Cerium oxide powder and cerium oxide dispersion
View Patent ↗Cerium oxide powder having carbonate groups and made of crystalline primary particles containing cerium oxide and having carbonate groups on the surface and in a region close to the surface, and having a BET surface area of from 25 to 150 m 2 /g, a mean diameter of from 5 to 50 nm, a carbonate concentration in the region close to the surface decreasing inwardly from the surface, a carbon content due to carbonate groups on the surface of from 5 to 50% by area, a carbon content due to carbonate groups at a depth of about 5 nm in a region close to the surface of from 0 to 30% by area, a content of cerium oxide calculated as CeO 2 and based on the powder of at least 99.5% by weight and a content of organic and inorganic carbon of from 0.01 to 0.3% by weight. A dispersion containing this powder.
1. A cerium oxide powder, consisting of:
crystalline primary particles comprising cerium oxide and having carbonate groups on the surface of the crystalline primary particles and in a region close to the surface of the crystalline primary particles, wherein
the powder has a BET surface area of from 25 to 150 m 2 /g,
the crystalline primary particles have a mean diameter of from 5 to 50 nm,
the region close to the surface of the crystalline primary particles is about 5 nm deep from the surface of the crystalline primary particles,
the carbonate concentration in the region close to the surface of the crystalline primary particles decreases inwards from the surface on which the carbonate concentration is highest,
the carbon content due to the carbonate groups on the surface of the crystalline primary particles is from 5 to 50% by area and the carbon content in the region at a depth of about 5 nm from the surface of the crystalline primary particles is from 0 to 30% by area,
the content of cerium oxide, calculated as CeO 2 and based on the total weight of the powder, is at least 99.5% by weight and
the content of carbon, encompassing organic and inorganic carbon, is from 0.01 to 0.3% by weight, based on the total weight of the powder.
2. The cerium oxide powder according to claim 1 , wherein the primary particles are aggregated.
3. The cerium oxide powder according to claim 1 , wherein the at least 80% of the crystalline primary particles are aggregated.
4. The cerium oxide powder according to claim 1 , wherein the at least 95% of the crystalline primary particles are aggregated.
5. The cerium oxide powder according to claim 1 , wherein sodium is present in an amount of <5 ppm and chlorine is present in an amount of <20 ppm based on the total amount of the powder.
6. The cerium oxide powder according to claim 1 , having a BET surface area of from 30 to 100 m 2 /g.
7. A process for preparing a cerium oxide powder having carbonate groups, comprising:
forming an aerosol having a volume-based mean droplet diameter D 30 of from 30 to 100 μm, by atomizing at least one solution consisting of an organic solvent or a solvent mixture, and an oxidizable, organic cerium (III) compound dissolved therein with at least one atomization gas,
reacting the aerosol with an oxygen-containing gas at a reaction temperature of from 600° C. to 1,500° C., in a reaction chamber to form a reaction mixture comprising a mixture of a powder and one or more gaseous substances, wherein the mean residence time of the aerosol in the reaction chamber is from 0.1 s to 5 s;
cooling the reaction mixture after the reaction mixture leaves the reaction chamber by spraying water droplets having a mean volume-based droplet diameter of less than 100 μm into the reaction mixture; wherein the water droplets are prepared by mixing water with the reaction mixture in an amount according to equation I
m H2O =[cp liq *( T b −T 0 )+ dh v +cp g *( T e −T b )]/3,600 *Q (I)
where
Q=total combustion enthalpy of all starting materials in KW
m H2O =amount of H 2 O in kg/h required to achieve the end temperature T e
T 0 =inlet temperature of water
T b =boiling point of water at 1 bar
T e =end temperature
dh v =enthalpy of vaporization of water
cp liq =heat capacity of water at 50° C.
cp g =heat capacity of water vapour at 150° C., and
T 0 =5-50° C., T b =100° C., T e =200-400° C., dh v =2,256.7 kJ/kg, cp liq =4.181 kJ/kg*K and cp g =1.98 kJ/kg*K; and subsequently
separating the powder from the gaseous substances with a filter; and
wherein
the organic solvent is 2-ethylhexanoic acid and/or lauric acid,
the oxidizable, organic cerium (III) compound is a 2-ethylhexanoate and or laurate, and
a ratio of throughput of the cerium (III) solution/amount of atomization gas is from 0.5 to 5 kg/standard m 3 .
8. The process according to claim 7 , further comprising:
adding a fuel gas to the reaction mixture before or during the reacting.
9. The process according to claim 7 , wherein lambda is ≧1.5, wherein lambda is calculated from the sum of oxygen in (air+atomization gas)/sum of (cerium (III) compound+fuel gas), in each case in mol/h.
10. A cerium oxide powder having carbonate groups obtained by the process of claim 7 .
11. A dispersion comprising the cerium oxide powder according to claim 1 .
12. The dispersion according to claim 11 , comprising only the cerium oxide powder, water and optionally a pH regulator.
13. The dispersion according to claim 11 , comprising only the cerium oxide powder, water and a pH regulator.
14. The dispersion according to claim 11 , wherein the content of cerium oxide powder is from 0.5 to 60% by weight based on the total weight of the powder.
15. The dispersion according to claim 11 , having a pH of from 3 to 8.
16. The dispersion according to claim 11 , having a mean particle size d 50 , determined by means of dynamic light scattering, of less than 120 nm.
17. The dispersion according to claim 11 , having a mean particle size d 90 , determined by means of dynamic light scattering, of less than 200 nm.
18. The dispersion according to claim 11 , having a zeta potential of at least 20 mV.
19. A process comprising:
chemomechanically polishing a surface with a composition comprising the cerium oxide powder according to claim 1 .
20. A process comprising:
chemomechanically polishing a surface with the dispersion of claim 11 .
21. A catalyst comprising the cerium oxide powder according to claim 1 .
22. A UV absorber comprising the cerium oxide power according to claim 1 .
23. A toner comprising the cerium oxide powder according to claim 1 .
24. A fuel cell comprising the cerium oxide powder according to claim 1 .
25. The cerium oxide powder according to claim 1 , wherein the crystalline primary particles comprises at least 99% of cerium oxide based on the total weight of the crystalline primary particles.
26. A cerium oxide powder, comprising:
crystalline primary particles comprising cerium oxide and having carbonate groups on the surface of the crystalline primary particles and in a region close to the surface of the crystalline primary particles, wherein
the powder has a BET surface area of from 25 to 150 m 2 /g,
the crystalline primary particles have a mean diameter of from 5 to 50 nm,
the region close to the surface of the crystalline primary particles is about 5 nm deep from the surface of the crystalline primary particles,
the carbonate concentration in the region close to the surface of the crystalline primary particles decreases inwards from the surface on which the carbonate concentration is highest,
the carbon content due to the carbonate groups on the surface of the crystalline primary particles is from 5 to 50% by area and the carbon content in the region at a depth of about 5 nm from the surface of the crystalline primary particles is from 0 to 30% by area,
the content of cerium oxide, calculated as CeO 2 and based on the total weight of the powder, is at least 99.5% by weight and
the content of carbon, encompassing organic and inorganic carbon, is from 0.01 to 0.3% by weight, based on the total weight of the powder.
27. A polishing agent, comprising:
the dispersion of claim 11 ,
having a pH of 7 to 8 and having no surface active additive.
28. The cerium oxide powder according to claim 26 , obtained by a process comprising:
forming an aerosol having a volume-based mean droplet diameter D 30 of from 30 to 100 μm, by atomizing at least one solution consisting of an organic solvent or a solvent mixture, and an oxidizable, organic cerium (III) compound dissolved therein with at least one atomization gas,
reacting the aerosol with an oxygen-containing gas at a reaction temperature of from 600° C. to 1,500° C., in a reaction chamber to form a reaction mixture comprising a mixture of a powder and one or more gaseous substances, wherein the mean residence time of the aerosol in the reaction chamber is from 0.1 s to 5 s;
cooling the reaction mixture after the reaction mixture leaves the reaction chamber by spraying water droplets having a mean volume-based droplet diameter of less than 100 μm into the reaction mixture; wherein the water droplets are prepared by mixing water with the reaction mixture in an amount according to equation I
m H2O =[cp liq *( T b −T 0 )+ dh v +cp g *( T e −T b )]/3,600 *Q (I)
where
Q=total combustion enthalpy of all starting materials in KW
m H2O =amount of H 2 O in kg/h required to achieve the end temperature T e
T 0 =inlet temperature of water
T b =boiling point of water at 1 bar
T e =end temperature
dh v =enthalpy of vaporization of water
cp liq =heat capacity of water at 50° C.
cp g =heat capacity of water vapour at 150° C., and
T 0 =5-50° C., T b =100° C., T e =200-400° C., dh v =2,256.7 kJ/kg, cp liq =4.181 kJ/kg*K and cp g =1.98 kJ/kg*K; and subsequently
separating the powder from the gaseous substances with a filter; and
wherein
the organic solvent is 2-ethylhexanoic acid and/or lauric acid,
the oxidizable, organic cerium (III) compound is a 2-ethylhexanoate and or laurate, and
a ratio of throughput of the cerium (III) solution/amount of atomization gas is from 0.5 to 5 kg/standard m 3 .