Mixed oxide composite comprising calcium oxide and tricalcium aluminate

Patent metadata

Field	Value
Publication number	US-12053759-B2
Application number	US-201917285789-A
Country	US
Kind code	B2
Filing date	Oct 14, 2019
Priority date	Oct 15, 2018
Publication date	Aug 6, 2024
Grant date	Aug 6, 2024

Abstract

The invention relates to a composite oxide comprising CaO stabilised by Ca 3 AI 2 O 6 (C3A), wherein the composite is in the form of particles. The mixed oxide composite is useful as a catalyst in the transesterification of triglycerides, e.g. in the production of biodiesel. Calcium leaching is more hindered in CaO—Ca 3 AI 2 O 6 (2Ca/AI) than in CaO-AI 2 O 3 .

First claim

The invention claimed is:

1. A mixed oxide composite comprising CaO and Ca 3 Al 2 O 6 , wherein the composite is in the form of particles, wherein the particles are supported on a porous support.

2. A mixed oxide composite according to claim 1 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is greater than 50 wt % of the total weight of the composite.

3. A mixed oxide composite according to claim 1 , comprising CaO in an amount of from 10 to 75 wt % based on the total weight of CaO and Ca 3 Al 2 O 6 .

4. A mixed oxide composite according to claim 1 , wherein the particles have an average size of from 10 nm to 100 μm.

5. A mixed oxide composite according to claim 1 , wherein the particles are moulded so as to form a self-supporting structure.

6. A mixed oxide composite according to claim 1 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is greater than 60 wt % of the total weight of the composite.

7. A mixed oxide composite according to claim 1 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is greater than 70 wt % of the total weight of the composite.

8. A mixed oxide composite according to claim 1 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is greater than 80 wt % of the total weight of the composite.

9. A mixed oxide composite according to claim 1 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is greater than 90 wt % of the total weight of the composite.

10. A mixed oxide composite according to claim 1 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is greater than 95 wt % of the total weight of the composite.

11. A mixed oxide composite according to claim 1 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is greater than 97 wt % of the total weight of the composite.

12. A mixed oxide composite according to claim 1 , comprising CaO in an amount of from 25 to 75 wt based on the total weight of CaO and Ca 3 Al 2 O 6 .

13. A mixed oxide composite according to claim 1 , comprising CaO in an amount of from 35 to 70 wt % based on the total weight of CaO and Ca 3 Al 2 O 6 .

14. A mixed oxide composite according to claim 1 , wherein the particles are moulded so as to form a honeycomb structure.

15. A method for preparing a mixed oxide composite, said method comprising:
(a) heating an aqueous solution comprising (i) aluminium nitrate or aluminium nitrate hydrate, (ii) calcium nitrate or calcium nitrate hydrate, and (iii) an organic fuel until the solution combusts to form a powder; and
(b) calcining the powder at a temperature of from 1000° C. or higher.

16. A method according to claim 15 , wherein step (a) comprises heating the aqueous solution comprising aluminium nitrate or aluminium nitrate hydrate, calcium nitrate or calcium nitrate hydrate and an organic fuel so as to evaporate water and form a gel, followed by heating the gel until it combusts to form a powder.

17. A method according to claim 15 , wherein the organic fuel is ethylene glycol, citric acid, urea, glycine, sucrose or mixtures thereof.

18. A method according to claim 17 , wherein the organic fuel is a mixture of ethylene glycol and citric acid.

19. A method according to claim 18 , comprising:
(a) diluting Ca(NO 3 ) 2 ·4H 2 O and Al(NO 3 ) 2 ·9H 2 O in deionised water with ethylene glycol and citric acid to form an aqueous solution; heating the solution under stirring at a temperature of 100° C. so as to evaporate the water and form a gel; heating the gel to a temperature of from 250 to 500° C. so as to combust the gel and form a powder; and
(b) calcining the powder at a temperature of from 1000 to 1300° C. for 2 to 12 hours.

20. A mixed oxide composite obtained by the method of claim 15 .

21. A method of activating a mixed oxide composite comprising CaO and Ca 3 Al 2 O 6 , comprising heating a C1 to C4 alcohol with glycerol in the presence of the mixed oxide composite so as to form calcium diglyceroxide.

22. An activated mixed oxide composite obtained by the method of claim 21 .

23. A method for producing fatty acid alkyl esters comprising reacting a feedstock comprising fatty acid monoglycerides, diglycerides or triglycerides with a C1 to C4 alcohol in the presence of a mixed oxide composite comprising CaO and Ca 3 Al 2 O 6 , or an activated mixed oxide composite according to claim 22 .

24. A method according to claim 23 , wherein the feedstock comprises a plant oil or an animal fat or oil.

25. A method according to claim 23 , wherein the process further comprises recovering the mixed oxide composite from the reaction mixture.

26. A method according to claim 25 , wherein recovering the mixed oxide composite from the reaction mixture comprises separating the composite from the reaction mixture, washing and drying the composite and, wherein the method further comprises reusing the composite for producing fatty acid alkyl esters.

27. A method according to claim 23 , wherein the feedstock comprises fatty acid triglycerides.

28. A method according to claim 23 , wherein the alcohol is methanol or ethanol.

29. A method for the transesterification of monoglycerides, diglycerides or triglycerides comprising the steps of:
heating a mixture of C1-C4 alcohol, glycerol and a mixed oxide catalyst comprising CaO and Ca 3 Al 2 O 6 , so as to form at least calcium diglyceroxide;
contacting the calcium diglyceroxide with monoglycerides, diglycerides or triglycerides; and
transesterifying the monoglycerides, diglycerides or triglycerides.

30. A mixed oxide composite comprising CaO and Ca 3 Al 2 O 6 , wherein the amount of CaO and Ca 3 Al 2 O 6 in the composite is 100 wt % of the total weight of the composite.

31. A mixed oxide composite comprising CaO and Ca 3 Al 2 O 6 , wherein the composite is a uniformly dispersed mixture of CaO and Ca 3 Al 2 O 6 .

Assignees

• Univ Court Univ St Andrews

Inventors

• Irvine John Thomas Sirr
• Bonaccorso Alfredo
• Papargyriou Despoina

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J2235/10

  Infrared [IR] · CPC title

• B01J35/57

  Honeycombs · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title