CN109529871A - A kind of sea urchin shape copper-based catalysts and its preparation method and application - Google Patents

A kind of sea urchin shape copper-based catalysts and its preparation method and application Download PDF

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Publication number
CN109529871A
CN109529871A CN201811525553.3A CN201811525553A CN109529871A CN 109529871 A CN109529871 A CN 109529871A CN 201811525553 A CN201811525553 A CN 201811525553A CN 109529871 A CN109529871 A CN 109529871A
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copper
sea urchin
based catalysts
urchin shape
manganese
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CN109529871B (en
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张海东
陈佳
熊昆
申渝
周玉凤
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Chongqing Technology and Business University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51Spheres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/50Carbon dioxide

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The present patent application belongs to metal oxide materials technical field, specifically discloses a kind of sea urchin shape copper-based catalysts, is spherical sea urchin structure, forms multiple columns dissipated outward on spherical sea urchin.The invention also discloses the preparation methods of above-mentioned sea urchin shape copper-based catalysts.The present invention also provides above-mentioned sea urchin shape copper-based catalysts with O2For oxidant, it is catalyzed the application of CO completely burned.Preparation method of the invention is simple, and catalyst shape obtained is unique, and CO is just oxidized to CO at 30-40 DEG C2

Description

A kind of sea urchin shape copper-based catalysts and its preparation method and application
Technical field
The present patent application belongs to metal oxide materials technical field, specifically disclose a kind of sea urchin shape copper-based catalysts and Preparation method and application.
Background technique
For for the fuel cell of fuel, about 5 are often contained in the hydrogen as made from low-carbon alcohols and hydro carbons using hydrogen ×105-2×106The CO of ppm (0.5-2%), the presence of CO can not only cause the electrode of fuel cell to be poisoned, but also meeting and hydrogen Gas competition, influences hydrogen and reacts with oxygen, the efficiency for eventually leading to fuel cell is greatly lowered, so needing in fuel cell CO eliminated.In the various methods for eliminating CO, by catalytic combustion elimination CO be it is a kind of it is easy, cheap, be easily achieved Method.
Catalysis burning is to carry out non-flaming combustion under low light-off temperature by catalyst, and by organic exhaust gas oxygenolysis For the technology of carbon dioxide and water.The essence of catalysis burning is the violent oxidation reaction that active oxygen participates in, catalytic active component By air oxygen activation, energy transmission occurs when contacting with reactant molecule, reactant molecule is activated, so that accelerated oxidation is anti- The progress answered.Compared with general flame combustion, catalysis burning has incomparable superiority, therefore is catalyzed burning and is eliminating Application in terms of CO receives the common concern of people.
Summary of the invention
The purpose of the present invention is to provide a kind of copper-based catalysts and preparation method thereof with sea urchin shape structure, and mention Supply the copper-based catalysts with O2For the application of catalyst CO completely burned.
In order to achieve the above object, base case of the invention are as follows:
A kind of sea urchin shape copper-based catalysts are spherical sea urchin structure, form multiple columns dissipated outward on spherical sea urchin Body.
The present invention also provides the preparation methods of above-mentioned sea urchin shape copper-based catalysts, comprising the following steps:
(1) copper precursor solution and manganese precursor solution are mixed, obtains copper-manganese mixed solution;
(2) water, cetyl trimethylammonium bromide and dehydrated alcohol are added into copper-manganese mixed solution, stirs at room temperature It mixes, mixing speed 80-100r/min;
(3) ammonium hydroxide is slowly added dropwise into the reaction mixture after step (2), stirs at room temperature, mixing speed 250- 350r/min;
(4) reaction mixture after step (3) is subjected to hydro-thermal process;
(5) reaction mixture that filtration step (4) obtains, obtains much filtrate, is rinsed to much filtrate, drying and calcination Afterwards, sea urchin shape copper-based catalysts are made.
The principle and beneficial effect of this sea urchin shape copper-based catalysts and preparation method thereof are:
Sea urchin shape catalyst of the invention can just be catalyzed CO completely burned under conditions of lower temperature.
The so-called room temperature of the present invention refers to that well known to a person skilled in the art 25 DEG C.
For this preparation method using cetyl trimethylammonium bromide as structure directing agent, water, dehydrated alcohol and ammonium hydroxide are auxiliary agent, Using hydrothermal synthesis method preparation have sea urchin shape structure feature copper-based catalysts, preparation method is simple, repeatability compared with It is good.
Under the stirring condition that this preparation method only needs low whipping speed to be respectively 80-100r/min and 250-350r/min It carries out, the common magnetic stirring apparatus in laboratory can reach.
The present invention also provides the applications of above-mentioned sea urchin shape copper-based catalysts, for being catalyzed under oxygen lean conditions with O2For oxygen The CO completely burned of agent, the reaction gas of the oxygen lean conditions include 0.5-5%CO, 0.5-5%O2And argon gas.This sea urchin shape copper Base catalyst is very suitable for eliminating the CO under oxygen lean conditions.
Further, the cross section of the column assumes diamond in shape, and 1 μm of the length > of column can effectively increase catalysis The contact area of agent and CO is allowed to that CO completely burned can be catalyzed under conditions of lower temperature.
Further, the copper precursors are copper nitrate, and manganese precursor is manganese nitrate.NO in copper precursors and manganese precursor3 -It can lead to Combustion heating removing is crossed, prevents it from remaining in the surface of oxide, influences the catalytic performance of oxide.
Further, molar ratio=0.5- of the copper in the copper precursors in the step (1) and the manganese in manganese precursor 1.65:1.It is preferable using the sea urchin shape structure of catalyst made from this preparation method under above-mentioned molar ratio.
Further, for being catalyzed under oxygen lean conditions with O2For the CO completely burned of oxidant, the oxygen lean conditions it is anti- Gas bag is answered to include 0.5-5%CO, 0.5-5%O2And argon gas, this sea urchin shape copper-based catalysts are very suitable for eliminating under oxygen lean conditions CO.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure for the sea urchin shape copper-based catalysts that embodiment 1 obtains;
Fig. 2 is that the spherical sea urchin shape copper-based catalysts that embodiment 1 obtains are catalyzed with O2For the CO completely burned of oxidant Performance;
Fig. 3 is the X ray diffracting spectrum of catalyst made from embodiment 1 and comparative example 1-4.
Specific embodiment
It is further described below by specific embodiment.In following embodiment and comparative example, mentioned Cu (NO3)2, 50%Mn (NO3)2Aqueous solution, CTAB, ammonium hydroxide, dehydrated alcohol are purchased from the smooth Science and Technology Co., Ltd. of upper Haitai, receive Directly use afterwards, using it is preceding not after further treatment.Carry out reaction gas [CO (0.5-5%)+O of CO catalytic removal reaction test2 (0.5-5%)+Ar (90-99%)] purchase is from Chongqing Zhaoyang Gas Co., Ltd., by high-purity O2, high-purity Ar, high-purity CO prepare and At.Element ratio contained by obtained catalyst (Cu:Mn) is measured using ICP method
Embodiment 1
(1) 19.9gCu (NO is weighed3)2With the Mn (NO of 5.9g50%3)2Aqueous solution mixing, is then added into mixed liquor 7.5ml distilled water is stirred to Cu (NO3)2It is completely dissolved, obtains copper-manganese mixed liquor.
(2) 112.5gH is added into copper-manganese mixed liquor2O, 5.6gCTAB, 135.1g dehydrated alcohol stirs 15 at room temperature After minute (mixing speed 80-100r/min).
(3) ammonium hydroxide 29.7g is slowly added dropwise in the reaction mixture obtained to step (2), after ammonium hydroxide drips, by mixed liquor (250-350r/min) 2h is stirred at room temperature.
(4) reaction mixture that step (3) obtains is transferred in hydrothermal synthesis kettle and carries out hydro-thermal process, at 120 DEG C Hydro-thermal process is for 24 hours.
(5) after hydro-thermal process, suction filtration obtains solid, is sufficiently washed after filtering out solid with distilled water, will filter out solid It is dry in 60 DEG C of rotary evaporator, it is finally putting into Muffle furnace, calcines 4h under 550 DEG C, air atmosphere, sea urchin shape is made Copper-based catalysts.
80mg catalyst is fitted into the crystal reaction tube of fixed bed catalyst furnace, be passed through proportion be CO (0.5-5%)+ The performance of the reaction gas test catalyst CO completely burned of O2 (0.5-5%)+Ar (90-99%).Reaction gas flow speed uses Mass flowmenter is controlled in 25ml/min, and the temperature of reaction tube is controlled by temperature controller, and heating rate is 10 DEG C/min.Use Britain The QIC-20 level four bars mass spectrum of Hiden Analytical Ltd. production carries out CO content, the CO2 content of generation in reaction gas Monitoring.
Fig. 1 is scanning electron microscope (SEM) figure for the spherical sea urchin shape copper-based catalysts that embodiment 1 obtains.As seen from Figure 1 This catalyst has spherical sea urchin shape structure, and this spherical sea urchin structure is dissipated by 1 μm of length > of column by center outward It constitutes, the cross section of each column assumes diamond in shape.
Fig. 2 is that the spherical sea urchin shape copper-based catalysts that embodiment 1 obtains are catalyzed with O2For the CO completely burned of oxidant Performance.It can be seen that CO starts CO being oxidized to CO at 34 DEG C2, 50% CO is oxidized to CO at 108 DEG C2, at 175 DEG C by CO All it is oxidized to CO2
Embodiment 2-5 and comparative example 1-4
The difference of embodiment 2-5, comparative example 1-4 and embodiment 1 is only that middle addition copper nitrate and nitric acid in step (1) The amount of manganese is different, causes the content of the Cu and Mn in finally obtained catalyst different, referring specifically to the following table 1.
Table 1
Conclusion:
(1) referring to comparative example 1-4, when the molar ratio of copper nitrate and manganese nitrate is not within the scope of 0.5-1.65:1, Final copper-based catalysts obtained are not sea urchin shapes, and it is 43-51 DEG C that CO, which starts oxidizing temperature, and 50%CO removal temperature is 130-142 DEG C, it is 190-219 DEG C that 100%CO, which removes temperature, is intended to be apparently higher than the associated temperature of embodiment 1-5, to sum up, I It can be concluded that, copper-based catalysts have sea urchin shape structure facilitate in lower temperature (30-40 DEG C, 100-110 DEG C and 170- 180 DEG C) it is catalyzed with O2For the CO completely burned of oxidant.
(2) X ray diffracting spectrum for the catalyst that Fig. 3 is embodiment 1 and comparative example 1-4 is obtained.From figure 3, it can be seen that The XRD spectrum of the copper-based catalysts and comparative example 1-4 obtained with sea urchin shape structure of embodiment 1 has significant difference.This says The catalyst that the Cu:Mn with sea urchin shape structure that bright embodiment 1 obtains is 1.65:1 and the catalyst tool that comparative example 1-4 is obtained There is dramatically different crystal phase structure.
What has been described above is only an embodiment of the present invention, and the common sense such as well known specific structure and characteristic are not made herein in scheme Excessive description.It, without departing from the structure of the invention, can be with it should be pointed out that for those skilled in the art Several modifications and improvements are made, these also should be considered as protection scope of the present invention, these all will not influence what the present invention was implemented Effect and patent practicability.

Claims (7)

1. a kind of sea urchin shape copper-based catalysts, which is characterized in that catalyst is spherical sea urchin structure, is formed on spherical sea urchin multiple The column dissipated outward.
2. a kind of sea urchin shape copper-based catalysts according to claim 1, which is characterized in that the cross section of the column is in Diamond shape, 1 μm of the length > of column.
3. a kind of preparation method of sea urchin shape copper-based catalysts according to claim 1 or 2, which is characterized in that including with Lower step:
(1) copper precursor solution and manganese precursor solution are mixed, obtains copper-manganese mixed solution;
(2) water, cetyl trimethylammonium bromide and dehydrated alcohol are added into copper-manganese mixed solution, is stirred at room temperature, stirs Mixing speed is 80-100r/min;
(3) ammonium hydroxide is slowly added dropwise in the reaction mixture obtained to step (2), stirs at room temperature, mixing speed 250-350r/ min;
(4) reaction mixture for obtaining step (3) carries out hydro-thermal process;
(5) reaction mixture that filtration step (4) obtains, obtains much filtrate, is rinsed to much filtrate, after drying and calcination, Sea urchin shape copper-based catalysts are made.
4. a kind of preparation method of sea urchin shape copper-based catalysts according to claim 3, which is characterized in that the copper precursors For copper nitrate, manganese precursor is manganese nitrate.
5. a kind of preparation method of sea urchin shape copper-based catalysts according to claim 3, which is characterized in that the step (1) molar ratio=0.5-1.65:1 of the copper in copper precursors in and the manganese in manganese precursor.
6. a kind of application of sea urchin shape copper-based catalysts according to claim 1, which is characterized in that with O2For catalyst, CO is just oxidized to CO by 30-40 DEG C2, 50% CO is oxidized to CO at 100-110 DEG C2, whole CO are aoxidized at 170-180 DEG C For CO2
7. a kind of application of sea urchin shape copper-based catalysts according to claim 8, which is characterized in that in oxygen lean conditions Lower catalysis is with O2For the CO completely burned of oxidant, the reaction gas of the oxygen lean conditions includes 0.5-5%CO, 0.5-5%O2And argon Gas.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006099716A1 (en) * 2005-03-24 2006-09-28 University Of Regina Catalysts for hydrogen production
CN101422730A (en) * 2008-11-20 2009-05-06 上海纳米技术及应用国家工程研究中心有限公司 Carbon monoxide room-temperature catalytic oxidation catalyst and preparation method thereof
CN102309965A (en) * 2010-06-25 2012-01-11 中国石油化工股份有限公司 Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof
CN102641736A (en) * 2012-03-19 2012-08-22 中国科学院过程工程研究所 Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof
CN103566947A (en) * 2012-08-07 2014-02-12 北京三聚环保新材料股份有限公司 Normal-temperature dearsenic agent as well as preparation method thereof
CN105668633A (en) * 2016-01-11 2016-06-15 大连工业大学 Sea urchin-shaped tungsten bronze particle prepared with template agent and preparation method thereof
KR20160102370A (en) * 2008-11-05 2016-08-30 슈드-케미 캐터리스트 이탈리아 에스.알.엘. Mixed oxides catalysts
CN106540707A (en) * 2016-11-03 2017-03-29 重庆工商大学 A kind of preparation method of polymolecularity Cu bases cerium oxide composite catalyst
CN107973333A (en) * 2016-10-25 2018-05-01 中国科学院苏州纳米技术与纳米仿生研究所 Metal composite oxide, its preparation method and application with hollow sea urchin shape structure
CN108671937A (en) * 2018-05-16 2018-10-19 华侨大学 A kind of preparation method and applications of copper-manganese composite oxide catalysts

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006099716A1 (en) * 2005-03-24 2006-09-28 University Of Regina Catalysts for hydrogen production
KR20160102370A (en) * 2008-11-05 2016-08-30 슈드-케미 캐터리스트 이탈리아 에스.알.엘. Mixed oxides catalysts
CN101422730A (en) * 2008-11-20 2009-05-06 上海纳米技术及应用国家工程研究中心有限公司 Carbon monoxide room-temperature catalytic oxidation catalyst and preparation method thereof
CN102309965A (en) * 2010-06-25 2012-01-11 中国石油化工股份有限公司 Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof
CN102641736A (en) * 2012-03-19 2012-08-22 中国科学院过程工程研究所 Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof
CN103566947A (en) * 2012-08-07 2014-02-12 北京三聚环保新材料股份有限公司 Normal-temperature dearsenic agent as well as preparation method thereof
CN105668633A (en) * 2016-01-11 2016-06-15 大连工业大学 Sea urchin-shaped tungsten bronze particle prepared with template agent and preparation method thereof
CN107973333A (en) * 2016-10-25 2018-05-01 中国科学院苏州纳米技术与纳米仿生研究所 Metal composite oxide, its preparation method and application with hollow sea urchin shape structure
CN106540707A (en) * 2016-11-03 2017-03-29 重庆工商大学 A kind of preparation method of polymolecularity Cu bases cerium oxide composite catalyst
CN108671937A (en) * 2018-05-16 2018-10-19 华侨大学 A kind of preparation method and applications of copper-manganese composite oxide catalysts

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHENGPENG MO ET AL.: "Low-temperature CO oxidation over integrated", 《CATALYSIS SCIENCE & TECHNOLOGY》 *
曹建亮著: "《一氧化碳低温催化氧化用氧化铜基纳米催化材料》", 31 August 2017, 中国矿业大学出版社 *
蔡丽娜: "铜锰氧化物制备改性及其CO催化氧化性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

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