is from the order of size successively: the standby catalyst of catalyst > frerrous chloride-Methanol prepared by catalyst > frerrous chloride-ethylene glycol prepared by frerrous chloride-hexadecanol.Adopt the BET area of frerrous chloride-ethylene glycol, frerrous chloride-hexadecanol, frerrous chloride-methyl alcohol gained multilevel hierarchy pore structure Fenton-like catalyst to be respectively 198.8 m
2/ g, 268.7 m
2/ g, 170.2 m
2/ g.And the BET area that independent frerrous chloride is prepared the heterogeneous Fenton-like catalyst of gained is 138.5 m
2/ g.
the preparation of the multilevel hierarchy pore structure Fenton-like catalyst of the different iron load capacity of embodiment 2
Get the mud that 20 g are dried, be placed in the 0.5 mol/L frerrous chloride-0.5 mol/L hexadecanol precursor solution of 200 ml, wherein the concentration of frerrous chloride precursor solution is respectively 0.25 mol/L, 0.5 mol/L, 1.0 mol/L.With sulfuric acid solution and sodium hydroxide solution, adjusting pH is 2.5, and in water bath chader, in 40 ℃ of vibration 24 h, taking-up is filtered dry, in 105 ℃ of electric drying oven with forced convections 12 hours.Then be placed in N
2in the tube furnace of protection atmosphere, with the temperature programming to 800 ℃ of 20 ℃/min speed, calcine 2 h.Cooling rear taking-up is washed 3 times by deionized water, in 105 ℃ of drying boxes, dries and takes out, and the content of load iron is measured by EDS.The concentration of frerrous chloride precursor solution is that the iron content that 0.25 mol/L, 0.5 mol/L, 1 mol/L make catalyst is respectively 3.37 wt.%, 8.44 wt.%, 12.77 wt.%.
the application that embodiment 3 multilevel hierarchy pore structure Fenton-like catalyst are removed toluene
Catalytic wet oxidation toluene reaction unit adopts the core apparatus that the reactor of glass material is system, as shown in Figure 4.Embodiment 1 is adopted to prepared by different precursor solutions multilevel hierarchy pore structure Fenton-like catalyst 10 g be filled in reactor, the toluene gas of 80 ppm enters catalytic reactor from bottom, via core, disperses to enter in reactor; Get pH value and be in 3.0 10.0 mmol/L aqueous hydrogen peroxide solution 70 mL injecting reactors.Gu treat that gas/liquid/three-phase system reaches adsorption equilibrium, sustained response 10 min.The exit concentration of toluene detects by being furnished with the gas chromatograph of fid detector, determines the catalytic efficiency of reaction.
Result as shown in Figure 5, react after 10 min, the efficiency that adopts frerrous chloride-ethylene glycol, frerrous chloride-hexadecanol, frerrous chloride-methyl alcohol, frerrous chloride to prepare the heterogeneous Fenton-like catalyst removal of gained toluene gas is respectively 90%, 96%, 87%, 81%.Result shows: the multilevel hierarchy pore structure Fenton-like catalyst of being prepared by frerrous chloride-ethylene glycol, frerrous chloride-hexadecanol, frerrous chloride-methyl alcohol precursor aqueous solution, owing to having abundant macropore, mesoporous and microcellular structure for catalytic reaction provides passage, is more conducive to the carrying out of reaction.
The reaction mechanism that heterogeneous Fenton-like catalyst is removed toluene is summarized as follows:
(1) absorption
First gas molecule is adsorbed in the surface of catalyst and the hole of carrier.
(2) heterogeneous Fenton-like catalyst and H
2o
2effect generates hydroxyl radical free radical
oFe
III + H
2O
2 → oFe
II + OOH + H
+ (1)
oFe
II + H
2O
2 → oFe
III + OH + OH
- (2)
(3) free radical is oxidized organic exhaust gas
OH· + organics → products or intermediates (3)。
the multilevel hierarchy pore structure Fenton-like catalyst of the different iron load capacity of embodiment 4 is removed CH
3
sH gas
Catalytic wet oxidation CH
3sH reaction unit adopts the core apparatus that the reactor of glass material is system, as shown in Figure 4.Multilevel hierarchy pore structure Fenton-like catalyst 10 g of the different iron load capacity that embodiment 2 is made are filled in reactor, the CH of 60 ppm
3sH gas enters catalytic reactor from bottom, via core, disperses to enter in reactor; Get pH value and be in 3.0 10.0 mmol/L aqueous hydrogen peroxide solution 70 mL injecting reactors.Gu treat that gas/liquid/three-phase system reaches adsorption equilibrium, sustained response 10 min.Use CH
3sH detector (U.S. Detcon DM-200-CH
3sH) detect CH
3sH exit concentration, determines the catalytic efficiency of reaction, and collects the solution after wet oxidation reaction, and use ion chromatography.
Result as shown in Figure 6, is reacted after 10 min, and iron load capacity is that the heterogeneous Fenton-like catalyst of 3.37 wt.%, 8.44 wt.%, 12.77 wt.% is removed CH
3the efficiency of SH gas pollutant is respectively 87%, 93%, 96%.CH
3the removal efficiency of SH increases with the increase of iron load capacity, shows that the increase of iron load capacity is conducive to the generation of OH free radical, thereby has improved catalyst to CH
3the purification removal efficiency of SH.
Under variable concentrations hydrogenperoxide steam generator, multilevel hierarchy pore structure Fenton-like catalyst is removed CH
3the device of SH adopts the catalytic wet oxidation CH described in embodiment 3
3sH reaction unit.The iron load capacity that embodiment 2 is made is that multilevel hierarchy pore structure Fenton-like catalyst 10 g of 8.44 wt.% are filled in reactor, the CH of 60 ppm
3sH gas enters catalytic reactor from bottom, via core, disperses to enter in reactor; Getting respectively concentration is 5.0 mmol/L, 7.5 mmol/L, 10.0 mmol/L, 13.5 mmol/L, 15.0 mmol/L, in the aqueous hydrogen peroxide solution 70 mL injecting reactors that pH value is 3.0.Gu treat that gas/liquid/three-phase system reaches adsorption equilibrium, sustained response 10 min.Use CH
3sH detector (U.S. Detcon DM-200-CH
3sH) detect CH
3sH exit concentration, determines the catalytic efficiency of reaction, and collects the solution after wet oxidation reaction, and use ion chromatography.
Result as shown in Figure 7, is reacted after 10 min, and multilevel hierarchy pore structure Fenton-like catalyst, in variable concentrations hydrogenperoxide steam generator, is removed CH
3the efficiency of SH gas pollutant is respectively 80%, 88%, 93%, 86%, 85%, and result shows: heterogeneous Fenton-like catalyst is to remove CH in 10.0 mmol/L hydrogenperoxide steam generators in concentration
3the efficiency of SH is best, excessive H
2o
2can affect CH
3the removal efficiency of SH.
Multilevel hierarchy pore structure Fenton-like catalyst is removed CH under condition of different pH
3the device of SH adopts the catalytic wet oxidation CH described in embodiment 3
3sH reaction unit.The iron load capacity that embodiment 2 is made is that multilevel hierarchy pore structure Fenton-like catalyst 10 g of 8.44 wt.% are filled in reactor, the CH of 60 ppm
3sH gas enters catalytic reactor from bottom, via core, disperses to enter in reactor; Get respectively pH value and be in 2.0,3.0,4.0,5.0 10.0 mmol/L aqueous hydrogen peroxide solution 70 mL injecting reactors.Gu treat that gas/liquid/three-phase system reaches adsorption equilibrium, sustained response 10 min.Use CH
3sH detector (U.S. Detcon DM-200-CH
3sH) detect CH
3sH exit concentration, determines the catalytic efficiency of reaction, and collects the solution after wet oxidation reaction, and use ion chromatography.
Result as shown in Figure 8, is 2.0,3.0,4.0,5.0 in pH value, reacts after 10 min, and multilevel hierarchy pore structure Fenton-like catalyst is removed CH
3the efficiency of SH gas pollutant is respectively 70%, 93%, 86% and 50%.Result shows: heterogeneous Fenton-like catalyst is to CH
3the removal effect of SH is affected by the pH value of solution medium.
the application that embodiment 7 multilevel hierarchy pore structure Fenton-like catalyst are removed dimethylbenzene
Catalytic wet oxidation toluene reaction unit adopts the core apparatus that the reactor of glass material is system, as shown in Figure 4.Embodiment 1 is adopted to prepared by different precursor solutions multilevel hierarchy pore structure Fenton-like catalyst 10 g be filled in reactor, the dimethylbenzene gas of 80 ppm enters catalytic reactor from bottom, via core, disperses to enter in reactor; Get pH value and be in 3.0 10.0 mmol/L aqueous hydrogen peroxide solution 70 mL injecting reactors.Gu treat that gas/liquid/three-phase system reaches adsorption equilibrium, sustained response 10 min.The exit concentration of dimethylbenzene detects by being furnished with the gas chromatograph of fid detector, determines the catalytic efficiency of reaction.
Result as shown in Figure 9, is reacted after 15 min, and the efficiency that adopts frerrous chloride-ethylene glycol, frerrous chloride-hexadecanol, frerrous chloride-Methanol to remove dimethylbenzene gas for the heterogeneous Fenton-like catalyst of gained is respectively 90%, 96%, 87%.Result shows: the multilevel hierarchy pore structure Fenton-like catalyst of being prepared by frerrous chloride-ethylene glycol, frerrous chloride-hexadecanol, frerrous chloride-methyl alcohol precursor aqueous solution, owing to having abundant macropore, mesoporous and microcellular structure for catalytic reaction provides passage, is more conducive to the carrying out of reaction.
Multilevel hierarchy pore structure Fenton-like catalyst is being removed CH
3the experiment of reusing of SH gas adopts the reaction unit described in embodiment 3.The iron load capacity that embodiment 2 is made is that multilevel hierarchy pore structure Fenton-like catalyst 10 g of 8.44 wt.% are filled in reactor, the CH of 60 ppm
3sH gas enters catalytic reactor from bottom, via core, disperses to enter in reactor; Get pH value and be in 3.0 10.0 mmol/L aqueous hydrogen peroxide solution 70 mL injecting reactors.Gu treat that gas/liquid/three-phase system reaches adsorption equilibrium, sustained response 10 min.Reaction finishes the used Fenton-like catalyst of rear taking-up, uses deionized water rinsing 3 times, puts into 105 ℃ of oven dry of electric drying oven with forced convection.Then the Fenton-like catalyst of getting after regeneration is removed CH
3sH experiment.Repeat catalytic oxidation CH
3sH experiment-regenerative process amounts to five times.
Reusable Fenton-like catalyst is to CH
3the removal efficiency of SH gas is shown in Figure 10.As seen from Figure 10, the Fenton-like catalyst of preparation is through five Reusabilities, to CH
3sH removal efficiency is still maintained at about 90%, and this result shows kind to take that the Fenton-like catalyst of the multilevel hierarchy pore structure that mud is prepared as presoma has good stability.
Claims (10)
1. a Fenton-like catalyst for multilevel hierarchy pore structure, is characterized in that, the Fenton-like catalyst of described multilevel hierarchy pore structure is prepared by following steps:
S1. prepare precursor solution, described precursor solution is the mixed solution of frerrous chloride and mesopore/macropore pore creating material; Described mesopore/macropore pore creating material is ethylene glycol, hexadecanol or methyl alcohol; The concentration of described frerrous chloride and mesopore/macropore pore creating material is 0.1 ~ 1.0 mol/L;
S2. dewatered sludge is soaked in the precursor solution of step S1 preparation, regulator solution pH is 2.5 ~ 4.5, and 12 ~ 24h vibrates under 20 ~ 40 ℃ of conditions;
S3. the mixed liquor in step S2 is filtered, solid can obtain product through super-dry, calcining, washing, oven dry.
2. the Fenton-like catalyst of multilevel hierarchy pore structure according to claim 1, is characterized in that, in step S2, the solid-liquid weight ratio of dewatered sludge and precursor solution is 1:4-1:10.
3. the Fenton-like catalyst of multilevel hierarchy pore structure according to claim 1, is characterized in that, described pore creating material is hexadecanol.
4. the Fenton-like catalyst of multilevel hierarchy pore structure according to claim 1, is characterized in that, in described precursor solution, the concentration of frerrous chloride is 0.25mol/L ~ 1.0mol/L.
5. the Fenton-like catalyst of multilevel hierarchy pore structure according to claim 1, is characterized in that, in described precursor solution, the concentration of frerrous chloride is 0.5mol/L.
6. the Fenton-like catalyst of multilevel hierarchy pore structure according to claim 1, is characterized in that, in step S3, described dry temperature is 80-105 ℃, and the dry time is 6-12h; The temperature of described calcining is 500 ~ 800 ℃, and the time of calcining is 2-6h; The temperature of described oven dry is 80-115 ℃, and the time of oven dry is 6-12h.
7. the application of the Fenton-like catalyst of multilevel hierarchy pore structure in removing organic exhaust gas according to claim 1.
8. the application of the Fenton-like catalyst of multilevel hierarchy pore structure in removing organic exhaust gas according to claim 7, it is characterized in that, the Fenton-like catalyst of described multilevel hierarchy pore structure adds aqueous hydrogen peroxide solution in the process of removing organic exhaust gas.
9. the Fenton-like catalyst of multilevel hierarchy pore structure according to claim 8, is characterized in that, in described aqueous hydrogen peroxide solution, the concentration of hydrogen peroxide is 2.5 ~ 20 mmol/L.
10. the application in removing organic exhaust gas according to the Fenton-like catalyst of multilevel hierarchy pore structure described in any one in claim 7 to 9, it is characterized in that, described organic exhaust gas is benzene,toluene,xylene, naphthalene, styrene, acetone, n-hexane, methane, propane or CH
3sH.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN105621848A (en) * | 2016-01-14 | 2016-06-01 | 上海交通大学 | Argillaceous biomass refuse solar interlayer drying device and two-stage drying method |
| CN108325379A (en) * | 2018-01-30 | 2018-07-27 | 南京师范大学 | A kind of method and its dedicated unit using VOCs in magnetic iron-based spinel structure materials purification flue gas of refuse burning |
| CN110124671A (en) * | 2019-04-16 | 2019-08-16 | 中山大学 | A kind of Cu1-XCoXFe2O4Class fenton catalyst and its preparation method and application |
| CN114433015A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-adsorbability molecular sieve adsorbent and preparation method thereof |
| CN116037116A (en) * | 2023-01-20 | 2023-05-02 | 山东大学 | Fenton sludge magnetic iron-based catalyst and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105481221A (en) * | 2016-01-14 | 2016-04-13 | 上海交通大学 | Method for realizing anti-shrinkage recarburization sludge drying |
| CN105621848A (en) * | 2016-01-14 | 2016-06-01 | 上海交通大学 | Argillaceous biomass refuse solar interlayer drying device and two-stage drying method |
| CN105481221B (en) * | 2016-01-14 | 2017-11-03 | 上海交通大学 | A kind of sludge drying anti-shrink carburetion method |
| CN105621848B (en) * | 2016-01-14 | 2018-08-14 | 上海交通大学 | Shale biomass garbage solar sandwich desiccation apparatus and two-period form drying method |
| CN108325379A (en) * | 2018-01-30 | 2018-07-27 | 南京师范大学 | A kind of method and its dedicated unit using VOCs in magnetic iron-based spinel structure materials purification flue gas of refuse burning |
| CN110124671A (en) * | 2019-04-16 | 2019-08-16 | 中山大学 | A kind of Cu1-XCoXFe2O4Class fenton catalyst and its preparation method and application |
| CN114433015A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-adsorbability molecular sieve adsorbent and preparation method thereof |
| CN114433015B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | High-adsorptivity molecular sieve adsorbent and preparation method thereof |
| CN116037116A (en) * | 2023-01-20 | 2023-05-02 | 山东大学 | Fenton sludge magnetic iron-based catalyst and preparation method and application thereof |
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