CN101391221A - Preparation method of cuprum cerium composite oxides catalyst - Google Patents
Preparation method of cuprum cerium composite oxides catalyst Download PDFInfo
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- CN101391221A CN101391221A CNA2008102020127A CN200810202012A CN101391221A CN 101391221 A CN101391221 A CN 101391221A CN A2008102020127 A CNA2008102020127 A CN A2008102020127A CN 200810202012 A CN200810202012 A CN 200810202012A CN 101391221 A CN101391221 A CN 101391221A
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Abstract
The invention discloses a preparation method of a copper-cerium composite oxide catalyst, comprising the following steps: a. positioning cupric salt, cerium salt and oxalic acid in a ball mill for grinding for 0.5 to 4h to obtain an oxalate precursor, wherein, the content of copper is 2 to 40 percent in molar percentage, the content cerium is 60 to 98 percent in molar percentage, and the molar quantity of oxalic acid is 0.5 to 5 times of the total molar quantity of copper and cerium; and b. drying the oxalate precursor at a temperature of between 60 and 160DEG C for 0.5 to 16h, then positioning the precursor in a muffle furnace for calcinations for 1 to 8h at a temperature of between 300 and 900DEG C, so as to prepare the copper-cerium composite oxide catalyst. The invention adopts the oxalate solid phase chemical reaction method to prepare the catalyst, and has advantages of simple preparation process, having no need of solvent, and very high catalytic activity of the prepared CuO/CeO2 catalyst to the carbon monoxide oxidation reaction.
Description
Technical field
The present invention relates to a kind of method for preparing cu-ce composite oxidation catalyst.
Background technology
Cu-ce composite oxidation catalyst is widely used in the reactions such as catalytic reduction, water gas shift reation, hydrogen peroxide decomposes, methane catalytic combustion and phenol wet oxidation of the low-temperature oxidation of carbon monoxide and selective oxidation, alcohols vapor reforming hydrogen production, nitrogen oxide.The reactivity worth of cu-ce composite oxidation catalyst is not only relevant with its composition, but also closely related with the Preparation of catalysts method.At present, prepare that the method for cu-ce composite oxidation catalyst is main two kinds, i.e. infusion process and coprecipitation.The immersion process for preparing cu-ce composite oxidation catalyst carries out in two steps, at first makes cerium oxide carrier, then active ingredient copper is immersed in the surface of cerium oxide carrier, makes cu-ce composite oxidation catalyst by dry and high-temperature roasting.As be entitled as " CuO/CeO
2Preparation of catalysts and application in the CO oxidation reaction " Chinese patent CN 1554480A (2004) disclosed and adopt infusion process active ingredient copper to be loaded on the cu-ce composite oxidation catalyst that forms on the cerium oxide carrier.Its concrete method for making prepares cerium oxide carrier for adopting sol-gel process earlier, then prepared cerium oxide carrier is joined in the copper nitrate solution, the heating concentrated solvent, 80 ℃ of following dryings promptly made cu-ce composite oxidation catalyst at last at 300-700 ℃ of following roasting 2-8 hour subsequently.This catalyst is used for the low-temperature oxidation reaction of carbon monoxide, and the temperature that carbon monoxide transforms fully is more than 140 ℃.This shows, above-mentioned catalyst preparation process complexity, and also catalytic activity is lower.It is to add precipitating reagent to make it to precipitate simultaneously in the mixed solution of cupric and ce metal ion that coprecipitation prepares cu-ce composite oxidation catalyst, then after filtration, washing, drying and high-temperature roasting obtain catalyst." chemistry circular, 1998, (5): 50 " have reported with NaOH to be that precipitating reagent prepares CuO/CeO
2It is 85 ℃ that catalyst, this catalyst are used for the temperature of CO oxidation reaction when the conversion ratio of CO is 95%.This shows that coprecipitation prepares CuO/CeO
2Though catalyst has higher activity, also there is significant disadvantages, promptly in order to eliminate Na
+To the influence of catalyst performance, need repeatedly process such as repeated washing, suction filtration, man-hour is longer.This shows above-mentioned several CuO/CeO that are used for
2All there is significant disadvantages in the Preparation of catalysts method, and for example loaded down with trivial details, consuming time length of preparation process and/or prepared catalyst are used for the reaction of CO low-temperature oxidation, and it is very satisfied that its activity can't be made us.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome CuO/CeO in the prior art
2Catalyst preparation process is loaded down with trivial details, consuming time longer, and catalyst is used for the not high shortcoming of CO low-temperature oxidation when reaction activity, provide a kind of preparation process simple cu-ce composite oxidation catalyst preparation method, the catalyst of this method preparation also has the good advantage of catalytic activity.
Technical solution of the present invention: the present invention adopts oxalates solid state reaction legal system to be equipped with CuO/CeO
2Catalyst comprises the following steps:
A. mantoquita, cerium salt and oxalic acid are placed grinding in ball grinder 0.5-4h, obtain the oxalates predecessor, wherein said mantoquita and cerium salt are selected from nitrate, acetate or carbonate, the content of copper is counted 2-40% with mole percent, the content of cerium is counted 60-98% with mole percent, and the mole of oxalic acid is copper and cerium mole total amount 0.5-5 a times;
B. with above-mentioned oxalates predecessor dry 0.5-16h under 60-160 ℃, place Muffle furnace, make described cu-ce composite oxidation catalyst at 300-900 ℃ of following roasting 1-8h.
The content of copper is counted 5-20% with mole percent among the step a, and the content of cerium is counted 80-95% with mole percent, and the mole of oxalic acid is the 0.8-2 of copper and cerium mole total amount.
Step b places Muffle furnace at 400--750 ℃ of following roasting 2-4h above-mentioned oxalates predecessor dry 2-10h under 80-120 ℃, makes described cu-ce composite oxidation catalyst.
The beneficial effect of the invention: the CuO/CeO of the inventive method preparation
2Its central principle of catalyst is to adopt oxalates solid state reaction legal system to be equipped with CuO/CeO
2Catalyst, so preparation process need not solvent, easy and simple to handle and preparation condition is easily controlled, and has overcome prior art for preparing CuO/CeO
2The shortcoming that loaded down with trivial details, consuming time length of catalyst process and preparation condition are difficult to grasp.And the prepared CuO/CeO of the inventive method
2Catalyst is used for the CO low-temp reaction and has the good advantage of catalytic activity.
The specific embodiment
Embodiment describes in further detail the present invention below by preparation, and a kind of preparation method who prepares cu-ce composite oxidation catalyst comprises the following steps:
A. mantoquita, cerium salt and oxalic acid are placed grinding in ball grinder 0.5-4h, obtain the oxalates predecessor, wherein said mantoquita and cerium salt are selected from nitrate, acetate or carbonate, the content of copper is counted 2-40% with mole percent, the content of cerium is counted 60-98% with mole percent, and the mole of oxalic acid is copper and cerium mole total amount 0.5-5 a times;
B. with above-mentioned oxalates predecessor dry 0.5-16h under 60-160 ℃, place Muffle furnace, make described cu-ce composite oxidation catalyst at 300-900 ℃ of following roasting 1-8h.
The content of copper is counted 5-20% with mole percent among the step a, and the content of cerium is counted 80-95% with mole percent, and the mole of oxalic acid is the 0.8-2 of copper and cerium mole total amount.
Step b places Muffle furnace at 400-750 ℃ of following roasting 2-4h 80-120 ℃ of following dry 2-10h of above-mentioned oxalates predecessor, makes described cu-ce composite oxidation catalyst.
The CuO/CeO of the present invention's preparation
2Catalyst can be used for the reactions such as catalytic reduction, water gas shift reation, hydrogen peroxide decomposes, methane catalytic combustion and phenol wet oxidation of the low-temperature oxidation of carbon monoxide and selective oxidation, alcohols vapor reforming hydrogen production, nitrogen oxide.
An example of the inventive method that is used for the reaction of CO low-temperature oxidation is hereinafter described:
It is 6mm that a certain amount of catalyst granules (20～40 order) is loaded in internal diameter, and length is in the stainless steel reactor of 300mm.Adopt electrical heating, temperature is controlled automatically.Reactor bottom filling 20～40 purpose inert materials are as supporter, a certain amount of catalyst of filling in the reactor, and filling 20～40 purpose inert materials in catalyst top are made for the usefulness of raw material preheating.The carbon monoxide oxidation reaction takes place and generates carbon dioxide from top to bottom by beds in unstripped gas.The composition of unstripped gas (volume fraction) is CO:1%, O
2: 10%, all the other are N
2The reaction pressure normal pressure; The volume space velocity of unstripped gas is 12000h
-1The GC9790 type gas chromatograph on-line analysis of adopting Fu Li company to produce, hydrogen is carrier gas, thermal conductivity detector (TCD), chromatographic column is the stainless steel column of TDX01 carbon molecular sieve of 2m * Φ 3mm.
[embodiment 1]
Get 1.21 gram copper nitrates, 41.2 gram cerous nitrates and 15.2 gram oxalic acid (molal quantity of oxalic acid is 1.2 times of molal quantity sum of copper and cerium) behind grinding in ball grinder 1h, gained oxalates predecessor is in 120 ℃ of dried overnight, and placing and obtaining CuO content (atomic percent Cu/ (Cu+Ce) * 100) behind 500 ℃ of roasting 4h of Muffle furnace is 5% CuO/CeO
2Catalyst A.
[embodiment 2]
Get 2.42 gram copper nitrates, 39.1 gram cerous nitrates and 15.2 gram oxalic acid, making CuO content with embodiment 1 is 10% CuO/CeO
2Catalyst B.
[embodiment 3]
Get 3.62 gram copper nitrates, 36.9 gram cerous nitrates and 15.2 gram oxalic acid, making CuO content with embodiment 1 is 15% CuO/CeO
2Catalyst C.
[embodiment 4]
Get 4.83 gram copper nitrates, 34.7 gram cerous nitrates and 15.2 gram oxalic acid, making CuO content with embodiment 1 is 20% CuO/CeO
2Catalyst D.
[embodiment 5]
With embodiment 1 preparation CuO content 15% CuO/CeO
2Catalyst, just sintering temperature is 450,650 and 700 ℃ three catalyst E, F and G.
[embodiment 6]
With embodiment 1 preparation CuO content 15% CuO/CeO
2Catalyst, just the molal quantity of oxalic acid is copper and cerium 0.8,1.0 and 2 times of the molal quantity sum three catalyst H, I and J.
[embodiment 7]
Carry out the CO oxidation reaction with embodiment 1～6 prepared catalyst A, B, C, D, E, F, G, H, I and J in continuous-flow fixed bed reaction evaluating apparatus, the loadings of catalyst is 0.2g.The composition of unstripped gas (volume fraction) is CO:1%, O
2: 10%, all the other are N
2The reaction pressure normal pressure; The volume space velocity of unstripped gas is 12000h
-1The GC9790 type gas chromatograph on-line analysis of adopting Fu Li company to produce, hydrogen is carrier gas, thermal conductivity detector (TCD), chromatographic column is the stainless steel column of TDX01 carbon molecular sieve of 2m * Φ 3mm.It is that conversion ratio is that 100% o'clock reaction temperature represents that evaluation result sees Table 1 that activity of such catalysts transforms fully with carbon monoxide.
The reactivity worth of table 1 catalyst
By table 1 data as seen, the CuO/CeO that adopts the inventive method to make
2Catalyst for the oxidation reaction of carbon monoxide, has very high catalytic activity.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (3)
1. a preparation method who prepares cu-ce composite oxidation catalyst comprises the following steps:
A. mantoquita, cerium salt and oxalic acid are placed grinding in ball grinder 0.5-4h, obtain the oxalates predecessor, wherein said mantoquita and cerium salt are selected from nitrate, acetate or carbonate, the content of copper is counted 2-40% with mole percent, the content of cerium is counted 60-98% with mole percent, and the mole of oxalic acid is copper and cerium mole total amount 0.5-5 a times;
B. with above-mentioned oxalates predecessor dry 0.5-16h under 60-160 ℃, place Muffle furnace then, make described cu-ce composite oxidation catalyst at 300-900 ℃ of following roasting 1-8h.
2. according to the preparation method of the described cu-ce composite oxidation catalyst of claim 1, it is characterized in that: the content of copper is counted 5-20% with mole percent among the step a, the content of cerium is counted 80-95% with mole percent, and the mole of oxalic acid is copper and cerium mole total amount 0.8-2 a times.
3. according to the preparation method of the described cu-ce composite oxidation catalyst of claim 1, it is characterized in that: step b is with above-mentioned oxalates predecessor dry 2-10h under 80-120 ℃, place Muffle furnace at 400-750 ℃ of following roasting 2-4h then, make described cu-ce composite oxidation catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489304A (en) * | 2011-12-01 | 2012-06-13 | 黑龙江大学 | Preparation method for spherical copper-cerium composite oxides |
| CN102614888A (en) * | 2012-03-12 | 2012-08-01 | 上海应用技术学院 | Method for preparing loaded CuO/CeO2 catalyst |
| CN103007979A (en) * | 2012-12-14 | 2013-04-03 | 南京大学 | Supported copper-cerium catalyst for selective oxidation of CO and preparation method of supported copper-cerium catalyst |
| CN109328108A (en) * | 2016-05-31 | 2019-02-12 | Ptt全球化学股份有限公司 | For preparing the preparation of the copper aluminum oxide catalyst and the catalyst of furfuryl alcohol by furfural |
| CN109433215A (en) * | 2018-11-26 | 2019-03-08 | 新疆大学 | One kind is based on heat treatment regulation CuOx-CeO2The method to interact between complex components |
| CN115353140A (en) * | 2022-07-27 | 2022-11-18 | 华中科技大学 | Copper cerium oxide and preparation method and application thereof |
-
2008
- 2008-10-30 CN CNA2008102020127A patent/CN101391221A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489304A (en) * | 2011-12-01 | 2012-06-13 | 黑龙江大学 | Preparation method for spherical copper-cerium composite oxides |
| CN102489304B (en) * | 2011-12-01 | 2013-04-03 | 黑龙江大学 | Preparation method for spherical copper-cerium composite oxides |
| CN102614888A (en) * | 2012-03-12 | 2012-08-01 | 上海应用技术学院 | Method for preparing loaded CuO/CeO2 catalyst |
| CN103007979A (en) * | 2012-12-14 | 2013-04-03 | 南京大学 | Supported copper-cerium catalyst for selective oxidation of CO and preparation method of supported copper-cerium catalyst |
| CN109328108A (en) * | 2016-05-31 | 2019-02-12 | Ptt全球化学股份有限公司 | For preparing the preparation of the copper aluminum oxide catalyst and the catalyst of furfuryl alcohol by furfural |
| CN109433215A (en) * | 2018-11-26 | 2019-03-08 | 新疆大学 | One kind is based on heat treatment regulation CuOx-CeO2The method to interact between complex components |
| CN115353140A (en) * | 2022-07-27 | 2022-11-18 | 华中科技大学 | Copper cerium oxide and preparation method and application thereof |
| CN115353140B (en) * | 2022-07-27 | 2024-03-01 | 华中科技大学 | Copper cerium oxide and preparation method and application thereof |
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