Un-corrected proof 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 Preparation of Aluminum Hydroxide from Bauxite with Alkaline Additives

SHAKILA BEGUM , MAQSOOM H. SHAH AND MOHAMMAD NAUMAN Pakistan Council of Scientific and Industrial Research Laboratories, Jamrud Road, Peshawar, Pakistan.
(Received on 29th January 2011,accepted in revised form 22nd September 2011 ) Summary: The goal of the present investigation was to study the leach conditions of a low grade bauxite in the area of Khushab district, Pakistan for local production of Al (OH)3. The chemical composition was 56.04 % Al2O3, 15.77 % Fe2O3, 19.59 % SiO2 and 3.94 % TiO2. Emphasis was placed on the effect of (CaO/Na2CO3) additives, pH and precalcination temperature on the percent recovery of Al (OH)3 and the extraction of Al2O3 from bauxite. Bauxite with the alkaline additives was fired at 550, 750 and 950 Co. The extraction efficiency of Al2O3 increased noticeably (96.58 %, 97.00 % and 98.09 % ) at 550, 750 and 950 Co by leaching sodium aluminate in soda based liquor in an open system and precipitating Al (OH)3 with CO2 gas than in a reflux condensed system (73.82 %, 78.94 % and 84.28 %) and neutralizing the leach solution with acid. The Al2O3 was 90.57 %, 92.00 % and 94.16 % by precipitating Al (OH)3 from water based liquor with CO2 gas over similar temperatures and leaching period of 25 minutes. The feasible conditions of the process were the addition of alkaline in 60 % by weight, 750 to 950 Co, precalcination temperature, 2 hours of calcination time, 25 minutes of leaching time and precipitation of Al (OH)3 from water based liquor by carbonation.

Introduction The development of new methods for in Southern France, where it was first discovered in 59 preparation of Al (OH)3 has always been important, 1821 by the geologist Pierre Berthier [19, 20]. 60 because Al (OH)3 is of great practical significance. 61 62 Bauxite is strip mined because it is found at Bauxite has received considerable attention the surface, with little or no overburden. 63 especially as potential raw material for the production Approximately 95% of the world's bauxite 64 of Al (OH)3. In Pakistan large deposits of bauxite are production is processed into aluminum. Bauxites are 65 found in Khushab district. It is evident that these ores typically classified according to their intended 66 will gain worth for the production of aluminum commercial application: metallurgical, abrasive, 67 hydroxide, alumina and eventually, if viable, for cement, chemical and refractory. 68 metallic aluminum in future. Pakistan is inadequate 69 in these commercial grade chemicals and the country 70 The two types of bauxites that are used largely depends upon the import of these materials. commercially as aluminum ores are laterite and karst. 71 The choice of process technology and the market of Lateritic bauxites (silicate bauxites) are distinguished 72 production are mainly influenced by the quality of from karst bauxites (carbonate bauxites) [21]. 73 bauxite with regard to its impurities mainly iron. 74 75 Nanoparticles of Al2O3 have antibacterial Bauxite deposits from Khushab have very properties [22, 23]. 76 high iron and silica contents. Production of Al2O3 In this study, bauxite from Khushab has been selected 77 from bauxite has been the subject of interest of for evaluation largely because of its bulk availability. 78 several researchers [1 14]. Some of the 79 investigators have recovered Al2O3 by acid leaching Results and Discussion 80 [15 18]. However, the present beneficiation 81 processes are undertaken to remove low-grade Effect of Alkaline Additives 82 materials from bauxite and to add value to bauxite as 83 an industrial raw material for the production of Al 84 Increasing the content of soda increases the (OH)3 and Al2O3. 85 dissolution of bauxite. When only soda is added to 86 the bauxite, it facilitates the occurrence of sodium Bauxite is the most important aluminum ore. aluminum silicates (Na2O. Al2O3. 2SiO2) or 87 It consists largely of the minerals gibbsite Al (OH)88 camegites and it decreases Al2O3 extraction. Thus the 3, boehmite -AlO(OH) and diaspore -AlO(OH), dissolution rate of only SiO2 increases. When CaO is 89 together with the iron oxides goethite and hematite, added, SiO2 shows lower efficiency of dissolution as 90 the clay mineral kaolinite and small amounts of it results into the formation of calcium silicates 91 anatase TiO2. It was named after the village Les Baux (Fig. 1). So, the extraction of Al2O3 increases. The 92

Un-corrected proof 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56
addition of soda and calcium oxide convert iron, 57 silica and titania impurities into insoluble sodium and 58 calcium ferrates, silicates as well as sodium titanate. 59 CaO was selected as an additive because with lime 60 stone bauxite first forms alumino silicate. Thus 61 with the addition of lime stone the dissolution rate of 62 SiO2 increases and then alumino silicates convert to 63 sodium aluminate at high temperature, which 64 is soluble in alkaline solution and to dicalcium silicate 65 which is insoluble in the same solution. The effect of 66 alkaline additives on Al2O3 extraction from bauxite is 67 mentioned in detail in the recent literature [24]. 68 high dissolving power of Na2CO3. The percent recovery in (a) is less than (b & c) because in accordance with the procedures (b & c), in an open system, a substantial amount of organic contaminants and humic substances are vented out from the liquor, which are extracted into the liquor from bauxite during digestion, thereby improving the productivity of the process. Effect of Solution Concentration: As the alkaline aluminates are formed by solid states reactions in the solid phase (Fig. 1), the treated material dissolves easily in the 2.5 M Na2CO3 solution as well as in H2O. Effect of Particle Size Various particle size distributions do not influence the dissolution of SiO2 from bauxite into the leaching solution as no detectable silica was observed in the recovered Al (OH)3. Similarly, the extraction of Al2O3 from bauxite is also not affected by particle size as it increases consistently with temperature. Effect of pH: (a): The liquor containing sodium aluminates hydrolyses with the addition of HCl at room temperature as shown in equation 1

69 For the calcium aluminates, e.i. CaO. Al2O3 70 formed in the lime soda sintering, the leach solution 71 must contain high concentration of Na2CO3 for 72 maximum Al2O3 extraction. Therefore, Na2CO3 was 73 used as a lixiviant (a & b). However, procedure (c) 74 demonstrates that Al2O3 dissolution in Na2CO3 and 75 H2O are comparable. These results reveal that when 76 bauxite is calcined with the chosen alkaline additives 77 at high temperature, the liquor is moderately clear 78 and does not require further purification. The results 79 show that equal percent amounts of soda and calcium 80 oxide are needed to increase the dissolution of 81 bauxite and to improve the brightness of the product. 82 83 Effect of Calcination Temperature 84 85 As shown in Table-2, the extraction of 86 Al2O3 from bauxite increases with increasing 87 precalcination temperature. The degree of extraction 88 at 750 and 950 Co is higher than the lower 89 temperature range of the calcination. Sodium and 90 Calcium aluminates occur highly proficiently in the 91
solid phase during precalcination at 950 Co as seen in Fig. 1. Table-3 also indicates that the production of 92 Al (OH)3 increases with temperature.

NaAlO 2 + HCl + H 2 O Al (OH ) 3 + NaCl

[1] white

93 94 95 After the attainment of precalcination 96 temperature, the homogenous mixtures of bauxite 97 with alkaline additives were calcined for two hours 98 after which little enhancement occurs over longer 99
Effect of Calcination Time period of time. Effect of Leaching Time:

and aluminum hydroxide precipitate at pH 6. 0 0.1.

results

into

The relationship of aluminum hydroxide with alumina is presented in equation (2):

2 Al (OH ) Al O + 3H O 3 2 3 2

100

[2]

101 (a): The treated homogenous mixtures were (b): In this procedure alumina extracts as sodium 102 leached for two hours in Na2CO3 solution after aluminate into the basic liquour. 103 boiling. (b): The homogenous mixtures were stirred Al O + Na CO 2 NaAlO + CO for 25 minutes in hot Na2CO3 solution while in 2 3 2 3 2 2 [3] 104 procedure (c) the mixtures were agitated in hot H2O for 25 minutes. In procedure (b) almost all of the extractable Al2O3 goes into solution because of 105 the 2

Un-corrected proof

H F I K J F F C K J I A B I D E
E A

H A C D C
G

A. Hematite [Fe2O3] B. Alumina [-Al2O3] C. Soda [Na2CO3] D. Calcium Oxide [CaO] E. Dicalcium silicate [2CaO.SiO2] F. Sodium aluminate [NaAlO2] G. Sodium ferrate [NaFeO2] H. Calcium ferrate [CaO.Fe2O3] I`. Dicalcium ferrate [2CaO.Fe2O3] J. Sodium calcium aluminate [2Na2O.3CaO.5Al2O3] K. Camegite [Na2O.Al2O3.2SiO2] L. Sodium meta silicate [Na2O.SiO2] M. Sodium titanate [Na2O.TiO2]
M F F J I C G F

Intensity

1 2 3

2 Fig. 1: X-ray diffraction pattern of calcinated (at 950 Co) bauxite with CaO and Na2CO3 in 60 % by weight.

Un-corrected proof 1 Carbonation neutralizes the basicity and precipitates 51 2 gibbsite. 52 3 2 NaAlO 2 + CO + 3 H 2 O 2 Al (OH ) 3 + Na CO53 2 2 54 3 4 [4] 55 5 56 6 (c): The dissolution of the sodium aluminate is 57 7 believed to proceed as follows. 58 8 59 + 60 9 NaAlO2 + 2 H O Al (OH ) 4 + Na [5] 61 2 62 10 63 11 Al (OH ) 4 Al (OH ) + OH [6] 64 3 65 12 66 13 2(OH ) + CO CO3 + H O [7] 67 2 2 68 14 69 15 Characterization of Aluminum Hydroxide: 70 16 71 17 Table-3 shows that the impurities in the 72 o 18 recovered Al (OH)3 are minimal at 950 C . The 73 19 production aptitude of Al (OH)3 is also elevated at 74 20 high temperatures. 75 21 76 22 Experimental 77 23 78 24 Experiments were performed with 79 25 representative samples of bauxite from Khushab 80 26 district, Pakistan. The ore was ground to particle size 81 27 ranging from less than 300 m and was analyzed 82 28 chemically by standard methods of chemical analysis 83 29 [25]. The data of the Chemical Analysis are given in 84 30 Table-1. 85 31 86 32 Alkaline additives 87 33 88 34 The equivalent weight percents of alkaline 89 35 compounds (CaO and Na2CO3) were blended with 90 36 150 g bauxite by Siebtechnik grinding machine in 91 37 order to form aluminate, silicate, ferrate and titanate 92 38 (Table-2). 93 39 94 40 Calcination Temperature 95 41 96 42 The homogenous mixtures were fired at 550, 97 o 43 750 and 950 C in a graphite crucible for two hours 98 44 after the attainment of temperature in a tilting 99 45 temperature controlled furnace having natural gas100 as 46 a source of heat. The fired samples were allowed101 to 47 cool. The homogenous sintered mixtures were again 102 48 ground with the same machine and a X-ray 103 49 diffraction pattern was recorded for treated bauxite 104 o 50 fired at 950 C (Fig. 1). 105 106
A great deal of effort has been expended in intensifying gibbsite precipitation from sodium aluminate liquor and progress has been achieved. The sintered material was processed and gibbsite was precipitated by three different procedures to obtain the maximum extraction of Al2O3 and formation of Al (OH)3. (a): Leaching Time: At each temperature 110 g calcined material containing calculated amount of 50 g bauxite was leached for two hours at the boiling temperature to determine the optimum leaching time. Solution Concentration: The calcined samples above were leached in 500 mL of 2. 5 M Na2CO3 solution. The other investigators [24] leached it in NaOH containing Na2O. The leaching experiments were carried out in a pyrex flask equipped with a reflux condenser placed over a hot plate with a magnetic stirrer. The experimental results indicated that an amount of 60 % by weight of each alkaline additive (Na2CO3 and CaO) to the bauxite sample lead to a significantly clear sodium aluminate liquor. (b): 20 gm of homogenous calcined mixtures containing 9. 0 gm of bauxite fired at 550, 750 and 950 Co were stirred for 25 minutes in boiling solution of 2. 5 M Na2CO3 in an open system. (c): The same amount of mixtures at the given temperatures in process (b) was agitated for 25 minutes in boiling H20. Separation of Mixtures: After leaching in process (a) the mixtures were cooled and then rapidly centrifuged while in process (b) and (c) the mixtures were filtered to separate the clear liquor from the residual bauxite or red mud. Particle Size Bauxite ore was ground to less than 300 m. Each sample with various particle size distributions was calcined together with CaO and Na2CO3 at different temperatures and leached for two hours in 2. 5 M Na2CO3 solutions (a), stirred in 2.5 M hot Na2CO3 solution (b) and hot H2O (c). Precipitation of Al (OH) 3

Un-corrected proof 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 After separation the pH of the clear liquor 59 obtained was approximately 13.0. For the percent 60 recovery known amount of liquor was titrated using 61 6M HCl as a titrant. Small amount of titrant was 62 added and the solution was constantly stirred with 63 a magnetic stirrer. Al (OH)3 was precipitated from the 64 undiluted leach solutions by neutralizing with 65 hydrochloric acid to pH 6. 0 0.1. 66 67 The minor adjustment of pH was done with 68 1M HCl. The recovered Al (OH)3 was washed 69 several times to remove any traces of chlorides and 70 other impurities. 71 72 (b) and (c) 73 74 After filtration the precipitation in the clear 75 liquor obtained in processes (b) and (c), the modified 76 procedures, was done by bubbling CO2 gas through 77 the liquor. 78 79 The precipitated Al (OH)3 obtained from 80 each process was kept overnight to settle down. 81 It was filtered through whatman 42 filter paper and 82 dried in an oven at 100C0. 83 84 Characterization of Recovered Aluminum Hydroxide 85 86 In (a) 1.0001, 1.0157 and 1.0304 g of Al 87 (OH)3 recovered at 550, 750 and 950 Co were 88 dissolved in aqua regia while in processes (b) and (c) 89 0. 2 g Al (OH)3 was dissolved and the volumes were 90 made to 250 mL. The solutions were further diluted 91 and then analyzed by atomic absorption 92 spectrophotometer in order to calculate percentages 93 of Al2O3 (Table-2), percentages of Al(OH)3 and 94 presence of iron in the product (Table-3). Calcium 95 and sodium were determined by flame photometer. 96 No detectable SiO2 by gravimetric methods was 97 found. For chlorides the Al (OH)3 at different 98 temperatures was dissolved in nitric acid. Chlorides 99 were determined in the solutions by AgNO3 titration 100 method. No chlorides were found (Table-3). 101 102 103 Conclusion 104 The maximum extraction efficiency 105 of Al2O3 obtained in process (a) was 84.28 % and in106 (b & c) were 98.09 % and 94.16 % with precalcination 107 at 950 Co. The low grade bauxite containing high 108 content of SiO2 can be easily evaluated by this 109 process because with the addition of CaO, SiO2 110 shows lowest efficiency of dissolution. Though 111 procedure (b) provides the highest recovery, 112
(a) however, procedure (c) is preferred most feasible for industrial purposes. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Q. Wang, J. Deng, X. Liu, Q. Zhang, S. Sun, C. Jiang and F. Zhou, Journal of Asian Earth Sciences, 39, 6, 701 (2010). T. Salmi, D. Y. Murzin and J. A. Mensah, Hydrometallurgy, 102, 22 (2010). Q. Wang, J. Deng, Q. Zhang, S. Sun and J. Meng, Journal of Geochemical Exploration, 105, 137 (2010). L. Bao and A. V. Nguyen, Hydrometallurgy, 104, 86 (2010) X. Li, S. Gu, Z. Yin, G. Wu and Y. Zhai, Hydrometallurgy, 104, 313 (2010) G.M. Brodie, G. Power and C.F. Vernon, Hydrometallurgy, 104, 278 (2010) H. Zamanian and E. Hejazi, Journal of Geochemical Exploration, 107, 77 (2010) H. Grnman, T. Salmi, D. Y. Murzin and J. A. Mensah, Hydrometallurgy, 102, 22 (2010) Y. Li, Y. Zhang, C. Yang and Y. Zhang, Hydrometallurgy, 98, 52 (2009) S. h. M. Z. Wen, J. N. Chen and S. l. Zheng, Minerals Engineering, 22, 793 (2009) S. O. Lee, K. H. Jung, C. J. Oh, Y. H. Lee, T. Tran and M. J. Kim, Hydrometallurgy, 98, 156 (2009) Y. Zhang, S. Zheng, H. Du, H. Xu, S. Wang and Y. Zhang, Hydrometallurgy, 98, 38 (2009) S. Cao, Y. Zhang and Y. Zhang, Hydrometallurgy, 98, 298 (2009) W. Haipeng, S. Peter, I. Don, Xu, Bingan, Zhang, Jian, Zhang, Yao, Newcombe, Bianca, Wang, Xiaodong, Weng, Wubiao, T. Yuan, Wang, Kai and N. Yung, Australia Chemeca, 36, 1678 (2008) C. Bazin, K. El-Ouassiti and V. Ouelle, Hydrometallurgy, 88, 196 (2007) B. R. Reddy, S. K. Mishra and G. N. Banerjee, Hydrometallurgy, 51, 131 (1999) D. Ivan, C. Zivkovi, D Nada and S. trbac, Hydrometallurgy, 36, 247 (1994) G. Patermarakis and Y. Paspaliaris, Hydrometallurgy, 23, 77 (1989) Eastern Industries (2007), http://www.eastern.net.cn/Bauxite.html http://en.wikipedia.org/wiki/List_of_countries_b y_bauxite_production http://en.wikipedia.org/wiki/Bauxite_ore W. Jiang, H. Mashayekhi, B. Xing, Environmental Pollution, 157, 1619 (2009) I. M. Sadiq, B. Chowdhury, N. Chandrasekaran and A. Mukherjee, Journal of Nanomedicine,

15. 16. 17. 18. 19. 20. 21. 22. 23.

Un-corrected proof 1 Nanotechnology, Biology and Medicine, 5, 3, 2 282 (2009) 3 24. A. Alp and A. O. Aydin, Canadian Metallurgical 4 Quarterly, 51, 1, 41 (2002) 5 25. W. W. Scott and N. H. Furman, Sixth Edition, 6 Vol(1) The Elements, D. Van Mostrand 7 Company, Inc. Princeton, New Jersey, p. 68 8 (1962).

Un-corrected proof 1 2

Table-1: Chemical Analysis of Bauxite

Compound Loss on Ignition Al2O3 Fe2O3 SiO2 TiO2 Na2O % 01. 77 56.04 15.77 19. 59 3.94 0. 13 Compound CaO SO3 MgO K2O CO2 % 1.47 0.48 0. 54 0. 21 No traces

3 4 5 6

Table-2: Effect of Leaching Solutions on Extraction of Al2O3 at Different Precalcination Temperatures

Temperature Alkaline Additives in Co wt % % Al2O3* in recovered Al(OH)3 (a) % Al2O3* % Al2O3* in recovered in recovered Al(OH)3 Al(OH)3 (b) (c)

7 8 9 10 11 12 13 14 15 16 17

CaO Na2CO3 950 60 60 84. 28 98. 09 94. 16 750 60 60 78. 94 97. 00 92.00 550 60 60 73. 82 96. 58 90. 57 Conditions: (a): Homogenous mixture 110 g containing bauxite: 50 g: Na2CO3: 2.5 M, leached for two hours in a reflux condensed system (b): 20 gm of homogenous mixtures containing 9. 0 gm of bauxite, stirred for 25 minutes in boiling solution of 2. 5 M Na2CO3 in an open system (c): same amount as in (b), agitated for 25 minutes in boiling H2O. *Concentration of Al determined by atomic absorption spectrophotometer in the recovered Al(OH)3, presenting percent recovery from bauxite

Table-3: Characterization of the Produced Al (OH)3, (a), (b) and (c)

Al(OH)3 Al(OH)3 Al(OH)3 wt % wt % wt % (a) (b) (c) 950 72.60 84. 50 81. 12 750 68.00 83. 90 79. 90 550 63.61 83. 20 78.03 Conditions: (a): precipitated by HCl , (b) and (c): precipitated by carbonation Temperature Co % Fe2O3 in product Al(OH)3 0. 01 0. 01 0. 01 % Chlorides in product Al(OH)3 0. 00 0. 00 0. 00 % Calcium in product Al(OH)3 0.00 0.00 0.00 % Sodium in product Al(OH)3 9. 02 10. 00 11. 19

18