CN108607543A - A kind of Magnetic Isolation formula catalytic unit and its application for eliminating hydrogen peroxide - Google Patents
A kind of Magnetic Isolation formula catalytic unit and its application for eliminating hydrogen peroxide Download PDFInfo
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- CN108607543A CN108607543A CN201810317009.3A CN201810317009A CN108607543A CN 108607543 A CN108607543 A CN 108607543A CN 201810317009 A CN201810317009 A CN 201810317009A CN 108607543 A CN108607543 A CN 108607543A
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- hydrogen peroxide
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 53
- 238000002955 isolation Methods 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 19
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 23
- 238000002798 spectrophotometry method Methods 0.000 claims description 12
- 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 11
- 238000012360 testing method Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 5
- 238000012946 outsourcing Methods 0.000 claims description 4
- -1 rare earth ion Chemical class 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 27
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000005307 ferromagnetism Effects 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 6
- 229910004416 SrxMnO3 Inorganic materials 0.000 abstract description 5
- 238000000926 separation method 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 6
- 239000002351 wastewater Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 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
- 230000000295 complement 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 230000005415 magnetization Effects 0.000 description 1
- 230000013011 mating Effects 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
- 238000011017 operating method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 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
- 239000000843 powder Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of magnetic catalysis material La for eliminating hydrogen peroxide1‑xSrxMnO3；It not only has excellent catalytic action, can be used for efficient catalytic degradation hydrogen peroxide, and have excellent ferromagnetism, facilitates the quick separating for carrying out catalyst and product, improve the efficiency of catalytic degradation hydrogen peroxide.Meanwhile a kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide is disclosed, including baffle, decomposition pipe and tile-type magnet；It is by magnetic perovskite oxide La1‑xSrxMnO3(0<X≤0.6) surrounding is dispersed in the decomposition pipe of magnet, so that the water sample to be measured containing residual hydrogen peroxide is uniformly contacted with catalyst, accelerates the decomposition reaction rate of residual hydrogen peroxide in water sample；And the step of fast implementing the separation of water sample and catalyst by magnet, saving catalyst filtration, save time and cost.
Description
Technical field
The invention belongs to environmental monitorings, are related to a kind of accurate determination techniques and dress for measuring waste water treatment index of correlation
It sets, specifically, is related to a kind of Magnetic Isolation formula catalytic unit and its application for eliminating hydrogen peroxide.
Background technology
In the technical field for the treatment of of Organic Wastewater, it is based on H2O2Fenton technologies and Fenton-like technology be extensive use
High-level oxidation technology.Such high-level oxidation technology is characterized in that being based on H2O2For oxidant, in Fe2+/Fe3+And other are non-
Under the catalytic action of phase catalyst, the free radical OH with higher oxygen reduction potential is generated, it can efficient degradation be various has
Machine pollutant is the water technology of a Green Sustainable.In addition, COD (COD) is evaluation Fenton skills
One important parameter index of the treatment effect of art and Fenton-like technology, therefore, the accurate measurement of COD were based on assessment
The treatment effeciency important in inhibiting of the high-level oxidation technology of hydrogen oxide.Potassium bichromate-spectrophotometry is most common at present
A kind of assay method of COD, but hydrogen peroxide remaining in water sample to be measured has certain reproducibility, strong acidic condition descended
For hydrogen oxide by potassium dichromate oxidation, this can cause COD value higher, to interfere the test result of COD, it is difficult to water sample by organic
The degree of object pollution is accurately assessed.Thus it is based on H2O2The water sample of high-level oxidation technology processing must eliminate remaining mistake
The interference that hydrogen oxide tests COD.
Common H2O2Removing method have screening agent method, heat resolve method, deduction method etc., but these removing methods are universal
There are the problems such as complicated for operation, of high cost or eradicating efficacy is undesirable.And catalytic decomposition is to utilize catalyst peroxidating
Hydroperoxide decomposition reaction, the process is simple, quick, easy to operate.But it is usually used in catalytic decomposition in the prior art and eliminates hydrogen peroxide
Catalyst be MnO2, there are the low defects of catalytic activity, and need just to make by filter operation after reaction water sample with
Catalyst detaches, and increases operating cost.
Therefore, a kind of efficient survey for eliminating hydrogen peroxide and quick separating water sample and catalyst is provided based on catalytic decomposition
Try device and method, with realize simplify using catalytic decomposition eliminate water sample in hydrogen peroxide operating procedure, save the time and
The effect of cost is current urgent problem to be solved.
Invention content
In view of this, the present invention provides a kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide and its users
Method, by that will have the magnetic perovskite oxide La of efficient catalytic decomposition activity to hydrogen peroxide1-xSrxMnO3(0<x≤
0.6) it is dispersed in equipped with cooling tube and surrounding is in the decomposition pipe of magnet, make the water sample to be measured containing residual hydrogen peroxide
It is uniformly contacted with catalyst, accelerates the decomposition of residual hydrogen peroxide in water sample；And can be fast implemented by magnet water sample with
The separation of catalyst, can conveniently detach water sample to be measured with catalyst the step of saving catalyst filtration.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of magnetic catalysis material for eliminating hydrogen peroxide, which is characterized in that the magnetism catalysis material is by calcium titanium
Mine type oxide forms, and the structural formula of the perovskite oxide is ABO3；The A cation includes rare earth ion
Or it is one or more in alkaline-earth metal ions；The B cation includes one or more in transition metal ions.
Perovskite oxide disclosed by the invention not only has excellent catalytic action, can be used for efficient catalytic
Degradation hydrogen peroxide, and there is excellent ferromagnetism, facilitate the quick separating for carrying out catalyst and product, improves catalytic degradation
The efficiency of hydrogen peroxide.
Preferably, the perovskite oxide is La1-xSrxMnO3, the x satisfactions 0<x≤0.6；The La1- xSrxMnO3Specific surface area be less than 10mgL-1。
Perovskite oxide La disclosed by the invention1-xSrxMnO3It is answered with excellent ferromagnetism, and as catalyst
Activation energy needed for reaction can be reduced during for hydrogen peroxide degradation, accelerates reaction rate, save time and cost.
Preferably, the La1-xSrxMnO3Presoma is first prepared using sol-gal process in preparation process, then in 900 DEG C of height
It calcines and is made in the Muffle furnace of temperature.
The La that the present invention uses1-xSrxMnO3Catalyst preparation process is simple, efficient, and preparation process yield is high.
It is a kind of for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide, which is characterized in that including baffle, decompose pipe and
Tile-type magnet；The baffle interior is equipped with magnet, and the side of the baffle is connected to the bottom end for decomposing pipe；The decomposition
A kind of magnetic catalysis material for eliminating hydrogen peroxide of filling, the decomposition pipe outsourcing are equipped with the tile-type magnet inside pipe.
Magnetic Isolation formula catalytic unit disclosed by the invention is by magnetic perovskite oxide La1-xSrxMnO3(0<x≤0.6)
Surrounding is dispersed in the decomposition pipe of tile-type magnet, keeps the water sample to be measured containing residual hydrogen peroxide and catalyst uniform
The decomposition reaction rate of residual hydrogen peroxide in water sample is accelerated in contact；And it can be quick by tile-type magnet and baffle internal magnet
It realizes the separation of water sample and catalyst, the step of saving catalyst filtration, saves time and cost.
Preferably, further include cooling tube, the bottom end of the cooling tube is enclosed construction, and the top of the cooling tube is connected to
The other side of the baffle, the cooling tube is interior to be equipped with cooling water.
It can be cooled down, prevented in hydrogen peroxide decomposable process, due to exothermic reaction to decomposing pipe by cooling tube
It generates a large amount of heat and causes danger.
Preferably, further include pipe close and screen pipe, the top mating connection of the pipe close and the decomposition pipe, the filtering
Pipe is arranged in the pipe close.
Preferably, the screen pipe is centrifugal filtration tube.
Can be convenient to use liquid-transfering gun by pipe close and screen pipe will decompose the survey water sample taking-up of the band in pipe, avoid using
During liquid-transfering gun takes out water sample, solid catalyst surveys water sample with band and enters liquid-transfering gun, to avoid damage to the instrument used.
A kind of assemble method for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide, which is characterized in that specific packet
Include following steps：
(1) magnetic catalysis material is granulated：A kind of magnetic catalysis material is pressed into the particle that grain size is more than 30-60 mesh；
(2) Magnetic Isolation formula catalytic unit assembles：Cooling tube, baffle, decomposition pipe are connected with each component of tile-type magnet, so
The above-mentioned particle being prepared is packed into afterwards and decomposes pipe.
A kind of assemble method for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide disclosed by the invention is simple, fast
Speed can assemble as needed, and obtained device can conveniently be applied to eliminate the hydrogen peroxide in detection water sample.
Preferably, magnetic catalysis material is placed in compression mold in the step (1), is pushed in 15-25M uniaxial pressures
2min is in blocks, and then this piece is placed in the sieve of 30-60 mesh and grinds granulation, will be left in the powder collection in sieve.
A kind of application for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide, which is characterized in that described magnetic point
The interference that COD is tested for efficiently eliminating hydrogen peroxide from formula catalytic unit.
Preferably, specifically comprise the following steps：
(a) it under the conditions of 20-25 DEG C, takes water sample to be measured to be added and decomposes in pipe, stand and decompose；
(b) after standing and decomposing, water sample to be measured is taken out by screen pipe using liquid-transfering gun；
(c) water sample to be measured is measured into its COD value according to potassium bichromate spectrophotometry.
Preferably, the time decomposed in the step (a) is 0-8min.
A kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide disclosed by the invention can be conveniently applied to
The hydrogen peroxide in water sample to be measured is eliminated, COD value is accurately measured from potassium bichromate spectrophotometry can be utilized.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of for disappearing
Except the magnetic catalysis material of hydrogen peroxide, not only there is excellent catalytic action, can be used for efficient catalytic degradation peroxidating
Hydrogen, and there is excellent ferromagnetism, facilitate the quick separating for carrying out catalyst and product, improves catalytic degradation hydrogen peroxide
Efficiency.In addition, the invention discloses a kind of Magnetic Isolation formula catalytic units for eliminating hydrogen peroxide, by magnetic perovskite
Oxide La1-xSrxMnO3(0<X≤0.6) surrounding is dispersed among the decomposition pipe of tile-type magnet, make containing remaining mistake
The water sample to be measured of hydrogen oxide uniformly, can be contacted adequately with catalyst, accelerate the decomposition rate of residual hydrogen peroxide in water sample,
It improves and eliminates efficiency；And by the way that detaching for water sample and catalyst can be fast implemented by tile-type magnet and baffle internal magnet,
The step of saving catalyst filtration saves time and cost.Also, Magnetic Isolation formula catalytic unit is applied to weight chromium by the present invention
The COD value of sour potassium water by Spectrophotometry sample can eliminate the influence of remaining hydrogen peroxide in water sample, improve and measure
Accuracy.
Description of the drawings
Fig. 1 attached drawings are the X-ray diffractogram of magnetic catalysis material disclosed in embodiment 1；
Fig. 2 attached drawings are magnetic catalysis material La0.4Sr0.6MnO3Hysteresis loop and electron microscope；
Fig. 3 attached drawings are a kind of structure for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide disclosed in embodiment 2
Schematic diagram；
Fig. 4 attached drawings are a kind of section for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide disclosed in embodiment 2
Figure；
Fig. 5 attached drawings are the relational graph using the embodiment 4-6 COD values and resolving time measured；
Fig. 6 attached drawings are a kind of cycle for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide disclosed in embodiment 2
The relational graph of the decomposition efficiency of access times and hydrogen peroxide.
Fig. 7 attached drawings are magnetic catalysis material La0.4Sr0.6MnO3Recycle front and back X-ray diffractogram；
In figure：1 is cooling tube, and 2 be baffle, and 3 is decompose pipe, and 4 be shoe magnet plate, and 5 be pipe close, and 6 be screen pipe.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
The embodiment of the present invention 1 disclose it is a kind of for eliminating the magnetic catalysis material of hydrogen peroxide, magnetic catalysis material by
Perovskite oxide forms, and the structural formula of perovskite oxide is ABO3；A cations include rare earth ion or alkali
It is one or more in earthmetal cations；B cations include one or more in transition metal ions.
For further optimisation technique scheme, perovskite oxide is La1-xSrxMnO3, x satisfactions 0<x≤0.6；
La1-xSrxMnO3Specific surface area be less than 10mg L-1。
For further optimisation technique scheme, La1-xSrxMnO3First sol-gal process is used to prepare forerunner in preparation process
Body, then calcine and be made in the Muffle furnace of 900 DEG C of high temperature.
For further optimisation technique scheme, a kind of magnetic catalysis material for eliminating hydrogen peroxide includes
La0.4Sr0.6MnO3、La0.5Sr0.5MnO3、La0.6Sr0.4MnO3、La0.7Sr0.3MnO3、La0.8Sr0.2MnO3Or La0.9Sr0.1MnO3。
For further optimisation technique scheme, a kind of magnetic catalysis material for eliminating hydrogen peroxide includes
La0.4Sr0.6MnO3。
Performance detection
(1) to magnetic catalysis material La disclosed above0.4Sr0.6MnO3、La0.5Sr0.5MnO3、La0.6Sr0.4MnO3、
La0.7Sr0.3MnO3、La0.8Sr0.2MnO3And La0.9Sr0.1MnO3X-ray diffraction detection is carried out, the results are shown in Figure 1, from all
The characteristic diffraction peak of magnetic catalysis material can be seen that La0.4Sr0.6MnO3、La0.5Sr0.5MnO3、La0.6Sr0.4MnO3、
La0.7Sr0.3MnO3、La0.8Sr0.2MnO3And La0.9Sr0.1MnO3It is respectively formed Perovskite Phase structure.
(2) to magnetic catalysis material La0.4Sr0.6MnO3Hysteresis loop and electron microscope detection are carried out, the results are shown in Figure 2.
It can be seen that from hysteresis loop figure, La0.4Sr0.6MnO3With mild ferromagnetism, under a complementary field, easy and aqueous solution
Separation, its saturation magnetization and coercivity is respectively 2.26emu/g and 56.0Oe；From electron microscope, it is apparent that
La0.4Sr0.6MnO3Particle diameter belong to nano material, and not special pattern between 100-300nm.
(3) magnetic catalysis material La is compared0.4Sr0.6MnO3With traditional catalyst MnO2To the decomposition efficiency of hydrogen peroxide.
Deionized water and hydrogen peroxide are prepared into the water sample to be measured that hydrogen peroxide volume fraction is 1%, take water to be measured every time
Sample 6mL respectively with 0.25g magnetism catalysis materials La0.4Sr0.6MnO3With traditional catalyst MnO2Mixing is stood, by the mistake in water sample
It is decomposed and is removed by catalysis method in hydrogen oxide, and water sampling measures its COD value under the different resolving times, and data result is returned
Always in the following table 1.
Table 1
By with traditional catalyst MnO2Catalytic activity comparison, La0.4Sr0.6MnO3It is right under the resolving time of 5min
The catalytic decomposition efficiency of hydrogen peroxide reaches 90.4%, illustrates La0.4Sr0.6MnO3Have to the decomposition of hydrogen peroxide more efficient
Catalytic activity.And La0.4Sr0.6MnO3With ferromagnetism, quickly water sample can be made to be detached with catalyst by magnet, taken out to be measured
Water sample is tested, so that eliminates the catalytic decomposition process more convenient and efficient of hydrogen peroxide.
Embodiment 2
The embodiment of the invention also discloses a kind of Magnetic Isolation formula catalytic units for eliminating hydrogen peroxide, including gear
Plate decomposes pipe and tile-type magnet；Baffle interior is equipped with magnet, and the side of baffle is connected to the bottom end for decomposing pipe；It decomposes in pipe
A kind of magnetic catalysis material for eliminating hydrogen peroxide is filled in portion, is decomposed pipe outsourcing and is equipped with tile-type magnet.
Further include cooling tube, the bottom end of cooling tube is enclosed construction, cooling tube for further optimisation technique scheme
Top is connected to the other side of baffle, and cooling water is housed in cooling tube.
Further include pipe close and screen pipe for further optimisation technique scheme, pipe close connects with the top cooperation for decomposing pipe
It connects, screen pipe is arranged in pipe close.
As shown in Figure 3-4, a kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide, including cooling tube 1, baffle
2, pipe 3, tile-type magnet 4, pipe close 5 and screen pipe 6 are decomposed；Cooling water is housed, the bottom end of cooling tube 1 is that closing is tied in cooling tube 1
Structure；The inside of baffle 2 is equipped with magnet, and the side of baffle 2 is connected to the top of cooling tube 1, and the other side of baffle 2 is connected to point
Solve 3 bottom end of pipe；Decompose magnetic catalysis material La disclosed in 3 inside filling embodiment 1 of pipe0.4Sr0.6MnO3, decompose 3 outsourcing of pipe
Equipped with tile-type magnet 4；Pipe close 5 is connected with the top for decomposing pipe 6；Screen pipe 6 is arranged in pipe close 5, one end band of screen pipe 6
There is uniform filter opening.
Embodiment 3
The embodiment of the invention also discloses a kind of assembling sides for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide
Method specifically comprises the following steps：
(1) magnetic catalysis material is granulated：Magnetic catalysis material in embodiment 1 is placed in compression mold, in 15-25M
Uniaxial pressure pushing 2min is in blocks, and then this piece is placed in the sieve of 30-60 mesh and grinds granulation, will be left in the particle in sieve
It collects, is pressed into the particle that grain size is more than 30-60 mesh；
(2) Magnetic Isolation formula catalytic unit assembles：To first be packed into cooling water inside cooling tube, then by cooling tube top with it is interior
Portion is equipped with the baffle side connection of magnet, then connects the other side for decomposing tube bottom end and baffle, finally by tile-type magnet
It is bonded in and decomposes on the outside of pipe；Then the above-mentioned particle being prepared is packed into and decomposes pipe；
(3) after the completion of to be decomposed, the pipe close for being equipped with screen pipe is installed on to the top for decomposing pipe so that screen pipe carries
One end of filter opening, which is stretched into, decomposes inside pipe.
Embodiment 4
A kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide tests COD for efficiently eliminating hydrogen peroxide
Interference, specifically comprise the following steps：
(a) it under the conditions of 25 DEG C, takes water sample to be measured to be added and decomposes in pipe, stand and decompose 3min；
(b) after standing and decomposing, water sample to be measured is taken out by screen pipe using liquid-transfering gun；
(c) water sample to be measured is measured into its COD value according to potassium bichromate spectrophotometry.
Embodiment 5
A kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide tests COD for efficiently eliminating hydrogen peroxide
Interference, specifically comprise the following steps：
(a) it under the conditions of 23 DEG C, takes water sample to be measured to be added and decomposes in pipe, stand and decompose 5min；
(b) after standing and decomposing, water sample to be measured is taken out by screen pipe using liquid-transfering gun；
(c) water sample to be measured is measured into its COD value according to potassium bichromate spectrophotometry.
Embodiment 6
A kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide tests COD for efficiently eliminating hydrogen peroxide
Interference, specifically comprise the following steps：
(a) it under the conditions of 20 DEG C, takes water sample to be measured to be added and decomposes in pipe, stand and decompose 8min；
(b) after standing and decomposing, water sample to be measured is taken out by screen pipe using liquid-transfering gun；
(c) water sample to be measured is measured into its COD value according to potassium bichromate spectrophotometry.
As a result it detects
One, in deionized water hydrogen peroxide removal
(1) a certain amount of deionized water is taken, the COD value of deionized water is first measured according to potassium bichromate spectrophotometry, as
Initial value；The water sample to be measured that hydrogen peroxide volume fraction is 1% is prepared with above-mentioned deionized water and hydrogen peroxide again, according to weight chromium
Sour potassium spectrophotometry measures its COD value, as blank control group；Again by the water sample to be measured of preparation respectively according to embodiment 4-6
Method measure its COD value, as a result as shown in table 2 below, according to the above results draw measure COD value and resolving time relationship
Figure, as shown in Figure 5.
Table 2
| Initial value | Blank control group | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| COD(mgL-1) | 0 | 989.2 | 185.7 | 50.6 | 8.4 |
It can be learnt by above-mentioned testing result：The COD value measured by embodiment 6 is closest with initial value, illustrates reality
It is best for the removal effect of hydrogen peroxide in deionized water to apply example 6.
(2) a certain amount of water sample to be measured as described above is taken to be divided into three parts, according to method as described in Example 6 identical
The disclosed Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide of embodiment 2 in, cycle measures peroxidating respectively three times
The removal rate of hydrogen, the results are shown in Figure 6.
Wherein the removal rate of hydrogen peroxide calculates as follows：
The COD value increased after the COD value of reduction/addition hydrogen peroxide after the removal rate of hydrogen peroxide=elimination hydrogen peroxide
× 100%.
By Fig. 6, it is apparent that the present invention utilizes the disclosed Magnetic Isolation for eliminating hydrogen peroxide of embodiment 2
Formula catalytic unit, recycles three times that it is for the catalytic decomposition similar efficiency of hydrogen peroxide in deionized water, and removal rate is equal
98.5% or more.
(3) the magnetic catalysis material La in above-mentioned Magnetic Isolation formula catalytic unit is taken0.4Sr0.6MnO3, recycle three times
Front and back to carry out X-ray diffraction respectively, the results are shown in Figure 7.By the structure in Fig. 7, it is apparent that magnetic catalysis material
La0.4Sr0.6MnO3After being recycled for a kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide, chemical nature
It is constant.
Two, in true waste water hydrogen peroxide removal
(1) take it is a certain amount of come from Liaoning Province Benxi region two-stage sanitary sewage, first according to potassium bichromate spectrophotometry
Measure its COD value, as initial value；It is 1% to be configured to hydrogen peroxide volume fraction again with above-mentioned sewage and hydrogen peroxide
Water sample to be measured measures its COD value, as blank control group according to potassium bichromate spectrophotometry；10mL is taken to prepare again to be measured
Water sample measures its COD value according to the method for embodiment 4-6 respectively, as a result as shown in table 3 below, measurement is drawn according to the above results
The relational graph of COD value and resolving time, as shown in Figure 5.
Table 3
| Initial value | Blank control group | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| COD(mgL-1) | 133.5 | 1155 | 362 | 236.4 | 127.4 |
It can be learnt by above-mentioned testing result：The COD value measured by embodiment 6 is closest with initial value, illustrates reality
It is best for the removal effect of hydrogen peroxide in waste water to apply example 6.
(2) a certain amount of water sample to be measured as described above is taken to be divided into three parts, according to method as described in Example 6 identical
The disclosed Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide of embodiment 2 in, tested, measured respectively three times
The removal rate of hydrogen oxide, the results are shown in Figure 6.
Wherein the removal rate of hydrogen peroxide calculates as follows：
The COD value increased after the COD value of reduction/addition hydrogen peroxide after the removal rate of hydrogen peroxide=elimination hydrogen peroxide
× 100%.
By Fig. 6, it is apparent that the present invention utilizes the disclosed Magnetic Isolation for eliminating hydrogen peroxide of embodiment 2
Formula catalytic unit, recycles three times that it is for the catalytic decomposition similar efficiency of hydrogen peroxide in waste water, and removal rate exists
99% or more.
Three, in Fenton processed waste waters residual hydrogen dioxide removal
Prepare 30mg L-1Phenolic waste water, sampling and testing its initial COD value is 423.6mg L-1；Fenton catalytic conditions
For 0.1g L-1Fe3O4, pH=3, [H2O2]0=10mM, reaction time 60min are sampled every 20min, and use the present invention
Magnetic Isolation formula Catalytic Decomposition of Hydrogen Peroxide device, and according to embodiment 6 in water sample to be measured hydrogen peroxide eliminate, carry out
The test of COD, data result are as shown in table 4 below.
Table 4
| Sample time | 0min | 20min | 40min |
| It decomposes pipe and eliminates H2O2(COD/mg L-1) | 423.6 | 315.5 | 260.4 |
| H is not eliminated2O2(COD/mg L-1) | 1672.1 | 1252.3 | 1041.7 |
By in above table statistics indicate that Magnetic Isolation formula Catalytic Decomposition of Hydrogen Peroxide pipe of the invention can be efficient
Hydrogen peroxide remaining in water sample is eliminated, for accurately estimating that the efficiency of Fenton processing has great economic and practical value.
Each embodiment is described by the way of progressive in this specification, the highlights of each of the examples are with other
The difference of embodiment, just to refer each other for identical similar portion between each embodiment.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so description is fairly simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest range caused.
Claims (10)
1. a kind of magnetic catalysis material for eliminating hydrogen peroxide, which is characterized in that the magnetism catalysis material is by perovskite
Type oxide forms, and the structural formula of the perovskite oxide is ABO3；It is described A cation include rare earth ion or
It is one or more in alkaline-earth metal ions；The B cation includes one or more in transition metal ions.
2. a kind of magnetic catalysis material for eliminating hydrogen peroxide according to claim 1, which is characterized in that the calcium
Titanium ore type oxide is La1-xSrxMnO3, the x satisfactions 0<x≤0.6.
3. a kind of magnetic catalysis material for eliminating hydrogen peroxide according to claim 2, which is characterized in that described
La1-xSrxMnO3Specific surface area be less than 10mg L-1。
4. a kind of for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide, which is characterized in that including baffle, decompose pipe and watt
Type magnet；The baffle interior is equipped with magnet, and the side of the baffle is connected to the bottom end for decomposing pipe；The decomposition pipe
A kind of magnetic catalysis material for eliminate hydrogen peroxide of the inside filling as described in claim 1-3 any one, described point
It solves pipe outsourcing and is equipped with the tile-type magnet.
5. a kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide according to claim 4, which is characterized in that
Further include cooling tube, the bottom end of the cooling tube is enclosed construction, and the top of the cooling tube is connected to the another of the baffle
Side, the cooling tube is interior to be equipped with cooling water.
6. a kind of Magnetic Isolation formula catalytic unit for eliminating hydrogen peroxide according to claim 4 or 5, feature exist
In further including pipe close and screen pipe, the pipe close is connected with the top for decomposing pipe, and the screen pipe is arranged in described
Pipe close.
7. a kind of group for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide as described in claim 4-6 any one
Dress method, which is characterized in that specifically comprise the following steps：
(1) magnetic catalysis material is granulated：A kind of magnetic catalysis material as described in claim 1-3 any one is suppressed into granulating
Diameter is more than the particle of 30-60 mesh；
(2) Magnetic Isolation formula catalytic unit assembles：Cooling tube, baffle, decomposition pipe are connected with each component of tile-type magnet, then will
The above-mentioned particle being prepared, which is packed into, decomposes pipe.
8. a kind of for eliminating answering for the Magnetic Isolation formula catalytic unit of hydrogen peroxide as described in claim 4-6 any one
With, which is characterized in that the interference that the Magnetic Isolation formula catalytic unit tests COD for efficiently eliminating hydrogen peroxide.
9. a kind of application for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide according to claim 8, special
Sign is, specifically comprises the following steps：
(1) it under the conditions of 20-25 DEG C, takes water sample to be measured to be added and decomposes in pipe, stand and decompose；
(2) after standing and decomposing, water sample to be measured is taken out by screen pipe using liquid-transfering gun；
(3) water sample to be measured is measured into its COD value according to potassium bichromate spectrophotometry.
10. a kind of application for eliminating the Magnetic Isolation formula catalytic unit of hydrogen peroxide according to claim 9, special
Sign is that the time decomposed in the step (1) is 0-8min.
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