CN113244754A - General formula AM2O5Application of compound as catalyst for treating ozone at room temperature - Google Patents
General formula AM2O5Application of compound as catalyst for treating ozone at room temperature Download PDFInfo
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- CN113244754A CN113244754A CN202110631401.7A CN202110631401A CN113244754A CN 113244754 A CN113244754 A CN 113244754A CN 202110631401 A CN202110631401 A CN 202110631401A CN 113244754 A CN113244754 A CN 113244754A
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- ozone
- compound
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- catalyst
- treatment
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Abstract
The invention provides a general formula AM2O5The application of the compound as a catalyst for efficiently treating ozone. General formula AM2O5The compound is mullite composite oxide, A is any one or more of lanthanide series metal elements, Bi and Y, and M is any one or more of first transition series transition metal elements. General formula AM2O5The compound has excellent ozone catalytic decomposition effect; the stability of the ozone treatment is extremely high, and the service life is long; AM (amplitude modulation)2O5The compound does not contain noble metal, so the cost is lower; meanwhile, the preparation method of the compound is mature and simple in the prior art, so that large-scale ozonolysis treatment can be carried out in mass production; furthermore, experiments prove that the ozone treatment device can be suitable for ozone treatment in different industries and under various environmental working conditions.
Description
Technical Field
The invention relates to the technical field of ozone treatment, and particularly relates to a general formula AM2O5The use of the compounds as catalysts for the catalytic decomposition of ozone at room temperature.
Background
Since the development of the action plan for three years of the win-win blue sky guard war, the environmental condition of China is remarkably improved and is in accordance with the increasing demand of good life of people. However, Nitrogen Oxides (NO) are heavily regulated in recent years by the nationx) The reduction of fine Particulate Matters (PM) and Volatile Organic Compounds (VOCs) in different degrees, but the continuous improvement of the concentration of ozone becomes the first difficult problem threatening the environmental safety and the healthy life of people.
Although the ozone layer 20 km from the ground is a protective umbrella of the earth, ozone (O) near the ground due to rapid development of global economy and industrialization3) Contamination has become a serious problem. The outdoor ozone pollutants close to the ground are mainly due to VOCs, CO and NO under the driving action of solar radiationxA photochemical reaction occurs therebetween. In addition, modern office equipment, such as copiers, laser printers, and ultraviolet disinfection, can cause ozone emissions in the room. In addition, O3Is widely used as a strong oxidant in grain warehouses, hospitals and water treatment plants, and is also used for VOCs oxidation, denitration treatment and the like in a plurality of plant post-treatment systems in recent years, and the places contain a large amount of residual O3And the concentration is higher, and the tail end of the ozone treatment device is urgently required to be additionally provided.
Even at low concentrations of O3If exposed to it for a long time, respiratory diseases such as asthma, cardiopulmonary diseases, cardiovascular diseases can also be causedDisease, aging can be accelerated and even premature death can result. In addition, indoor ozone can produce a range of oxidation products, including unsaturated hydrocarbons, VOCs, and Secondary Organic Aerosols (SOA), which are more harmful to humans than ozone itself. Therefore, for public health and the whole ecosystem, the research on the decomposition of ozone at room temperature by catalysts has important significance for environmental protection and human health, and the task of eliminating ground ozone is urgent.
At present, the mainstream ozone treatment idea is to dissolve ozone in wastewater, promote the decomposition of ozone into active OH by adding a catalyst, oxidize and decompose macromolecular organic matters in the wastewater, and achieve the purpose of reducing the wastewater and purifying. For the ozone gas in the atmosphere including outdoor near ground and indoor, the existing indoor temperature high-efficiency catalytic ozone purification technology is rare, and the mainstream ozone gas purification technology at present comprises an absorption method, an adsorption method, a direct combustion method, a catalytic combustion method, a photocatalysis method and the like. At present, most of catalysts used in the ozone purification market are manganese dioxide, and the purpose of removing ozone is achieved by adding low-temperature heating treatment. If the catalyst has the capability of removing ozone at room temperature, the catalyst does not need to be heated and combusted, so that the energy consumption is greatly reduced, the secondary pollution is avoided, and the catalyst is consistent with the concept of carbon neutralization. Patent publication No. CN106512715A discloses that noble metal or transition metal oxide as an active component is combined with active carbon, molecular sieve or organic metal framework material as an adsorption component for purifying ozone-removing gas in an airplane cabin, and the design structure is novel, but the cost of the catalyst and the adsorbent is high; the patent with publication number CN108889116A discloses a formed catalyst prepared by loading europium on activated carbon, which is very portable and can be directly applied, but the preparation process is complicated and ozone is not completely removed within a certain period of time. The patent with publication number CN110575848A is to prepare a zeolite-expanded graphite-chitosan composite catalyst loaded with manganese dioxide active components by reacting with O3And the catalyst is treated together with VOCs, so that the effect better than that of a commercial catalyst is achieved. The patent with publication number CN107376926A prepares LaFeO by citric acid sol-gel method3The perovskite type ozone catalyst can achieve near 100 percent of ozone conversion under the dry environment at room temperatureThe rate did not decrease within 8 hours, but the test conditions were not severe enough.
The prior art has the defects that the service performance is poor under the conditions of high humidity, extremely low temperature, extremely high temperature and large air volume, the durability experiment is not involved, the raw materials are expensive, the preparation method is complex, the industrialization is difficult to realize, the efficiency is low, the service life is short, the regeneration is difficult, the moisture absorption is easy and the like, and the catalyst which can efficiently treat the ozone at room temperature, has low price, can realize industrialized mass production and can catalytically treat the ozone at the harsh conditions such as room temperature, low temperature or high temperature is urgently needed in the market at present.
General formula is AM2O5-xCompared with other manganese oxide compounds, the mullite compound contains two crystal field structures of octahedron and pyramid, and the two crystal fields can play a synergistic role, so that the catalytic capability of the mullite compound is greatly improved. Meanwhile, the A site element plays a role in stabilizing a crystal framework in the structure, so that the compound has extremely strong stability, is not easy to inactivate in the reaction, and has excellent hydrothermal aging resistance. The composition has an overall synergistic crystal structure, and is characterized by having a crystal structure in O relative to single crystal field manganese oxide compounds and mixed manganese oxide compositions3、VOCs、CO、NOxThe purification and other aspects have more excellent performance.
Disclosure of Invention
The invention mainly aims at providing a general formula AM2O5-xThe application of the compound as a catalyst for catalytic treatment of ozone can overcome the defects of the prior art, solve the problem of high-efficiency treatment of the existing ground ozone gas, and has the capability of treating ozone in sewage and soil.
To achieve the above object, according to one aspect of the present invention, there is provided a general formula AM2O5-xThe application of the compound as a catalyst for catalytic treatment of ozone has a general formula AM2O5-xThe compound is mullite composite oxide, A is any one or more of lanthanide series metal elements, Bi and Y, M is any one or more of first transition series transition metal elements, and x is more than or equal to 0 and less than or equal to 1.
Further, A is selected from any one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi and Y, preferably A is selected from any one or more of Sm, Gd and Y.
Further, M is selected from any one or more of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, preferably M is selected from any one or more of Mn, Fe and Co.
Further, M is essentially Mn, and is preferably represented by the general formula AM2O5-xThe compound has the structural formula of AMn2-yEyO5-xWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and E is Ti, V, Cr, Fe, Co, Ni or Cu.
Further, the above-mentioned A must contain Y element, and is preferably represented by the general formula AM2O5-xThe compound has the structural formula YzD1-zM2O5-xWherein x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and D is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Bi.
Further, the above general formula AM2O5-xThe compound has the structural formula YzD1-zMn2-yEyO5-xWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, E is Ti, V, Cr, Fe, Co, Ni or Cu, D is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Bi.
Further, the above general formula AM2O5-xThe microscopic shape of the compound is a nanoparticle, nanorod, nanosheet, nanowire and/or nanotube, preferably AM2O5-xThe particle size of the compound is between 5 and 100nm, preferably between 20 and 45nm, and the compound is preferably represented by the general formula AM2O5-xThe specific surface area of the compound is more than 30m2A concentration of 50 to 150 m/g2Between/g; said general formula AM2O5-xThe macroscopic shape of the compound is powder, sphere, granule, ceramic, etc.
Further, the above general formula AM2O5-xWhen the compound is used as a catalyst for catalyzing and purifying ozone, the general formula AM2O5-xThe compound is mixed with a carrier and an adsorbent to form a composite catalyst or is coated on the carrier in the form of slurry, wherein the carrier is preferably a carbon material, a ceramic material, a foam material or a solid acidic material, and is more preferably ZrO2、TiO2、SiO2、WO3、Nb2O5、SnO2、Al2O3、Co3O4、CeO2、Fe2O3Activated carbon, graphene, clay, zeolites, organometallic frameworks, honeycomb ceramics, ceramic foams, cermets, foams, sponges.
Further, the form in which the above ozone exists includes pure ozone, ozone existing in a mixed gas at an arbitrary ratio, ozone in water, ozone in soil, and the like existing in arbitrary forms.
Further, the above-described forms of ozone treatment include catalytic oxidation of ozone alone and/or treatment of ozone with other contaminants. Other contaminants include NOxCO, organic compounds (including VOCs volatile organic compounds, water-soluble organic compounds, and fat-soluble organic compounds), and the like.
Further, the above application comprises subjecting the ozone contained in said general formula AM to a temperature in the range of-40 ℃ to 500 ℃ and a relative humidity in the range of 0 to 100%2O5-xThe treatment is carried out under the catalytic action of the compound, and particularly, when ozone is present as a mixed gas component, the treatment efficiency is 90% or more, preferably 92% or more, more preferably 95% or more, and in some cases 98% or more.
Further, the above treatment temperature is-20 ℃ to 50 ℃, preferably 0 ℃ to 25 ℃; the treatment humidity is 5 to 90 percent, preferably 5 to 60 percent; said ozone concentration in said gas stream is less than 10000 ppm; preferably 0.1 to 1500 ppm; the space velocity of the gas is 1200-1200000 ml g-1·h-1Preferably 60000 to 600000 ml/g-1·h-1。
The technical scheme of the invention is applied, and the general formula is AM2O5-xThe compound has good effect of catalyzing and purifying ozone; AM (amplitude modulation)2O5-xThe compound is MoThe lithoid composite oxide has higher combination stability among the components than a physical loading mode, so that the catalytic purification of ozone by using the lithoid composite oxide has higher stability and longer service life; general formula AM2O5-xThe compound does not contain noble metal, so the cost is lower; meanwhile, the preparation method of the compound is mature and simple in the prior art, so that the compound can be produced in large quantity to be beneficial to the treatment of ozone with large air quantity and high concentration; furthermore, experiments prove that the compound has good catalytic effect on ozone in high and low temperature, high and low humidity, high and low air volume and high and low concentration environments, so that the compound can be suitable for ozone purification treatment in different industries.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph of 20-hour empty tube concentration used in the present specification to explain stability and accuracy of ozone concentration;
FIG. 2 shows the nanoparticle catalyst YMn obtained in example 1 of the present invention2O5X-ray diffraction pattern (XRD);
FIG. 3 shows the nanoparticle catalyst YMn obtained in example 1 of the present invention2O5Scanning Electron Micrographs (SEM);
FIG. 4 is a schematic view of the apparatus for detecting the generation of a mixed gas containing ozone according to the present invention;
FIG. 5 shows the nanoparticle catalyst YMn obtained in example 1 of the present invention2O5Graph of ozone conversion results;
FIG. 6 shows a nanowire/tube catalyst YMn obtained in example 3 of the present invention2O5Scanning Electron Micrographs (SEM);
FIGS. 7 to 17 are graphs or histograms showing the ozone conversion rate results of examples 2 to 10 according to the present invention and comparative examples 1 and 2 in this order.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The invention mainly aims at a catalytic purification method, and through optimizing the design of a catalyst in the reaction process, ozone pollutants can be efficiently treated and purified while the reaction temperature and the energy consumption are reduced, so that the method plays an extremely important role in pollution treatment of different industries, atmospheric environment protection and guarantee of life health and safety of people.
The application provides a general formula AM in order to solve the problem that commercial catalyst in the field of catalytic purification by ozone is high in cost2O5-xThe application of the compound as a catalyst for catalyzing and purifying ozone has a general formula AM2O5-xThe compound is mullite composite oxide, A is any one or more of lanthanide series metal elements, Bi and Y, M is any one or more of first transition series elements, and x is more than or equal to 0 and less than or equal to 1.
General formula AM2O5-xThe compound has good effect of catalyzing and purifying ozone; general formula AM2O5-xThe compound is mullite composite oxide, and has a general formula AM relative to other manganese oxide compounds2O5-xThe compound comprises two crystal field structures of octahedron and pyramid, and the two crystal fields can play a mutual synergistic role, so that the catalytic capability of the compound is greatly improved. General formula AM2O5-xThe combination stability among the components of the compound is larger than that of a physical loading mode, so that the catalytic purification of ozone by using the compound has higher stability and longer service life; general formula AM2O5-xThe compound does not contain noble metal, so the cost is lower; meanwhile, the preparation method of the compound is mature and simple in the prior art, so that the compound can be produced in large quantity to be beneficial to the treatment of ozone with large air quantity and high concentration; furthermore, experiments prove that the compound has good catalytic effect on ozone in high and low temperature, high and low humidity, high and low air volume and high and low concentration environments, so that the compound can be suitable for ozone purification treatment in different industries.
General formula AM2O5-xThe mullite-type oxide can be prepared by various methods including, but not limited to, hydrothermal synthesis, coprecipitation synthesis, templating method, sol-gel synthesis, organic solution combustion, spinning, mechanical synthesis, etc., wherein the hydrothermal synthesis is preferred to obtain the general formula AM because of the lower synthesis temperature and better dispersion of the sample2O5-xAnd (3) a type oxide.
General formula AM2O5-xA in the mullite type oxide can be selected from lanthanoid Bi and lanthanoid Y optionally, preferably, A is selected from any one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi and Y, and through experimental comparison, further preferably, A is selected from any one or more of Sm, Gd and Y.
General formula AM2O5-xM in the mullite-type oxide may be optionally contained in the first transition metal element, and preferably, the M is one or more selected from Ti, V, Cr, Mn, Fe, Co, Ni and Cu. Through experimental comparison, M is further preferably selected from any one or more of Mn, Fe and Co.
In one embodiment of the present application, M must contain Mn, and is preferably represented by the formula AM2O5-xThe compound has the structural formula of AMn2-yEyO5-xWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and C is Ti, V, Cr, Fe, Co, Ni or Cu.
Having the above AMn2-yEyO5-xAM of structural formula2O5-xThe compound contains metal dimer (Mn-dimer) catalytic active sites, and strong p-d electron hybridization between Mn and O weakens the action of Mn and external O, so that the efficiency of small molecule oxidation is improved. In addition, the existing manganese oxide types and corresponding manganese element valence states are more, and the oxidation states can be mutually converted at low temperature, so that the low-temperature activity is good. Mullite-type AM2O5-xThe compound changes Mn by introducing rare earth metal elementsoct3p orbital and ObulkThe 2p orbital of (a) performs a level of hybridization, and due to the tight connection between the two manganese ions, ObulkAnd MnotcIn betweenHybridization to MnpyrThe electron properties of (2) have a great influence, resulting in electrons in MnoctMore localized atomically, Obulk2p orbital and MnpyrThere is more overlap. Thus, closest to EfDz of2Rail (Mn)pyr) Will be expelled resulting in dz2The energy of the track is increased. Due to MnpyrDz of2The orbitals strongly interact with the 2p orbitals of O, and this energy increase leads to O and MnpyrThe bonding strength between the two is improved, and the difficulty of releasing O is increased. On the contrary, when Mnoct3d orbital and ObulkThe hybridization between the 2p orbitals is strong, the electrons have more iterative action, O and MnpyrThe internal interactions become weaker, and the O-Mn is weakerpyrThe bonds help the catalyst surface to release O easily to complete oxidation to form the corresponding oxide. While for other transition metals in the M position, the d orbitals and dz2The position of (a) may vary slightly and the strength of the action of the metal with oxygen may vary, thereby affecting the catalytic performance to a varying extent. In addition, compared with more types and manganese valence states of manganese oxide, the valence states of other transition metal elements are relatively less, so that the difficulty of oxidation reduction is increased, and the catalytic performance is influenced.
In another preferred embodiment of the present application, the above-mentioned A must contain Y element, preferably of the formula AM2O5-xThe compound has the structural formula YzD1-zM2O5-xWherein x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and D is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Bi. The interaction between the Y element and the transition metal is more obvious, so that the efficiency of catalyzing ozone is more outstanding.
In one embodiment of the present application, in order to further utilize the synergistic catalytic effect between the elements, the above general formula AM is preferred2O5-xThe compound has the structural formula YzD1-zMn2-yEyO5-xWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, E is Ti, V, Cr, Fe, Co, Ni or Cu, D is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Bi.
The skilled person knows that the particle size of the catalyst affects the effectiveness of the contact of the catalyst with the substrate and the stability of the catalyst present in the equipment, the difference in effectiveness of the contact directly leading to a difference in catalytic efficiency, and in order to balance the above effects of contact and stability, AM is preferred2O5-xThe microscopic shape of the compound is nanoparticle, nanorod, nanosheet, nanowire and/or nanotube, more preferably the AM described above2O5-xThe particle size of the compound is 5 to 100nm, and more preferably 20 to 45 nm. In principle, the smaller the particle size, the higher the specific surface area, the more the exposed active sites, the more the catalytic performance is superior, but on the one hand, the performance is not greatly improved due to the further improvement of the specific surface area, and on the other hand, the synthesis process, conditions and the like need to be adjusted due to the improvement of the specific surface area of the substance, and a more severe process is generally needed, which will result in the general formula AM2O5-xThe production cost of the compound is greatly increased; in addition, the increase in the specific surface area may lead to the general formula AM2O5-xThe strength of the compound is reduced and the compound is more easily sintered during long-term use, and the reduction of the specific surface area is rapid, thereby resulting in a shortened service life thereof. Therefore, in combination with the above factors, the general formula AM is preferred2O5-xThe specific surface area of the compound is more than 30m2A specific surface area of 50 to 150m is more preferable2Between/g. Through experimental verification, the general formula AM2O5-xThe particle diameter and/or specific surface area of the compound is controlled within the above range, and the compound is represented by the general formula AM having a large particle diameter and a small specific surface area2O5-xThe compound has obviously improved catalytic efficiency, and is mainly characterized in that the temperature required by catalysis can be obviously reduced while high conversion rate is maintained.
General formula AM2O5-xWhen the compound is used as a catalyst for catalyzing and purifying ozone, the general formula AM2O5-xThe compound powder was granulated and then put into the apparatus for use. In order to reduce the catalytic costs and to minimize the loss of catalyst during the treatment due to gas purging, it is preferred to use the general formula AM2O5-xChemical combinationThe product is mixed with a carrier to form a composite catalyst. For example, general formula AM2O5-xThe solution and/or slurry of the compound is coated on a carrier such as a carbon material, a ceramic material, a foam material or a solid acidic material, so that the carrier is used for immobilizing the compound, thereby being beneficial to the passing of the gas to be treated and the contact with the catalyst on one hand, reducing the loss of the catalyst on the other hand, prolonging the service life of the catalyst and reducing the use cost of the catalyst; meanwhile, the specific surface area of the loaded integral composite catalyst can be increased, and the catalytic efficiency is further improved. It is further preferred that the support is ZrO2、TiO2、SiO2、WO3、Nb2O5、SnO2、Al2O3、Co3O4、CeO2、Fe2O3Activated carbon, graphene, clay, zeolite, organometallic framework, honeycomb ceramic, ceramic foam, cermet, foam, or sponge. The zeolite molecular sieve can be natural zeolite or synthetic zeolite. Of course, in addition to the above-mentioned carriers, carriers currently used for ozone treatment catalysts can be applied to the present application, and are not listed here.
As mentioned above, the compound can play a good catalytic effect on ozone under common conditions (such as room temperature), and in specific application, the compound can be used for single components or mixed components, such as ozone, VOCs and NOx、COxThe compounds described above in this application can be used in the mixture and have a corresponding catalytic oxidation effect.
When the compound is used as a catalyst for catalytic purification of ozone, the catalytic conditions, the process flow and the like of the compound can be compatible with the catalytic conditions and the process flow in the prior art, for example, the general formula AM of the compound is adopted2O5-xThe compound replaces the existing catalyst, and other process parameters and equipment maintain the original data.
In one embodiment of the present application, the above application comprises subjecting the ozone-containing gas stream to a temperature in the range of-40 ℃ to 500 ℃ (preferably in the range of-20 ℃ to 50 ℃, more preferably in the range of 0 ℃ to 25 ℃), in the general formula AM2O5-xThe compound is decomposed by contact under the catalysis of the compound. The temperature range does not mean that ozone gas can be treated only in the temperature range, but is obtained under certain catalyst and certain treatment conditions.
In one embodiment of the present application, the above application comprises flowing the gas stream comprising ozone in a relative humidity range of 0 to 100% (preferably 5-60%), in the general formula AM2O5-xThe compound is decomposed by contact under the catalysis of the compound. The above-mentioned relative humidity range does not mean that ozone gas can be obtained under a certain catalyst and a certain treatment condition, but only by treating the ozone gas within the above-mentioned relative humidity range.
General formula AM of the present application2O5-xThe compound can be applied to the treatment of near-ground photochemical synthesis pollution, industrial discharge or indoor discharge ozone in various concentration ranges, for example, the concentration of an ozone gas flow is less than 10000ppm, preferably 0.10-1500 ppm.
In another embodiment of the application, the treatment efficiency and the actual requirements of the simulation industry can be controlled by controlling the reaction space velocity, and the reaction space velocity is preferably 1200-1200000 ml-g-1·h-1Preferably 60000 to 600000 ml/g-1·h-1. If the reaction space velocity is too large, the conversion rate may be lowered, and if the reaction space velocity is too small, the treatment efficiency of the VOC gas may be lowered, which may affect the economic cost for industrial use, so it is recommended to control the reaction space velocity within the above range.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Aiming at the treatment of gas flow containing ozone, a general formula AM of environment test with constant temperature and humidity is adopted2O5-xCatalytic ozone performance of the compounds as catalysts, in particular:
a certain amount of catalyst is taken to be put into a reaction tube with the inner diameter of 4mm after being granulated, and air flow containing a certain amount of ozone gas is introduced. The ozone conversion device realizes intermittent temperature and humidity change through the constant-temperature and constant-humidity box, the air distribution device and the ozone generator, can adjust the flow and the concentration at the same time, is constant in a certain time, detects the ozone concentration in every two seconds through the ozone detector, and calculates the ozone conversion rate. Wherein the test time for each of the examples and comparative examples in the present invention is at least 5 hours, and the condition is unchanged for 5 hours, and the ozone concentration per hour is defined as the sum of the average values of the ozone concentration data collected over the period. The final product of the catalyst-converted ozone is oxygen, and no other by-product gas is produced.
The design of the test refers to the national standard manganese series ozone decomposition catalyst activity test method (HG/T5419-2018), including filler, leakage detection, ozone concentration calculation methods and the like, and regarding ozone detection means, the test in the patent application directly adopts a calibrated commercial ozone detector (3S-J5000, Tonglin ozone) to carry out the test, the concentration can be measured in real time, the commercial ozone detector conforms to the national ozone generator safety and sanitation standard (GB28232-2011), the ozone concentration test is carried out by adopting the principle of an ultraviolet light absorption method, and the detailed content can refer to corresponding national standard. For the stability of the test, the standard HG/T5419-2018 requires that the analysis is performed every 0.5-1 hour in the same state, and if the extreme difference value of the ozone conversion rate of 3 continuous analyses is less than or equal to 1%, the experiment can be ended and the stability is determined. In the test of this patent application, test lasts 5 hours at least every turn, can guarantee the stability and the accuracy of test result. In which the empty reaction tube was tested for ozone concentration for 20 hours, and the graph is shown in FIG. 1, the average value was 105ppm and the maximum deviation rate was < 0.1% in 20 hours, and thus, the stability and accuracy of the test were confirmed.
Example 1
The introduced mixed gas contains ozone with a concentration of 105ppm, the gas flow is 1L/min, and the catalyst is nano-particle YMn2O5Nanoparticle YMn2O5The preparation method adopts a hydrothermal synthesis method, and comprises the following preparation processes:
firstly, adding precursors of yttrium nitrate and manganese nitrate in a certain metering ratio into 50ml of deionized water, and stirring at the rotating speed of 400 r/min;
secondly, adding potassium permanganate which is an oxidant according with a stoichiometric ratio in the stirring process, and continuously stirring for one hour;
thirdly, dropwise adding a sodium hydroxide solution prepared in advance to enable the pH value of the mixed solution to be more than 10, and continuously stirring for two hours;
fourthly, adding the mixed solution obtained by stirring into a reaction kettle, and heating for 18 hours in an oven at 200 ℃;
fifthly, removing mixed liquid after the hydrothermal reaction, performing suction filtration, respectively performing soaking washing and drying by deionized water and 1% dilute nitric acid, and then drying at 100 ℃ to obtain YMn2O5A nanoparticle sample.
The XRD test result shows that the mullite structure is a pure-phase mullite structure, and is shown in figure 2. YMn2O5The morphology is nano-granular, the SEM test result is shown in figure 3, and the grain diameter of the microscopic nano-particles is between 25 and 45 nm. In order to ensure that the test airflow is smoother and the diffusion pressure is reduced, the catalyst is granulated, and particles with the particle size of 40-60 meshes are selected for ozone catalysis, and the schematic diagram of the purification device is shown in FIG. 4. The specific dosage of the catalyst is 100mg, and the reaction space velocity is 600000ml g-1·h-1The reaction temperature was 20 ℃ and the relative humidity of the gas was 20%, the conversion of ozone was represented by the consumption rate of ozone, the test results are shown in Table 1, and the result curve is shown in FIG. 5. The results show that the ozone conversion remains above 92.18% over 5 hours with unchanged conditions.
Example 2
The introduced mixed gas contains ozone with a concentration of 105ppm, the gas flow is 1L/min, and the catalyst is nanotube YMn2O5Nanotube YMn2O5The preparation method adopts electrostatic spinning and comprises the following steps:
firstly, adding a certain amount of precursor yttrium nitrate, manganese nitrate and a proper amount of ethanol into 30ml of deionized water, and stirring for 1 hour at the rotating speed of 400 r/min;
secondly, putting the mixed solution obtained by stirring into a needle tube, and adding 15kV high voltage for spinning;
thirdly, drying the spun precursor sample at 100 ℃ for 12 hours, grinding the sample, and then putting the ground sample into a muffle furnace for calcination under the calcination conditions of 800 ℃ and 8 hours;
fourthly, grinding the mixture after cooling to obtain the nano tube YMn2O5And (3) sampling.
The XRD test result also shows that the mullite structure is a pure-phase mullite structure. YMn2O5The morphology is nanotube, the diameter is within 100nm, the length is more than 5 μm, and the SEM topography is shown in figure 6. In order to ensure that the test airflow is smoother and the diffusion pressure is reduced, the catalyst is granulated, and particles with the particle size of 40-60 meshes are selected for ozone catalysis. The specific dosage of the catalyst is 100mg, and the reaction space velocity is 600000ml g-1·h-1The reaction temperature was 20 ℃ and the relative humidity of the gas was 20%, the conversion of ozone was represented by the consumption rate of ozone, the test results are shown in Table 1, and the result curve is shown in FIG. 7. The results show that the ozone conversion remains above 91.34% for 5 hours with unchanged conditions, which are slightly lower than the nanoparticle YMn2O5。
TABLE 1 YMn in different morphologies2O5Comparison of the ozone conversion of the samples over a reaction time of 5 hours (experimental conditions: 105ppm O)3，600000ml·g-1·h -120 ℃ 20% relative humidity)
Example 3
The introduced mixed gas contains ozone with a concentration of 105ppm, the gas flow is 1L/min, and the catalyst is selected to be the nano-particle YMn in example 12O5And gamma-MnO prepared by hydrothermal synthesis method2After the sample is granulated, selecting particles with the granularity of 40-60 meshes for ozone catalysis, wherein the dosage is 100mg each time, and the reaction space velocity is 600000 ml/g-1·h-1The reaction temperature was 20 ℃, the relative humidity of the gas was 20%, the conversion rate of ozone was represented by the consumption rate of ozone, and the test time was extended to 100 hours for the purpose of investigating the durability of the catalyst, and the conditions were not satisfied during the testThe results of the test are shown in FIG. 8. The results show that YMn2O5The ozone conversion rate is kept above 91.76% in the whole process of the durability test, and the conversion rate after 100 hours is reduced by no more than 0.1%. Comparative gamma-MnO2The overall ozone conversion decreased over time, eventually from the initial 41.08% to 14.85% after 100 hours, showing a constant loss of active ingredient, which by comparison shows YMn2O5The mullite material has ultrahigh stability.
Example 4
The introduced mixed gas contained ozone with a concentration of 105ppm, the gas flow rate was 1L/min, and the catalyst was YMn in example 12O5After sample granulation, selecting particles with the particle size of 40-60 meshes for ozone catalysis, wherein the dosage of the particles is 100mg, and the reaction space velocity is 600000 ml/g-1·h-1In order to investigate the influence of low temperature conditions on the catalytic ozone purification capacity and stability, the reaction temperature was adjusted to-20 deg.C, -10 deg.C, 0 deg.C, 10 deg.C, and 20 deg.C one by one, the ozone conversion rate was represented by the ozone consumption rate, each test was continued for at least 5 hours, the ozone concentration and conversion rate were calculated as the average value over 5 hours, and the histogram of the test results is shown in FIG. 9. The results show that YMn in example 4 immediately after the temperature is lowered to-20 ℃2O5The ozone conversion rate of the nano-particle catalyst is still kept at 56.13% under the experimental conditions, and the ultrahigh activity and low temperature resistance of the catalyst are demonstrated.
Example 5
The introduced mixed gas contained ozone with a concentration of 105ppm, the gas flow rate was 1L/min, and the catalyst was the nanoparticle YMn in example 12O5After the sample is granulated, selecting particles with the particle size of 40-60 meshes for ozone catalysis, wherein the dosage of the particles is 100mg, and the reaction space velocity is 600000 ml-g-1·h-1The gas relative humidity was 20%, in order to investigate the effect of high temperature conditions on the stability of the catalyst to catalyze ozone, the reaction temperature was adjusted to 500 ℃, the conversion of ozone was expressed by the consumption rate of ozone, and the test lasted at least 5 hours, and the test results are shown in fig. 10. The results show high temperature bars at 500 deg.CUnder the condition, the ozone conversion rate is always kept at 100%, the excellent high-temperature stability is shown, and the method can be suitable for working conditions and environments with various temperatures.
Example 6
The introduced mixed gas contained ozone with a concentration of 105ppm, the gas flow rate was 1L/min, and the catalyst was the nanoparticle YMn in example 12O5After the sample is granulated, selecting particles with the particle size of 40-60 meshes for ozone catalysis, wherein the dosage of the particles is 100mg, and the reaction space velocity is 600000 ml-g-1·h-1The reaction temperature is 20 ℃, in order to investigate the influence of the relative humidity of the gas on the catalytic ozone purification, the reaction humidity is adjusted to 5%, 20%, 40%, 60% and 80% one by one, the conversion rate of ozone is represented by the consumption rate of ozone, each test lasts at least 5 hours, the calculation of the concentration and the conversion rate of ozone is the average value of 5 hours, and the bar chart of the test results is shown in fig. 11. The results showed that YMn in example 6 was observed under low humidity conditions (RH ═ 5%)2O5The nano-particle catalyst can keep the ozone conversion rate of more than 94.94 percent, and is suitable for the ozone pollution purification treatment in dry areas. And when the relative humidity is gradually increased to 80%, the catalyst still keeps 80.45% of ozone conversion rate, has excellent high humidity resistance, and can be suitable for working conditions and environments with various relative humidities.
Example 7
The mixed gas containing ozone at a concentration of 105ppm was introduced, and the catalyst was the nano-particle YMn in example 12O5After sample granulation, particles with the particle size of 40-60 meshes are selected for ozone catalysis, the reaction temperature is 20 ℃, the relative humidity of gas is 20%, in order to explore the influence of the reaction space velocity on catalytic ozone purification, the reaction space velocity is respectively controlled to be 60000 ml.g by changing the gas flow and the catalyst mass successively-1·h-1、300000ml·g-1·h-1、600000ml·g-1·h-1、900000ml·g-1·h-1、1200000ml·g-1·h-1The ozone conversion is expressed as the ozone depletion rate, each test lasts at least 5 hours, the test results are shown in table 2, and the result curves are shown in fig. 12. Knot(s) and knot(s)Fruit analysis, YMn2O5The catalyst is at 60000ml g-1·h-1The ozone conversion rate is maintained to be more than 98.03 percent at the airspeed of (1), and when the airspeed is gradually increased to 900000 ml-g-1·h-1Even higher 1200000ml g-1·h-1And meanwhile, the conversion efficiency of 88.87% and 75.92% are still maintained, the ultrahigh conversion frequency (TOF) is displayed, and the method can be suitable for industrial-grade air volume degree and has extremely high practical value.
TABLE 2 YMn in example 1 at different reaction space velocities2O5Comparison of the ozone conversion of the samples over a reaction time of 5 hours (experimental conditions: 105ppm O)320 ℃ 20% relative humidity)
Example 8
The introduced mixed gas contains ozone with a certain concentration, the gas flow is 1L/min, and the catalyst is the nano-particle YMn in the embodiment 12O5After the sample is granulated, particles with the particle size of 40-60 meshes are selected for ozone catalysis, the dosage of the particles is 100mg, the reaction temperature is 20 ℃, the relative humidity of gas is 20%, and the reaction space velocity is 600000 ml/g-1·h-1To investigate the effect of the concentration of ozone in the mixed gas on the catalytic ozone purification, the concentrations of ozone were adjusted to 50ppm, 105ppm, 300ppm and 1500ppm one by one, the conversion of ozone was expressed by the consumption rate of ozone, each test was continued for at least 5 hours, the test results are shown in Table 3, and the result curve is shown in FIG. 13. The results show that when the concentration of ozone in the mixed gas is 50ppm, the conversion efficiency of the catalyst to ozone reaches over 95.99%, and when the concentration of ozone is increased to 300ppm or even 1500ppm, the catalyst still has high conversion rates of 89.06% and 74.25%, thus completely meeting the actual requirements of different industries.
TABLE 3 YMn in example 1 at different ozone concentrations2O5Comparison of the ozone conversion of the samples over a reaction time of 5 hours (Experimental conditions: 600000 ml. g)-1·h -120 ℃ 20% relative humidity)
Example 9
The introduced mixed gas contains 105ppm ozone, the gas flow is 1L/min, and in order to investigate the influence of element doping or replacement on A site and M site of the catalyst, Y is prepared by hydrothermal synthesis method0.5La0.5Mn2O5、SmMn2O5、CeMn2O5、YMn1.5Co0.5O5、YFe2O5、YV2O5、Y0.5Gd0.5Mn1.5Ni0.5O5After granulation, selecting particles with the particle size of 40-60 meshes for ozone catalysis respectively, wherein the dosage of each catalyst in each test is 100mg, and the reaction space velocity is 600000 ml-g-1·h-1The reaction temperature was 20 ℃ and the relative humidity of the gas was 20%, the conversion of ozone was represented by the consumption rate of ozone, each test lasted at least 5 hours, the test results are shown in table 4, and the result curve is shown in fig. 14.
The result shows that when La is doped on the Y at the A position, the effect of catalyzing ozone is improved to a certain extent and reaches more than 93.39%, which indicates that the crystal mechanism is changed by adding La, the interaction of the Y element and the transition metal is more obvious, the efficiency of catalyzing ozone is improved more remarkably, and the synergistic effect among the elements is embodied; if Sm is replaced by Y, the catalytic effect is slightly reduced, but the Sm is still maintained to be more than 91.67%; and if Ce is used for replacing the site A of Y, the ozone conversion efficiency is reduced to 85.37%, which indicates that Ce is not the preferred element of the site A. Substantially phase-pure YMn when Co-doping is performed on the M site2O5The effect is consistent, which shows that the M bit is doped with CoThe overall crystal field structure can not be changed; when Mn at the M site was entirely replaced with Fe, the ozone conversion decreased to 89.36%, and when Mn was replaced with V, the ozone conversion decreased to 81.57%, indicating that Mn, Fe are preferred elements for the M site element, and V is not. When Gd and Ni were doped into A, M sites simultaneously, the ozone purifying effect was comparable to that of pure phase YMn in example 12O5Improved, consistent with the foregoing analysis, embodying the importance of crystal field regulation and the important role of synergy between elements. But relative to the phase-pure YMn2O5In example 9, the improvement of the ozone conversion rate by each doping component is not so large, and pure phase YMn is considered in consideration of the problems of metal price and preparation cost2O5Still the optimal choice.
TABLE 4 pairs of YMn in example 12O5Comparison of ozone conversion in 5 hours of reaction time for each sample with element doping or replacement (Experimental conditions: 105ppm O)3，600000ml·g-1·h -120 ℃ 20% relative humidity)
Example 10
The introduced mixed gas contains 105ppm ozone, the gas flow is 1L/min, and TiO is selected for researching the influence of the carrier on the catalytic ozone effect of the catalyst2As vectors, YMn was separately introduced2O5And TiO2Physical mixing granulation is carried out according to the mass ratio of 1:1 to obtain YMn2O5/TiO2-1, and YMn2O5And TiO2Mixing the raw materials in a ratio of 1: obtaining YMn by 1 mass ratio synchronous hydrothermal synthesis2O5/TiO 22, simultaneous selection of the individual TiO2Controls were run as blanks.
The above YMn2O5All in accordance with the sample of example 1. After granulation, granules with the granularity of 40-60 meshes are selected for ozone catalysis, and YMn2O5/TiO2-1、YMn2O5/TiO2-2 and TiO2The dosage of the catalyst is 100mg, and the reaction space velocity is 600000ml g-1·h-1The reaction temperature was 20 ℃ and the relative humidity of the gas was 20%, the conversion of ozone was represented by the consumption rate of ozone, each test lasted at least 5 hours, the test results are shown in table 5, and the result curve is shown in fig. 15. The results show that the blank TiO2The ozone-oxidizing activity of the catalyst was only 8.03%, but through the interaction with YMn2O5After physical grinding or in-situ hydrothermal synthesis mixing is carried out according to the mass ratio of 1:1, the ozone conversion rate can be kept at a higher level (more than or equal to 87.28 percent), and YMn is reduced2O5Is used in a cost-effective manner, and is formed by adding a carrier (not limited to TiO)2) Exploration of (A) makes YMn2O5The nanoparticles indicate orientation in practical applications. In addition, it can be seen that YMn prepared by physical mixing2O5/TiO2Ozone conversion of-1 slightly lower than in situ synthesized YMn2O5/TiO 22, indicating that the tightness of the active component and the carrier loading can directly influence the actual catalytic effect of the catalyst.
TABLE 5YMn2O5/TiO2-1、YMn2O5/TiO2-2 and TiO2Comparison of the ozone conversion in the 5 h reaction time (experimental conditions: 105ppm O)3，600000ml·g-1·h -120 ℃ 20% relative humidity)
Comparative example 1
The introduced mixed gas contains a concentrated gasOzone with a degree of 105ppm and a gas flow of 1L/min, for comparison, the AM is prominent2O5-xThe capacity of the catalyst for purifying ozone at room temperature is selected from commercial activated carbon and commercial 1% Pt/Al2O3、SiO2And mullite-type YMn obtained in example 1 of the present invention2O5Carrying out catalytic decomposition on ozone, granulating each sample, and selecting particles with the particle size of 40-60 meshes for ozone catalysis, wherein the dosage of each test is 100mg, the reaction temperature is 20 ℃, the relative humidity of gas is 20%, and the reaction space velocity is 600000 ml.g-1·h-1The ozone conversion is expressed as the ozone depletion rate, each test lasts at least 20 hours, the test results are shown in table 6, and the result curve is shown in fig. 16. The results show that YMn is present under the same experimental conditions2O5The material has the capability of efficiently decomposing and removing ozone at room temperature and has ultrahigh stability, and the commercial activated carbon mainly depends on the capability of adsorbing ozone and then slowly decomposes the ozone, so the initial efficiency is only 10.34 percent and the performance is reduced to 0.70 percent by quickly adsorbing the ozone to be close to saturation. In addition, the more expensive 1% Pt/Al contrast is2O3Catalyst, the conversion capacity of ozone after 20 hours was only 12.07%, indicating unsuitable for the field of ozone purification. And SiO2The sample has obvious effects on the decomposition of ozone, has no activity, is consistent with the concentration of ozone in an empty tube state, and can play a role of blank control.
TABLE 6 different reference catalysts from YMn in example 12O5Comparison of the ozone conversion of the samples over a reaction time of 20 hours (experimental conditions: 105ppm O)3，600000ml·g-1·h -120 ℃ 20% relative humidity)
Comparative example 2
The introduced mixed gas contained ozone at a concentration of 105ppm, and a gas flow rate of 1L/min was used for comparison of AM2O5-xThe YMnO is selected relative to the capability of common oxides on purifying ozone at room temperature3、γ-MnO2、OSM-2、Mn3O4、Y2O3And mullite-type YMn obtained in example 1 of the present invention2O5Carrying out catalytic decomposition on ozone, granulating each sample, and selecting particles with the particle size of 40-60 meshes for ozone catalysis, wherein the dosage of each test is 100mg, the reaction temperature is 20 ℃, the relative humidity of gas is 20%, and the reaction space velocity is 600000 ml.g-1·h-1The ozone conversion is expressed as the ozone depletion rate, each test lasts at least 20 hours, the test results are shown in table 7, and the result curve is shown in fig. 17. The results show that mullite-type YMn having a double crystal field of pyramid-type and octahedron-type2O5The material has the capability of efficiently decomposing and removing ozone at room temperature and has ultrahigh stability, and only has perovskite type YMnO with octahedral crystal field3The material has only 10.51% of decomposition capacity to ozone when reacting for 20 hours at room temperature. Gamma-MnO as the most active in manganese dioxide materials2And the ozone conversion efficiency is only about 40% under the same conditions, and the ozone conversion material does not have high durability of long-time reaction, and if the ozone conversion efficiency needs to be higher, the temperature obviously needs to be increased, and more energy consumption is generated. The ozone conversion rate of the manganese oxide octahedral molecular sieve OMS-2 is more than 29.23 percent, and the manganese oxide octahedral molecular sieve OMS-2 has certain catalytic activity due to larger specific surface area and more active sites, while the manganese oxide octahedral molecular sieve has a comparative example Mn3O4And Y2O3It does not have a high catalytic ozone activity and is deactivated quickly. The comparison of the above different materials on the ozone decomposition treatment within 20 hours shows that the mullite type YMn is very obvious2O5The excellent activity of the material can be considered to be capable of efficiently treating ozone at room temperature and efficiently decomposing ozone under a plurality of extremely harsh working conditions by combining the above embodiments, so that the purpose of protecting the environment is achieved.
Table 7 partial reference oxide catalysts and YMn in example 12O5Comparison of the ozone conversion of the samples over a reaction time of 20 hours (experimental conditions: 105ppm O)3，600000ml·g-1·h -120 ℃ 20% relative humidity)
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
from a comparison of example 1 and example 2, it can be seen that the pure phase mullite YMn of different micro-morphologies2O5All have the capability of efficiently catalyzing and purifying ozone at room temperature, and the YMn in the form of nano-particles2O5Is superior to nanotube-shaped YMn2O5. Example 3 YMn prepared in example 12O5The nanoparticles are subjected to a durability test for 100 hours, and the test result shows that the mullite material has excellent stability and catalytic activity. Examples 4, 5, 6, 7, and 8 phase-pure YMn prepared in example 1 was sequentially subjected to2O5The nano particles are subjected to an experiment of the influence of reaction conditions such as low temperature, high temperature, relative humidity, reaction space velocity, ozone concentration and the like on the catalytic effect of ozone, and the general formula AM is proved2O5The mullite oxide material has excellent ozone catalytic activity at low temperature, high temperature, low humidity, high reaction space velocity and high ozone concentration, and can be suitable for external conditions of various complex environments.
Comparative example 1 common commercial adsorbent activated carbon and commercial catalyst 1% Pt/Al were selected2O3Blank control SiO2And YMn prepared in example 12O5The nanoparticles are subjected to a comparative test under the same condition, and through comparison, the general formula AM is shown2O5The efficient ozone catalytic capability of the mullite oxide material. Comparative example 2A selection of YMnO which is common in manganese-based oxides3Perovskite, OSM-2 molecular sieves, gamma-MnO2And a binary oxide Mn3O4、Y2O3YMn prepared in example 12O5The nanoparticles were tested in the same conditions for comparison, and in the same manganese-based oxide comparison, YMn2O5Mullite still exhibits far higher activity than other manganese oxides by reacting with Mn3O4And Y2O3Shows YMn2O5The catalyst is not a simple oxide combination, but a novel oxide catalyst with double crystal fields, and the ultrahigh ozone catalytic activity is obtained by regulating and controlling the crystal fields of different elements at A, M.
Further, on the basis of pure-phase mullite, the A site and the M site are respectively doped and replaced by elements in the embodiment 9, the importance of crystal field regulation on the catalytic process is pointed out by the phenomenon that the catalytic performance of ozone is improved after the doping of the elements, and the preferred elements of which the catalytic capacity of ozone is slightly reduced after the replacement of the elements are respectively A, M sites are provided by the phenomenon that Y, Sm, Mn and Fe are respectively preferred elements. At the same time, although partially doped catalyst is relative to phase-pure YMn2O5The ozone conversion capacity is improved to a certain extent, but the improvement range is not large, and pure phase YMn is obtained by considering the problems of metal price and preparation cost2O5Still the optimal choice.
Further, example 10 embodies YMn2O5Nanoparticles and support TiO2The mixed composite catalyst is subjected to high-efficiency purification capacity on ozone through physical grinding or in-situ hydrothermal synthesis, and a foundation is provided for the forming and loading of the catalyst.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. General formula AM2O5The application of the compound as a catalyst for catalytic treatment of ozone, and the general formula AM2O5The compound is mullite composite oxide, A is any one or more of lanthanide series metal elements, Bi and Y, and M is any one or more of first transition series transition metal elements.
2. Use according to claim 1, wherein a is selected from any one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi and Y, preferably a is selected from any one or more of Sm, Gd, Y.
3. Use according to claim 1 or 2, wherein M is selected from any one or more of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, preferably from any one or more of Mn, Fe, Co.
4. Use according to claim 1 or 2, characterized in that said M essentially comprises the element Mn, preferably of said general formula AM2O5The compound has the structural formula of AMn2-yEyO5Wherein y is more than or equal to 0 and less than or equal to 1, and E is Ti, V, Cr, Fe, Co, Ni or Cu.
5. Use according to claim 1 or 3, wherein A must contain the element Y, preferably of the general formula AM2O5The compound has the structural formula YzD1-zM2O5Wherein z is more than or equal to 0 and less than or equal to 1, and D is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Bi.
6. Use according to claim 1, characterized in that said general formula AM2O5The compound has the structural formula YzD1- zMn2-yEyO5Wherein y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, E is Ti, V, Cr, Fe, Co, Ni or Cu, D is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Fe, Ni or Cu,Er, Tm, Yb, Lu or Bi.
7. Use according to claim 1, characterized in that said general formula AM2O5The microscopic shape of the compound is nanoparticle, nanorod, nanosheet, nanowire and/or nanotube, preferably the general formula AM2O5The particle size of the compound is between 5 and 100nm, preferably between 20 and 45nm, and the compound is preferably represented by the general formula AM2O5The specific surface area of the compound is more than 30m2A concentration of 50 to 150 m/g2Between/g; said general formula AM2O5The macroscopic shape of the compound is powder, sphere, granule, ceramic, etc.
8. Use according to claim 1, characterized in that said general formula AM2O5When the compound is used as a catalyst for catalyzing and purifying ozone, the general formula AM2O5The compound is mixed with a carrier and an adsorbent to form a composite catalyst or is coated on the carrier in the form of slurry, preferably the carrier is a carbon material, a ceramic material, a foam material or a solid acidic material, and more preferably ZrO2、TiO2、SiO2、WO3、Nb2O5、SnO2、Al2O3、Co3O4、CeO2、Fe2O3Activated carbon, graphene, clay, zeolites, organometallic frameworks, honeycomb ceramics, ceramic foams, cermets, foams, sponges.
9. The use of claim 1, wherein the ozone is present in any form including pure ozone, ozone present in any proportion in a gas mixture, ozone in water, ozone in soil, and the like.
10. Use according to claim 1, wherein the ozone treatment modality comprises catalytic purification of ozone alone and/or treatment of ozone together with other pollutants.
11. The use according to claim 1, characterized in that it comprises subjecting said ozone contained in said general formula AM to a temperature ranging from-40 ℃ to 500 ℃ at a relative humidity ranging from 0 to 100%2O5The treatment is carried out under the catalysis of the compound, and particularly, when ozone exists as a mixed gas component, the treatment efficiency reaches more than 92.18 percent at the room temperature of 20 ℃; preferably, the treatment temperature is-20 ℃ to 50 ℃; further preferably 0 ℃ to 25 ℃; preferably, the treatment humidity is 5% to 90%, and more preferably 5% to 60%; preferably, the concentration of said ozone in said gas stream is less than 10000 ppm; further preferably, said concentration in said gas stream is from 0.1 to 1500 ppm; preferably, the space velocity of the gas is 1200-1200000 ml-g-1·h-1More preferably 60000 to 600000 ml/g-1·h-1。
12. The use of claim 1, wherein the ozone catalyst is used in the form of, but not limited to, household air purifiers, wastewater treatment devices, waste gas treatment devices, medical ozone removal equipment, ultraviolet lamp ozone protection devices, equipment coating materials, and other ozone purification products.
13. An ozone purification article characterized by: use of the catalyst according to claims 1 to 12, preferably for domestic air purifiers, waste water treatment plants, waste gas treatment plants, medical ozone removal plants, uv lamp protection against ozone, plant coating materials.
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| CN115739106A (en) * | 2022-11-10 | 2023-03-07 | 南开大学 | Preparation method and application of composite oxide |
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