CN105251476B - A kind of CeO2‑Cr2O3‑Nb2O5The preparation method of composite oxide catalysts - Google Patents
A kind of CeO2‑Cr2O3‑Nb2O5The preparation method of composite oxide catalysts Download PDFInfo
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- CN105251476B CN105251476B CN201510651148.6A CN201510651148A CN105251476B CN 105251476 B CN105251476 B CN 105251476B CN 201510651148 A CN201510651148 A CN 201510651148A CN 105251476 B CN105251476 B CN 105251476B
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Abstract
A kind of CeO provided by the invention2‑Cr2O3‑Nb2O5The preparation method of composite oxide catalysts, with chromic nitrate, cerous nitrate and with acid Nb2O5Oxide or niobium oxalate ammonia are raw material, and CeO is prepared using using precipitation deposition or coprecipitation2‑Cr2O3‑Nb2O5Composite oxide catalysts, Ce/Cr mol ratio is 4 in catalyst:1, (Cr2O3+CeO2)/Nb2O5Mass ratio be 4:1~1:9.Catalyst preparation process is simple, cost is low, has good catalytic degradation activity and stability, CO to chlorine-containing organic compounds such as dichloromethane (DCM), dichloroethanes (DCE), trichloro ethylene (TCE) and chlorobenzenes2Produced with HCl selectivity height and without accessory substances such as polychlorocarbons.
Description
Technical field
The present invention relates to a kind of preparation method of high performance chloride organic exhaust gas combustion catalyst, more particularly to
CeO2-Cr2O3-Nb2O5The preparation method of composite oxide catalysts.
Background technology
Chloride volatile organic matter (CVOCs) is a kind of compound for having high risks to environment and human health, often
That sees has dichloromethane (DCM), chloroform (CF), dichloroethanes (DCE), trichloro ethylene (TCE), carbon tetrachloride (CT), chlorine
Benzene (PhCl) etc., because they have good chemical stability, usually as half in organic solvent and chemical process
Finished product and be widely used.Catalytic combustion technology is important and very one of effective means of CVOCs pollutant purifications processing,
Therefore, extensive use of the chloride organic exhaust gas combustion catalyst of exploitation efficiently, stable for catalytic combustion technology has important
Meaning.Although noble metal catalyst has higher catalytic activity to all kinds of VOCs catalyzing oxidizing degrading, for chloro
Hydro carbons or containing chlorohydrocarbon VOCs catalytic removals reaction for, be vulnerable to during the course of the reaction chlorinated compound decompose caused by
Cl2With HCl poisoning effects；Oxychlorination compound is easily generated in high-temperature region and is inactivated；On the other hand, noble metal catalyst is to Deacon
Reaction and chlorination activity are also very high, more chloro organic cpds are easily produced during catalytic degradation, particularly with chloro
The processing of aromatic hydrocarbons often produces toxicity bigger more chlorine aromatic hydrocarbons and dioxin compounds.In general, base metal aoxidizes
The catalytic activity of thing (VB, II B) is lower than noble metal, but slightly strong in terms of anti-hetero atom such as Cl, Br, S poisoning capability.So
And CeO2And its composite oxides store oxygen ability and lattice oxygen mobility with good, in catalytic removal CVOCs reaction
In show good oxidation susceptibility, its catalytic activity and selectivity even it is higher than noble metal catalyst, therefore, cause people
Extensive concern.
The content of the invention
It is an object of the invention to provide a kind of high performance chloride organic exhaust gas combustion catalyst, in particular to CeO2-
Cr2O3-Nb2O5The preparation method of composite oxide catalysts.
The present invention is achieved through the following technical solutions：
A kind of CeO2-Cr2O3-Nb2O5The preparation method of composite oxide catalysts, with chromic nitrate, cerous nitrate, Nb2O3
Oxide or niobium oxalate ammonia are primary raw material, and CeO is prepared using precipitation-deposition or coprecipitation2-Cr2O3-Nb2O5Combined oxidation
Thing catalyst, Ce/Cr mol ratio is 4 in catalyst:1, (Cr2O3+CeO2)/Nb2O5Mass ratio be 4:1~1:9, specific system
Standby step is as follows：
By the CeO2+Cr2O3/Nb2O5Mass ratio, setting concentration cerous nitrate [Ce (NO3)3·6H2O] and nitre
Sour chromium [Cr (NO3)3·9H2O] add in mixed solution set amount Nb predecessor, dripped under vigorous stirring after stirring
Add (the NH for determining concentration4)2CO3Precipitating reagent, it is added dropwise to room temperature after solution ph reaches 9.0 and places ageing 12 hours, then mistake
Filter, deionized water and ethanol washing are repeatedly neutral to filtrate, are calcined 2 hours and handle at being dried 2 hours, 500 DEG C at 110 DEG C,
CeO is made2-Cr2O3-Nb2O5Composite oxide catalysts.
As a further improvement, (Cr of the present invention2O3+CeO2)/Nb2O5Optimum quality ratio be 3:4~1:4.
As a further improvement, cerous nitrate [Ce (NO of the present invention3)3·6H2O] and chromic nitrate [Cr
(NO3)3·9H2O] predecessor that adds Nb in mixed solution is Nb2O5Powder or niobium oxalate ammonia [(NH4)3NbO(C2O4)3·
4H2O]。
As a further improvement, cerous nitrate [Ce (NO of the present invention3)3·6H2O] and chromic nitrate [Cr
(NO3)3·9H2O] mixed solution concentration (CCe+Cr), or cerous nitrate [Ce (NO3)3·6H2O], chromic nitrate [Cr (NO3)3·
9H2O] and niobium oxalate ammonia [(NH4)3NbO(C2O4)3·4H2O] mixed solution concentration (CCe+Cr+Nb) it is 0.25mol/L.
As a further improvement, (NH of the present invention4)2CO3The concentration of precipitating reagent is 0.5mol/L.
It is the device have the advantages that as follows：
Cheap cerous nitrate, chromic nitrate and niobium oxalate ammonia or niobium oxide are used as raw material, using precipitation-deposition or coprecipitated
Shallow lake legal system obtains CeO2-Cr2O3-Nb2O5Composite oxide catalysts, preparation technology is simple, and catalyst cost is low, there is good catalysis
Degrading activity and stability, it is a kind of high performance chloride organic exhaust gas combustion catalyst, to extensively should for catalytic combustion technology
With having great importance.
Embodiment
Technical scheme is further described below by specific embodiment：
Embodiment 1
By 3.6gCr (NO3)3·9H2O and 15.6gCe (NO3)3·6H2O is dissolved in 180mL water, is stirring evenly and then adding into
13.8gNb2O5Powder.(NH is added dropwise under vigorous stirring4)2CO3Precipitating reagent, it is added dropwise to room temperature after solution ph reaches 9.0 and places
Ageing 12 hours, then filtering, deionized water and ethanol washing are repeatedly neutral to filtrate, are dried 2 hours, 500 DEG C at 110 DEG C
Lower roasting is handled for 2 hours, and CeO is made2-Cr2O3-Nb2O5Composite oxide catalysts.Ce/Cr mol ratio is in the catalyst
4:1, (Cr2O3+CeO2)/Nb2O5Mass ratio 1:2.
Embodiment 2
Operated with the identical of embodiment 1, difference is：By 1.1gCr (NO3)3·9H2O、4.7gCe(NO3)3·
6H2(NH is added dropwise in 180mL water in O and 15.6g niobium oxalate ammonia co-dissolves under vigorous stirring after stirring4)2CO3It is heavy
Shallow lake agent.Ce/Cr mol ratio is 4 in the catalyst:1, (Cr2O3+CeO2)/Nb2O5Mass ratio 1:2.
Embodiment 3
Operated with the identical of embodiment 1, difference is：By 0.6gCr (NO3)3·9H2O、2.8gCe(NO3)3·
6H2(NH is added dropwise in 180mL water in O and 18.4g niobium oxalate ammonia co-dissolves under vigorous stirring after stirring4)2CO3It is heavy
Shallow lake agent.Ce/Cr mol ratio is 4 in the catalyst:1, (Cr2O3+CeO2)/Nb2O5Mass ratio 1:4.
Embodiment 4
Operated with the identical of embodiment 1, difference is：By 3.6gCr (NO3)3·9H2O and 15.6gCe (NO3)3·
6H2O is dissolved in 180mL water, and (NH is added dropwise after stirring under vigorous stirring4)2CO3Precipitating reagent.Ce/Cr in the catalyst
Mol ratio be 4:1, without Nb2O5。
Embodiment 5
Operated with the identical of embodiment 1, difference is：By 2.3gCr (NO3)3·9H2O、9.9gCe(NO3)3·
6H2(NH is added dropwise in 180mL water in O and 8.2g niobium oxalate ammonia co-dissolves under vigorous stirring after stirring4)2CO3Precipitation
Agent.Ce/Cr mol ratio is 4 in the catalyst:1, (Cr2O3+CeO2)/Nb2O5Mass ratio 2:1.
Catalyst is as shown in the table to the catalytic degradation activity of chlorinated organics in 1~4 example：
Note：0.3mL, the catalyst that particle diameter is 40-60 mesh, air speed 15000h- 1。
Listed above is only some embodiments of the present invention, it is clear that the invention is not restricted to above example, may be used also
To have many deformations, all changes that one of ordinary skill in the art directly can export or associate from present disclosure
Shape, it is considered as protection scope of the present invention.
Claims (4)
- A kind of 1. CeO2-Cr2O3-Nb2O5The preparation method of composite oxide catalysts, it is characterized in that, it is sub- with chromic nitrate, nitric acid Cerium, Nb2O3Oxide or ammonium niobium oxalate are primary raw material, and CeO is prepared using precipitation-deposition or coprecipitation2-Cr2O3-Nb2O5 Composite oxide catalysts, Ce/Cr mol ratio is 4 in catalyst:1, (Cr2O3+CeO2)/Nb2O5Mass ratio be 4:1~1: 9, specific preparation process is as follows：By the CeO2+Cr2O3/Nb2O5Mass ratio, setting concentration cerous nitrate [Ce (NO3)3·6H2O] and chromic nitrate [Cr(NO3)3·9H2O] add in mixed solution set amount Nb predecessor, be added dropwise and set under vigorous stirring after stirring Determine (the NH of concentration4)2CO3Precipitating reagent, it is added dropwise to room temperature after solution ph reaches 9.0 and places ageing 12 hours, then filter, go Ionized water and ethanol washing are repeatedly neutral to filtrate, are calcined 2 hours and handle at being dried 2 hours, 500 DEG C at 110 DEG C, are made CeO2-Cr2O3-Nb2O5Composite oxide catalysts.
- 2. CeO according to claim 12-Cr2O3-Nb2O5The preparation method of composite oxide catalysts, it is characterized in that, institute (the Cr stated2O3+CeO2)/Nb2O5Optimum quality ratio be 3:4~1:4.
- 3. CeO according to claim 1 or 22-Cr2O3-Nb2O5The preparation method of composite oxide catalysts, its feature It is described cerous nitrate [Ce (NO3)3·6H2O] and chromic nitrate [Cr (NO3)3·9H2O] mixed solution concentration (CCe+Cr), Or cerous nitrate [Ce (NO3)3·6H2O], chromic nitrate [Cr (NO3)3·9H2O] and ammonium niobium oxalate [(NH4)3NbO(C2O4)3· 4H2O] mixed solution concentration (CCe+Cr+Nb) it is 0.25mol/L.
- 4. CeO according to claim 1 or 22-Cr2O3-Nb2O5The preparation method of composite oxide catalysts, its feature It is described (NH4)2CO3The concentration of precipitating reagent is 0.5mol/L.
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| CN109422638B (en) * | 2017-08-31 | 2021-11-23 | 中国科学院大连化学物理研究所 | Method for preparing ketone compound by ABE fermentation liquor conversion |
| CN112371106A (en) * | 2020-11-30 | 2021-02-19 | 绍兴文理学院 | Synthesis method and application of Ce-Nb-O composite metal oxide catalyst |
| CN112958071B (en) * | 2021-03-08 | 2023-08-15 | 上海睿筑环境科技有限公司 | High-stability catalyst for low-temperature catalytic combustion of chlorine-containing volatile organic compounds and preparation method thereof |
| CN113244938A (en) * | 2021-05-21 | 2021-08-13 | 华东理工大学 | P-Nb/Co for low-temperature vinyl chloride catalytic combustion3O4Catalyst, preparation method and application thereof |
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| CN104368329A (en) * | 2014-09-19 | 2015-02-25 | 中国科学院生态环境研究中心 | Cerium-niobium-zirconium composite oxide catalyst, preparation method and uses thereof |
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| EP1491218A1 (en) * | 2003-05-30 | 2004-12-29 | Taiwan Fluorescent Lamp Co., Ltd. | Illuminator capable of cleaning air |
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