CN101385976A - Preparation method of cuprum cerium composite oxides catalyst - Google Patents
Preparation method of cuprum cerium composite oxides catalyst Download PDFInfo
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- CN101385976A CN101385976A CNA2008102020184A CN200810202018A CN101385976A CN 101385976 A CN101385976 A CN 101385976A CN A2008102020184 A CNA2008102020184 A CN A2008102020184A CN 200810202018 A CN200810202018 A CN 200810202018A CN 101385976 A CN101385976 A CN 101385976A
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Abstract
The invention discloses a method used for preparing Cu-Se composite oxide catalyst by a citric acid complex method, comprising the steps as follows: a. copper salt and Se salt are added in anhydrous alcohol solution; b. the citric acid is added in the mixed solution and mixed so as to be completely dissolved, and heated and continuously mixed till sol is generated; wherein, the molar quantity of the added citric acid is 0.5-5 times of the molar quantity of the Cu-Se; C. after the sol is heated, the sol is foamed rapidly to form loose and porous gel which is dried subsequently and roasted in a muffle furnace under the temperature of 300-900 DEG C, thus gaining the Cu-Se composite oxide catalyst. The method has simple preparation process; furthermore, the prepared CuO/CeO2 catalyst has extremely high catalytic activation on CO oxidation reaction.
Description
Technical field
The present invention relates to a kind of preparation method of composite oxide catalysts, relate to a kind of CuO/CeO in particular
2The preparation method of composite oxide catalysts.
Background technology
CuO/CeO
2Catalyst 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.CuO/CeO
2The reactivity worth of catalyst is not only relevant with its composition, but also closely related with the Preparation of catalysts method.At present, preparation CuO/CeO
2The method of catalyst is main two kinds, i.e. infusion process, 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
2Catalyst, being used for the temperature of CO oxidation reaction when conversion ratio is 95% is 85 ℃.This shows that coprecipitation prepares CuO/CeO
2Though catalyst has higher activity, also there is significant disadvantages, promptly, need repeatedly process such as repeated washing, suction filtration in order to eliminate the influence of Na to catalyst performance, man-hour is longer.
This shows existing preparation CuO/CeO
2All there is significant disadvantages in the composite oxide catalysts method, and for example to be used for CO low-temperature oxidation reactivity unsatisfactory for loaded down with trivial details, the consuming time long and/or prepared catalyst of preparation process.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome loaded down with trivial details, the consuming time length of prior art for preparing cu-ce composite oxidation catalyst process, catalyst is used for the not high shortcoming of CO low-temperature oxidation reactivity, and the simple citric acid complex method cu-ce composite oxidation catalyst of a kind of preparation process preparation method is provided.
Technical solution of the present invention: a kind of preparation method of cu-ce composite oxidation catalyst comprises the following steps:
A. mantoquita and cerium salt are joined in the absolute alcohol solvent, wherein said mantoquita and cerium salt be selected from solubility nitrate, acetate or carbonate one of them, the content of copper is counted 2-40% with mole percent, the content of cerium is counted 60-98% with mole percent, and described absolute alcohol solvent is selected from the mixture of ethanol, normal propyl alcohol, isopropyl alcohol one of them or more than one;
B. citric acid is joined in the above-mentioned mixed solution, stirring is dissolved it fully, and heating and continuous stirring are until producing colloidal sol under 50～150 ℃ of temperature then, and the mole that adds citric acid is 0.5-5 a times of copper cerium mole total amount;
C. above-mentioned colloidal sol is heated under 80～200 ℃ of temperature, colloidal sol foams rapidly, form the gel of bulk multi-hole, gel drying was placed in the Muffle furnace 300-900 ℃ of roasting temperature 2～8 hours in 2～8 hours, make described cu-ce composite oxidation catalyst.
The mole of the citric acid that adds among the step b is 0.8-2 a times of copper cerium mole total amount.
Gel drying is placed in the Muffle furnace at 450-750 ℃ of roasting temperature among the step c.
Beneficial effect of the present invention: the CuO/CeO of the inventive method preparation
2Its central principle of catalyst is to adopt improved citric acid complex method to prepare CuO/CeO
2Catalyst, promptly replacing water with absolute alcohol in preparation during presoma is solvent, so preparation process is simple and be used for the CO oxidation reaction and have advantages of high catalytic activity, has overcome prior art for preparing CuO/CeO
2Loaded down with trivial details, consuming time length of catalyst process and preparation condition are difficult to grasp or are used for the active relatively poor shortcoming of CO oxidation reaction catalysis.
The specific embodiment
Below by preparation embodiment and comparing embodiment the present invention is described in further detail, a kind of preparation method of cu-ce composite oxidation catalyst comprises the following steps:
A. mantoquita and cerium salt are joined in the absolute alcohol solvent, wherein said mantoquita and cerium salt be selected from solubility nitrate, acetate or carbonate one of them, the content of copper is counted 2-40% with mole percent, the content of cerium is counted 60-98% with mole percent, and described absolute alcohol solvent is selected from the mixture of ethanol, normal propyl alcohol, isopropyl alcohol one of them or more than one;
B. citric acid is joined in the above-mentioned mixed solution, stirring is dissolved it fully, and heating and continuous stirring are until producing colloidal sol under 50～150 ℃ of temperature then, and the mole that adds citric acid is 0.5-5 a times of copper cerium mole total amount;
C. above-mentioned colloidal sol is heated under 80～200 ℃ of temperature, colloidal sol foams rapidly, form the gel of bulk multi-hole, gel drying was placed in the Muffle furnace 300-900 ℃ of roasting temperature 2～8 hours in 2～8 hours, make described cu-ce composite oxidation catalyst.
The mole of the citric acid that adds among the step b is 0.8-2 a times of copper cerium mole total amount.
Gel drying is placed in the Muffle furnace at 450-750 ℃ of roasting temperature among the step c.
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 analysis of the TDX01 carbon molecular sieve of 2m * Φ 3mm.
[embodiment 1]
2.42 gram copper nitrates and 39.1 gram cerous nitrates are dissolved in 100 milliliters the ethanol, add the citric acids of 2.3 grams then, stir it is dissolved fully.Heating and be continuously stirring to generation colloidal sol in 80 ℃ of water-baths changes it over to rapidly before this at 120 ℃ down in the bulk containers of heating, and colloidal sol foams rapidly, forms the Gel Precursor of bulk multi-hole.In Muffle furnace, obtain CuO/CeO behind the dry 2h at 650 ℃ of following roasting 4h
2Catalyst A.
[embodiment 2]
With embodiment 1 preparation CuO/CeO
2Catalyst B and C just replace ethanol with propyl alcohol and butanols respectively.
[embodiment 3]
With embodiment 1 preparation CuO/CeO
2Catalyst D and E, just the addition of citric acid is respectively 1.54 grams and 3.46 grams.
[embodiment 4]
With embodiment 1 preparation CuO/CeO
2Catalyst F and G, just the sintering temperature of xerogel is respectively 500 ℃ and 600 ℃.
[comparative example 1]
With embodiment 1 preparation CuO/CeO
2Catalyst H just replaces ethanol with water.
[embodiment 5]
Carry out gas-phase reaction with embodiment 1,2,3,4 and comparative example 1 prepared catalyst A, B, C, D, E, F, G and H 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 30000h
-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. the preparation method of a cu-ce composite oxidation catalyst comprises the following steps:
A. mantoquita and cerium salt are joined in the absolute alcohol solvent, wherein said mantoquita and cerium salt be selected from solubility nitrate, acetate or carbonate one of them, the content of copper is counted 2-40% with mole percent, the content of cerium is counted 60-98% with mole percent, and described absolute alcohol solvent is selected from the mixture of ethanol, normal propyl alcohol, isopropyl alcohol one of them or more than one;
B. citric acid is joined in the above-mentioned mixed solution, stirring is dissolved it fully, and heating and continuous stirring are until producing colloidal sol under 50～150 ℃ of temperature then, and the mole that adds citric acid is 0.5-5 a times of copper cerium mole total amount;
C. above-mentioned colloidal sol is heated under 80～200 ℃ of temperature, colloidal sol foams rapidly, form the gel of bulk multi-hole, gel drying was placed in the Muffle furnace 300-900 ℃ of roasting temperature 2～8 hours in 2～8 hours, make described cu-ce composite oxidation catalyst.
2. the preparation method of cu-ce composite oxidation catalyst according to claim 1 is characterized in that: the mole of the citric acid that adds among the step b be copper cerium mole total amount 0.8-2 doubly.
3. the preparation method of cu-ce composite oxidation catalyst according to claim 1, it is characterized in that: gel drying is placed in the Muffle furnace at 450-750 ℃ of roasting temperature among the step c.
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Cited By (21)
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| CN102489304A (en) * | 2011-12-01 | 2012-06-13 | 黑龙江大学 | Preparation method for spherical copper-cerium composite oxides |
| CN102674432A (en) * | 2012-05-19 | 2012-09-19 | 黑龙江大学 | Preparation method of cubic copper-cerium composite oxides |
| CN104028275A (en) * | 2014-06-10 | 2014-09-10 | 浙江大学 | Cerium-copper composite oxide catalyst for SO3 catalytic decomposition and preparation method of cerium-copper composite oxide catalyst |
| CN104028277A (en) * | 2014-06-10 | 2014-09-10 | 浙江大学 | Cerium and copper binary compound oxide catalyst and preparation method thereof |
| CN104624195A (en) * | 2015-01-19 | 2015-05-20 | 陕西科技大学 | Method for preparing Sm2O3/CuO nano composite through sol-gel process |
| CN104971726A (en) * | 2015-05-18 | 2015-10-14 | 深圳职业技术学院 | Catalyst used in catalytic oxidation of refractory organics, and preparation method and application method thereof |
| CN106946282A (en) * | 2017-02-27 | 2017-07-14 | 广东省稀有金属研究所 | A kind of preparation method of porous cerium-based composite oxides |
| CN106966466A (en) * | 2017-03-07 | 2017-07-21 | 北京化工大学 | A kind of method of utilization cupric oxide ceria Electrocatalysis Degradation phenol |
| CN108246285A (en) * | 2018-02-10 | 2018-07-06 | 浙江大学 | A kind of method for preparing porous oxidation Mn catalyst |
| CN108339545A (en) * | 2018-02-10 | 2018-07-31 | 浙江大学 | A method of preparing manganese metal oxides material |
| CN108355639A (en) * | 2018-02-10 | 2018-08-03 | 浙江大学 | A method of preparing porous oxidation cerium catalysis material |
| CN108448123A (en) * | 2018-03-23 | 2018-08-24 | 福州大学 | A kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction |
| 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 |
| CN110479326A (en) * | 2019-09-10 | 2019-11-22 | 清华大学 | A kind of phosphorus doping copper cerium metal composite oxide bifunctional catalyst and its preparation method and application |
| CN111871418A (en) * | 2020-06-29 | 2020-11-03 | 润泰化学（泰兴）有限公司 | Coated nano catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof |
| CN112517016A (en) * | 2020-11-17 | 2021-03-19 | 上海应用技术大学 | Carbon monoxide catalytic oxidation catalyst and preparation method and application thereof |
| CN112657501A (en) * | 2020-12-23 | 2021-04-16 | 上海应用技术大学 | CO oxidation catalyst and preparation method and application thereof |
| CN113117727A (en) * | 2021-03-29 | 2021-07-16 | 国能龙源环保有限公司 | Preparation method of honeycomb ceramic catalyst for CO catalytic oxidation of flue gas |
| CN114870849A (en) * | 2022-03-31 | 2022-08-09 | 南京工业大学 | Composite oxide aerogel catalytic material and preparation method and application thereof |
| CN114989444A (en) * | 2022-07-06 | 2022-09-02 | 杭州师范大学 | Preparation method and nitrogen fixation application of citric acid-based metal organic framework material |
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| 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 |
| CN102674432A (en) * | 2012-05-19 | 2012-09-19 | 黑龙江大学 | Preparation method of cubic copper-cerium composite oxides |
| CN104028275A (en) * | 2014-06-10 | 2014-09-10 | 浙江大学 | Cerium-copper composite oxide catalyst for SO3 catalytic decomposition and preparation method of cerium-copper composite oxide catalyst |
| CN104028277A (en) * | 2014-06-10 | 2014-09-10 | 浙江大学 | Cerium and copper binary compound oxide catalyst and preparation method thereof |
| CN104624195A (en) * | 2015-01-19 | 2015-05-20 | 陕西科技大学 | Method for preparing Sm2O3/CuO nano composite through sol-gel process |
| CN104971726A (en) * | 2015-05-18 | 2015-10-14 | 深圳职业技术学院 | Catalyst used in catalytic oxidation of refractory organics, and preparation method and application method thereof |
| 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 |
| CN106946282A (en) * | 2017-02-27 | 2017-07-14 | 广东省稀有金属研究所 | A kind of preparation method of porous cerium-based composite oxides |
| CN106966466A (en) * | 2017-03-07 | 2017-07-21 | 北京化工大学 | A kind of method of utilization cupric oxide ceria Electrocatalysis Degradation phenol |
| CN108246285A (en) * | 2018-02-10 | 2018-07-06 | 浙江大学 | A kind of method for preparing porous oxidation Mn catalyst |
| CN108339545A (en) * | 2018-02-10 | 2018-07-31 | 浙江大学 | A method of preparing manganese metal oxides material |
| CN108355639A (en) * | 2018-02-10 | 2018-08-03 | 浙江大学 | A method of preparing porous oxidation cerium catalysis material |
| CN108448123A (en) * | 2018-03-23 | 2018-08-24 | 福州大学 | A kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction |
| CN108448123B (en) * | 2018-03-23 | 2020-08-11 | 福州大学 | Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof |
| CN110479326A (en) * | 2019-09-10 | 2019-11-22 | 清华大学 | A kind of phosphorus doping copper cerium metal composite oxide bifunctional catalyst and its preparation method and application |
| CN111871418A (en) * | 2020-06-29 | 2020-11-03 | 润泰化学（泰兴）有限公司 | Coated nano catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof |
| CN112517016A (en) * | 2020-11-17 | 2021-03-19 | 上海应用技术大学 | Carbon monoxide catalytic oxidation catalyst and preparation method and application thereof |
| CN112657501A (en) * | 2020-12-23 | 2021-04-16 | 上海应用技术大学 | CO oxidation catalyst and preparation method and application thereof |
| CN113117727A (en) * | 2021-03-29 | 2021-07-16 | 国能龙源环保有限公司 | Preparation method of honeycomb ceramic catalyst for CO catalytic oxidation of flue gas |
| CN113117727B (en) * | 2021-03-29 | 2023-08-08 | 国能龙源环保有限公司 | Preparation method of honeycomb ceramic catalyst for catalytic oxidation of flue gas CO |
| CN114870849A (en) * | 2022-03-31 | 2022-08-09 | 南京工业大学 | Composite oxide aerogel catalytic material and preparation method and application thereof |
| CN114989444A (en) * | 2022-07-06 | 2022-09-02 | 杭州师范大学 | Preparation method and nitrogen fixation application of citric acid-based metal organic framework material |
| CN114989444B (en) * | 2022-07-06 | 2023-04-18 | 杭州师范大学 | Preparation method and nitrogen fixation application of citric acid-based metal organic framework material |
| 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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