CN101733116A - Cu3Mo2O9 catalyst and preparation method and application thereof - Google Patents

Cu3Mo2O9 catalyst and preparation method and application thereof Download PDF

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Publication number
CN101733116A
CN101733116A CN 200810226634 CN200810226634A CN101733116A CN 101733116 A CN101733116 A CN 101733116A CN 200810226634 CN200810226634 CN 200810226634 CN 200810226634 A CN200810226634 A CN 200810226634A CN 101733116 A CN101733116 A CN 101733116A
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catalyst
tail gas
powder
goes out
cigarette ash
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CN101733116B (en
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褚卫国
王汉夫
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National Center for Nanosccience and Technology China
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National Center for Nanosccience and Technology China
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Abstract

The invention provides a Cu3Mo2O9 catalyst which is Cu3Mo2O9 powder with nano-scaled grain diameter, as well as a preparation method thereof and application of the catalyst in the oxidizing reaction of carbon-contained substances. The invention provides a catalyst used in the oxidizing reaction of carbon-contained substances and comprises the Cu3Mo2O9 catalyst. The invention provides a method for catalyzing and oxidizing tail gas discharged by motors, wherein the power containing the nano-scaled Cu3Mo2O9 is used as a catalyst. In the invention, when the powder containing the nano-scaled Cu3Mo2O9 is used as a catalyst, ash of the tail gas discharged by engines can be oxidized, and the oxidizing temperature of the tail gas can be reduced by 150-250 DEG C in comparison with a catalyst without the nano-scaled Cu3Mo2O9 powder.

Description

Cu 3Mo 2O 9Catalysts and its preparation method and application
Technical field
The present invention relates to a kind of Cu 3Mo 2O 9Catalysts and its preparation method and application, particularly, the present invention relates to contain particle diameter is nano level Cu 3Mo 2O 9The oxidation catalysis of cigarette ash in the tail gas that fine catalyst and to carbonaceous material, particularly engine emission go out.
Background technology
The catalysis characteristics of catalyst usually and size of catalyst and surface state thereof and structure closely related.Along with the minimizing of catalyst size, because the joint effect on quantum and surface can cause its catalytic performance to obtain improving in various degree.Therefore, utilize nanometer technology can realize change to catalyst catalytic performance.
Oxide is used very extensive at catalytic field, as CeO 2The cell catalyst that acts as a fuel, MoO 3As catalyst of some oxidation operation etc.For Cu 3Mo 2O 9The variation of chemical valence because appraising at the current rate all can appear in its Cu and Mo, may take place in complex oxide in catalytic process, therefore can cause the improvement of its catalytic performance.Cigarette ash is a kind of composition that leaves in the waste gas that engine discharges by gas extraction system, and for the tail gas that diesel engine is discharged as engine, main component is a carbon-bearing particulate matter.If directly be discharged in the air, can cause the pollution of atmosphere, therefore cigarette ash need be continued oxidizing fire.Just be based on this thought, we have carried out Cu 3Mo 2O 9Complex oxide is as the research of soot oxidation catalyst.The result shows Cu 3Mo 2O 9Complex oxide can reduce the temperature that oxidation takes place cigarette ash effectively in atmosphere, have significant catalytic effect.
In application number is the Chinese patent application of 200610021650.x, a kind of ester exchange synthesizing diphenyl carbonate bimetal composite oxide catalyst has been proposed, this catalyst basic composition is molybdenum oxide and Cu oxide, wherein the mol ratio of molybdenum copper is: Mo: Cu=100: 1-100, this catalyst does not require for size of catalyst, and this catalyst is used for dimethyl carbonate and phenol ester ester exchange synthesizing diphenyl carbonate.
Summary of the invention
The present invention's one purpose provides a kind of Cu 3Mo 2O 9Catalyst, this catalyst are that particle diameter is nano level Cu 3Mo 2O 9Powder.
Another object of the present invention provides the method for the described catalyst of preparation.
A further object of the present invention provides the purposes of a kind of described catalyst in catalysis carbonaceous material oxidation reaction.
A further object of the present invention provides a kind of catalyst of carbonaceous material oxidation reaction.
A further object of the present invention provides the method for the tail gas that a kind of catalytic oxidation engine emission goes out.
One aspect of the present invention provides a kind of Cu 3Mo 2O 9Catalyst, this catalyst are that particle diameter is nano level Cu 3Mo 2O 9Powder.
The present invention also provides a kind of method for preparing described catalyst on the other hand, and this method may further comprise the steps:
A. be nano level Cu with particle diameter 2O and MoO 3Powder is with 3: the mixed in molar ratio of 4-4.2;
B. with above-mentioned mixture at 480-520 ℃ of following sintering 3-5 hour, obtain described Cu 3Mo 2O 9Catalyst.
Further aspect of the present invention also provides a kind of method for preparing described catalyst, and this method may further comprise the steps:
A. at first with copper sulphate and ammonium molybdate by 10.5-10.8: 1 mol ratio is dissolved in the water;
B. the aqueous solution that step a is obtained heated 2-24 hour down at 120-150 ℃, collected the sediment that obtains;
C. the sediment that obtains of drying steps b, and with dried sediment 500-550 ℃ of roasting, obtain described Cu 3Mo 2O 9Catalyst.
Further aspect of the present invention also provides the purposes of described catalyst in the oxidation reaction of catalysis carbonaceous material.
Preferably, described carbonaceous material is the cigarette ash in the tail gas that goes out of engine emission.
Further aspect of the present invention provides a kind of catalyst of oxidation reaction of carbonaceous material, and this catalyst comprises described Cu 3Mo 2O 9Catalyst.
Preferably, wherein said carbonaceous material is the cigarette ash in the tail gas that goes out of engine emission.
Preferably, the tail gas that goes out of described engine emission is the tail gas that diesel engine goes out as engine emission.
Preferably, the tail gas that goes out of described engine emission is vehicle exhaust.
Further aspect of the present invention provides the method for the tail gas that a kind of catalytic oxidation engine emission goes out, and wherein using above-mentioned particle diameter is nano level Cu 3Mo 2O 9Powder is as catalyst.
Cu among the present invention 3Mo 2O 9Catalyst fines is a nanoscale, and prior art does not require this size of catalyst, finds nano level Cu after deliberation 3Mo 2O 9Powder has the effect of catalytic oxidation carbonaceous material.Cigarette ash is as a kind of composition in the motor exhaust, and its harmful components mainly are hydrocarbon (C nH m) and carbon monoxide (CO) etc., directly be discharged in the atmosphere serious environment pollution.Diesel engine is during as engine, and dust content is higher in the tail gas that it gives off, and environmental pollution is more serious.
Adopt nano level Cu among the present invention 3Mo 2O 9Powder can be oxidized to CO with the harmful components of these carbon containings in the motor exhaust cigarette ash during as catalyst 2, contain nanoscale Cu with respect to not adding 3Mo 2O 9Fine catalyst, the oxidizing temperature of tail gas cigarette ash have reduced 150-250 ℃.
Nanometer powder Cu 3Mo 2O 9During as the catalyst of catalytic oxidation carbonaceous material, can be used for containing in the tail gas industrial circle that main component is the cigarette ash of carbonaceous particles, as the oxidation processes of cigarette ash in the diesel engine vent gas etc.In addition, Cu 3Mo 2O 9Also may be organic and the catalyst of inorganic matter oxidation processes as other similar carbon containings.
Description of drawings
Fig. 1 represents the Cu that embodiment 1 is prepared from 3Mo 2O 9The elemental composition analysis chart of catalyst.
Fig. 2 represents X-ray diffracting spectrum, and wherein the Cu of the embodiment of the invention 1 preparation is represented on the top of this figure 3Mo 2O 9The X-ray diffracting spectrum of catalyst, Cu is represented in the lower part of this figure 3Mo 2O 9The theoretical X-ray diffracting spectrum of ternary oxide.
Fig. 3 is the differential thermal analysis curve of cigarette ash, and wherein curve 1 is illustrated in nano level Cu 3Mo 2O 9Under the fine catalyst effect, the temperature-heat flow curve of cigarette ash; Under the curve 2 expression catalyst-free effects, the temperature-heat flow curve of cigarette ash.
Fig. 4 is the thermogravimetric analysis figure of cigarette ash, and wherein curve 1 is illustrated in nano level Cu 3Mo 2O 9Under the fine catalyst effect, the temperature of cigarette ash-weightless relation curve; Under the curve 2 expression catalyst-free effects, the temperature of cigarette ash-weightless relation curve.
The specific embodiment
Embodiment 1
Nano level Cu 3Mo 2O 9The preparation of fine catalyst: with nano level Cu 2O and MoO 3Powder mixes with 3: 4 mol ratio, nano level Cu 2The O powder is bought from Shanghai duty worker inorganic salts Co., Ltd, and commodity are called cuprous oxide, and article number is 060316; Nano level MoO 3Powder is bought from Beijing chemical reagents corporation, and commodity are called molybdenum trioxide, and article number is 060406.
With nano level Cu 2O and nano level MoO 3The mixture of powder was 500 ℃ of following sintering 3 hours, and obtaining particle diameter is nano level Cu 3Mo 2O 9Fine catalyst.
The evaluation of catalyst component: the Cu that adopts method for preparing to form 3Mo 2O 9Elementary analysis figure such as Fig. 1 of fine catalyst, result show and only have Cu, Mo and three kinds of elements of O in this compound that its ratio is as follows: Cu 3Mo 2.11O 8.52The Cu that adopts method for preparing to form 3Mo 2O 9The X-ray diffracting spectrum of fine catalyst such as Fig. 2, wherein the Cu of the inventive method preparation is represented on the top of this figure 3Mo 2O 9The X-ray diffracting spectrum of catalyst, Cu is represented in the lower part of this figure 3Mo 2O 9The theoretical X-ray diffracting spectrum of ternary oxide, the result shows that this two-part X ray collection of illustrative plates coincide, and other dephasign do not occur, has confirmed the Cu that adopts method for preparing to obtain 3Mo 2O 9Catalyst is a pure material.
Containing particle diameter is nano level Cu 3Mo 2O 9The application experiment of fine catalyst: the catalyst that will prepare by above method, can satisfy commercial Application.Catalytic test is finished on differential thermal-thermogravimetric (DTA-TG) linkage analysis instrument.The nanometer Cu that method for preparing is gone out 3Mo 2O 9The standard cigarette ash of powder and purchase evenly mixed by weight 4: 1, and the gross weight of mixed-powder is about 5mg.Place the crucible of differential thermal-thermogravimetric (DTA-TG) linkage analysis instrument to carry out differential thermal-thermogravimetric analysis in this powder.In order to compare, carried out cigarette ash oxidation experiment in atmosphere simultaneously, it the results are shown in the accompanying drawing.
The analysis of experimental result: from the temperature-heat flow curve of Fig. 3 cigarette ash as can be known, with Cu 3Mo 2O 9After the powder, the oxidizing reaction temperature of cigarette ash is reduced to 430 ℃, sees the temperature of curve-1 peak value correspondence; During catalyst-free, the oxidizing temperature of cigarette ash is about 600 ℃, sees the temperature of curve-2 peak value correspondence.This illustrates Cu 3Mo 2O 9Significantly reduce the oxidizing temperature of cigarette ash, had good catalytic effect.Fig. 4 is the temperature-weightless relation curve of cigarette ash.Wherein curve 1 is at Cu 3Mo 2O 9Temperature-the weight-loss curve of cigarette ash under the catalyst action, the weightless temperature of cigarette ash is 430 ℃ as can be known; Temperature-weight-loss curve under the effect of curve-2 expression catalyst-free, from its as can be known the weightless temperature of cigarette ash be 600 ℃.This illustrates Cu 3Mo 2O 9Significantly reduce the oxidizing temperature of cigarette ash, had good catalytic effect.
Embodiment 2
Nano level Cu 3Mo 2O 9The preparation of fine catalyst: at first copper sulphate and the ammonium molybdate mol ratio by 10.5: 1 is dissolved in the water, the aqueous solution reaction under 150 ℃ that obtains was obtained sediment in 24 hours, and it is carried out drying handle, carry out roasting at 500 ℃ then, obtain being of a size of nano level Cu 3Mo 2O 9Fine catalyst.
Nano level Cu 3Mo 2O 9The composition identification experiment of fine catalyst, application experiment and interpretation are with embodiment 1.

Claims (10)

1. Cu 3Mo 2O 9Catalyst, this catalyst are that particle diameter is nano level Cu 3Mo 2O 9Powder.
2. method for preparing the described catalyst of claim 1, this method may further comprise the steps:
A. be nano level Cu with particle diameter 2O and MoO 3Powder is with 3: the mixed in molar ratio of 4-4.2;
B. with above-mentioned mixture at 480-520 ℃ of following sintering 3-5 hour, obtain described Cu 3Mo 2O 9Catalyst.
3. method for preparing the described catalyst of claim 1, this method may further comprise the steps:
A. at first with copper sulphate and ammonium molybdate by 10.5-10.8: 1 mol ratio is dissolved in the water;
B. the aqueous solution that step a is obtained heated 2-24 hour down at 120-150 ℃, collected the sediment that obtains;
C. the sediment that obtains of drying steps b, and with dried sediment 500-550 ℃ of roasting, obtain described Cu 3Mo 2O 9Catalyst.
4. the purposes of the described catalyst of claim 1 in the oxidation reaction of catalysis carbonaceous material.
5. purposes according to claim 4, wherein said carbonaceous material are the cigarette ash in the tail gas that goes out of engine emission.
6. the catalyst of the oxidation reaction of a carbonaceous material, this catalyst comprises the described Cu of claim 1 3Mo 2O 9Catalyst.
7. catalyst according to claim 6, wherein said carbonaceous material are the cigarette ash in the tail gas that goes out of engine emission.
8. catalyst according to claim 7, the tail gas that wherein said engine emission goes out are the tail gas that diesel engine goes out as engine emission.
9. catalyst according to claim 7, the tail gas that wherein said engine emission goes out are vehicle exhaust.
10. the method for the tail gas that goes out of a catalytic oxidation engine emission, wherein using the described particle diameter of claim 1 is nano level Cu 3Mo 2O 9Powder is as catalyst.
CN2008102266343A 2008-11-18 2008-11-18 Cu3Mo2O9 catalyst and preparation method and application thereof Expired - Fee Related CN101733116B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502838A (en) * 2011-11-07 2012-06-20 河北联合大学 Preparation method for copper molybdate microsphere super structure assembled by nanosheets
CN107221670A (en) * 2017-06-20 2017-09-29 扬州大学 A kind of synthetic method of lithium ion battery negative material nanometer rods
CN109126814A (en) * 2018-09-28 2019-01-04 南昌航空大学 A kind of method of micro nano structure copper molybdate growth in situ
CN112439422A (en) * 2020-12-07 2021-03-05 岭南师范学院 Cu3Mo2O9/BiVO4Nano heterostructure composite material and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10050153A1 (en) * 1999-10-12 2001-08-09 Hitachi Maxell Active material for a positive electrode and a lithium cell comprising this material
CN1986893A (en) * 2005-12-20 2007-06-27 中国科学院兰州化学物理研究所 Electrochemical reducing process for preparing nanometer MOS2 particle
CN100589902C (en) * 2007-09-26 2010-02-17 中南大学 Ultra-fine or nanometer molybdenum cuprum composite powder and method of producing the alloy thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502838A (en) * 2011-11-07 2012-06-20 河北联合大学 Preparation method for copper molybdate microsphere super structure assembled by nanosheets
CN107221670A (en) * 2017-06-20 2017-09-29 扬州大学 A kind of synthetic method of lithium ion battery negative material nanometer rods
CN109126814A (en) * 2018-09-28 2019-01-04 南昌航空大学 A kind of method of micro nano structure copper molybdate growth in situ
CN109126814B (en) * 2018-09-28 2021-09-03 南昌航空大学 Method for in-situ growth of copper molybdate with micro-nano structure
CN112439422A (en) * 2020-12-07 2021-03-05 岭南师范学院 Cu3Mo2O9/BiVO4Nano heterostructure composite material and preparation method and application thereof

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