3.1 Effect of the mass ratio of bentonite to carbide slag on the particles
Bentonite and carbide slag were mixed at mass ratios of 9:1 ~ 1:9, and 5 wt% Na2CO3 was added. Then, the slag was roasted at 500°C for 1 h to obtain a series of particles. The removal rate of Cu2+ and loss rate of particles prepared with different mass ratios of bentonite and calcium carbide are shown in Fig. 1. Increasing the proportion of carbide slag was conducive to the formation of Cu2+ precipitates. When the ratio of bentonite to carbide slag decreased from 9:1 to 5:5, the particle loss rate decreased from 40.36–8.98%. However, when the ratio decreased to 1:9, the particle loss rate increased to 40.1%. This indicated that the loss rate could be controlled by changing the ratio.
The loss of three typical particles in water are shown in Fig. 2 (a)–(c). As the contact time with water increased, the 9:1 particles gradually ruptured into small blocks, while the 1:9 particles gradually became spherical. This morphological change indicates that when the ratio of bentonite to carbide slag is greater than 5:5, the internal force is caused by bentonite swelling due to water absorption[]. When the ratio is less than 5:5, external forces such as flow shear and friction are concentrated at the corner of the particle, leading to the separation of powder from the particle surface. This separation is the main reason for the increase in loss rate, indicating that the internal cohesion of the particle is insufficient. When the ratio of bentonite to carbide slag is 5:5, the particle morphology is complete, indicating that the cohesive force inside the particle can overcome the expansion of bentonite, water shear and friction to achieve balance; thus, the loss rate reaches a minimum.
The surface morphologies of the three typical particles are compared in Fig. 2 (d)-(f). As shown in Fig. 2d, the 9:1 particle surface exhibits a smooth, crack-free compact structure. Figure 2e corresponds to the 5:5 particles and obvious small cracks are observed on their surface. These cracks provide buffer space for bentonite to absorb water and expand, thereby reducing the particle loss rate. The surface morphology of the 1:9 particles is shown in Fig. 2f. The surface became rough, and the number of cracks decreased. This structure shows that the particles exposed to the surface more easily fall off in water under the action of shear and friction, as shown by the macro-morphology in Fig. 2c.
The changes in the interlayer spacing of montmorillonite in unburned bentonite, calcined bentonite (500°C) and 9:1 particles are shown in Fig. 3a. No characteristic peaks representing the interlayer spacing were found in the 5:5 and 1:9 particles, indicating that the layered structure disappeared. The d001 value of unburned bentonite was 1.06 nm, which is the characteristic peak of sodium montmorillonite. After calcination at 500°C, the d001 value decreased to 0.96 nm. This result was consistent with the interlayer spacing of montmorillonite without interlayer-bound water. However, when a small amount of carbide slag was added, there were two weak characteristic peaks within 2θ = 6–10°. The d001 value of the characteristic peak of the layered structure increased to 1.28 nm. This result is consistent with the d001 value of Ca-montmorillonite containing a layer of crystal water[], indicating that Ca2+ in carbide slag enters the interlayer of montmorillonite, resulting in the transformation of some Na-bentonite to Ca-bentonite. The d001 value of another characteristic peak was consistent with that of montmorillonite, which had its lost interlayer-bound water. This part of the bentonite is the main cause of the water swelling and cracking of particles.
Figure 3b compares the phase change of particles at different ratios. The 9:1 particles showed an obvious increase between 18° and 25°, indicating that new crystalline phases were formed, but their crystallinity was too low. The characteristic SiO2 peaks at 35.89° and 31.28° widened, and a flat and wide peak was observed at 27.79°. Phase analysis showed that SiO2 was transformed into NaAl2(AlSiO3)O10(OH)2 (PDF 24-1047), indicating that the crystallinity of SiO2 decreased and participated in the formation of silicate. As the ratio was decreased to 5:5, the characteristic peaks of SiO2 at 28.43° and 31.28° disappeared, but no peaks appeared, indicating that SiO2 existed in an amorphous form. When the ratio was further decreased to 1:9, the characteristic peak of montmorillonite at 19.88° disappeared, indicating that montmorillonite transformed into an amorphous state.
The above results indicate that the formation of an amorphous gel is conducive to enhancing the mechanical strength of particles, and SiO2 in bentonite is preferentially converted to an amorphous state over montmorillonite. Therefore, when the proportion of bentonite is greater than 1, the layered structure of montmorillonite is retained, and the particles are more likely to be destroyed due to water absorption and expansion. When the proportion of bentonite is less than 1, the insufficient production of gel leads to an increase in the loss rate.
3.2 Effect of Na2CO3 dose on the particles
It can be seen from Sect. 3.1 that increasing the proportion of carbide slag can effectively improve the removal rate of Cu2+ ions, and the formation of amorphous gel is conducive to enhancing the particle strength. According to Provis at al[], since the formation of CSH, CAH, and CASH gels depends on the activation of alkali metal hydroxides or carbonates (i.e., Na2CO3). We expect to increase the proportion of calcium carbide slag as much as possible while maintaining a low loss rate. Therefor a series of particles were obtained by increasing the dose of Na2CO3 from 0–10% at different ratios (5:5, 4:6, 3:7) and roasting at 500°C for 1 h.
Figure 4 shows the loss rate and Cu2+ removal rate of the different particles. The Na2CO3 content increased from 0–10%, and the loss rates of the three groups of particles exhibited different degrees of decrease. The 7:3 series of particles decreased the most, from 63.56–7.40%. When 10% Na2CO3 was added, the loss rate of the 3:7 particles was 7.40%, which was similar to the loss rate (5.82%) of the 5:5 particles (Fig. 4a). These loss rate results indicate that increasing the amount of Na2CO3 can reduce the loss rate.
The removal rate of Cu2+ decreased when increasing the Na2CO3 dose from 0–10% (Fig. 4b), indicating that the addition of Na2CO3 had a negative effect on the removal of Cu2+. However, the copper ion removal rate of the 7:3 particles was better than that of the other particles. The loss rate of the 7:3 particles with 10% Na2CO3 was less than 10%.
The surface morphologies of the 7:3 particles with 0% and 10% Na2CO3 are shown in Fig. 5. The surfaces of the particles without Na2CO3 mainly consisted of large irregular particles stacked together in a loose structure, and the edges were rough (Fig. 5a). This structure led to a high loss rate of particles. The XRD analysis of the particles without Na2CO3 (Fig. 6) shows that the composition of the particles included montmorillonite and SiO2 from the bentonite and Ca(OH)2 and CaCO3 from the carbide slag. This indicated that the main composition remain unchanged A slight bulge in the substrate was observed between 25° and 40° because Ca(OH)2 can generate amorphous CSH through the pozzolanic reaction[,]; however, the amount of amorphous CSH was not enough to reduce the loss rate.
When increasing the Na2CO3 content to 10%, the particle surface flattened, and cracks with clear edges appeared, indicating that the particles lost water and shrunk; thus, the structure became compact (Fig. 5b). Based on Fig. 6, for the particles with 10% Na2CO3, the characteristic peaks at 19.79° and 21.73° disappeared, and the background hump between 25° and 40° became more obvious than that for the particles without Na2CO3. This result indicates that Na2CO3 plays a promoting role in the transformation of montmorillonite and SiO2 to an amorphous state because Na2CO3 can enhance the reactivity of Al and Si in clay and promote the formation of gels[]. Therefore, with an increasing Na2CO3 dose, the transformation of SiO2 and montmorillonite to an amorphous state was promoted, the gel content in the particles increased, and the particle loss rate was effectively reduced.
3.3 Effect of the roasting temperature
When the mass ratio of bentonite to carbide slag was 3:7 and the dose of Na2CO3 was 10% of the total mass, a series of particles were obtained after treatment for 1 h at different calcination temperatures to study the effect of calcination temperature on the particles. Regarding the particles prepared at room temperature, the loss rate reached 44.07%, and the removal rate of Cu2+ reached 100%. Regarding the particles calcined at 200°C, the loss rate greatly decreased to 18.73%, and the Cu2+ removal rate decreased to 83.46% (Fig. 7). This decrease indicates that the mechanical strength of uncalcined particles is poor, and an excessive loss rate leads to the removal of Cu2+, which is consistent with the research results of Zhan[]. However, an excessive loss rate leads to an increase in effluent turbidity and sludge. When increasing the temperature from 200°C to 500°C, the loss rate of particles decreased from 18.73–8.69%. However, when the calcination temperature was increased to 800°C, the loss rate increased to 19.14%. The removal rate of Cu2+ decreased with an increasing preparation temperature. According to Fig. 7, the loss rate of particles calcined at 500°C was the smallest, and the removal ratio of Cu2+ was 73.65%. Therefore, 500°C was set as the preparation temperature of the particles.
The XRD patterns of the particles prepared at different temperatures are compared in Fig. 8. In the uncalcined particles, Na2Ca(CO3)2·5H2O was detected based on the characteristic peaks at 2θ = 13.84°, 37.83° and 32.86°, while the characteristic peaks of Na2CO3 disappeared. This result indicates that a hydration reaction between Na2CO3 and carbide slag occurs, providing a precursor for the combination of bentonite and carbide slag after calcination. The characteristic peak of SiO2 from the bentonite disappeared, while the montmorillonite structure was retained. This is because montmorillonite with Al and Si in its crystal structure cannot participate in the volcanic ash reaction[]. Therefore, SiO2 preferentially transforms to an amorphous state over montmorillonite, forming CSH and other hydrates. The formation of hydration products gives the particles a certain mechanical strength, but insufficient production leads to a high particle loss rate. As the calcination temperature was increased to 500°C, the characteristic peaks of montmorillonite at 7.12° and 19.72° disappeared, indicating that the layered structure collapsed, and that the montmorillonite structure was destroyed. This is because the increase in the content of amorphous silicate transferred from Si and Al in the montmorillonite crystal structure with the increase of temperature further decreased the loss rate. This is consistent with the research results of Okano[].
The reaction of Ca(OH)2 with silicoaluminate can be summarized as[38,]:
6CH(s) + AS2(s) + 9H(l) → C4AH13(s) + 2CSH(s)
5CH(s) + AS2(s) + 3H(l) → C3AH6(s) + 2CSH(s)
3CH(s) + AS2(s) + 6H(l) → C2ASH8(s) + CSH(s)
When the temperature was increased from 500°C to 600°C, the background hump became obvious between 30° and 40°, indicating that new crystalline phases were formed and the crystallinity increased, which was caused by the transformation of the gel to a crystalline state at high temperature[]. In the same range, the characteristic peaks of the particles prepared at 800°C corresponded to Ca2SiO4, Na2Si3O7 and Ca12Al14O33. This result indicated that the pre-product was a silicate gel containing Ca and Na, the crystallinity increased between 600°C and 700°C, and the crystalline phase was formed at 800°C. Therefore, the crystallization of silicate gel decreases the binding force between bentonite and carbide slag and increases the loss rate of particles. Regarding the particles prepared at 600°C, the characteristic peaks of Ca(OH)2 at 17.82° and 33.97° became flat and wide, and the characteristic peaks of CaO were found, which was due to the dehydration of Ca(OH)2 to CaO. This finding was consistent with previous conclusions[,].
Figure 9 shows the SEM images of the surface morphologies of particles prepared at different temperatures. As Fig. 9a shows, the surface morphologies of the uncalcined particles are rough, and the layered structure is clearly visible. Due to the evaporation of free water inside the particles calcined at 200°C, small cracks appeared, and the layered structure became blurred (Fig. 9b). This is consistent with the XRD results. Regarding the particles calcined at 500°C, the surface morphologies became smooth, and the layered structure disappeared. The condensation of hydration products clarified the edge of the crack. Notably, this structure can more closely combine bentonite and carbide slag[]. Since Ca(OH)2 in the particles calcined at 600°C was dehydrated and converted to CaO, the surface morphologies became more smooth (Fig. 9d). However, when the calcination temperature was increased to 800°C (Fig. 9e), many irregularly distributed silicate crystals appeared on the complex surface morphologies of the particles. The crystals filled the original pores and blurred the edges of the surface cracks. A rough surface is not conducive to resisting the flow shear force and friction between particles, which is one of the reasons for the increase in the loss rate. However, the increase in crystallization is not conducive to the removal of Cu2+ and leads to a continuous decrease in the Cu2+ removal rate.
3.4 Alkali sustained-release property analysis
Based on the above experiments, when the mass ratio of bentonite to carbide slag was 3:7, the dose of Na2CO3 was 10% of the total mass, and the particles were calcined at 500°C for 1 h. The prepared particles had the best mechanical strength and Cu2+ removal rate. The sustained release properties of the alkali particles were analysed. Figure 10 shows the time it took to achieve a pH balance for 200 mg of particles (containing 126 mg of carbide slag) and 126 mg of carbide slag powder in initial solutions at pH 3. The time for the release of basicity from the optimal particles to reach equilibrium was 180 min, four times that for carbide slag powder (45 min). Therefore, the composite particles demonstrated a good slow-release effect of basicity in water.
The (001), (101) and (110) crystal planes of Ca(OH)2 in the raw carbide slag powder, uncalcined particles, and calcined particles at 200°C and 500°C were fitted by XRD, and the grain size was calculated by the Toylor formula. The effect of calcination temperature on the grain size of Ca(OH)2 was compared and analysed. The fitting results are shown in Table 2.
Table 2
Fitting results for the grain size of Ca(OH)2.
Crystal planes | (001) | (101) | (110) | Fit Size (nm) |
FWHM | XS(nm) | FWHM | XS(nm) | FWHM | XS(nm) |
carbide slag | 0.309 | 275 | 0.347 | 250 | 0.298 | 313 | 267 |
25℃ | 0.303 | 281 | 0.340 | 256 | 0.325 | 284 | 268 |
200℃ | 0.321 | 363 | 0.370 | 233 | 0.320 | 289 | 249 |
500℃ | 0.361 | 232 | 0.439 | 194 | 0.389 | 234 | 211 |
Table 2 shows that the grain size of Ca(OH)2 in the carbide slag powder is 267 nm. After mixing with bentonite and Na2CO3 in the optimal proportion, the grain size of Ca(OH)2 in the particles without calcination was 268 nm, and the grain size exhibited little change. After calcination, the grain size of Ca(OH)2 decreased from 268 nm to 211 nm. This indicates that calcination effectively reduces the grain size of Ca(OH)2. This decrease in grain size can make the amorphous gel better encapsulate carbide slag, thus buffering the alkalinity release of the particles.