CN113083332A - Ferric oxychloride-titanium dioxide composite catalyst - Google Patents
Ferric oxychloride-titanium dioxide composite catalyst Download PDFInfo
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- CN113083332A CN113083332A CN202110379129.8A CN202110379129A CN113083332A CN 113083332 A CN113083332 A CN 113083332A CN 202110379129 A CN202110379129 A CN 202110379129A CN 113083332 A CN113083332 A CN 113083332A
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- titanium dioxide
- composite catalyst
- oxychloride
- iron oxychloride
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- YPLPZEKZDGQOOQ-UHFFFAOYSA-M iron oxychloride Chemical compound [O][Fe]Cl YPLPZEKZDGQOOQ-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 38
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000000593 degrading effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 16
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 6
- YUVLVONHNMXKBW-UHFFFAOYSA-L [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O YUVLVONHNMXKBW-UHFFFAOYSA-L 0.000 description 6
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 6
- 229910000370 mercury sulfate Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- -1 iron oxychloride-titanium dioxide Chemical compound 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229940032296 ferric chloride Drugs 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses an iron oxychloride/titanium dioxide composite catalyst, which comprises a composite catalyst, wherein the composite catalyst comprises an iron oxychloride shell or titanium dioxide particles, the composite catalyst is in a core-shell structure, the core is titanium dioxide, and the shell is iron oxychloride. The composite catalyst shows the synergistic effect of photocatalytic oxidation of titanium dioxide and Fenton oxidation of ferric oxychloride, and improves the efficiency of degrading organic pollutants. The composite catalyst has a catalytic decomposition effect on the residual hydrogen peroxide in the process of degrading organic pollutants, and avoids the influence of the residual hydrogen peroxide on COD and subsequent biochemical treatment.
Description
Technical Field
The invention relates to the technical field of composite catalysts, and particularly relates to an iron oxychloride-titanium dioxide composite catalyst.
Background
The industrial wastewater difficult to treat is generally characterized by large concentration, complex components, high COD, chromaticity and salinity, poor biodegradability, biotoxicity and the like, so that the biochemical treatment is limited. Advanced oxidation is an important water treatment technology, wherein the Fenton oxidation technology is applied to wastewater treatment, and can improve the biodegradability of wastewater and break the limit of biochemical treatment.
The classical Fenton reaction is hydrogen peroxide (H)2O2) In the presence of catalyst Fe2+In the presence of the catalyst, hydroxyl free radicals (. OH) with strong oxidizing property are generated by high-efficiency decomposition, so that organic pollutants difficult to degrade are subjected to ring opening, bond breaking, addition, substitution, electron transfer and the like, macromolecular organic matters difficult to degrade are converted into small molecular substances easy to degrade, and even CO is directly generated2And H2And O. Firstly, the utilization rate of hydrogen peroxide in a Fenton system is low, the conversion rate of reducing ferric ions into ferrous ions is low, so that the degradation of organic pollutants is incomplete and the reagent cost is overhigh; secondly, the residual hydrogen peroxide in the reaction can have adverse effects on COD and the subsequent biochemical treatment; finally, fenton oxidation requires the addition of iron salts as catalysts to the system, excess iron ions are present in the aqueous solution or slurry, and the resulting iron sludge needs to be disposed of as hazardous waste, which is time and labor consuming and increases the treatment cost.
Chlorine oxideIron (FeOCl) as a heterogeneous Fenton-like catalyst can effectively decompose H2O2OH is generated, and further organic pollutants are degraded. Anatase titanium dioxide (TiO)2) Is considered to be the most active photo-fenton oxidation catalyst under uv irradiation. Due to the physical and chemical stability, low cost, reusability and non-toxicity, the photocatalyst is one of the most studied photocatalytic materials at present. However, because of its wide band gap (2.9eV), it cannot utilize sunlight efficiently by using it alone, and it is a hot spot of current research to red-shift its photoresponse range into the visible region. Thus, a novel multifunctional FeOOH/TiO (FeOCl/TiO) oxide was prepared2) The composite material can further improve the efficiency of degrading organic pollutants by light-Fenton and expand TiO2The visible light response area increases the Fenton reaction range, the activity and the stability of the reaction, deeply explores the catalytic mechanism of the Fenton reaction range, and has important theoretical and practical values for searching a catalyst with better application potential in environmental application.
Disclosure of Invention
The invention aims to provide an iron oxychloride-titanium dioxide composite catalyst, which solves the problem that iron oxychloride (FeOCl) is used as a heterogeneous Fenton-like catalyst and can effectively decompose H2O2OH is generated, and further organic pollutants are degraded. Anatase titanium dioxide (TiO2) is believed to be the most active photo-fenton oxidation catalyst under uv light irradiation. Due to the physical and chemical stability, low cost, reusability and non-toxicity, the photocatalyst is one of the most studied photocatalytic materials at present. However, because of its wide band gap (2.9eV), it cannot utilize sunlight efficiently by using it alone, and it is a thermal problem that is currently studied to red-shift its photoresponse range into the visible region.
In order to achieve the purpose, the invention provides the following technical scheme: the iron oxychloride-titanium dioxide composite catalyst comprises a composite catalyst, wherein the composite catalyst comprises an iron oxychloride shell or titanium dioxide particles, the composite catalyst is of a core-shell structure, the core is titanium dioxide, and the shell is iron oxychloride.
As a preferred embodiment of the present invention, the titanium dioxide is in anatase form.
In a preferred embodiment of the present invention, the titanium dioxide has a particle size of 5 to 100 nm or 10 to 50 nm.
As a preferred embodiment of the present invention, the ferric oxychloride is produced by the thermal transformation of ferric trichloride in air.
In a preferred embodiment of the present invention, the iron oxychloride accounts for 1 to 50% by mass of the titanium dioxide.
As a preferred embodiment of the present invention, the preparation method comprises the steps of:
step 1: grinding and mixing titanium dioxide and ferric chloride according to the mass ratio, and diffusing at the constant temperature of 60-140 ℃, preferably 70-100 ℃ for 12-36 hours, preferably 18-30 hours.
Step 2: and firing the mixture after constant temperature diffusion at 140-360 ℃, preferably from 180-260 ℃ in a muffle furnace for 0.5-4 hours, preferably for 1-3 hours.
And step 3: the burned mixture was cooled to room temperature, ground and allowed to stand.
Compared with the prior art, the invention has the following beneficial effects:
the composite catalyst shows the synergistic effect of photocatalytic oxidation of titanium dioxide and Fenton oxidation of ferric oxychloride, and improves the efficiency of degrading organic pollutants. The composite catalyst has a catalytic decomposition effect on the residual hydrogen peroxide in the process of degrading organic pollutants, and avoids the influence of the residual hydrogen peroxide on COD and subsequent biochemical treatment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention provides a preparation method of an iron oxychloride/titanium dioxide core-shell catalyst, which comprises the following steps:
10 g of titanium dioxide P-25 (Degussa, mixed crystal type, anatase and rutile weight ratio is about 80/20, particle size is 21 nm, specific surface area is 50 nm/g) and 4.8 g of ferric chloride hexahydrate (Tianjin Tansheng chemical analysis pure) are ground and mixed, and are diffused in an oven at the constant temperature of 80 ℃ for 24 hours; burning the mixture after the diffusion in a muffle furnace at 200 ℃ for 3 hours; and cooling the burned mixture to room temperature, and grinding to obtain the core-shell catalyst.
Example 2
The invention provides a preparation method of an iron oxychloride/titanium dioxide core-shell catalyst, which comprises the following steps:
grinding and mixing 10 g of titanium dioxide VK-TA60 (Zhejiang Zhi titanium purification science and technology Limited, anatase, particle size 60 nm, specific surface area 50-100 sq m/g) and 4.8 g of ferric chloride hexahydrate (Tianjin far chemical analysis pure), and diffusing in an oven at 80 ℃ for 24 hours at constant temperature; burning the mixture after the diffusion in a muffle furnace at 220 ℃ for 2 hours; and cooling the burned mixture to room temperature, and grinding to obtain the core-shell catalyst.
Example 3
The invention provides a preparation method of an iron oxychloride/titanium dioxide core-shell catalyst, which comprises the following steps:
grinding and mixing 10 g of titanium dioxide VK-TA15 (Zhejiang Zhi titanium purification science and technology Limited, anatase, particle size 15 nm, specific surface area 60-120 dm/g) and 2.0 g of ferric chloride hexahydrate (Tianjin far chemical analysis pure), and diffusing in an oven at 80 ℃ for 24 hours at constant temperature; burning the mixture after the diffusion in a muffle furnace at 240 ℃ for 1 hour; and cooling the burned mixture to room temperature, and grinding to obtain the core-shell catalyst.
Preparation of control iron oxychloride catalyst
Example 4
The invention provides a preparation method of an iron oxychloride catalyst, which comprises the following steps:
4.8 g of ferric chloride hexahydrate (Tianjin Tansheng chemical analysis pure) is kept in an oven at the temperature of 80 ℃ for 24 hours; then burning the mixture for 3 hours in a muffle furnace at the temperature of 200 ℃; and cooling the burned substance to room temperature, and grinding to obtain the reference ferric oxychloride catalyst.
Testing of a ferric oxychloride/titanium dioxide core-shell catalyst:
the catalyst test with bisphenol a as the target pollutant can be extended to any organic pollutant because the hydroxyl radicals produced by catalysis are not selective for degrading organic pollutants.
Example 5
100mg of bisphenol A was dissolved in 1L of deionized water, and the pH was adjusted to 3.0 with hydrochloric acid. 2 g of hydrogen peroxide (27.5%) and 5g of the composite catalyst (example 2) were added, and the reaction was stirred at room temperature for 30 minutes.
COD before and after the reaction was measured by the HJ828-2017 dichromate method (reagent E followed by reagent D, reagent D being a mixture of potassium dichromate and mercury sulfate, and reagent E being a sulfuric acid-silver sulfate solution).
Example 6
100mg of bisphenol A was dissolved in 1L of deionized water, and the pH was adjusted to 3.0 with hydrochloric acid. 2 g of hydrogen peroxide (27.5%) and 5g of the composite catalyst (example 2) were added and the reaction was stirred at room temperature for 30 minutes under UV irradiation.
COD before and after the reaction was measured by the HJ828-2017 dichromate method (reagent E followed by reagent D, reagent D being a mixture of potassium dichromate and mercury sulfate, and reagent E being a sulfuric acid-silver sulfate solution).
Example 7
100mg of bisphenol A was dissolved in 1L of deionized water, and the pH was adjusted to 3.0 with hydrochloric acid. 2 g of hydrogen peroxide (27.5%) and 5g of control iron oxychloride catalyst (example 4) were added and the reaction was stirred at room temperature for 30 minutes.
COD before and after the reaction was measured by the HJ828-2017 dichromate method (reagent E followed by reagent D, reagent D being a mixture of potassium dichromate and mercury sulfate, and reagent E being a sulfuric acid-silver sulfate solution).
Example 8
100mg of bisphenol A was dissolved in 1L of deionized water, and the pH was adjusted to 3.0 with hydrochloric acid. 2 g of hydrogen peroxide (27.5%) and 5g of a control iron oxychloride catalyst (example 4) were added and the reaction was stirred at room temperature for 30 minutes under UV irradiation.
COD before and after the reaction was measured by the HJ828-2017 dichromate method (reagent E followed by reagent D, reagent D being a mixture of potassium dichromate and mercury sulfate, and reagent E being a sulfuric acid-silver sulfate solution).
The COD results were as follows:
in example 5, the composite catalyst has a remarkable catalytic effect on the degradation of bisphenol A by hydrogen peroxide, and the removal rate of COD reaches 78.3%; in example 6, the photocatalytic oxidation of titanium dioxide and the fenton oxidation of iron oxychloride showed a certain synergistic effect under ultraviolet light, and the COD removal rate reached 81.4%. In contrast, the iron oxychloride catalyst (without a titanium dioxide carrier) has a certain catalytic effect on the degradation of bisphenol a by hydrogen peroxide, and under the conditions of no ultraviolet illumination and ultraviolet illumination, the COD removal rate is about 60.2% (examples 7 and 8), and the ultraviolet illumination has no influence on the catalytic activity of the iron oxychloride.
In addition, the composite catalyst of the invention has catalytic decomposition effect on the residual hydrogen peroxide when degrading organic pollutants, and avoids the influence of the residual hydrogen peroxide on COD and subsequent biochemical treatment. Regarding the catalytic decomposition effect of the composite catalyst on hydrogen peroxide, the examples are as follows:
example 9
A0.1% aqueous hydrogen peroxide solution was prepared, and 5g/L of the iron oxychloride/titanium dioxide composite catalyst of example 2 was added to the solution, followed by stirring and reacting at room temperature for 30 minutes.
COD before and after the reaction was measured by the HJ828-2017 dichromate method (reagent E followed by reagent D, reagent D being a mixture of potassium dichromate and mercury sulfate, and reagent E being a sulfuric acid-silver sulfate solution).
Example 10
A0.1% aqueous hydrogen peroxide solution was prepared, and 5g/L of the control iron oxychloride catalyst of example 4 was added to the solution, followed by stirring and reacting at room temperature for 30 minutes.
COD before and after the reaction was measured by the HJ828-2017 dichromate method (reagent E followed by reagent D, reagent D being a mixture of potassium dichromate and mercury sulfate, and reagent E being a sulfuric acid-silver sulfate solution).
The COD results were as follows:
compared with a control ferric chloride catalyst, the ferric chloride/titanium dioxide composite catalyst has obvious catalytic action on the decomposition of hydrogen peroxide, and can avoid the influence of redundant hydrogen peroxide on COD (chemical oxygen demand) and subsequent biochemical treatment
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. An iron oxychloride/titanium dioxide composite catalyst is characterized in that: the catalyst comprises a composite catalyst, wherein the composite catalyst comprises a shell of iron oxychloride or titanium dioxide particles, the composite catalyst is of a core-shell structure, the core is titanium dioxide, and the shell is the iron oxychloride.
2. The iron oxychloride/titanium dioxide composite catalyst of claim 1, wherein: the titanium dioxide is in anatase form.
3. The iron oxychloride/titanium dioxide composite catalyst of claim 1, wherein: the particle size of the titanium dioxide is 5-100 nanometers or 10-50 nanometers.
4. The iron oxychloride/titanium dioxide composite catalyst of claim 1, wherein: the ferric oxychloride is generated by the thermal transformation of ferric trichloride in air.
5. The iron oxychloride/titanium dioxide composite catalyst of claim 1, wherein: the mass of the iron oxychloride accounts for 1-50% of the mass of the titanium dioxide.
6. The method for preparing the iron oxychloride/titanium dioxide composite catalyst according to claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
step 1: grinding and mixing titanium dioxide and ferric chloride according to the mass ratio, and diffusing at the constant temperature of 60-140 ℃, preferably 70-100 ℃ for 12-36 hours, preferably 18-30 hours.
Step 2: and firing the mixture after constant temperature diffusion at 140-360 ℃, preferably from 180-260 ℃ in a muffle furnace for 0.5-4 hours, preferably for 1-3 hours.
And step 3: the burned mixture was cooled to room temperature, ground and allowed to stand.
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| CN202011157458X | 2020-10-26 | ||
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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