Recycle of titanium diboride materials
View Patent ↗A method to recycle TiB2 articles, and in particular, a method to recycle a TiB2 feedstock including TiB2 articles and Ti-ore and/or Ti-slag by chlorination.
1. A method to produce a titanium product, comprising:
preparing a TiB2 feedstock; and
chlorinating the prepared TiB2 feedstock to produce a titanium chloride product wherein the chlorinating of the prepared TiB2 feedstock comprises chlorinating the prepared TiB2 feedstock with chlorine gas and coke under a reducing atmosphere.
2. The method of claim 1 , wherein the TiB2 feedstock comprises TiB2 articles, and the preparing of the TiB2 feedstock comprises crushing the TiB2 articles to a predetermined average TiB2 particle size or TiB2 particle size distribution.
3. The method of claim 2 , wherein the TiB2 articles comprise at least one of TiB2 armor products, TiB2 tool products, TiB2 coatings, TiB2 electrodes, and TiB2 powders.
4. The method of claim 3 , wherein the crushed TiB2 articles comprise at least one of sodium and fluorine residues.
5. The method of claim 3 , wherein the crushed TiB2 articles comprise no more than 2% sodium and fluorine residues.
6. The method of claim 2 , wherein the preparing of the TiB2 feedstock further comprises combining the TiB2 articles with at least one of Ti-containing ores and Ti-slag.
7. The method of claim 3 , wherein preparing of the TiB2 feedstock further comprises crushing the combination of TiB2 articles with at least one of Ti-containing ores and Ti-slag to a predetermined average particle size or particle size distribution to prepare the TiB2 feedstock.
8. The method of claim 7 , wherein the Ti-containing ore comprises Ilmenite.
9. The method of claim 8 , wherein the Ti-containing ore comprises has a TiO2 content of at least 80% by weight.
10. The method of claim 9 , wherein the Ti-slag comprises smelting products of ilmenite ore processed to lower the iron content thereof.
11. The method of claim 10 , wherein the Ti-slag has a TiO2 content of at least 85%.
12. The method of claim 11 , wherein the TiB2 feedstock comprises no more than 10% TiB2 articles.
13. The method of claim 12 , wherein the TIB2 feedstock comprises impurities.
14. The method of claim 13 , wherein the impurities comprise at least one of Fe, Ni, Co, W, NA, F, Al, Li, Mg, Ca, Cl, halide salts, borates, and combinations thereof.
15. The method of claim 14 , wherein the impurities comprise residual salts, residual electrolytic bath, sodium-containing materials, calcium-containing materials, and fluoride containing materials.
16. The method of claim 1 , wherein the chlorinating of the prepared TiB2 feedstock comprises chlorinating the prepared TiB2 feedstock with chlorine gas and coke at above 700° C.
17. The method of claim 1 , wherein the chlorinating of the prepared TiB2 feedstock comprises chlorinating the prepared TiB2 feedstock with chlorine gas and coke at under 900° C.
18. The method of claim 15 , wherein the chlorinating of the prepared TiB2 feedstock comprises chlorinating the prepared TiB2 feedstock through a fluidized bed chlorinator at between 900° C. and 1000° C.
19. The method of claim 1 , wherein the chlorinating of the prepared TiB2 feedstock comprises chlorinating the prepared TiB2 feedstock with chlorine gas and coke at under 900° C.
20. The method of claim 1 , wherein the chlorinating of the prepared TiB2 feedstock comprises chlorinating the prepared TiB2 feedstock with chlorine gas and coke at under 800° C.
21. The method of claim 1 , wherein the chlorinating of the prepared TiB2 feedstock comprises chlorinating the prepared TiB2 feedstock with chlorine gas and coke at under 700° C.
22. The method of claim 1 , further comprises producing a titanium chloride product and a boron chloride product.
23. The method of claim 15 , wherein the prepared TiB2 feedstock is consumed through chlorination and substantially transformed into titanium chloride vapor.
24. The method of claim 1 , further comprising:
purifying the chlorinated TiB2 feedstock to remove by-products.
25. The method of claim 22 , further comprising:
purifying the titanium chloride product to remove by-products.
26. The method of claim 24 , wherein the purifying of the chlorinated TiB2 feedstock comprises separating low, medium, and high boiling chlorides via fractional distillation.
27. The method of claim 26 , wherein the purifying of the chlorinated TiB2 feedstock further comprises separation of non-chloride compounds or slag.
28. The method of claim 27 , further comprising:
reacting the titanium chloride product to produce a TiB2 product.
29. The method of claim 28 , wherein the reacting the titanium chloride product comprises:
oxidizing the titanium chloride product to produce a titanium oxide product; and
reacting the titanium oxide product via a carbothermic reaction to produce the TiB2 product.
30. The method of claim 29 , wherein the reacting of the titanium oxide product via a carbothermic reaction to produce the TiB2 product comprises adding a boron oxide product to the carbothermic reaction.
31. The method of claim 30 , wherein the oxidizing of the titanium chloride product comprises adding additional titanium chloride to the prepared TiB2 feedstock during the chlorinating to produce the titanium chloride product.
32. The method of claim 31 , further comprising recovering chlorine from the oxidizing of the titanium chloride product, and directing the recovered chlorine for use during the chlorinating of the prepared TiB2 feedstock to produce the titanium chloride product.
33. The method of claim 25 , further comprising:
reacting the titanium chloride product and the boron chloride product to produce a TiB2 product.
34. The method of claim 33 , wherein the reacting the titanium chloride product comprises:
oxidizing the titanium chloride product and the boron chloride product to produce a titanium oxide product and a boron oxide product; and
reacting the titanium oxide product and the boron oxide product via a carbothermic reaction to produce the TiB2 product.
35. The method of claim 34 , wherein no significant amount of titanium chloride product or boron chloride product is added.
36. The method of claim 35 , wherein the reacting of the titanium oxide product via a carbothermic reaction to produce the TiB2 product does not require adding a boron oxide product to the carbothermic reaction.