CN108479762A - A kind of manganese oxide catalyst and its preparation method and application - Google Patents
A kind of manganese oxide catalyst and its preparation method and application Download PDFInfo
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- CN108479762A CN108479762A CN201810210948.8A CN201810210948A CN108479762A CN 108479762 A CN108479762 A CN 108479762A CN 201810210948 A CN201810210948 A CN 201810210948A CN 108479762 A CN108479762 A CN 108479762A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
Abstract
The present invention relates to a kind of manganese oxide catalyst and its preparation method and application, the method is：The mixture in manganese source or manganese source and composition metal source is dissolved, urea is added, is separated by solid-liquid separation after solution agitating and heating is precipitated；It will be roasted after the washing of gained solid phase, drying, obtain manganese oxide catalyst.The present invention is using urea as precipitating reagent, manganese oxide catalyst is prepared using homogeneous co-precipitation, gained catalyst has many advantages, such as highly selective, high activity, high stability, low light-off temperature and long life when ethyl acetate is burnt in catalysis, for more existing noble metal catalyst, catalytic activity higher, catalytic temperature section is lower, and material source is extensive, preparation process is simple, application prospect with good economic efficiency and wide.
Description
Technical field
The present invention relates to catalyst preparation and atmosphere pollution purification techniques fields, and in particular to a kind of Mn oxide catalysis
Agent and its preparation method and application.
Background technology
Currently, as the movable intensity of human industry increases, a large amount of volatile organic matter (Volatile Organic
Compound, VOCs) it is discharged into atmospheric environment, it is reacted by sequence of chemical and causes environmental pollution.Such as some activity are strong
With another atmosphere pollution nitrogen oxides (NOx) photochemical reaction can occur for VOCs, cause surface ozone concentration to increase, shape
At photochemical pollution；It is molten that the VOCs that some steam force down can also pass through complex process nucleation and growth process formation Secondary Organic gas
Glue, and secondary organic aerosol is exactly the important component of fine particle PM2.5.It can be seen that VOCs be to be formed photochemical pollution and
The important precursor of Brownish haze.In addition to this, VOCs itself can also constitute grave danger to health.Such as it is common
VOCs such as formaldehyde, benzene, toluene etc. has carcinogenic, teratogenesis harm.Therefore, photochemical fog is removed, Particulate Pollution is reduced,
Urban air-quality is improved, protects the health of the common people, VOCs emission controls and removal imperative.
VOCs's derives from a wealth of sources, and includes mainly oil, chemical industry, medicine, packaging, printing, application etc., is with paint industry
Example, nearly 7,000,000 tons/year of VOCs discharge capacitys account for about the 1/3 of VOCs total releases.Purification neck is eliminated in paint industry VOCs
Domain, west Main Developed Countries and Japan's starting are more early.It has just been promulgated in the nineteen fifty-five U.S.《Air Pollution Control Board preparation method》, right
Air pollutant emission classification and total amount have done detailed regulation, promulgate again later《Pure air method》, and in 1970 and
Nineteen ninety has done revises twice；Technicality regulation also is formulated exclusively for the VOCs of paint industry discharges in 1966, i.e. " 66 methods
Rule ".Law obligate the promotion with company interest under, difference eliminate VOCs technologies be developed and use.
China pays much attention to the pollution problem of VOCs at present, it is desirable that arrive the year two thousand twenty, it is basic realize VOCs from raw material to product,
From production to the overall process emission reduction of consumption.Therefore, the emission-reduction technology of VOCs has obtained extensive research and probe.Wherein catalysis burning
Technology has preferable application prospect, and the exploitation of new catalyst is hot spot and the forward position of research.
It is a kind of widely used fine chemical product in ethyl acetate, has excellent dissolubility, quick-drying, purposes wide
It is general, be a kind of very important Organic Chemicals and fabulous industrial solvent, be widely used in acetate fiber, ethyl cellulose,
In the production process of chlorinated rubber, vinyl, acetate fiber resin, synthetic rubber, coating and paint etc..Root is it is estimated that every
The big appointment in the year whole world uses about 1,300,000 tons of ethyl acetate, the wherein overwhelming majority to be used as solvent.According to statistics, about 77%
Ethyl acetate solvent causes air pollution among being discharged into air, influences environmental quality and common people's health.
The catalyst of existing catalytic decomposition VOCs is mostly noble metal catalyst, such as CN106391009A discloses one kind
The preparation method of catalyst for VOCs catalytic oxidation uses has obtained Pt and has been supported on TiO2On catalysis oxidation VOCs catalysis
Agent.CN105854890A provides a kind of VOCs catalyst and preparation method thereof, and ion-exchange is utilized to synthesize (FeSnO
(OH)5) micro-nano material, by micro-nano material using infusion process in its area load Pt nano particles, finally by sample in air gas
Compound thermocatalyst is prepared in calcining under atmosphere.CN106607056A provides a kind of graphene-supported noble metal composite oxide
Subcoat is distributed with using graphene as carrier in VOCs catalyst and preparation method on the multiple-level surface of carrier, basis applies
Layer material includes TiO2, cerium zirconium sosoloid and oxide catalyst, noble metal catalyst is distributed on base coating material.
Above-mentioned loaded noble metal catalyst is expensive, does not utilize large-scale promotion, when being catalyzed ethyl acetate decomposition
Catalytic efficiency is unsatisfactory, need could effectively to carry out at a higher temperature (>300 DEG C), it is therefore desirable to development cost is cheap
The new catalyst of the good efficient catalytic burning ethyl acetate of stability.
Invention content
In view of problems of the prior art, the purpose of the present invention is to provide a kind of manganese oxide catalyst and its systems
Manganese oxide catalyst, gained catalysis is prepared using homogeneous co-precipitation using urea as precipitating reagent in Preparation Method and application
Agent has highly selective, high activity, high stability, low light-off temperature and long life etc. when ethyl acetate is burnt in catalysis
Advantage, for more existing noble metal catalyst, catalytic activity higher, catalytic temperature section is lower, and material source is extensive, system
Standby application prospect simple for process, with good economic efficiency and wide.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of method preparing manganese oxide catalyst, the method includes following steps
Suddenly：
(1) mixture in manganese source or manganese source and composition metal source is dissolved, urea is added, solution agitating and heating is precipitated
After be separated by solid-liquid separation；
(2) it is roasted after obtained solid phase washing, drying being separated by solid-liquid separation, obtains manganese oxide catalyst.
The present invention utilizes urea as precipitating reagent, selects homogeneous co-precipitation that manganese oxide catalyst has been prepared, and urinates
With the rising of temperature slowly hydrolysis occurs for element in aqueous solution, gradually releases OH-And CO3 2-Ion.The process will not change
Become the concentration of metal ions in solution, opposite other precipitating reagents such as ammonium hydroxide and ammonium hydrogen carbonate, it can be more advantageous to evengranular
Precipitation.
According to the present invention, step (1) described manganese source is potassium permanganate, manganese acetate, manganese nitrate, manganese sulfate, manganese acetate, carbonic acid
In sub- manganese, manganese sulfate, manganese chloride or phosphate dihydrogen manganese any one or at least two combination, such as can be permanganic acid
It is any one in potassium, manganese acetate, manganese nitrate, manganese sulfate, manganese acetate, carbonic acid Asia manganese, manganese sulfate, manganese chloride or phosphate dihydrogen manganese
Kind, typical but non-limiting is combined as：Potassium permanganate and manganese acetate, manganese nitrate and manganese sulfate, carbonic acid Asia manganese and manganese sulfate,
Manganese chloride and phosphate dihydrogen manganese, potassium permanganate, manganese acetate and carbonic acid Asia manganese etc., as space is limited and for concise consideration, this hair
Bright no longer exclusive list.
According to the present invention, step (1) the composition metal source be platinum nitrate, palladium nitrate, indium nitrate, silver nitrate, cerous nitrate,
In ferric nitrate, copper nitrate, ferric sulfate or copper sulphate etc. any one or at least two combination, such as can be platinum nitrate,
Any one in palladium nitrate, indium nitrate, silver nitrate, cerous nitrate, ferric nitrate, copper nitrate, ferric sulfate or copper sulphate etc., it is typical but
Non-limiting is combined as：Platinum nitrate and palladium nitrate, indium nitrate and silver nitrate, cerous nitrate and ferric nitrate, ferric sulfate and copper sulphate
Deng as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the molar ratio of the manganese in step (1) described manganese source and the metal in composition metal source is (20-
80):1, such as can be 20:1、30:1、40:1、50:1、60:1、70:1 or 80:It is specific between 1 and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the molar ratio of the manganese in above-mentioned manganese source and the metal in composition metal source is preferably 40:1.
According to the present invention, excessive urea is added in step (1).
According to the present invention, the temperature heated in step (1) is 65-95 DEG C, for example, can be 65 DEG C, 70 DEG C, 75 DEG C, 80
DEG C, 85 DEG C, 90 DEG C or the specific point value between 95 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
According to the present invention, the time heated in step (1) is 1-25h, for example, can be 1h, 5h, 10h, 15h, 20h or
Specific point value between 25h and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
Step (2) of the present invention is as long as gained solid phase is dried in the drying, and is not done to specific temperature and time
It is specific to limit.
According to the present invention, the temperature of step (2) described roasting is 400-700 DEG C, for example, can be 400 DEG C, 450 DEG C, 500
DEG C, 550 DEG C, 600 DEG C, 650 DEG C or the specific point value between 700 DEG C and above-mentioned numerical value, examining as space is limited and for concise
Consider, the present invention no longer exclusive list.
According to the present invention, the temperature of step (2) described roasting is preferably 500 DEG C.
According to the present invention, time of step (2) described roasting is 1-5h, such as can be 1h, 2h, 3h, 4h or 5h, and
Specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the method that homogeneous co-precipitation of the present invention prepares manganese oxide catalyst includes following step
Suddenly：
(1) mixture in manganese source or manganese source and composition metal source is dissolved, excess urea is added, by solution agitating and heating
It is separated by solid-liquid separation after to 65-95 DEG C of precipitation reaction 1-25h；The manganese source is potassium permanganate, manganese acetate, manganese nitrate, manganese sulfate, acetic acid
In manganese, carbonic acid Asia manganese, manganese sulfate, manganese chloride or phosphate dihydrogen manganese any one or at least two combination, it is described compound
Source metal is in platinum nitrate, palladium nitrate, indium nitrate, silver nitrate, cerous nitrate, ferric nitrate, copper nitrate, ferric sulfate or copper sulphate etc.
Any one or at least two combination, wherein the molar ratio of the manganese in manganese source and the metal in composition metal source be (20-
80):1；
(2) it will be separated by solid-liquid separation after obtained solid phase washing, drying and roast 1-5h at 400-700 DEG C, obtain Mn oxide
Catalyst.The present invention selects the operation that means commonly used in the art are separated by solid-liquid separation, for example, can be filtering, filter, centrifugation,
Sedimentation etc., but it is non-be only limitted to this, should be specifically chosen according to actual separation situation.
Second aspect, the present invention provides the Mn oxide catalysis that a kind of method as described in relation to the first aspect is prepared
Agent.
The third aspect, the present invention provides the manganese oxide catalysts that a kind of method as described in relation to the first aspect is prepared
Application, the manganese oxide catalyst be applied to catalysis burning ethyl acetate.
For the present invention using urea as precipitating reagent, the manganese oxide catalyst prepared using homogeneous co-precipitation can be 200
Realize at DEG C to the efficient catalytic of ethyl acetate, compared with conventional precious metal catalyst catalytic temperature (>300 DEG C) for, not only drop
Low catalytic temperature, and catalytic effect is more preferably is a kind of high, resistance to high-speed at low cost, active, catalytic temperature is low, performance is good
New catalyst.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention has very excellent activity using manganese oxide catalyst prepared by homogeneous co-precipitation, than normal
The noble metal catalyst activity of rule is more preferable, can be catalyzed, and cost is lower, be can be widely applied at lower temperatures
The purified treatment field of ethyl acetate.
(2) even if catalyst produced by the present invention still shows excellent catalytic performance, and this under high-speed environment
Body small volume can facilitate and make small reactor, reduce the cost of fixed investment.
(3) catalyst produced by the present invention has very excellent CO2Selectivity is generated, by-product is very in catalytic process
It is few.
(4) preparation method provided by the invention is simple, easily operated and of low cost, is suitable for industrialization promotion.
Description of the drawings
Catalysis effect when the catalyst ethyl acetate that Fig. 1 is 1-5 of the embodiment of the present invention and comparative example 1 obtains decomposes
Fruit is schemed；
When Fig. 2 is that the catalyst ethyl acetate that the embodiment of the present invention 1,6,7,8 and comparative example 1,2 obtain decomposes
Catalytic effect figure；
Catalysis when the catalyst ethyl acetate that Fig. 3 is 9-14 of the embodiment of the present invention and comparative example 1 obtains decomposes
Design sketch；
Fig. 4 is that the catalyst that the embodiment of the present invention 1 obtains is catalyzed ethyl acetate decomposition efficiency and carbon dioxide production at 200 DEG C
Rate design sketch.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
For the present invention is better described, it is easy to understand technical scheme of the present invention, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
(1) using potassium permanganate as the sources Mn, the mole according to Mn is that 0.1mol is added in 273mL deionized waters, is made
At solution, and excess urea 63g is added thereto as precipitating reagent, is continuously stirred under 90 DEG C of water bath conditions for 24 hours, then to heavy
Starch is filtered；
(2) sediment that step (1) obtains is placed in baking oven at 100 DEG C dry 12h by washing, then in horse
3h not is roasted at 500 DEG C in stove, under air atmosphere, obtains powder catalyst.
Embodiment 2
Compared with implementing 1, other than manganese source potassium permanganate is replaced with manganese acetate, other steps and condition and embodiment 1
It is identical.
Embodiment 3
Compared with implementing 1, other than manganese source potassium permanganate is replaced with manganese sulfate, other steps and condition and embodiment 1
It is identical.
Embodiment 4
Compared with implementing 1, other than manganese source potassium permanganate is replaced with manganese nitrate, other steps and condition and embodiment 1
It is identical.
Embodiment 5
Compared with implementing 1, other than manganese source potassium permanganate is replaced with manganese chloride, other steps and condition and embodiment 1
It is identical.
Embodiment 6
Compared with implementing 1, other than the mole 0.1mol of Mn is replaced with 0.05mol, other steps and condition and reality
It is identical to apply example 1.
Embodiment 7
Compared with implementing 1, other than the mole 0.1mol of Mn is replaced with 0.15mol, other steps and condition and reality
It is identical to apply example 1.
Embodiment 8
Compared with implementing 1, other than the mole 0.1mol of Mn is replaced with 0.2mol, other steps and condition and implementation
Example 1 is identical.
Embodiment 9
(1) using manganese acetate as the sources Mn, using palladium nitrate as presoma composite noble metal (Pd), Mn is controlled:Pd molar ratios are
40:1, the mole according to Mn is that manganese acetate and palladium nitrate are added in 273mL deionized waters by 0.1mol, and solution is made, and
Excess urea is added thereto as precipitating reagent, 10h is continuously stirred under 90 DEG C of water bath conditions, then sediment is taken out
Filter；
(2) sediment that step (1) obtains is placed in baking oven at 100 DEG C dry 12h by washing, then in horse
3h not is roasted at 500 DEG C in stove, under air atmosphere, obtains powder catalyst.
Embodiment 10
Compared with Example 9, other than palladium nitrate to be replaced with to platinum nitrate (Pt), other steps and condition and embodiment 9
It is identical.
Embodiment 11
Compared with Example 9, other than palladium nitrate to be replaced with to yttrium nitrate (Ir), other steps and condition and embodiment 9
It is identical.
Embodiment 12
Compared with Example 9, other than palladium nitrate to be replaced with to cerous nitrate (Ce), other steps and condition and embodiment 9
It is identical.
Embodiment 13
Compared with Example 9, other than palladium nitrate to be replaced with to ferric nitrate (Fe), other steps and condition and embodiment 9
It is identical.
Embodiment 14
Compared with Example 9, other than palladium nitrate to be replaced with to copper nitrate (Cu), other steps and condition and embodiment 9
It is identical.
Comparative example 1
Noble metal catalyst Pd/Al is prepared in accordance with the following methods2O3。
Powder Oxidation aluminium 10g is weighed, 500ml deionized waters are once used, is eluted repeatedly by Buchner funnel suction filtration, it is primary to elute
About 30 minutes, sample was drained spare；Two water palladium nitrate 0.25g are weighed, is put into 100ml deionized waters, stirs and evenly mixs；It will be above-mentioned
Alumina powder is added among 100ml solution, impregnates 1h.Above-mentioned solid-liquid system is transferred in rotary evaporation bottle, it is gradual by room temperature
It is warming up to 60 DEG C, evaporation of the solvent is clean；The product after dipping is put into baking oven later, 100 DEG C are continued to dry 12h；Then it takes
Go out, be down to room temperature, is put into roasting, 5 DEG C of heating rate in Muffle furnace and often assigns to 500 DEG C of constant temperature 3h, then Temperature fall, obtains expensive
Metallic catalyst Pd/Al2O3。
Comparative example 2
Compared with Example 1, other than urea is replaced with ammonium hydrogen carbonate, other steps and condition and embodiment 1 are homogeneously
Together, i.e., it is co-precipitated using other precipitating reagents.
As shown in Figure 2, the performance for the catalyst burning ethyl acetate that this comparative example obtains is poor, only at 300 DEG C
There is about 80% conversion ratio.
Performance test
Catalyst sample made from embodiment 1-15 and comparative example 1-2 is subjected to tabletting, grinding, sieving, takes 40-60
Mesh particle carries out ethyl acetate purification activity rating, evaluating catalyst condition on fixed bed reactors：The group of reaction mixture gas
Become：Ethyl acetate [C4H8O2]=1500ppm, [O2]=20%, N2Make Balance Air, total gas flow rate 300mL/min, air speed
For 90L/ (gh), 150-400 DEG C of reaction temperature.Benzene, two are measured using gas chromatograph (Agilent -7980B, FID and TCD)
The gas concentrations such as carbonoxide, oxygen.As a result as shown in Figs 1-4.
Comparing result is it is found that catalyst prepared by homogeneous co-precipitation of the present invention has the energy of significantly removal ethyl acetate
Power, activity is above the noble metal catalyst of existing business, and different manganese sources, different manganese content catalytic effect difference are not
Greatly；When being catalyzed ethyl acetate decomposition, ethyl acetate decomposition efficiency and yield of carbon dioxide are very high, CO2It is good to generate selectivity.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method preparing manganese oxide catalyst, which is characterized in that the described method comprises the following steps：
(1) mixture in manganese source or manganese source and composition metal source is dissolved, urea is added, it is solid after solution agitating and heating is precipitated
Liquid detaches；
(2) it is roasted after obtained solid phase washing, drying being separated by solid-liquid separation, obtains manganese oxide catalyst.
2. the method as described in claim 1, which is characterized in that step (1) described manganese source is potassium permanganate, manganese acetate, nitric acid
Any one in manganese, manganese sulfate, manganese acetate, carbonic acid Asia manganese, manganese sulfate, manganese chloride or phosphate dihydrogen manganese or at least two
Combination.
3. method as claimed in claim 1 or 2, which is characterized in that step (1) the composition metal source is platinum nitrate, nitric acid
Any one in palladium, indium nitrate, silver nitrate, cerous nitrate, ferric nitrate, copper nitrate, ferric sulfate or copper sulphate etc. or at least two
Combination.
4. method as described in any one of claims 1-3, which is characterized in that the manganese in step (1) described manganese source and compound gold
The molar ratio of metal in category source is (20-80):1, preferably 40:1.
5. method according to any one of claims 1-4, which is characterized in that excessive urea is added in step (1).
6. method as described in any one in claim 1-5, which is characterized in that the temperature heated in step (1) is 65-95 DEG C；
Preferably, the time heated in step (1) is 1-25h.
7. the temperature of method as claimed in any one of claims 1 to 6, step (2) described roasting is 400-700 DEG C, preferably
500℃；
Preferably, the time of step (2) described roasting is 1-5h, preferably 3h.
8. such as claim 1-7 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) mixture in manganese source or manganese source and composition metal source is dissolved, excess urea is added, solution is heated with stirring to 65-
It is separated by solid-liquid separation after 95 DEG C of precipitation reaction 1-25h；The manganese source is potassium permanganate, manganese acetate, manganese nitrate, manganese sulfate, manganese acetate, carbon
In sour Asia manganese, manganese sulfate, manganese chloride or phosphate dihydrogen manganese any one or at least two combination, the composition metal source
It is any one in platinum nitrate, palladium nitrate, indium nitrate, silver nitrate, cerous nitrate, ferric nitrate, copper nitrate, ferric sulfate or copper sulphate etc.
Kind or at least two combination, wherein the molar ratio of the manganese in manganese source and the metal in composition metal source be (20-80):1；
(2) it will be separated by solid-liquid separation after obtained solid phase washing, drying and roast 1-5h at 400-700 DEG C, obtain Mn oxide catalysis
Agent.
9. the manganese oxide catalyst prepared such as claim 1-8 any one of them methods.
10. such as the application of manganese oxide catalyst prepared by claim 1-8 any one of them methods, which is characterized in that institute
It states manganese oxide catalyst and is applied to catalysis burning ethyl acetate.
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| CN112694130A (en) * | 2020-12-02 | 2021-04-23 | 中国科学院城市环境研究所 | alpha-MnO taking (211) crystal face as dominant crystal face2And preparation method and application thereof |
| CN113145108A (en) * | 2021-04-26 | 2021-07-23 | 中国科学院城市环境研究所 | MnO capable of adjusting oxygen species distributionxCatalyst, preparation method and application thereof |
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