CN104148116A - Preparation method of low-cost large-specific-surface-area cerium oxide - Google Patents
Preparation method of low-cost large-specific-surface-area cerium oxide Download PDFInfo
- Publication number
- CN104148116A CN104148116A CN201410394910.2A CN201410394910A CN104148116A CN 104148116 A CN104148116 A CN 104148116A CN 201410394910 A CN201410394910 A CN 201410394910A CN 104148116 A CN104148116 A CN 104148116A
- Authority
- CN
- China
- Prior art keywords
- oxide
- low
- cerium oxide
- preparation
- bigger serface
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a solid solution carrier catalysis, and specifically relates to a preparation method of low-cost large-specific-surface-area cerium oxide. According to the invention, water solutions corresponding to all raw materials are mixed; a surfactant is added; the pH value is regulated to 8-10, such that a gel precipitate is obtained; washing and roasting are carried out; drying and grinding are carried out; trifluoromethanesulfonic acid is added to the product, and the mixture is well mixed; and drying is carried out, such that the cerium oxide is obtained. The raw materials are cheap, and the process procedure of the method is simple. With the method, a doping defect caused by doping in a cerium oxide carrier is overcome. Also, performance indexes such as thermal stability, aging specific surface area, oxygen storage capacity, and the like of the carrier catalyst are greatly improved.
Description
Technical field
The present invention relates to a kind of solid solution carried catalyst, be specifically related to a kind of preparation method of low-cost bigger serface cerium oxide.
Background technology
Cerium oxide, as a kind of important catalyst carrier, has unique oxygen storage capacity and other excellent properties.Under oxidation or reducing atmosphere, there is Ce in cerium ion
3+and Ce
4+between redox reaction, thereby realize storage oxygen and put oxygen function, contribute to realize the catalyzed conversion of vehicle exhaust etc., but pure cerium oxide is sintering very easily at high temperature, cause storing oxygen ability and decline, by the zirconium that adulterates appropriate, form cerium zirconium base oxide solid solution in cerium oxide, can improve to a great extent cerium oxide high-temperature ageing resistance and store oxygen performance, therefore, the study on the synthesis round cerium zirconium base oxide solid solution gets more and more people's extensive concerning.But there is the defects such as production cost is high, powder reuniting is serious, specific area is little in existing cerium oxide carrying body catalyst.
In prior art, majority is usingd cerous carbonate, cerium hydroxide, cerium chloride ammonium, tetravalence cerium chloride as the primary raw material of producing cerium oxide, and above these raw materials exist the defect that production cost is high and environmental pollution is serious, so be difficult to realize industrialization; Have, most research at present is still hovered in the field of reaction under high pressure, microwave reaction and mesoporous reaction again, and this experimental program existence investment is large, production cost is high, danger coefficient is high, process control is loaded down with trivial details, is difficult for realizing industrialization.
Summary of the invention
For the deficiencies in the prior art, the preparation method who the object of this invention is to provide a kind of low-cost bigger serface cerium oxide, cost of material is cheap, technical process is simple, overcome the doping defect of adulterating produced in cerium oxide carrier, greatly improved the performance indications such as the heat endurance of carried catalyst and aging specific area, oxygen storage capacity simultaneously.
The preparation method of low-cost bigger serface cerium oxide of the present invention, comprises the following steps:
(1) by the aqueous solution of the aqueous solution of cerium chloride, salt that other rare earth oxide is corresponding and salt corresponding to transition metal oxide, obtain mixed liquor, the surfactant that adds the 0.1-1% for mixed liquor of parts by weight, is placed on standing 1-2 hour in thermostat after stirring;
(2) ammoniacal liquor or ammonium carbonate are added in the feed liquid after step (1) is processed, control pH value between 8-10, can obtain a kind of gelatinous precipitate;
(3) gelatinous precipitate obtaining in step (2) is washed by deionized water and dewatered;
(4) product dehydration in step (3) being obtained is put in kiln roasting 4-6 hour under 400-500 ℃ of condition;
(5) product obtaining after roasting is ground, grind size is all less than 10um; In ground product, add trifluoromethane sulfonic acid to mix again, after drying, obtain low-cost bigger serface cerium oxide.
In step (1), other rare earth oxides are: the mixture of lanthana, praseodymium oxide, neodymia, yittrium oxide and samarium oxide; Transition metal oxide is: the mixture of vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide and cupric oxide.
The salt that in step (1), other rare earth oxide is corresponding is its corresponding chlorate or nitrate; The salt that transition metal oxide is corresponding is its corresponding chlorate or nitrate.
Surfactant described in step (1) is non-ionic surface active agent or anion surfactant.
Non-ionic surface active agent is one or more in polyethylene glycols, oleic acid or alkyl amine.
Anion surfactant is one or more in phosphate or sulfonate.
In step (1), the temperature constant of thermostat is at 40-50 ℃.
In step (5), ground product and the weight ratio of trifluoromethane sulfonic acid are 1:0.5.
In step (5), dry and be: under vacuum state, carry out, bake out temperature is 160-200 ℃, and drying time is 4-8 hour.
The present invention, by the product obtaining after roasting is ground, then adds trifluoromethane sulfonic acid to carry out fatty acid treatment, and the carried catalyst obtaining has very high specific area and high oxygen storage power.
The chemical composition of the preferred low-cost bigger serface cerium oxide of the present invention forms and weight content is:
Cerium oxide 90-95 part, lanthana 0.5-1 part, praseodymium oxide 0.5-1 part, neodymia 0.5-1 part, yittrium oxide 0.5-1 part, samarium oxide 1-5 part, vanadium oxide 0.2-1 part, chromium oxide 0.2-0.5 part, manganese oxide 0.1-0.5 part, iron oxide 0.2-0.3 part, cobalt oxide 0.4-0.5 part, cupric oxide 0.5-1 part, trifluoromethane sulfonic acid 47.3-53.9 part.
Select transition metal as carrier catalysis agent aid, because the oxidability of manganese is excellent, but add merely the oxide that manganese is difficult to manufacture porous, bigger serface, and the present invention selects Fe, Co, Cu, V, Cr to immerse reaction as auxiliary agent, and generation interacts, solve the structural defect of manganese oxide, thereby brought into play to greatest extent specific area and the oxygen storage capacity of carried catalyst, significantly improved catalytic activity, high-temperature stability and the decay resistance of carried catalyst.
In addition, other rare earth oxides that adulterate in cerium oxide carrier can improve its specific area and oxygen storage capacity, especially during samaria doped, the oxygen storage capacity of depositing of catalyst has had very large improvement, when samaria doped in carried catalyst, in low doping concentration scope, increase along with doping oxide concentration, the oxygen storage capacity of depositing of carried catalyst has rising trend, but in high concentration range, further increase along with doping oxide concentration, carried catalyst deposit oxygen storage capacity and high-temperature stability step-down on the contrary, when cerium oxide 90-95 part, samarium oxide preferably adds samarium oxide 1-5 part, within the scope of this carried catalyst deposit oxygen storage capacity and high-temperature stability is the strongest.
In sum, the present invention has the following advantages:
(1) the invention provides a kind of preparation method of low-cost bigger serface cerium oxide, cost of material is cheap, and technical process is simple, is conducive to large-scale industrialization and produces.
(2) carried catalyst that the present invention prepares is to exist with solid solution form, and its grain size is: 1-10nm, the fresh specific area through 700-900 ℃ of calcining after 4-6 hour is: 220-250m
2/ g, calcines aging specific area after 10 hours for 1000 ℃ and is greater than 150m
2/ g, oxygen storage capacity is higher than 2500umol/g.
The specific embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Prepare a kind of low-cost bigger serface cerium oxide, chemical composition forms and weight content is:
92 parts of cerium oxide, 0.8 part of lanthana, 0.8 part of praseodymium oxide, 0.7 part of neodymia, 0.8 part of yittrium oxide, 3 parts of samarium oxides, 0.6 part of vanadium oxide, 0.4 part, chromium oxide, 0.3 part of manganese oxide, 0.2 part of iron oxide, 0.4 part of cobalt oxide, 0.8 part of cupric oxide, 50 parts of trifluoromethane sulfonic acids.
Preparation method comprises the following steps:
(1) by the aqueous solution of cerium chloride, lanthanum chloride, praseodymium chloride, neodymium chloride, yttrium chloride, samarium trichloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride and copper chloride, obtain mixed liquor, 0.5% the surfactant (polyethylene glycol) for mixed liquor that adds parts by weight, after stirring, be placed in thermostat standing 1.5 hours, the temperature constant of thermostat is at 45 ℃;
(2) ammoniacal liquor or ammonium carbonate are added in the feed liquid after step (1) is processed, control pH value 9, can obtain a kind of gelatinous precipitate;
(3) gelatinous precipitate obtaining in step (2) is washed by deionized water and dewatered;
(4) product dehydration in step (3) being obtained is put in kiln under 450 ℃ of conditions roasting 5 hours;
(5) product obtaining after roasting is ground, grind size is all less than 10um; In ground product, add trifluoromethane sulfonic acid to mix again, ground product and the weight ratio of trifluoromethane sulfonic acid are 1:0.5, under vacuum state, dry, and bake out temperature is 180 ℃, drying time is 6 hours, obtains low-cost bigger serface cerium oxide.
The grain size of the carried catalyst that embodiment 1 prepares is: 5nm, the fresh specific area through 900 ℃ of calcinings after 6 hours is: 250m
2/ g, calcines aging specific area 180m after 10 hours for 1000 ℃
2/ g, oxygen storage capacity 2750umol/g.
Embodiment 2
Prepare a kind of low-cost bigger serface cerium oxide, chemical composition forms and weight content is:
90 parts of cerium oxide, 0.5 part of lanthana, 0.5 part of praseodymium oxide, 1 part of neodymia, 1 part of yittrium oxide, 5 parts of samarium oxides, 0.2 part of vanadium oxide, 0.2 part, chromium oxide, 0.5 part of manganese oxide, 0.3 part of iron oxide, 0.5 part of cobalt oxide, 1 part of cupric oxide, 53.9 parts of trifluoromethane sulfonic acids.
Preparation method comprises the following steps:
(1) by the aqueous solution of cerium chloride, lanthanum chloride, praseodymium chloride, neodymium chloride, yttrium chloride, samarium trichloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride and copper chloride, obtain mixed liquor, 0.5% the surfactant (oleic acid) for mixed liquor that adds parts by weight, after stirring, be placed in thermostat standing 2 hours, the temperature constant of thermostat is at 40 ℃;
(2) ammoniacal liquor or ammonium carbonate are added in the feed liquid after step (1) is processed, control pH value 10, can obtain a kind of gelatinous precipitate;
(3) gelatinous precipitate obtaining in step (2) is washed by deionized water and dewatered;
(4) product dehydration in step (3) being obtained is put in kiln under 500 ℃ of conditions roasting 4 hours;
(5) product obtaining after roasting is ground, grind size is all less than 10um; In ground product, add trifluoromethane sulfonic acid to mix again, ground product and the weight ratio of trifluoromethane sulfonic acid are 1:0.5, under vacuum state, dry, and bake out temperature is 160 ℃, drying time is 8 hours, obtains low-cost bigger serface cerium oxide.
The grain size of the carried catalyst that embodiment 2 prepares is: 2nm, the fresh specific area through 900 ℃ of calcinings after 6 hours is: 220m
2/ g, calcines aging specific area 160m after 10 hours for 1000 ℃
2/ g, oxygen storage capacity 2650umol/g.
Embodiment 3
Prepare a kind of low-cost bigger serface cerium oxide, chemical composition forms and weight content is:
95 parts of cerium oxide, 1 part of lanthana, 1 part of praseodymium oxide, 0.5 part of neodymia, 0.5 part of yittrium oxide, 1 part of samarium oxide, 1 part of vanadium oxide, 0.5 part, chromium oxide, 0.1 part of manganese oxide, 0.2 part of iron oxide, 0.4 part of cobalt oxide, 0.5 part of cupric oxide, 47.3 parts of trifluoromethane sulfonic acids.
Preparation method comprises the following steps:
(1) by the aqueous solution of cerium chloride, lanthanum chloride, praseodymium chloride, neodymium chloride, yttrium chloride, samarium trichloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride and copper chloride, obtain mixed liquor, 0.5% the surfactant (magnesium phosphate) for mixed liquor that adds parts by weight, after stirring, be placed in thermostat standing 1 hour, the temperature constant of thermostat is at 50 ℃;
(2) ammoniacal liquor or ammonium carbonate are added in the feed liquid after step (1) is processed, control pH value 8, can obtain a kind of gelatinous precipitate;
(3) gelatinous precipitate obtaining in step (2) is washed by deionized water and dewatered;
(4) product dehydration in step (3) being obtained is put in kiln under 400 ℃ of conditions roasting 6 hours;
(5) product obtaining after roasting is ground, grind size is all less than 10um; In ground product, add trifluoromethane sulfonic acid to mix again, ground product and the weight ratio of trifluoromethane sulfonic acid are 1:0.5, under vacuum state, dry, and bake out temperature is 200 ℃, drying time is 4 hours, obtains low-cost bigger serface cerium oxide.
The grain size of the carried catalyst that embodiment 3 prepares is: 8nm, the fresh specific area through 900 ℃ of calcinings after 4 hours is: 240m
2/ g, calcines aging specific area 155m after 10 hours for 1000 ℃
2/ g, oxygen storage capacity 2540umol/g.
Claims (10)
1. a preparation method for low-cost bigger serface cerium oxide, is characterized in that: comprise the following steps:
(1) by the aqueous solution of the aqueous solution of cerium chloride, salt that other rare earth oxide is corresponding and salt corresponding to transition metal oxide, obtain mixed liquor, the surfactant that adds the 0.1-1% for mixed liquor of parts by weight, is placed on standing 1-2 hour in thermostat after stirring;
(2) ammoniacal liquor or ammonium carbonate are added in the feed liquid after step (1) is processed, control pH value between 8-10, can obtain a kind of gelatinous precipitate;
(3) gelatinous precipitate obtaining in step (2) is washed by deionized water and dewatered;
(4) product dehydration in step (3) being obtained is put in kiln roasting 4-6 hour under 400-500 ℃ of condition;
(5) product obtaining after roasting is ground, grind size is all less than 10um; In ground product, add trifluoromethane sulfonic acid to mix again, after drying, obtain low-cost bigger serface cerium oxide.
2. the preparation method of low-cost bigger serface cerium oxide according to claim 1, is characterized in that: in step (1), other rare earth oxides are: the mixture of lanthana, praseodymium oxide, neodymia, yittrium oxide and samarium oxide; Transition metal oxide is: the mixture of vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide and cupric oxide.
3. the preparation method of low-cost bigger serface cerium oxide according to claim 1, is characterized in that: in step (1), salt corresponding to other rare earth oxide is its corresponding chlorate or nitrate; The salt that transition metal oxide is corresponding is its corresponding chlorate or nitrate.
4. the preparation method of low-cost bigger serface cerium oxide according to claim 1, is characterized in that: the surfactant described in step (1) is non-ionic surface active agent or anion surfactant.
5. the preparation method of low-cost bigger serface cerium oxide according to claim 4, is characterized in that: non-ionic surface active agent is one or more in polyethylene glycols, oleic acid or alkyl amine.
6. the preparation method of low-cost bigger serface cerium oxide according to claim 4, is characterized in that: anion surfactant is one or more in phosphate or sulfonate.
7. the preparation method of low-cost bigger serface cerium oxide according to claim 1, is characterized in that: in step (1), the temperature constant of thermostat is at 40-50 ℃.
8. the preparation method of low-cost bigger serface cerium oxide according to claim 1, is characterized in that: in step (5), ground product and the weight ratio of trifluoromethane sulfonic acid are 1:0.5.
9. the preparation method of low-cost bigger serface cerium oxide according to claim 1, is characterized in that: in step (5), oven dry is: under vacuum state, carry out, bake out temperature is 160-200 ℃, and drying time is 4-8 hour.
10. according to the preparation method of the arbitrary described low-cost bigger serface cerium oxide of claim 1-9, it is characterized in that: the chemical composition of described low-cost bigger serface cerium oxide forms and weight content is:
Cerium oxide 90-95 part, lanthana 0.5-1 part, praseodymium oxide 0.5-1 part, neodymia 0.5-1 part, yittrium oxide 0.5-1 part, samarium oxide 1-5 part, vanadium oxide 0.2-1 part, chromium oxide 0.2-0.5 part, manganese oxide 0.1-0.5 part, iron oxide 0.2-0.3 part, cobalt oxide 0.4-0.5 part, cupric oxide 0.5-1 part and trifluoromethane sulfonic acid 47.3-53.9 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410394910.2A CN104148116B (en) | 2014-08-12 | 2014-08-12 | The preparation method of low cost bigger serface cerium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410394910.2A CN104148116B (en) | 2014-08-12 | 2014-08-12 | The preparation method of low cost bigger serface cerium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104148116A true CN104148116A (en) | 2014-11-19 |
| CN104148116B CN104148116B (en) | 2016-05-18 |
Family
ID=51873856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410394910.2A Active CN104148116B (en) | 2014-08-12 | 2014-08-12 | The preparation method of low cost bigger serface cerium oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104148116B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277021A (en) * | 2015-06-12 | 2017-01-04 | 常州卓煜新材料科技有限公司 | A kind of large-specific surface area nano Dineodymium trioxide preparation method |
| CN106732518A (en) * | 2016-11-17 | 2017-05-31 | 陈思南 | The preparation method of inexpensive bigger serface cerium-aluminium composite oxide |
| CN108929634A (en) * | 2018-07-11 | 2018-12-04 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of rare-earth base polishing crystal powder |
| CN109761259A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | A kind of high preparation method at colloidality cerium glue |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785815A (en) * | 2005-08-28 | 2006-06-14 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN102395643A (en) * | 2009-04-15 | 2012-03-28 | 罗地亚(中国)有限公司 | A cerium-based particle composition and the preparation thereof |
-
2014
- 2014-08-12 CN CN201410394910.2A patent/CN104148116B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785815A (en) * | 2005-08-28 | 2006-06-14 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN102395643A (en) * | 2009-04-15 | 2012-03-28 | 罗地亚(中国)有限公司 | A cerium-based particle composition and the preparation thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277021A (en) * | 2015-06-12 | 2017-01-04 | 常州卓煜新材料科技有限公司 | A kind of large-specific surface area nano Dineodymium trioxide preparation method |
| CN106732518A (en) * | 2016-11-17 | 2017-05-31 | 陈思南 | The preparation method of inexpensive bigger serface cerium-aluminium composite oxide |
| CN108929634A (en) * | 2018-07-11 | 2018-12-04 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of rare-earth base polishing crystal powder |
| CN109761259A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | A kind of high preparation method at colloidality cerium glue |
| CN109761259B (en) * | 2019-03-27 | 2021-04-02 | 淄博加华新材料有限公司 | Preparation method of cerium glue with high gelling property |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104148116B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104190438B (en) | High-performance cerium zirconium oxide and production method of high-performance cerium zirconium oxide | |
| CN103191712B (en) | Cerium oxide and zirconium oxide based composite rare earth oxide with favorable ageing resistance and high reduction activity and preparation method of cerium oxide and zirconium oxide based composite rare earth oxide | |
| CN107456964A (en) | For the extra specific surface area perovskite type composite oxide catalyst of hydrocarbon low-temperature oxidation and its preparation | |
| CN104148116B (en) | The preparation method of low cost bigger serface cerium oxide | |
| CN103191711A (en) | Cerium oxide-zirconium oxide based composite rare-earth oxide with high specific surface area and high oxygen storage capacity and preparation method thereof | |
| CN103706360B (en) | A kind of Ru/BaCeO3 ammonia synthesis catalyst and preparation method thereof | |
| CN106025178B (en) | It is a kind of to prepare the method for metal oxide and its application in lithium cell cathode material by template of MOF | |
| CN104117363B (en) | Multi-element doping cerium zirconium carried catalyst and preparation method thereof | |
| CN102962073A (en) | Catalyst for directly decomposing N2O and preparation method of catalyst | |
| CN104128174A (en) | Binary cerium-zirconium doped supported catalyst and preparation method thereof | |
| CN103372441B (en) | Preparation method of methanol synthesis catalyst | |
| CN102824918B (en) | Graphene oxide rare-earth composite methane catalyst | |
| CN111013597A (en) | Preparation method of cerium-based composite oxide low-temperature SCR catalyst with Ce-MOF as precursor | |
| CN102728381B (en) | Tourmalinite-containing composite methane catalyst | |
| CN104437458B (en) | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof | |
| CN103372436B (en) | Oxygen carrier, preparation method and applications | |
| CN105478158A (en) | Preparation method of composite molecular sieve catalyst for diesel-car tail gas | |
| CN103372440B (en) | Preparation method of methanol synthesis catalyst | |
| CN103936083B (en) | Nickel-magnesia mixed oxide and preparation method thereof | |
| CN103372439B (en) | The preparation method of catalst for synthesis of methanol | |
| CN107185544A (en) | A kind of mesoporous loaded catalyst CuO LaCoO3Preparation method | |
| CN104148087B (en) | Praseodymium doped cerium zirconium carried catalyst and preparation method thereof | |
| CN103384008A (en) | Lithium ion battery cathode active material and its preparation method | |
| CN103316658B (en) | A kind of nanometer composite cerium zirconium solid solution and preparation method thereof | |
| CN104128173B (en) | Low-cost and high-performance carried catalyst and preparation method thereof |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210125 Address after: 255400 west side of No.9 Jiahua Road, Jinshan Town, Linzi District, Zibo City, Shandong Province Patentee after: Zibo Jiahua New Material Co.,Ltd. Address before: 9 Jiahua Road, Jinshan Town, Linzi District, Zibo City, Shandong Province Patentee before: ZIBO ZAMR NEW MATERIAL RESOURCE Co.,Ltd. |