CN1278771C - Rare earth based loaded type catalyst for wet oxidation and preparation method thereof - Google Patents
Rare earth based loaded type catalyst for wet oxidation and preparation method thereof Download PDFInfo
- Publication number
- CN1278771C CN1278771C CN 200410009224 CN200410009224A CN1278771C CN 1278771 C CN1278771 C CN 1278771C CN 200410009224 CN200410009224 CN 200410009224 CN 200410009224 A CN200410009224 A CN 200410009224A CN 1278771 C CN1278771 C CN 1278771C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hour
- tio
- ceo
- wet oxidation
- 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
Images
Abstract
The present invention relates to a supported rare earth catalyst used in wet oxidation, and a preparation method thereof, and belongs to the field of water treatment technology and environmental functional material. In order to reduce the operational conditions of wet oxidation reaction and improve the deep oxidation effect or the pre-processing performance of organic matter in waste water, the present invention provides a CeO2 multi-component supported nano-catalyst with high activity and high stability for wet oxidation, and a preparation method thereof. The catalyst of the present invention comprises CeO2-TiO2 and the oxides MOx of noble metal, and is prepared according to the following method: CeO2-TiO2 is firstly prepared by taking cerate and titanium salt as raw materials through a sol-gel method; the CeO2-TiO2 is then impregnated in the salt solution of noble metal, wherein the supporting capacity of noble metal is 1 to 3 wt%; MOx/CeO2-TiO2 catalysts are obtained after the processes of impregnation, drying and roasting.
Description
Technical field
The present invention develops rare earth based loaded catalyst and preparation method thereof based on nano material preparation technology, can be used for wet oxidation and handle high concentration, indegradable industrial effluent, belongs to water technology and environment functional material field.
Background technology
The wet oxidation technology is the oxidation technology of a kind of effective processing high concentration, poisonous, harmful, organic wastewater with difficult degradation thereby, advantages such as the consersion unit volume is little, the time is short, secondary pollution is few and receive very big concern, present good prospects for application, wherein catalyst is one of wet oxidation The Application of Technology key.
Catalyst can be divided into homogeneous phase and heterogeneous catalyst by form.Homogeneous catalyst has advantages such as activity is high, reaction speed is fast, but catalyst is water-soluble, becomes estranged to second environmental pollution for fear of catalyst stream, need carry out subsequent treatment, makes technological process become complicated.Heterogeneous catalyst is to exist with solid-state form, easily separate with waste water, avoided catalyst loss, flow process is simple, therefore the heterogeneous catalyst of studying advantages such as having activity is high, easily separated, good stability has been subjected to common attention, has become the research focus of wet oxidizing catalyst.Wherein, the noble metal catalyst series has advantages of high catalytic activity and stability, but the catalyst cost is higher; Metal oxide catalyst, for example though catalytic activity is preferably arranged, there is more serious catalytic component stripping phenomenon in catalyst such as copper, iron, manganese, cobalt series in reaction, catalyst activity reduction, and can cause the secondary pollution problem.
The rare earth resources of China is very abundant, rare earth oxide CeO
2Activity and stable is preferably arranged, can be used for the harshness reaction of wet oxidation reaction, therefore carry out Rare-Earth Ce O
2The research of multicomponent catalyst promptly reduces or has avoided expensive precious metal material, and having solved copper, iron, manganese again is the stripping problem of transition metal oxide, has been subjected to paying attention to widely.The particle size of catalyst is controlled at Nano grade, makes catalyst have huge specific area and numerous blemish positions, and this helps absorption and the catalytic reaction of material on catalyst, and activity is much higher than traditional catalyst.Therefore adopt nano particle preparation technology, development active height, good stability, the nano Ce O that cost is low and suitable China develops
2The support type multicomponent catalyst will help wet oxidation The Application of Technology and popularization.
Summary of the invention
The present invention seeks to propose a kind of nanoscale CeO that is used for the active height of wet oxidation, good stability
2Multicomponent loaded catalyst and preparation method thereof to reduce the operating condition of wet oxidation reaction, improves organic deep oxidation effect or preliminary treatment performance in the waste water, promotes the wet oxidation broad application.
The invention provides a kind of rare earth based loaded catalyst that is used for wet oxidation, it is characterized in that this catalyst comprises CeO
2-TiO
2With metal oxide containing precious metals MOx, M is a noble metal, and described catalyst prepares by the following method:
1) be raw material with cerium salt and titanium salt, the Ce mole percent is 15%-85%, adopts sol-gel process to prepare the mixture of Ce and Ti;
2), the muffle furnace roasting of air atmosphere, 350-700 ℃ 2-5 hour, obtain CeO then with dry 24-48 hour of described mixture
2-TiO
2
3) with CeO
2-TiO
2Impregnated in the precious metal salt solution, the noble metal load capacity is 1-3wt%, and dip time is 10-20 hour, dry afterwards 12-24 hour;
4) dried mixture is in air atmosphere, in the muffle furnace of 350-600 ℃ roasting 2-7 hour, obtains being used for the MOx/CeO of wet oxidation
2-TiO
2Catalyst.
The present invention also provides a kind of preparation method who is used for the rare earth based loaded catalyst of wet oxidation, it is characterized in that described preparation method comprises the steps:
1) be raw material with cerium salt and titanium salt, the Ce mole percent is 15%-85%, adopts sol-gel process to prepare the mixture of Ce and Ti;
2), the muffle furnace roasting of air atmosphere, 350-700 ℃ 2-5 hour, obtain CeO then with dry 24-48 hour of described mixture
2-TiO
2
3) with CeO
2-TiO
2Impregnated in the precious metal salt solution, the load capacity of noble metal is 1-3wt%, and dip time is 10-20 hour, dry afterwards 12-24 hour;
4) dried mixture is in air atmosphere, in the muffle furnace of 350-600 ℃ roasting 2-7 hour, obtains being used for the MOx/CeO of wet oxidation
2-TiO
2Catalyst.
Noble metal of the present invention is Ru, Pt or Pd.
Utilize the 1L autoclave to MOx/CeO of the present invention
2-TiO
2Catalyst has carried out the research of wet-type oxidation degradation organic matter, little carboxylic acids with high concentration---when acetate and butyric acid are object, in reaction temperature is 230 ℃, gross pressure is 5MPa, react after 2 hours, the COD of wet-type oxidation degradation carboxylic acid (being abbreviated as COD) place to go rate is higher, and carried out the research of wet-type oxidation degradation high concentration phenol solution with this catalyst, in reaction temperature is 150 ℃, gross pressure is 3MPa, react after 2 hours, the place to go rate of phenol is also higher, and this illustrates MOx/CeO
2-TiO
2Catalyst has good catalytic activity.In addition, utilize ICP-MS to MOx/CeO
2-TiO
2Catalyst stripping situation of M, Ce and three kinds of ions of Ti in wet-type oxidation degradation organic matter process is measured, and the stripping quantity of finding metal ion is all less than 0.6mg/L, and this illustrates that this catalyst has good stable.In addition, utilize the MOx/CeO of X-ray powder diffraction to invention
2-TiO
2Catalyst is analyzed, and obtains crystallite dimension in the catalyst at 10-20nm, shows to adopt this preparation technology can prepare nanocatalyst than small particle size.Simultaneously, MOx/CeO of the present invention
2-TiO
2The consumption of noble metal is less in the catalyst, thereby has reduced the cost of catalyst.Therefore, adopt above catalyst preparation process can obtain the low nanoscale MOx/CeO of high activity, stability and price
2-TiO
2Catalyst, this helps applying of wet oxidation technology.
Based on the above results, MOx/CeO of the present invention
2-TiO
2The rare earth based loaded catalyst has the following advantages:
(1) catalyst has good catalytic activity for high concentration, organic wastewater with difficult degradation thereby;
(2) catalyst has good stable in wet-type oxidation degradation organic matter process;
(3) the catalyst crystallite dimension is a nanoscale;
(4) catalyst production cost is lower.
Description of drawings
Fig. 1 represent wet-type oxidation degradation acetate the COD clearance (230 ℃, 5MPa, 120min).
Fig. 2 represent the wet-type oxidation degradation butyric acid the COD clearance (230 ℃, 5MPa, 120min).
The specific embodiment
MOx/CeO of the present invention
2-TiO
2Catalyst helps reducing the operating condition that high dense degree of falling, hardly degraded organic substance are separated in wet oxidation, and can improve organic deep oxidation effect.
The rare earth based loaded catalyst that is used for wet oxidation of the present invention comprises CeO
2-TiO
2With metal oxide containing precious metals MOx, M is a noble metal, can be Ru, Pt or Pd.Described Preparation of catalysts method is exemplified below:
Embodiment 1:
With Ce (NO
3)
36H
2O and Ti (OC
4H
9)
4Be raw material, the Ce mole percent is 25%-50%, adopts sol-gel process to prepare the mixture of Ce and Ti, in air atmosphere in 80 ℃ baking oven dry 48h, place muffle furnace afterwards, 400 ℃ of roasting 3h obtain CeO in air atmosphere
2-TiO
2With 5g CeO
2-TiO
2Impregnated in and contain 0.3881g RuCl
3RuCl
3In the solution, at room temperature flood 12h, dry 12h in 110 ℃ of baking ovens in air atmosphere afterwards, then in air, in muffle furnace 300 ℃ of roasting 3h, prepare RuO
2/ CeO
2-TiO
2Catalyst.
Get 2.5gRuO
2/ CeO
2-TiO
2The little molecule acid of catalyst wet oxidation---acetate, COD is 5600mg/L, and reaction temperature is 230 ℃, and the reaction gross pressure is 5MPa, and the reaction time is 2h, the results are shown in Figure 1.Find out that by Fig. 1 when not using catalyst, in the wet-type oxidation degradation acetate, behind the reaction 2h, acetate is degraded hardly; When in course of reaction, adding RuO
2/ CeO
2-TiO
2Behind the catalyst, behind the wet-type oxidation degradation acetic acidreaction 2h, its COD clearance is more than 90%.
Embodiment 2:
With CeCl
3And TiCl
4Be raw material, the Ce mole percent is 50%-85%, and the employing sol-gel process prepares the mixture of Ce and Ti, in air atmosphere, and dry 24h in 100 ℃ of baking ovens, in muffle furnace, 500 ℃ of roasting 3h obtain CeO in air atmosphere afterwards
2-TiO
25gCeO
2-TiO
2Impregnated in and contain 0.2584g RuCl
3RuCl
3In the solution, at room temperature flood 10h, dry 24h in 100 ℃ of baking ovens in air afterwards, then in air, in muffle furnace 400 ℃ of roasting 3h, prepare RuO
2/ CeO
2-TiO
2Catalyst.
Get 2.5gRuO
2/ CeO
2-TiO
2Catalyst wet-type oxidation degradation small molecular organic acid---n-butyric acie, COD are 8700mg/L, and reaction temperature is 230 ℃, and the reaction gross pressure is 5MPa, and the reaction time is 2h, and the result as shown in Figure 2.As seen from the figure, add RuO
2/ CeO
2-TiO
2During catalyst, behind the reaction 1h, the COD clearance reaches 85%, far above the degradation effect of catalyst-free.
Embodiment 3:
With CeCl
3And Ti (SO
4)
2Be raw material, the Ce mole percent is 15%-60%, adopts sol-gel process to prepare the mixture of Ce and Ti, and dry 36h in 85 ℃ the baking oven in air atmosphere places afterwards in 500 ℃ of roasting 2h of muffle furnace, obtains CeO
2-TiO
25gCeO
2-TiO
2Impregnated in the aqueous solution that contains the 0.0981g chloroplatinic acid, at room temperature flood 15h, afterwards in air atmosphere, dry 10h in 120 ℃ of baking ovens, then in air, 400 ℃ of roasting 3h, prepare catalyst.
Get the prepared catalyst of 2.5g, the wet-type oxidation degradation phenol solution, solution C OD is 10000mg/L, is 150 ℃ in reaction temperature, and the reaction gross pressure is 3MPa, reacts for behind the 2h, and the COD of phenol is more than 40%, shows good catalytic activity.
In like manner, utilize the salting liquid of precious metals pd to carry out load, can realize the present invention equally.
Claims (2)
1. be used for the rare earth based loaded catalyst of wet oxidation, it is characterized in that, this catalyst comprises CeO
2-TiO
2With metal oxide containing precious metals MOx, M is Ru, Pt or Pd, and described catalyst prepares by the following method:
1) be raw material with cerium salt and titanium salt, the Ce mole percent is 15%-85%, adopts sol-gel process to prepare the mixture of Ce and Ti;
2), the muffle furnace roasting of air atmosphere, 350-700 ℃ 2-5 hour, obtain CeO then with dry 24-48 hour of described mixture
2-TiO
2
3) with CeO
2-TiO
2Impregnated in the precious metal salt solution, the noble metal load capacity is 1-3wt%, and dip time is 10-20 hour, dry afterwards 12-24 hour;
4) dried mixture is in air atmosphere, in the muffle furnace of 350-600 ℃ roasting 2-7 hour, obtains being used for the MOx/CeO of wet oxidation
2-TiO
2Catalyst.
2. be used for the preparation method of the rare earth based loaded catalyst of wet oxidation, it is characterized in that, described preparation method comprises the steps:
1) be raw material with cerium salt and titanium salt, the Ce mole percent is 15%-85%, adopts sol-gel process to prepare the mixture of Ce and Ti;
2), the muffle furnace roasting of air atmosphere, 350-700 ℃ 2-5 hour, obtain CeO then with dry 24-48 hour of described mixture
2-TiO
2
3) with CeO
2-TiO
2Impregnated in the precious metal salt solution, the load capacity of noble metal is 1-3wt%, and dip time is 10-20 hour, and dry afterwards 12-24 hour, described noble metal was Ru, Pt or Pd;
4) dried mixture is in air atmosphere, in the muffle furnace of 350-600 ℃ roasting 2-7 hour, obtains being used for the MOx/CeO of wet oxidation
2-TiO
2Catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410009224 CN1278771C (en) | 2004-06-18 | 2004-06-18 | Rare earth based loaded type catalyst for wet oxidation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410009224 CN1278771C (en) | 2004-06-18 | 2004-06-18 | Rare earth based loaded type catalyst for wet oxidation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1593755A CN1593755A (en) | 2005-03-16 |
| CN1278771C true CN1278771C (en) | 2006-10-11 |
Family
ID=34662391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410009224 Expired - Fee Related CN1278771C (en) | 2004-06-18 | 2004-06-18 | Rare earth based loaded type catalyst for wet oxidation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1278771C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754777A (en) * | 2016-08-19 | 2018-03-06 | 中国科学院大连化学物理研究所 | It is a kind of for the catalyst of oxidation reaction and its preparation and application |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460070C (en) * | 2005-07-12 | 2009-02-11 | 沈阳化工研究院 | Preparation of multi-component titanium-based catalyst carrier |
| WO2007143043A2 (en) | 2006-06-01 | 2007-12-13 | Carrier Corporation | Air purification system |
| CN103043773B (en) * | 2011-10-17 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of Catalytic Wet Oxidation method of flue gas desulphurization waste solution |
| CN106732581B (en) * | 2016-12-02 | 2020-07-17 | 北京工业大学 | Ru/CeTiO for low-temperature SCR reactionxProcess for preparing catalyst |
| CN106732582A (en) * | 2016-12-08 | 2017-05-31 | 中国科学院兰州化学物理研究所 | Meso-porous nano CeO2Hollow ball supported catalyst and its preparation method and application |
| CN107670658A (en) * | 2017-11-09 | 2018-02-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Catalyst for chlorobenzene low-temperature catalytic burning and its preparation method and application |
| CN109908935B (en) * | 2019-02-19 | 2022-03-04 | 江苏海普功能材料有限公司 | Pt-Ru bimetallic nano catalyst for high-concentration organic wastewater catalytic wet oxidation and preparation method thereof |
| CN115295816B (en) * | 2022-09-30 | 2023-01-20 | 国家电投集团氢能科技发展有限公司 | Anti-reversal catalyst, preparation method thereof and fuel cell |
-
2004
- 2004-06-18 CN CN 200410009224 patent/CN1278771C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754777A (en) * | 2016-08-19 | 2018-03-06 | 中国科学院大连化学物理研究所 | It is a kind of for the catalyst of oxidation reaction and its preparation and application |
| CN107754777B (en) * | 2016-08-19 | 2021-01-01 | 中国科学院大连化学物理研究所 | Catalyst for oxidation reaction and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1593755A (en) | 2005-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1317070C (en) | RE CeO2 supporting wet oxidizing catalyst and its prepn | |
| CN101992089B (en) | Three-dimensional ordered porous-mesoporous iron-based perovskite oxide catalyst and preparation method thereof | |
| CN101485987B (en) | Catalyst for normal temperature and pressure catalysis wet-type oxidation technology and preparation method | |
| CN101185887A (en) | Catalyst for wet oxidation technique and preparation method thereof | |
| CN1278771C (en) | Rare earth based loaded type catalyst for wet oxidation and preparation method thereof | |
| CN107684907B (en) | Noble metal catalyst for catalyzing wet oxidation of industrial wastewater, preparation method and application thereof | |
| CN1772383A (en) | Porous catalytic filtering metal material and its prepn | |
| CN101711978B (en) | High mechanical property and low cost SCR denitration catalyst and preparation method thereof | |
| CN111135823B (en) | Wet oxidation catalyst and preparation method and application thereof | |
| CN101053832A (en) | Magnenese-cerium composite oxide supported catalyst for purifying formaldehyde in the indoor air | |
| CN103043773B (en) | A kind of Catalytic Wet Oxidation method of flue gas desulphurization waste solution | |
| CN108176396A (en) | A kind of formaldehyde remover and its preparation method and application | |
| CN101432069A (en) | Catalyst carrier particle, method for producing the same, and exhaust gas purifying catalyst | |
| CN113019364A (en) | Preparation method of porous ruthenium dioxide-cerium dioxide microsphere composite material | |
| CN104399460A (en) | Catalyst for industrial wastewater treatment and preparation method of catalyst | |
| CN101385971A (en) | Catalyst preparation method for efficiently catalyzing organic pollutant in ozone oxidation water | |
| CN103977792A (en) | Composite oxide catalyst for catalytic combustion of soot in diesel engine exhaust, and preparation method of catalyst | |
| CN103041810B (en) | Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method | |
| CN108031472A (en) | A kind of Pd-Pt catalyst for purifying organic waste gas and preparation method thereof | |
| CN105536823A (en) | Sulfur-resistant catalytic combustion catalyst and preparation method thereof | |
| CN110252332A (en) | A method of honeycomb VOCs catalyst is prepared using useless SCR catalyst | |
| CN1669643A (en) | Rare earth composite oxide catalyst in catalytic wet oxidation process and preparing method thereof | |
| CN111569922A (en) | Rare earth doped hydrotalcite-like derivative oxide catalyst for catalytic combustion of VOC waste gas and preparation method thereof | |
| CN1824384A (en) | High performance low noble metal triple effect catalyst | |
| CN1752012A (en) | Preparation method of cerium lanthanium complex oxide |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061011 |