3.1 SEM
It could be seen that in the SEM photos shown in Fig. 1 that the rice grain had a quite compact and undulating surface for the whole one, while if made a closeup observation it could be found that the inner surface of the rice grain was quite different from the outer one, as illustrated in the rupture place on the rice grain crust in Fig. 1a, there were many small cells filled with a great number of tiny spherical rice protein particles. This photo disclosed the inner structure of rice grain for the first time, and it might give us more inspiration and learning about the leaching behavior about the common rice consumed in our daily lunch. After leaching,it could be f, und that the plane section of the rice grain would be left with the wound by the acid leaching, which suggested that some part of the rice grain would be lost by dissolution in the acidic solution. Certainly, it was anticipated in this study that only the cadmium was extracted from the rice grain but not the dissolution loss of rice protein, while this fact told us that it was not possible to realize this aim. There must be a critical point for balance of the cadmium removal efficiency and the dissolution loss of the rice grain.
3.2 Effect of acid concentration
It could be found that the extraction efficiency of cadmium from the rice grain was a strongly pH-dependent process, as shown in Fig. 2a, at pH 1, the cadmium extraction percentage (%) increased monotonously to reach around 70% after 4h leaching for the whole grain. At pH 2, the corresponding extraction percentage would decrease to 60%. It was confirmed that at pH 6 there was almost no extraction for cadmium, which could be concluded that the common water washing in our everyday cooking had not any removal efficiency and was not able to remove cadmium from the rice grain. By calculation, it could be found that after leaching at pH 1 ~ 2 for about 4h, the residual cadmium content in the whole rice grain could decrease below 0.2mg/kg, meeting the food quality standard of China. It was also found that during the cadmium extraction process, the rice protein would dissolve into the aqueous solution with 7–8% mass loss at pH 1–2, as demonstrated in Fig. 3a, and only about 1% mass loss occurred at pH 6. Hence, it could be seen that solution pH would affect the cadmium extraction efficiency and dissolution loss of the rice grain in the leaching process, or it could be concluded that the extraction of cadmium from rice grain and the rice dissolution process were both the strongly pH-dependent process.
3.3 Effect of solid/liquid ratio
As shown in Fig. 2b and Fig. 3b, at the S/L ratio of 1/3 ~ 1/4 g/ml, the cadmium extraction efficiency and dissolution loss of rice grain both increased simultaneously to 70–80% and 8.5% mass, which appeared that at higher S/L ratio, these two index did not vary again. While at the lower S/L ratio, they reached 45% cadmium removal and 4% mass dissolution loss respectively. It could be understanded that the more acidic lixiviant was provided for leaching, the more cadmium would be extracted according to the. Therefore, S/L at 1/3 g/ml was recommended for practical leaching.
3.4 Effect of temperature
Figure 2c and Fig. 3c indicated that temperature would promote the cadmium removal and rice protein dissolution loss, and it could be found that the Cd% removal and rice dissolution loss would reach 70%, 77%, 85%, and 8%, 9.5%, 10% at 298K, 308K and 318K respectively. It was clear that temperature would lead to the faster diffusion of protons through the rice grain, intensifying the leaching kinetic rate coefficient. Considering the comprehensive effect, the leaching of rice grain at room temperature was recommended for following cadmium extraction experiments.
3.5 Effect of stirring rate
Figure 2d and Fig. 3d showed that stirring rate had positive promotion effect on the cadmium extraction and dissolution loss of the rice grain during the leaching process. While the effect was not so large as that of pH or S/L ratio, meant the suitable stirring rate could be set at 350 rpm for rice grain leaching.
3.6 Effect of size of rice grain
Figure 2e and Fig. 3e suggested that the long axis grain size had remarkable promotion of the cadmium extraction and dissolution rate, which had much more effect on the leaching results. Obviously, it could be understood clearly that the smaller grain size would shorten the diffusion distance of proton or cadmium ions, and also exhibited larger specific surface area for exposure to the acidic solution. Though the crack of the rice grain would promote the leaching efficiency, while the rice dissolution loss would also increase correspondingly as shown in the Fig. 3e. By overall evaluation, the rice grain with a half size appeared better for cadmium extraction with the low dissolution loss.
To better learn the cadmium extraction efficiency in the acidic solutions, the related leaching results of the rice grain in the acids were collected and listed in Table 1, and it could be found that the acidic leaching was quite effective to extract cadmium from the rice grain, though the acids used for leaching was quite different, suggesting that the dominant component for cadmium extraction was protons, but not the ligands. As compared in Table 1, the pH as well as other conditions set in present study was suitable for cadmium extraction effectively.
Table 1
Comparison of cadmium extraction efficiency in acids in open reported literature.
No.
|
Initial Cd content (mg/kg)
|
Leaching conditions
|
Extraction efficiency (%)
|
Residual Cd content(optimal)
(mg/kg)
|
Reference
|
1
|
0.27 ~ 0.92
|
Hydrochloric acid,
0.06M-0.18M
|
45 ~ 85
|
0.14
|
Feng et al., 2021
|
2
|
0.22 ~ 0.96
|
Citric acid,
0.02-0.08M
|
80 ~ 94
|
0.06
|
Wu et al., 2016
|
3
|
0.26
|
Acetic acid, pH = 3, ultrasound assisted extraction
|
66 ~ 93
|
0.02
|
Luo et al., 2021a
|
4
|
0.18 ~ 0.26
|
Acetic acid, pH = 5.5,
high-pressure extraction
|
43 ~ 82
|
0.05
|
Luo et al., 2021b
|
5
|
1.02
|
Hydrochloric acid,
pH = 1–2
|
60 ~ 92
|
0.08
|
This study
|
3.7 Reusability of leaching solution
Figure 2f showed that the same batch of HCl solution was repeatedly used for rice leaching, but adjusting pH to 1 by adding an aliquot of acid before next leaching operation, and it could be seen that the cadmium concentration in the acid solution increased monotonously at the average rate of around 80% for each leaching. Obviously, each leaching would increase the dissoluble protein concentration in the acidic solution as well as the viscosity of the solution, but it appeared no negative effect on the extraction efficiency of cadmium from the rice grain, further confirmed that the protons were the principal component for extraction of cadmium. Obviously, the effectiveness of reusability of the acidic solution would help to save the lixiviant and reduce the water consumption in the practical leaching process enormously, leading to the design of effective, ecofriendly and economical technology for cadmium extraction from rice grain.
3.8 Leaching kinetic model
Based on aforementioned results under different leaching conditions, it could de deduced that the cadmium extraction process from rice grain might occur according to the following reaction:
Rice-Cd + 2H+ = Rice-2H+ + Cd2+(aq) (3)
Cd2+(aq) + Cl− = CdCl+(aq) (4)
By thermodynamic calculation of the Cd (II)-Cl−-H2O solution system on the basis of the equilibrium reactions, as shown in Fig. 4b, it could be found that at pH 1–2, the cadmium existed in the dominant species of Cd2+ and CdCl+ in the aqueous solution, and they both played the exchange role with protons during the leaching process.
Above study suggested that the extraction of cadmium was actually a cation exchange process, as shown in reaction (3) and (4), and the diffusion rate of cadmium or proton in the solution bulk, liquid film locating in the interface of the grain-solution, and intraparticle of rice grain might become the limiting or bottleneck step for the whole leaching process. On the basis of the traditional leaching models for mineral ores in hydrometallurgical process (Li 2002), the related study was carried out to evaluate the leaching process by a quantitative way so that the leaching mechanism and fundamental characteristic parameters could be explored for better understanding the leaching process.
Fig. 5a and Fig. 5b showed the fitting plots based on the above leaching experimental results as shown in Fig. 2c, and the positive correlation of diffusion rate of cadmium vs 1/R2 in Fig. 5c, it confirmed that the intraparticle diffusion model could describe the cadmium extraction rate better. So on the basis of above results, the apparent activated energy value of the cadmium extraction process could be estimated to be 16.67 KJ/mol,as shown Fig., d, which suggested that the leaching process was controlled by the diffusion of cadmium or protons in the rice grain part. Hence it could be concluded that the most effective means to promote the cadmium extraction process was by crack rice grain into smaller size, for more convenient diffusion of protons inwards the grain and more specific surface area for exposure to the acidic solution.