CN111495411B - Catalyst for decomposing ozone and preparation method thereof - Google Patents

Catalyst for decomposing ozone and preparation method thereof Download PDF

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CN111495411B
CN111495411B CN202010360934.1A CN202010360934A CN111495411B CN 111495411 B CN111495411 B CN 111495411B CN 202010360934 A CN202010360934 A CN 202010360934A CN 111495411 B CN111495411 B CN 111495411B
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catalyst
ozone
mno
mnac
melamine
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CN111495411A (en
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罗孟飞
方晨涛
陈建
李丹丹
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Zhejiang Normal University CJNU
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Zhejiang Normal University CJNU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The invention provides a catalyst for decomposing ozone, which is prepared from MnO and Mn 2 N 0.86 And C. The invention also provides a method for preparing the catalyst, mnAc 2 ·4H 2 Adding O into ethanol, stirring thoroughly to dissolve, adding melamine, mixing uniformly, stirring, evaporating to dryness, and roasting the evaporated sample to obtain MnO-Mn 2 N 0.86 -a C catalyst. The catalyst has the advantages that the catalyst still has high activity and stability even under the condition of 90% relative humidity, the raw materials and conditions for preparing the catalyst are easy to obtain, the preparation cost is low, and the large-scale production and popularization are easy.

Description

Catalyst for decomposing ozone and preparation method thereof
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to a catalyst for decomposing ozone and a preparation method thereof.
Background
It is well known that ozone acts as a double-edged sword for human depending living environment. In the stratosphere, ozone can resist ultraviolet rays to directly irradiate the earth, and is a natural protective barrier of nature; tropospheric ozone is a greenhouse gas that can lead to global warming and air quality degradation. High concentrations of tropospheric ozone can also have deleterious effects on ecosystems such as grain yield loss, reduced forest and grassland productivity, and direct threat to biodiversity. In addition, as a strong oxidant, ozone is widely used in the industries of food, sewage treatment, medical treatment, health and the like. Ozone residues result in the emission of tail gases containing a concentration of ozone which is required to be removed before the tail gases can be emitted. With the popularization of modern office equipment, a large amount of machines such as laser printers, copiers, and ozone disinfection equipment are used, ozone is generated by high-voltage discharge, corona discharge, or ultraviolet radiation, and the concentration of ozone is greatly increased in a short time in a closed environment. It is reported that people in a short-term ozone environment with high concentration can cause injury to respiratory system including cough, dyspnea, and lung function decline. The long-term ozone exposure of humans can have a variety of deleterious effects including neurological disorders, reduced lung function, airway inflammation, hypertension, accelerated aging, and the like. Thus, ozone decomposition studies have significant implications for environmental protection and human health.
At present, the ozone removal method includes a chemical adsorption method, an electromagnetic wave radiation method, a thermal decomposition method, a catalytic decomposition method and the like. The catalytic decomposition method is widely researched and applied because of the characteristics of low energy consumption, simple operation, high conversion efficiency and the like. The catalyst for catalytic decomposition of ozone mainly comprises noble metal and transition metal oxide.
Studies (Journal of Hazardous Materials,2009, 172, 631-634) have reported the decomposition of ozone by pd—mn catalysts at space velocity (GHSV) = 635000h -1 The ozone conversion rate is 90% after the reaction for 80 hours under the condition of 40 ℃ of reaction temperature, and the excellent ozonolysis performance is shown. However, the production cost of such a catalyst using noble metal Pd is quite high. Chinese patent CN102513106A, CN101402047A, CN101757933a discloses a composite catalyst using transition metal oxides such as manganese oxide and iron oxide as active components, the synthesis process generally requires high temperature and high pressure, the production process is complex, the energy consumption is high, and the catalytic performance of a part of the catalyst is greatly interfered by humidity. Therefore, it is necessary to find a low cost ozonolysis catalyst that is simple to prepare and has high stability in humid environments.
Disclosure of Invention
In order to solve the problem of poor stability of the catalyst in the wet environment in the prior art, the invention provides a catalyst for decomposing ozone and a preparation method thereof, and the aim of the invention is that the preparation method and the conditions are easy to obtain and operate, and the prepared catalyst still has high activity and stability even under the condition that the relative humidity is 90 percent.
In order to achieve the above purpose, the technical scheme disclosed by the invention is as follows: the invention provides a catalyst for decomposing ozone, which is prepared from MnO and Mn 2 N 0.86 And C, the mass percentages of the components in the catalyst are respectively as follows: mnO is 38%, mn 2 N 0.86 60 percent,c is 2%.
The invention also provides a method for preparing the catalyst, which comprises the following steps:
according to manganese acetate MnAc 2 ·4H 2 The mass ratio of O to melamine is 2:1, and the mass of ethanol is MnAc 2 ·4H 2 10 times of total mass of O and melamine, mnAc 2 ·4H 2 Adding O into ethanol, stirring thoroughly to dissolve, adding melamine, mixing uniformly, stirring in water bath at 90deg.C, evaporating to dryness, and roasting the evaporated sample under nitrogen atmosphere at 5 deg.C/min at 850 deg.C for 1 hr to obtain MnO-Mn 2 N 0.86 -a C catalyst.
The beneficial effects of the invention are as follows: the catalyst prepared by the invention has the ozone concentration of 22+/-1 ppm and the airspeed of 120000h before reaction under the conditions of normal temperature of 20 ℃ and high relative humidity of 90 percent by test -1 Under the condition that the ozone reaction conversion rate is 100%, the catalyst has high activity and stability even under the condition that the relative humidity is 90%, the raw materials and the conditions for preparing the catalyst are easy to obtain, the preparation cost is low, and the catalyst is easy to realize large-scale production and popularization.
Drawings
FIG. 1 shows MnO-Mn in example 1 2 N 0.86 XRD pattern of the-C catalyst.
Fig. 2 is a graph of stability of example 1 and comparative example 1 to an ozonolysis reaction.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Embodiment one: (1) MnO-Mn 2 N 0.86 Preparation of-C
According to manganese acetate (MnAc) 2 ·4H 2 The mass ratio of O) to melamine is 2:1, and the mass of ethanol is MnAc 2 ·4H 2 And 10 times of the total mass of O and melamine. MnAc 2 ·4H 2 Adding O into ethanol, stirring thoroughly to dissolve, adding melamine, mixing uniformly, stirring in water bath at 90deg.C, evaporating to dryness, and heating at a heating rate of 5deg.C/min under nitrogen atmosphereRoasting for 1 hour at 850 ℃ to obtain MnO-Mn 2 N 0.86 -a C catalyst.
The catalyst is prepared from MnO and Mn through testing 2 N 0.86 And C is composed of MnO, mn 2 N 0.86 And C is 38%, 60% and 2% by mass, respectively.
The XRD pattern of the catalyst is shown in figure 1
(2) Catalyst Performance test
The ozonolysis activity of the catalyst was evaluated by a fixed bed reactor (i.d. =14mm). The catalyst was pressed into tablets and sieved (40 mesh) before use, the catalyst was used in an amount of 0.6mL each time, and the fixed bed containing the catalyst was maintained at 20 ℃. The air is excited by a 185nm ultraviolet lamp (power 6W) to generate ozone, the ozone is brought into the reactor through the air, and the concentration of the ozone is measured to be 22+/-1 ppm before the reaction. The flow rate was 1.2L/min and the airspeed was 120000h -1 The reaction gas was bubbled through 18.5 ℃ water to saturate the water content of the reaction gas at 18.5 ℃ and then passed over a 20 ℃ catalyst at which the relative humidity of the gas was 90%. Ozone concentration at the inlet and outlet of the fixed bed reactor was analyzed by an ozone detector (model 106-L,2BTechnologies, USA) to calculate ozone decomposition rate, and the specific formula is as follows:
O 3 conversion= (C in -C out )/C in x100％
C in the formula in Is the concentration of ozone (ppm) and C before the reaction out Is the concentration of ozone (ppm) after the reaction. The ozonolysis efficiency of the catalyst is shown in FIG. 2 as a function of reaction time.
Comparative example 1:
(1)Mn 2 O 3 -Mn 3 O 4 is prepared from
According to manganese acetate (MnAc) 2 ·4H 2 The mass ratio of O) to melamine is 2:1, and the mass of ethanol is MnAc 2 ·4H 2 And 10 times of the total mass of O and melamine. MnAc 2 ·4H 2 Adding O into ethanol, stirring thoroughly to dissolve, adding melamine, mixing uniformly, stirring in water bath at 90deg.C, evaporating to dryness, and heating to 850 deg.C at a heating rate of 5deg.C/min under air atmosphereRoasting for 1 hour to obtain Mn 2 O 3 -Mn 3 O 4 Catalyst phase analysis by XRD of catalyst phase from Mn 2 O 3 And Mn of 3 O 4 Composition of the composition
(2) Catalyst performance test the same as in example 1 and the catalytic reactivity is shown in figure 2.
As can be seen from FIG. 2, the catalyst of example 1 was 100% in ozone decomposition rate and very stable, and it was demonstrated that the catalyst of example 1 (MnO-Mn 2 N 0.86 Comparative example 1 catalyst (Mn) prepared by calcination in an air atmosphere with significantly better performance than that of the catalyst (C) 2 O 3 -Mn 3 O 4 ). In conclusion, mnO-Mn 2 N 0.86 The catalyst C has high activity and stability to the catalytic decomposition of ozone, and the catalyst has simple manufacturing process and good reproducibility.
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 (1)

1. The application of the catalyst for decomposing ozone is characterized in that the catalyst consists of MnO and Mn 2 N 0.86 And C, the mass percentages of the components in the catalyst are respectively as follows: mnO is 38%, mn 2 N 0.86 60% and 2% C;
a method of preparing the catalyst comprising the steps of:
according to manganese acetate MnAc 2 ·4H 2 The mass ratio of O to melamine is 2:1, and the mass of ethanol is MnAc 2 ·4H 2 10 times of total mass of O and melamine, mnAc 2 ·4H 2 Adding O into ethanol, stirring thoroughly to dissolve, adding melamine, mixing uniformly, and stirring at 90 o C stirring in water bath, evaporating to dryness, and evaporating to drynessUnder nitrogen atmosphere at 5 o The temperature rise rate of C/min is increased to 850 o Roasting C for 1 hour to obtain MnO-Mn 2 N 0.86 -a C catalyst;
the catalyst is used for ozonolysis reaction, the relative humidity is 90% at the normal temperature of 20 ℃, the concentration of ozone before the reaction is 22+/-1 ppm, and the airspeed is 120000 -1 Under the condition of h, the conversion rate of ozone reaction is 100%.
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CN105810959A (en) * 2016-05-16 2016-07-27 中南大学 High-performance oxygen reduction catalyst MnOx/Mn2N-N-C composite catalyst and preparation method and application thereof
CN106430146A (en) * 2016-11-22 2017-02-22 重庆文理学院 Nitrogen-manganese co-doped hierarchical porous carbon material preparation method
JP2017192429A (en) * 2016-04-18 2017-10-26 株式会社キャタラー Catalyst filter, deodorization device and air cleaning device
CN109678146A (en) * 2019-01-22 2019-04-26 中国科学院福建物质结构研究所 A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application

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JP2017192429A (en) * 2016-04-18 2017-10-26 株式会社キャタラー Catalyst filter, deodorization device and air cleaning device
CN105810959A (en) * 2016-05-16 2016-07-27 中南大学 High-performance oxygen reduction catalyst MnOx/Mn2N-N-C composite catalyst and preparation method and application thereof
CN106430146A (en) * 2016-11-22 2017-02-22 重庆文理学院 Nitrogen-manganese co-doped hierarchical porous carbon material preparation method
CN109678146A (en) * 2019-01-22 2019-04-26 中国科学院福建物质结构研究所 A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application

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