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DOI: 10.1002/kin.21398
ARTICLE
KEYWORDS
colemanite, dissolution kinetics, gluconic acid, solid-liquid reaction, саlсium bоrоgluсоnаtе
TA B L E 1 The studies on the dissolution kinetics of colemanite ore with organic and inorganic acids
Borate mineral Acid Researcher and date Reference
Acetic acid Ozmetin et al (1996) 20
Oxalic acid Bayca et al (2014) 21
Citric acid Cavus and Kuslu (2005) 22
Colemanite Phosphoric acid Temur et al (2000) 23
Ammonium nitrate Gur (2008) 24
Sulfuric acid Sis et al (2019) 25
2CaO ⋅ 3B2 O3 ⋅ 5H2 O(s) + 4[HC6 H11 O7 ](aq) + 2H2 O(l) The effects of process factors such as the gluconic acid
concentration, the solution temperature, colemanite par-
→ 2Ca+2 (aq) + 4[C6 H11 O7 ]− (aq) + 6H3 BO3 (aq) (3) ticle size, solid/liquid ratio, and stirring speed on the dis-
solution rate of colemanite were examined. The chosen
4[C6 H11 O7 ]− (aq) + 4H3 BO3 (aq) + 2Ca+2 (aq) parameters for dissolution of colemanite in gluconic acid
→ 2[C12 H20 B2 CaO16 ](s) + 8H2 O(l) (4) solutions and their values can be seen in Table 4. Table 4
also shows that the parameters that were kept constant
and the final reaction: at values that are underlined, while the impact of other
parameters in the experiments was examined. The stirring
2CaO ⋅ 3B2 O3 ⋅ 5H2 O(s) + 4[HC6 H11 O7 ](aq) speed was kept constant in all the experiments at 500 rpm
to maintain the homogeneity of suspension in the reac-
→ 2[C12 H20 B2 CaO16 ](s) + 2H3 BO3 (aq) + 6H2 O(l)
tor. The data obtained from experiments were plotted in
(5) the form of time versus fractional conversion as shown in
4 DEMIR et al.
concentration, 1/500 g⋅mL−1 solid/liquid ratio, stirring obtained from the heterogeneous and homogeneous reac-
speed of 500 rpm, and 227 μm particle size. The obtained tion models. In the homogeneous reaction model, the liq-
results from experimental data are shown in Figure 4. As uid reactant enters the surface of the particle and reacts
seen in Figure 4, the dissolution rate increases as the tem- at all times throughout the particle. Thus, the solid reac-
perature increases. The dissolution rate at high tempera- tive behave as if it were dissolved.29 In the heterogeneous
ture was 97%. model, the reaction is considered to take place at the outer
surface of the unreacted particle. With the increase in con-
version, the unreacted core of the particle shrinks and
3.6 Effect of stirring speed the layer of the solid product thickens. The kinetics of
a noncatalytic reaction between solid and fluid can be
To determine the effect of the stirring speed on the dis- studied utilizing the unreacted shrinking core model. One
solution rate of colemanite, effect of stirring speed was of the three ideal stages can represent the process rate
investigated at 400, 500, 600, and 700 rpm. The change controlled by diffusion through fluid film control, diffu-
between stirring speed and conversion rate can be seen sion through product film control, and chemical reaction
in Figure 5. It can be seen from Figure 5 that there is control.30 Here, the model that determines the reaction
no effect of stirring speed on the dissolution rate of cole- rate is the model that depends on the highest resistance.
manite when the other parameters were kept constant To determine the rate of the control step, the empirical
at 227 μm, 1 M, 1/500 g⋅mL−1 , and 30◦ C. Similar results data were analyzed. The kinetic equations were also exam-
have been reported in the literature for dissolution of ined to determine the rate of B2 O3 passing into solution
colemanite.20,22,29 Homogeneous suspension was obtained considering the effects of the parameters. Multiple regres-
at a stirring speed of 500 rpm. Therefore, the stirring speed sion analysis in the Statistica Package 8.0 program, and
rate of 500 rpm was chosen as the constant value in all graphical method were applied to determine which step
experiments. controls the present system in terms of the unreacted core
and the other models. The integrated rate equations and
the correlation coefficients for these models are given in
3.7 Effects of acid concentration Table 5.
Table 5 shows that the best r2 values and experimen-
The effects of colemanite dissolution in gluconic acid in tal data correlate well with equation, which means that
different concentrations were studied. The experiments the dissolution rate is controlled by the diffusion through
were carried out with different gluconic acid concentra- the product layer. As colemanite particles are nonporous,
tions of 0.05, 0.1, 0.15, and 0.2 M where other parameters the most appropriate reaction model appears to be that
were fixed at 227 μm, 500 rpm, 1/500 g⋅mL−1 , and 60◦ C. of shrinking nonporous particles. Since the stirring speed
The experimental data is plotted in Figure 6. The results is not impacted by the dissolution rate, it is deduced that
showed that the increase in acid concentration causes an the diffusion through the fluid film does not act as a rate-
increase in the rate of colemanite dissolution. controlling step.
The integrated rate equation for diffusion through prod-
uct film for spherical solids with diameter D is given by
3.8 Effect of solid/liquid ratio Equation (7):
2∕3
The effect of the solid/liquid ratio on colemanite disso- 1 − 3(1 − 𝑋) + 2 (1 − 𝑋) = 𝑘𝑡. (7)
lution rate was studied for 0.5/500, 0.75/500, 1/500, and
1.5/500 g⋅mL−1 , while other parameters were kept constant In this model, the fractional conversion, X, is given as
at 227 μm, 500 rpm, 0.1 M, and 30◦ C, as shown in Figure 7. a function of the reaction time. The variation of [1 − 3(1 −
According to Figure 7, the decrease in the solid/liquid ratio X)2/3 + 2(1 − X)] with time is plotted for colemanite particle
leads to an increase in the dissolution rate. This result can sizes and reaction temperatures in Figures 8 and 9, respec-
be attributed to the decrease in the number of colemanite tively. It can be seen from these figures that the straight
particles per amount of solutions. lines for all samples have correlation coefficients between
0.9575 and 0.9951.
When the reaction is product layer diffusion controlled,
3.9 Kinetic analysis Rs 2 and t* values must be linearly dependent. If the t* val-
ues are plotted versus Rs 2 , the obtained curve is a straight
Solid-fluid reactions are abundant and have considerable line and this verifies that the reaction is product layer dif-
industrial significance. The solid-fluid reaction rate can be fusion controlled (Figure 10).
6 DEMIR et al.
TA B L E 5 Integrated rate equations for the unreacted core and the other models, and regression analyses
Rate controlling Step rate equation r2
𝑅
𝑡 ρB
Film diffusion = 𝑋B 𝑡 ∗ = 0.8309
𝑡∗ 3𝑏𝑘𝑔 𝐶A
2
𝑡 ρB 𝑅
Diffusion through product = 1 − 3(1 − 𝑋𝐵 )2∕3 + 2(1 − 𝑋𝐵 ) 𝑡∗ = 0.9696
𝑡∗ 6𝑏𝐷𝑒 𝐶A
t 1∕3 ∗ ρB R
Chemical reaction = 1 − (1 − XB ) t = 0.9468
t∗ 𝑏𝑘𝜍 CA
1∕2 ∗ ρB 𝑅
Film diffusion (large grain) 𝑘𝑡 = 1 − (1 − 𝑋) 𝑡 = 0.9245
𝑏𝑘ς 𝐶A
2∕3 ∗ ρB 𝑅
Film diffusion (small grain) 𝑘𝑡 = 1 − (1 − 𝑋) 𝑡 = 0.8966
𝑏𝑘𝜍 𝐶A
FIGURE 8 Variation of the model time for different particle FIGURE 10 Agreement between t* and Rs 2
sizes
The rate constants (k) obtained from the slopes of Fig- According to Equation (9), a plot of ln k versus 1/T
ure 9 are used in the Arrhenius equation (8): should be a straight line with a slope −E/R and intercept
ln k0 (Figure 11). The B2 O3 apparent activation energy and
𝑘 = 𝑘0 𝑒−𝐸∕𝑅𝑇 , (8) preexponential factor from Figure 11 were calculated as
8.39 kJ⋅mol−1 and 1.2 s−1 respectively.
𝐸 The activation energy of processes controlled with diffu-
ln𝑘 = ln𝑘0 − . (9) sion is characterized to be from 4.18 to 12.55 kJ⋅mol−1 , while
𝑅𝑇
DEMIR et al. 7
ORCID
Fatih Demir https://orcid.org/0000-0003-0264-1074
REFERENCES
1. Simsek HM, Guliyev R, Bese AV. Dissolution kinetics of boro-
gypsum in di-ammonium hydrogen phosphate solutions. Int J
F I G U R E 1 2 Agreement between observed values and pre- Hydrogen Energy. 2018;43(44):20262-20270.
dicted values from the model 2. Cetin E, Eroglu I, Ozkar S. Kinetics of gypsum formation and
growth during the dissolution of colemanite in sulfuric acid. J
Cryst Growth. 2001;231(4):559-567.
3. Sis H, Bentli I, Demirkiran N, Ekmekyapar A. Dissolution kinet-
for a chemically controlled process it is usually greater than
ics of colemanite in HCl solutions by measuring particle size dis-
41.84 kJ⋅mol−1 .31 tributions. Sep Sci Technol. 2018;53(1):198-205.
Since the activation energy is low, it can be said that the 4. Sahinkaya HU, Ozkan A. Investigation of shear flocculation
diffusion from the product layer was controlling the disso- behaviors of colemanite with some anionic surfactants and inor-
lution rate of colemanite in gluconic acid solutions. Similar ganic salts. Sep Purif Technol. 2011;80(1):131-139.
results were found by Alkan and Dogan,29 Guliyev et al,8 5. Tunc M, Kocakerim MM, Kucuk O, Aluz M. Dissolution of
and Karagoz and Kuslu.22 They found that the dissolution colemanite in (NH4 )(2)SO4 solutions. Korean J Chem Eng.
rate of colemanite was controlled by diffusion through the 2007;4(1):55-59.
6. Demirkiran N. A study on dissolution of ulexite in ammonium
product layer, and the activation energies are 39.71, 26.34,
acetate solutions. Chem Eng J. 2008;141(1-3):180-186.
and 28.65 kJ⋅mol−1 , respectively. 7. Karagoz O, Kuslu S. Dissolution kinetics of colemanite in potas-
When k and E are plugged into Equation (9), the follow- sium dihydrogen phosphate solution (KH2 PO4 ). Int J Hydrogen
ing kinetic model (Equation 10) is obtained: Energy. 2017;42(36):23250-23259.
8. Guliyev R, Kuslu S, Calban T, Colak S. Leaching kinetics of
1 − 3(1 − 𝑋)2∕3 + 2(1 − 𝑋) = 1.2 𝑒−8.39∕𝑅𝑇 𝑡. (10) colemanite in potassium hydrogen sulphate solutions. J Ind Eng
Chem. 2012;18(1):38-44.
9. Kizilcа M, Cоpur M. Kinеtic invеstigаtiоn оf rеаctiоn
The comparison between the observed values and pre-
bеtwееn cоlеmаnitе оrе аnd mеthаnоl. Chеm Еng Cоmmun.
dicted values obtained from this model can be seen in Fig-
2015;202:1528-1534.
ure 12. The values obtained from the model were found to 10. Kavci E, Calban T, Colak S, Kuslu S. Leaching kinetics of ulex-
be in good agreement with the observed values. ite in sodium hydrogen sulphate solutions. J Ind Eng Chem.
2014;20(5):2625-2631.
11. Piskin MB. Investigation of sodium borohydride production pro-
4 CONCLUSION cess: “wexite mineral as a boron source”. Int J Hydrogen Energy.
2009;34(11):4773-4779.
12. Ekmekyapar A, Demirkiran N, Kunkul A. Dissolution kinet-
In this study, the dissolution of colemanite in gluconic
ics of ulexite in acetic acid solutions. Chem Eng Res Des.
acid solutions was investigated. Five parameters such 2008;86(9a):1011-1016.
as acid concentration, reaction temperature, solid/liquid 13. Taylan N, Gurbuz H, Bulutcu AN. Effects of ultrasound on the
ratio, particle size, and stirring speed were investigated. reaction step of boric acid production process from colemanite.
It was found that the increase in the acid concentration Ultrason Sonochem. 2007;4(5):633-638.
and the reaction temperature increased the dissolution 14. Bayrak B, Lacin O, Bakan F, Sarac H. Investigation of dissolution
rate, the decrease in particle size, and solid/liquid ratio kinetics of natural magnesite in gluconic acid solutions. Chem
caused an increase in the dissolution rate. Based on the Eng J. 2006;117(2):109-115.
15. Pal P, Kumar R, Banerjee S. Manufacture of gluconic acid: a
result of the examination, the impact of stirring speed
review towards process intensification for green production.
on the rate of the dissolution of colemanite in gluconic Chem Eng Process. 2016;104:160-171.
acid was found to have no effect, which explains that the 16. Ramachandran S, Fontanille P, Pandey A, Larroche C. Gluconic
diffusion through the fluid film does not act as a rate- acid: properties, applications and microbial production. Food
controlling step. It was found that the rate-controlling step Technol Biotech. 2006;44(2):185-195.
8 DEMIR et al.
17. Rao DS, Panda T. Comparative-analysis of calcium gluconate particle size measurements. Sep Sci Technol. 2019;54(8):1353-
and sodium gluconate techniques for the production of gluconic 1362.
acid by Aspergillus niger. Bioprocess Eng. 1993;8(5-6):203-207. 26. Seifi HA, Mohri M, Zadeh JK. Use of pre-partum urine pH to
18. Bao J, Furumoto K, Fukunaga K, Nakao K. A kinetic study on air predict the risk of milk fever in dairy cows. Vet J. 2004;167(3):281-
oxidation of glucose catalyzed by immobilized glucose oxidase 285.
for production of calcium gluconate. Biochem Eng J. 2001;8(2):91- 27. Chamberlin WG, Middleton JR, Spain JN, Johnson GC, Eller-
102. sieck MR, Pithua P. Subclinical hypocalcemia, plasma biochem-
19. Vavrusova M, Skibsted LH. Spontaneous supersaturation of cal- ical parameters, lipid metabolism, postpartum disease, and fer-
cium d-gluconate during isothermal dissolution of calcium l- tility in postparturient dairy cows. J Dairy Sci. 2013;96(11):7001-
lactate in aqueous sodium d-gluconate. Food Funct. 2014;5(1):85- 7013.
91. 28. Gulensoy H. Kompleksometrik Titrasyonlar ve Komplek-
20. Ozmetin C, Kocakerim MM, Yapici S, Yartasi A. A semiem- sometrinin Temelleri. Istanbul, Turkey: Fatih Yayınevi;
pirical kinetic model for dissolution of colemanite in aqueous 1974.
CH3 COOH solutions. Ind Eng Chem Res. 1996;35(7):2355-2359. 29. Alkan M, Dogan M. Dissolution kinetics of colemanite in oxalic
21. Bаycа SU, Kоcаn F, Аbаli Y. Dissоlutiоn оf cоlеmаnitе acid solutions. Chem Eng Process. 2004;43(7):867-872.
prоcеss wаstе in оxаlic аcid sоlutiоns. Environ Prog Sustain. 30. Levenspiel O. Chemical Reaction Engineering. 3rd edn. New
2014;33(4):1111-1116. York, NY: Wiley; 1999.
22. Cavus F, Kuslu S. Dissolution kinetics of colemanite in citric acid 31. Abdel-Aal EA. Kinetics of sulfuric acid leaching of low-grade
solutions assisted by mechanical agitation and microwaves. Ind zinc silicate ore. Hydrometallurgy. 2000;55:247.
Eng Chem Res. 2005;44(22):8164-8170.
23. Temur H, Yartasi A, Copur M, Kocakerim MM. The kinetics of
dissolution of colemanite in H3 PO4 solutions. Ind Eng Chem Res.
How to cite this article: Demir F, Al-Ani AOA,
2000;39(11):4114-4119.
24. Gur A. A kinetic study on leaching of colemanite in ammonium Lacin O. А kinеtiс аnаlysis fоr prоduсtiоn of
nitrate solutions. Chinese J Inorg Chem. 2008;24(3):467-473. саlсium bоrоgluсоnаtе frоm colemanite. Int J Chem
25. Sis H, Bentli I, Demirkiran N, Ekmekyapar A. Investigat- Kinet. 2020;1-8. https://doi.org/10.1002/kin.21398
ing dissolution of colemanite in sulfuric acid solutions by