CN1736558A - Novel catalyst for microwave catalytic cleaning nitrogen oxide, its preparation process and application - Google Patents
Novel catalyst for microwave catalytic cleaning nitrogen oxide, its preparation process and application Download PDFInfo
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- CN1736558A CN1736558A CN 200510027964 CN200510027964A CN1736558A CN 1736558 A CN1736558 A CN 1736558A CN 200510027964 CN200510027964 CN 200510027964 CN 200510027964 A CN200510027964 A CN 200510027964A CN 1736558 A CN1736558 A CN 1736558A
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Abstract
The invention discloses a novel catalyst prepared with manganese dioxide as the active component and aluminum oxide as the carrier, and discloses the method for purifying nitrogen oxide with the catalyst in a microwave field. The microwave has a strong subsidiary catalytic effect on chemical reaction. And with effect of the catalyst and the microwave, the elimination ratio of nitrogen oxide can achieve more than 90%. The catalyst has a simple preparation process and has a high practical value.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method who removes nitrogen oxide, with and under the effect of micro ware auxiliary catalysis to the method for purification of nitrogen oxides.
Background technology
Environmental pollution and control are the focuses that each country pays close attention to always, and nitrogen oxide is one of primary pollution source that causes atmosphere pollution, discuss and research because of it is difficult to effectively be removed enjoy.The catalytic eliminating nitrogen oxide is acknowledged as researching value at present most, the most promising purification method; And microwave has tangible auxiliary catalysis effect to chemical reaction, with both in conjunction with utilization, the nitrogen oxide and the oxygen molecule that are attracted on the catalyst surface are excited into active material (electronics under microwave field, negative ions or free radical), and reconfigure---decompose or oxidized, thereby reach the purpose and the effect of removal of nitrogen oxide.
Utilize the corona discharge plasma method to remove the existing a lot of reports of nitrogen oxide at home and abroad.Its shortcoming is that investment is big, and energy utilization rate is low, the operating cost height, and with catalyst together the Use Limitation fruit is bad.
Microwave discharge is compared with corona discharge, and advantage is the method for heating in heating using microwave belongs to, and temperature increase is fast, no thermograde and energy utilization rate height, and operating cost is low.
In recent years, microwave catalysis has been obtained significant progress, and the research report to microwave catalytic cleaning nitrogen oxide also increases year by year both at home and abroad.Domestic Dalian Chemiclophysics Inst., Chinese Academy of Sciences that takes the lead in carrying out microwave catalysis research has researched and developed multiple catalyst and catalytic unit, and has delivered multinomial patent.To be the catalyst told about in 98114335.0 the patent be made up of the molecular sieve of load active component indium and iron oxide with wave absorbtion matter application number, in the atmosphere that has a large amount of oxygen to exist, with methane is reducing agent, and the conversion ratio that nitric oxide is reduced into nitrogen reaches 100%.The catalyst of narration is to be that matrix and the aluminium oxide that contains the high specific surface of noble metal or its oxide are that coating constitutes with the porous honeycomb ceramic in the Chinese invention patent (application number is 00136248.8), under the microwave field effect, when temperature reached more than 400 ℃, the NO conversion ratio reached more than 90%.
Catalyst used in the above-mentioned patent all contains noble metal or rare metal, and cost of material is high, and that preparation technology requires is loaded down with trivial details, the cycle is longer, thereby has limited its application in heavy industrialization.
Summary of the invention
The object of the present invention is to provide new catalyst of a kind of microwave catalytic cleaning nitrogen oxide and its production and application.
Catalyst for purification of nitrogen oxides of the present invention is an active component to have the manganese dioxide that absorbs microwave property, is carrier with the aluminium oxide, and wherein: manganese dioxide is 1: 4～1: 30 with the alumina weight ratio;
Preparation of catalysts method of the present invention comprises the steps:
With manganese dioxide, aluminium oxide and water mixed grinding (addition of water be manganese dioxide and aluminium oxide gross weight 5～15%), (pressure is 40～80Mpa) to compressing tablet then, air-dry (time is 3～5 hours), be ground into 10-20 purpose particle again, dried by the fire 2～5 hours down in 120～140 ℃, promptly obtain catalyst of the present invention;
Or adopt following method to prepare:
Elder generation is 30～70% manganese nitrate solution and aluminium oxide mixed grinding with weight concentration, left standstill 1～3 hour, (pressure is 40～80Mpa) to compression molding, air-dry (time is 3～5 hours), then 200～230 ℃ of down bakings 2～5 hours, treat the color blackening after, 400～1000 ℃ of following roastings 8～12 hours, pulverize, promptly get catalyst of the present invention.
Catalyst of the present invention is used under the auxiliary catalysis effect of microwave the purification to nitrogen oxide.Microwave frequency is 2450 ± 50MHz, and microwave power is 330W～390W.
Key problem in technology of the present invention is to develop a kind of novel mixed catalyst, and manganese dioxide wherein is can stablize and the material of strong absorption microwave, and it has stronger catalytic activity in the chemical reaction of purifying nitrogen oxide; And aluminium oxide is the carrier mass with huge specific area, and both are processed into a kind of novel catalyst, the nitrogen oxide that is adsorbed on the catalyst surface is excited under microwave field decomposes or oxidation, thereby play purification effects.
The principle of microwave purifying nitrogen oxide of the present invention is that the nitrogen oxide and the oxygen molecule that are adsorbed on the catalyst surface are excited into active material (electronics under microwave field, negative ions or free radical), reorganization runs foul of each other between them, final nitrogen oxide is oxidized or be decomposed, and reaches the purpose that removes nitrogen oxide.
Catalyst cost of the present invention is low, preparation technology is simple, and is with short production cycle, has very high practical value.
Description of drawings
Fig. 1 is the microwave reactor structural representation.
The specific embodiment
Below by EXPERIMENTAL EXAMPLE the present invention is specifically described; it is important to point out that present embodiment only is used for that the present invention will be further described; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1 Preparation of catalysts
Pressed disc method prepares catalyst: inhale ripple material manganese dioxide for analyzing pure (content 85%), alumina catalyst support is the neutral chromatography aluminium oxide, and particle diameter is the 100-200 order.Take by weighing a certain amount of manganese dioxide and aluminium oxide and put into mortar, add an amount of distilled water, fully mix, tablet press machine lower sheeting (pressure is 50Mpa), air-dry 3 hours, be ground into 10-20 purpose particle more then, dried by the fire 3 hours down in 120 ℃, sample takes out standby.
The immersion process for preparing catalyst: solution is 50% manganese nitrate solution (manganese nitrate is pure for analyzing), and alumina catalyst support is the same.Take by weighing a certain amount of aluminium oxide and manganese nitrate solution, fully mix in mortar, infiltration was evenly left standstill 2 hours, the moulding of tablet press machine lower sheeting (pressure is 50Mpa), air-dry 3 hours, change over to then in the drying box 210 ℃ of bakings 3 hours down, treat the color blackening after, place this moment roaster to burn 10 hours down again at 500 ℃, break into pieces, sieve out 10-20 purpose particle, standby.
Embodiment 2
The catalyst that uses pressed disc method to make adopts the quartz tube reactor of Fig. 1 under microwave field nitrogen oxide to be removed.
Atmosphere is NO 500ppm, O in the example
210%, all the other are N
2, air speed 1500h
-1
The quartz tube reactor internal diameter is 2.5cm, and height is 25cm, and it is 50 purpose glass sieves that the lower end is provided with the aperture, and the quartz ampoule that it is the sealing of 5mm that there is an internal diameter pipe inside reaches the reactor outside, is used to place thermocouple to measure the catalyst layer temperature.The catalyst granules for preparing is placed on the glass sieve, gas is fed reactor, open microwave, microwave power is controlled by pressure regulator, and gas componant is recorded by the KM900 fume component analysis instrument that Britain kane company makes.
Table 1 pressed disc method catalyst removing to NO
| Temperature (℃) | NO(out) | α(％) |
| 100 | 185 | 63.0 |
| 150 | 86 | 82.8 |
| 200 | 65 | 87.0 |
| 250 | 53 | 89.4 |
| 300 | 45 | 91.0 |
Annotate: gas concentration unit is ppm, and α is a removal efficiency, and microwave frequency is 2450 ± 50MHz, and pressure regulator power is 370W.
Embodiment 3
The catalyst that uses infusion process to make, study its under microwave field to removal of nitrogen oxide.
Experimental rig such as embodiment 2.Atmosphere is NO 500ppm, O in the example
210%, all the other are N
2, air speed 1500h
-1
Table 2 infusion process catalyst removing to NO
| Temperature (℃) | NO(out) | α(％) |
| 100 | 165 | 67.0 |
| 150 | 74 | 85.2 |
| 200 | 58 | 88.4 |
| 250 | 49 | 90.2 |
| 300 | 41 | 91.8 |
Annotate: gas concentration unit is ppm, and α is a removal efficiency, and pressure regulator power is 370W.Microwave frequency is 2450 ± 50MHz.
Embodiment 4
The catalyst of the different proportionings that the employing infusion process makes is studied its reactivity to nitrogen oxide under microwave field.
The catalyst microwave catalysis reactivity of the different proportionings of table 3
| MnO 2∶Al 2O 3(weight ratio) | 1∶4 | 1∶5 | 1∶10 | 1∶20 | 1∶30 |
| Removal efficiency (%) | 87.5 | 91.8 | 83.2 | 78.4 | 80.2 |
Annotate: import NO 500ppm, O
210%, all the other are N
2, air speed 1500h
-1, pressure regulator power is 370W, removal efficiency is to record under 300 ℃.Microwave frequency is 2450 ± 50MHz.
Claims (4)
1. a catalyst for purification of nitrogen oxides is an active component to have the manganese dioxide that absorbs microwave property, is carrier with the aluminium oxide with high-specific surface area, it is characterized in that manganese dioxide is 1: 4～1: 30 with the alumina weight ratio in the catalyst system therefor.
2. according to the preparation method of the described catalyst for purification of nitrogen oxides of claim 1, it is characterized in that, comprise the steps: earlier manganese dioxide, aluminium oxide and water mixed grinding, (pressure is 40～80Mpa) with its compressing tablet then, air-dry (time is 3～5 hours), after being ground into 10-20 purpose particle, dried by the fire 2～5 hours down in 120～140 ℃ again, promptly obtain catalyst of the present invention;
Or adopt following method to prepare:
With weight concentration 30～70% manganese nitrate solution and aluminium oxide mixed grinding, left standstill 1～3 hour, (pressure is 40～80Mpa) to compression molding, air-dry (time is 3～5 hours), then 200～230 ℃ of down bakings 2～5 hours, treat the color blackening after, 400～1000 ℃ of following roastings 8～12 hours, through pulverizing, can obtain catalyst of the present invention again.
3. a method that removes nitrogen oxide is characterized in that used catalyst is claim 1 or the described catalyst for purification of nitrogen oxides of claim 2, by its under the auxiliary catalysis effect of microwave to purification of nitrogen oxides.
4. according to the described method that removes nitrogen oxide of claim 3, it is characterized in that microwave frequency is 2450 ± 50MHz, microwave power is 330W～390W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510027964 CN1736558A (en) | 2005-07-21 | 2005-07-21 | Novel catalyst for microwave catalytic cleaning nitrogen oxide, its preparation process and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510027964 CN1736558A (en) | 2005-07-21 | 2005-07-21 | Novel catalyst for microwave catalytic cleaning nitrogen oxide, its preparation process and application |
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| CN1736558A true CN1736558A (en) | 2006-02-22 |
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ID=36079627
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102274733A (en) * | 2010-06-11 | 2011-12-14 | 南京理工大学 | Catalyst used for catalytically oxidizing NO and preparation method thereof |
| CN102553573A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院过程工程研究所 | Nitrogen oxide oxidizing catalyst and preparation method of nitrogen oxide oxidizing catalyst |
| WO2013097676A1 (en) * | 2011-12-30 | 2013-07-04 | 湘潭大学 | Process for removing nitrogen oxides by microwave catalysis |
| CN104474890A (en) * | 2014-12-05 | 2015-04-01 | 湘潭大学 | Method for denitrifying NO by directly decomposing NO catalytically by using supported metal oxide catalyst |
| CN106513009A (en) * | 2016-11-08 | 2017-03-22 | 昆明理工大学 | Vanadium-titanium-iron concentrate catalyst for NO catalytic oxidation and preparation method thereof |
| CN113786703A (en) * | 2021-10-14 | 2021-12-14 | 辽宁科技大学 | Method for efficiently adsorbing and purifying flue gas by using microwave outfield and industrial waste residues |
| CN115957619A (en) * | 2021-10-11 | 2023-04-14 | 华北电力大学（保定） | Microwave catalytic oxidation denitration method for ferro-manganese based molecular sieve |
-
2005
- 2005-07-21 CN CN 200510027964 patent/CN1736558A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102274733A (en) * | 2010-06-11 | 2011-12-14 | 南京理工大学 | Catalyst used for catalytically oxidizing NO and preparation method thereof |
| CN102274733B (en) * | 2010-06-11 | 2013-03-27 | 南京理工大学 | Catalyst used for catalytically oxidizing NO and preparation method thereof |
| CN102553573A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院过程工程研究所 | Nitrogen oxide oxidizing catalyst and preparation method of nitrogen oxide oxidizing catalyst |
| WO2013097676A1 (en) * | 2011-12-30 | 2013-07-04 | 湘潭大学 | Process for removing nitrogen oxides by microwave catalysis |
| CN104474890A (en) * | 2014-12-05 | 2015-04-01 | 湘潭大学 | Method for denitrifying NO by directly decomposing NO catalytically by using supported metal oxide catalyst |
| CN104474890B (en) * | 2014-12-05 | 2016-10-05 | 湘潭大学 | A kind of method of Engineering of Supported Metal Oxide Catalysts catalysis Direct Resolution NO denitration |
| CN106513009A (en) * | 2016-11-08 | 2017-03-22 | 昆明理工大学 | Vanadium-titanium-iron concentrate catalyst for NO catalytic oxidation and preparation method thereof |
| CN106513009B (en) * | 2016-11-08 | 2019-01-04 | 昆明理工大学 | A kind of sefstromite concentrate catalyst and preparation method thereof for NO catalysis oxidation |
| CN115957619A (en) * | 2021-10-11 | 2023-04-14 | 华北电力大学（保定） | Microwave catalytic oxidation denitration method for ferro-manganese based molecular sieve |
| CN113786703A (en) * | 2021-10-14 | 2021-12-14 | 辽宁科技大学 | Method for efficiently adsorbing and purifying flue gas by using microwave outfield and industrial waste residues |
| CN113786703B (en) * | 2021-10-14 | 2022-11-11 | 辽宁科技大学 | Method for efficiently adsorbing and purifying flue gas by using microwave outfield and industrial waste residues |
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