Introduction

Incineration is one of the mainstream technologies for treatment of wastes such as municipal solid waste (MSW), medical waste, and other hazardous wastes, due to its volume reduction ability, energy recovery and high efficiency. An important issue for environmental safety and human health is the increased stringency of environmental standards for controlling pollutions. There are still barriers for pollutions control, including toxic chlorinated aromatic compounds and dioxin-like compounds. De novo synthesis1,2, precursor synthesis1,3,4,5 and homogeneous gas synthesis6,7,8,9,10 have been reported to be the main mechanisms for the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs)11. De novo synthesis occurs in the presence of fly ash and chlorine in the post-combustion zone12,13,14, which is believed to contribute more to the generation of PCDD/Fs11. Generally, temperatures that favor de novo synthesis range within 300–400 °C11 and the role of CuCl2 in de novo synthesis is more significant than other metal compounds9,15,16,17. Gullett et al.18 proposed that CuCl2 catalyzes Cl2 generation by the Deacon reaction between HCl and O2, thus promoting dioxin formation. However, the Deacon reaction has been proven not to play such a decisive role13,15. Addink et al.13 compared the effects of chlorination with HCl and Cl2 on dioxin formation and observed the parallel production of PCDD/Fs. In the presence of oxygen, CuCl2 directly provides Cl, a donor for C, thus forming dioxin-like compounds19,20; this reaction has been confirmed by another study21. Takaoka et al.22 inferred that CuCl2 is involved in cyclic conversion via dechlorination and chlorination with oxygen and organic/inorganic chloride. Their theory was reconfirmed by Shao et al.23 In conclusion, CuCl2 is a potential catalyst or Cl donor that promotes the formation of chlorinated aromatic compounds.

On the basis of the known mechanism of dioxin formation, diverse inhibitors have been used in the source control or end-of-pipe removal for dioxin, including nitrogen-containing compounds (NH3, urea and (NH4)2SO4)24,25,26,27, sulfur-containing compounds (elemental sulfur, SO2, (NH4)2SO4 and coal)25,28,29,30,31, hydroxy-functional groups23 and selective catalysts for reduction (SCR)32,33,34,35. Among them, the most well-known dioxin inhibitors are highly efficient SCR, such as VOx/TiO232, V2O5/WO333 and TiO2/V2O5/WO334,35 catalysts, which usually require a complex preparation process and have high cost. Lundin and Jansson36 found that the toxic equivalent quantity of PCDF concentration decreased by 75% when the ratio of (NH4)2SO4 to HCl increased from 3:1 to 6:1. The study of Hajizadeh et al.27 indicated that SO2 was more effective than NH3 in inhibiting the formation of PCDD/Fs, while the contrast29 between (NH4)2SO4 and CO(NH2)2 was contrary. In recent years, the suppression mechanisms of the formation of chlorinated aromatic pollutants by sulfur-containing and nitrogen-containing compounds have been discussed20,28,37,38,39, including (1) transformation of Cl2 to HCl, (2) sulfonation of dioxins or precursors and (3) conversion of metal chlorides (CuCl2 or FeCl3) with high catalytic activity to inert compounds. Yan et al.29 attributed the reduction of PCDD/Fs production by urea to the reaction of ammonia with active oxidant Cl2. Shao et al.40 and Fujimori et al.28 proposed that SO2 and H2O can convert CuCl or CuCl2 to CuSO4 or CuO by detecting the residues, which was also proved by the thermodynamic equilibrium calculation41. However, the fundamental information that enables an understanding of these mechanisms is still insufficient.

Amino compounds decompose at low temperature, and their reactions with CuCl2 at low temperature are thermodynamically favorable, thereby they are generally advantageous in inhibiting CuCl2 from donating Cl to form C–Cl bonds. In this study, we studied the inhibitory effects and mechanisms of four amino compounds on chlorobenzenes (CBzs), which are important precursors42 and indicators of dioxin43. Except (NH4)2SO4, the other three were used as inhibitor for the first time and their effects were compared with (NH4)2SO4. Thermal analysis, which is beneficial to distinguishing the characteristic thermal reactions between inhibitors and model fly ash, was conducted combining with the simulated experiments, to reveal which one was more effective in inhibiting CBzs formation and why (mechanism).

Results

Effect of inhibitors on CBzs formation

The yields of the five CBzs and their total value on the mass basis of the SFA (μg/g-fly ash) are shown in Fig. 1. The total chlorine in the CBzs (equation (1)) and the degree of chlorination (equation (2)) were calculated from these yields (Fig. 1). The inhibition ratios for CBzs formation with each inhibitor were calculated through equation (3) and presented in Fig. 2.

Figure 1
figure 1

CBzs yields, total chlorine in CBzs and the degree of chlorination under air (a) and nitrogen (b) flow.

Figure 2: Inhibition ratios of CBzs and total chlorine in CBzs under air (a) and nitrogen (b) flow (The concentration of 1,4-CBz from SFA-N2 was below the detection limit, thus the inhibition ratios were not calculated.
figure 2

The slight increases of 1,4-CBz in IP-N2, Is-N2, IF-N2, IBr-N2 were found, i.e., 0.08, 0.02, 0.007, and 0.1 μg/g-fly ash compared with SFA-N2).

where i is the type of CBzs, j is the type of sample, and TCl, j is the total amount of chlorine in the CBzs on mass basis of the SFA sample j (μg/g-fly ash), Yi, j and Yi, SFA are the yields of CBz i on the mass basis of the SFA sample j and SFA, respectively (μg/g-fly ash), F i is the mass fraction of chlorine in CBz i (dimensionless), DCl, j is the degree of chlorination of sample j (dimensionless), ni is the number of chlorine atoms in the CBz molecule i (dimensionless), MWi is the molecular weight of i (mol/g), and IRi, j is the inhibition ratio of CBz i for the sample j (%).

Under air flow, the yields of low-chlorinated CBzs (1,2di-CBz, 1,3di-CBz, and 1,4di-CBz) were much lower than those of high-chlorinated CBzs (penta-CBz and hexa-CBz) in SFA, similar to the trends for the NH4H2PO4 (IP), (NH4)2SO4 (IS), NH4HF2 (IF), and NH4Br (IBr) runs. This result indicated that high-chlorinated CBzs formed more easily than low-chlorinated CBzs did. A study by Fujimori et al.28 also showed similar distribution ratios, but the absolute yield of each CBz in the present study was higher because of the larger amount of CuCl2·2H2O added, which is necessary for determining the mechanism. As shown in Fig. 1, chlorine from the two CBzs accounted for a large proportion of the total chlorine because of the high yield and high fraction of chlorine in penta-CBz and hexa-CBz.

Compared with that of SFA, the total yield of CBzs and the total chlorine in CBzs decreased by various degrees upon addition of inhibitors under air flow, especially in the case with NH4H2PO4 addition. The yields of low-chlorinated CBzs (1,2di-CBz, 1,3-CBz, 1,4-CBz) and high-chlorinated CBzs (penta-CBz, hexa-CBz) for the SFA–Air mixture were 1.7 and 71 μg/g-fly ash respectively, which significantly decreased to 0.28 and 1.2 μg/g-fly ash for the IP–Air mixture. Formation of all CBzs was inhibited by 41%–100%. The total chlorine from CBzs also decreased, and the degree of chlorination changed from 5.5 to 3.3. The other three inhibitors had different effects on the yields of different CBzs. To evaluate the reduction of CBzs formation, NH4H2PO4 was compared with those inhibitors. Kuzuhara25 found that the amount of formed PCDD/Fs decreased significantly upon addition of ammonia or urea. A possible mechanism for the suppression is a competing reaction of organic compounds with NHi and CN radicals, which are produced from urea or ammonia decomposition. However, they suggested that further studies are necessary to evaluate the effect of these compounds on the behavior of copper and the role in the de novo synthesis.

With IS under air flow, the total yield of CBzs decreased by 37%, and the penta-CBz yield decreased by 92% to 3.0 μg/g-fly ash. The degree of chlorination did not decrease, but the total chlorine from CBzs declined by 36%. In Yan’s29 study, (NH4)2SO4 reduced the yield of PCDD/Fs in the gas phase by about 93% (about 60% PCDDs and 98% PCDFs); when gaseous SO2 was used28, the yields of CBzs, PCDDs, and PCDFs were reduced by about 50%, 30%, and 50%, respectively. Thus, (NH4)2SO4 and SO2 are effective inhibitors of dioxin and CBzs formation. The mechanism of (NH4)2SO4 inhibition of CBzs de novo synthesis is discussed later. Some S-containing or N-containing compounds showed inhibitory effects on dioxin synthesis, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and Na2S44. These effects were explained owing to the interaction between inhibitors and catalysts such as Cu.

Based on the inhibitory effects of the amino compounds on CBzs formation, NH4HF2 and NH4Br were selected to study their potential effects on controlling CBzs. The results show that the inhibition effect of NH4HF2 is similar to that of (NH4)2SO4 on the synthesis of low-chlorinated CBzs and penta-CBz, while NH4HF2 is better on the hexa-CBz inhibition. The degree of chlorination in IF decreased from 5.5 to 5.2 with inhibitions on penta-CBz and hexa-CBz. The effect of NH4Br was smaller than that of the other three, but it still reduced the formation of all CBzs and the total yield of CBzs by 3%–88.7%.

Under nitrogen flow, CBzs yields in all cases were very low compared with those obtained under air flow. This difference is due to the difficulty of C–C bond scission in the absence of oxygen, which leads to formation of aromatic compounds22, in agreement with the study of Yan29. Upon addition of any of the inhibitors, the total yield of CBzs decreased along with the significant decrease in the yield of penta-CBz and hexa-CBz (Fig. 2b). The concentration of 1,4-CBz from SFA-N2 was below the detection limit, thus the inhibition ratios were not calculated. The slight increases of 1,4-CBz in IP-N2, Is-N2, IF-N2, IBr-N2 were found, i.e., 0.08, 0.02, 0.007, and 0.1 μg/g-fly ash compared with SFA-N2.

Chlorobenzenes are closely associated with PCDD/Fs production43,45,46. The amounts of the most toxic congeners, 2,3,7,8-TCDD and 2,3,4,7,8-PeCDF, with respect to amounts of penta-CBz have high correlation coefficients45. In this study, all additives showed clear inhibitory effects on CBzs synthesis; they decreased the total CBzs yields under air or nitrogen flow (Fig. 2c,d). The inhibitory effects on CBzs production follow the order NH4H2PO4 > NH4HF2 > (NH4)2SO4 > NH4Br under air flow and NH4H2PO4 ≈ (NH4)2SO4 ≈ NH4HF2 >NH4Br under nitrogen flow. Many studies reported the effects of N-containing and S-containing compounds on PCDD/Fs formation, but less on CBzs formation. NH4H2PO4 in this study showed significantly higher inhibition on CBzs formation than gaseous SO2 by Fujimori et al.28, while (NH4)2SO4 showed a little less inhibition effect. In Hajizadeh’s study, both SO2 and NH3 were effective in inhibiting the formation of PCDD/Fs27, and the effect of SO2 was more significant than that of NH3. Even though some controversies existed in the synergistic or competitive effect on PCDD/Fs inhibition by S-containing and N-containing compounds, (NH4)2SO4 as a complex of S and N has been confirmed to have the restraint effect on PCDD/Fs29 as well as CBzs in this study. In the contrast of (NH4)2SO4 with NH4H2PO4 and NH4HF2, especialy NH4H2PO4, showed the significant increase of inhibition efficiency on CBzs. Thus, the amino compounds can decompose and produce reactive radicals that are highly-efficient on suppressing CBzs.

Thermal analysis of the SFA samples

As discussed above, the four amino compounds influence the profile of CBzs. However, the reason why they showed different inhibitory results, and how they affected CBzs formation were not clear, which might be related to their thermochemistry. To better understand the inhibition mechanism and to observe the physical transformation or chemical reactions, thermal analysis using TGA and DSC was conducted. The fraction of CuCl2 was increased to higher than that in real fly ash, so that the important physical-chemical changes could be observed together with the change of CBzs formation. Commonly used (NH4)2SO4 was included in this studies for the comparison.

As shown in Fig. 3a,b, CuCl2·2H2O gradually underwent dehydration (21 wt.%) at 50–100 °C and started to lose weight at 343 °C (air) or 348 °C (nitrogen). When the temperature reached 900 °C, the weight decreased by about 55% under air flow and by 65% under nitrogen flow. Under both atmospheres, one endothermic peak was produced at 441–445 °C. Another appeared at 471 °C only in the presence of oxygen. Under nitrogen flow at 350 °C, CuCl2 dechlorinated, forming CuCl, which volatilized at 438–441 °C. Therefore, the residue formed at 400 °C and detected by XRD includes CuCl only (Fig. 4b). A similar finding was reported by Liu et al.47 Under air flow, the residue obtained at 400 °C includes CuCl only (data not shown), whereas that obtained at 500 °C consisted of CuCl and CuO (Fig. 4a), which is in accord with the dechlorination observed by Takaoka et al.22 The endothermic peak on the DSC curve and the smaller weight loss (10% less) compared with that under nitrogen flow suggest that oxygen oxidizes CuCl to CuO. The reactions and corresponding temperatures are indicated in equations (4)–(7). In the absence of other chlorine source, CuCl2 produces chlorinated aromatic compounds, behaving as a Cl resource, transferring Cl to the C surface, and bonding with C. Takaoka et al.16 and Fujimori et al.28 found that the thermochemical conversion of CuCl2 and thermal reaction of CuCl2 with SO2 occurred at below 300 °C and 280–350 °C respectively. In this study, the thermal conversion observed by DSC gave a direct and specific temperature that CuCl2 decomposed, which is propitious to mechanism study.

Figure 3
figure 3

TGA-DSC of CuCl2·2H2O, AC, SFA, NH4H2PO4 and IP under the air (a,c,e,g,i,k) and nitrogen (b,d,f,h,j,l) flow.

Figure 4
figure 4

XRD patterns of the residues under air (a) and nitrogen (b) flow.

To identify the characteristic DSC peaks, AC and silica were respectively analyzed by TGA and DSC, respectively. In the presence of oxygen, AC started to combust at 400 °C (Fig. 3e), producing an intense exothermic peak. This also quickly increased the interior temperature, while the weight and heat flow remained stable under nitrogen flow (Fig. 3f). As no significant changes in TGA and DSC curves for silica were observed, they are not displayed.

The calculated weight loss of SFA consisting of AC and CuCl2·2H2O under air flow (according to the weight loss in TGA and mass fraction) was 9.5%, and the actual weight loss was 15%. This difference is probably caused by the greater volatilization of CuCl at higher internal temperature and the greater emission of aromatic compounds in the presence of oxygen. Under nitrogen flow, there was almost no difference in weight losses. XRD patterns (Fig. 4) show that the residue under air flow includes Cu2OCl2 and CuO and that under nitrogen flow includes CuCl, Cu, and Cu2Cl(OH)3. The presence of CuO under air flow contradicts with the results of thermal analysis in the 50–400 °C range (Fig. 3c), probably because the combustion of carbon in this system can increase the interior temperature.

Discussion

According to Fig. 3i,j, NH4H2PO4 started to decompose at 203 °C under either air or nitrogen flow. An endothermic peak appeared at almost the same temperatures. NH4H2PO4 decomposed into gaseous NH3 and H2O and solid-phase HPO3, as shown by the weight loss (~30%) and by thermodynamic calculation (equation (8)). The weight loss for IP under air flow was calculated by summing the respective weight losses of silica, AC, CuCl2·2H2O, and NH4H2PO4. The sum should be ~20% if there was no interaction between CuCl2 and NH4H2PO4. The real weight loss was 10% less than the calculated value, indicating the occurrence of interaction. In addition, endothermic peaks were produced at 100 °C and 191 °C under both atmospheres (Fig. 3k,l) and an exothermic peak was produced at 400 °C under air flow. Both indicate dehydration, a reaction between NH4H2PO4 and CuCl2, and carbon combustion. According to the XRD results (Fig. 4), the products included Cu2P2O7 (Cu(PO3)2·CuO) (air), as well as CuCl and Cu(PO3)2 (nitrogen), which suggest that CuCl2 reacted with NH4H2PO4 (equation (9)). In contrast to SFA, CuCl2 converted to Cu(PO3)2 at a lower temperature instead of transferring Cl to C; thus, CBzs formation was restrained significantly. This not only explains the mechanism, but also suggests that CuCl2 was the main Cl source. The diminution of the total chlorine in CBzs when NH4H2PO4 was applied was caused by the decrease in the yield of CBzs and the degree of chlorination.

The suppression effects of (NH4)2SO4, (NH4)2S2O3, CO(NH2)2S, and SO2 on the formation of PCDD/Fs have been studied23,25,28,29,36, but the mechanisms with these inhibitors are not as clear as that with SO2. One proposed mechanism is the conversion of copper into non-reactive sulfates30. Partial sulfation of CuCl2 by SO2 in the presence of O2 to CuSO4 and Cl2 has been reported28. Below 400 °C in this study (Fig. 5), (NH4)2SO4 completely decomposed into gaseous NH3, H2O, and SO3, producing endothermic peaks at 293 °C (air) and 297 °C (nitrogen) (equation (10)). Upon addition of (NH4)2SO4 to SFA, endothermic peaks were produced at 100, 260, and 312 °C under air flow, as well as at 100, 263, and 312 °C under nitrogen flow. An exothermic peak at 400 °C was also produced under air flow. The characteristic peaks at 260–263 °C under both atmospheres do not correspond to the constituents of IS, indicating that a reaction between CuCl2 and remaining (NH4)2SO4 occurred with this endothermic phenomenon (equation (11)). When there was no interaction between SFA and (NH4)2SO4, the calculated weight loss was 9% less than the experimental value, suggesting that some products remained in the residues. The XRD results show Cu2OCl2, CuO, and weak CuSO4·H2O peaks, which indicate that dechlorination and sulfation were simultaneous, with dechlorination being dominant. Therefore, the inhibitory effect was weaker than that of NH4H2PO4. Although the total yield of CBzs and the total chlorine in CBzs decreased, the degree of chlorination did not decline because hexa-CBz easily formed with the stable structure.

Figure 5
figure 5

TGA-DSC of (NH4)2SO4 and IS under air (a,c) and nitrogen (b,d) flow.

NH4HF2 easily decomposed as shown in Fig. 6. It transformed into gas from 80 to 270 °C under both air and nitrogen flow (equation (12)). There was a characteristic endothermic peak at 130 °C signifying this decomposition process. When NH4HF2 was added, faint endothermic peaks were produced at 95, 205, and 400 °C under air flow, as well as at 98 and 213 °C under nitrogen flow. Multiple-step weight losses occurred at temperature ranges of 72–114 °C, 158–216 °C, and 325–400 °C under air flow, as well as at 75–112 °C and 159–297 °C under nitrogen flow. These weight losses correspond to hydration, a reaction between CuCl2 and NH4HF2, and carbon combustion. The residue (Fig. 4) formed under air flow was a mixture of CuO, Cu2OCl2, and CuF2, whereas that formed under nitrogen flow consisted of CuF2. The reaction temperature for equation (13) was higher than that for NH4HF2 decomposition. In addition, the amount of the functional radical of F did not exceed that of Cu2+, thus decreasing the degree of conversion and the inhibitory effect. The yields of CBzs and the degree of chlorination of IF were lower than those of IP, indicating low degree of conversion.

Figure 6
figure 6

TGA-DSC of NH4HF2 and IF under air (a,c) and nitrogen (b,d) flow.

Similar to NH4HF2, NH4Br is an unstable amino compound below 400 °C, producing an endothermic peak at 155 °C (Fig. 7). From 180 to 375 °C, NH4Br started to decompose (equation (14)) and lost weight completely. As the TGA curves show, two-step weight losses occurred at 179–313 °C and 350–400 °C under air flow, and one-step loss occurred at 176–350 °C under nitrogen flow when NH4Br was added to SFA. The DSC curves obtained under air flow show weak endothermic peaks at 144 and 268 °C and intense peaks at 400 °C. Those obtained under nitrogen flow have peaks at 100, 146, and 277 °C. New peaks at 268 °C (air) and 277 °C (nitrogen) are characteristic of the product IBr, indicating that there was an interaction between SFA and NH4Br. This interaction is also evidenced by comparison between the actual and calculated weight losses. The residues obtained under air flow (Fig. 3) and under nitrogen flow consisted of CuO and CuBr, respectively. Consistent with the results of thermal analysis and XRD, CuCl2 could react with NH4Br during its decomposition (equation (15)). As these two changes occurred under almost same temperature ranges, the inhibitory effect decreased.

Figure 7
figure 7

TGA-DSC of NH4Br and IBr under air (a,c) and nitrogen (b,d) flow.

Methods

Materials

The mass composition of the simulated fly ash (SFA) in each experiment is shown in Table 1. The inhibitors were added at Cu/H2PO4, Cu/SO42−, Cu/HF2 and Cu/Br molar ratios of 0.5 and then blended with other constituents.

Table 1 Mass fraction of the compounds used in the experimental runs.

Before use, activated carbon (AC) was milled to <150 μm and heated at 600 °C under nitrogen flow to allow desorption. Amorphous silica milled to <150 μm was used as a matrix to avoid high intensities of diffraction peaks. Analytical-reagent-grade AC, CuCl2·2H2O and the amino compound inhibitors (NH4H2PO4, (NH4)2SO4, NH4HF2, NH4Br), as well as reagent-grade 1,3,5-tribromobenzene (internal standard), were purchased from Sinopharm Chemical Reagent Co. Ltd. (China). Guaranteed reagent grade CBzs mixture standard (1,2di-CBz, 1,3di-CBz, 1,4di-CBz, penta-CBz, and hexa-CBz), HPLC-grade hexane, acetone, and XAD-II resin (Supelco) were purchased from Sigma-Aldrich Company. Florisil solid-phase extraction columns were obtained from ANPEL Laboratory Technologies (Shanghai) Incorporated.

Simulation experiments

The experiments were carried out in duplicate with a tube furnace, equipped with an XAD-II resin tube and two impingers in series (the first being empty and the second filled with 100 mL of hexane), which absorbed CBzs in the flue gas. The temperature was maintained at 400 °C, and the gas flow (air and nitrogen) was set at 1000 mL/min. Each quartz crucible was filled with 5 g of the sample, placed in the middle chamber in 30 s, and then held there for 60 min. Then the residues in the crucibles were cooled down under the air or nitrogen flow, and were collected for X-ray diffraction measurement (XRD, D8 Advance, Bruker, Germany) using Cu Kα radiation.

The XAD-II resin was collected and extracted with 100 mL of hexane at 140 °C for 5 h by using an automatic Soxhlet extractor (Soxtec TM 2050, Foss, USA). The extract was then mixed with the absorption solvent and concentrated to about 10 mL by rotary vacuum evaporation (R1002B, Senco, China) in water bath at 85 °C. Then nitrogen evaporation (N-EVAD, Organmation, USA) with 2 mL/min N2 flow was used to further concentrate the liquid to 2 mL. The concentrate was loaded into a Florisil solid-phase extraction cartridge (Visiprep DL SPE, supelco, USA) for purification, and then eluted by 10 mL of the mixture of acetone and hexane (1/9, v/v). The elute was concentrated by the nitrogen evaporation to 1 mL before analysis by gas chromatography (GC) (Trace, Thermo, USA).

The GC was equipped with a HP-5MS column (30 m × 0.25 mm ID) (Agilent, USA) and an electron capture detector. The oven temperature program was set at: 40 °C for 1.5 min, 10 °C/min to 100 °C with 3 min holding time, 10 °C/min to 240 °C with a final hold of 1 min. The carrier gas was helium (30 mL/min), the detector temperature and transfer line temperature were set at 300 °C and 250 °C respectively. The analysis of 1,2di-CBz, 1,3di-CBz as well as 1,4di-CBz were splitless, penta-CBz and hexa-CBz were split with split ratio 10:1. The yields of 1,2di-CBz, 1,3di-CBz, 1,4di-CBz, penta-CBz, and hexa-CBz were calculated on the mass basis of fly ash. The recovery ratios for the analysis of CBzs in the resins ranged within 70%–130%.

Thermogravimetric analysis (TGA) and differential scanning calorimeters (DSC) (Q600 SDT, TA instrument, USA) were used for thermal analysis of the samples. Heating was done at a rate of 10 °C/min from 50 °C to specified values, at which the temperature was maintained for more than 60 min. The flow rate of air or nitrogen was adjusted to 100 mL/min.

Additional Information

How to cite this article: Wang, S.-J. et al. Amino Compounds as Inhibitors of De Novo Synthesis of Chlorobenzenes. Sci. Rep. 6, 23197; doi: 10.1038/srep23197 (2016).