CN106693954A - Manganese oxide loaded cerium oxide catalyst, preparation and application - Google Patents
Manganese oxide loaded cerium oxide catalyst, preparation and application Download PDFInfo
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- CN106693954A CN106693954A CN201611028968.0A CN201611028968A CN106693954A CN 106693954 A CN106693954 A CN 106693954A CN 201611028968 A CN201611028968 A CN 201611028968A CN 106693954 A CN106693954 A CN 106693954A
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- cerium
- manganese
- oxide
- catalyst
- manganese oxide
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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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a manganese oxide loaded cerium oxide catalyst, preparation and application. The manganese oxide loaded cerium oxide catalyst is prepared by taking manganese oxide as a carrier and loading cerium oxide by a fractional precipitation method. A preparation method comprises the steps of dissolving a manganous nitrate solution in deionized water, dropwise adding an ammonium carbonate aqueous solution during stirring at a room temperature, continuing stirring for 1-3h, performing filtration, drying and roasting obtained solid to form black manganese oxide MnOx, dissolving a cerous nitrate precursor in the deionized water to form a cerium solution, putting manganese oxide in the cerium solution, dropwise adding the ammonium carbonate aqueous solution during the stirring, continuing stirring for 1-3h, performing the filtration, and drying and roasting obtained solid to form the manganese oxide loaded cerium oxide catalyst. A mole ratio of cerium to manganese is (0-1.0):1. The catalyst is used for selective catalytic reduction of nitric oxide; a conversion rate of nitric oxide can reach 73% at 175 DEG C; in addition, the raw materials for preparing the catalyst are easy to obtain; a technology is simple; the cost is lower; and the industrial production is easy to achieve.
Description
Technical field
The present invention relates to a kind of manganese oxide load cerium oxide catalyst and preparation, it is adaptable to which environmental contaminants are nitric oxide production
SCR, has application prospect in depollution of environment field.
Background technology
Nitrogen oxides（NOx）It is one of major pollutants in atmospheric environment, SCR（SCR）Technology is de-
Except one of effective ways of NOx in discharge flue gas.From the point of view of the present Research of domestic and international SCR technology, most widely used industrialization
Technology is with NH3It is reducing agent, V is main active component, TiO2It is the catalyst of carrier, it is de- when reaction temperature is more than 350 DEG C
Except NOx.The major advantage of the catalyst shows high activity and high antisulphuric ability, but operation temperature is higher, thus can only be by
SCR reactors are arranged between economizer and deduster, the dust containing high concentration in the flue gas of the process section, the alkali in dust
The materials such as metal, arsenic and mercury can produce very strong erosion and poisoning effect to catalyst, influence its life-span.
For these reasons, researching and developing SCR catalyst active under cryogenic has important economy
And practical significance, low-temperature SCR reactor can be directly configured at after dedusting and desulfurizer, largely reduce dust and
Sulphur poisons to catalyst.Research finds that the catalyst of alumina load noble metal has good low temperature active, reaction temperature
Can be carried out at 225 DEG C, but catalyst is relatively costly.It is more to low-temperature SCR catalyst active component research at present to be
Manganese and its metal oxide catalyst, reason are that the variable valence of manganese element is more, and electron exchange compares agreement, is conducive to oxygen
Change the generation of reduction reaction, and contain more Lattice Oxygen in Mn oxide crystal structure, the nitric oxide of absorption can be made effective
Reduction, and Mn oxide species is more, and in reaction, different valence state Mn oxide can be converted mutually, be equally beneficial for oxidation
The carrying out of reduction reaction.
Usual manganese oxide is to be supported on to investigate its performance on different carriers as the form of active component, and of the invention
In, it is, both as active component, and as carrier loaded cerium oxide, to obtain manganese oxide load cerium oxide catalyst using manganese oxide,
And investigate its performance to nitric oxide selective catalytic reduction reaction.
The content of the invention
The invention aims to overcome the deficiencies in the prior art, there is provided a kind of manganese oxide load cerium oxide catalyst and
Prepare and apply.
A kind of preparation method of manganese oxide load cerium oxide catalyst, it is characterised in that the catalyst is made with manganese oxide
It is carrier, Supporting cerium oxide is prepared by step-by-step precipitation method, and it is comprised the following steps that：
Weigh 35.8 gram of 50 wt% manganese nitrate solution to be dissolved in 400 ml deionized waters, 60 millis are added dropwise while stirring at room temperature
The ammonium carbonate solution of 2.0 mol/Ls is risen, is filtered after continuing to stir 1-3 hours, gained solid is put into 60-80 DEG C of baking oven
Dry 12 hours, then in 400-600 DEG C of Muffle kiln roasting 3-5 hours, obtain black oxidation manganese MnOx；
Nitric acid cerium precursor is dissolved in 50 ml deionized waters, cerium solution is obtained, then weighing 1.0 grams of manganese oxide, to be put into cerium molten
In liquid, 5.0 milliliters of ammonium carbonate solutions are added dropwise while stirring, are filtered after continuing to stir 1-3 hours, gained solid is put into 60-
Dried in 80 DEG C of baking ovens 12 hours, be then calcined 3-5 hours at 400-600 DEG C, obtain manganese oxide load cerium oxide catalyst, its
Middle cerium is 0-1.0 with the mol ratio of manganese: 1.
A kind of manganese oxide load cerium oxide catalyst prepared by method described above.
A kind of manganese oxide load cerium oxide catalyst the nitric oxide production SCR of environmental contaminants application,
It is characterized in that specific reaction condition is as follows：20-400 DEG C of reaction temperature, the mL/min of total gas flow rate 500, reaction gas constitutes and is
100-500 ppm nitric oxides, 100-500 ppm ammonias, 3-10% oxygen, remaining is nitrogen.
In the present invention, manganese oxide load cerium oxide catalyst is both as active component and negative as carrier using manganese oxide
Cerium oxide is carried, is prepared by the method for fractional precipitation, with catalysis activity higher, use it for nitric oxide production selection
Property catalysis reduction, conversion of nitric oxide gas rate can reach 73% at 175 DEG C, and the present invention prepares the raw material of catalyst and is easy to get, work
Skill is simple, and cost is relatively low, easily realizes industrialized production.And the raw material for preparing catalyst is easy to get, and process is simple, cost is relatively low,
Easily realize industrialized production.
Brief description of the drawings
Fig. 1 is the NH of catalyst described in embodiment of the present invention 1-53- SCR reactivity figures.
Specific embodiment
It is described in detail with reference to specific embodiment：The present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed implementation method and specific operation process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
Weigh 35.8 gram of 50 wt% manganese nitrate solution to be dissolved in 400 ml deionized waters, 60 millis are added dropwise while stirring at room temperature
The ammonium carbonate solution of 2.0 mol/Ls is risen, is filtered after continuing to stir 2 hours, gained solid is put into 70 DEG C of baking ovens and dries 12
Hour, then in 500 DEG C of Muffle kiln roastings 4 hours, obtain black oxidation manganese MnOx；
Weigh 1.25 grams of cerous nitrates to be dissolved in 50 ml deionized waters, obtain cerium solution, then weighing 1.0 grams of manganese oxide, to be put into cerium molten
In liquid, 5.0 milliliter of 1.03 mol/L ammonium carbonate solution is added dropwise while stirring, is filtered after continuing to stir 2 hours, gained is consolidated
Body is dried 12 hours in being put into 70 DEG C of baking ovens, is then calcined 4 hours at 500 DEG C, obtains manganese oxide load cerium oxide catalyst 1,
Wherein Ce:Mn=0.25:1.
Embodiment 2
Compared with Example 1 compared with, unlike the quality of cerous nitrate be 2.50 grams, the concentration of ammonium carbonate solution is rubbed for 2.06
You/liter, unclassified stores consumption and operating condition is same as Example 1 obtains manganese oxide load cerium oxide catalyst 2, wherein Ce:
Mn=0.5:1。
Embodiment 3
Compared with Example 1 compared with, unlike the quality of cerous nitrate be 5.00 grams, the concentration of ammonium carbonate solution is rubbed for 4.12
You/liter, unclassified stores consumption and operating condition is same as Example 1 obtains manganese oxide load cerium oxide catalyst 3, wherein Ce:
Mn=1:1。
Test case
Fresh obtained catalyst is respectively taken to be attached separately in crystal reaction tube.Test temperature from 20-400 DEG C, 100-400 DEG C it
Between, a test point is taken every 25 DEG C, respectively kept for 10 minutes in each test point.Nitric oxide production conversion ratio as shown in figure 1, from
As can be seen that the reactivity of pure zirconia cerium is very low in figure, pure zirconia manganese has certain reactivity, the activity at 175 DEG C
It is 60%, with the increase of cerium load capacity, reactivity is presented the trend for first raising and reducing afterwards.When cerium is with the mol ratio of manganese
0.25:When 1, catalyst reactivity at 175 DEG C is 83%.When the mol ratio of cerium and manganese is 0.5:When 1, catalyst is 175
DEG C when reactivity be 67%.When the mol ratio of cerium and manganese is 1:When 1, catalyst activity is low than pure zirconia manganese, at 175 DEG C
Reactivity is 54%.
Claims (3)
1. a kind of preparation method of manganese oxide load cerium oxide catalyst, it is characterised in that the catalyst be using manganese oxide as
Carrier, Supporting cerium oxide is prepared by step-by-step precipitation method, and it is comprised the following steps that：
Weigh 35.8 gram of 50 wt% manganese nitrate solution to be dissolved in 400 ml deionized waters, 60 millis are added dropwise while stirring at room temperature
The ammonium carbonate solution of 2.0 mol/Ls is risen, is filtered after continuing to stir 1-3 hours, gained solid is put into 60-80 DEG C of baking oven
Dry 12 hours, then in 400-600 DEG C of Muffle kiln roasting 3-5 hours, obtain black oxidation manganese MnOx；
Nitric acid cerium precursor is dissolved in 50 ml deionized waters, cerium solution is obtained, then weighing 1.0 grams of manganese oxide, to be put into cerium molten
In liquid, 5.0 milliliters of ammonium carbonate solutions are added dropwise while stirring, are filtered after continuing to stir 1-3 hours, gained solid is put into 60-
Dried in 80 DEG C of baking ovens 12 hours, be then calcined 3-5 hours at 400-600 DEG C, obtain manganese oxide load cerium oxide catalyst, its
Middle cerium is 0-1.0 with the mol ratio of manganese: 1.
2. a kind of manganese oxide load cerium oxide catalyst prepared by claim 1 methods described.
3. as manganese oxide load cerium oxide catalyst described in claim 2 in the nitric oxide production selective catalysis of environmental contaminants also
Former application, it is characterised in that specific reaction condition is as follows：20-400 DEG C of reaction temperature, the mL/min of total gas flow rate 500, instead
Should gas composition be 100-500 ppm nitric oxides, 100-500 ppm ammonias, 3-10% oxygen, remaining is nitrogen.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537514A (en) * | 2017-07-21 | 2018-01-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Ferromanganese cobalt monoblock type SCR low temperature catalysts preparation method, product and its application |
| CN115805080A (en) * | 2022-11-14 | 2023-03-17 | 山东科技大学 | Low-temperature efficient green denitration catalyst and preparation method thereof |
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| CN101462049A (en) * | 2007-12-20 | 2009-06-24 | 苏州工业园区安泽汶环保技术有限公司 | High-dispersion manganese-cerium composite oxides and preparation method thereof |
| CN102861565A (en) * | 2012-09-14 | 2013-01-09 | 上海电力学院 | Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof |
| CN104492425A (en) * | 2014-12-18 | 2015-04-08 | 华东理工大学 | Catalyst for ammonia selective reduction of nitrogen oxide and preparation method of catalyst |
| CN105251506A (en) * | 2015-10-30 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Load type cobalt and manganese compound oxide catalyst and preparation method of load type cobalt and manganese compound oxide catalyst |
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2016
- 2016-11-22 CN CN201611028968.0A patent/CN106693954B/en active Active
Patent Citations (4)
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| CN101462049A (en) * | 2007-12-20 | 2009-06-24 | 苏州工业园区安泽汶环保技术有限公司 | High-dispersion manganese-cerium composite oxides and preparation method thereof |
| CN102861565A (en) * | 2012-09-14 | 2013-01-09 | 上海电力学院 | Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof |
| CN104492425A (en) * | 2014-12-18 | 2015-04-08 | 华东理工大学 | Catalyst for ammonia selective reduction of nitrogen oxide and preparation method of catalyst |
| CN105251506A (en) * | 2015-10-30 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Load type cobalt and manganese compound oxide catalyst and preparation method of load type cobalt and manganese compound oxide catalyst |
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| 廖伟平，等: "不同制备方法的Mn-Ce催化剂低温SCR性能研究", 《化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537514A (en) * | 2017-07-21 | 2018-01-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Ferromanganese cobalt monoblock type SCR low temperature catalysts preparation method, product and its application |
| CN115805080A (en) * | 2022-11-14 | 2023-03-17 | 山东科技大学 | Low-temperature efficient green denitration catalyst and preparation method thereof |
| CN115805080B (en) * | 2022-11-14 | 2024-04-26 | 山东科技大学 | Low-temperature efficient green denitration catalyst and preparation method thereof |
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