CN101733064A - Low-concentration nitrogen oxide adsorbent and preparation method thereof - Google Patents

Low-concentration nitrogen oxide adsorbent and preparation method thereof Download PDF

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CN101733064A
CN101733064A CN200910049370A CN200910049370A CN101733064A CN 101733064 A CN101733064 A CN 101733064A CN 200910049370 A CN200910049370 A CN 200910049370A CN 200910049370 A CN200910049370 A CN 200910049370A CN 101733064 A CN101733064 A CN 101733064A
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oxide
adsorbent
concentration nitrogen
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cerium zirconium
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崔香枝
陈航榕
施剑林
叶争青
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention provides a low-concentration nitrogen oxide adsorbent and a preparation method thereof, which belongs to the field of environmental protection. In the invention, blocky honeycomb carbon or honeycomb ceramic is used as a carrier material, one or more in Al2O3, a (Zr, Ce)O2 solid solution and/or TiO2 is/are used a carrier surface transition layer, and one or more or the composition of more metal oxides in cerium oxide, ruthenium oxide, manganese oxide/copper oxide is used as an adsorption active material. The low-concentration nitrogen oxide adsorbent can effectively adsorb multiple ppm grades of low-concentration NOx (NO, NO2 and the like) gas containing a large amount of water.

Description

Low-concentration nitrogen oxide adsorbent and preparation method thereof
Technical field
The invention provides a kind of low-concentration nitrogen oxide adsorbent and corresponding preparation method thereof, this summary of the invention belongs to field of environment protection.
Background technology
NO xBe the general name of nitrogen oxide, wherein the binding ability of the ferroheme in NO and the blood is also stronger than CO, people is poisoned and dead, NO 2Be that a kind of brown toxic gas has the specific stimulation stink, infringement people's eyes and lung, it is the main cause that produces acid rain and cause climate change, generation smog, becomes the emission of automobile wastes public hazards.Though be low concentration (10 -5~10 -6) nitrogen oxide, but, also will produce very big harm to human beings'health in the medium-term and long-term accumulation of air.For example, automobile tunnel is convenient human current a kind of Architectural Equipments, also be a kind of Critical policies of alleviating communications and transportation, yet the tunnel is the space of a duct type, has only and imports and exports very difficult diffusion of pollutant that automobile is discharged in the tunnel that communicates with atmosphere.When the tail gas of motor vehicle emission, when in the tunnel, reaching finite concentration, will make people produce dizziness, blind, poison even death by suffocation the serious harm human beings'health.Eliminate the NO of these low concentrations ppm level xBecome the focus that the country and even the whole world are paid close attention to.
Wherein there is report to use the adsorbent of Al-Si system complex oxides such as alumina silicate, zeolite, be considered to have stable on heating adsorbent, but their acid resistance is poor, owing to carry out NO repeatedly as carrier xAbsorption, desorb and absorption property is reduced.In addition, the silica-rich zeolite that acid resistance is high, the carrier fine pore is very little, and below 5, when impregnation carrier band metal oxide, aperture is blocked, and existence can not obtain sufficient NO xThe problem of absorption property.In addition, there is report in Japan with noncrystalline TiO 2Adsorb the metal oxide activated centre as carrier and prepare adsorbent.Though this adsorbent has NO relatively preferably xAbsorption property, but it to be powder with the shape that looses adsorb NO x, the sprills adsorbent that looses not only loads and unloads and carries inconvenience, and it is higher relatively to use cost, thereby has limited such adsorbent in low concentration of NO xThe interior on a large scale use of accumulating.
Low-concentration nitrogen oxide adsorbent of the present invention, be to be carrier with suitable carrying and block honeycomb carbon or the ceramic honey comb piled up, cerium zirconium sosoloid or other oxides with high-specific surface area are transition zone, supported active adsorption component and making can effectively adsorb and remove the low-concentration nitrogen oxide (NO that contains moisture and number ppm in the air x) gas such as gas, roads and tunnels ventilation in nitrogen oxide.At present in this respect, particularly honeycomb carbon, ceramic honey comb are made the monoblock type sorbent material both at home and abroad and carry out low-concentration nitrogen oxide (NO x) research of absorption aspect, yet there are no this type of report.。
Summary of the invention
The purpose of this invention is to provide a kind of low-concentration nitrogen oxide adsorbent, it is characterized in that:
1) carrier material of adsorbent is honeycomb carbon or ceramic honey comb, and this honeycomb carbon or ceramic honey comb have the connection endoporus, 50~200 orders, and the endoporus aperture is 0.5~2mm.Its photo as shown in Figure 1.Wherein, the adsorbing agent carrier preferred size is 5 * 5 * 5cm or 10 * 10 * 10cm.
2) be coated with buffer layer material and metal oxide active material on the adsorbing agent carrier inner hole wall, the two can successively in turn load on the adsorbing agent carrier, loads on the carrier together after also can mixing mutually.
Described buffer layer material is aluminium oxide, mesoporous cerium zirconium sosoloid and/or titanium dioxide.Described aluminium oxide specific area is 250~300m 2/ g; Mesoporous cerium zirconium sosoloid specific area is 220~300m 2/ g, the aperture is 5~9nm, cerium zirconium ratio is 1: (1~5); The specific area of titanium dioxide is 80~150m 2/ g.Wherein the proportioning of aluminium oxide, mesoporous cerium zirconium sosoloid and/or titanium dioxide is 1: (1~7): (0~2), the ratio of preferred aluminium oxide and mesoporous cerium zirconium sosoloid is 1: (4~6).
Described metal oxide active material is one or more the combination in cerium oxide, ruthenium-oxide, manganese oxide, cupric oxide, calcium oxide, the barium monoxide.When six kinds of components selecting for use wherein, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide: cupric oxide: calcium oxide: barium monoxide=(1~7): (1~3): 1: 1: (1~5): (1~5); When selecting wherein five kinds combinations for use, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide: cupric oxide: calcium oxide/barium monoxide=(1~7): (1~3): 1: 1: (1~5); When selecting wherein four kinds combinations for use, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide/cupric oxide: calcium oxide/barium monoxide=(1~7): (1~3): 1: (1~5); In the times of select for use wherein three kinds, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide/cupric oxide=(1~7): (1~3): 1.
In in the described metal oxide active material in preferred cerium oxide, ruthenium-oxide, the manganese oxide/cupric oxide one or both and the calcium oxide/barium monoxide one or both.When six kinds of components selecting for use wherein, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide: cupric oxide: calcium oxide: barium monoxide=(2~5): (1~2): 1: 1: (1~2): (1~2); When selecting wherein four kinds combinations for use, its proportioning is a cerium oxide:: ruthenium-oxide: in manganese oxide/cupric oxide: calcium oxide/barium monoxide=(2~5): (1~2): 1: (1~2).
3) shape of described adsorbing agent carrier can be for being communicated with cube, hexahedron and the cylinder of endoporus arbitrarily.
Another object of the present invention provides a kind of above-mentioned preparation of adsorbent method.May further comprise the steps:
1) selecting honeycomb carbon or ceramic honey comb for use is the adsorbing agent carrier material, and this honeycomb carbon or ceramic honey comb have the connection endoporus, 50~200 orders, and the endoporus aperture is 0.5~2mm.Its photo as shown in Figure 1.Wherein, the adsorbing agent carrier preferred size is 5 * 5 * 5cm or 10 * 10 * 10cm.
2) select for use in mesoporous cerium zirconium sosoloid, aluminium oxide and/or the titanium dioxide one or more as buffer layer material.Described aluminium oxide specific area is 250~300m 2/ g; Mesoporous cerium zirconium sosoloid specific area is 220~300m 2/ g, the aperture is 5~9nm, cerium zirconium ratio is 1: 3; The specific area of titanium dioxide is 80~150m 2/ g.Wherein the proportioning of aluminium oxide, mesoporous cerium zirconium sosoloid and/or titanium dioxide is 1: (1~7): (0~2), the ratio of preferred aluminium oxide and mesoporous cerium zirconium sosoloid is 1: (4~6).
3) select for use in cerium oxide, ruthenium-oxide, manganese oxide, cupric oxide, calcium oxide, the barium monoxide one or more be combined as metal oxide activated adoption composition material.When six kinds of components selecting for use wherein, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide: cupric oxide: calcium oxide: barium monoxide=(1~7): (1~3): 1: 1: (1~5): (1~5); When selecting wherein five kinds combinations for use, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide: cupric oxide: calcium oxide/barium monoxide=(1~7): (1~3): 1: 1: (1~5); When selecting wherein four kinds combinations for use, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide/cupric oxide: calcium oxide/barium monoxide=(1~7): (1~3): 1: (1~5); In the times of select for use wherein three kinds, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide/cupric oxide=(1~7): (1~3): 1.
In in the described metal oxide active material in preferred cerium oxide, ruthenium-oxide, the manganese oxide/cupric oxide one or both and the calcium oxide/barium monoxide one or both.When six kinds of components selecting for use wherein, its proportioning is a cerium oxide: ruthenium-oxide: manganese oxide: cupric oxide: calcium oxide: barium monoxide=(2~5): (1~2): 1: 1: (1~2): (1~2); When selecting wherein four kinds combinations for use, its proportioning is a cerium oxide: ruthenium-oxide: in manganese oxide/cupric oxide: calcium oxide/barium monoxide=(2~5): (1~2): 1: (1~2).
Metal oxide decomposes and prepares through Overheating Treatment with its corresponding nitrate, acetate and chloride.Comprise cerous nitrate, copper nitrate, manganese nitrate, calcium nitrate, barium acetate, ruthenic chloride, buy by Shanghai traditional Chinese medicines chemical reagent work.
When selecting wherein six kinds combinations for use, the proportioning of its corresponding salt is a cerous nitrate: ruthenic chloride: manganese nitrate: copper nitrate: calcium nitrate: barium acetate=(5~20): (0.2~3): (0.5~5): (0.5~5): (1~10): (1~10); When selecting wherein five kinds combinations for use, the proportioning of its corresponding salt is a cerous nitrate: ruthenic chloride: manganese nitrate: copper nitrate: calcium nitrate/barium acetate=(5~20): (0.2~3): (0.5~5): (0.5~5): (1~10); When selecting wherein four kinds combinations for use, the proportioning of its corresponding salt is a cerous nitrate: ruthenic chloride: manganese nitrate/copper nitrate: calcium nitrate/barium acetate=(5~20): (0.2~3): (0.5~5): (1~10); In the times of select for use wherein three kinds, the proportioning of its corresponding salt is a cerous nitrate: ruthenic chloride: manganese nitrate/copper nitrate=(5~20): (0.2~3): (0.5~5).
In in the pairing salt of described metal oxide activated adoption composition in preferred cerous nitrate, ruthenic chloride, the manganese nitrate/copper nitrate one or both and the calcium nitrate/barium acetate one or both.When six kinds of components selecting for use wherein, its proportioning is a ruthenic chloride: manganese nitrate: copper nitrate: calcium nitrate: barium acetate=(8~12): (0.2~1): (0.5~3): (0.5~3): (1~5): (1~5); When selecting wherein four kinds combinations for use, its proportioning is a ruthenic chloride: manganese nitrate/copper nitrate: calcium nitrate/barium acetate=(8~12): (0.2~1): (0.5~3): (1~5).
4) buffer layer material and the pairing salt of metal oxide activated adoption composition material and water being mixed with solid content is 10~50% slurry, and with mill ball with 1~5: 1 ratio is carried out ball milling and is obtained homodisperse dipping suspension.Wherein, the slurries of buffer layer material slurries and the pairing salt of metal oxide activated adoption composition material can be carried on the honeycomb substrate successively successively, also may be mixed together to obtain ball milling slurry and being carried on the honeycomb substrate simultaneously.
5) honeycomb substrate fully floods in above-mentioned suspension, and after removing unnecessary maceration extract, oven dry.
6) with the sorbent precursor thing that obtains in the step 5 under weakly reducing atmosphere, as contain 1~7%H 2N 2, Ar, He, 300~500 ℃ of heat treatments 2~4 hours.
In above-mentioned adsorption component composition, aluminium oxide, titanium oxide and mesoporous cerium zirconium sosoloid are the oxides with high-specific surface area, are to make the transition zone of metal oxide activated adoption composition carrier band on ceramic honey comb or honeycomb carbon; Nitrate (cerous nitrate, copper nitrate, manganese nitrate, calcium nitrate), barium acetate, ruthenic chloride can form corresponding metal oxide after by heat treatment, have NO xAbsorption property.Total load capacity of transition zone and absorption composition degree is 12~16% of each honeycomb block adsorbent weight.The above-mentioned percentage range of the combination of these components and each component determines that by a large amount of tests combinations thereof and percentage range make adsorbent of the present invention, can adsorb the NO of the several ppm level low concentrations that contain large quantity of moisture effectively xGas.
Further specify the present invention below by embodiment and Comparative Examples.In the following Examples and Comparative Examples, characterize the formation of the metal oxide in the adsorbent of the present invention with X-ray diffraction (XRD), test on the RigakuD/MAM-2550V X-ray diffractometer, (λ=0.15406nm), operating voltage, electric current are respectively 40kV and 40mA to adopt Cu target K alpha ray.Adsorbent is to NO xThe absorption property test of gas is at Thermol 42I-HL-NO 2-NO xTest on the analyzer.The absorption property of adsorbent is evaluated with it NO xAdsorption efficiency (denitration rate) be evaluation criterion, calculation equation is as follows:
Figure G2009100493703D00041
Figure G2009100493703D00042
This numerical value is high more, illustrates that this adsorbent is to NO xThe absorption property of gas is good more; And represent the absorption stability of adsorbent over time with adsorption efficiency, if adsorption efficiency illustrates that with the prolongation substantially constant of adsorption time absorption property is good.
Nitric oxide adsorbent of the present invention has high NO xAdsorption efficiency, its adsorption efficiency to NO can reach 85%, to NO 2Adsorption efficiency can arrive 98%; The prolongation in time of its adsorption efficiency does not significantly descend, and has stable NOx absorption property; And, this adsorbent 180~250 ℃ activate 1h after, still have high absorption property, it is to NO and NO 2Adsorption efficiency can reach 8% respectively, right adsorption efficiency can arrive 97%.
Description of drawings
(Fig. 1 is the photo of adsorbing agent carrier, a: be the honeycomb carbon carrier; B: be honeycomb ceramic carrier)
(Fig. 2 is the XRD figure spectrum of prepared adsorbent, a: for preparing adsorbent among the embodiment 1; B: be the adsorbent of preparation among the embodiment 2; Illustrate that the image of absorption composition shows as the ZrO of big content 2And CeO 2)
(Fig. 3 is the absorption property of the honeycomb substrate adsorbent of preparation to NO, a: the adsorbent that is preparation among the embodiment 1; B: be the adsorbent of preparation among the embodiment 3; Illustrate that prepared block adsorbent is adsorbable a large amount of NO at short notice)
(Fig. 4 be among the embodiment 5 prepared adsorbent to NO xThe absorption life test; Illustrate that this adsorbent still keeps higher absorption property after adsorbing for a long time)
(Fig. 5 be among the embodiment 6 prepared honeycomb ceramic carrier adsorbent to NO xThe absorption life test; Explanation is that adsorbing agent carrier prepares adsorbent and also can keep high NO for a long time with the ceramic honey comb xAbsorption property)
(Fig. 6 be the honeycomb ceramic carrier adsorbent in embodiment 7 under the condition to NO xAbsorption test; NO is described xThe size of initial concentration does not influence the adsorption efficiency of this adsorbent)
The specific embodiment
Embodiment 1
Under normal temperature and normal pressure, will be used as the Al of adsorbent buffer layer material 2O 3(specific area: 250~300m 2/ g) and mesoporous (Zr.Ce) O 2Solid solution (specific area: 220~300m 2/ g) mix with 1: 5 ratio after, forming solid content with water is 40% suspension, and this suspension and mill ball are carried out ball milling 12h (450 rev/mins) with formation high dispersive transition zone suspension with 2.5: 1 ratio; Is 3: 0.2: 2 with the pairing cerous nitrate of metal oxide adsorption activity composition, ruthenic chloride, manganese nitrate, copper nitrate, calcium nitrate, barium acetate with ratio: mix at 1: 2: 2, same and water formation solid content is 40% suspension, and carries out ball milling 12h (450 rev/mins) to form the suspension of high dispersion metal salt with mill ball with 2.5: 1 ratio.Adopting 100 purpose honeycomb carbon is adsorbing agent carrier, fully floods this transition zone suspension and dries by the fire 2h afterwards in 100 ℃~200 ℃ baking ovens.The honeycomb carbon that load after the oven dry is had a buffer layer material is the impregnating metal salting liquid once more, and dry in 100 ℃ of baking ovens abundant back to be impregnated, and after the neutralization, place 450 ℃ of heat treatment 2h of stove promptly to obtain honeycomb carbon carrier adsorbent in reducing atmosphere.The XRD figure spectrum of this adsorbent is shown in a among Fig. 2, to NO xThe adsorption efficiency of gas shown in a among Fig. 3, NO wherein xAdsorption efficiency can reach 80.7%/every adsorbent (125cm 3).
Embodiment 2
Used experimental raw kind and operation are with embodiment 1, but heat treatment temperature is 380 ℃ of insulation 2h, preparation honeycomb carbon carrier NO xWhole adsorbent, the XRD figure spectrum of gained adsorbent is shown in b among Fig. 2.
Embodiment 3
Used experimental raw kind and operation prepare NO with embodiment 1 but the ball milling time is 4h xAdsorbent, the gained adsorbent is to NO xAbsorption property shown in b among Fig. 3, wherein the adsorption efficiency of NO is 77%/every adsorbent (125cm 3).
Embodiment 4
Used experimental raw kind and operation are with embodiment 1, but the pairing slaine maceration extract of transition zone slurries and metal oxide mixes, and is impregnated into simultaneously on the honeycomb carbon carrier.Al with buffer layer material 2O 3, titanium oxide and mesoporous (Zr.Ce) O 2After solid solution mixes with 1: 2: 5 ratio, and with the pairing cerous nitrate of metal oxide adsorption activity composition, ruthenic chloride, manganese nitrate, copper nitrate, calcium nitrate, barium nitrate (ratio is 2: 0.2: 1.5: 0.5: 2: 2) carry out mixing and ball milling with the suspension that forms high dispersion metal salt with material.With the prepared adsorbent of this maceration extract to NO xThe adsorption efficiency of gas shown in c among Fig. 3, NO wherein xAdsorption efficiency can reach 74.7%/every adsorbent (125cm 3).
Embodiment 5
Technology of preparing and experimental implementation are with embodiment 4, with the Al of buffer layer material 2O 3With mesoporous (Zr.Ce) O 2After solid solution mixes with 1: 2.5 ratio, and with the pairing cerous nitrate of metal oxide adsorption activity composition, ruthenic chloride, manganese nitrate, calcium nitrate (ratio is 2: 0.1: 1: 2) carry out mixing and ball milling with the suspension that forms high dispersion metal salt with material.Load on prepared adsorbent behind the honeycomb carbon carrier with this maceration extract, to NO xThe absorption life-span, the result as shown in Figure 4, this adsorbent is after continuously using 100min, it still keeps teaching high adsorption efficiency.
Embodiment 6
The comparative example 1, wherein replaces the honeycomb carbon carrier to carry out the priority load successively of buffer layer material and metal oxide activated adoption composition material with honeycomb ceramic carrier, and prepared honeycomb ceramic carrier adsorbent is to NO xAbsorption shown in a among Fig. 5, NO wherein xAdsorption efficiency can reach 98.7%/every adsorbent (125cm 3).
Embodiment 7
The comparative example 4, load when wherein replacing the honeycomb carbon carrier to carry out buffer layer material and metal oxide activated adoption composition material with honeycomb ceramic carrier, and prepared honeycomb ceramic carrier adsorbent is to NO xAbsorption shown in the b among Fig. 5, NO wherein xAdsorption efficiency can reach 98%/every adsorbent (125cm 3).
Embodiment 8
Technology of preparing and experimental implementation wherein replace the honeycomb carbon carrier to carry out buffer layer material (Al with honeycomb ceramic carrier with embodiment 5 2O 3With mesoporous (Zr.Ce) O 2Solid solution) and the load pairing cerous nitrate of metal oxide activated adoption composition, ruthenic chloride, manganese nitrate, calcium nitrate dipping slurries the time, prepared honeycomb ceramic carrier adsorbent is to NO xAbsorption as shown in Figure 6, through after this adsorbents adsorb, last NO in the atmosphere xAmount almost approach 0, the size of institute's ventilation is little to the influence of its adsorption efficiency, illustrates that this adsorbent has high adsorption efficiency to nitrogen oxide.
Embodiment 9
Used experimental raw kind and operation are with embodiment 1, but heat treatment temperature is 400 ℃/2h, and prepared honeycomb carbon carrier adsorbent is to NO xThe absorption situation shown in data in the table 1.When its adsorb saturated after, again with its 180~250 ℃ the activation 1h after, once more to NO xAbsorption, this adsorbent before and after activation to the absorption situation of nitrogen oxide shown in data in the table 1, illustrate that the adsorbent after activating still keeps higher NO xAdsorption efficiency illustrates that adsorbent of the present invention has reusable performance.
Table 3: the honeycomb ceramic carrier adsorbent in embodiment 9 under the condition to NO xAbsorption property
Figure G2009100493703D00081

Claims (11)

1. low-concentration nitrogen oxide adsorbent is characterized in that,
The carrier material of adsorbent is honeycomb carbon or ceramic honey comb, and this honeycomb carbon or ceramic honey comb have the connection endoporus, 50~200 orders, and the endoporus aperture is 0.5~2mm;
Be coated with buffer layer material and metal oxide materials on the adsorbing agent carrier inner hole wall;
Described buffer layer material is aluminium oxide, mesoporous cerium zirconium sosoloid and/or titanium dioxide.
2. by the described low-concentration nitrogen oxide adsorbent of claim 1, it is characterized in that, the proportioning of described aluminium oxide, mesoporous cerium zirconium sosoloid and/or titanium dioxide is 1: (1~7): (0~2), the ratio of preferred aluminium oxide and mesoporous cerium zirconium sosoloid is 1: (4~6).
3. by the described low-concentration nitrogen oxide adsorbent of claim 1, it is characterized in that described aluminium oxide specific area is 250~300m 2/ g; Mesoporous cerium zirconium sosoloid specific area is 220~300m 2/ g, the aperture is 5~9nm, cerium zirconium ratio is 1: 1~5; The specific area of titanium dioxide is 80~150m 2/ g.
4. by claim 1 or 2 or 3 described low-concentration nitrogen oxide adsorbents, it is characterized in that described metal oxide materials is one or more the combination in cerium oxide, ruthenium-oxide, manganese oxide, cupric oxide, calcium oxide, the barium monoxide.
5. by claim 1 or 2 or 3 described low-concentration nitrogen oxide adsorbents, it is characterized in that described metal oxide materials is a cerium oxide, or ruthenium-oxide, or in manganese oxide and the cupric oxide one or both, or in calcium oxide and the barium monoxide one or both.
6. by claim 1 or 2 or 3 described low-concentration nitrogen oxide adsorbents, it is characterized in that the shape of described adsorbing agent carrier can be for being communicated with cube, hexahedron and the cylinder of endoporus arbitrarily.
7. the preparation method of low-concentration nitrogen oxide adsorbent.May further comprise the steps:
1) selecting honeycomb carbon or ceramic honey comb for use is the adsorbing agent carrier material, and honeycomb carbon or ceramic honey comb have the connection endoporus, 50~200 orders, and the endoporus aperture is 0.5~2mm;
2) select for use in mesoporous cerium zirconium sosoloid, aluminium oxide and/or the titanium dioxide as buffer layer material;
3) select for use in cerium oxide, ruthenium-oxide, manganese oxide, cupric oxide, calcium oxide, the barium monoxide one or more be combined as the metal oxide active material.
4) buffer layer material and the pairing salt of metal oxide active material and water being mixed with solid content is 10~50% slurry, and dip loading is on honeycomb substrate;
5) oven dry; 300~500 ℃ of heat treatment is 2~4 hours under reducing atmosphere.
8. press the preparation method of the described low-concentration nitrogen oxide adsorbent of claim 7, it is characterized in that, the proportioning of described aluminium oxide, mesoporous cerium zirconium sosoloid and/or titanium dioxide is 1: (1~7): (0~2), the ratio of preferred aluminium oxide and mesoporous cerium zirconium sosoloid is 1: (4~6).
9. by the preparation method of the described low-concentration nitrogen oxide adsorbent of claim 7, it is characterized in that described aluminium oxide specific area is 250~300m 2/ g; Mesoporous cerium zirconium sosoloid specific area is 220~300m 2/ g, the aperture is 5~9nm, cerium zirconium ratio is 1: 1~5; The specific area of titanium dioxide is 80~150m 2/ g.
10. press the preparation method of the described low-concentration nitrogen oxide adsorbent of claim 7, it is characterized in that, in one or both in the described metal oxide active material in preferred cerium oxide, ruthenium-oxide, the manganese oxide/cupric oxide and the calcium oxide/barium monoxide one or both.
11. the preparation method by the described low-concentration nitrogen oxide adsorbent of claim 7 is characterized in that described reducing atmosphere is for containing 1~7%H 2N 2, Ar, He.
CN200910049370A 2009-04-15 2009-04-15 Low-concentration nitrogen oxide adsorbent and preparation method thereof Pending CN101733064A (en)

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CN103492068A (en) * 2011-04-22 2014-01-01 三井金属矿业株式会社 Carrier for internal-combustion engine exhaust gas purification catalyst
CN105251478A (en) * 2015-09-24 2016-01-20 哈尔滨工程大学 Marine diesel engine low temperature selective catalytic reduction system titanium-based catalyst and preparation method thereof
CN106076322A (en) * 2016-06-13 2016-11-09 湘潭大学 A kind of catalyst of room temperature fast decoupled ozone and preparation method thereof
CN109715269A (en) * 2016-10-14 2019-05-03 黄华丽 A kind of purifying agent for harmful gases and its preparation and purification method
CN109939662A (en) * 2019-03-28 2019-06-28 广东石油化工学院 Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil
CN112264001A (en) * 2020-10-26 2021-01-26 国家电投集团远达环保催化剂有限公司 Calcium-doped cerium-based medium-temperature denitration catalyst and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103492068A (en) * 2011-04-22 2014-01-01 三井金属矿业株式会社 Carrier for internal-combustion engine exhaust gas purification catalyst
CN103492068B (en) * 2011-04-22 2016-01-27 三井金属矿业株式会社 For the carrier of purifying internal combustion engine tail gas catalyst
CN105251478A (en) * 2015-09-24 2016-01-20 哈尔滨工程大学 Marine diesel engine low temperature selective catalytic reduction system titanium-based catalyst and preparation method thereof
CN106076322A (en) * 2016-06-13 2016-11-09 湘潭大学 A kind of catalyst of room temperature fast decoupled ozone and preparation method thereof
CN109715269A (en) * 2016-10-14 2019-05-03 黄华丽 A kind of purifying agent for harmful gases and its preparation and purification method
CN109939662A (en) * 2019-03-28 2019-06-28 广东石油化工学院 Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil
CN109939662B (en) * 2019-03-28 2021-11-16 广东石油化工学院 Dealkalized nitrogen adsorbent for light fraction obtained by sump oil rectification in ethylene production process
CN112264001A (en) * 2020-10-26 2021-01-26 国家电投集团远达环保催化剂有限公司 Calcium-doped cerium-based medium-temperature denitration catalyst and preparation method thereof

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Application publication date: 20100616