CN107626317B - A kind of Ce base oxide catalyst and its preparation and application - Google Patents
A kind of Ce base oxide catalyst and its preparation and application Download PDFInfo
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- CN107626317B CN107626317B CN201710677887.1A CN201710677887A CN107626317B CN 107626317 B CN107626317 B CN 107626317B CN 201710677887 A CN201710677887 A CN 201710677887A CN 107626317 B CN107626317 B CN 107626317B
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Abstract
The invention discloses a kind of Ce base oxide catalyst and its preparation and application, are with CeO2For carrier, the temperature of the reducing agent type being added by control, dosage and hydro-thermal reaction, to regulate and control the pattern of catalyst, so that Co/CeO be made2Catalyst.Preparation process of the present invention is simple, easy to operate, at low cost, high conversion rate, gained catalyst show higher catalytic oxidation activity in wider temperature range, can be used for the catalysis oxidation of toluene and propane etc., and higher thermal stability is showed, there is apparent industrial application value.
Description
Technical field
The invention belongs to field of nanometer technology, and in particular to a kind of Ce base oxide catalyst and its preparation and application.
Background technique
Human survival and development be unable to do without suitable environment, and with the development of industry, environmental pollution is got worse or even prestige
The survival and development of the mankind are coerced, therefore very urgent to the protection of environment.Arene substance to the toxicity of people and animal compared with
Greatly, if contacted through long period larger concentration, the symptoms such as nausea, headache, dizziness can be caused.In addition, the polycyclic virtue in petroleum
Hydrocarbons have strong three-induced effect.The hydrocarbons such as the crude oil of leakage such as open fire, will cause fire incident；If let out
The hydro carbons of leakage enters in restricted clearance, easily explodes, or even the catastrophic failure of the dead group's wound of group is caused to occur.Therefore it removes
Hydro carbons is all of great significance to human body and environment.Catalytic oxidation is one of the effective ways that hydro carbons is eliminated, Pt, Pd, Au
Low temperature hydrocarbon, which is showed, with noble metal-based catalysts such as Ag eliminates performance.However, due to the expensive price of noble metal, high temperature is easy
The reasons such as sintering and noble metal reserves are limited, limit the extensive use of noble metal-based catalysts industrially.In recent years, CeO2
Due to good oxygen storage capacity and redox property, and there is Surface Oxygen defective bit abundant, is conducive to Ce3+Pass through
The path Mars-van Krevelen carries out reoxidizing process, the favor by many researchers.However, due to pure CeO2Itself
Surface acidity position is less, causes low-temperature catalytic activity and selection performance far from meeting actual requirement.
Summary of the invention
The purpose of the present invention is to provide a kind of Ce base oxide catalyst and the preparation method and application thereof, which is
A kind of low temperature, high activity, high thermal stability and highly selective cheap catalyst, performance is high in wider temperature range
Catalytic oxidation activity, can be using the elimination of the hydro carbons such as toluene, propane.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of Ce base oxide catalyst, is in CeO2It is upper load 1-10wt% Co and be made.The shape of gained catalyst
Looks structure includes nanometer rods, nano cubic block, nanosphere, any one in nanocone.
The preparation method of the Ce base oxide catalyst is to carry out the presoma of Ce in the solvent containing reducing agent
Then hydro-thermal reaction roasts products therefrom, the catalyst is made.It specifically comprises the following steps:
1) presoma of Ce, cobalt nitrate and reducing agent dissolved in a certain amount of solvent, mixed；
2) gained mixed solution is subjected to hydro-thermal reaction in reaction kettle；
3) solution after reaction is centrifuged, alternately washing is dried in vacuo afterwards for several times for products therefrom water and ethyl alcohol；
4) product after drying is roasted, the catalyst is made.
The presoma of the Ce is cerous nitrate.
The presoma of Ce used and the molar ratio of reducing agent are 1:1.05-1:2.67.
The reducing agent is urea or NaOH, and concentration in a solvent is 6-9 mol/L；The solvent is water, ethyl alcohol
One or both of.
The temperature of the hydro-thermal reaction is 100-180 DEG C, and the time is 10-24 h.
Heating rate when roasting is 1-3 DEG C/min, and maturing temperature is 500-550 DEG C, and calcining time is 2-6 h.
Promotor can also be added in the mixed solution of step 2, to regulate and control the synthesis of nanocone and nanosphere；The promotion
Agent is hydrochloric acid, and additional amount is 12 mol/L.
Gained Ce base oxide catalyst can be used for the hydro carbons such as organic toluene of catalytic methane, propane and coal-fired flue-gas discharge
Catalysis oxidation.It can be used in granular form when its concrete application, can also be used as coating load in honeycombs such as cordierites
Carrier on be prepared into monolithic porous formula catalyst.
The present invention is with CeO2For carrier, and it is compound by Ce and transition metal element Co, to significantly change the surface of Ce, shape
At more surface oxygen defects, to improve the redox ability of catalyst, and the empty rail for more receiving lone pair electrons is formed
Road promotes the absorption of hydro carbons.Meanwhile the oxide of Co is due to the unsaturation electricity with unsaturated 3d electronic structure, on d track
Son is readily migrate on c h bond, is conducive to improve low-temperature catalytic activity.
Remarkable advantage of the invention is:
(1) present invention passes through type, concentration and the hydrothermal temperature for controlling reducing agent used, to regulate and control the shape of catalyst
Looks structure, and then realize the regulation of catalyst activity.Such as when reducing agent is NaOH, by regulating and controlling its concentration and hydro-thermal reaction temperature
Degree, can prepare the Ce base oxide catalyst with nanometer rods and nano cubic block structure；When reducing agent is urea, pass through
Urotropinum Cl and control hydrothermal temperature are added, the Ce base oxide with nanosphere and nanometer cone structure can be prepared
Catalyst.Meanwhile when catalyst morphology difference, exposure crystal face is also different.
(2) present invention gained catalyst shows higher catalytic oxidation activity in wider temperature range.Such as Co/
CeO2Nano cubic block 90% has been reached to the catalytic conversion of toluene at 237 DEG C, and Co/CeO2Nanometer rods are at 254 DEG C to third
The catalytic conversion of alkane has reached 90%, and effect is better than traditional toluene and propane catalyst for catalytic oxidation.
(3) preparation process of catalyst of the present invention is simple, easy to operate, at low cost, and catalytic conversion is high, has apparent
Industrial application value.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of catalyst made from embodiment 1-4, wherein (A) is CeO2Nano cubic block, (B) are
CeO2Nanosphere, (C) are CeO2Nanocone, (D) are CeO2Nanometer rods.
Fig. 2 is toluene conversion of the catalyst made from embodiment 1-4 in different temperature points.
Fig. 3 is conversion of propane of the catalyst made from embodiment 1-4 in different temperature points.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
1 Co/CeO of embodiment2The preparation of nanocube
By 1.736 g Ce (NO3)3·6H2O(molecular weight 434.12) and 0.034g Co (NO3)2·6H2O(molecular weight
291.03) it is dissolved in the deionized water of 10 mL, and the NaOH solution of 70 mL, 6mol/L is added dropwise, stir 1h at room temperature, so
After be transferred in water heating kettle, 100 DEG C of 24 h of reaction, centrifugation, products therefrom deionized water and ethyl alcohol are respectively washed 3 times, then in 60
DEG C 12 h of vacuum drying are warming up to 500 DEG C with the rate of 3 DEG C/min, roast 3h then in Muffle furnace.
2 Co/CeO of embodiment2The preparation of nanosphere
By 0.434 g Ce (NO3)3·6H2O(molecular weight 434.12), 0.010g Co (NO3)2·6H2O(molecular weight
291.03) with 8 g urea (molecular weight 60), it is added to the mixed solvent being made of 70 mL deionized waters and 10 mL ethyl alcohol together
In, 1 h is stirred at room temperature, and the HCl(12M of 0.1mL is then added), it is vigorously stirred 1 h at room temperature, is then transferred to water heating kettle
In, 160 DEG C of 12 h of reaction, centrifugation, products therefrom deionized water and ethyl alcohol are respectively washed 3 times, then in 60 DEG C of vacuum drying 12
H is warming up to 550 DEG C with the rate of 3 DEG C/min, roasts 2h then in Muffle furnace.
3 Co/CeO of embodiment2The preparation of nanocone
By 1.042 g Ce (NO3)3·6H2O(molecular weight 434.12), 0.033g Co (NO3)2·6H2O(molecular weight
291.03) it with 0.384 g urea (molecular weight 60), is dissolved in the deionized water of 80mL together, stirs 1 h at room temperature, then
It is transferred in water heating kettle, 120 DEG C of 8 h of reaction, is centrifuged, products therefrom deionized water and ethyl alcohol are respectively washed 3 times, then true in 60 DEG C
Dry 12 h of sky are warming up to 500 DEG C with the rate of 3 DEG C/min, roast 6 h then in Muffle furnace.
4 Co/CeO of embodiment2The preparation of nanometer rods
By 1.736 g Ce (NO3)3·6H2O(molecular weight 434.12) and 0.069g Co (NO3)2·6H2O(molecular weight
291.03) it is dissolved in the deionized water of 10 mL, and the NaOH solution of 70 mL, 9 mol/L is added dropwise, stir 1h at room temperature,
Then be transferred in water heating kettle, 180 DEG C of 24 h of reaction, be centrifuged, products therefrom deionized water and ethyl alcohol respectively wash 3 times, then in
60 DEG C of 12 h of vacuum drying are warming up to 500 DEG C with the rate of 3 DEG C/min, roast 3 h then in Muffle furnace.
Fig. 1 is the scanning electron microscope (SEM) photograph of catalyst obtained by embodiment 1-4.
Performance test
Each 0.1g of catalyst of embodiment 1-4 preparation is respectively adopted, carries out toluene in the miniature fixed bed continuously flowed
It is measured with conversion of propane, 90000 mL/ of mass space velocity (gh), the variation of toluene and propane concentration passes through gas phase color in tail gas
Spectrum detection, reaction gas composition are as follows: 1000 ppm toluene or propane, 20vol%O2And N2For Balance Air.It is surveyed at 200-400 DEG C
Catalyst is determined to the changing effect of toluene and propane.
Fig. 2 is toluene conversion of the catalyst made from embodiment 1-4 in different temperature points.Figure it is seen that Co/
CeO2Nano cubic block catalyst has reached 90% in 237 DEG C of toluene conversion, can compare favourably with noble metal-based catalysts.
Fig. 3 is conversion of propane of the catalyst made from embodiment 1-4 in different temperature points.From figure 3, it can be seen that Co/
CeO2Nano cubic block shows excellent propane low-temperature oxidation activity, has reached 80% in 246 DEG C of conversion of propane.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (3)
1. a kind of preparation method of Ce base oxide catalyst, it is characterised in that: by the presoma of Ce and cobalt nitrate containing also
Hydro-thermal reaction is carried out in the solvent of former agent, then roasts products therefrom, and the catalyst is made；Co's is negative in the catalyst
Carrying capacity is 1-10 wt%；
The presoma of the Ce is cerous nitrate；The presoma of Ce and the molar ratio of reducing agent are 1:1.05-1:2.67；
The concentration of reducing agent is 6-9 mol/L in solvent；Wherein, the reducing agent is urea or NaOH, and the solvent is water, second
One or both of alcohol；
The temperature of the hydro-thermal reaction is 100-180 DEG C, and the time is 10-24 h；
Heating rate when roasting is 1-3 DEG C/min, and maturing temperature is 500-550 DEG C, and calcining time is 2-6 h；
The appearance structure of gained catalyst includes nanometer rods, nano cubic block, nanosphere, any one in nanocone.
2. the preparation method of Ce base oxide catalyst according to claim 1, it is characterised in that: hydro-thermal reaction it is anti-
Answering further includes promotor in system；The promotor is hydrochloric acid, and dosage is 12 mol/L.
3. a kind of application of Ce base oxide catalyst made from method as described in claim 1, it is characterised in that: be used for hydro carbons
Catalysis oxidation；
The hydro carbons includes organic toluene of alkane or coal-fired flue-gas discharge.
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| CN108736030B (en) * | 2018-05-17 | 2020-12-25 | 福州大学 | Porous carbon-free catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN109529856A (en) * | 2018-11-22 | 2019-03-29 | 福州大学 | Ammonia synthesis catalyst and preparation method thereof under a kind of Co base temperate condition |
| CN110508288A (en) * | 2019-09-24 | 2019-11-29 | 福州大学 | A kind of preparation and its application of the rodlike Copper-cladding Aluminum Bar ceria with porous structure |
| CN112467154B (en) * | 2020-12-03 | 2022-04-19 | 福州大学 | Preparation method of cerium oxide loaded nickel-iron catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106256427A (en) * | 2015-06-18 | 2016-12-28 | 内蒙古大学 | The box-like CuO-CeO of multi-layer nano for prior oxidation of co in hydrogen-riched gas reaction of one-step synthesis method2the preparation method of catalyst |
| CN107008335A (en) * | 2017-05-16 | 2017-08-04 | 福州大学 | A kind of cerium oxide is cobalt-based ammonia synthesis catalyst of carrier and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106256427A (en) * | 2015-06-18 | 2016-12-28 | 内蒙古大学 | The box-like CuO-CeO of multi-layer nano for prior oxidation of co in hydrogen-riched gas reaction of one-step synthesis method2the preparation method of catalyst |
| CN107008335A (en) * | 2017-05-16 | 2017-08-04 | 福州大学 | A kind of cerium oxide is cobalt-based ammonia synthesis catalyst of carrier and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 纳米CeO2担载的钴氧化物催化剂的制备、表征及其对柴油碳烟的催化燃烧性能的研究;王季秋 等;《第十五届全国稀土催化学术会议论文集》;20080430;第339页摘要 * |
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