CN117897226A - Cerium-manganese composite oxide catalyst and preparation method thereof - Google Patents
Cerium-manganese composite oxide catalyst and preparation method thereof Download PDFInfo
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- CN117897226A CN117897226A CN202180099251.8A CN202180099251A CN117897226A CN 117897226 A CN117897226 A CN 117897226A CN 202180099251 A CN202180099251 A CN 202180099251A CN 117897226 A CN117897226 A CN 117897226A
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- YOSLGHBNHHKHST-UHFFFAOYSA-N cerium manganese Chemical compound [Mn].[Mn].[Mn].[Mn].[Mn].[Ce] YOSLGHBNHHKHST-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 6
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 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 description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 40
- 230000000694 effects Effects 0.000 abstract description 27
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/66—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Disclosed herein are cerium manganese composite oxide catalysts and methods of preparing the same. In embodiments disclose a cerium manganese composite oxide catalyst CeMn 10 O x Wherein Ce is present in valence III or valence IV and Mn is present in valence III or valence IV, comprising: mixing a divalent manganese source, a trivalent cerium source, potassium permanganate and water under the condition of pH 4-5, and adding the mixture into a reactor to obtain a mixture; heating the reactor to 90-110 ℃ through circulation heating of heat conduction oil, and stirring the mixture to obtain a cerium-manganese composite oxide catalyst precursor; and adding water into the cerium-manganese composite oxide catalyst precursor for water washing, standing, removing supernatant, and drying to obtain the cerium-manganese composite oxide catalyst. The preparation method realizes the industrial-grade preparation of the cerium-manganese composite oxide catalyst, and the synthesized catalyst showsExcellent ozone catalytic decomposition activity is obtained.
Description
The invention relates to a cerium-manganese composite oxide catalyst and a preparation method thereof.
Ozone (O) 3 ) Is an unstable gas with an undesirable odor (sometimes referred to as "fishy smell") that has an adverse effect on the environment. In the stratosphere, ozone is capable of withstanding direct irradiation of the earth with Ultraviolet (UV) rays, which is beneficial to the environment, whereas at the earth's surface ("working environment" or "living environment"), ozone is a great hazard, and can have varying degrees of impact on humans and other organisms, including adverse effects on the human skin and adverse effects on the immune and nervous systems. It is therefore desirable to reduce ozone levels in our working environment for a number of reasons.
The World Health Organization (WHO) prescribes that the concentration of ozone in the working environment for 8 hours of continuous operation should not exceed 0.1ppm (4X 10) -9 mol/L). In recent years, ozone is widely applied to industries such as medical and health, food preservation, water treatment and the like due to its strong oxidation property. Ozone, however, can easily cause residues during use due to its long half-life, and it can be discharged directly into the atmosphere, which will seriously affect our living environment. Meanwhile, in our living area, the printer can generate ozone during work and high-voltage discharge, and the ozone can have adverse effects on human health. There is therefore an urgent need to treat the ozone discharged so as to make it harmless to the human body and our living and working environment.
The current method for treating ozone mainly comprises the following steps: thermal decomposition method, active carbon method, pre-ozonation method, dilution method, electromagnetic wave radiation decomposition method, liquid medicine absorption method and catalysis method. The catalytic decomposition of ozone has the advantages of safety, high efficiency, environmental protection and the like, and becomes a key point of research. The catalysts for treating ozone at present can be mainly classified into manganese-containing catalysts, transition metal-containing catalysts and noble metal catalysts.
CN 107519861A discloses a cerium manganese composite oxide catalyst having the following chemical composition: ceMn (CeMn) a O x The valence of Mn is mainly +4, where a is selected from natural numbers between 10 and 25. CN 107519861A further discloses a preparation method of the cerium-manganese composite oxide catalyst, which comprises adding ammonium sulfate into a solution containing a cerium source and a divalent manganese source, and then sequentially performing hydrothermal reaction and heating processes, thereby obtaining the cerium-manganese composite oxide catalyst. However, the preparation method is only stopped at a laboratory preparation stage, and the cerium-manganese composite oxide catalyst CeMn obtained by the method 10 O x Only 79% ozone decomposition efficiency at 70% relative humidity.
The existing catalyst still has the unexpected events of low yield, incapability of realizing industrialized preparation, low ozone catalytic decomposition activity and the like.
Disclosure of Invention
In the embodiments herein, a method is described, and in the embodiments, an industrial-scale preparation method of a cerium-manganese composite oxide catalyst is described, so as to solve the problems that the yield of a catalyst for decomposing ozone is low, industrial preparation cannot be realized, and/or catalytic decomposition activity of ozone is low in the known method.
In one aspect, provided herein is a method, in embodiments, an industrial-scale method of preparing a cerium manganese composite oxide catalyst having the following chemical composition: ceMn (CeMn) 10 O x Wherein Ce exists in III or IV and Mn exists in III or IV, and the industrial-grade preparation method of the cerium-manganese composite oxide catalyst comprises the following steps: mixing a divalent manganese source, a trivalent cerium source, potassium permanganate and water under the condition of pH 4-5, and adding the mixture into a reactor to obtain a mixture; heating the reactor to 90-110deg.C by circulating heat transfer oil while stirring the mixtureA compound to obtain a cerium-manganese composite oxide catalyst precursor; and adding water into the cerium-manganese composite oxide catalyst precursor for water washing, standing, removing supernatant, and drying to obtain the cerium-manganese composite oxide catalyst.
Further, the molar ratio of the divalent manganese source, the trivalent cerium source, and potassium permanganate is 1:0.13:0.31.
further, the conduction oil circulation heating is external conduction oil circulation heating.
Further, the duration of the cyclic heating of the conduction oil is 12-24 hours.
Further, the cerium-manganese composite oxide catalyst precursor is washed with water to a pH of 6 to 7.
Further, the trivalent cerium source is selected from any one or a mixture of at least two of cerium (III) acetate, cerium (III) nitrate, cerium (III) chloride, and cerium (III) sulfate.
Further, the divalent manganese source is selected from any one or a mixture of at least two of manganese (II) acetate, manganese (II) sulfate, manganese (II) chloride, and manganese (II) nitrate.
Further, the stirring speed of the mixture is 200-300rpm.
Further, the reactor is heated to 100 ℃ for 10-15 hours, or about 12 hours.
In addition, the invention also discloses a cerium-manganese composite oxide catalyst prepared by the preparation method.
By adopting the technical scheme, after components (a divalent manganese source, a trivalent cerium source, potassium permanganate and water) required by catalyst synthesis are added into a large-capacity reactor, the reactor is circularly heated at the temperature of 90-110 ℃ and stirred at the same time, so that the mixture in the reactor can keep stable temperature distribution (90-110 ℃) and stable heat transfer, the temperature of reactants at all positions in the reactor can be kept in a stable state, the reactants in the reactor can be stably converted, and the cerium-manganese composite oxide catalyst CeMn can be realized with remarkably high yield 10 O x Is suitable for industrial production. To cerium-manganese composite oxide catalystThe cerium-manganese composite oxide catalyst can be industrially prepared by adding water into the catalyst precursor for water washing, standing and precipitating, and removing supernatant, and treating the cerium-manganese composite oxide catalyst precursor by the simplified and easy-to-operate precipitation method.
By the preparation method described herein, up to 5000 times improvement in catalyst yield from laboratory research to industrial-scale preparation can be achieved, in embodiments, yield of industrial-scale preparation of cerium manganese composite oxide catalyst can be achieved; and the synthetic cerium manganese composite oxide catalyst CeMn described herein 10 O x Shows excellent ozone catalytic decomposition activity. The cerium manganese composite oxide catalyst shows a high ozone catalytic decomposition activity even in a low temperature of about-5 ℃ or a high humidity environment of about 90%.
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
The existing ozonolysis catalyst has the adverse events of low yield, incapability of realizing industrial preparation, low ozone catalytic decomposition activity and the like. In order to solve the technical problems, the application provides an industrial-grade preparation method of a cerium-manganese composite oxide catalyst, wherein the cerium-manganese composite oxide catalyst has the following chemical composition: ceMn (CeMn) 10 O x Wherein Ce is present in valence III or valence IV and Mn is present in valence III or valence IV, the methods described herein, in embodiments, the industrial-scale preparation of the cerium manganese composite oxide catalyst, comprise: mixing a divalent manganese source, a trivalent cerium source, potassium permanganate and water under the condition of pH 4-5, and adding the mixture into a reactor to obtain a mixture; heating the reactor to a temperature of 90-110 ℃ through circulation heating of heat conduction oil, and stirring the mixture to obtain a cerium-manganese composite oxide catalyst precursor; adding water into the cerium-manganese composite oxide catalyst precursor for water washing. The method further comprises standing, removing supernatant, and drying to obtain the cerium-manganese composite oxide catalyst.
In the preparation method, after components (a divalent manganese source, a trivalent cerium source, potassium permanganate and water) required for catalyst synthesis are added into a large-capacity reactor, the reactor is circularly heated by heat conduction oil and stirred at the same time, so that the mixture in the reactor can keep stable temperature distribution (90-110 ℃) and stable heat transfer, the temperature of reactants at all positions in the reactor can be kept in a stable state, the reactants in the reactor can be stably converted, and the cerium-manganese composite oxide catalyst CeMn is improved 10 O x Is an industrial yield of (a). The cerium-manganese composite oxide catalyst precursor is treated by the precipitation method by adding water into the cerium-manganese composite oxide catalyst precursor for water washing, standing and precipitating, and removing supernatant, so that the industrial-grade preparation of the cerium-manganese composite oxide catalyst can be realized.
The preparation method can realize the cerium-manganese composite oxide catalyst CeMn 10 O x Up to 5000 times the yield increase from laboratory studies to industrial-scale preparation, whereby the yield of industrial-scale preparation of cerium-manganese composite oxide catalysts can be achieved.
Cerium manganese composite oxide catalyst CeMn obtained by the preparation method 10 O x Shows excellent ozone catalytic decomposition activity, and furthermore, shows higher ozone catalytic decomposition activity even in a low temperature of about-5 ℃ or a high humidity environment of about 90%.
In some embodiments of the present application, the molar ratio of the divalent manganese source, the trivalent cerium source, and the potassium permanganate is 1:0.13:0.31. the molar ratio of the divalent manganese source, the trivalent cerium source and the potassium permanganate in the range can be used for controlling the atomic ratio of Ce to Mn in the obtained cerium-manganese composite oxide catalyst and improving the CeMn of the cerium-manganese composite oxide catalyst 10 O x Ensures consistency of composition and catalytic activity of the obtained catalyst, reduces the generation of byproducts, and further improves the CeMn of the cerium-manganese composite oxide catalyst 10 O x Ozone catalytic decomposition activity of (a).
In some embodiments of the present application, the conduction oil hydronic heating is external conduction oil hydronic heating and/or internal conduction oil hydronic heating. Compared with other heating modes such as heating wires, the temperature distribution of the mixture in the reactor can be more uniform by using the circulation heating of external and/or internal heat conduction oil and the stirring operation in the reactor, the heat transfer is more stable, and the local overheating and supercooling are prevented, so that the consistency of reaction products is ensured, the occurrence of side reactions is reduced, and the cerium-manganese composite oxide catalyst CeMn described in the specification is further improved 10 O x And ozone catalytic decomposition activity.
In an embodiment, the heating means uses external conduction oil circulation heating. The use of the external heat conduction oil circulation heating can avoid the occupation of the space of the pipeline which internally holds the heat conduction oil in the reactor, thereby further improving the utilization space of the reactor, increasing the capacity of reactants in the reactor and further improving the yield of the cerium-manganese composite oxide catalyst.
In an embodiment, the temperature at which the heat transfer oil is circulated and heated is about 90 to 110 ℃, for example, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, and the heating temperature is controlled within a range of ±2 ℃. The circulating heating temperature of the conduction oil lower than the lower limit value of the range can slow down the reaction rate, and is unfavorable for the industrialized mass production of the cerium-manganese composite oxide catalyst. The circulating heating temperature of the heat conduction oil higher than the upper limit value of the range can lead to energy waste, obviously increase side reaction and influence the obtained cerium-manganese composite oxide catalyst CeMn 10 O x Ozone catalytic decomposition activity of (a).
In some embodiments of the present application, the conduction oil cycle heating is for a duration of about 12-24h, e.g., 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h. The duration of the cyclic heating of the heat conducting oil is within the range, which is favorable for further improving the CeMn of the cerium-manganese composite oxide catalyst 10 O x And ozone catalytic decomposition activity. Duration below the lower limit of the above range can reduce the cerium-manganese composite oxide catalyst CeMn 10 O x Yield and productivity of (2). The duration time higher than the upper limit value of the range can lead to energy waste, is unfavorable for the energy saving requirement of industrial mass production, obviously increases side reaction and reduces the obtained cerium-manganese composite oxide catalyst CeMn 10 O x Yield and productivity of (2).
In some embodiments of the present application, the cerium manganese complex oxide catalyst precursor is washed with water to a pH of 6-7, e.g., 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9. The cerium-manganese composite oxide catalyst CeMn described herein can be further improved by maintaining the pH of the cerium-manganese composite oxide catalyst precursor within the above-described range 10 O x Ozone catalytic decomposition activity of (a).
In some embodiments of the present application, the trivalent cerium source includes, but is not limited to, any one of cerium (III) acetate, cerium (III) nitrate, cerium (III) chloride, and cerium (III) sulfate, or a mixture of at least two thereof. The use of several trivalent cerium sources as described above facilitates further enhancement of the cerium-manganese composite oxide catalyst CeMn described herein compared to other cerium sources 10 O x And ozone catalytic decomposition activity.
In some embodiments of the present application, the divalent manganese source includes, but is not limited to, any one or a mixture of at least two of manganese (II) acetate, manganese (II) sulfate, manganese (II) chloride, and manganese (II) nitrate. The use of several divalent manganese sources as described above is advantageous for further enhancing the cerium-manganese composite oxide catalyst CeMn described herein compared to other manganese sources 10 O x And ozone catalytic decomposition activity.
In some embodiments of the present application, the stirring speed of the mixture is 200-300rpm, e.g., 210rpm, 220rpm, 230rpm, 240rpm, 250rpm, 260rpm, 270rpm, 280rpm, 290rpm, which is controlled within a range of + -5 rpm. The stirring speed within the above range can further increase the reactants in the reactorTemperature uniformity, heat transfer stability and reaction uniformity, so that the reaction is continuously and stably carried out, and side reactions are reduced, thereby further improving the CeMn of the cerium-manganese composite oxide catalyst 10 O x And ozone catalytic decomposition activity.
In some embodiments of the present application, the reactor is heated to about 100 ℃ for 10-15 hours, or about 12 hours, by conduction oil recycle heating. The cerium-manganese composite oxide catalyst CeMn can be further improved by adopting the heating temperature and the heating duration 10 O x Industrial production and ozone catalytic decomposition activity.
In some embodiments of the present application, a cerium manganese composite oxide catalyst is provided, which is prepared by the industrial-scale preparation method of the cerium manganese composite oxide catalyst herein. The cerium manganese composite oxide catalyst prepared by the industrial-grade preparation method of the cerium manganese composite oxide catalyst described in the embodiments herein shows excellent ozone catalytic decomposition activity and higher ozone catalytic decomposition activity even in a low temperature of-5 ℃ or a high humidity environment of 90%.
In the applications herein, the near surface is referred to as a "work environment" or "living environment".
In the present application, the term "low temperature" means a temperature below 20 ℃, such as below 15 ℃, below 10 ℃, below 5 ℃ or below 0 ℃, or even up to-5 ℃.
In the present application, the term "high humidity" means a humidity of 40% or more, for example 45% or more, 60% or more, 70% or more, 80% or more, or 90% or more.
In the applications herein, the "ozone catalytic decomposition activity" is characterized by ozone conversion and is calculated from the following equation:
O 3 conversion= (C in -C out )/C in ×100％
Wherein C is in And C out The measured inlet and outlet concentrations of ozone are shown, respectively.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
An industrial-grade preparation method of a cerium-manganese composite oxide catalyst, wherein the cerium-manganese composite oxide catalyst has the following chemical composition: ceMn (CeMn) 10 O x The industrial-grade preparation method of the cerium-manganese composite oxide catalyst comprises the following steps:
(1) 18.34kg of manganese acetate tetrahydrate (74.86 mol) and 100L of deionized water are added into a hydrothermal reaction kettle with the volume of 600L, fully stirred until the manganese acetate tetrahydrate is fully dissolved, 3.115kg of cerium acetate (9.83 mol) is added, fully stirred until the cerium acetate is fully dissolved, and 12.5L of acetic acid is added to regulate the pH to 4-5;
(2) Adding 100L of potassium permanganate aqueous solution with the concentration of 3.61kg/L (namely 22.85 mol) into a reaction kettle, stirring to be uniform, carrying out external heat conduction oil circulation heating on the reactor at the temperature of about 110 ℃ for 12 hours, and stirring at about 300rpm while heating;
(3) Cooling to room temperature, adding 2500L deionized water into a reactor, washing until the pH of the mixed solution is about 7, standing and precipitating for 10h, removing supernatant, and drying at 100deg.C for 12h to obtain cerium-manganese composite oxide catalyst CeMn for decomposing ozone at low temperature and high humidity 10 O x 。
Example 2
The differences from example 1 are: the reactor was heated by external conduction oil circulation at a temperature of about 90 ℃.
Example 3
The differences from example 1 are: the reactor was heated by external conduction oil circulation at a temperature of about 100 ℃.
Example 4
The differences from example 1 are: the reactor was heated by external conduction oil circulation at a temperature of 100 ℃ for 24 hours while stirring at about 200rpm, and the mixture was washed to a pH of about 6.
Comparative example 1
The differences from example 1 are: manganese acetate tetrahydrate and cerium acetate were added in amounts of 2.41kg (i.e., 9.83 mol) and 23.73kg (i.e., 74.86 mol), respectively, and 100L of an aqueous potassium permanganate solution having a concentration of 3.61kg/L (i.e., 22.85 mol) was added to the reaction vessel.
Comparative example 2
The differences from example 1 are: the reactor was heated by external conduction oil circulation at a temperature of about 150 ℃.
Example 3
The differences from example 1 are: the reactor was heated by external conduction oil circulation at a temperature of about 80 ℃.
Comparative example 4
The differences from example 1 are: the deionized water washing step was not performed.
Table 1 below summarizes the parameters and experimental results of the above examples.
TABLE 1
From the above description, it can be seen that the embodiments described herein achieve the following technical effects: the method can realize an industrial-grade cerium-manganese composite oxide catalyst CeMn 10 O x Is prepared by the steps of (1); and synthesized cerium-manganese composite oxide catalyst CeMn 10 O x Shows excellent ozone catalytic decomposition activity, and shows significantly higher ozone catalytic decomposition activity even in a low-temperature environment of-5 ℃.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
- A method for preparing a cerium-manganese composite oxide catalyst, the cerium-manganese composite oxide catalyst having the following chemical composition: ceMn (CeMn) 10 O x The preparation method of the cerium-manganese composite oxide catalyst is characterized in that Ce exists in III valence or IV valence, mn exists in III valence or IV valence, and the preparation method comprises the following steps:mixing a divalent manganese source, a trivalent cerium source, potassium permanganate and water under the condition of pH 4-5, and adding the mixture into a reactor to obtain a mixture;heating the reactor to a temperature of 90-110 ℃ through circulation heating of heat conduction oil, and stirring the mixture to obtain a cerium-manganese composite oxide catalyst precursor; andand adding water into the cerium-manganese composite oxide catalyst precursor for water washing, standing, removing supernatant, and drying to obtain the cerium-manganese composite oxide catalyst.
- The method for preparing a cerium-manganese composite oxide catalyst according to claim 1, wherein the molar ratio of the divalent manganese source, the trivalent cerium source and potassium permanganate is 1:0.13:0.31.
- the method for producing a cerium-manganese composite oxide catalyst according to claim 1 or 2, wherein the conduction oil circulation heating is external conduction oil circulation heating.
- The method for producing a cerium-manganese composite oxide catalyst according to claim 1 or 2, wherein the duration of the cyclic heating of the heat transfer oil is 12 to 24 hours.
- The method for producing a cerium-manganese composite oxide catalyst according to claim 1 or 2, wherein the cerium-manganese composite oxide catalyst precursor is washed with water to a pH of 6 to 7.
- The method for producing a cerium-manganese composite oxide catalyst according to claim 1 or 2, wherein the trivalent cerium source is selected from any one or a mixture of at least two of cerium (III) acetate, cerium (III) nitrate, cerium (III) chloride, and cerium (III) sulfate.
- The method for producing a cerium-manganese composite oxide catalyst according to claim 1 or 2, wherein the divalent manganese source is selected from any one or a mixture of at least two of manganese (II) acetate, manganese (II) sulfate, manganese (II) chloride, and manganese (II) nitrate.
- The method for producing a cerium-manganese composite oxide catalyst according to claim 1 or 2, wherein the stirring speed of the mixture is 200 to 300rpm.
- The method for producing a cerium manganese composite oxide catalyst according to claim 1 or 2, wherein the reactor is heated to about 100 ℃ for about 12 hours.
- A cerium-manganese composite oxide catalyst, characterized in that the cerium-manganese composite oxide catalyst is prepared by the method according to any one of claims 1 to 9.
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