Porous ceramic products of titanium sub-oxides

Patent metadata

Field	Value
Publication number	US-10934218-B2
Application number	US-201716471152-A
Country	US
Kind code	B2
Filing date	Dec 20, 2017
Priority date	Dec 20, 2016
Publication date	Mar 2, 2021
Grant date	Mar 2, 2021

Abstract

Method for manufacturing porous products consisting essentially of titanium suboxide(s) of general formula TiOx, the value of x being between 1.6 and 1.9, the method including a) mixing the raw materials including at least one source of titanium dioxide, a reducing agent comprising carbon, b) forming the product, c) optionally, in particular when organic products are used during step a), thermal treatment under air or an oxidizing atmosphere, d) sintering, for example at a temperature above 1150° C. but not exceeding 1430° C., under a neutral or reducing atmosphere, in which the source of titanium dioxide consists of at least 55 wt % of anatase.

First claim

The invention claimed is:

1. A method of manufacturing a porous product consisting essentially of titanium suboxide(s) of general formula TiO x , the value of x being between 1.6 and 1.9, said method comprising:
a) mixing raw materials comprising at least one source of titanium dioxide, a reducing agent comprising carbon and optionally one or more organic products,
b) forming the product,
c) optionally, performing a thermal treatment under air or an oxidizing atmosphere at a temperature sufficient to allow removal of a high proportion of the one or more organic products and below the evaporation temperature of the reducing agent,
d) sintering at a temperature above 1150° C. but not exceeding 1430° C., under a neutral or reducing atmosphere,
in which the source of titanium dioxide consists of at least 55 wt % of anatase,
wherein
a distribution of pore diameters in the porous product is approximately monomodal,
the median diameter d 50 of the pores of the porous product is between 0.5 and 5 micrometers,
the open porosity of the porous product is above 34%, and
the porous product comprises more than 90 wt %, in total, of Magnéli phases selected from Ti 4 O 7 , Ti 5 O 9 , Ti 6 O 11 or a mixture of at least two of these phases.

2. The method of manufacture as claimed in claim 1 , in which the amount of reducing agent is adjusted in such a way that the porous product corresponds to the general formula TiOx, the value of x being between 1.6 and 1.9.

3. The method as claimed in claim 1 , in which the initial mixture comprises more than 90 wt % of anatase as the source of titanium dioxide.

4. The method as claimed in claim 1 , in which the reducing agent comprising carbon is selected from carbon black, cokes or any other organic compound comprising at least 50 wt % of carbon, or at least 70 wt % or even 80 wt % of carbon.

5. The method as claimed in claim 1 , in which the reducing agent is carbon black.

6. The method as claimed in claim 1 , in which the initial mixture comprises between 1.5 and 5.0 wt % of carbon, relative to the total weight of titanium dioxide.

7. The method as claimed in claim 1 , in which step d) is performed under a neutral atmosphere.

8. The method as claimed in claim 1 , in which step d) is performed under a reducing atmosphere.

9. The method as claimed in claim 1 , in which the mixture of raw materials comprises, by weight, at least 90% of titanium dioxide in the anatase form, and at least 3% of carbon black, and in which the sintering temperature is adjusted between 1300 and 1450° C.

10. The method as claimed in claim 1 , in which the porous product consists essentially of Magnéli phases selected from Ti 4 O 7 and/or Ti 5 O 9 .

11. The method as claimed in claim 1 , in which the initial mixture of raw materials comprises mineral material other than titanium dioxide, in an amount below 5.0% of the total mineral mass.

12. The method as claimed in claim 1 , in which the initial mixture of raw materials comprises mineral material other than titanium dioxide, said mineral material being selected from the group consisting of silica SiO 2 , the oxides Nb 2 O 5 or Ta 2 O 5 , V 2 O 5 , ZrO 2 or the oxides of Ba, Sr, Mn, Cr, Fe, the oxides of alkali metals or of alkaline-earth metals.

13. The method as claimed in claim 1 , wherein the one or more organic products are mixed with a solvent such as water.

14. The method as claimed in claim 13 , wherein the solvent is a water.

15. The method as claimed in claim 1 , wherein step c) is performed when the one or more organic products are used during step a).

16. The method of manufacture as claimed in claim 2 , in which the value of x being between 1.75 and 1.85.

17. The method as claimed in claim 9 , in which the sintering is done under a neutral atmosphere.

18. A porous product, wherein:
the material making up said product corresponds to the general formula TiO x , the value of x being between 1.6 and 1.9,
the distribution of pore diameters is approximately monomodal,
the median diameter d 50 of the pores is between 0.5 and 5 micrometers,
the open porosity is above 34%, and
the porous product comprises more than 90 wt %, in total, of Magnéli phases selected from Ti 4 O 7 , Ti 5 O 9 , Ti 6 O 11 or a mixture of at least two of these phases.

19. The porous product as claimed in claim 18 , in which the median diameter d 50 of the pores is between 1 and 2.5 micrometers.

20. The porous product as claimed in claim 18 , further comprising, in said porous product, a mineral material other than TiO x , in an amount below 5.0% of the total mineral mass, said additional mineral material being selected from silica SiO 2 , the oxides Nb 2 O 5 or Ta 2 O 5 , V 2 O 5 , ZrO 2 or the oxides of Ba, Sr, Mn, Cr, Fe, the oxides of alkali metals or of alkaline-earth metals.

Assignees

• Saint Gobain Ct Recherches

Inventors

• Raffy Stéphane
• Aubert Brice
• Urffer Daniel
• Marlin Samuel

Classifications

• C04B38/068 Primary

  Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons · CPC title

• C04B38/0074

  expressed as porosity percentage · CPC title

• C04B35/46

  based on titanium oxides or titanates (containing also zirconium or hafnium oxides, zirconates or hafnates C04B35/49) · CPC title

• C04B2235/3418

  Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint · CPC title

• C04B2235/3251

  Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof · CPC title