CN107519900B - A kind of fenton catalyst and its preparation method and application - Google Patents

A kind of fenton catalyst and its preparation method and application Download PDF

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CN107519900B
CN107519900B CN201710683701.3A CN201710683701A CN107519900B CN 107519900 B CN107519900 B CN 107519900B CN 201710683701 A CN201710683701 A CN 201710683701A CN 107519900 B CN107519900 B CN 107519900B
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crucible
catalyst
powder
presoma
fenton catalyst
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CN107519900A (en
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孙猛
李多
贾荣利
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Kunshan Zhonghuan Keben Technology Development Co.,Ltd.
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Beijing Environmental Protection Technology Co Ltd Corrado
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

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  • Organic Chemistry (AREA)
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  • Hydrology & Water Resources (AREA)
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Abstract

The invention discloses a kind of preparation methods of fenton catalyst, and this method comprises the following steps, and a is by presoma FeCl3·6H2O grind into powder；B is by presoma FeCl3·6H2O powder, which is placed in crucible, to be sealed；Sealing in the step b is placed in baking oven equipped with the crucible of presoma chlorination iron powder and calcines by c；Calcined crucible in the step c is naturally cooled to room temperature by d, and crucible bottom is sintered to the solid to be formed and takes out simultaneously grind into powder, is cleaned, drying.The preparation method reaction time of fenton catalyst of the invention is short, and mild condition, raw material is few, is easy to large-scale industrial production, and catalyst obtained is in Fenton's reaction, to pH value strong applicability, still has efficient catalytic activity under conditions of neutral ph.

Description

A kind of fenton catalyst and its preparation method and application
Technical field
The present invention relates to a kind of preparation method of catalyst, more particularly to a kind of preparation method of fenton catalyst, with And the application of the fenton catalyst is further further related to using fenton catalyst made from this method.
Background technique
Fenton's reaction refers to that with hydrogen peroxide homogeneous catalytic reaction can occur for ferrous ion in acid condition, generates strong The hydroxyl radical free radical of oxidisability.Reaction product hydroxyl radical free radical can further resolve into organic pollutants direct oxidation CO2And water, therefore the reaction is commonly used for the processing and disposition of organic pollution aquifer.In general, homogeneous Fenton's reaction rate Mainly influenced by following factor: 1) pH value of solution condition, i.e. ferrous ion react speed with maximum in pH=3 with hydrogen peroxide Rate, but reaction is hardly happened under pH neutrallty condition；2) the oxidation product ferric ion of ferrous ion and hydrogen peroxide Reaction rate is very low, not only slows down the circulation of iron substance, and the floccule body that will form iron is precipitated from solution, easily causes iron Secondary pollution problem.
In recent years, the development of the heterogeneous fenton catalyst of alternative ferrous ion receives more and more attention.It is such Catalyst have with catalytic effect similar in ferrous ion, can efficient catalytic hydrogen peroxide generate hydroxyl radical free radical.Such as apply Number Chinese invention patent for being CN201610843498.7 and CN201610845646.9, the two utilizes heterogeneous catalysis Special physico-chemical property or structure feature, regulation participate in the release of the iron ion of catalysis reaction, promote recycling for iron, realization is urged The high efficiente callback of agent reduces the secondary pollution of unnecessary iron, improves hydrogen peroxide utilization rate.Meanwhile heterogeneous Fenton is urged The reaction condition of change is based on catalyst surface structure, does not relate to compared to milder for the catalysis reaction of more homogeneous Fenton, catalytic process And release and the losing issue of ion, therefore there is wider pH applicability, great application prospect.
But although the heterogeneous fenton catalyst of foregoing invention expands the pH of Fenton catalysis reaction to a certain extent Applicability, but catalytic efficiency in neutral conditions still has larger gap in acid condition with it.Therefore, overcome heterogeneous urge Catalytic performance is weak under agent neutrallty condition, and research and development can generate the non-of hydroxyl radical free radical by efficient catalytic hydrogen peroxide in neutral conditions Homogeneous fenton catalyst has highly important application prospect and value.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of under conditions of neutral ph with the chlorine oxygen of high-efficiency catalytic activity The preparation method of iron heterogeneous catalysis, this method reaction time is short, and mild condition, raw material is few, is easy to large-scale industrial production.
In order to solve the above technical problems, this method includes such as the present invention provides a kind of preparation method of fenton catalyst Lower step,
A is by presoma FeCl3·6H2O grind into powder；
B is by presoma FeCl3·6H2O powder, which is placed in crucible, to be sealed；
Sealing in the step b is placed in baking oven equipped with the crucible of presoma chlorination iron powder and calcines by c；
Calcined crucible in the step c is naturally cooled to room temperature by d, and crucible bottom is sintered to the solid to be formed and is taken out And grind into powder, it cleans, drying.
The preparation method of above-mentioned fenton catalyst, wherein in the step b, presoma FeCl3·6H2O powder and crucible Volume ratio be 0.1-0.2.
The preparation method of above-mentioned fenton catalyst, wherein in the step c, the sealing is equipped with presoma chlorination iron powder The calcination temperature of the crucible at end in an oven is 140-220 DEG C.
The preparation method of above-mentioned fenton catalyst, wherein in the step c, the sealing is equipped with presoma chlorination iron powder The heating rate of the crucible at end in an oven is 1-10 DEG C/min.
The preparation method of above-mentioned fenton catalyst, wherein in the step c, the sealing is equipped with presoma chlorination iron powder The calcination time of the crucible at end in an oven is 0.5-2 hours, preferably 1 hour.
The preparation method of above-mentioned fenton catalyst, wherein in the step d, using acetone eccentric cleaning.
The present invention also provides a kind of fenton catalysts of above method preparation.
Present aspect additionally provides above-mentioned fenton catalyst in the application of processing organic pollutants.
Above-mentioned fenton catalyst processing organic pollutants application, wherein the organic pollutant be bisphenol-A, Estrogen, cimetidine bisfentidine, ampicillin antibiotic, parachlorophenol insecticide or 2,4,6- trichloro-benzenes Phenol bacteriostatic agent.
The preparation method of fenton catalyst of the invention has the following beneficial effects:
1, the raw material that fenton catalyst preparation method of the invention uses is simple, contains 6 just with single presoma The iron chloride of a crystallization water prepares chlorine oxygen iron oxide red brown powder solid catalyst by one step of temperature-programmed mode, and presoma exists The chlorine itself evaporated during heating can react immediately with vapor generates hydrogen chloride gas and hypochlorous acid, with association shape At iron oxide effect, chlorine atom is doped in oxide structure, and then form the coordination knot of new iron, chlorine and oxygen Structure forms new chlorine oxygen iron compound；
2, the molecular structure of catalyst chlorine oxygen iron compound made from the preparation method of fenton catalyst of the invention is presented Lamellar structure, interlayer are interacted by the Van der Waals force formed between chlorine atom and are connected, and iron, oxygen, chlorine atom content ratio are approximately 1:1:1, the laminated structure of radial growth around is presented centered on the nuclei of crystallization in micro-scaled structures under scanning electron microscope, single About 1 to 200 μm of leaf length, thickness about 10 to 200nm, surface is smooth, sharpness of border；
3, the preparation method of fenton catalyst of the invention, catalyst obtained is in Fenton's reaction, to pH value applicability By force, still there is efficient catalytic activity under conditions of neutral ph, water pollutant can be effectively removed in a short time, gone Except rate height.
4, the preparation method of fenton catalyst of the invention, the reaction time is short, and mild condition, raw material is few, is easy to extensive Industrial production.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture for the chlorine oxygen iron catalyst that embodiment 1 synthesizes；
Fig. 2 is the scanning electron microscopic picture for the chlorine oxygen iron catalyst that embodiment 2 synthesizes；
Fig. 3 is that the Elemental Composition for the chlorine oxygen iron catalyst that embodiment 2 synthesizes analyses map；
Fig. 4 is the scanning electron microscopic picture for the chlorine oxygen iron catalyst that embodiment 3 synthesizes；
Fig. 5 is the X ray diffracting spectrum for the chlorine oxygen iron catalyst that embodiment 3 synthesizes；
Fig. 6 is the x-ray photoelectron spectroscopy figure for the chlorine oxygen iron catalyst that embodiment 3 synthesizes；
Fig. 7 is the X ray diffracting spectrum of the chlorine oxygen iron catalyst synthesized under different calcination temperatures.
Fig. 8 is removal effect figure of the chlorine oxygen iron catalyst to different organic pollutants of the synthesis of embodiment 2.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1
By presoma FeCl3·6H2O grind into powder is saved after dry, is then placed in precursor powder close in crucible The volume ratio of envelope, precursor powder and crucible is about 0.2, and sealing is placed in baking oven equipped with the crucible of iron chloride powder precursor In, 140 DEG C are warming up to the heating rate of 1 DEG C/min, and keep 2h, after being cooled to room temperature, the crucible of sealing are taken out, the bottom of by Portion is sintered the deep brownish red solid to be formed and takes out and grind into powder, and with drying after acetone eccentric cleaning 3 times, kept dry. The scanning electron microscopic picture of the chlorine oxygen iron catalyst of the present embodiment synthesis is shown in Fig. 1.
Embodiment 2
By presoma FeCl3·6H2O grind into powder is saved after dry, is then placed in precursor powder close in crucible The volume ratio of envelope, precursor powder and crucible is about 0.14, and sealing is placed in baking oven equipped with the crucible of iron chloride powder precursor In, 200 DEG C are warming up to the heating rate of 5 DEG C/min, and keep 1h, after being cooled to room temperature, the crucible of sealing are taken out, the bottom of by Portion is sintered the deep brownish red solid to be formed and takes out and grind into powder, and with drying after acetone eccentric cleaning 3 times, kept dry. The scanning electron microscopic picture of the chlorine oxygen iron catalyst of the present embodiment synthesis is shown in that Fig. 2, Elemental Composition analysis map are shown in Fig. 3.Utilize scanning Matched X-ray energy spectrometer directly carries out the Elemental redistribution that selected areas is analyzed under scanning electron microscope qualitative fixed in Electronic Speculum Amount analysis, test condition are X-ray energy 10kV, test thickness 1um, the great Qu EDAX results and member of the FeOCl in Fig. 2 Cellulose content is shown in Table 1.
Table 1
Element Atomic orbital Intensity (c/s) Atom content (%) Mass fraction (wt.%)
O Ka 59.05 31.535 14.40
Cl Ka 303.83 35.273 33.27
Fe La 61.06 33.192 53.33
100.000 100.00
By table 1 it is found that iron, oxygen, chlorine atom content ratio in the FeOCl catalyst that the present invention synthesizes are approximately 1:1:1.
The chlorine oxygen iron catalyst that the present embodiment synthesizes is subjected to Fenton's reaction, the hydroxyl free of generation under condition of different pH Base concentration is shown in Table 2.
Table 2
As table 2 it is found that FeOCl catalyst made from the present embodiment is in the case where pH value is 3 reaction condition, the hydroxyl of generation Number of free radical highest has reached 39.23727 μM, when reaction is in neutrallty condition namely pH value is 7, although the hydroxyl generated Base number of free radical is significantly lower than hydroxy free radical concentration when pH is 3, but still generates considerable hydroxyl radical free radical. Isopropanol is the exclusive capturing agent of hydroxyl radical free radical in this test, and hydroxy free radical concentration is equal after exclusive capturing agent isopropanol is added Be down to 0.1 μM hereinafter, illustrate generate free radical be hydroxyl radical free radical, captured by isopropanol.
Embodiment 3
By presoma FeCl3·6H2O grind into powder is saved after dry, is then placed in precursor powder close in crucible The volume ratio of envelope, precursor powder and crucible is about 0.1, and sealing is placed in baking oven equipped with the crucible of iron chloride powder precursor In, 220 DEG C are warming up to the heating rate of 10 DEG C/min, and keep 0.5h, after being cooled to room temperature, take out the crucible of sealing, The deep brownish red solid that bottom frit is formed takes out and grind into powder, and with drying after acetone eccentric cleaning 3 times, dry to protect It deposits.The scanning electron microscopic picture of the chlorine oxygen iron catalyst of the present embodiment synthesis is shown in that Fig. 4, X ray diffracting spectrum are shown in Fig. 5, X-ray photoelectricity Sub- energy spectrum diagram is shown in Fig. 6.
Comparative example 1
Chlorine oxygen iron catalyst heterogeneous ferrum-based catalyst similar with equivalent that embodiment 2 synthesizes and homogeneous ferrous ion are existed The concentration for the hydroxyl radical free radical that catalytic phase is generated with concentration of hydrogen peroxide under condition of different pH compares, in this comparative example in addition to Outside the chlorine oxygen iron catalyst that embodiment 2 synthesizes, other can be bought with market for the catalyst of comparison and be obtained.Not by 0.2g/L With catalyst respectively with 15mM H2O2Hydroxy free radical concentration is tested in reaction after five minutes, and comparing result is shown in Table 3.
Table 3
pH FeOCl(μM) Fe2O3(μM) Fe3O4(μM) FeOOH(μM) Fe2+(μM)
3 39.23727 <0.1 <0.1 <0.1 10.4061
4 31.97691 <0.1 <0.1 <0.1 9.631
5 26.59246 <0.1 <0.1 <0.1 9.42074
6 17.17996 <0.1 <0.1 <0.1 5.15358
7 10.96681 <0.1 <0.1 <0.1 3.71882
8 9.18986 <0.1 <0.1 <0.1 1.48423
Through table 3 it is found that under same catalyst amount, FeOCl catalyst made from embodiment 2 is anti-in progress Fenton At once, the hydroxy free radical concentration of generation is apparently higher than other ferrum-based catalysts, and is higher than homogeneous ferrous ion and is catalyzed peroxide Change the hydroxy free radical concentration that hydrogen generates.Under conditions of pH value is 3, FeOCl catalyst carries out the hydroxyl of Fenton's reaction generation The concentration of free radical is 39.23727 μM, and the concentration for the hydroxyl radical free radical that homogeneous ferrous ion carries out Fenton's reaction generation is 10.4061 μM, when pH value is 7, i.e., under neutrallty condition, FeOCl catalyst carries out the hydroxyl radical free radical of Fenton's reaction generation Concentration is 10.96681 μM, and the concentration that homogeneous ferrous ion carries out the hydroxyl radical free radical of Fenton's reaction generation is 3.71882 μM, FeOCl catalyst generates hydroxy free radical concentration and is apparently higher than homogeneous ferrous ion progress Fenton under same pH value condition React the hydroxy free radical concentration generated.Moreover, FeOCl catalyst carries out the hydroxyl of Fenton's reaction generation certainly in neutral conditions The hydroxyl radical free radical that Fenton's reaction generation is carried out when i.e. pH is 3 in acid condition with homogeneous ferrous ion substantially by base concentration is dense Degree is suitable.As it can be seen that FeOCl catalyst made from preparation method of the invention has very high catalytic activity, to pH value applicability By force, the hydroxy free radical concentration of the catalytic activity with higher in neutral conditions, generation exists with homogeneous ferrous ion The hydroxy free radical concentration that pH value generates when being 3 is on close level.
Comparative example 2
The preparation method of catalyst is identical with embodiment 2, the difference is that calcination temperature is different, under different calcination temperatures The X ray diffracting spectrum of the catalyst of synthesis is shown in Fig. 7.
As shown in fig. 7, calcination temperature available FeOCl catalyst between 140 DEG C to 220 DEG C, each corresponding peak position It is corresponding with the diffraction maximum of FeOCl standard crystal (FeOCl PDF), illustrate that it has and the consistent crystal structure of standard crystal. But calcination temperature, in 130 DEG C and 230 DEG C, the diffraction maximum of product cannot be corresponding with the diffraction maximum of standard FeOCl crystal, have compared with More miscellaneous peaks appear between 10 ° to 40 °, illustrate that calcination temperature significantly affects the generation of FeOCl, therefore, the present invention preferably forges Burning temperature is 140-220 DEG C.
The application of the removal organic pollutants of embodiment 4
The application test of organic pollutants is removed to the catalyst that embodiment 2 synthesizes, respectively to having in water Machine pollutant bisphenol-A, Estrogen, cimetidine bisfentidine, ampicillin antibiotic, parachlorophenol insecticide With 2,4,6- trichlorophenol, 2,4,6,-T bacteriostatic agents are handled, and the initial concentration of all contaminants is 1mM, and 0.2g/L embodiment 2 is added The FeOCl catalyst and 15mM H of synthesis2O2, reacted five minutes under the conditions of pH value is 6.97, the processing of different organic matters imitated Fruit sees Fig. 8.
As shown in Figure 8, the FeOCl catalyst that the present invention synthesizes removes organic pollutants in neutral conditions to be had Very high catalytic activity, after reaction five minutes, organic pollutant bisphenol-A, Estrogen, cimetidine bisfentidine Reach 100% with the removal rate of ampicillin antibiotic, parachlorophenol insecticide and 2,4,6- trichlorophenol, 2,4,6,-T bacteriostatic agents Removal rate reached 60%.As it can be seen that the fenton catalyst pH that preparation method of the invention synthesizes is adaptable, in neutrallty condition Under it is still highly active, can effectively remove organic pollutants in a short time.

Claims (7)

1. a kind of fenton catalyst is in the application of processing organic pollutants, the organic pollutant of fenton catalyst processing Estrogen, cimetidine bisfentidine and ampicillin antibiotic, the preparation method packet of the fenton catalyst Include following steps,
A is by presoma FeCl3·6H2O grind into powder；
B is by presoma FeCl3·6H2O powder, which is placed in crucible, to be sealed；
Sealing in the step b is placed in baking oven equipped with the crucible of presoma chlorination iron powder and calcines by c；
Calcined crucible in the step c is naturally cooled to room temperature by d, and crucible bottom is sintered to the solid to be formed and takes out and grinds It clays into power, cleans, drying.
2. fenton catalyst as described in claim 1 is in the application of processing organic pollutants, wherein in the step b, Presoma FeCl3·6H2The volume ratio of O powder and crucible is 0.1-0.2.
3. fenton catalyst as claimed in claim 1 or 2 is in the application of processing organic pollutants, wherein the step c In, the calcination temperature of the crucible of the sealing equipped with presoma chlorination iron powder in an oven is 140-220 DEG C.
4. fenton catalyst as claimed in claim 3 is in the application of processing organic pollutants, wherein in the step c, The heating rate of the crucible of the sealing equipped with presoma chlorination iron powder in an oven is 1-10 DEG C/min.
5. fenton catalyst as claimed in claim 3 is in the application of processing organic pollutants, wherein in the step c, The calcination time of the crucible of the sealing equipped with presoma chlorination iron powder in an oven is 0.5-2 hours.
6. fenton catalyst as claimed in claim 5 is in the application of processing organic pollutants, wherein in the step c, The calcination time of the crucible of the sealing equipped with iron chloride powder precursor in an oven is 1 hour.
7. fenton catalyst as claimed in claim 1 or 2 is in the application of processing organic pollutants, wherein the step d In, using acetone eccentric cleaning.
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CN111118087B (en) * 2020-01-07 2022-11-15 河南农业大学 Lignocellulose pretreatment system based on FeOCl and application thereof
CN111774076A (en) * 2020-06-30 2020-10-16 北京交通大学 Iron oxychloride-loaded ceramic membrane and preparation method thereof
CN114345121A (en) * 2021-12-20 2022-04-15 武汉大学 Preparation method and application of volatile organic compound waste gas washing liquid
CN114848580B (en) * 2022-04-19 2023-07-21 南京邮电大学 Microconvironment responsive nanocomposite for efficiently removing tumor cells, preparation method and application thereof
CN115634703A (en) * 2022-09-15 2023-01-24 贵州黔大生态环境与健康研究院有限公司 Catalyst and application thereof
CN116371434B (en) * 2023-04-06 2024-04-26 中国科学院生态环境研究中心 Novel iron-based solid Fenton catalyst and preparation method and application thereof

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CN102659235A (en) * 2012-05-17 2012-09-12 华东师范大学 Method for treating dye wastewater
CN106517484A (en) * 2016-12-27 2017-03-22 武汉纺织大学 Method for treating organic wastewater by use of ferric oxychloride to catalyze and activate mono-persulfate
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CN102491429A (en) * 2011-11-16 2012-06-13 华东师范大学 Preparation method of FeOCl
CN102659235A (en) * 2012-05-17 2012-09-12 华东师范大学 Method for treating dye wastewater
CN106517484A (en) * 2016-12-27 2017-03-22 武汉纺织大学 Method for treating organic wastewater by use of ferric oxychloride to catalyze and activate mono-persulfate
CN106698525A (en) * 2017-01-13 2017-05-24 福州大学 One-step synthesis of nanometer layered porous material of FeOCl and application thereof

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