CN106466609A - The catalyst of carbon monoxide under low temperature catalysis reduction removing nitrogen oxides - Google Patents
The catalyst of carbon monoxide under low temperature catalysis reduction removing nitrogen oxides Download PDFInfo
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- CN106466609A CN106466609A CN201510514291.0A CN201510514291A CN106466609A CN 106466609 A CN106466609 A CN 106466609A CN 201510514291 A CN201510514291 A CN 201510514291A CN 106466609 A CN106466609 A CN 106466609A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The present invention relates under a kind of cryogenic conditions catalyzing carbon monoxide reduction removing nitrogen oxides catalyst, mainly solves the problems, such as to exist in prior art catalyst active low under cryogenic or under the high temperature conditions poor selectivity it is impossible to effectively remove nitrogen oxides.The present invention passes through to adopt to load with the oxide of copper or silver as active component on the alumina support, carry out the technical scheme of modification again with rare earth oxide and VIB, VIIB family metal oxide, preferably solve this problem, can be used in the commercial production that low temperature removes nitrogen oxides.
Description
Technical field
The present invention relates to a kind of catalyst of carbon monoxide under low temperature catalysis reduction removing nitrogen oxides.
Background technology
With the fast development of countries in the world modern industry, atmospheric pollution has become an increasingly serious global problem.
One of Air Pollutant Discharge that NOx is well recognized as.China is the developing country based on fire coal, in longer time from now on
Interior, energy resource structure based on coal for the China will not change, and the coal-fired nitrogen oxides producing are to produce acid rain, photochemical fog
And the principal element that relevant environment is destroyed.Acid rain can be to soil productivity, crops, forest, inland lake, building etc.
Damage.In addition, NOx can induce many human body diseases, human health is particularly had greatly to upgrowth and development of children
Harm.
United States Patent (USP) US6685897 discloses a kind of catalyst exchanging molecular sieve with alkali metal cation, and this catalyst has
There are high specific surface and big pore structure, catalyst operating temperature range is 150～450 DEG C.
United States Patent (USP) US4925825 proposes one kind with ammonia as reducing agent, the method for catalytic reduction of NOx, the catalysis of use
Agent is with TiO2-V2O5-Mo2O3For active component, it is more than 350 DEG C using temperature, this is that one kind is suitable under mesophilic condition
The catalyst for reduction of oxides of nitrogen using.
Chinese patent CN01131952.6 discloses a kind of catalyst of ammonia selective reducing nitrogen oxide, and this catalyst is oxygen
Change copper, the Mn complex oxide catalyst of aluminum load, under conditions of 150～350 DEG C of reaction temperature, catalyst has high
Activity and stability.
Chinese patent CN87100737A disclose a kind of in the presence of ammonia by nitrogen oxide selective reduction be nitrogen catalyst,
This catalyst, with cobalt oxide and zeolite as main active component, also contains the oxide being selected from vanadium and copper on a small quantity as co-catalysis
Agent.This catalyst belongs to mixed oxide type catalyst, at 350 DEG C, the NOx of 1600ppm can be made to reduce 90%.
Disclose one kind in United States Patent (USP) US4981659 and NOx is optionally reduced to nitrogen in the presence of hydrogen reducing agent
Catalyst.This catalyst employs VIII race's noble metal, and active component is made up of one or more of Pt, Pd, Ir mixing.
It is in place of the novelty of catalyst to employ hydrophobicity organic polymer as catalyst carrier.Heat-resisting due to organic polymer
Poor-performing, therefore catalyst using temperature more than 200 DEG C when, the conversion ratio of NOx is less than 90%.
We adopt and load on the alumina support with the oxide of copper or silver as active component, then with rare earth oxide and
VIB, VIIB family metal oxide carries out the technical scheme of modification, and the catalyst obtaining is used for containing carbon monoxide simultaneously
In the waste gas of nitrogen oxides, the effective nitrogen oxides reduction of carbon monoxide can be made, go while denitrification, to reduce an oxidation
Carbon content, catalyst has high activity and high selectivity and longer service life.
Content of the invention
The technical problem to be solved is that existing ammonia selective reducing nitrogen oxide catalyst activity is high, stability is poor
Problem, provide a kind of catalyst of Carbon monoxide reduction nitrogen oxides, this catalyst has that reaction temperature is low, reactivity
Feature high, that stability is high.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of carbon monoxide under low temperature catalysis reduction removing
The catalyst of nitrogen oxides, comprises following components by weight percentage：
A) 2～20% copper oxide or silver oxide；
B) 1～10% VIB, VIIB family metal oxide；
C) 0～5% rare earth oxide；
D) 65～97% alumina support.
In technique scheme, in terms of catalyst weight percent, the content preferred scope of copper oxide or silver oxide is 3～15%,
The content preferred scope of VIB, VIIB family metal oxide is 2～8%, and the content preferred scope of rare earth oxide is 0.5～3%.
VIB, VIIB family metal oxide preferred version is selected from least one of Cr, Mo, W, Mn, Re, rare-earth oxidation
Thing preferred version is selected from least one of La, Ce, Pr, Nd.
In technique scheme, preferred technical scheme is that catalyst by weight percentage, also comprises in the periodic table of elements
At least one in II B race element or its oxide.In technique scheme, preferred technical scheme is that II race of B race is first
At least one in Zn, Cd for the element.
Preferably technical scheme is that, in terms of catalyst weight percent, the content of II B race element or its metal-oxide is
0.1～10%.Preferably technical scheme is, in terms of catalyst weight percent, the containing of II B race element or its metal-oxide
Measure as 0.2～5%.
The preparation method of catalyst of the present invention is equi-volume impregnating, and active component that will be required and dressing agent adopt equal-volume
The method of dipping loads to alumina carrier surface, and drying, roasting are obtained finished catalyst.
At present, Catalytic Decomposition of Nitric Oxide typically adopts NH3SCR (NH3- SCR) technology, although this technology
Obtain industrial applications, but still suffer from a lot of defects：(1)NH3It is a kind of poisonous corrosive gas, store and transport
Trouble, has high demands to pipeline equipment, involves great expense；(2) in this process, NH3Need to control addition, easily reveal
Or reaction is not exclusively, thus causing secondary pollution；(3) operating temperature range is narrow, wayward.Therefore, finding one kind can
Replace NH3Reducing agent significant.We adopt CO as reducing agent, solve with NH3Each for reducing agent presence
The problem of kind, especially for the reaction system that there are nitrogen oxides and carbon monoxide simultaneously, eliminates the trouble of additional reducing agent,
And while removing nitrogen oxides, also consumes part carbon monoxide, strengthen the effect of environmental conservation.
The catalyst of catalyzing carbon monoxide nitrogen oxides reduction of the present invention effectively overcome poor catalyst stability in prior art,
The not high shortcoming of transformation efficiency of the oxides of nitrogen, by optimizing reaction condition, transformation efficiency of the oxides of nitrogen, up to 100%, achieves relatively
Good technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Example 1】
First measure the water absorption rate of alumina support.According to carrier water absorption rate and plan load capacity, prepare containing 3% copper oxide,
8% chromium oxide and the mixed solution of 0.5% lanthana, after being impregnated 5 hours using equi-volume impregnating, in 120 DEG C of baking ovens
Dry, then at 580 DEG C of Muffle kiln roastings 10 hours, obtain the catalyst that required carbon monoxide under low temperature removes nitrogen oxides
Cu3Cr8La0.5.
【Example 2】
According to the carrier water absorption rate measuring and plan load capacity, prepare containing 5% copper oxide, 2% molybdenum oxide and 3% cerium oxide
Mixed solution, using equi-volume impregnating impregnate 5 hours after, in 120 DEG C of baking ovens dry, then at 580 DEG C of Muffle furnaces
Middle roasting 10 hours, obtains the catalyst Cu5Mo2Ce3 that required carbon monoxide under low temperature removes nitrogen oxides.
【Example 3】
According to the carrier water absorption rate measuring and plan load capacity, prepare containing 8% silver oxide, 5% molybdenum oxide and 1% praseodymium oxide
Mixed solution, using equi-volume impregnating impregnate 5 hours after, in 120 DEG C of baking ovens dry, then at 580 DEG C of Muffle furnaces
Middle roasting 10 hours, obtains the catalyst Ag8Mo5Pr1 that required carbon monoxide under low temperature removes nitrogen oxides.
【Example 4】
According to the carrier water absorption rate measuring and plan load capacity, prepare containing 10% copper oxide, 6% tungsten oxide and 2% Dineodymium trioxide
Mixed solution, using equi-volume impregnating impregnate 5 hours after, in 120 DEG C of baking ovens dry, then at 580 DEG C of Muffle furnaces
Middle roasting 10 hours, obtains the catalyst Cu10W6Nd2 that required carbon monoxide under low temperature removes nitrogen oxides.
【Example 5】
According to the carrier water absorption rate measuring and plan load capacity, prepare containing 12% silver oxide, 8% manganese oxide and 0.5% oxidation
The mixed solution of cerium, after being impregnated 5 hours using equi-volume impregnating, is dried, then at 580 DEG C of Muffles in 120 DEG C of baking ovens
Kiln roasting 10 hours, obtains the catalyst Ag12Mn8Ce0.5 that required carbon monoxide under low temperature removes nitrogen oxides.
【Example 6】
According to the carrier water absorption rate measuring and plan load capacity, prepare containing 15% copper oxide, 2% chromium oxide and 1% lanthana
Mixed solution, using equi-volume impregnating impregnate 5 hours after, in 120 DEG C of baking ovens dry, then at 580 DEG C of Muffle furnaces
Middle roasting 10 hours, obtains the catalyst Cu15Cr2La1 that required carbon monoxide under low temperature removes nitrogen oxides.
【Example 7】
According to the carrier water absorption rate measuring and plan load capacity, prepare containing 6% silver oxide, 4% rheium oxide and 2% praseodymium oxide
Mixed solution, using equi-volume impregnating impregnate 5 hours after, in 120 DEG C of baking ovens dry, then at 580 DEG C of Muffle furnaces
Middle roasting 10 hours, obtains the catalyst Ag6Re4Pr2 that required carbon monoxide under low temperature removes nitrogen oxides.
【Example 8】
According to the carrier water absorption rate measuring and plan load capacity, prepare containing 5% copper oxide, 3% manganese oxide and 0.5% cerium oxide
Mixed solution, using equi-volume impregnating impregnate 5 hours after, in 120 DEG C of baking ovens dry, then at 580 DEG C of Muffle furnaces
Middle roasting 10 hours, obtains the catalyst Cu5Mn3Ce0.5 that required carbon monoxide under low temperature removes nitrogen oxides.
【Example 9】
The catalyst being obtained with embodiment 1～8, carries out carbon monoxide under low temperature catalysis also on normal miniature fixed-bed reactor
The reactivity worth of former nitrogen oxides is investigated.Catalyst loading amount is 1.05 grams, and gaseous mixture consists of NO 1.1%, CO 3.5%,
Remaining for nitrogen, gas space velocity is 1200h-1, 150～300 DEG C of reaction temperature, reaction result such as table 1 shows.
Table 1
Claims (10)
1. a kind of catalyst of carbon monoxide under low temperature catalysis reduction removing nitrogen oxides, by weight percentage, comprises following
Component：
A) 2～20% copper oxide or silver oxide；
B) 1～10% VIB, VIIB family metal oxide；
C) 0～5% rare earth oxide；
D) 65～97% alumina support.
2. according to claim 1 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that with catalyst
The content of percentage by weight meter, copper oxide or silver oxide is 3～15%.
3. according to claim 1 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that with catalyst
Percentage by weight meter, the content of VIB, VIIB family metal oxide is 2～8%.
4. according to claim 1 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that with catalyst
Percentage by weight meter, the content of rare earth oxide is 0.5～3%.
5. according to claim 1 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that VIB, VIIB
Family metal oxide is selected from least one of Cr, Mo, W, Mn, Re.
6. according to claim 1 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that rare-earth oxidation
Thing is selected from least one of La, Ce, Pr, Nd.
7. according to claim 1 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that catalyst
By weight percentage, II B race element in the periodic table of elements or at least one in its oxide are also comprised.
8. according to claim 7 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that II B race
Race's element is selected from least one in Zn, Cd.
9. according to claim 8 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that with catalyst
Percentage by weight meter, the content of II B race element or its metal-oxide is 0.1～10%.
10. according to claim 9 the catalyst of low-temperature catalyzed reduction removing nitrogen oxides it is characterised in that with catalyst
Percentage by weight meter, the content of II B race element or its metal-oxide is 0.2～5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892547A (en) * | 2021-01-18 | 2021-06-04 | 北京科技大学 | Catalyst for simultaneously removing nitrogen oxide and carbon monoxide and preparation method thereof |
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| CN112892547A (en) * | 2021-01-18 | 2021-06-04 | 北京科技大学 | Catalyst for simultaneously removing nitrogen oxide and carbon monoxide and preparation method thereof |
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