Xinye Wang*a,
Hao Xiea,
Rong Dua,
Yuying Liua,
Pingfang Lina,
Jubing Zhanga,
Changsheng Bua,
Yaji Huang*b and
Wen Zhangc
aJiangsu Provincial Key Laboratory of Materials Cycling and Pollution Control, School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing 210042, Jiangsu, China. E-mail: xinye.wang@njnu.edu.cn
bKey Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China. E-mail: heyyj@seu.edu.cn
cNanjing Shangyuan Industrial Gas Plant, Nanjing 211100, Jiangsu, China. E-mail: zw25102@163.com
First published on 8th October 2018
Municipal solid-waste incineration leads to emission of lead (Pb) and cadmium (Cd), which vaporize in furnace and condense in flue. NaCl in waste has been proven to enhance volatilization of Pb and Cd at high temperatures via chlorination of oxides to chlorides; however, this process was not well-understood so far due to its complexity. This study decoupled the indirect chlorination process and direct chlorination process so that these two processes were investigated separately. A horizontal tube furnace was used to heat the mixtures of NaCl and Si/Al matrix for indirect chlorination and the mixtures of NaCl, PbO/CdO and Si/Al matrix for direct chlorination. A set of dynamic sampling devices was designed and used to obtain dynamic data during temperature rising. The indirect chlorination process was initiated above 800 °C in O2 + H2O atmosphere and O2 atmosphere and above 1000 °C in N2 atmosphere. Al2O3 exhibited higher activity than SiO2 to react with NaCl, releasing HCl or Cl2. In the Cl release reaction, NaCl was in the gas phase. The direct chlorination process was initiated at 650–700 °C when the Si/Al matrix contained SiO2 only and at around 800 °C when the Si/Al matrix contained Al2O3 only or both SiO2 and Al2O3. SiO2 exhibited higher activity than Al2O3 in direct chlorination. The pre-reaction between PbO/CdO and Si/Al matrices was considered as the necessary condition for direct chlorination. During chlorination in O2 + H2O atmosphere, indirect chlorination and direct chlorination occurred simultaneously, and the latter dominated the volatilization of Pb and Cd.
In the combustion system, Pb and Cd are considered as semi-volatile metals, which evaporate from MSW in the furnace to flue gas and then condense as a solid phase.5–7 During this evaporation–condensation process, a small amount of Pb and Cd is converted to submicron aerosols (PM1), which cannot be captured by dedusting equipments with high efficiency.6,7 The escaping aerosols are very harmful to the human body.8
Chlorine (Cl) has been proven to be able to enhance the volatilization of Pb, Cd and other metals during combustion. The typical forms of Cl in MSW are polyvinyl chloride (PVC, organic Cl) and NaCl (inorganic Cl).9 In the previous research of fixed bed incineration, the addition of 1% Cl in the form of PVC or NaCl into simulated MSW caused an increase in the volatilization fractions of Pb and Cd from around 20% and 50% to around 80% and 90%, respectively.10 Most incineration researches using fixed bed, fluidized bed or kiln indicated a similar effect.11–14
The positive roles of PVC and NaCl in metal volatilization during incineration are usually interpreted by thermodynamic equilibrium investigation. Pb and Cd are considered to transform from oxides with a melting point of around 900 °C to chlorides with a melting point of around 500 °C in the presence of Cl during incineration according to the calculations based on Gibbs free energy minimization.10,15–17 Overall, chlorination is the key to the positive effects of PVC and NaCl on Pb and Cd volatilization.
There have been some investigations on the chlorination mechanisms of PVC. Wang et al. considered that the chlorination reaction between PVC and PbO was indirect.18 PVC released HCl at 225 °C; then, HCl reacted with PbO, producing PbCl2 and finally, PbCl2 volatilized above 500 °C.18 This process was described as indirect chlorination, which has been reported by other researchers.10,19,20 However, not all the PVC-metal oxide systems follow indirect chlorination. Kosuda et al. found direct chlorination between PVC and ZnO for the catalysis of ZnO.21
There is less research on the chlorination process between NaCl and metal oxides during incineration. The research group of Zhang and He conducted great studies on this topic.22,23 They used thermogravimetric analysis combined with differential scanning calorimetry (TG-DSC) to detect the chlorination of PbO and other metals by NaCl. It was found that NaCl alone reacted with PbO via a liquid–solid reaction but not with CdO, ZnO and CuO.22 The chlorination of PbO by NaCl was promoted in the presence of Al2O3 or SiO2.23 Many researchers have also used NaCl to remove heavy metals from ash successfully; however, few chlorination mechanisms were reported except some kinetic and dynamic studies.24–26
In the present study, further mechanisms of chlorination of PbO and CdO by NaCl were revealed to help the prediction and control of heavy metal emission during incineration. Unlike the experimental method (TG-DSC) used by the previous research, a dynamic sampling device was designed and used so that the dynamic release of chlorine and metals from the horizontal tube furnace was detected directly. Moreover, the tube furnace was more flexible regarding atmosphere selection (most TG cannot afford water vapour) and sample composition selection (samples are used in micrograms in TG so that the complex component cannot be prepared in stable proportions in different experiments). Therefore, the effects of water vapour and SiO2/Al2O3 molar ratio could be taken into consideration as well. The chlorination process was decoupled into indirect chlorination and direct chlorination, which were investigated separately. In indirect chlorination, first, NaCl releases Cl-containing gases (HCl or Cl2) and then, the Cl-containing gases chlorinate metal oxides.27 In direct chlorination, NaCl donates Cl to metals without releasing any gas.27
The contents of reactants for indirect chlorination and direct chlorination are listed in Table 1, according to a previous research.10 SiO2, Al2O3, PbO, CdO and NaCl used were guaranteed reagents. Two steps were used for decoupling. In the first step, no PbO and CdO were added in the indirect chlorination experiments and chlorine release was used to represent the occurrence of indirect chlorination. The reactions between Cl-containing gas and heavy metal oxides were fast and easy; thus, when Cl-containing gas was produced, indirect chlorination occurred.28 Three atmospheres (N2, O2, and 85% O2 + 15% H2O) were compared in the indirect chlorination experiments. In the second step, only N2 atmosphere was used to avoid the release of Cl in direct chlorination experiments. Heavy metal release was used to evaluate the direct chlorination processes. The reducibility of combustible matter can enhance the volatilization of Pb and Cd.10 Consequently, carbon particles were excluded from the reaction system to ensure that chlorination was the only factor used to enhance metal volatilization besides temperature in direct chlorination experiments. Equally, carbon particles were excluded in indirect chlorination experiments. More details about decoupling are presented in Sections 4.1 and 4.4.
Case | Combustible matter | Incombustible matter | Chlorine | Heavy metal | |
---|---|---|---|---|---|
Carbon particle (not added actually) | SiO2 + Al2O3a (MP = 1650/2000 °C, BP = 2230/2977 °C, d < 0.5 mm) | NaCla (MP = 801 °C, BP = 1465 °C, d < 0.5 mm) | PbOa (MP = 888 °C, BP = 1470 °C, d < 0.5 mm) | CdOa (MP = 900 °C, BP = 1385 °C, d < 0.5 mm) | |
a MP, melting point; BP, boiling point; d, particle size. | |||||
Indirect chlorination (N2, O2, O2 + H2O) | 10.5 g (70%) | 4.5 g (30%) | 0.25 g (1% Cl) | 0 | 0 |
Direct chlorination (N2) | 2.42 mg (1500 mg Pb per kg) | 25.7 mg (1500 mg Cd per kg) |
Traditional heavy metal sampling methods are filtering or adsorption outside a furnace at low temperature.10,16 With decreasing temperature, some amount of evaporated Pb and Cd can condense on the surfaces of the furnace exit and sampling pipeline, resulting in sampling loss. Therefore, the recovery rate is usually below 80% accompanied with several seconds of delay during sampling.10,16 A set of high-temperature sampling tubes (Fig. 1) were designed to capture evaporated Pb and Cd with high efficiency and good dynamic response. During metal sampling, the pumping flow rate was greater than the supplying flow rate; thus, the air outside was pumped in a reverse manner into the sampling tube, which cooled the sampling gas. The evaporated Pb and Cd partly condensed on the inner surface of the sampling tube. The remaining species were collected by a fiberglass filtering cartridge inserted at the end of the sampling tube. The sampling tube was replaced by a new one every 5 min.
During Cl sampling, the sampling tube was used as well to remove the evaporated NaCl, and the alternative absorption bottle with 1 mol L−1 NaOH solution was used to collect HCl or Cl2 gas. The atmosphere of 85% O2 + 15% H2O was generated by two sages of saturated vapour using O2 as the carrier gas, which was similar to the method used by Fraissler et al.29 The sampling time of each bottle was 10 min for dynamic Cl emission data.
In O2 atmosphere, Cl release was initiated at 700–800 °C with a small amount (Fig. 2, solid line and solid symbol). The Cl release fraction in the case of Si/Al = 0:
1 was close to that in the case of Si/Al = 2
:
1 at each temperature, but it was clearly higher than that in the case of Si/Al = 1
:
0. When H2O was added to O2, producing 85% O2 + 15% H2O, Cl release was enhanced significantly in all three cases of different Si/Al molar ratios (Fig. 2, dot line and half up symbol). The initial temperature of Cl release was still 700–800 °C, and it was not lowered in the presence of H2O. In N2 atmosphere, Cl was released significantly above 1000 °C, and no Cl release occurred at 1000 °C (Fig. 2, dash line and hollow symbol). Overall, the positive effect of atmospheres on Cl release followed the sequence of O2 + H2O > O2 > N2. In all cases, the Cl release fractions were less than 20% when the temperature increased to 1100 °C.
The Cl release rate was calculated by dividing the Cl amount in each sampling bottle by 10 min. There were two types of Cl release rate changes with increasing temperature (Fig. 3). The first type was the bimodal form or the tendency at least in O2 and O2 + H2O atmospheres except for the change with Si/Al = 1:
0 in O2 atmosphere; this was the second type, which was similar to that in N2 atmosphere. In the bimodal form of Cl release rate change, one peak was at around 850 °C, whereas one valley was at around 950 °C. The Cl release rate followed different sequences in three atmospheres. In O2 + H2O atmosphere, the sequence was Si/Al = 0
:
1 > Si/Al = 2
:
1 > Si/Al = 1
:
0 at 850 °C and Si/Al = 1
:
0 > Si/Al = 2
:
1 ≈ Si/Al = 0
:
1 at 1050 °C. In O2 atmosphere, the sequence was Si/Al = 0
:
1 > Si/Al = 2
:
1 > Si/Al = 1
:
0 at 850 °C, and it was very close at 1050 °C. In N2 atmosphere, the change in the Cl release rate was simple, and the sequence was Si/Al = 2
:
1 > Si/Al = 0
:
1 > Si/Al = 1
:
0 at 1050 °C. In all cases, the Cl release rates were less than 1% min−1 when the temperature increased to 1100 °C.
The volatilization rate in the case of Si/Al = 1:
0 was higher than that in other cases below 1000 °C (Fig. 4(c)); it was initiated at 650–700 °C and increased nonlinearly. With increasing temperature, the increase in the volatilization rate first slowed down at 750–850 °C and then speeded up at 850–1000 °C. When the temperature increased to 1050 °C, the volatilization rates decreased in all cases.
The volatilization characteristics of Cd with NaCl addition in N2 atmosphere were similar to that of Pb, but the volatilization process was weaker. The accumulative volatilization fraction of Cd in the case of Si/Al = 1:
0 was higher than that in other cases as well (Fig. 4(b)). When the matrix consisted of Al2O3, the curves of the accumulative volatilization fraction and volatilization rate were close to each other at each temperature (Fig. 4(b) and (d)). Cd volatilization was initiated at around 700 °C in the case of Si/Al = 1
:
0 and at around 800 °C in other cases, which was similar to that observed for Pb volatilization.
The volatilization rate in the case of Si/Al = 1:
0 was higher than that in other cases below 850 °C and then became the same as that in other cases above 850 °C (Fig. 4(c)); it was initiated at 650–700 °C and increased nonlinearly. With increasing temperature, the increase in the volatilization rate first slowed down at 750–850 °C and then speeded up at 850–1000 °C, which was the same as the observations for Pb volatilization. When the temperature was above 1050 °C, the volatilization rates decreased slightly in all cases.
![]() | ||
Fig. 5 Accumulative volatilization fractions of (a) Pb and (b) Cd and volatilization rates of (c) Pb and (d) Cd with increasing temperature in 85% O2 + 15% H2O atmosphere and N2 atmosphere. |
According to the results in Section 3.1, 85% O2 + 15% H2O was the most favourable atmosphere among the three for indirect chlorination, which started at 700–800 °C. The effect of O2 atmosphere was similar to that of 85% O2 + 15% H2O atmosphere, but it was weaker. The results indicated that H2O enhanced indirect chlorination and the reaction rate of NaCl + Si/Al matrix + H2O was higher than that of NaCl + Si/Al matrix + O2; this was supported by the results of thermodynamic researches and experimental researches.15,31,32 H2O and O2 are usually considered as the necessary reactants for Cl release from NaCl.23,33 The Cl release in N2 atmosphere has not been paid attention to in most previous researches; however, it was proven in this research. The results indicated that indirect chlorination could occur above 1000 °C without the participation of O2 and H2O. As we know, drying process, pyrolysis/gasification process and combustion are separated on grate; thus, the atmosphere around MSW is complex and variable during incineration. The O2 and H2O-free atmosphere is available in the mechanical grate furnace. Furthermore, this finding provided important reference for decoupling indirect chlorination from direct chlorination. Overall, the positive effect of atmospheres on indirect chlorination followed the sequence of H2O > O2 > N2. Wang et al. found no Cl release in NaCl + SiO2 system and NaCl + Al2O3 system in air atmosphere at 850 °C; this may be due to the chlorine detecting method and the weak release amount at this temperature.23
The XRD pattern of the residue in NaCl + Al2O3 case was indistinct in the same ordinate when compared with those of other cases. Therefore, it was plotted separately in Fig. 7(b). Al2O3 was crystallized partially at 800 °C accompanied with the formation of a small quantity of sodium aluminates. NaAl5O8 was one of the sodium aluminates, and its peak matched the diffraction peaks well. There were still some amorphous substances that were unknown. The XRD pattern of the residue in NaCl + SiO2 + Al2O3 case (not shown here) indicated the formation of sodium silicoaluminates. Moreover, calcinations at higher temperatures in N2/O2 atmospheres were carried out. The formations of sodium silicates, sodium aluminates and sodium silicoaluminates were found in the case of NaCl + SiO2, NaCl + Al2O3and NaCl + SiO2 + Al2O3, respectively. The formation temperatures were in accordance with Cl release temperatures. The specific compositions could not be distinguished due to the diversification of products and the disorder of XRD patterns resulting from amorphous substances.
The indirect chlorination path was surmised by the proposed reaction equations (PbO for example), where T indicates the initial temperature of the reaction:
(1) Cl release
NaCl(g) + SiO2 + O2(g) → NaxSiyOz + Cl2(g) T > 800 °C |
NaCl(g) + Al2O3 + O2(g) → NaxAlyOz + Cl2(g) T > 800 °C |
NaCl(g) + SiO2 + Al2O3 + O2(g) → NawSixAlyOz + Cl2(g) T > 800 °C |
NaCl(g) + SiO2 + H2O(g) → NaxSiyOz + HCl(g) T > 800 °C |
NaCl(g) + Al2O3 + H2O(g) → NaxAlyOz + HCl(g) T > 800 °C |
NaCl(g) + SiO2 + Al2O3 + H2O(g) → NawSixAlyOz + HCl(g) T > 800 °C |
NaCl(g) + SiO2→NaxSiyOz + Cl2(g) T > 1000 °C |
NaCl(g) + Al2O3 → NaxAlyOz + Cl2(g) T > 1000 °C |
NaCl(g) + SiO2 + Al2O3 → NawSixAlyOz + Cl2(g) T > 1000 °C |
(2) Chlorination
Cl2(g) + PbO → PbCl2 + O2(g) T > 800 °C or >1000 °C |
HCl(g) + PbO → PbCl2 + H2O(g) T > 800 °C |
(3) Volatilization
PbCl2 → PbCl2(g) T > 800 °C or >1000 °C |
Wang et al. found that NaCl could chlorinate PbO without Si/Al matrix participation above 800 °C by liquid–solid reaction.23 Herein, the Si/Al matrix was involved in each case. Trace amounts of NaCl and PbO/CdO caused low probability of their liquid–solid contact. The volatilization of Pb and Cd below 800 °C and the effect of Si/Al matrix also contradicted this possibility. Therefore, direct chlorination was considered to occur with the participation of the Si/Al matrix.
According to the characteristics of Pb and Cd volatilization below 1000 °C in N2 atmosphere, the characteristics of direct chlorination were obtained. The Si/Al matrix component was found to be an important factor. When the Si/Al matrix consisted of SiO2 only, the initial temperature of direct chlorination was 650–700 °C. When Al2O3 was involved, it increased to 800–850 °C for Pb and 750–800 °C for Cd. The direct chlorination of Pb was faster than that of Cd. Wang et al. reported similar results in which the initial temperature of direct chlorination in the NaCl + PbO + SiO2 system was 600–611 °C and that in the NaCl + PbO + Al2O3 system was 745 °C.23 The lower temperature may be due to the high proportion of NaCl and PbO in the reactant system (NaCl:
PbO
:
PbO molar ratio = 50
:
25
:
25), causing sufficient contact with reactant.23
The XRD patterns of the residues derived at 500 °C are shown in Fig. 9. PbO/CdO reacted with SiO2 but not Al2O3 at 500 °C. The reaction products were lead silicates (PbSiO3, Pb3SiO5, etc.), cadmium silicates (CdSiO3, etc.) and some other substances difficult to distinguish without amorphous substance formation (Fig. 9(a)). In the PbO + CdO + Al2O3 case, at 500 °C, no lead aluminates and cadmium aluminates were found until the temperature increased up to 800 °C (Fig. 9(a) and (b)). The reaction products were lead aluminates (PbAl2O4, Pb2Al2O5, etc.), cadmium aluminates (CdAl2O4, CdAl4O7, etc.) and some amorphous substances. The reaction fractions of PbO and CdO in the PbO + CdO + Al2O3 case were lower than that in the PbO + CdO + SiO2 case because the remaining PbO and CdO were found in PbO + CdO + Al2O3 but not in the PbO + CdO + SiO2 case.
![]() | ||
Fig. 9 XRD patterns of residues derived from PbO, CdO and Si/Al mixture calcination at (a) 500 °C and (b) 800 °C in N2 atmosphere. |
Consequently, the following suspicion was proven to be true: PbO/CdO reacted with the Si/Al matrix before the occurrence of direct chlorination. Moreover, the reaction between PbO/CdO and Si/Al matrices seemed to be the necessary condition for direct chlorination. In this view, it could be called pre-reaction. In the PbO + CdO + SiO2 case, the initial temperature of the pre-reaction was below 500 °C and the initial temperature of direct chlorination was 650–700 °C. In the PbO + CdO + Al2O3 case, the initial temperature of pre-reaction was 700–800 °C and the initial temperature of direct chlorination was 800–850 °C. This indicated that this so-called pre-reaction occurred before direct chlorination. Another evidence was that the pre-reaction fraction of CdO was lower than that of PbO, and the direct chlorination fraction of CdO was lower than that of PbO as well. Based on the analysis above, the reactions between PbO/CdO and Si/Al matrices were considered as the necessary condition of direct chlorination. In the PbO + CdO + SiO2+Al2O3 case, Al2O3 seemed to inhibit the reaction between PbO/CdO and SiO2; the pre-reaction started at 700–800 °C with the products of silicates, aluminates and aluminosilicates. The inhibition effect was due to the occupation of SiO2 by Al2O3 to form silicoaluminate. The reactions in O2 or O2+H2O atmosphere were similar to that in N2 atmosphere.
The direct chlorination path was surmised by the proposed reaction equations (PbO for example), where T indicates the initial temperature of the reaction:
(1) Pre-reaction
PbO + SiO2 → PbxSiyOz T < 500 °C |
PbO + SiO2 + O2 → PbxSiyOz T < 500 °C |
PbO + Al2O3 → PbxAlyOz T > 700 °C |
PbO + Al2O3 + O2 → PbxAlyOz T > 700 °C |
PbO + SiO2 + Al2O3 → PbwSixAlyOz T > 700 °C |
PbO + SiO2 + Al2O3 + O2 → PbwSixAlyOz T > 700 °C |
(2) Chlorination
NaCl + PbxSiyOz → PbCl2 + NaxSiyOz T > 650 °C |
NaCl + PbxAlyOz → PbCl2 + NaxAlyOz T > 800 °C |
NaCl + PbwSixAlyO → PbCl2 + NawSixAlyOz T > 800 °C |
(3) Volatilization
PbCl2 → PbCl2(g) T > 650 °C or >800 °C |
The indirect chlorination was initiated above 800 °C in O2 + H2O atmosphere and O2 atmosphere and above 1000 °C in N2 atmosphere. The positive effect of atmospheres on indirect chlorination followed the sequence of H2O > O2 > N2. Compared with SiO2, Al2O3 had higher activity for reacting with NaCl, releasing HCl or Cl2. In the Cl release reaction, NaCl was in the gas phase.
The direct chlorination was initiated at 650–700 °C when the Si/Al matrix contained SiO2 only and at around 800 °C when the Si/Al matrix contained Al2O3 only or both SiO2 and Al2O3. SiO2 exhibited higher activity in direct chlorination than Al2O3. The pre-reaction between PbO/CdO and Si/Al matrices was considered as the necessary condition for direct chlorination. This indicated that NaCl reacted with the silicates, the aluminates and the aluminosilicates of Pb and Cd to produce PbCl2 and CdCl2.
During the chlorination in O2 + H2O atmosphere, indirect chlorination and direct chlorination occurred simultaneously, and the latter dominated Pb and Cd volatilization.
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