ARTICLE IN PRESS

Journal of Crystal Growth 267 (2004) 372–379

Crystallization of calcium sulfate dihydrate under simulated conditions of phosphoric acid production in the presence of aluminum and magnesium ions
M.M. Rashad*, M.H.H. Mahmoud, I.A. Ibrahim, E.A. Abdel-Aal
Material Science Department, Central Metallurgical Research & Development Institute, P.O. Box 87, Helwan, Cairo 11421 Egypt Received 15 March 2004; accepted 27 March 2004 Communicated by T.F. Kuech

Abstract The effect of Al3+ and Mg2+ ions, as additives, on the crystallization of gypsum was studied under simulated conditions of the phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 C, and the turbidity of the reaction mixture was measured at different time periods to calculate the induction time of gypsum crystals formation. Addition of Al3+ ions up to 2% decreased the induction time and increased the growth efficiency while addition of Mg2+ increased the induction time and decreased the growth efficiency compared with in absence of additives. Interestingly, the crystals mean and median diameters were found to increase in the presence of Al3+ and decrease in the presence of Mg2+. The surface energy increased with Al3+ and decreased with Mg2+ compared to the baseline (without additives). Gypsum morphology changed from needle-like type in absence of additives to thick-rhombic in the presence of Al3+ ions. r 2004 Elsevier B.V. All rights reserved.
Keywords: A1. Crystallization; A1. Impurities; A1. Induction time; B1. Gypsum; B1. Phosphoric acid

1. Introduction Crystallization of calcium sulfate dihydrate plays a very important role in phosphoric acid production by the wet process. The increase of gypsum crystals growth means increase in the filtration rate of gypsum, i.e., increase in the
*Corresponding author. Tel.: +2025010642; fax: +2025010639. E-mail address: rashad133@yahoo.com (M.M. Rashad).

productivity of phosphoric acid. The phosphate rocks contain some aluminum but the content varies widely from 1% to 3% as Al2O3. On the other hand, most phosphate rocks contains about 0.2–0.6% of magnesium expressed as MgO but high dolomitic phosphate rocks up these values to 2%. The effect of aluminum and magnesium ions on the crystallization of gypsum is not clear. The presence of aluminum in phosphoric acid has a positive influence on the crystal habits, size and consequently filterability [1,2]. Aluminum is said

0022-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jcrysgro.2004.03.060

ARTICLE IN PRESS
M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372–379 373

to promote regular crystal growth in all directions by yielding much thicker crystals. This reduces the surface to volume ratio of the crystals and hence improving the filtration rate [3–5]. Budz et al. [6] showed that aluminum reduces the nucleation and growth rates of gypsum but promoted the agglomeration of the smaller crystals. In case of magnesium, It is believed that magnesium ions hinder the gypsum filtration by either increasing the viscosity of the filtrate or affecting the gypsum crystal size [1,2]. However, wet process phosphoric acid could be produced from high MgO phosphate rock by accepting a weaker filter acid, higher filtration temperature and thinner gypsum cake thickness [7,8]. Li et al. [9] showed that the presence of magnesium ions alone decreased the crystal length of gypsum crystals. On the other hand, Lin et al. [10] showed that the presence of Mg and Fe together during the reaction of calcium monohydrogen phosphate with sulfuric acid at 60 C increased the width of gypsum crystals. The present research aims at study the primary nucleation of gypsum under conditions simulating the production of phosphoric acid with and without addition of Al2O3 and MgO using pure chemicals (calcium hydrogen phosphate and sulfuric acid in phosphoric acid medium).

Reaction and crystallization: The following solutions were prepared: Solution (1): 27.5% P2O5/2.5% H2SO4. Solution (2): 20% P2O5. Solution (3): 32.5% H2SO4. A 500 ml of solution [1] was heated to 80 C in a 1000 ml Pyrex three-neck bottle, using a thermostatically controlled water bath. The calculated amount of calcium hydrogen phosphate was dissolved in a 100 ml of solution [2] which added to the heated solutions. The desired amounts of solution [3] and a 50 ml of deionized water containing aluminum and magnesium were also added. The reaction was maintained at 80 C with constant agitation at 550 rpm. These conditions simulate the DH process for phosphoric acid production. Turbidity measurements: Samples of the reaction mixture were withdrawn at different time intervals to measure the turbidity during the course of the reaction using a digital direct reading turbidimeter (Orbeco-Hellige, USA). Average two readings of two samples are taken and plotted. Crystal size distribution: At the end of the experiment (when the turbidity of the solution first exceeded 1000 NTU), about 5 ml of the reaction mixture was taken and dispersed with about 50 ml of methanol. Then, size distribution of the formed crystals was determined using a Coulter laser size analyzer (Analysete 22, FRITCH, Germany). Gypsum morphology: Scanning Electron Microscope (S-7200, Hitachi, Japan) was employed for investigation of crystal morphology. 2.3. Correlation between induction time and supersaturation The surface energy (interfacial tension) between the crystals and the aqueous solution is a fundamental parameter for understanding the rate of both nucleation and crystal growth. Based on the classic homogeneous nucleation theory, the induction time can be related to the supersaturation using the following

2. Experimental procedure 2.1. Materials Calcium hydrogen phosphate CaHPO4 (ADWIC, Egypt), sulfuric acid H2SO4 (MERCK, Germany) and phosphoric acid H3PO4 (BDH, England) were chemical reagent grade. Aluminum hydroxide Al(OH)3 and magnesium oxide MgO purchased from El-Nasr Pharmaceutical chemicals (ADWIC), Egypt were used as a source of aluminum and magnesium ions, respectively. 2.2. Procedure The main steps are reaction and crystallization, filtration and washing, drying and characterization of gypsum.

ARTICLE IN PRESS
374 M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372–379

correlation [11,12]: B ; Logðtind Þ ¼ A þ 3 ðlog2 SÞ T ð1Þ

Supersaturation ratio ðSÞ of the solution was calculated as shown below: % CaHPO4 ¼ wt: CaHPO4 Â 100; Total soln: wt ð6Þ

where A is an empirical constant (dimensionless) and B depends on the number of variables, and is given by Eq. (2): B¼
2 bg3 Vm NA f ðyÞ ; ð2:3RTÞ3

ð2Þ

Cð%CaSO4 Á 2H2 OÞ ¼ %CaHPO4 Mwt: CaSO4 Á 2H2 O Â ; Mwt: CAHPO4 S¼ C ; CÃ

ð7Þ ð8Þ

where b is a geometric (shape) factor of 16p=3 for the spherical nucleus, f ðyÞ is a correction factor, when purely homogeneous nucleation takes place, it is f ðyÞ ¼ 1 and when heterogeneous nucleation occurs it is f ðyÞ ¼ 0:01; Vm is the molar volume (74.69 cm3/mol for gypsum), T is the absolute temperature ðKÞ and R is the gas constant (J/mol K), g is the surface energy (J/m2), NA is the Avogadro number (molÀ1). Plotting of log tind against 1=½log2 SŠ over a relatively high range of supersaturations (1.618–1.979) for a fixed temperature gives a straight line with slope ðB=T 3 Þ; related to homogeneous nucleation. The nucleation rate, i.e. the number of nuclei formed per unit time per volume is given by Eq. (3): Js ¼
2 F expfÀbg3 Vm NA f ðyÞg ; 3 ðRT Þ ln2 S

where C Ã is the value of calcium sulfate dihydrate solubility at 80 C and 27.5% P2O5=0.83 [1]. Crystallization experiments were carried out at different S values where these values were calculated at different added amounts of CaHPO4 and H2SO4 as shown in Table 1. 3.1. Determination of the induction time and growth efficiency Induction time ðtind Þ is defined as the time elapsed between achievement of supersaturation by addition of reactants and appearance of nuclei. Generally the value of tind can be determined by monitoring the turbidity of the supersaturated solution. The turbidity is plotted against time of crystallization, and this plot was used to obtain the induction time. Fig. 1 shows an example of the obtained plots at S ¼ 1:88 in absence of additives. It can be seen that, the turbidity increases very slowly up to 3.3 min and then sudden increased. The time corresponds to this inflection is referred as induction time, (tind ¼ 3:3 min in this case). To study the effect of Al3+ or Mg2+ ions on the crystal growth of gypsum, experiments were

ð3Þ

where F is a frequency constant and is known as the pre-exponential factor and has a theoretical value of 1030 nuclei/cm3 s [13].

3. Results and discussion Calcium sulfate dihydrate can be formed by reaction of calcium hydrogen phosphate with sulfuric acid in which phosphoric acid is produced as follows: CaHPO4 þ H2 SO4 þ 2H2 O-H3 PO4 þ CaSO4 Á 2H2 O: ð4Þ

Table 1 Calculated values of supersaturation ratios at different amounts of CaHPO4 Wt. CaHPO4 (g) 5.3968 6.4762 8.0952 9.4444 9.9417 C 0.921 1.103 1.380 1.612 1.643 CÃ 0.83 0.83 0.83 0.83 0.83 S 1.088 1.301 1.618 1.880 1.979

This reaction was carried out at conditions simulating the industrial production of phosphoric acid and the crystallization of gypsum was followed up in the absence and in the presence of Al3+ and Mg2+ ions.

ARTICLE IN PRESS
M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372–379
1200 1000 Turbidity, NTU

375

1200 1000

800

400 200 0 0 1 2 4 3 Time,min.

Induction time

Turbidity, NTU

600

800 600 400 200 0 0 1 2 3 4 Time, min. 5 6 7
without 1.00% 1.50% 2.00% 3.00%

5

6

7

Fig. 1. Induction time of gypsum crystals without additives at supersaturation 1.880.

Turbidity, NTU

carried out at different percentages of ions and different supersaturation ratios under simulated conditions of phosphoric acid production. The tind was calculated as described above and the crystal growth efficiency ðGEÞ was calculated from values of the tind with and without each metal ions ðT1 Þ and ðT0 Þ; respectively, as follows in Eq. (9), [14– 16]: GE ¼ T0 À T1 Â 100: T0 ð9Þ

Fig. 2. Effect of Al2O3, % on the gypsum turbidity at supersaturation ratio 1.880.

1200 1000 800 600 400 200 0 0 100 200 300 Time, Sec. 400 500 600
without 1.00% 2.00%

3.2. Effect of Al3+ and Mg2+ ions on the induction time and growth efficiency The effects of Al3+ and Mg2+ ions as Al2O3 and MgO% from 0.0% to 3.0%, on gypsum crystallization were studied at different supersaturation ratios from 1.088 to 1.979. A sample of the obtained turbidity plots at S ¼ 1:880 is shown in Figs. 2 and 3 for Al3+ and Mg2+, respectively. Addition of 1% Al2O3 shifted the plots towards shorter time whereas addition of 1% MgO shifted the plots towards longer time compared with the plot without additives. The induction time and the growth efficiency were estimated and presented in Table 2. In addition, increasing aluminum ions up to 2% as Al2O3 decreases the induction time. Further increase in Al3+ ions up to 3% increases the induction time and then decreases the growth efficiency of gypsum (GE À8.30%). From literature [3], Al3+ ions adsorb on [1 0 1] faces formed

Fig. 3. Effect of MgO, % on the gypsum turbidity at supersaturation 1.880.

Table 2 Induction time and growth efficiency of gypsum crystals in the presence of Al2O3 and MgO at supersaturation ratio 1.880 % Al2O3 tind 00.0 1.00 1.50 2.00 3.00
a

MgO GE (%)a — 41.09 40.48 21.45 À5.74 tind 3.31 4.12 — 4.71 — GE (%) — À24.47 — À42.29 —

3.31 1.95 1.97 2.60 3.50

GE=Growth efficiency.

ARTICLE IN PRESS
376 M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372–379
3.1 2.9 2.7 2.5 Log tind 2.3 2.1 1.9 1.7 1.5 10
y = 0.0498x + 1.6468 y = 0.0478x + 1.7657

gypsum crystals. This leads to formation as shown in Fig. 6 using SEM. This is in consistence with data reported by Budz et al. [6] as they stated that aluminum ions promote the agglomeration of the small crystals of gypsum. It is also reported that Al3+ ions helps in formation of rhombic crystals [17,18]. So, it is expected that Al3+ ions decrease the induction time. However, high Al3+ ions content (about 3% Al2O3) leads to increasing the viscosity of the medium [17,18] that in consequent elongates the induction time and inhibits crystallization growth rate. In case of Mg2+ ions, The obtained results reveal that the presence of MgO increasing the induction time and consequently decreases the growth efficiency comparing with the control test (without additives). Thus, the presence of MgO in phosphate ore may retard the gypsum crystal growth i.e., smaller crystals are formed that block the filter cloth opening and decrease the filtration rate. 3.3. Correlation between supersaturation ratio and induction time The interfacial tension (surface energy) between the gypsum crystals and the aqueous solution is a fundamental parameter for understanding the rate of both nucleation and crystal growth. Relation between tind against 1=log2 S with and without 1% Al2O3 and MgO over a relatively high supersaturation ratios from 1.618 to 1.979 gives straight lines (Fig 4). The surface energies are calculated from the slopes of these lines-as shown in the experimental section—and given in Table 3. The calculated surface energies are 8.39, 9.53 and 8.05 mJ/m2 without additives, with 1% Al2O3 and with 1% MgO, respectively. It is clear that the surface energy is increased by addition of 1% Al2O3 and slightly decreased by addition of 1% MgO. The nucleation rate, i.e., the number of nuclei formed per unit time per volume can be calculated according to the relation mentioned in the experimental section by known surface energy value. The obtained of nucleation rates at 1.880 are given in Table 3. The nucleation rate is relatively lower in the presence of 1% Al2O3 compared with the

baseline Al2O3 MgO

y = 0.057x+1.292

12

14

16

18

20

22

24

1/log2 S

Fig. 4. Relation between log tind and 1/logÀ2 supersaturation ratio with and without 1% Al2O3 and 1% MgO.

Table 3 Surface energy and nucleation rate with 1% of Al2O3 and 1% MgO Item Surface energy (mJ/m2) 8.39 9.53 8.05 Nucleation rate (Nuclei/ cm3 s  1028) 71.8 58.1 74.8

Without 1% Al2O3 1% MgO

control test (without additives). In contrast, in the presence of 1% MgO, the nucleation rate is relatively higher than the control test. Low nucleation rate in case of 1% Al2O3 means that a small number of nuclei are formed. These nuclei have higher chance to grow to large crystals compared with high number of formed nuclei in case of MgO. This result is in consistence with obtained increase in crystal growth efficiency with addition of 1% Al2O3 and with crystal size distribution results as given below. 3.4. Effect of Al2O3 and MgO on crystal size distribution The crystal size distribution of gypsum in the presence of 1% Al2O3, 3% Al2O3 1% MgO and

ARTICLE IN PRESS
M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372–379 377

2% MgO compared with the baseline (without additives) at supersaturation ratio of 1.880 is given in Tables 4 and 5. The obtained results reveal that the percentage of fine crystals (o20 mm) without additives is 23.0% and this was dropped to 6.40% in the presence of 1% of Al2O3 and was increased to 38.7% in the presence of 3% Al2O3. On the other hand, this value was as high as 39.7% and 57.3% with addition of 1% and 2% MgO, respectively. Table 4 shows also that the median and mean diameter of gypsum crystals are higher with 1% Al2O3 compared with 1% MgO. The
Table 4 Cumulative size analysis of gypsum crystals with and without Al2O3 and MgO at supersaturation ratio 1.880 Crystal size mm Mesh Cumulative volume % passing Control test (without additives) — — 23.0 30.3 36.4 40.7 44.7 51.1 63.6 86.5 93.1 99.2 Al2O3 MgO

lower content of fine crystals and the higher mean diameter in the case of 1% Al2O3 may indicate that the gypsum crystal growth is enhanced compared with the baseline. On contrary, the higher contents of fine crystals and lower values of mean diameter in case of 3% Al2O3 and MgO may imply the lower gypsum crystal growth. 3.5. Gypsum morphology One of the most important factors affecting the filtration rate is gypsum morphology (size and shape of crystals). For the best filtration rates, crystals of uniform size are most desirable. Very large crystals co-existing with very small ones in absence of intermediate size crystals will offer poor filtration characteristics [1,17–19]. The SEM of gypsum crystals in absence of additives is given in Fig. 5 which indicates that the shapes of crystals are needle-type crystals. On the other hand, cluster crystals are formed in the presence of 1% Al2O3 (Fig. 6). The morphology of gypsum crystals in the presence of 1% MgO is needle type (Fig. 7). The average length to width ratio (L/W) of 10 crystals is 12:1 without additives, 3.0:1 with 1% Al2O3 and 12.5:1 with 1% MgO. Cluster formation together with smaller contents of fine crystals with Al2O3 (Table 4) would be favorable for the flow of the liquid phase through these crystals. This will have industrial impact in phosphoric acid industry by dihydrate process which depends

1% 5 15 20 30 45 60 75 100 150 250 300 500 — — 635 — 325 — 200 — 100 60 50 36 — — 6.40 10.44 16.39 21.88 26.39 34.87 51.50 82.20 90.74 98.81

3% — — 38.71 59.76 79.88 88.81 92.14 93.06 93.17 93.19 93.26 97.31

1% 4.99 27.09 39.74 61.04 82.48 93.28 98.06 99.75 100 100 100 100

2% 12.01 45.01 57.27 79.64 97.71 99.80 100 100 100 100 100 100

Table 5 Statistics of gypsum crystals size in the presence of Al2O3 and MgO compared with baseline (without additives) at supersaturation ratio 1.880 Item 0.0% Al2O3 (baseline) 1% MgO 3% 1% 2%

9.59 d10 (mm) Median ðd50 Þ (mm) 95.39 d90 (mm) 269.45 Mean diameter (mm) 121.82 Specific surface area 0.22 (m2/g)

28.89 7.47 7.18 4.78 145.53 24.98 24.45 17.06 294.28 63.10 53.76 36.48 156.48 28.50 27.04 18.18 0.10 0.38 0.37 0.59 Fig. 5. SEM of gypsum crystals in absence of additives.

dx ¼ x % Fraction passing the corresponding size.

ARTICLE IN PRESS
378 M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372–379

Fig. 6. SEM of gypsum crystals in the presence of 1% Al2O3.

contrast, the presence of 1–2% MgO inhibited the gypsum crystals at all supersaturation ratios. Surface energy is increased in the presence of 1% Al2O3 and decreased with 1% MgO compared with the baseline. Nucleation rate is decreased in the presence of 1% Al2O3 and increased with 1% MgO compared with baseline. The mean diameter of the formed crystals is increased and the fine crystals less than 20 mm is decreased in the presence of 1% Al2O3 and increased in the presence of 3% Al2O3 compared with the baseline. On the other hand, Mean diameter of the formed crystals is decreased and the fine crystals less than 20 mm is increased the presence of MgO. Interestingly, the majority of the formed crystals are clusters with 1% Al2O3 and needle-like type with MgO and baseline.

References
[1] P. Becker, Phosphates and Phosphoric Acid: Raw Materials Technology and Economics of the Wet Processes, Marcel-Dekker, Inc., New York, 1989. [2] K.S. Chari, Techno-economic evaluation of phosphate rock for wet process phosphoric acid, Fertilizers News, 1989, p. 21. [3] R.L. Gilbert, Ind. Eng. Chem. Process. Des. Develop. 5 (4) (1966) 388. [4] R.L. Glabisz, H. Gabreyel, Przem Chem. 52 (4) (1973) 293. [5] J. Li, J. Wang, Y. Zhang, Ind. Eng. Chem. Res. 36 (1997) 2657. [6] Z. Budz, A.G. Jones, J.W. Mullin, J. Chem. Technol. Biotechnol. 36 (1986) 153. [7] F.T. Nielsson, Some operating experience using high magnesia phosphate rock in wet process phosphoric acid manufacture, International Conference on Fertilizers, London, 1979. [8] A. Davister, S.V. Houghting, A Route Saving Raw Materials Makes P2O5 Available Through Wet Process Phosphoric Acid Process, ISNA, Orlando, FL, 1978. [9] J. Li, G. Ware, B. Zhong, Huauxe Gongye Yu Gongchang 14(2) (1997) 1 ((Ch) C.A. 127, 125429u, 1997). [10] B. Lin, J. Li, Lin Fei Yu Fufei 12(2) (1997) 6 ((Ch), C.A., 126, 253033b, 1997). [11] S. He, J.E. Oddo, M.B. Tomson, J. Colloid, Interface Sci. 162 (1994) 297. [12] A. Lancia, D. Musmarra, M. Prisciandaro, AIChE J. 45 (1999) 390k. [13] A.S. Myerson, Hand Book of Industrial Crystallization, Butterworth-Heinemann Series in Chemical Engineering, Butterworth-Heinemann, USA, 1993.

Fig. 7. SEM of gypsum crystals in the presence of 1% MgO.

mainly on the filtration of phosphoric acid through gypsum medium.

4. Conclusions Effect of Al3+ and Mg2+ ions on calcium sulfate dihydrate (gypsum) crystallization under simulated conditions of phosphoric acid production is studied. The results showed that Al3+% from 1% to 2% decreases the induction time at all supersaturation ratios compared with the Mg2+ which increases the induction time at all supersaturation ratios. The growth efficiency increases with addition of 1% Al2O3 up to 41% and decreases by increasing Al2O3 content to 3%. On

ARTICLE IN PRESS
M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372–379 [14] G.S. Georgiev, M.D. Djarova, J.I. Petkova, N.S. Koseva, Polym. J. 27 (4) (1995) 441. [15] H. El-Shall, B. Moudgil, E.A. Abdel-Aal, Cost effective reagents as defoamers and crystal modifiers to enhance the filtration rate of phosphogypsum, FIPR publication No. 01-14-162, March (1999). [16] H. El-Shall, M.M. Rashad, E.A. Abdel-Aal, Crystal Res. Technol. J. 37 (12) (2002) 1264. 379

[17] A.V. Slack, Phosphoric Acid, Marcel Dekker, Inc., New York, 1968. [18] E.A. Adel-Aal, Industrial simulation for wet process phosphoric acid production, Ph. D. Thesis, Chemistry Department, Faculty of Science, Cairo University, 1989. [19] M.H.H. Mahmoud, M.M. Rashad, I.A. Ibrahim, E.A. Abdel-Aal, J. Colloid Interface Sci. 270 (2004) 99.