CN103071492B - Preparation method of efficient formaldehyde catalytic conversion catalyst - Google Patents
Preparation method of efficient formaldehyde catalytic conversion catalyst Download PDFInfo
- Publication number
- CN103071492B CN103071492B CN201210549364.6A CN201210549364A CN103071492B CN 103071492 B CN103071492 B CN 103071492B CN 201210549364 A CN201210549364 A CN 201210549364A CN 103071492 B CN103071492 B CN 103071492B
- Authority
- CN
- China
- Prior art keywords
- solution
- ceo
- preparation
- catalyst
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a preparation method of an efficient formaldehyde catalytic conversion catalyst. The catalyst treating CeO2 as a carrier successfully loads Au-Pd alloy nanoparticles. The preparation method comprises the following steps: synthesizing the carrier CeO2 through treating cerium nitrate, polyvinylpyrrolidone and ethanol as main raw materials; and fully processing CeO2, fully mixing the processed CeO2 with palladium chloride and a chloroauric acid solution, and loading the Au-Pd alloy nanoparticles on the surface of CeO2 through a sodium borohydride reduction method in order to obtain an Au-Pd/CeO2 catalyst. The preparation method of the catalyst has the advantages of simple process, easy operation, and easy industrialized production.
Description
Technical field
The invention belongs to technical field of chemistry, relate to a kind of preparation method of efficient catalytic formaldehyde reforming catalyst.
Background technology
Formaldehyde (HCHO) is a kind of typical finishing type indoor air pollutants, at room temperature highly volatile, and along with the rising of temperature, evaporation rate is accelerated.The harm of formaldehyde to human body, is mainly manifested in and can causes at aspects such as allotriosmia, stimulation, allergy, abnormal pulmonary function, dysfunction of liver and immunologic dysfunctions.Therefore, effectively reduce the content of formaldehyde in indoor air and other pernicious gases and become an important content of current indoor environment protection.
Catalytic oxidation technology is the method for current optimal elimination formaldehyde of generally acknowledging, utilizes catalytic oxidation can at normal temperatures and pressures formaldehyde be converted into nontoxic CO
2and H
2o, and elimination HCHO efficiency is high, treating capacity large, there is no secondary pollution, and the processing that low concentration formaldehyde is polluted is very effective.
Common catalyst has ceria, zirconium dioxide, titanium dioxide, alundum (Al2O3), lanthanum sesquioxide, magnesia, zinc oxide etc.The PARA FORMALDEHYDE PRILLS(91,95) catalyzed conversions such as Precious Metals-Gold (Au), palladium (Pd) have special effect, have higher activity, and the life-span is long, high temperature resistant, can approach under room temperature condition the multiple pernicious gas such as catalyzed conversion formaldehyde effectively.
The invention provides a kind ofly for the high activated catalyst close to catalyzed conversion low concentration formaldehyde under room temperature condition, this catalyst is taking rare earth oxide as carrier, and on rare earth oxide carried noble metal Au-Pd alloy nanoparticle.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of efficient catalytic formaldehyde reforming catalyst, the method is a kind of with CeO
2for carrier, the preparation method of the catalyst of area load Au-Pd alloy nanoparticle.Utilize the present invention can obtain the Au-Pd/CeO with good catalyzed conversion activity
2catalyst.In the time of 323K, this catalyst can all be converted into carbon dioxide and water by formaldehyde.Au-Pd/CeO
2catalyst does not need other additional external condition in use, can save the energy.Its preparation method is that a kind of technique is simple, and processing ease is easy to the method for suitability for industrialized production.
Concrete technical scheme is:
A preparation method for efficient catalytic formaldehyde reforming catalyst, comprises the following steps:
1) support C eO
2preparation
By the Ce (NO of 5mmol
3)
36H
2o and 10mmol surfactant polyvinylpyrrolidone (PVP) are dissolved in 30ml ethanol and 10ml deionized water, at room temperature stir, and make it to mix, by Ce (NO
3)
36H
2o mixed solution is transferred in special reaction vessel and seals, and is placed in 160 DEG C of baking ovens and reacts 2.5 hours.After reaction finishes, product centrifugation, obtains CeO after being dried
2carrier;
2) CeO
2carrier surface carried noble metal Au-Pd alloy nanoparticle
Preparation HAuCl
44H
2o and PdCl
2solution, is mixed, and adds polyvinyl alcohol (PVA) solution, and solution is through strong stirring, and rotating speed is 800r/min,, after mixing, add sodium borohydride solution (NaBH
4), and by the pH value to 1 of sulfuric acid regulation solution, stir 30min.By step 1) CeO of gained
2carrier joins in mixed solution by amount under stirring condition, continues to stir 2h, leaves standstill afterwards 24h, will precipitate centrifugal, washing, after being dried, obtains Au-Pd/CeO
2catalyst.
Described Ce (NO
3)
36H
2o mixed solution is 160 DEG C of reactions, and the reaction time is 2.5h.
Described HAuCl
44H
2o and PdCl
2the concentration of solution is for being 1g/L, PdCl
2the consumption of solution is 11ml, HAuCl
44H
2the consumption of O solution is 25ml.
Described polyvinyl alcohol (PVA) concentration of polymer solution is 1wt%, and addition is 2.2ml.
Sodium borohydride solution concentration is 0.1mol/L, and addition is 6ml.
Described carrier is pure cerium salt, purity (CeO
2/ TREO) be 98%-99.99%.
Beneficial effect of the present invention: catalyst A u-Pd/CeO prepared by the method for the invention
2, have efficient catalysis formaldehyde conversion performance.Experiment showed, Au-Pd/CeO by formaldehyde catalyzed conversion
2catalyst can all be converted into carbon dioxide and water by formaldehyde in the time of 50 DEG C, and has good chemical stability.Preparation technology is simple, easy to operate, has good effect for the purification of room air.
Brief description of the drawings
Fig. 1: the CeO that preparation method of the present invention obtains
2eSEM and transmission electron microscope photo;
CeO prepared by Fig. 1 a hydro-thermal reaction
2scanning electron microscope (SEM) photograph, reaction condition: 160 DEG C, 2.5h;
CeO prepared by Fig. 1 b hydro-thermal reaction
2transmission electron microscope picture, reaction condition: 160 DEG C, 2.5h;
Fig. 2: the CeO that preparation method of the present invention obtains
2specific area curve;
Fig. 3: the Au-Pd/CeO that preparation method of the present invention obtains
2the transmission electron microscope photo of catalyst;
Fig. 3 a Au-Pd/CeO
2transmission electron microscope picture, reaction condition: 160 DEG C, 2.5h;
Fig. 3 b Au-Pd/CeO
2high-resolution-ration transmission electric-lens figure, reaction condition: 160 DEG C, 2.5h;
Fig. 4: the Au-Pd/CeO that preparation method of the present invention obtains
2the performance map of catalyzed conversion formaldehyde.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, method of the present invention is described in more detail.
Support C eO
2preparation:
In reactor, add 5mmol Ce (NO
3)
36H
2the PVP of O, 10mmol and volume fraction are 75% ethanolic solution 40ml, stir 30min, make it to mix.Under air-proof condition, 160 DEG C are reacted 2.5 hours.The product obtaining, through centrifugal, washing, dry, obtains CeO
2carrier.
Au-Pd/CeO
2the preparation of catalyst:
The PdCl of 1g/L
2solution 11ml and 1g/L HAuCl
44H
2o solution 25ml mixes in container.Add wherein the PVA solution 2.2ml of 1wt%, in mixed solution, add while stirring the 0.1mol/L sodium borohydride solution 6ml being made into, continue to stir 30min.By the support C eO of 0.6g
2join in the above-mentioned solution stirring, continue to stir 2 hours.Afterwards, solution left standstill 24 hours.Product, through centrifugal, washing, dry, obtains Au-Pd/CeO
2catalyst.
Can be observed by Fig. 1 a and Fig. 1 b: when hydrothermal temperature is 160 DEG C, the reaction time is while being 2.5 hours, the CeO of gained
2for spherical nano particle, particle diameter mainly concentrates on 400-500nm, and shows good dispersive property.Can also clearly find out CeO from the stereoscan photograph of figure mono-a
2by several little CeO
2nano particle is piled up and is formed through secondary agglomeration.
The CeO that preparation method of the present invention obtains
2specific area curve.
Fig. 3 a is Au-Pd/CeO
2the high-resolution-ration transmission electric-lens photo of catalyst, load the CeO after Au-Pd nano particle
2still be spheric granules, granularity does not have significant change.Can find out from Fig. 3 b high-resolution-ration transmission electric-lens photo, Au-Pd alloy nano particle is scattered in CeO uniformly
2carrier surface.The interplanar distance d=0.23nm of (111) crystal face of Au-Pd alloy, has further proved that Au-Pd nano particle has successfully loaded to CeO
2carrier surface.
As shown in Figure 4, Au-Pd/CeO
2catalyst can all be converted into carbon dioxide and water by formaldehyde in the time of 50 DEG C, and has good chemical stability.Preparation technology is simple, easy to operate, has good effect for the purification of room air.
The above; it is only preferably detailed description of the invention of the present invention; protection scope of the present invention is not limited to this; any be familiar with those skilled in the art the present invention disclose technical scope in, the simple change of the technical scheme that can obtain apparently or equivalence replace all fall within the scope of protection of the present invention.
Claims (1)
1. a preparation method for efficient catalytic formaldehyde reforming catalyst, is characterized in that, comprises the following steps:
1) support C eO
2preparation
By the Ce (NO of 5mmol
3)
36H
2o and 10mmol surfactant polyvinylpyrrolidone (PVP) are dissolved in 30mL ethanol and 10mL deionized water, at room temperature stir, and make it to mix, by Ce (NO
3)
36H
2o mixed solution proceeds to sealing in reaction vessel and reacts, and after reaction finishes, product centrifugation, obtains CeO after being dried
2carrier;
2) CeO
2carrier surface carried noble metal Au-Pd nano particle
Preparation HAuCl
44H
2o and PdCl
2solution, is mixed, and adds polyvinyl alcohol (PVA) solution, and solution is through strong stirring, and rotating speed is 800r/min, after mixing, adds sodium borohydride solution, and sulfuric acid regulation solution pH value to 1 stirs 30min, by step 1) CeO of gained
2carrier joins in mixed solution under stirring condition, continues 2h, leaves standstill afterwards 24h, will precipitate centrifugal, washing, after being dried, obtains Au-Pd/CeO
2catalyst;
Described Ce (NO
3)
36H
2o mixed solution is 160 DEG C of reactions, and the reaction time is 2.5h;
Described HAuCl
44H
2o and PdCl
2the concentration of solution is for being 1g/L, PdCl
2the consumption of solution is 11mL, HAuCl
44H
2the consumption of O solution is 25mL;
Described polyvinyl alcohol (PVA) concentration of polymer solution is 1wt%, and addition is 2.2mL;
Sodium borohydride solution concentration is 0.1mol/L, and addition is 6mL;
Described carrier is pure cerium salt, purity (CeO
2/ TREO) be 98%-99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210549364.6A CN103071492B (en) | 2012-12-07 | 2012-12-07 | Preparation method of efficient formaldehyde catalytic conversion catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210549364.6A CN103071492B (en) | 2012-12-07 | 2012-12-07 | Preparation method of efficient formaldehyde catalytic conversion catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103071492A CN103071492A (en) | 2013-05-01 |
| CN103071492B true CN103071492B (en) | 2014-10-01 |
Family
ID=48148309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210549364.6A Expired - Fee Related CN103071492B (en) | 2012-12-07 | 2012-12-07 | Preparation method of efficient formaldehyde catalytic conversion catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103071492B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415752B (en) * | 2013-08-27 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of liquid phase selective hydrogenation of C 3 hydrocarbons catalyst and its preparation method and application |
| CN104722299B (en) * | 2013-12-20 | 2017-10-31 | 中国科学院大学 | A kind of catalyst for eliminating formaldehyde at room temperature |
| CN105148917B (en) * | 2015-07-08 | 2017-12-08 | 中山大学惠州研究院 | A kind of method and its formaldehyde catalyst for improving formaldehyde catalyst catalytic efficiency |
| CN106268802B (en) * | 2016-07-27 | 2018-10-12 | 济南大学 | The preparation method and products obtained therefrom of a kind of strawberry shape noble metal-cerium oxide nano particle and application |
| CN108610793A (en) * | 2016-12-27 | 2018-10-02 | 天津众华鑫环保科技有限公司 | A kind of preparation method of radiator coating |
| CN106622227B (en) * | 2016-12-29 | 2019-03-08 | 天津大学 | A kind of preparation method of the monatomic catalyst of indoor air purification |
| CN108654698B (en) * | 2018-05-17 | 2020-11-06 | 湖南师范大学 | Preparation method and application of chiral nanogold photocatalyst |
| CN109046350A (en) * | 2018-08-03 | 2018-12-21 | 张家瑞 | A kind of vehicle exhaust efficient process catalyst and preparation method thereof |
| CN110694666B (en) * | 2019-11-07 | 2023-01-13 | 江汉大学 | C 3 N 4 @CeO 2 Supported low-content gold catalyst and preparation method and application thereof |
| CN111151237A (en) * | 2020-01-20 | 2020-05-15 | 云南电网有限责任公司电力科学研究院 | Preparation method of noble metal catalyst |
| CN113070062B (en) * | 2021-03-24 | 2022-08-09 | 西安交通大学 | Cerium-based nano-sphere catalyst for catalyzing formic acid to produce hydrogen and preparation method thereof |
| CN113509929A (en) * | 2021-04-14 | 2021-10-19 | 西安交通大学 | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795970A (en) * | 2004-12-28 | 2006-07-05 | 中国科学院生态环境研究中心 | High performance catalyst for catalyzing formaldehyde to complete oxidation under room temperature temperature |
| CN101559366A (en) * | 2009-05-21 | 2009-10-21 | 浙江师范大学 | Catalyst for eliminating formaldehyde, preparation method and application thereof |
| CN101618352A (en) * | 2008-06-30 | 2010-01-06 | 比亚迪股份有限公司 | Preparation method of supported metal catalyst |
| JP2012030178A (en) * | 2010-07-30 | 2012-02-16 | Jgc Catalysts & Chemicals Ltd | Method of manufacturing metal particle-supported catalyst, metal particle-supported catalyst, and reaction method |
| CN102574106A (en) * | 2009-08-05 | 2012-07-11 | 巴斯夫公司 | Preparation of diesel oxidation catalyst via deposition of colloidal nanoparticles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2866249B1 (en) * | 2004-02-18 | 2006-12-15 | Rhodia Acetow Gmbh | GOLD AND CERIUM OXIDE COMPOSITION, PREPARATION METHOD AND USE AS CATALYST, IN PARTICULAR FOR OXIDATION OF CARBON MONOXIDE |
-
2012
- 2012-12-07 CN CN201210549364.6A patent/CN103071492B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795970A (en) * | 2004-12-28 | 2006-07-05 | 中国科学院生态环境研究中心 | High performance catalyst for catalyzing formaldehyde to complete oxidation under room temperature temperature |
| CN101618352A (en) * | 2008-06-30 | 2010-01-06 | 比亚迪股份有限公司 | Preparation method of supported metal catalyst |
| CN101559366A (en) * | 2009-05-21 | 2009-10-21 | 浙江师范大学 | Catalyst for eliminating formaldehyde, preparation method and application thereof |
| CN102574106A (en) * | 2009-08-05 | 2012-07-11 | 巴斯夫公司 | Preparation of diesel oxidation catalyst via deposition of colloidal nanoparticles |
| JP2012030178A (en) * | 2010-07-30 | 2012-02-16 | Jgc Catalysts & Chemicals Ltd | Method of manufacturing metal particle-supported catalyst, metal particle-supported catalyst, and reaction method |
Non-Patent Citations (6)
| Title |
|---|
| Au/CeO2催化剂的制备及其对HCHO催化氧化性能的研究;海锋等;《第五届全国环境催化与环境材料学术会议论文集》;20070731;第211-212页 * |
| 保护剂对Au-Pd/CeO_2催化剂甲醇部分氧化性能的影响;陈清波等;《天然气化工(C1化学与化工)》;20080225;第33卷(第01期);第14-19页 * |
| 李洪芳等.载体对负载型金催化剂上甲醛催化氧化的影响.《催化学报》.2009,第30卷(第10期),第1001-1006页. |
| 海锋等.Au/CeO2催化剂的制备及其对HCHO催化氧化性能的研究.《第五届全国环境催化与环境材料学术会议论文集》.2007,第211-212页. |
| 载体对负载型金催化剂上甲醛催化氧化的影响;李洪芳等;《催化学报》;20091015;第30卷(第10期);第1001-1006页 * |
| 陈清波等.保护剂对Au-Pd/CeO_2催化剂甲醇部分氧化性能的影响.《天然气化工(C1化学与化工)》.2008,第33卷(第01期),第14-19页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103071492A (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103071492B (en) | Preparation method of efficient formaldehyde catalytic conversion catalyst | |
| CN101827651B (en) | Rare earth alumina particulate manufacturing method and application | |
| CN113209976B (en) | Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction | |
| CN103170334B (en) | Carbon-supported cobalt oxide catalyst and preparation and application thereof | |
| CN103212413B (en) | Thermal stabilization core-shell structure nano three-way catalyst and preparation method thereof | |
| CN102029167B (en) | Catalytic agent containing nano perovskite type rare-earth oxides and preparation method thereof | |
| CN1899966A (en) | Flower structure nano cerium oxide base composite material and its preparing method and use | |
| CN106423161B (en) | A kind of preparation method and catalyst of hydrogenation catalyst | |
| CN103055893A (en) | Supported cobalt-platinum superlattice alloy nano particle composite catalyst and preparation method thereof | |
| CN104630538A (en) | Multicomponent nano porous palladium-base alloy and preparation method thereof | |
| CN102824918A (en) | Graphene oxide rare-earth composite methane catalyst | |
| CN102728381B (en) | Tourmalinite-containing composite methane catalyst | |
| CN102389836B (en) | Polyaniline/titanium dioxide/clay nanometer composite photocatalyst and preparation method thereof | |
| CN102319570A (en) | The ternary compound oxides Catalysts and its preparation method of carbon monoxide oxidation | |
| CN101623637B (en) | Catalyst Au/MnOx-CeO2 used for preferential oxidation of carbon monoxide and preparation method thereof | |
| CN113398920B (en) | Ultra-long cerium dioxide nanorod-loaded manganese oxide low-temperature denitration catalyst and preparation method thereof | |
| CN102451680A (en) | Composite oxide modified wet oxidation catalyst and preparation method thereof | |
| CN104399460A (en) | Catalyst for industrial wastewater treatment and preparation method of catalyst | |
| CN108355686B (en) | A kind of PtO/Pt4+- BiOCl photochemical catalyst and its preparation method and application | |
| KR20150067253A (en) | Method for producing composite oxide and composite oxide catalyst | |
| CN101966454B (en) | Catalyst for use in preparation of hydrogen peroxide by anthraquinone method and preparation method thereof | |
| CN113663671A (en) | Ternary metal catalyst and preparation method and application thereof | |
| JP4928931B2 (en) | Ceria-zirconia composite oxide and method for producing the same | |
| CN101618323B (en) | Structural catalyst for catalyzing and reducing nitrogen oxide and preparation method thereof | |
| WO2017094688A1 (en) | Steam reforming catalyst for hydrocarbons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141001 Termination date: 20151207 |
|
| EXPY | Termination of patent right or utility model |