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1. WO2021042212 - NANOPARTICULES D'OXYDE DE CALCIUM STABILISÉES PAR DE LA ZIRCONE POUR LA CAPTURE DE CO2 À DES TEMPÉRATURES ÉLEVÉES

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CLAIMS

1. A method of synthesizing a zirconium-stabilized calcium oxide nanoparticle sorbent, comprising:

a) forming a calcium oxide nanoparticle by treating calcium compounds in a calcium compound treatment comprising:

i) dissolving a calcium alkoxide in a mixed aromatic and alcoholic solvent to form a calcium alkoxide solution;

ii) adding water to the calcium alkoxide solution to form a liquid calcium hydroxide alcogel;

iii) drying the calcium hydroxide alcogel, to provide a calcium oxide nanoparticle composition; and,

b) admixing a zirconium compound with one or more of the calcium compounds in the calcium compound treatment, to form the zirconium-stabilized calcium oxide nanoparticle sorbent;

wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a BET surface area of at least 100 m2/g, an average particle size of between 100 and 500 nm, and a carbon dioxide capture capacity of at least 10 mole/kg sorbent.

2. The method of claim 1 , wherein the calcium alkoxide has the formula (RO)3Ca, and wherein each R is a straight chain alkyl group.

3. The method of claim 2, wherein each R is a methyl or ethyl group.

4. The method of any one of claims 1 to 3, wherein the zirconium compound is a zirconium alkoxide.

5. The method of claim 4, wherein the zirconium alkoxide is zirconium(IV) ethoxide (Zr(ethoxide)4), zirconium(IV) propoxide (Zr(propoxide)4) or zirconium(IV) tertiary butoxide (Zr(t-Butoxide)4).

6. The method of any one of claims 1 to 3, wherein admixing the zirconium compound comprises one or more of (1 ) mixing a zirconium stabilizer precursor with the calcium alkoxide in step (i) or (ii), so that the liquid calcium hydroxide alcogel comprises zirconium; or, (2) incipient wetness impregnation (IWI) of the calcium oxide nanoparticle composition with a zirconium stabilizer precursor solution; or (3) shelling the calcium oxide nanoparticle composition surface, before or after calcining the calcium oxide nanoparticle composition, in a core-shell treatment with a core-shell surfactant.

7. The method of claim 6, wherein the zirconium stabilizer precursor is a zirconium alkoxide.

8. The method of claim 7, wherein the zirconium alkoxide is zirconium(IV) ethoxide (Zr(ethoxide)4), zirconium(IV) propoxide (Zr(propoxide)4) or zirconium(IV) tertiary butoxide (Zr(t-Butoxide)4).

9. The method of any one of claims 6 to 8, wherein mixing the zirconium stabilizer precursor with the calcium alkoxide in step (i) or (ii), comprises dissolving the zirconium stabilizer precursor in the mixed aromatic and alcoholic solvent.

10. The method of claim 6, wherein shelling comprises adding a mesoporous zirconia to calcined calcium oxide nanoparticles by the core-shell treatment using the core-shell surfactant.

11.The method of claim 6 or 10, wherein the core-shell surfactant is P 123 or TMA.

12. The method of any one of claims 1 to 11, wherein admixing the zirconium compound comprises adding zirconium tertiary butoxide to calcium methoxide in the mixed aromatic and alcoholic solvent.

13. The method of claim 12, wherein zirconium tertiary butoxide and calcium methoxide are added to the mixed aromatic and alcoholic solvent in a ratio of 0.05-0.1 moles of Zr(t-Butoxide)4 per mole of Ca(CH30)2.

14. The method of any one of claims 1 to 13, wherein adding water comprises adding 2-5 moles of H2O per mole of calcium alkoxide.

15. The method of any one of claims 1 to 14, further comprising mixing the calcium hydroxide alcogel for an alcogel aging period to provide an aged alcogel and drying the calcium hydroxide alcogel comprises drying the aged alcogel.

16. The method of any one of claims 1 to 15, wherein the calcium alkoxide solution comprises zirconium in an opaque slurry.

17. The method of any one of claims 1 to 16, wherein the liquid calcium hydroxide alcogel comprises zirconium and is clear and colorless.

18. The method of any one of claims 1 to 17, wherein drying the calcium hydroxide alcogel comprises supercritical drying and vacuum dehydration.

19. The method of any one of claims 1 to 17, wherein the calcium hydroxide alcogel comprises zirconium and drying the calcium hydroxide alcogel comprises a thermal dehydration of zirconium-calcium hydroxide nanoparticles to provide dehydrated zirconium-calcium hydroxide nanoparticles.

20. The method of claim 19, wherein the thermal dehydration is carried out at least partially under a dehydrating vacuum pressure.

21. The method of claim 19 or 20, wherein the thermal dehydration is carried out at a dehydration temperature of at least 450°C.

22. The method of any one of claims 19 to 21, further comprising calcining the dehydrated zirconium-calcium hydroxide nanoparticles to provide a calcined mixed zirconia-calcium oxide sorbent.

23. The method of claim 22, wherein calcining is carried out at a temperature of at least 850°C.

24. The method of any one of claims 1 to 23, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity of at least 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 5 mole/kg sorbent.

25. The method of any one of claims 1 to 24, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity that loses no more than 10, 9, 8, 7, 6, 5, 4, 3 or 2% carbon dioxide capture capacity after 20 cycles.

26. The method of any one of claims 1 to 25, wherein active CaO conversion by carbon dioxide capture of the zirconium-stabilized calcium oxide nanoparticle sorbent is at least 90, 91 , 92, 93, 94, 95, or 96% in a first carbon capture cycle.

27. The method of any one of claims 1 to 26, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a BET surface area of at least 140 m2/g, 150 m2/g, 160 m2/g, 170 m2/g, 180 m2/g or 190 m2/g.

28. The method of any one of claims 1 to 27, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has an average particle size of less than 500nm,

400 nm, 350nm, 300nm, 250nm, 200nm, 150nm, 100nm or 90nm.

29. The method of any one of claims 1 to 28, further comprising pelletizing the zirconium-stabilized calcium oxide nanoparticle sorbent, to provide a pelletized zirconium-stabilized calcium oxide nanoparticle sorbent.

30. The zirconium-stabilized calcium oxide nanoparticle sorbent produced by the method of any one of claims 1 to 28, or the pelletized zirconium-stabilized calcium oxide nanoparticle sorbent produced by the method of claim 29.

31. Use of the zirconium-stabilized calcium oxide nanoparticle sorbent produced by the method of any one of claims 1 to 28 as a carbon dioxide sorbent.

32. Use of the pelletized zirconium-stabilized calcium oxide nanoparticle sorbent of claim 29, as a carbon dioxide sorbent in a fixed-bed calcium looping process.

33. Use of a zirconium-stabilized calcium oxide nanoparticle composition as a carbon dioxide sorbent, wherein the composition comprises intermixed zirconium and calcium oxide nanoparticles in a solid zirconium-calcium oxide sorbent having a BET surface area of at least 100 m2/g with average particle size of between 100 and 500 nm.

34. The use according to claim 33, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity of at least 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 5 mole/kg sorbent.

35. The use according to claim 33 or 34, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity that loses no more than 10, 9, 8, 7, 6, 5, 4, 3 or 2% carbon dioxide capture capacity after 20 cycles.

36. The use according to any one of claims 33 to 35, wherein active CaO conversion by carbon dioxide capture of the zirconium-stabilized calcium oxide

nanoparticle sorbent is at least 90, 91 , 92, 93, 94, 95, or 96% in a first carbon capture cycle.

37. The use according to any one of claims 33 to 36, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a BET surface area of at least 140 m2/g, 150 m2/g, 160 m2/g, 170 m2/g, 180 m2/g or 190 m2/g.

38. The use according to any one of claims 33 to 37, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has an average particle size of less than 500nm, 400 nm, 350nm, 300nm, 250nm, 200nm, 150nm, 100nm or 90nm.

39. A method of adsorbing carbon dioxide, comprising exposing a carbon dioxide gas to a zirconium-stabilized calcium oxide nanoparticle composition, wherein the composition comprises intermixed zirconium and calcium oxide nanoparticles in a solid zirconium-calcium oxide sorbent having a BET surface area of at least 100 m2/g with average particle size of between 100 and 500 nm.

40. The method of claim 39, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity of at least 5, 6, 7, 8, 9, 10,

11, 12, 13, 14 or 5 mole/kg sorbent.

41. The method of claim 39 or 40, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity that loses no more than 10, 9, 8, 7, 6, 5, 4, 3 or 2% carbon dioxide capture capacity after 20 cycles.

42. The method of any one of claims 39 to 41 , wherein active CaO conversion by carbon dioxide capture of the zirconium-stabilized calcium oxide nanoparticle sorbent is at least 90, 91 , 92, 93, 94, 95, or 96% in a first carbon capture cycle.

43. The method of any one of claims 39 to 42, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a BET surface area of at least 140 m2/g, 150 m2/g, 160 m2/g, 170 m2/g, 180 m2/g or 190 m2/g.

44. The method of any one of claims 39 to 43, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has an average particle size of less than 500nm, 400 nm, 350nm, 300nm, 250nm, 200nm, 150nm, 100nm or 90nm.

45. The method of any one of claims 39 to 44, wherein the sorbent reversibly adsorbs CO2 at 650-700 °C to form CaC03.

46. The method of claim 45, wherein the sorbent is regenerated from CaC03 at 850-900°C with the release of CO2.

47. A zirconium-stabilized calcium oxide nanoparticle composition, wherein the composition comprises intermixed zirconium and calcium oxide nanoparticles in a solid zirconium-calcium oxide sorbent having a BET surface area of at least 100 m2/g with average particle size of between 100 and 500 nm.

48. The composition of claim 47, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity of at least 5, 6, 7, 8, 9, 10,

11, 12, 13, 14 or 5 mole/kg sorbent.

49. The composition of claim 47 or 48, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a carbon dioxide capture capacity that loses no more than 10, 9, 8, 7, 6, 5, 4, 3 or 2% carbon dioxide capture capacity after 20 cycles. 50. The composition of any one of claims 47 to 49, wherein active CaO conversion by carbon dioxide capture of the zirconium-stabilized calcium oxide nanoparticle sorbent is at least 90, 91 , 92, 93, 94, 95, or 96% in a first carbon capture cycle.

51. The composition of any one of claims 47 to 50, wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has a BET surface area of at least 140 m2/g, 150 m2/g, 160 m2/g, 170 m2/g, 180 m2/g or 190 m2/g.

52. The composition of any one of claims 47 to 51 , wherein the zirconium-stabilized calcium oxide nanoparticle sorbent has an average particle size of less than 500nm, 400 nm, 350nm, 300nm, 250nm, 200nm, 150nm, 100nm or 90nm.

53. The composition of any one of claims 47 to 52, wherein the sorbent reversibly adsorbs CO2 at 650-700 °C to form CaC03.

54. The composition of claim 53, wherein the sorbent is regenerated from CaC03 at 850-900°C with the release of CO2.