Process for the preparation of magnesia (MgO) from crude Mg (OH)2

Abstract

The process provides for the preparation of MgO from the reaction of magnesium salt and alkali/lime. The crude Mg(OH)2 is directly calcined and then treated with water to disintegrate the mass spontaneously to yield a slurry and dissolve away the soluble salts. This slurry is much easier to filter and wash than the original Mg(OH)2 slurry, which helps to speed up the purification operation and also conserve fresh water. Another important advantage of the present method is that even pasty or dough like reaction products that are processed using dough mixers and similar equipment can be worked up with ease. There is no compromise in the quality of MgO achieved in this manner.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are X-Ray Diffraction (XRD) analysis graphs of the MgO powder produced in Example 1;

FIG. 2 is an X-Ray Diffraction (XRD) analysis graph of the MgO powder produced in Example 5; and

FIGS. 3A, 3B and 3C are X-Ray Diffraction (XRD) analysis graphs of the crude and purified MgO powder produced in Example 6.

Claims

1. A process for the preparation of MgO, the process comprising the steps of: a. desulphating brine or bittern with CaCl2;b. evaporating the clarified brine/bittern after separation of gypsum to separate out the common salt and carnallite (KCl.MgCl2.6H2O);c. recovering MgCl2 rich and other salt free end bittern from step (b);d. evaporating the end bittern of step (c) to obtain crystalline MgCl2.6H2O;e. mixing MgCl2.6H2O with seeds of Mg(OH)2, followed by treating with alkali or hydrated lime/lime slurry to obtain by precipitation reaction a crude Mg(OH)2 paste/slurry;f. optionally filtering the resultant paste/slurry to obtain crude Mg(OH)2 and calcium chloride, or alternatively using crude Mg(OH)2 paste as such without filtration;g. drying the crude Mg(OH)2 paste, followed by calcining the crude Mg(OH)2 to convert Mg(OH)2 into MgO, and converting adhering MgCl2 into MgO and HCl gas;h. optionally treating the calcined mass of MgO with water to crumble the lumps and thereby dissolving calcium chloride and other soluble salts in water to obtain a MgO slurry;i. optionally filtering the MgO slurry, followed by washing the residue with water to make a wet cake substantially free from impurities;j. drying the resultant MgO and recalcining it to obtain a purified MgO; andk. using the CaCl2 solution filtrate obtained in steps (f) or (i), for desulphatation of brine or bittern in step (a) if lime is used in step (e).

2. A process as claimed in claim 1, wherein the bittern used in step (a) is obtained from ocean brine, sea brine, sub-soil brine or lake brine.

3. A process as claimed in claim 1, wherein the bitterns used in step (a) of claim 1 are desulphated in the density range of 29-32° Be′.

4. A process as claimed in claim 1, wherein the carnallite (KCl.MgCl2.6H2O) obtained in step (b) of claim 1 is crystallized between 32-36° Be′ either through solar or forced evaporation and the end bittern of step (c) of claim 1 having density of 35.5-36.0° Be′ comprises between 450-460 gL−1 of MgCl2, 5-10 gL−1 of NaCl, 5-10 gL−1 of KCl, 5-15 gL−1 of Ca, 0-5 gL−1 of sulphate, 6-7 gL−1 of Br−, and 0.02-0.04% B2O3.

5. A process as claimed in claim 1, wherein the end bittern of step (c) of claim 1 is debrominated to recover bromine and simultaneously reduces the Br− impurity in the debrominated bittern to less than 0.5 gL−1.

6. A process as claimed in claim 1, wherein the end bittern of step (c) of claim 1 is evaporated in step (d) of claim 1 to reduce the volume by 20-25% so as to crystallize out the MgCl2.6H2O in 60-80% yield.

7. A process as claimed in claim 1, further comprising recovering soluble magnesium from the bittern.

8. A process as claimed in claim 1, wherein the alkali used in step (e) of claim 1 is lime, caustic soda, ammonia, or combinations thereof.

9. A process as claimed in claim 1, wherein the lime used in step (e) of claim 1 is selected from quicklime, hydrated lime, dolime in solid or slurry form, or combinations thereof.

10. A process as claimed in claim 1, wherein the hydrated lime used in step (e) of claim 1 is prepared by slaking of quicklime followed by cycloning and dewatering to yield upgraded solid hydrated lime and lime water that can be reused for slaking of a fresh batch of quicklime.

11. A process as claimed in claim 1, wherein the stoichiometric equivalent of alkali used in step (e) of claim 1 is in the range of 0.8-1.0.

12. A process as claimed in claim 1, wherein the amount of Mg(OH)2 seed used in step (e) of claim 1 is in the range of 0-10% mole for mole of magnesium salt taken.

13. A process as claimed in claim 1, wherein the temperature of the precipitation reaction in step (e) of claim 1 is in the range of 20-120° C.

14. A process as claimed in claim 1, wherein a reaction time used in the precipitation reaction in step (e) of claim 1 is in the range of 5-90 minutes under intimate mixing conditions.

15. A process as claimed in claim 1, wherein the drying of the paste obtained in step (f) of claim 1 is carried out at 70-120° C. in conventional ovens or through solar drying.

16. A process as claimed in claim 1, wherein the calcination operation in step (g) of claim 1 is carried out at a temperature in the range of 500-1000° C.

17. A process as claimed in claim 16, wherein the temperature is in the range of 600-900° C.

18. A process claimed in claim 16, wherein the calcination operation is carried out in a muffle furnace or rotary calciner or vertical kiln depending on the physical form of the dry matter.

19. A process as claimed in claim 1, wherein the calcination operation in step (g) of claim 1 converts adhering MgCl2 into MgO with concomitant release of HCl vapour and CaCl2.2H2O into fused CaCl2 that is hydrated with release of heat and provides the driving force for the disintegration of the crude mass and also the rapid solubilisation of the CaCl2.

20. A process as claimed in claim 1, wherein the water used in step (h) of claim 1 comprises recycled washings from previous batches and the amount of water taken is sufficient to dissolve all soluble salts in the MgO, and wherein the temperature of the slurry is controlled at a temperature in the range of 40-90° C., for the higher solubility of salts such as CaCl2 at higher temperature and to minimize the hydrolysis of MgO.

21. A process as claimed in claim 20, wherein the temperature is controlled in the range of 55-65° C.

22. A process as claimed in claim 1, wherein the water used in steps (h) and (i) of claim 1 comprises additives to remove boron impurities in MgO.

23. A process as claimed in claim 1, wherein the washing and filtration operations of step (i) of claim 1 are expedited 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-á-vis Mg(OH)2.

24. A process as claimed in claim 1, wherein the requirement of water for purification of the calcined mass in step (i) of claim 1 is reduced by a factor of 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-á-vis Mg(OH)2.

25. A process as claimed in claim 1, wherein the wet cake obtained in step (g) of claim 1 is useful for the preparation of milk of magnesia.

26. A process as claimed in claim 1, wherein the wet cake obtained in step (i) of claim 1 is dried to yield MgO or recalcined at a temperature in the range of 500-2200° C. to obtain the desired product.

27. A process as claimed in claim 1, wherein the operations of steps (h) and (i) of claim 1 are not required when alkali used in step (e) is ammonia and the calcination operation of step (g) removes all impurities to yield highly pure MgO.

28. A process as claimed in claim 1, wherein the purity of MgO obtained is greater than 99%.