CN108751260A - A kind of preparation method of perovskite type rare earth complex oxide - Google Patents
A kind of preparation method of perovskite type rare earth complex oxide Download PDFInfo
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Abstract
A kind of preparation method of perovskite type rare earth complex oxide, belongs to perovskite material technical field, preparation method：1) nonstoichiometric molar ratio of metallic element chloride is mixed, organic compound is added after being dissolved in water, obtains chloride mixed solution；2) chloride mixed solution is formed into droplet by nozzle atomization, and is sprayed into from pyrolysis furnace bottom or top, after gas solid separation, obtain mixture solid；3) after roasting mixture solid, RE perovskite type nano-powder is obtained；The present invention is using rare earth-iron-boron as raw material, by controlling the reaction condition in chloride solution pyrolysis oven, purity higher perovskite type rare earth complex oxide is synthesized under conditions of relative low temperature, reduces cost of material and energy consumption.
Description
Technical field
The invention belongs to perovskite material technical field, more particularly to a kind of preparation of perovskite type rare earth complex oxide
Method.
Technical background
REB1-xCxO3Or RE1-xBxCO3The synthesis of perovskite composite oxide mostly uses coprecipitation, hydrolysis of alkoxide
Method, hydrothermal synthesis method and sol-gel method etc., in recent years, spray pyrolysis because its product have grain size is small, bigger serface,
The features such as distributed components, is widely used in field of functional materials, passes through metal chloride spray pyrolysis synthesis oxide
And composite oxides, conventional method preparation process complex procedures can be solved, the time is long, and the problem that wastewater flow rate is big.
For the contaminated wastewater environment and soil salinization problem in traditional rare earth composite oxides production process, to La,
The hydrolysis of tetra- kinds of complexes of Ce, Pr and Nd carries out calculation of thermodynamics, has shown that the temperature for being converted into oxide is suitable
Sequence is LaCl3>NdCl3>PrCl3>CeCl3, and LaCl3Pyrolysis intermediate product LaOCl cannot be still decomposed at 1200 DEG C or more
Oxide.
The study found that preparing (OH) containing LaOCl, La using pyrolysismethod is first passed through2Cl and other metal oxide (metallic hydrogens
Oxide or chloride) presoma, then roast synthesis REB1-xCxO3Or RE1-xBxCO3The side of perovskite composite oxide
Formula, theoretical temperatures are substantially reduced.Chinese application number 201510311060.X and 201610263034.9 patent applications disclose spray
The method that mist pyrolysis prepares lanthanum aluminate and Lanthanum Chromite, first spray pyrolysis prepare presoma, through after baking sintetics, and obtain
Purity is more than 99% bigger serface lanthanum aluminate/Lanthanum Chromite product, mixture solid be Lanthanum monochloride monoxide and aluminium oxide or
The microcrystalline state solid solution of chromium oxide, but prepare hydroxyl oxychloride rare earth and other gold about pyrolytical condition spray pyrolysis is changed
Belong to the mix precursor of oxide, hydroxide and chloride, roasting obtains RE perovskite type REB1-xCxO3Or RE1- xBxCO3The method of composite oxides has not been reported.
Invention content
For existing REB1-xCxO3Or RE1-xBxCO3The technology of preparing of perovskite composite oxide there are the problem of,
The present invention provides a kind of preparation method of perovskite type rare earth complex oxide, by control chloride solution concentration and it is each at
The stoichiometric ratio divided, reaction temperature and gas flow rate are not being produced using rare-earth industry product of production line rare earth-iron-boron as raw material
In the case of raw pollution, the higher REB of purity is produced1-xCxO3Or RE1-xBxCO3Perovskite composite oxide.
A kind of perovskite type rare earth complex oxide, general formula REB1-xCxO3Or RE1-xBxCO3, wherein RE is rare earth element
La, Ce, Pr, Nd, Sm, Eu or Gd, B and C are same or different transition metal, alkali metal, alkaline-earth metal, 0≤x≤1.
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by the stoichiometric molar of required metallic element chloride
Than mixing, organic compound is added after being dissolved in water, obtains chloride mixed solution raw material；
(2) using air or oxygen as carrier gas, chloride mixed solution is formed into droplet by nozzle atomization, droplet is from pyrolysis
Furnace bottom or top spray into, and pyrolysis temperature is 300~1200 DEG C, and pyrolysis time is 0.1~20s, after gas solid separation, are mixed
Object solid；
(3) mixture solid is roasted into 0.5~12h in 500~1200 DEG C, obtains RE perovskite type nano-powder.
A kind of preparation method of above-mentioned perovskite type rare earth complex oxide, wherein：
In the step 1, organic compound is one kind in carboxylic acid, and addition is n (metal ion):N (organic compounds
Object)=1:(0.1~7).
In the step 1, the mass concentration of chloride mixed solution is 5~360g/L.
In the step 2, flow rate of carrier gas is 1~12000L/h, and solution is blown into roaster by compressor and is roasted
It burns, air velocity is 5~8000L/h during injection.
In the step 2, after the completion of pyrolysis, gas solid separation is carried out using separator, the gas of generation is through tail gas absorber
Carry out recycling hydrochloric acid.
In the step 2, mixture solid is carbon containing rare earth oxide or oxychloride or hydroxy chloride rare earth and gold
Belong to the mixture of oxide or chloride or hydroxide.
In the step 3, roasted in roaster.
A kind of preparation method of above-mentioned perovskite type rare earth complex oxide, the chemical equation of generation are expressed as (1
~22)：
RECl3+H2O(g)→REOCl+HCl(g) (1)
RECl3+H2O(g)→RE(OH)2Cl+HCl(g) (2)
RECl3+H2O(g)→RE2O3(or REO2)+HCl(g) (3)
BCl2(or BCl3)+H2O (g) → BO (or B2O3)+HCl(g) (4)
BCl2(or BCl3)+H2O (g) → BO (or B2O3)+HCl(g)+BCl2(or BCl3) (5)
BCl2(or BCl3)+H2O(g)→B(OH)2(or B (OH)3)+HCl(g) (6)
CCl2(or CCl3)+H2O (g) → CO (or C2O3)+HCl(g) (7)
CCl2(or CCl3)+H2O (g) → CO (or C2O3)+HCl(g)+CCl2(or CCl3) (8)
CCl2(or CCl3)+H2O(g)→C(OH)2(or C (OH)3)+HCl(g) (9)
REOCl+1-xBO (or B2O3)+xCO (or C2O3)→REB1-xCxO3+Cl2(g) (10)
1-xREOCl+xBO (or B2O3)+CO (or C2O3)→RE1-xBxCO3+Cl2(g) (11)
REOCl+1-xBCl2(or BCl3)+xCO (or C2O3)+O2(g)→REB1-xCxO3+Cl2(g) (12)
1-xREOCl+xBCl2(or BCl3)+CO (or C2O3)+O2(g)→RE1-xBxCO3+Cl2(g) (13)
1-xREOCl+x-yBCl2(or BCl3)+yBO (or B2O3)+CO (or C2O3)+O2(g)+CCl2(or CCl3)→RE1- xBxCO3+Cl2(g) (14)
REOCl+1-xB(OH)2(or B (OH)3)+xCO(C2O3)→REB1-xCxO3+HCl(g)+HClO(g)+1-xREOCl+
xB(OH)2(or B (OH)3)+CO (or C2O3)→RE1-xBxCO3+HCl(g)+HClO(g) (15)
RE(OH)2Cl+1-xBO (or B2O3)+xCO (or C2O3)→REB1-xCxO3+HCl(g)+HClO(g)+Cl2(g)(16)
RE(OH)2Cl+1-xBCl2(or BCl3)+xCO (or C2O3)→REB1-xCxO3+HCl(g)+HClO(g)+Cl2(g)
(17)
RE(OH)2Cl+1-xB(OH)2(or B (OH)3)+xCO (or C2O3)→REB1-xCxO3+HCl(g)+H2O(g)(18)
REOCl+1-xB(OH)2(or B (OH)3)+xC(OH)2(or C (OH)3)→REB1-xCxO3+HCl(g)+H2O(g)
(19)
RE2O3(or REO2)+1-xBO (or B2O3)+xCO (or C2O3)→REB1-xCxO3(20)
RE2O3(or REO2)+1-xB(OH)2(or B (OH)3)+xC(OH)2(or C (OH)3)→REB1-xCxO3+H2O(g)
(21)
RE2O3(or REO2)+1-xBCl2(or BCl3)+xCO (or C2O3)+x-yCCl2(or CCl3)+yCO (or C2O3)→
REB1-xCxO3+Cl2(g) (22)
Wherein RE is rare earth element La and Ce, Pr, Nd, Sm, Eu and Gd, and B and C are same or different transition metal, alkali
Metal and alkaline-earth metal, 0≤x≤1；The chemical reaction that may occur when after baking is one kind or more in above-mentioned chemical formula
Kind.
A kind of preparation method of perovskite type rare earth complex oxide of the present invention, it is compared with prior art, of the invention
It feature and has the beneficial effect that：
The present invention is anti-in chloride solution pyrolysis oven by controlling using industrial production line product rare earth-iron-boron as raw material
Condition is answered, overcomes rare earth-iron-boron pyrolysis intermediate product (oxychloride rare earth or hydroxy chloride rare earth oxide) at relatively high temperatures
The problem of capable of could being reacted with other metal oxides, metal chloride and metal hydroxides, under conditions of relative low temperature
The higher perovskite type rare earth complex oxide of purity is synthesized, cost of material and energy consumption are reduced.
Specific implementation mode
A kind of perovskite type rare earth complex oxide in following Examples 1 to 22, general formula REB1-xCxO3Or RE1- xBxCO3, wherein RE is rare earth element La and Ce, Pr, Nd, Sm, Eu or Gd, and B and C are same or different transition metal, alkali gold
Belong to, alkaline-earth metal, 0≤x≤1.
Embodiment 1
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Mn:Al=3:2:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:0.5 sucrose, obtains quality
The chloride mixed solution raw material of a concentration of 10g/L；
(2) using air as carrier gas, chloride mixed solution is formed droplet by flow rate of carrier gas 4L/h by nozzle atomization,
Droplet is sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 400 DEG C, pyrolysis time 20s, after the completion of pyrolysis, using separation
Device carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 0.5h in 1200 DEG C in roaster, obtains RE perovskite type
LaMn0.67Al0.33O3Nano-powder.
Embodiment 2
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Pr:
Mn:Fe=5:2:N (metal ion) is added after being dissolved in water in 3 mixing:N (organic compound)=1:0.1 sucrose, obtains quality
The chloride mixed solution raw material of a concentration of 360g/L；
(2) using air as carrier gas, flow rate of carrier gas is that chloride mixed solution is formed mist by 12000L/h by nozzle atomization
Drop, droplet from pyrolysis furnace bottom or top spray into, pyrolysis temperature be 1000 DEG C, pyrolysis time 1s, after the completion of pyrolysis, using point
Gas solid separation is carried out from device, the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 2h in 800 DEG C in roaster, obtains RE perovskite type PrMn0.4Fe0.6O3It receives
Rice flour body.
Embodiment 3
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Ce:
Mn:Co=2:1:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:1.5 citric acid, obtains matter
Measure the chloride mixed solution raw material of a concentration of 180g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 9000L/h by nozzle atomization
Drop, droplet from pyrolysis furnace bottom or top spray into, pyrolysis temperature be 700 DEG C, pyrolysis time 5s, after the completion of pyrolysis, using point
Gas solid separation is carried out from device, the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.5h in 900 DEG C in roaster, obtains RE perovskite type CeMn0.5Co0.5O3
Nano-powder.
Embodiment 4
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Ce:
Mn:Cu=10:9.5:N (metal ion) is added after being dissolved in water in 0.5 mixing:N (organic compound)=1:2 citric acid, obtains
Mass concentration is the chloride mixed solution raw material of 20g/L；
(2) using air as carrier gas, chloride mixed solution is formed droplet by flow rate of carrier gas 20L/h by nozzle atomization,
Droplet is sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 400 DEG C, pyrolysis time 15s, after the completion of pyrolysis, using separation
Device carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1h in 1000 DEG C in roaster, obtains RE perovskite type CeMn0.95Cu0.05O3
Nano-powder.
Embodiment 5
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Mn:Co=4:3:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:1.5 EDTA, obtains quality
The chloride mixed solution raw material of a concentration of 200g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 220L/h by nozzle atomization
Drop, droplet from pyrolysis furnace bottom or top spray into, pyrolysis temperature be 800 DEG C, pyrolysis time 20s, after the completion of pyrolysis, using point
Gas solid separation is carried out from device, the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.5h in 900 DEG C in roaster, obtains RE perovskite type
LaMn0.75Co0.25O3Nano-powder.
Embodiment 6
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Ni:Co=8:7:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:1.2 EDTA, obtains quality
The chloride mixed solution raw material of a concentration of 240g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 260L/h by nozzle atomization
Drop, droplet from pyrolysis furnace bottom or top spray into, pyrolysis temperature be 700 DEG C, pyrolysis time 2s, after the completion of pyrolysis, using point
Gas solid separation is carried out from device, the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1h in 950 DEG C in roaster, obtains RE perovskite type LaMi0.875Co0.125O3
Nano-powder.
Embodiment 7
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Fe:Co=4:1:N (metal ion) is added after being dissolved in water in 3 mixing:N (organic compound)=1:7 tartaric acid, obtains quality
The chloride mixed solution raw material of a concentration of 180g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 240L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 750 DEG C, pyrolysis time 2.5s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1h in 1000 DEG C in roaster, obtains RE perovskite type LaFe0.75Co0.25O3
Nano-powder.
Embodiment 8
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Pr:
Fe:Co=4:3:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:5 tartaric acid, obtains quality
The chloride mixed solution raw material of a concentration of 220g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 260L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 800 DEG C, pyrolysis time 1.9s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.6h in 900 DEG C in roaster, obtains RE perovskite type
PrFe0.25Co0.75O3Nano-powder.
Embodiment 9
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Sr:Mn=4:1:N (metal ion) is added after being dissolved in water in 5 mixing:N (organic compound)=1:7 acetic acid, it is dense to obtain quality
Degree is the chloride mixed solution raw material of 260g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 500L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 850 DEG C, pyrolysis time 1.8s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1h in 900 DEG C in roaster, obtains RE perovskite type La0.75Sr0.25MnO3
Nano-powder.
Embodiment 10
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Sr:Co=3:2:N (metal ion) is added after being dissolved in water in 5 mixing:N (organic compound)=1:7 acetic acid, it is dense to obtain quality
Degree is the chloride mixed solution raw material of 190g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 400L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 750 DEG C, pyrolysis time 2.2s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 2h in 850 DEG C in roaster, obtains RE perovskite type La0.6Sr0.4CoO3It receives
Rice flour body.
Embodiment 11
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:Fe
=1:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:7 ethylenediamine, obtaining mass concentration is
The chloride mixed solution raw material of 200g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 400L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 850 DEG C, pyrolysis time 1.2s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 2h in 850 DEG C in roaster, obtains RE perovskite type LaFeO3Nano powder
Body.
Embodiment 12
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Cs:Fe=3:2:N (metal ion) is added after being dissolved in water in 5 mixing:N (organic compound)=1:6 ethylenediamine, obtains quality
The chloride mixed solution raw material of a concentration of 190g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 400L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 750 DEG C, pyrolysis time 2.2s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 2h in 850 DEG C in roaster, obtains RE perovskite type La0.6Cs0.4FeO3It receives
Rice flour body.
Embodiment 13
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Pb:Fe=4:1:N (metal ion) is added after being dissolved in water in 5 mixing:N (organic compound)=1:2 ammonium citrate, obtains matter
Measure the chloride mixed solution raw material of a concentration of 300g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 400L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 900 DEG C, pyrolysis time 1.5s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.7h in 900 DEG C in roaster, obtains RE perovskite type La0.8Pb0.2FeO3
Nano-powder.
Embodiment 14
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Cs:Al=1:1:N (metal ion) is added after being dissolved in water in 2 mixing:N (organic compound)=1:1.8 ammonium citrate, obtains
Mass concentration is the chloride mixed solution raw material of 300g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 400L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 900 DEG C, pyrolysis time 1.5s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.7h in 900 DEG C in roaster, obtains RE perovskite type La0.5Cs0.5AlO3
Nano-powder.
Embodiment 15
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio La:
Cs:Pb=2:1:N (metal ion) is added after being dissolved in water in 3 mixing:N (organic compound)=1:1.8 citric acid, obtains matter
Measure the chloride mixed solution raw material of a concentration of 260g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 300L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 800 DEG C, pyrolysis time 1.3s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.8h in 850 DEG C in roaster, obtains RE perovskite type
La0.67Cs0.33PbO3Nano-powder.
Embodiment 16
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Nd:
Cs:Pb=3:1:N (metal ion) is added after being dissolved in water in 4 mixing:N (organic compound)=1:1.8 oxalic acid, obtains quality
The chloride mixed solution raw material of a concentration of 260g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 220L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 780 DEG C, pyrolysis time 1.2s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 3h in 750 DEG C in roaster, obtains RE perovskite type Nd0.75Cs0.25PbO3
Nano-powder.
Embodiment 17
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Nd:
Co:Pb=4:3:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:1.8 citric acid, obtains matter
Measure the chloride mixed solution raw material of a concentration of 220g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 220L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 780 DEG C, pyrolysis time 1.2s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 3h in 950 DEG C in roaster, obtains RE perovskite type NdCo0.75Pb0.25O3
Nano-powder.
Embodiment 18
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Nd:
Fe:Cr=5:4:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:1 citric acid, obtains quality
The chloride mixed solution raw material of a concentration of 220g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 280L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 650 DEG C, pyrolysis time 6.2s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 2.5h in 970 DEG C in roaster, obtains RE perovskite type NdFe0.8Cr0.2O3
Nano-powder.
Embodiment 19
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Sm:
Fe:Co=5:2:N (metal ion) is added after being dissolved in water in 3 mixing:N (organic compound)=1:1 EDTA, it is dense to obtain quality
Degree is the chloride mixed solution raw material of 100g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 150L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 550 DEG C, pyrolysis time 9.5s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.5h in 900 DEG C in roaster, obtains RE perovskite type SmFe0.4Co0.6O3
Nano-powder.
Embodiment 20
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Eu:
Fe:Co=5:3:N (metal ion) is added after being dissolved in water in 2 mixing:N (organic compound)=1:1.2 EDTA, obtains quality
The chloride mixed solution raw material of a concentration of 200g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 200L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 750 DEG C, pyrolysis time 1.5s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 2.5h in 800 DEG C in roaster, obtains RE perovskite type EuFe0.6Co0.4O3
Nano-powder.
Embodiment 21
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Gd:
Mn:Al=3:2:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:1.5 EDTA, obtains quality
The chloride mixed solution raw material of a concentration of 20g/L；
(2) using air as carrier gas, chloride mixed solution is formed droplet by flow rate of carrier gas 7L/h by nozzle atomization,
Droplet is sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 450 DEG C, pyrolysis time 18s, after the completion of pyrolysis, using separation
Device carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1h in 1000 DEG C in roaster, obtains RE perovskite type GdMn0.67Al0.33O3
Nano-powder.
Embodiment 22
A kind of preparation method of perovskite type rare earth complex oxide, carries out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, by metallic element chloride according to stoichiometric ratio Gd:
Cs:Pb=3:2:N (metal ion) is added after being dissolved in water in 1 mixing:N (organic compound)=1:2 EDTA, it is dense to obtain quality
Degree is the chloride mixed solution raw material of 200g/L；
(2) using air as carrier gas, chloride mixed solution is formed mist by flow rate of carrier gas 170L/h by nozzle atomization
Drop, droplet are sprayed into from pyrolysis furnace bottom or top, and pyrolysis temperature is 750 DEG C, pyrolysis time 1.8s, after the completion of pyrolysis, are used
Separator carries out gas solid separation, and the gas of generation carries out recycling hydrochloric acid through tail gas absorber, obtains mixture solid；
(3) mixture solid is roasted into 1.5h in 900 DEG C in roaster, obtains RE perovskite type
GdCs0.67Pb0.33O3Nano-powder.
Claims (6)
1. a kind of preparation method of perovskite type rare earth complex oxide, which is characterized in that carry out according to the following steps：
(1) chemical composition for pressing perovskite composite oxide, the nonstoichiometric molar ratio of required metallic element chloride is mixed
It closes, organic compound is added after being dissolved in water, obtains chloride mixed solution raw material；
(2) using air or oxygen as carrier gas, chloride mixed solution is formed into droplet by nozzle atomization, droplet is from pyrolysis oven bottom
Portion or top spray into, and pyrolysis temperature is 300~1200 DEG C, and pyrolysis time is 0.1~20s, and after gas solid separation, it is solid to obtain mixture
Body；
(3) mixture solid is roasted into 0.5~12h in 500~1200 DEG C, obtains RE perovskite type nano-powder.
2. a kind of preparation method of perovskite type rare earth complex oxide according to claim 1, which is characterized in that described
In step 1, organic compound is one kind in carboxylic acid, and addition is n (metal ion):N (organic compound)=1:(0.1~
7)。
3. a kind of preparation method of perovskite type rare earth complex oxide according to claim 1, which is characterized in that described
In step 1, the mass concentration of chloride mixed solution is 5~360g/L.
4. a kind of preparation method of perovskite type rare earth complex oxide according to claim 1, which is characterized in that described
In step 2, flow rate of carrier gas is 1~12000L/h, and solution is blown into roaster by compressor and is roasted, during injection
Air velocity is 5~8000L/h.
5. a kind of preparation method of perovskite type rare earth complex oxide according to claim 1, which is characterized in that described
In step 2, after the completion of pyrolysis, the gas of generation carries out recycling hydrochloric acid through tail gas absorber.
6. a kind of preparation method of perovskite type rare earth complex oxide according to claim 1, which is characterized in that described
The general formula of perovskite type rare earth complex oxide prepared by method is REB1-xCxO3Or RE1-xBxCO3, wherein RE is rare earth element
La, Ce, Pr, Nd, Sm, Eu or Gd, B and C are same or different transition metal, alkali metal, alkaline-earth metal, 0≤x≤1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876792A (en) * | 2019-03-12 | 2019-06-14 | 聊城大学 | A kind of application method of perovskite composite oxides in photocatalytic hydrogen production by water decomposition |
| CN112844354A (en) * | 2020-12-23 | 2021-05-28 | 甄崇礼 | Process for producing perovskite compound |
| CN113637241A (en) * | 2021-09-07 | 2021-11-12 | 赛轮集团股份有限公司 | Rubber composition for tire steel wire belt and preparation method thereof |
| CN113860349A (en) * | 2021-10-27 | 2021-12-31 | 福建省长汀金龙稀土有限公司 | Method for preparing rare earth oxide powder in short-process green manner |
| CN114455638A (en) * | 2021-12-28 | 2022-05-10 | 天津巴莫科技有限责任公司 | Solid electrolyte material with high lithium ion diffusivity and preparation method thereof |
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| CN105905935A (en) * | 2016-04-26 | 2016-08-31 | 东北大学 | Method for preparing large-specific-surface-area rare earth oxides or composite oxides through spray pyrolysis |
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2018
- 2018-06-27 CN CN201810678665.6A patent/CN108751260A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105905935A (en) * | 2016-04-26 | 2016-08-31 | 东北大学 | Method for preparing large-specific-surface-area rare earth oxides or composite oxides through spray pyrolysis |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876792A (en) * | 2019-03-12 | 2019-06-14 | 聊城大学 | A kind of application method of perovskite composite oxides in photocatalytic hydrogen production by water decomposition |
| CN112844354A (en) * | 2020-12-23 | 2021-05-28 | 甄崇礼 | Process for producing perovskite compound |
| CN113637241A (en) * | 2021-09-07 | 2021-11-12 | 赛轮集团股份有限公司 | Rubber composition for tire steel wire belt and preparation method thereof |
| CN113637241B (en) * | 2021-09-07 | 2023-02-28 | 赛轮集团股份有限公司 | Rubber composition for tire steel wire belt and preparation method thereof |
| CN113860349A (en) * | 2021-10-27 | 2021-12-31 | 福建省长汀金龙稀土有限公司 | Method for preparing rare earth oxide powder in short-process green manner |
| CN114455638A (en) * | 2021-12-28 | 2022-05-10 | 天津巴莫科技有限责任公司 | Solid electrolyte material with high lithium ion diffusivity and preparation method thereof |
| CN114455638B (en) * | 2021-12-28 | 2023-11-10 | 天津巴莫科技有限责任公司 | Solid electrolyte material with high lithium ion diffusivity and preparation method thereof |
| CN116477671A (en) * | 2023-03-10 | 2023-07-25 | 华友新能源科技（衢州）有限公司 | Lithium battery material precursor, preparation method and application thereof |
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