CN108607543B - Magnetic separation type catalytic device for eliminating hydrogen peroxide and application thereof - Google Patents
Magnetic separation type catalytic device for eliminating hydrogen peroxide and application thereof Download PDFInfo
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- CN108607543B CN108607543B CN201810317009.3A CN201810317009A CN108607543B CN 108607543 B CN108607543 B CN 108607543B CN 201810317009 A CN201810317009 A CN 201810317009A CN 108607543 B CN108607543 B CN 108607543B
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 74
- 238000007885 magnetic separation Methods 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 24
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 12
- 238000002798 spectrophotometry method Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 11
- 230000008030 elimination Effects 0.000 claims description 8
- 238000003379 elimination reaction Methods 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 abstract description 7
- 230000005307 ferromagnetism Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 229910004416 SrxMnO3 Inorganic materials 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 20
- 238000003421 catalytic decomposition reaction Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910003367 La0.5Sr0.5MnO3 Inorganic materials 0.000 description 3
- 229910002148 La0.6Sr0.4MnO3 Inorganic materials 0.000 description 3
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 description 3
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- BGPVFRJUHWVFKM-UHFFFAOYSA-N N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] Chemical compound N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] BGPVFRJUHWVFKM-UHFFFAOYSA-N 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- -1 rare earth metal ions Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- C02F2101/10—Inorganic compounds
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Abstract
The invention discloses a magnetic catalytic material La for eliminating hydrogen peroxide1‑xSrxMnO3(ii) a The catalyst has excellent catalytic action, can be used for efficiently catalyzing and degrading the hydrogen peroxide, has excellent ferromagnetism, is convenient to rapidly separate the catalyst from a product, and improves the efficiency of catalyzing and degrading the hydrogen peroxide. Meanwhile, a magnetic separation type catalytic device for eliminating hydrogen peroxide is disclosed, which comprises a baffle plate, a decomposition pipe and a tile-shaped magnet; which will be magnetic perovskite oxide La1‑xSrxMnO3(0<x is less than or equal to 0.6) is uniformly dispersed in a decomposition tube surrounding the magnet, so that a water sample to be detected containing residual hydrogen peroxide is uniformly contacted with the catalyst, and the decomposition reaction rate of the residual hydrogen peroxide in the water sample is accelerated; and the separation of the water sample and the catalyst is rapidly realized through the magnet, so that the step of filtering the catalyst is omitted, and the time and the cost are saved.
Description
Technical Field
The invention belongs to the field of environmental monitoring, relates to a determination technology and a determination device for accurately determining relevant indexes of wastewater treatment, and particularly relates to a magnetic separation type catalytic device for eliminating hydrogen peroxide and application thereof.
Background
In the technical field of organic waste water treatment, based on H2O2The Fenton technology and the Fenton-like technology are widely applied advanced oxidation technologies. Such advanced oxidation techniques are characterized by being based on H2O2As an oxidizing agent in Fe2+/Fe3+And free radicals OH with higher oxidation-reduction potential are generated under the catalytic action of other heterogeneous catalysts, so that various organic pollutants can be efficiently degraded, and the method is a green sustainable water treatment technology. In addition, Chemical Oxygen Demand (COD) is an important parameter index for evaluating the treatment effect of the Fenton technology and the Fenton-like technology, and therefore, accurate measurement of COD is of great significance for evaluating the treatment efficiency of the advanced oxidation technology based on hydrogen peroxide. At present, potassium dichromate-spectrophotometry is the most common method for determining COD, but residual hydrogen peroxide in a water sample to be determined has certain reducibility, and the hydrogen peroxide is oxidized by potassium dichromate under a strong acid condition, so that the COD value is higher, the COD test result is interfered, and the degree of organic matter pollution of the water sample is difficult to accurately evaluate. Thus based on H2O2The water sample treated by the advanced oxidation technology of (1) must eliminate the interference of residual hydrogen peroxide on the COD test.
General purpose of H2O2The elimination method of (2) includes a masking agent method, a thermal decomposition method, a deduction method and the like, but the elimination methods generally have the problems of complicated operation, high cost, undesirable elimination effect and the like. The catalytic decomposition method is to utilize a catalyst to catalyze the hydrogen peroxide decomposition reaction, and the process is simple, quick and easy to operate. However, the catalyst commonly used in the prior art for eliminating hydrogen peroxide by catalytic decomposition is MnO2The method has the defect of low catalytic activity, and the water sample and the catalyst can be separated only by filtering operation after the reaction is finished, so that the operation cost is increased.
Therefore, it is an urgent need to solve the problem of providing a testing apparatus and method for efficiently eliminating hydrogen peroxide and rapidly separating a water sample and a catalyst based on a catalytic decomposition method, so as to achieve the effects of simplifying the operation steps of eliminating hydrogen peroxide in the water sample by using the catalytic decomposition method and saving time and cost.
Disclosure of Invention
In view of the above, the present invention provides a magnetic separation type catalytic apparatus for eliminating hydrogen peroxide and a method for using the same, by providing a magnetic perovskite oxide La having a high catalytic decomposition activity for hydrogen peroxide1-xSrxMnO3(0<x is less than or equal to 0.6) is uniformly dispersed in a decomposition tube which is provided with a cooling tube and surrounds the magnet on the periphery, so that a water sample to be detected containing residual hydrogen peroxide is uniformly contacted with a catalyst, and the decomposition of the residual hydrogen peroxide in the water sample is accelerated; and can realize the separation of water sample and catalyst fast through magnet, save the step that the catalyst filters, can convenient and fast with the water sample and the catalyst separation that await measuring.
In order to achieve the purpose, the invention adopts the following technical scheme:
the magnetic catalytic material for eliminating hydrogen peroxide is characterized by consisting of perovskite oxide, wherein the structural formula of the perovskite oxide is ABO3(ii) a The A site cation comprises one or more of rare earth metal ions or alkaline earth metal ions; the B site cations include one or more of transition metal ions.
The perovskite oxide disclosed by the invention not only has excellent catalytic action and can be used for efficiently catalyzing and degrading hydrogen peroxide, but also has excellent ferromagnetism, so that the catalyst and a product can be conveniently and rapidly separated, and the efficiency of catalyzing and degrading the hydrogen peroxide is improved.
Preferably, the perovskite oxide is La1-xSrxMnO3Said x satisfies 0<x is less than or equal to 0.6; the La1- xSrxMnO3Has a specific surface area of less than 10mgL-1。
The invention discloses a perovskite oxide La1-xSrxMnO3Has excellent ferromagnetism, and can reduce trans-activity when being used as a catalyst in the process of degrading hydrogen peroxideThe activation energy is required, the reaction rate is accelerated, and the time and the cost are saved.
Preferably, the La1-xSrxMnO3In the preparation process, a precursor is prepared by a sol-gel method, and then the precursor is calcined in a muffle furnace at a high temperature of 900 ℃.
La used in the invention1-xSrxMnO3The catalyst has simple and efficient preparation process and high yield in the preparation process.
A magnetic separation type catalytic device for eliminating hydrogen peroxide is characterized by comprising a baffle plate, a decomposition pipe and a tile-shaped magnet; a magnet is arranged in the baffle, and one side of the baffle is connected to the bottom end of the decomposition tube; the interior of the decomposition tube is filled with a magnetic catalytic material for eliminating hydrogen peroxide, and the tile-shaped magnet is wrapped outside the decomposition tube.
The invention discloses a magnetic separation type catalytic device for preparing magnetic perovskite oxide La1-xSrxMnO3(0<x is less than or equal to 0.6) is uniformly dispersed in a decomposition tube surrounding the tile-shaped magnet, so that a water sample to be detected containing residual hydrogen peroxide is uniformly contacted with a catalyst, and the decomposition reaction rate of the residual hydrogen peroxide in the water sample is accelerated; and the separation of the water sample and the catalyst can be rapidly realized through the tile-shaped magnet and the magnet in the baffle, so that the step of filtering the catalyst is omitted, and the time and the cost are saved.
Preferably, the cooling device further comprises a cooling pipe, the bottom end of the cooling pipe is of a closed structure, the top end of the cooling pipe is connected to the other side of the baffle, and cooling water is filled in the cooling pipe.
The decomposition tube can be cooled by the cooling tube to prevent danger caused by a large amount of heat generated by exothermic reaction during the decomposition of hydrogen peroxide.
Preferably, the device also comprises a pipe plug and a filter pipe, wherein the pipe plug is matched and connected with the top end of the decomposition pipe, and the filter pipe is arranged on the pipe plug in a penetrating way.
Preferably, the filter pipe is a centrifugal filter pipe.
Through stopcock and filter tube can be convenient use the liquid-transfering gun take out the area water sample of decomposing in the pipe, avoid using the in-process that the liquid-transfering gun took out the water sample, solid catalyst gets into the liquid-transfering gun along with taking the water sample to avoid destroying the instrument of use.
The assembling method of the magnetic separation type catalytic device for eliminating the hydrogen peroxide is characterized by comprising the following steps:
(1) magnetic catalytic material granulation: pressing a magnetic catalytic material into particles with the particle size of more than 30-60 meshes;
(2) assembling a magnetic separation type catalytic device: connecting the cooling pipe, the baffle, the decomposing pipe and the tile-shaped magnet, and then filling the prepared particles into the decomposing pipe.
The assembling method of the magnetic separation type catalytic device for eliminating hydrogen peroxide disclosed by the invention is simple and rapid, and can be assembled according to needs, and the obtained device can be conveniently applied to eliminating hydrogen peroxide in a detected water sample.
Preferably, in the step (1), the magnetic catalytic material is placed in a tabletting mold, the tablet is pressed under 15-25M unidirectional pressure for 2min, then the tablet is placed in a screen with 30-60 meshes for grinding and granulation, and particles left in the screen are collected.
The application of the magnetic separation type catalytic device for eliminating the hydrogen peroxide is characterized in that the magnetic separation type catalytic device is used for efficiently eliminating the interference of the hydrogen peroxide on a COD test.
Preferably, the method specifically comprises the following steps:
(a) adding a water sample to be detected into a decomposition tube at the temperature of 20-25 ℃, and standing for decomposition;
(b) after standing and decomposing, taking out a water sample to be detected through a filter pipe by using a liquid transfer gun;
(c) and (3) measuring the COD value of the water sample to be measured according to a potassium dichromate spectrophotometry.
Preferably, the time for decomposition in step (a) is 0-8 min.
The magnetic separation type catalytic device for eliminating hydrogen peroxide disclosed by the invention can be conveniently applied to eliminating hydrogen peroxide in a water sample to be detected, so that the COD value can be accurately determined by using a potassium dichromate spectrophotometry.
According to the technical scheme, compared with the prior art, the magnetic catalytic material for eliminating hydrogen peroxide disclosed by the invention has an excellent catalytic effect, can be used for efficiently catalyzing and degrading hydrogen peroxide, has excellent ferromagnetism, is convenient for quickly separating a catalyst from a product, and improves the efficiency of catalyzing and degrading hydrogen peroxide. In addition, the invention discloses a magnetic separation type catalytic device for eliminating hydrogen peroxide, which is prepared by using magnetic perovskite oxide La1-xSrxMnO3(0<x is less than or equal to 0.6) is uniformly dispersed in the decomposition tube surrounding the tile-shaped magnet, so that a water sample to be detected containing residual hydrogen peroxide can be uniformly and fully contacted with the catalyst, the decomposition rate of the residual hydrogen peroxide in the water sample is accelerated, and the elimination efficiency is improved; and the separation of the water sample and the catalyst can be rapidly realized through the tile-shaped magnet and the magnet in the baffle, so that the step of filtering the catalyst is omitted, and the time and the cost are saved. In addition, the magnetic separation type catalytic device is applied to the potassium dichromate spectrophotometry to determine the COD value of the water sample, so that the influence of residual hydrogen peroxide in the water sample can be eliminated, and the determination accuracy is improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of the magnetic catalytic material disclosed in example 1;
FIG. 2 is a drawing showing a magnetic catalytic material La0.4Sr0.6MnO3A hysteresis loop and an electron microscope image of (a);
FIG. 3 is a schematic structural diagram of a magnetic separation type catalytic device for eliminating hydrogen peroxide disclosed in example 2;
FIG. 4 is a sectional view of a magnetic separation type catalytic apparatus for eliminating hydrogen peroxide disclosed in example 2;
FIG. 5 is a graph showing the COD value measured in examples 4 to 6 as a function of decomposition time;
FIG. 6 is a graph showing the relationship between the number of cycles of use and the decomposition efficiency of hydrogen peroxide in the magnetic separation type catalytic apparatus for eliminating hydrogen peroxide disclosed in example 2.
FIG. 7 is a drawing showing a magnetic catalytic material La0.4Sr0.6MnO3X-ray diffraction patterns before and after recycling;
in the figure: 1 is a cooling pipe, 2 is a baffle, 3 is a decomposition pipe, 4 is a tile-shaped magnet plate, 5 is a pipe plug, and 6 is a filter pipe.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 embodiment 1 of the invention discloses a magnetic catalytic material for eliminating hydrogen peroxide, wherein the magnetic catalytic material consists of perovskite oxide, and the structural formula of the perovskite oxide is ABO3(ii) a The A site cation comprises one or more of rare earth metal ions or alkaline earth metal ions; the B site cations include one or more of transition metal ions.
In order to further optimize the technical scheme, the perovskite oxide is La1-xSrxMnO3X satisfies 0<x≤0.6；La1-xSrxMnO3Has a specific surface area of less than 10mg L-1。
For further optimization of the technical solution, La1-xSrxMnO3In the preparation process, a precursor is prepared by a sol-gel method, and then the precursor is calcined in a muffle furnace at a high temperature of 900 ℃.
In order to further optimize the technical scheme, the magnetic catalytic material for eliminating the hydrogen peroxide comprises La0.4Sr0.6MnO3、La0.5Sr0.5MnO3、La0.6Sr0.4MnO3、La0.7Sr0.3MnO3、La0.8Sr0.2MnO3Or La0.9Sr0.1MnO3。
In order to further optimize the technical scheme, the magnetic catalytic material for eliminating the hydrogen peroxide comprises La0.4Sr0.6MnO3。
Performance detection
(1) Magnetic catalytic material La as disclosed above0.4Sr0.6MnO3、La0.5Sr0.5MnO3、La0.6Sr0.4MnO3、La0.7Sr0.3MnO3、La0.8Sr0.2MnO3And La0.9Sr0.1MnO3The results of X-ray diffraction measurements are shown in FIG. 1, and La is seen from the characteristic diffraction peaks of all the magnetic catalytic materials0.4Sr0.6MnO3、La0.5Sr0.5MnO3、La0.6Sr0.4MnO3、La0.7Sr0.3MnO3、La0.8Sr0.2MnO3And La0.9Sr0.1MnO3All form a perovskite phase structure.
(2) For magnetic catalytic material La0.4Sr0.6MnO3The results of the hysteresis loop and the electron micrograph are shown in FIG. 2. La can be seen from the hysteresis loop0.4Sr0.6MnO3The magnetic material has mild ferromagnetism, is easy to separate from an aqueous solution under an additional magnetic field, and has the saturation magnetization and the coercive force of 2.26emu/g and 56.0Oe respectively; as is evident from the electron micrograph, La0.4Sr0.6MnO3The particle diameter of (1) is between 100 and 300nm, belongs to a nano material, and has no special morphology.
(3) Comparative magnetic catalytic material La0.4Sr0.6MnO3MnO compared with traditional catalyst2Decomposition efficiency for hydrogen peroxide.
Preparing a water sample to be detected with the hydrogen peroxide volume fraction of 1% by using deionized water and hydrogen peroxide, and taking 6mL of the water sample to be detected and 0.25g of magnetic catalytic material La respectively0.4Sr0.6MnO3And conventional catalyst MnO2Mixing and standing, decomposing and removing hydrogen peroxide in a water sample by a catalytic method, taking the water sample at different decomposition time to determine the COD value, and summarizing the data results in the following table 1.
TABLE 1
By contact with a conventional catalyst MnO2Comparison of catalytic activity of La0.4Sr0.6MnO3The catalytic decomposition efficiency of the catalyst on the hydrogen peroxide reaches 90.4 percent under the decomposition time of 5min, which indicates that La0.4Sr0.6MnO3Has more efficient catalytic activity for the decomposition of hydrogen peroxide. And La0.4Sr0.6MnO3Have ferromagnetism, can make water sample and catalyst separation fast through magnet, take out the water sample that awaits measuring and test, make the catalytic decomposition process of eliminating hydrogen peroxide more convenient high-efficient like this.
Example 2
The embodiment of the invention also discloses a magnetic separation type catalytic device for eliminating hydrogen peroxide, which comprises a baffle, a decomposition pipe and a tile-shaped magnet; a magnet is arranged in the baffle, and one side of the baffle is connected to the bottom end of the decomposition tube; the interior of the decomposition tube is filled with a magnetic catalytic material for eliminating hydrogen peroxide, and the exterior of the decomposition tube is covered with tile-shaped magnet.
In order to further optimize the technical scheme, the cooling device further comprises a cooling pipe, the bottom end of the cooling pipe is of a closed structure, the top end of the cooling pipe is connected to the other side of the baffle, and cooling water is filled in the cooling pipe.
For further optimization technical scheme, still include stopcock and filter tube, the stopcock is connected with the top cooperation of decomposition tube, and the filter tube is worn to locate the stopcock.
As shown in fig. 3-4, a magnetic separation type catalytic apparatus for eliminating hydrogen peroxide comprises a cooling pipe 1, a baffle plate 2, a decomposition pipe 3, a tile-shaped magnet 4, a pipe plug 5 and a filter pipe 6; cooling water is filled in the cooling pipe 1, and the bottom end of the cooling pipe 1 is of a closed structure; the baffle 2 is internally provided withOne side of the baffle 2 is connected to the top end of the cooling pipe 1, and the other side of the baffle 2 is connected to the bottom end of the decomposition pipe 3; the decomposition tube 3 was filled with the magnetic catalyst material La disclosed in example 10.4Sr0.6MnO3The decomposing pipe 3 is externally coated with a tile-shaped magnet 4; the pipe plug 5 is connected with the top end of the decomposition pipe 6 in a matching way; the filter pipe 6 is arranged through the pipe plug 5, and one end of the filter pipe 6 is provided with uniform filter holes.
Example 3
The embodiment of the invention also discloses an assembly method of the magnetic separation type catalytic device for eliminating hydrogen peroxide, which comprises the following steps:
(1) magnetic catalytic material granulation: placing the magnetic catalytic material in the embodiment 1 in a tabletting mold, pressing the magnetic catalytic material into tablets under 15-25M unidirectional pressure for 2min, then placing the tablets in a 30-60 mesh screen for grinding and granulating, collecting particles remained in the screen, and pressing the particles into particles with the particle size of more than 30-60 meshes;
(2) assembling a magnetic separation type catalytic device: firstly, filling cooling water into the cooling pipe, then connecting the top end of the cooling pipe with one side of a baffle plate internally provided with a magnet, then connecting the bottom end of the decomposition pipe with the other side of the baffle plate, and finally bonding a tile-shaped magnet on the outer side of the decomposition pipe; then the prepared particles are loaded into a decomposition tube;
(3) after the decomposition is finished, the pipe plug with the filter pipe is arranged at the top end of the decomposition pipe in a penetrating mode, and one end, provided with the filter hole, of the filter pipe extends into the decomposition pipe.
Example 4
A magnetic separation type catalytic device for eliminating hydrogen peroxide is used for efficiently eliminating the interference of hydrogen peroxide on COD test, and specifically comprises the following steps:
(a) adding a water sample to be detected into a decomposition tube at 25 ℃, standing and decomposing for 3 min;
(b) after standing and decomposing, taking out a water sample to be detected through a filter pipe by using a liquid transfer gun;
(c) and (3) measuring the COD value of the water sample to be measured according to a potassium dichromate spectrophotometry.
Example 5
A magnetic separation type catalytic device for eliminating hydrogen peroxide is used for efficiently eliminating the interference of hydrogen peroxide on COD test, and specifically comprises the following steps:
(a) adding a water sample to be detected into a decomposition tube at 23 ℃, standing and decomposing for 5 min;
(b) after standing and decomposing, taking out a water sample to be detected through a filter pipe by using a liquid transfer gun;
(c) and (3) measuring the COD value of the water sample to be measured according to a potassium dichromate spectrophotometry.
Example 6
A magnetic separation type catalytic device for eliminating hydrogen peroxide is used for efficiently eliminating the interference of hydrogen peroxide on COD test, and specifically comprises the following steps:
(a) adding a water sample to be detected into a decomposition tube at 20 ℃, standing and decomposing for 8 min;
(b) after standing and decomposing, taking out a water sample to be detected through a filter pipe by using a liquid transfer gun;
(c) and (3) measuring the COD value of the water sample to be measured according to a potassium dichromate spectrophotometry.
Result detection
First, removal of hydrogen peroxide from deionized water
(1) Taking a certain amount of deionized water, and firstly determining the COD value of the deionized water according to a potassium dichromate spectrophotometry method to obtain an initial value; preparing a water sample to be detected with the hydrogen peroxide volume fraction of 1% by using the deionized water and the hydrogen peroxide, and determining the COD value of the water sample to be detected according to a potassium dichromate spectrophotometry to be used as a blank control group; then, the prepared water sample to be tested was measured for its COD value according to the methods of examples 4 to 6, and the results are shown in table 2 below, and a graph of the measured COD value versus the decomposition time is drawn based on the above results, as shown in fig. 5.
TABLE 2
| Initial value | Blank control group | Example 4 | Example 5 | Example 6 | |
| COD(mgL-1) | 0 | 989.2 | 185.7 | 50.6 | 8.4 |
The following can be known from the detection results: the COD value measured by example 6 was closest to the initial value, indicating that example 6 is most effective in removing hydrogen peroxide from deionized water.
(2) A certain amount of the water sample to be measured was divided into three portions, and the removal rate of hydrogen peroxide was measured in the same magnetic separation type catalytic apparatus for eliminating hydrogen peroxide disclosed in example 2 by the method shown in example 6, three times in a cycle, and the results are shown in fig. 6.
Wherein the hydrogen peroxide removal rate is calculated as follows:
the removal rate of hydrogen peroxide is the COD value decreased by elimination of hydrogen peroxide/COD value increased by addition of hydrogen peroxide × 100%.
As is apparent from fig. 6, the catalytic decomposition efficiency of the magnetic separation catalytic apparatus for eliminating hydrogen peroxide disclosed in example 2 is similar to that of hydrogen peroxide in deionized water after three times of recycling, and the removal rate is over 98.5%.
(3) Taking the magnetic catalytic material La in the magnetic separation type catalytic device0.4Sr0.6MnO3The results of X-ray diffraction before and after three cycles are shown in FIG. 7. As is apparent from the structure in FIG. 7, the magnetic catalytic material La0.4Sr0.6MnO3The chemical nature of the magnetic separation type catalytic device for eliminating the hydrogen peroxide is not changed after the magnetic separation type catalytic device is recycled.
Secondly, removing hydrogen peroxide in real wastewater
(1) Taking a certain amount of secondary domestic sewage from a certain area in Benxi City of Liaoning province, and measuring the COD value of the secondary domestic sewage according to a potassium dichromate spectrophotometry, namely an initial value; preparing a water sample to be detected with the hydrogen peroxide volume fraction of 1% by using the sewage and the hydrogen peroxide, and determining the COD value of the water sample to be detected according to a potassium dichromate spectrophotometry to be used as a blank control group; then 10mL of the prepared water sample to be tested was used to determine the COD value according to the methods of examples 4-6, and the results are shown in Table 3 below, and a graph showing the relationship between the COD value and the decomposition time is drawn according to the above results, as shown in FIG. 5.
TABLE 3
| Initial value | Blank control group | Example 4 | Example 5 | Example 6 | |
| COD(mgL-1) | 133.5 | 1155 | 362 | 236.4 | 127.4 |
The following can be known from the detection results: the COD value measured in example 6 was closest to the initial value, indicating that example 6 is most effective in removing hydrogen peroxide from wastewater.
(2) A certain amount of the water sample to be measured was divided into three portions, and three tests were performed in the same magnetic separation type catalytic apparatus for eliminating hydrogen peroxide disclosed in example 2 according to the method shown in example 6, and the removal rate of hydrogen peroxide was measured, respectively, and the results are shown in fig. 6.
Wherein the hydrogen peroxide removal rate is calculated as follows:
the removal rate of hydrogen peroxide is the COD value decreased by elimination of hydrogen peroxide/COD value increased by addition of hydrogen peroxide × 100%.
As is apparent from fig. 6, the catalytic decomposition efficiency of the invention for hydrogen peroxide in wastewater is similar when the magnetic separation catalytic device for eliminating hydrogen peroxide disclosed in example 2 is recycled three times, and the removal rate is above 99%.
Thirdly, removing residual hydrogen peroxide in the wastewater after Fenton treatment
Preparing 30mg L-1The initial COD value of the phenol wastewater is 423.6mg L by sampling and testing-1(ii) a The Fenton catalytic condition is 0.1g L-1Fe3O4，pH＝3，[H2O2]0Reaction time 60min at 10mM, sample every 20min, and use the magnetic separation peroxide of the present inventionThe hydrogen catalytic decomposition device eliminates hydrogen peroxide in the water sample to be tested according to the embodiment 6, and COD test is carried out, and the data results are shown in the following table 4.
TABLE 4
| Time of sampling | 0min | 20min | 40min |
| Decomposition tube eliminating H2O2(COD/mg L-1) | 423.6 | 315.5 | 260.4 |
| Not eliminating H2O2(COD/mg L-1) | 1672.1 | 1252.3 | 1041.7 |
The data in the table show that the magnetic separation type hydrogen peroxide catalytic decomposition tube can effectively eliminate residual hydrogen peroxide in a water sample, and has great economic and applicable values for accurately estimating the efficiency of Fenton treatment.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A magnetic separation type catalytic device for eliminating hydrogen peroxide is characterized by comprising a baffle plate, a decomposition pipe and a tile-shaped magnet; a magnet is arranged in the baffle, and one side of the baffle is connected to the bottom end of the decomposition tube; the interior of the decomposing tube is filled with a magnetic catalytic material, and the decomposing tube is wrapped with the tile-shaped magnet;
the magnetic catalytic material is composed of perovskite oxide, and the perovskite oxide is La1-xSrxMnO3Said x satisfies 0<x is less than or equal to 0.6; the La1-xSrxMnO3Has a specific surface area of less than 10mg L-1；
The bottom end of the cooling pipe is of a closed structure, the top end of the cooling pipe is connected to the other side of the baffle, and cooling water is filled in the cooling pipe;
the pipe plug is connected with the top end of the decomposition pipe in a matching mode, and the filter pipe penetrates through the pipe plug.
2. The method for assembling a catalytic device with magnetic separation for eliminating hydrogen peroxide according to claim 1, characterized in that it comprises the following steps:
(1) magnetic catalytic material granulation: compressing a magnetic catalytic material of claim 1 into particles having a size greater than 30-60 mesh;
(2) assembling a magnetic separation type catalytic device: connecting the cooling pipe, the baffle, the decomposing pipe and the tile-shaped magnet, and then filling the prepared particles into the decomposing pipe.
3. The use of a magnetic separation catalyst device for eliminating hydrogen peroxide according to claim 1, wherein the magnetic separation catalyst device is used for efficiently eliminating the interference of hydrogen peroxide on COD test.
4. Use of a magnetic separation catalytic unit for the elimination of hydrogen peroxide according to claim 3, characterized in that it comprises in particular the following steps:
(1) adding a water sample to be detected into a decomposition tube at the temperature of 20-25 ℃, and standing for decomposition;
(2) after standing and decomposing, taking out a water sample to be detected through a filter pipe by using a liquid transfer gun;
(3) and (3) measuring the COD value of the water sample to be measured according to a potassium dichromate spectrophotometry.
5. Use of a magnetic separation catalyst device for hydrogen peroxide elimination according to claim 4, characterized in that the decomposition time in step (1) is 0-8 min.
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