CN118079980A - Carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst and preparation method and application thereof - Google Patents
Carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011032 tourmaline Substances 0.000 title claims abstract description 46
- 229940070527 tourmaline Drugs 0.000 title claims abstract description 46
- 229910052613 tourmaline Inorganic materials 0.000 title claims abstract description 46
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 20
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000000926 separation method Methods 0.000 claims description 48
- 238000001556 precipitation Methods 0.000 claims description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 235000006408 oxalic acid Nutrition 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910000859 α-Fe Inorganic materials 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000007774 longterm Effects 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 cerium ions Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/04—Mixing
-
- 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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to an ozone oxidation catalyst of carbon-nitrogen doped ceria/tourmaline and a preparation method and application thereof, wherein the catalyst raw materials comprise ferrite powder, vinasse and cerium nitrate, and the mass percentage of the ferrite powder is 50-80%. The catalyst has good catalytic activity, stability and recovery performance through carbon-nitrogen doping and interaction of cerium dioxide and tourmaline, and is favorable for wide popularization in the field of water treatment.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an ozone oxidation catalyst of carbon-nitrogen doped ceria/tourmaline, and a preparation method and application thereof.
Background
An ozone catalytic oxidation technology is a technology for efficiently treating organic wastewater which is difficult to degrade. The technology is to add a proper catalyst in the ozone oxidation process, so as to achieve the purposes of reducing the ozone consumption, improving the oxidation treatment effect and accelerating the reaction speed. Currently, the engineering application is mainly in the form of a fixed bed. However, the form of the fixed bed has the original problem that is difficult to solve, such as channeling and dead zones are easy to form in the fixed bed, and only a small amount of catalyst can contact with the sewage and ozone, so that the catalytic effect of the fixed bed is not obvious. On the other hand, ozone bubbles are trapped by the fixed bed catalyst in the rising process, so that the ozone bubbles are combined into large bubbles, the ozone utilization rate is low, and the operation cost is increased.
Thus, to overcome the above problems, a series of fluidized bed type ozone catalytic oxidation processes have been developed by those skilled in the art. The fluidized bed process generally adopts the form of powder catalyst to overcome the primary problem of a fixed bed, but the long-term catalytic effect, separation recovery performance, abrasion resistance and the like of the catalyst become new problems. In the prior art, the catalyst is mainly recovered by means of membrane separation or cyclone separation and the like, so that additional operation cost is increased; on the other hand, the powder material for the fluidized bed has insufficient strength, and is crushed particularly in continuous operation, so that the fine powder is difficult to separate, and on the one hand, secondary pollution is caused to the water body, and on the other hand, the performance of the catalyst is also affected.
As paper "Catalytic ozonation of hard COD in coking wastewater with Fe2O3/Al2O3-SiC:From catalyst design to industrial application" discloses a Fe 2O3/Al2O3-SiO2 catalyst, which has good long-term use property and wear resistance, but the catalyst needs to use cyclone separation as a separation means, so that the electricity cost and the manual maintenance cost are increased, and the engineering application is not facilitated. The invention patent CN 114471664A discloses a preparation method of a cerium oxide photocatalytic material with a wood-based carbon modified protonated carbon nitride/wood structure, and designs and constructs the cerium oxide photocatalytic material with the wood-based carbon modified protonated carbon nitride/wood structure, which has larger specific surface area, good thermal stability and chemical stability and good photocatalytic performance. However, the material takes the carbonaceous material and the ceria as main components, has insufficient wear resistance and strength, and can be damaged in long-term use, thereby causing secondary pollution; the invention patent CN112979021B discloses a FeO/TiO 2 -tourmaline catalyst for catalyzing ozone oxidation to degrade shale gas fracturing flowback fluid. However, the elemental iron component contained in the catalyst has reducibility, and after long-term use, oxides are formed on the surface, so that the catalytic effect is reduced, and the further application of the catalyst in practical engineering is prevented.
In summary, there is an urgent need to develop a high-efficiency ozone oxidation catalyst that has high strength, can be reused, can be simply separated without additional energy sources, and does not produce secondary pollution.
Disclosure of Invention
Based on the above, in order to solve at least one technical problem in the prior art, the invention provides an ozone oxidation catalyst of carbon-nitrogen doped ceria/tourmaline, and aims to solve the technical problems of poor catalyst strength, insufficient performance, difficulty in separation and secondary pollution risk.
The invention provides an ozone oxidation catalyst of carbon-nitrogen doped cerium oxide/tourmaline, which comprises the following raw materials: the iron tourmaline powder, the vinasse and the cerium nitrate, wherein the mass percentage of the iron tourmaline powder is 50% -80%.
According to the ozone oxidation catalyst, tourmaline is used as a base material, so that on one hand, the wear resistance is improved, precipitation and separation are easy, and in addition, a micro-electric field can be generated by using tourmaline, so that the mass transfer speed of ozone from a gas phase to a liquid phase is improved, and the catalytic oxidation effect and the ozone utilization rate are improved; in addition, the catalyst of the invention also takes vinasse as a raw material to introduce carbon and nitrogen doping, so that a bridge for electron transfer can be established, the rate of electron transfer between ozone molecules and catalysis is improved, the yield of active free radicals is improved, and the removal rate of pollutants is improved; in addition, cerium ions are introduced through cerium nitrate, and the transfer and transfer of the Ce 4+/Ce3+ and Fe 2+/Fe3+ electron pair contained in the tourmaline are realized, so that the catalyst material can be ensured to have long-term high-efficiency catalytic capability. Therefore, the catalyst of the invention is efficient, abrasion-resistant and has long-acting catalytic capability.
In one embodiment, the catalyst has a particle size of 100-150 meshes, and has better precipitability and abrasion resistance, and is more beneficial to recovery.
The invention also provides a preparation method of the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst, which comprises the following steps: fully grinding and mixing cerium nitrate, vinasse and ferroelectric stone powder, roasting, grinding and sieving to obtain a final product.
In one embodiment, the mass portion ratio of the cerium nitrate, the vinasse to the tourmaline powder of iron is 10-50: 15-50: 100.
In one embodiment, the ferroelectric powder has a particle size in the range of 75 to 150 μm.
In one embodiment, the firing temperature is 500 ℃ to 700 ℃ and the firing time is 2 hours.
The invention also provides an application of the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst in treating oxalic acid in sewage.
In one embodiment, the method comprises the following steps:
S1, putting the obtained catalyst into the bottom of a reaction zone of a reactor, wherein the reactor also comprises a precipitation separation zone communicated with the reaction zone, and water flow firstly enters the reaction zone from the outside, then overflows from the top of the reaction zone to the bottom of the precipitation separation zone and then ascends to flow out of the reactor;
S2, introducing ozone into the reaction zone from the bottom through a titanium microporous aeration disc;
s3, continuously feeding water into the reactor, and recycling the catalyst precipitated at the bottom of the precipitation separation zone to the reaction zone.
The method can recycle the catalyst and avoid secondary pollution of the water body.
In one embodiment, the concentration of oxalic acid in the inlet water is 100-300 mg/L; the concentration of the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst in the reaction area is 0.5-1.5 g/L.
In one embodiment, the residence time of the inlet water in the reaction zone is 60-90 min, the residence time in the precipitation separation zone is 30-60 min, and the water flow rising speed in the precipitation separation zone is 6-12 m/h.
Compared with the prior art, the ozone oxidation catalyst has the following beneficial effects:
(1) The ozone oxidation catalyst takes tourmaline as a carrier, and the Morse strength of the tourmaline is 7, which is greatly superior to common metal oxide and active carbon. The tourmaline is used as a carrier of the catalyst, so that the wear resistance of the catalyst can be greatly enhanced, the true density of the catalyst is high, and the catalyst is easy to precipitate and separate;
(2) The tourmaline can spontaneously generate a micro-electric field, so that the association degree of water molecules can be reduced, the cluster of water molecules can be reduced, and the speed of ozone mass transfer from gas phase to liquid phase can be greatly improved, thereby improving the catalytic oxidation effect and the ozone utilization rate;
(3) The carbon-nitrogen doping can establish a bridge for electron transfer, so that the rate of electron transfer between ozone molecules and the catalyst is improved, and the yield of active free radicals is improved, thereby improving the removal rate of pollutants;
(4) Cerium ions are introduced, and a Ce 4+/Ce3+ electron pair and a Fe 2+/Fe3+ electron pair contained in tourmaline realize transfer, so that the catalyst material has long-term high-efficiency catalytic capability;
The ozone oxidation catalyst has the advantages of long-term high efficiency of catalytic capability, simple and convenient preparation, low raw material cost, good wear resistance, convenient precipitation, separation and recovery, and wide popularization.
Drawings
FIG. 1 is a schematic view of a reactor structure;
fig. 2 is a comparison of catalyst particle changes before and after 30 consecutive days of example 1, wherein fig. 2a: before use; fig. 2b: after use;
FIG. 3 is a graph showing the comparison of the effect of catalytic degradation of oxalic acid in different experimental groups.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The cerium nitrate used as the raw material in the embodiment of the invention is cerium nitrate hexahydrate, and the molecular formula is Ce (NO 3)3·6H2 O).
The examples do not identify specific experimental procedures or conditions, which may be followed by routine experimental procedures or conditions described in the literature in this field; the materials used in the preparation process are conventional reagent products which are commercially available.
Example 1
An ozone oxidation catalyst of carbon-nitrogen doped cerium oxide/tourmaline, which comprises the following raw materials: 10g of tourmaline powder, 3g of commercially available distillers grains, and 5g of cerium nitrate hexahydrate, wherein the granularity of the tourmaline powder is 75 mu m. The preparation method comprises the following steps:
Weighing the raw materials, grinding and mixing uniformly, roasting for 2 hours at 600 ℃ in vacuum, grinding and sieving, and taking particles between 100 meshes and 150 meshes; obtaining the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst.
The finished catalyst is placed at the bottom of a reaction zone of a reactor shown in fig. 1, the reactor comprises a precipitation separation zone, the reaction zone is communicated with the reaction zone, water flow firstly enters the reaction zone from the outside, then overflows from the top of the reaction zone to the bottom of the precipitation separation zone, and then flows upwards out of the reactor.
Ozone is introduced into the reaction zone from the bottom through a titanium microporous aeration disc; the reactor can continuously feed and discharge water, and the catalyst precipitated at the bottom of the precipitation separation zone is recycled to the reaction zone through a peristaltic pump.
The artificial simulated oxalic acid wastewater is used as experimental wastewater, the experimental wastewater is operated in a continuous flow mode, the concentration of oxalic acid in inlet water is 200mg/L, the adding amount of a catalyst in a reaction zone is 1g/L, the residence time of inlet water in the reaction zone is 60min, the residence time of a precipitation separation zone is 30min, and the water flow rising speed of the precipitation separation zone is 12m/h. And respectively taking the water inlet and outlet of the reaction zone to measure the total organic carbon concentration, and taking the water inlet and outlet of the precipitation separation zone to measure the SS concentration. In particular, a sample of the catalyst from example 1 was taken for particle size analysis after 30 days of continuous operation.
Example 2
An ozone oxidation catalyst of carbon-nitrogen doped cerium oxide/tourmaline, which comprises the following raw materials: 10g of tourmaline, 4g of commercial distilled grain and 4g of cerium nitrate hexahydrate, wherein the granularity of the iron tourmaline powder is 90 mu m. The preparation method comprises the following steps:
Weighing the raw materials, grinding and mixing uniformly, roasting for 2 hours at 600 ℃ in vacuum, grinding and sieving, and taking particles between 100 meshes and 150 meshes; obtaining the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst.
The finished catalyst is placed at the bottom of a reaction zone of a reactor shown in fig. 1, the reactor comprises a precipitation separation zone, the reaction zone is communicated with the reaction zone, water flow firstly enters the reaction zone from the outside, then overflows from the top of the reaction zone to the bottom of the precipitation separation zone, and then flows upwards out of the reactor.
Ozone is introduced into the reaction zone from the bottom through a titanium microporous aeration disc; the reactor can continuously feed and discharge water, and the catalyst precipitated at the bottom of the precipitation separation zone is recycled to the reaction zone through a peristaltic pump.
The artificial simulated oxalic acid wastewater is used as experimental wastewater, the experimental wastewater is operated in a continuous flow mode, the oxalic acid is 200mg/L, the catalyst addition amount is 1g/L, the residence time of a reaction zone is 60min, the residence time of a precipitation separation zone is 30min, and the water flow rising speed of the precipitation separation zone is 12m/h. And respectively taking the water inlet and outlet of the reaction zone to measure the total organic carbon concentration, and taking the water inlet and outlet of the precipitation separation zone to measure the SS concentration.
Example 3
An ozone oxidation catalyst of carbon-nitrogen doped cerium oxide/tourmaline, which comprises the following raw materials: 10g of tourmaline, 5g of commercial distillers grains, and 4g of cerium nitrate hexahydrate, wherein the granularity of the iron tourmaline powder is 150 mu m. The preparation method comprises the following steps:
Weighing the raw materials, grinding and mixing uniformly, roasting for 2 hours at 600 ℃ in vacuum, grinding and sieving, and taking particles between 100 meshes and 150 meshes; obtaining the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst.
The finished catalyst is placed at the bottom of a reaction zone of a reactor shown in fig. 1, the reactor comprises a precipitation separation zone, the reaction zone is communicated with the reaction zone, water flow firstly enters the reaction zone from the outside, then overflows from the top of the reaction zone to the bottom of the precipitation separation zone, and then flows upwards out of the reactor.
Ozone is introduced into the reaction zone from the bottom through a titanium microporous aeration disc; the reactor can continuously feed and discharge water, and the catalyst precipitated at the bottom of the precipitation separation zone is recycled to the reaction zone through a peristaltic pump.
The artificial simulated oxalic acid wastewater is used as experimental wastewater, the experimental wastewater is operated in a continuous flow mode, the oxalic acid is 200mg/L, the catalyst addition amount is 1g/L, the residence time of a reaction zone is 60min, the residence time of a precipitation separation zone is 30min, and the water flow rising speed of the precipitation separation zone is 12m/h. And respectively taking the water inlet and outlet of the reaction zone to measure the total organic carbon concentration, and taking the water inlet and outlet of the precipitation separation zone to measure the SS concentration.
Comparative example 1
The comparative example provides an ozone catalytic oxidizer, which comprises the following raw materials: 10g of tourmaline. The preparation method comprises the following steps:
vacuum roasting at 600 deg.c for 2 hr, grinding, sieving and taking 100-150 mesh granular matter; obtaining the ozone catalytic oxidant.
The catalyst after the preparation was put into a reactor as shown in FIG. 1, and the artificial simulated oxalic acid wastewater was used as experimental wastewater, and was operated in a continuous flow mode, the oxalic acid as fed water was 200mg/L, the catalyst addition was 1g/L, the residence time in the reaction zone was 60min, the residence time in the precipitation separation zone was 30min, and the water flow rising rate in the precipitation separation zone was 12m/h. And respectively taking the water inlet and outlet of the reaction zone to measure the total organic carbon concentration, and taking the water inlet and outlet of the precipitation separation zone to measure the SS concentration.
Comparative example 2
The comparative example provides an ozone catalytic oxidizer, which comprises the following raw materials: 10g of tourmaline and 3g of commercially available distilled grains. The preparation method comprises the following steps:
Weighing the raw materials, grinding and mixing uniformly, roasting for 2 hours at 600 ℃ in vacuum, grinding and sieving, and taking particles between 100 meshes and 150 meshes; obtaining the ozone catalytic oxidant.
The catalyst after the preparation was put into a reactor as shown in FIG. 1, and the artificial simulated oxalic acid wastewater was used as experimental wastewater, and was operated in a continuous flow mode, the oxalic acid as fed water was 200mg/L, the catalyst addition was 1g/L, the residence time in the reaction zone was 60min, the residence time in the precipitation separation zone was 30min, and the water flow rising rate in the precipitation separation zone was 12m/h. And respectively taking the water inlet and outlet of the reaction zone to measure the total organic carbon concentration, and taking the water inlet and outlet of the precipitation separation zone to measure the SS concentration.
Comparative example 3
The comparative example provides an ozone catalytic oxidizer, which comprises the following raw materials: 9g of commercial distillers grains and 15g of cerium nitrate hexahydrate.
Weighing the raw materials, grinding and mixing uniformly, roasting for 2 hours at 600 ℃ in vacuum, grinding and sieving, and taking particles between 100 meshes and 150 meshes; obtaining the ozone catalytic oxidant.
The catalyst after the preparation was put into a reactor as shown in FIG. 1, and the artificial simulated oxalic acid wastewater was used as experimental wastewater, and was operated in a continuous flow mode, the oxalic acid as fed water was 200mg/L, the catalyst addition was 1g/L, the residence time in the reaction zone was 60min, the residence time in the precipitation separation zone was 30min, and the water flow rising rate in the precipitation separation zone was 12m/h. And respectively taking the water inlet and outlet of the reaction zone to measure the total organic carbon concentration, and taking the water inlet and outlet of the precipitation separation zone to measure the SS concentration.
Comparative example 4
According to the comparative example, no catalyst is added, a reactor shown in the figure 1 is used, artificial simulated oxalic acid wastewater is used as experimental wastewater, the experimental wastewater is operated in a continuous flow mode, the oxalic acid inflow is 200mg/L, the catalyst addition amount is 1g/L, the residence time of a reaction zone is 60min, the residence time of a precipitation separation zone is 30min, and the water flow rising speed of the precipitation separation zone is 12m/h. And respectively taking the water inlet and outlet of the reaction zone to measure the total organic carbon concentration, and taking the water inlet and outlet of the precipitation separation zone to measure the SS concentration.
Table 1 comparison table of effect of precipitated effluent SS
As can be seen from fig. 2, the particle size of the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst of example 1 is not changed significantly after 30 days of operation, which proves the stability of the catalyst in the use process, and a large amount of fine powder is not generated along with the use, thus secondary pollution is generated; as can be seen from Table 2, the catalyst containing the ferroelectric stone component is simply settled, and the catalyst does not run off along with effluent, and effluent SS meets the standard of 10mg/L of first-stage a; as can be seen from fig. 3, in example 1, the average total organic carbon removal rates of example 2 and example 3 are 92.9%,89.1% and 84.8%, and in comparative examples 1,2, 3 and 4 are 44.6%, 59.4%, 58.9% and 21.6%, respectively, which are significantly improved as compared with comparative examples, it is seen that the carbon nitrogen doped ceria/tourmaline ozone oxidation catalyst of the present invention has good catalytic activity, stability and recovery performance through carbon nitrogen doping and interaction of ceria/tourmaline.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst is characterized by comprising the following raw materials: the iron tourmaline powder, the vinasse and the cerium nitrate, wherein the mass percentage of the iron tourmaline powder is 50% -80%.
2. The ozone oxidation catalyst of claim 1, wherein the catalyst has a particle size of 100-150 mesh.
3. The method for preparing the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst according to any one of claims 1 to 2, comprising the steps of: fully grinding and mixing cerium nitrate, vinasse and ferroelectric stone powder, roasting, grinding and sieving to obtain a final product.
4. The preparation method of claim 3, wherein the mass portion ratio of the cerium nitrate, the vinasse to the tourmaline powder is 10-50: 15-50: 100.
5. A method of producing according to claim 3, wherein the particle size of the ferroelectric stone powder is in the range of 75 to 150 μm.
6. The method according to claim 3, wherein the baking temperature is 500 ℃ to 700 ℃ and the baking time is 2 hours.
7. The use of the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst according to claim 1 for treating oxalic acid in sewage.
8. The use according to claim 7, characterized by the steps of:
S1, putting the obtained catalyst into the bottom of a reaction zone of a reactor, wherein the reactor also comprises a precipitation separation zone communicated with the reaction zone, and water flow firstly enters the reaction zone from the outside, then overflows from the top of the reaction zone to the bottom of the precipitation separation zone and then ascends to flow out of the reactor;
S2, introducing ozone into the reaction zone from the bottom through a titanium microporous aeration disc;
s3, continuously feeding water into the reactor, and recycling the catalyst precipitated at the bottom of the precipitation separation zone to the reaction zone.
9. The use according to claim 8, wherein the concentration of oxalic acid in the feed water is 100-300 mg/L; the concentration of the carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst in the reaction area is 0.5-1.5 g/L.
10. The use according to claim 9, characterized in that the residence time of the feed water in the reaction zone is 60-90 min, the residence time in the precipitation separation zone is 30-60 min, and the water flow rising rate in the precipitation separation zone is 6-12 m/h.
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