CN110433822A - One kind being used for NH3The Co-Mn catalyst of catalysis oxidation, preparation method and applications - Google Patents
One kind being used for NH3The Co-Mn catalyst of catalysis oxidation, preparation method and applications Download PDFInfo
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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
- B01D53/8634—Ammonia
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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Abstract
The invention discloses one kind to be used for NH3The Co-Mn catalyst of catalysis oxidation, preparation method and applications belong to environmentally friendly catalytic treatment technical field.Preparation method main body is improved coprecipitation, and by ammonium hydroxide as precipitating reagent, then fractional precipitation has obtained the spinel structure catalyst of Co-Mn, then impregnates to form defect by tetrabutylammonium hydroxide, WO3Surface modification, the WO3‑CoMn2O4Catalyst shows good NH3Catalytic performance and N2Selectivity.WO3‑CoMn2O4Catalyst can reach 100% NH under conditions of 200 DEG C3The N of conversion ratio and 90% or more2Selectively, and the catalyst is after stable operation for 24 hours, NH3Catalytic performance and N2Selectivity still remains unchanged, and illustrates the WO3‑CoMn2O4Catalyst structure is stablized, and catalytic performance is excellent, has good actual application prospect.
Description
Technical field
WO is used the present invention relates to a kind of3The Co-Mn selective catalytic oxidation NH for the spinel structure modified3Catalysis
Agent and preparation method thereof belongs to environmentally friendly catalytic treatment technical field.
Background technique
Air quality difference is one of the main Environmental Problems of China's concern.And ammonia is colourless as one kind and has stimulation
Property foul odour air pollutants, inflammable and toxic, the atmospheric environment of respiratory health to human body and China all causes
It threatens.Although the NH in atmospheric environment3Concentration be far below other main air pollutants, as sulfur dioxide, nitrogen oxides and
Ozone etc., but NH3Inorganic PM2.5 (particulate matter of the aerodynamic diameter less than 2.5 μm) generation is not only directly contributed to,
It can also be and then important to having been formed for secondary organic aerosol by react forming condensable salt with gas phase organic acid
Effect.Thus China is to NH3Stringent limited drainage is carried out, in " Indoor Air Quality standards " and " odorant pollutant discharge
Standard " in regulation, indoor NH3Concentration standard be 0.20mg/m3, factory circle NH3Concentration limit primary standard be 1.0mg/
m3。NH3Main source be agriculture nitrogen fertilizer, indoor ornament materials, the exhaust emissions of automobile and industrial chemical production in NH3
Sliding phenomenon, it may be said that be that source is wide, discharge amount is big.Therefore, NH3Control and processing technique cause the attention of people.
Selective catalytic oxidation ammonia (NH3- SCO) it is a kind of very promising NH3Removing method, because it can be in oxygen
By NH under the conditions of existing3It is converted into harmless nitrogen and water.In recent years, people study various types of catalyst,
These metallic catalysts can be divided into three classes: be that noble metal catalyst, catalyst of transition metal oxide and molecular sieve type are urged respectively
Agent.Wherein noble metal catalyst mainly studies precious metals ag, Au, Pt, Pd etc., the complete conversion of these noble metal catalysts
NH3Temperature is all relatively low, but N2Selectivity it is also relatively low, be easy to produce N2The secondary pollutions such as O, and noble metal this personal value
Lattice are expensive, and stability is also poor, these all limit its possibility in practical applications.Catalyst of transition metal oxide master
If studying Cu, Co, Mn, Fe etc., the complete conversion NH of these transition metal3Temperature is relatively high, but N2Selectivity compared with
It is good, and transition metal itself is cheap, and reserves also enrich on the earth.Third class is molecular sieve type catalyst, mainly logical
Cross prepare it is various have the opposite biggish molecular sieve of specific surface area as carrier, the then noble metal or mistake different by load
Metal is crossed as active component, therefore, its advantages and disadvantage are roughly the same with 2 class of front.And transition metal oxide is catalyzed
In agent, Co and Mn base catalyst has obtained extensive research due to cheap and good redox property.
In principle, due to depositing very strong interaction between metal oxide, O composite metallic oxide catalyst is often
With new catalytic performance, and its activity is generally greater than single oxide.So being regulated and controled by doped metallic elements
The surface composition and fault of construction of metal oxide have become a kind of primary hand of catalytic performance for improving metal oxide
Section.
Qu is prepared for MnO2Catalyst, NH3Conversion completely, N are realized at 170 DEG C2Selectivity is only 50% (Qu Z, et
al.Applied Surface Science,2015,351:573-579.).It can be seen that single Mn is in NH3Oxidation is anti-
Just there is the activity of superelevation in answering, but selectivity is also very low, product is largely secondary pollution N2O.And Song is prepared for
MnOx-TiO2Catalyst is supported on TiO using Mn as active component2On carrier, wherein MnOx(0.25)–TiO2Performance it is best,
NH3Conversion completely, N are realized at 200 DEG C2Selectivity for 80% (Song D, et al.RSC Advances, 2016,6 (91):
88117-88125.).Tang is prepared for CoOx -CuOx/TiO2Catalyst is supported on TiO using Co and Cu as active component2Carrier
On, wherein 7.5CoOx-7.5CuOx/TiO2Performance it is best, NH3Conversion completely, N are realized at 225 DEG C2Selectivity is 70%
(Tang X,Li J,et al.Energy&Fuels,2017,31(8):8580-8593.).Therefrom we can see that in order to change
Kind Co and Mn poor phenomenon of selectivity in ammoxidation reaction, uses acid metal as carrier, but improvement is not
It is it is obvious that nitrogen selective is still very low.For such issues that, development framework is simple, NH3Active good and N2Selectivity is high
O composite metallic oxide catalyst be particularly important.
Summary of the invention
The purpose of the present invention is to provide a kind of WO3The Co-Mn catalyst of the spinel structure of modification and its preparation side
Method, the special construction based on spinelle strengthen NH3Catalytic performance, pass through WO3Modification improve N2Selectivity, synthesis side
The features such as method, which has, to be simply easy to control, low in cost, reproducible.Therefore, the present invention prepares spinelle using coprecipitation
The Co-Mn catalyst of structure, is impregnated to form surface defect with organic solvent tetrabutylammonium hydroxide, then pass through on this basis
WO3It is modified, obtains WO3-CoMn2O4Catalyst, redox property is good, stable structure, in lower temperature range
(160-200 DEG C) can achieve the high conversion ratio of ammonia, and (120-200 DEG C) its N in entire Range of measuring temp2
Selectivity be all larger than 90%, have a extensive future.
Technical solution of the present invention:
One kind being used for NH3The Co-Mn catalyst of catalysis oxidation, the Co-Mn catalyst are WO3Modification has surface defect
CoMn2O4Spinel catalyst, WO3It is carried on the CoMn of surface defect2O4On spinelle, WO3Load capacity be have surface lack
Sunken CoMn2O4The 10%wt of spinelle.
One kind being used for NH3The preparation method of the Co-Mn catalyst of catalysis oxidation first prepares CoMn using coprecipitation2O4；
Then CoMn is handled with tetrabutylammonium hydroxide2O4, form surface defect；Finally use WO3It is modified, obtains WO3-CoMn2O4
Catalyst；Steps are as follows:
(1) manganese presoma is dispersed in ethanol-water solution, the volume ratio of ethyl alcohol and water is that 1:10 is mixed, before manganese
Driving concentration of the body in system is 0.2mol/l；Then the ammonia spirit of 25wt% is added, it is sufficiently mixed in 20-30 DEG C of stirring 1h
It closes reaction and forms solution A；The additional amount of ammonium hydroxide is related with mixed solution pH value, guarantees that the pH of mixed solution is greater than 11；
(2) cobalt precursor dissolution being dispersed in ethanol-water solution, the volume ratio of ethyl alcohol and water is 1:10 mixing,
Concentration of the cobalt precursor in system is 0.1mol/l, forms solution B；Solution B is added in solution A, solution A and solution B
Volume ratio is 2:1, after 20-30 DEG C of mixing time is 1h；2-3h is reacted under the conditions of 180 DEG C, it is cooling, in 200 DEG C of air gas
5h is calcined in atmosphere, 2 DEG C/min of heating rate obtains the CoMn of spinel structure2O4；
(3) uniform ammonium metatungstate will be ground and calcine 5h in 500 DEG C of air atmospheres, 2 DEG C/min of heating rate is obtained
WO3；
(4) by the CoMn of the spinel structure of step (2) preparation2O4It is dissolved in the tetrabutylammonium hydroxide water of 0.05mol/l
In solution, CoMn2O4Molar ratio with tetrabutylammonium hydroxide is 0.4:1, stirs 6-12h at 20-30 DEG C, is then centrifuged for washing
It washs, obtains the CoMn with surface defect after dry in 105 DEG C2O4Spinelle；
(5) CoMn for obtaining step (4)2O4Dissolution is dispersed in ethanol solution, is slowly added to surface defect
CoMn2O4The WO that the step of spinelle 10%wt (3) obtains3, 1-2h is stirred at 20-30 DEG C, is warming up to 80 DEG C, stirs 1-3h
After evaporating water, Co-Mn catalyst is obtained；
The manganese presoma is manganese nitrate；The cobalt precursor is cobalt nitrate.
WO of the invention3-CoMn2O4Catalyst is used for NH3Catalysis oxidation: 1000ppm NH3, 10vol%O2, He is as flat
Weigh gas, air speed 40000h-1, the activity and selectivity test experiments of catalyst operate continuously in fixed bed reactors.
WO of the invention3-CoMn2O4Catalyst (160-200 DEG C) within the scope of lower temperature can achieve ammonia compared with
High conversion, (120-200 DEG C), N in entire Range of measuring temp2Selectivity be all larger than 90%.
Beneficial effects of the present invention:
(1) WO of the present invention3-CoMn2O4The main component of catalyst is the Co-Mn oxide of spinel structure, spinelle knot
Structure property is stablized, so that catalyst of the present invention physically shows excellent mechanical strength, shows in chemical property excellent
Different stability；Meanwhile Co and Mn have excellent performance ammonia catalytic, present invention introduces a small amount of WO3Modify spinelle knot
The Co-Mn oxide of structure, increases the acidic site of catalyst, makes catalyst in NH3There is excellent N in-SCO reaction2Selection
Property.
(2) WO of the present invention3-CoMn2O4The group of catalyst become Co, Mn and W, the rich reserves of China Co, Mn and W, therefore
Cost is relatively low for catalyst.
(3) present invention selects tetrabutylammonium hydroxide to impregnate the spinelle knot prepared during preparing catalyst
The CoMn of structure2O4, this is because tetrabutylammonium hydroxide can be from CoMn2O4Edge enter middle layer, thus in weakening
Van der Waals force between interbed makes the CoMn of spinel structure2O4Form surface defect, increase more unsaturated Co and Mn from
Son, WO on dipping3Later, increase the CoMn of spinel structure2O4With the interaction of W, meanwhile, surface defect can also increase
CoMn2O4Specific surface area, increase and WO3Contact area, increase to NH3Absorption and activation capacity, so WO3The tool of modification
The Co-Mn catalyst of defective spinel structure has high NH simultaneously3Active and high N2Selectivity, 200 DEG C reach 100%
NH3Conversion ratio, while N2Selectivity reaches 90% or more in the reaction temperature.
Detailed description of the invention
Fig. 1 (a) is the NH of the catalyst of the embodiment of the present invention 1 and comparative example 1-3 preparation3Conversion ratio figure；
Fig. 1 (b) is the N of the catalyst of the embodiment of the present invention 1 and comparative example 1-3 preparation2Selective figure.
Fig. 2 is WO prepared by the embodiment of the present invention 13-CoMn2O4The NH of catalyst3Stability activity figure.
Fig. 3 (a) is the XRD diagram of catalyst prepared by comparative example 1 of the present invention；
Fig. 3 (b) is the XRD diagram of catalyst prepared by comparative example 2 of the present invention；
Fig. 3 (c) is the XRD diagram of catalyst prepared by the embodiment of the present invention 1.
Specific embodiment
It elaborates below to specific embodiments of the present invention.For the present invention using Co and Mn as active component, use is coprecipitated
The preparation of shallow lake method, impregnates using tetrabutylammonium hydroxide solution, finally loads WO with ethanol solution infusion process3, preparation flow phase
To simple, controllability and favorable repeatability.
Embodiment 1
WO3-CoMn2O4The preparation of catalyst:
(1) manganese nitrate solution of 50wt% is dispersed in ethanol-water solution (wherein ethyl alcohol is 1ml, water 10ml), In
It is stirred at 25 DEG C, forms the manganese nitrate solution of 10ml0.2mol/l.The concentrated ammonia solution of 10ml 25wt% is slowly added dropwise, holds
Continuous mixing time is 1h, after being sufficiently mixed reaction, is denoted as solution A.Cobalt nitrate dissolution is dispersed in ethanol-water solution (wherein
Ethyl alcohol is 1ml, water 10ml), stirring forms the cobalt nitrate solution of 10ml 0.1mol/l at 25 DEG C, is denoted as solution B.It will be molten
Liquid B is slowly added dropwise into solution A, is 1h in 25 DEG C of lasting mixings time, is sufficiently mixed reaction.It is then transferred to heated at constant temperature
In equipment, 3h is reacted under the conditions of 180 DEG C, it is cooling, 5h is calcined in 200 DEG C of air atmospheres, 2 DEG C/min of heating rate is obtained
The CoMn of spinel structure2O4, remember catalyst A.
(2) 5h will be directly calcined in 500 DEG C of air atmospheres after ammonium metatungstate grinding uniformly, 2 DEG C/min of heating rate is obtained
To WO3。
(3) 0.5gCoMn of above-mentioned preparation is chosen2O4, the tetrabutylammonium hydroxide for being dissolved in 100ml0.05mol/l is water-soluble
In liquid, 25 DEG C of lasting mixings time are 6h.It is then centrifuged for washing for several times, 105 DEG C of dry removal excessive moistures, formation has surface
The CoMn of defect2O4, it is denoted as catalyst B.
(4) by the CoMn for having surface defect in 0.5g step (3)2O4Dissolution is dispersed in the ethanol solution of 50ml, slowly
The WO of 0.05g is added3, it is 1h in 25 DEG C of lasting mixings time.80 DEG C are then heated to, obtains WO after heating 3h evaporating water3-
CoMn2O4Catalyst is denoted as catalyst C.
Comparative example 1
The catalyst A that embodiment 1 is prepared is comparative example 1.
Comparative example 2
The catalyst B that embodiment 1 is prepared is comparative example 2.
Prepared by catalyst to embodiment 1, comparative example 1 and comparative example 2 and carries out XRD characterization, structure is as shown in figure 3, from figure
3- (1) is it can be found that successfully prepare CoMn2O4Structure catalyst.From Fig. 3-(2) it can be found that passing through tetrabutylammonium hydroxide
The CoMn of immersion2O4The structure of its spinelle will not be changed, the characteristic peak of (211) this maximum intensity deviates to the left, partially from 36.4
36.2 are moved on to, this explanation is in CoMn2O4Surface forms defect sturcture.From Fig. 3-(3) it can be found that WO3Modification will not change
Become CoMn2O4Structure exist simultaneously WO and without miscellaneous peak3With the CoMn of spinel structure2O4。
Comparative example 3
The catalyst B that embodiment 1 is prepared passes through the method equally impregnated and loads 10%TiO2(online purchase
P25), TiO is obtained2-CoMn2O4, it is denoted as catalyst D.
Embodiment 2
WO prepared by embodiment 13-CoMn2O4The Co-Mn of catalyst and the spinel structure of comparative example 1-3 preparation
(CoMn2O4), the Co-Mn (CoMn impregnated by tetrabutylammonium hydroxide2O4) and TiO2-CoMn2O4Carry out NH3Catalysis oxidation,
NH3Catalytic oxidation performance test is to operate continuously to carry out on fixed bed reactors, and He does Balance Air, using NH3Analyzer and
Gaseous material NH after gas chromatograph on-line analysis reaction3And N2。
Reaction condition specifically: 1000ppm NH3, 10vol%O2, He is as Balance Air, reaction velocity 40000h-1,
Catalyst quality is 0.2g.NH3Conversion ratio and N2Selective calculation formula is as follows: NH3Conversion ratio %=[(NH before reacting3Concentration-
NH after reaction3Concentration)/react preceding NH3Concentration] * 100, N2Selectivity=[(N after reaction2N before concentration-reaction2Concentration)/500/
(NH before reacting3NH after concentration-reaction3Concentration)/react preceding NH3Concentration] * 100.Reactivity is as shown in Figure 1, of the invention
WO3-CoMn2O4Catalyst (catalyst C) reaches 100%NH at 200 DEG C3The catalyst of conversion ratio, comparative example 1 and comparative example 2 is same
Sample reaches 100%NH at 200 DEG C3Conversion ratio, wherein the CoMn of defective structure prepared by comparative example 22O4Catalyst activity is more
Add it is excellent, this explanation, is formationed of defect sturcture has the performance boost conducive to catalyst, but nitrogen selective is relatively poor,
Catalyst prepared by inventive embodiments 1, first passes through tetrabutylammonium hydroxide in CoMn2O4Surface forms defect, then introduces WO3
Load modification, on the basis of keeping excellent activity, considerably increases the nitrogen selective of catalyst, N2Selectivity is reached at 200 DEG C
To 90% or more.Comparative example 1 (catalyst A) and comparative example 2 (catalyst B) nitrogen selective are only 50% or so.Comparative example 3
(catalyst D) NH3Activity decreases drastically, and just reaches 100%NH at 220 DEG C3Conversion ratio, N2Selectivity only has at 220 DEG C
70% or so.
Embodiment 3
WO prepared by embodiment 13-CoMn2O4Catalyst investigates the stability of the catalyst, is keeping embodiment 2 anti-
Condition is answered, then in the stability of 200 DEG C of continuous operation test catalyst, stability is as shown in Figure 2.The catalyst exists
After stable operation for 24 hours, NH3Catalytic performance and N2Selectivity still remains unchanged, and shows excellent stability.
Embodiment 4
XPS characterization is carried out to catalyst prepared by comparative example 1 and comparative example 2, surface-element composition as shown in table 1, is deposited
It is less than the value of catalyst A, and CoMn in the value of (Co+Mn)/O of the catalyst B of surface defect2O4The stoichiometry of surface atom
Theoretical ratio is 0.75, this ratio be less than theoretical ratio when, reflection be catalyst surface defect sites number, the present invention
Catalyst B by tetrabutylammonium hydroxide handle, hence it is evident that form more surface defects.
Table 1
Claims (4)
1. one kind is used for NH3The Co-Mn catalyst of catalysis oxidation, which is characterized in that the Co-Mn catalyst is WO3Modification has table
The CoMn of planar defect2O4Spinel catalyst, WO3It is carried on the CoMn of surface defect2O4On spinelle, WO3Load capacity be
There is the CoMn of surface defect2O4The 10%wt of spinelle.
2. one kind is used for NH3The preparation method of the Co-Mn catalyst of catalysis oxidation, which is characterized in that first prepared using coprecipitation
CoMn2O4；Then CoMn is handled with tetrabutylammonium hydroxide2O4, form surface defect；Finally use WO3It is modified, obtains WO3-
CoMn2O4Catalyst；Steps are as follows:
(1) manganese presoma is dispersed in ethanol-water solution, the volume ratio of ethyl alcohol and water is 1:10 mixing, manganese presoma
Concentration in system is 0.2mol/l；Then the ammonia spirit of 25wt% is added, in 20-30 DEG C of stirring 1h, is sufficiently mixed anti-
Solution A should be formed；The additional amount of ammonium hydroxide is related with mixed solution pH value, guarantees that the pH of mixed solution is greater than 11；
(2) cobalt precursor dissolution is dispersed in ethanol-water solution, the volume ratio of ethyl alcohol and water is that 1:10 is mixed, before cobalt
Driving concentration of the body in system is 0.1mol/l, forms solution B；Solution B is added in solution A, the volume of solution A and solution B
Than for 2:1, after 20-30 DEG C of mixing time is 1h；2-3h is reacted under the conditions of 180 DEG C, it is cooling, in 200 DEG C of air atmospheres
5h is calcined, 2 DEG C/min of heating rate obtains the CoMn of spinel structure2O4；
(3) uniform ammonium metatungstate will be ground and calcine 5h in 500 DEG C of air atmospheres, 2 DEG C/min of heating rate obtains WO3；
(4) by the CoMn of the spinel structure of step (2) preparation2O4It is dissolved in the tetrabutylammonium hydroxide aqueous solution of 0.05mol/l
In, CoMn2O4Molar ratio with tetrabutylammonium hydroxide is 0.4:1, stirs 6-12h at 20-30 DEG C, is then centrifuged for washing, in
The CoMn with surface defect is obtained after 105 DEG C of dryings2O4Spinelle；
(5) CoMn for obtaining step (4)2O4Dissolution is dispersed in ethanol solution, is slowly added to the CoMn of surface defect2O4Point
The WO that the step of spar 10%wt (3) obtains3, 1-2h is stirred at 20-30 DEG C, is warming up to 80 DEG C, stirs 1-3h evaporating water
Afterwards, Co-Mn catalyst is obtained.
3. preparation method according to claim 2, which is characterized in that the manganese presoma is manganese nitrate；
The cobalt precursor is cobalt nitrate.
4.Co-Mn catalyst is used for NH3Catalysis oxidation: 1000ppm NH3, 10vol%O2, He is as Balance Air, air speed
40000h-1, the activity and selectivity test experiments of catalyst operate continuously in fixed bed reactors.
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| CN113237926A (en) * | 2021-03-30 | 2021-08-10 | 中国石油大学(华东) | NiCo2O4/WO3Nano composite material and preparation method and application thereof |
| CN116607170A (en) * | 2023-07-20 | 2023-08-18 | 北京科技大学 | Preparation method of electrocatalyst, electrocatalyst and application of electrocatalyst |
| CN116607170B (en) * | 2023-07-20 | 2023-10-27 | 北京科技大学 | Preparation method of electrocatalyst, electrocatalyst and application of electrocatalyst |
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