CN109761260A - Rare earth and the ceria and preparation method thereof of zirconium doping - Google Patents
Rare earth and the ceria and preparation method thereof of zirconium doping Download PDFInfo
- Publication number
- CN109761260A CN109761260A CN201910238861.6A CN201910238861A CN109761260A CN 109761260 A CN109761260 A CN 109761260A CN 201910238861 A CN201910238861 A CN 201910238861A CN 109761260 A CN109761260 A CN 109761260A
- Authority
- CN
- China
- Prior art keywords
- feed liquid
- rare earth
- ceria
- zirconium
- oxide
- 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalyst material technical fields, and in particular to a kind of rare earth and the ceria and preparation method thereof of zirconium doping.Chemical component composition and weight percentage are as follows: cerium oxide 50-95%, rare earth oxide 5-40% and zirconium oxide 0-10%, wherein the combination of one or more of rare earth element La, Pr, Nd or Y.The present invention also provides preparation methods to be added dispersing agent, be washed to conductivity < 5ms/cm, calcination obtains ceria oxide powder after precipitating reagent precipitating is added in cerium feed liquid；After rare-earth liquid, zirconium feed liquid and ceria oxide powder are mixed, drying, calcination obtain oxide powder.The present invention changes the surface nature of oxide by the method for doping, increases the mobility of Lattice Oxygen, and aging specific surface is high, in use, being not easy agglomeration, the redox ability of cerium oxide base combination of compounds greatly improved；Preparation method, it is scientific and reasonable, simple and easy.
Description
Technical field
The invention belongs to catalyst material technical fields, and in particular to a kind of rare earth and the ceria and its system of zirconium doping
Preparation Method.
Background technique
As a kind of important rare-earth oxide, ceria is in polishing material, ultraviolet absorber, optical glass member
The fields such as part, ceramic additive, solid fuel cell and catalyst are widely used.Ceria because it has Lacking oxygen,
Preferable oxygen storage capacity and redox ability are made it have, has a wide range of applications market in automotive exhaust catalysis field.
By the method for doping, increase the mobility of Lattice Oxygen, its redox property can be improved.Wherein, CeZr Composite is studied
Close the most extensive of object.
CN101400609B: the present composition of the oxide based on zirconium and cerium has the at most cerium oxide of 50 weight %
Content.Its preparation is as follows: forming the aqueous mixture of the compound comprising zirconium and cerium；The mixture is heated at least 100 DEG C, and
And it is set to reach alkaline pH after heating；The additive of surfactant type is added to the sediment obtained by the mixture, with
And at least 900 DEG C at a temperature of calcine the sediment then at least 600 DEG C of temperature in inert gas or under vacuum
Under calcined in oxidizing atmosphere.The patent needs to carry out two step calcinings, and calcination condition requirement is relatively harsh, wants to appointed condition
Ask high.
Summary of the invention
To solve the above problems, passing through doping the object of the present invention is to provide the ceria that a kind of rare earth and zirconium adulterate
Method, change the surface nature of oxide, increase the mobility of Lattice Oxygen, aging specific surface is high, in use, being not easy to burn
Conglomeration is poly-, and the redox ability of cerium oxide base combination of compounds greatly improved；The present invention also provides preparation method, science
Rationally, simple and easy.
The ceria of rare earth and zirconium doping of the present invention, chemical component composition and weight percentage are as follows:
Cerium oxide 50-95%, rare earth oxide 5-40% and zirconium oxide 0-10%, wherein rare earth element La, Pr, Nd or Y
One or more of combination.
The preparation method of the ceria of rare earth and zirconium doping of the present invention, comprising the following steps:
(1) cerium feed liquid is squeezed into blend tank, adds pure water to dilute feed concentration to 0.5-2.0mol/L, puts into ammonium carbonate or carbon
Sour hydrogen ammonium, by feed acidity and the Ratio control of concentration in 0.05-1.5, then plus pure water dilute feed liquid to concentration be 0.05-
0.3mol/L；
(2) feed liquid is heated to 80-120 DEG C, keeps the temperature 3-20h, after cooling, turns feed liquid to settling tank；
(3) precipitating reagent is added in feed liquid and is precipitated, control pH=8-10；
(4) dispersing agent is added, stirs 0.5-2h, binder to sheet frame or centrifuge drying, is washed to conductivity < 5ms/
cm；
(5) lotion is placed in incinerator, 300-600 DEG C of calcination 3-7h obtains ceria oxide powder；
(6) rare-earth liquid and zirconium feed liquid and pure water are added in tank, opens stirring, ceria oxide powder is added, stirs 1-3h；
(7) by 80-120 DEG C of material drying in (6)；
(8) material drying is obtained into oxide powder in 300-600 DEG C of calcination 3-7h.
Wherein:
The cerium feed liquid is ammonium ceric nitrate feed liquid, Ce (NO3)3Feed liquid or CeCl3Feed liquid.
The precipitating reagent is ammonium hydroxide, ammonium carbonate or ammonium hydrogen carbonate.The ammonium carbonate or ammonium hydrogen carbonate can also be in water
It is added in the form of ammonium carbonate solution or ammonium bicarbonate aqueous solution after dissolution.
The dispersing agent is saturated fatty acid, cetyl trimethylammonium bromide, ammonium lauryl sulfate, ethylene glycol, third
The mixture of one or more of glycol, polyethylene glycol, glycerine or ethers.The preferred lauric acid of saturated fatty acid.Institute
State the preferred diethylene glycol monobutyl ether of ethers.
The dispersing agent is the 10-50% of oxide powder quality.The oxide powder is the oxygen of plan preparation
Compound powder.
The rare-earth liquid be corresponding element nitric rare earth feed liquid or rare earth chloride liquid, corresponding element be La,
The combination of one or more of Pr, Nd or Y.
The zirconium feed liquid is zirconyl nitrate feed liquid, zirconyl chloride feed liquid or zirconium oxysulfate feed liquid.
In step (8), directly the calcination under air atmosphere, process are simply energy saving.
Index based on product made from above method is as follows:
SA (fresh)=100-160m2/ g, SA (800 DEG C/3h)=60-100m2/ g, SA (900 DEG C/5h)=25-60m2/
G, SA (1000 DEG C/5h)=12-25m2/ g, SA (1100 DEG C/5h)=5-15m2/ g, D50=3-10 μm.NOx storage(100
DEG C)=0.55~0.8%, NOx storage (300 DEG C)=0.35~0.55%.
Compared with prior art, beneficial effects of the present invention are as follows:
1, the present invention changes the surface nature of oxide, increases the mobility of Lattice Oxygen by the method for doping, controls
Its aging specific surface is made in certain level, in use, being not easy agglomeration, cerium oxide base combination of compounds greatly improved
Redox ability.
2, preparation method of the present invention, it is scientific and reasonable, simple and easy.
Specific embodiment
The present invention is described further with reference to embodiments.
Raw material used in the examples is unless otherwise specified marketable material.
Embodiment 1
Rare earth involved in the present embodiment and the ceria of zirconium doping, chemical component composition and weight percentage are as follows:
55% cerium oxide, 19% praseodymium oxide, 20% neodymium oxides and 6% Zirconium oxide.
Preparation method is as follows:
(1) after appropriate pure water being added in molten batch can, ammonium ceric nitrate is dissolved limpid, acidity and concentration ratio are 1.0.By cerium
Blend tank is added in feed liquid, adds pure water to dilute feed concentration to 0.55mol/L, ammonium carbonate is put into, by the ratio of feed acidity and concentration
Value control 1.3, then plus pure water dilution feed concentration in 0.28mol/L.
(2) feed liquid is heated to 115 DEG C, keeps the temperature 4h, after cooling, turns feed liquid to settling tank.
(3) ammonium carbonate solution is added in feed liquid and is precipitated, control pH=8.5.
(4) cetyl trimethylammonium bromide is added, additional amount is the 45% of oxide powder weight, stirs 2h.From
Scheming is washed to conductivity < 5ms/cm and dries.
(5) lotion is placed in incinerator, 600 DEG C of progress calcination 3h obtain ceria oxide powder.
(6) praseodymium nitrate feed liquid, neodymium nitrate feed liquid and the zirconyl chloride feed liquid and pure water of corresponding proportion are added in mashing tank,
Stirring is opened, ceria oxide powder is added, stirs 3h.
(7) 85 DEG C of material are dried；
(8) material drying is obtained into oxide powder in 500 DEG C of calcination 5h.
The index of product obtained is as follows:
SA (fresh)=155m2/ g, SA (800 DEG C/3h)=91m2/ g, SA (900 DEG C/5h)=52m2/ g, SA (1000
DEG C/5h)=23m2/ g, SA (1100 DEG C/5h)=13m2/ g, D50=7.52 μm.NOx storage (100 DEG C)=0.760%,
NOx storage (300 DEG C)=0.405%
Embodiment 2
Rare earth involved in the present embodiment and the ceria of zirconium doping, chemical component composition and weight percentage are as follows:
76% cerium oxide, 9% lanthanum-oxides, 5% yttrium oxide and 10% Zirconium oxide.
(1) hydrogen peroxide is squeezed into blend tank, then by Ce (NO3)3Feed liquid is squeezed into blend tank, is stood 1h, is stirred for 1h, dense
Degree is 3.0mol/L, acidity 0.5N.Blend tank is added in cerium feed liquid, pure water is added to dilute feed concentration to 2.0mol/L, investment
Ammonium hydrogen carbonate, by feed acidity and the Ratio control of concentration 0.05, then plus pure water dilution feed concentration in 0.05mol/L.
(2) feed liquid is heated to 85 DEG C, keeps the temperature 20h, after cooling, turns feed liquid to settling tank.
(3) ammonium carbonate solution is added in feed liquid and is precipitated, control pH=10.
(4) polyethylene glycol is added, additional amount is the 10% of oxide weight, stirs 0.5h.Centrifuge is washed to conductance
Rate < 5ms/cm is simultaneously dried.
(5) lotion is placed in incinerator, 500 DEG C of progress calcination 4h obtain ceria oxide powder.
(6) lanthanum nitrate feed liquid, yttrium nitrate feed liquid and the zirconyl nitrate feed liquid and pure water of corresponding proportion are added in mashing tank,
Stirring is opened, ceria oxide powder is added, stirs 1h.
(7) 120 DEG C of material are dried.
(8) material drying is obtained into oxide powder in 600 DEG C of calcination 4h.
The index of product obtained is as follows:
SA (fresh)=147m2/ g, SA (800 DEG C/3h)=89m2/ g, SA (900 DEG C/5h)=55m2/ g, SA (1000
DEG C/5h)=19m2/ g, SA (1100 DEG C/5h)=12m2/ g, D50=6.58 μm.NOx storage (100 DEG C)=0.712%,
NOx storage (300 DEG C)=0.381%
Embodiment 3
Rare earth involved in the present embodiment and the ceria of zirconium doping, chemical component composition and weight percentage are as follows:
88% cerium oxide, 10% lanthanum-oxides and 2% neodymium oxides.
(1) after nitric acid being added in molten batch can, stirring is opened, then put into cerium hydroxide, is warming up to 105 DEG C, heat preservation 3 is small
When, obtain Ce (NO3)4Feed liquid；Wherein, the molar ratio of nitric acid and cerium hydroxide is 6.5:1, Ce (NO3)4The concentration of feed liquid is
1.5mol/L, acidity and concentration ratio are 4.5.Blend tank is added in cerium feed liquid, adds pure water to dilute feed concentration to 1.0mol/L, throws
Enter ammonium carbonate, by feed acidity and the Ratio control of concentration 0.5, then plus pure water dilution feed concentration in 0.15mol/L.
(2) feed liquid is heated to 105 DEG C, keeps the temperature 8h, after cooling, turns feed liquid to settling tank.
(3) ammonium hydroxide is added in feed liquid and is precipitated, control pH=9.
(4) lauric acid is added, additional amount is the 30% of oxide weight, stirs 1h.Binder is washed to conductance to sheet frame
Rate < 5ms/cm.
(5) lotion is placed in incinerator, 550 DEG C of progress calcination 4h obtain ceria oxide powder.
(6) lanthanum nitrate feed liquid, neodymium nitrate feed liquid and the pure water of corresponding proportion are added in mashing tank, opens stirring, is added
Ceria oxide powder stirs 2h.
(7) 95 DEG C of material are dried.
(8) material drying is obtained into oxide powder in 500 DEG C of calcination 4h.
The index of product obtained is as follows:
SA (fresh)=118m2/ g, SA (800 DEG C/3h)=78m2/ g, SA (900 DEG C/5h)=33m2/ g, SA (1000
DEG C/5h)=16m2/ g, SA (1100 DEG C/5h)=8.5m2/ g, D50=5.21 μm.NOx storage (100 DEG C)=0.601%,
NOx storage (300 DEG C)=0.485%
Embodiment 4
Rare earth involved in the present embodiment and the ceria of zirconium doping, chemical component composition and weight percentage are as follows:
92% cerium oxide, 8% neodymium oxides.
(1) hydrogen peroxide is squeezed into blend tank, then by CeCl3Feed liquid is squeezed into blend tank, is stood 1h, is stirred for 1h, concentration
For 1.5mol/L, acidity 0.8N.Blend tank is added in cerium feed liquid, adds pure water to dilute feed concentration to 1.0mol/L, puts into carbon
Sour hydrogen ammonium, by feed acidity and the Ratio control of concentration 0.8, then plus pure water dilution feed concentration in 0.2mol/L.
(2) feed liquid is heated to 100 DEG C, keeps the temperature 20h, after cooling, turns feed liquid to settling tank.
(3) ammonium bicarbonate aqueous solution is added in feed liquid and is precipitated, control pH=10.
(4) diethylene glycol monobutyl ether is added, additional amount is the 20% of oxide weight, stirs 0.5h.Centrifuge washing
To conductivity < 5ms/cm and dry.
(5) lotion is placed in incinerator, 500 DEG C of progress calcination 5h obtain ceria oxide powder.
(6) the neodymium chloride feed liquid and pure water of corresponding proportion are added in mashing tank, opens stirring, ceria oxide powder is added,
Stir 2h.
(7) 100 DEG C of material are dried.
(8) material drying is obtained into oxide powder in 520 DEG C of calcination 4h.
The index of product obtained is as follows:
SA (fresh)=125m2/ g, SA (800 DEG C/3h)=71m2/ g, SA (900 DEG C/5h)=29m2/ g, SA (1000
DEG C/5h)=19m2/ g, SA (1100 DEG C/5h)=9m2/ g, D50=5.12 μm.NOx storage (100 DEG C)=0.645%,
NOx storage (300 DEG C)=0.493%.
Claims (8)
1. a kind of rare earth and the ceria of zirconium doping, it is characterised in that: chemical component composition and weight percentage are as follows:
Cerium oxide 50-95%, rare earth oxide 5-40% and zirconium oxide 0-10%, wherein in rare earth element La, Pr, Nd or Y
One or more of combinations.
2. the preparation method of a kind of rare earth described in claim 1 and the ceria of zirconium doping, it is characterised in that: including following
Step:
(1) cerium feed liquid is squeezed into blend tank, adds pure water to dilute feed concentration to 0.5-2.0mol/L, puts into ammonium carbonate or bicarbonate
Ammonium, by feed acidity and the Ratio control of concentration in 0.05-1.5, then plus pure water dilute feed liquid to concentration be 0.05-0.3mol/
L；
(2) feed liquid is heated to 80-120 DEG C, keeps the temperature 3-20h, after cooling, turns feed liquid to settling tank；
(3) precipitating reagent is added in feed liquid and is precipitated, control pH=8-10；
(4) dispersing agent is added, stirs 0.5-2h, binder to sheet frame or centrifuge drying, is washed to conductivity < 5ms/cm；
(5) lotion is placed in incinerator, 300-600 DEG C of calcination 3-7h obtains ceria oxide powder；
(6) rare-earth liquid and zirconium feed liquid and pure water are added in tank, opens stirring, ceria oxide powder is added, stirs 1-3h；
(7) by 80-120 DEG C of material drying in (6)；
(8) material drying is obtained into oxide powder in 300-600 DEG C of calcination 3-7h.
3. the preparation method of rare earth according to claim 1 and the ceria of zirconium doping, it is characterised in that: the cerium material
Liquid is ammonium ceric nitrate feed liquid, Ce (NO3)3Feed liquid or CeCl3Feed liquid.
4. the preparation method of rare earth according to claim 1 and the ceria of zirconium doping, it is characterised in that: the precipitating
Agent is ammonium hydroxide, ammonium carbonate or ammonium hydrogen carbonate.
5. the preparation method of rare earth according to claim 1 and the ceria of zirconium doping, it is characterised in that: the dispersion
Agent is saturated fatty acid, cetyl trimethylammonium bromide, ammonium lauryl sulfate, ethylene glycol, propylene glycol, polyethylene glycol, third
The mixture of one or more of triol or ethers.
6. the preparation method of rare earth according to claim 1 and the ceria of zirconium doping, it is characterised in that: the dispersion
Agent is the 10-50% of oxide powder quality.
7. the preparation method of rare earth according to claim 1 and the ceria of zirconium doping, it is characterised in that: the rare earth
Feed liquid is the nitric rare earth feed liquid or rare earth chloride liquid of corresponding element, and corresponding element is one of La, Pr, Nd or Y
Or several combination.
8. the preparation method of rare earth according to claim 1 and the ceria of zirconium doping, it is characterised in that: the zirconium material
Liquid is zirconyl nitrate feed liquid, zirconyl chloride feed liquid or zirconium oxysulfate feed liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910238861.6A CN109761260B (en) | 2019-03-27 | 2019-03-27 | Rare earth and zirconium doped cerium dioxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910238861.6A CN109761260B (en) | 2019-03-27 | 2019-03-27 | Rare earth and zirconium doped cerium dioxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109761260A true CN109761260A (en) | 2019-05-17 |
| CN109761260B CN109761260B (en) | 2021-10-12 |
Family
ID=66459934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910238861.6A Active CN109761260B (en) | 2019-03-27 | 2019-03-27 | Rare earth and zirconium doped cerium dioxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109761260B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022135608A1 (en) * | 2020-12-25 | 2022-06-30 | 安集微电子（上海）有限公司 | Synthesis method and use method for cerium oxide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040069404A (en) * | 2003-01-29 | 2004-08-06 | 한국화학연구원 | Preparation method of ceria particles with nano-size |
| CN104128173A (en) * | 2014-08-12 | 2014-11-05 | 淄博加华新材料资源有限公司 | Low-cost high-performance supported catalyst and preparation method thereof |
| CN104128174A (en) * | 2014-08-12 | 2014-11-05 | 淄博加华新材料资源有限公司 | Binary cerium-zirconium doped supported catalyst and preparation method thereof |
| CN105771955A (en) * | 2016-04-14 | 2016-07-20 | 江门市科恒实业股份有限公司 | Preparation method of ceria-zirconia solid solution |
| CN105983403A (en) * | 2015-02-09 | 2016-10-05 | 有研稀土新材料股份有限公司 | Cerium-zirconium composite oxide, preparation method of cerium-zirconium composite oxide and use of catalyst |
| CN106430304A (en) * | 2016-07-31 | 2017-02-22 | 包头稀土研究院 | Preparation method of high-specific surface and high-temperature-resistant ceria-zirconia solid solution |
| CN107673391A (en) * | 2017-11-07 | 2018-02-09 | 西安文理学院 | One kind bundle shape ceria metal oxides and preparation method thereof |
-
2019
- 2019-03-27 CN CN201910238861.6A patent/CN109761260B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040069404A (en) * | 2003-01-29 | 2004-08-06 | 한국화학연구원 | Preparation method of ceria particles with nano-size |
| CN104128173A (en) * | 2014-08-12 | 2014-11-05 | 淄博加华新材料资源有限公司 | Low-cost high-performance supported catalyst and preparation method thereof |
| CN104128174A (en) * | 2014-08-12 | 2014-11-05 | 淄博加华新材料资源有限公司 | Binary cerium-zirconium doped supported catalyst and preparation method thereof |
| CN105983403A (en) * | 2015-02-09 | 2016-10-05 | 有研稀土新材料股份有限公司 | Cerium-zirconium composite oxide, preparation method of cerium-zirconium composite oxide and use of catalyst |
| CN105771955A (en) * | 2016-04-14 | 2016-07-20 | 江门市科恒实业股份有限公司 | Preparation method of ceria-zirconia solid solution |
| CN106430304A (en) * | 2016-07-31 | 2017-02-22 | 包头稀土研究院 | Preparation method of high-specific surface and high-temperature-resistant ceria-zirconia solid solution |
| CN107673391A (en) * | 2017-11-07 | 2018-02-09 | 西安文理学院 | One kind bundle shape ceria metal oxides and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022135608A1 (en) * | 2020-12-25 | 2022-06-30 | 安集微电子（上海）有限公司 | Synthesis method and use method for cerium oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109761260B (en) | 2021-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107195886B (en) | A kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application | |
| CN109065880A (en) | A kind of high voltage monocrystalline ternary material and preparation method thereof | |
| CN110124660A (en) | A kind of Z- mechanism Bi rich in Lacking oxygen2O3@CeO2Photochemical catalyst and the preparation method and application thereof | |
| CN101113010A (en) | Method for preparing cerium oxide nano particle by auxiliary microwave | |
| CN102259931A (en) | Method for preparing lithium manganese oxide battery material | |
| CN108899524A (en) | A kind of lithium ion battery mangaic acid lithium anode material and preparation method thereof | |
| CN107857300B (en) | A kind of preparation method of β type bismuth oxide | |
| CN104128174A (en) | Binary cerium-zirconium doped supported catalyst and preparation method thereof | |
| CN102698735B (en) | Method of preparing flower-ball shaped Bi4V2O11 visible-light catalyst | |
| CN104193397B (en) | Perovskite structure porous Ba 0.5sr 0.5co 0.8fe 0.2o 3-δmaterial and preparation method thereof | |
| CN108682849A (en) | A kind of preparation method for mixing aluminium cobalt acid lithium | |
| CN106745303B (en) | A kind of three-dimensional flower ball-shaped cadmium ferrite bismuth meal body and preparation method thereof | |
| CN104117363B (en) | Multi-element doping cerium zirconium carried catalyst and preparation method thereof | |
| CN101891236B (en) | Method for synthesizing monodisperse samarium-doped rare earth cerium oxide nanocrystal | |
| CN103933957B (en) | Porous monocrystalline nano titanium dioxide photocatalyst that a kind of high crystallization, size are controlled, high-energy surface exposes and its preparation method and application | |
| CN104437458A (en) | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof | |
| CN109761260A (en) | Rare earth and the ceria and preparation method thereof of zirconium doping | |
| CN104148116B (en) | The preparation method of low cost bigger serface cerium oxide | |
| CN109761261A (en) | The environment-friendly preparation method thereof of partial size morphology controllable bigger serface cerium dioxide powder | |
| CN104492414B (en) | Preparation method of cerium-zirconium based solid solution | |
| CN106602115A (en) | Preparation method of low-temperature type solid electrolyte material | |
| CN109860566A (en) | A kind of preparation method of modified nickel-cobalt lithium manganate cathode material | |
| CN111215085A (en) | Two-step solar thermochemical energy storage non-noble metal catalyst and preparation and application thereof | |
| CN104128173A (en) | Low-cost high-performance supported catalyst and preparation method thereof | |
| CN104148087A (en) | Praseodymium-doped cerium-zirconium carrier catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210126 Address after: 255400 west side of No.9 Jiahua Road, Jinshan Town, Linzi District, Zibo City, Shandong Province Applicant after: Zibo Jiahua New Material Co.,Ltd. Address before: 9 Jiahua Road, Jinshan Town, Linzi District, Zibo City, Shandong Province Applicant before: ZIBO ZAMR NEW MATERIAL RESOURCE Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |