Journal of Hazardous Materials 221–222 (2012) 193–198

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Journal of Hazardous Materials

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Removal of brominated flame retardant from electrical and electronic waste

plastic by solvothermal technique
Cong-Cong Zhang, Fu-Shen Zhang ∗
Research Center For Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085, China

a r t i c l e i n f o a b s t r a c t

Article history: Brominated flame retardants (BFRs) in electrical and electronic (E&E) waste plastic are toxic, bioaccu-
Received 29 January 2012 mulative and recalcitrant. In the present study, tetrabromobisphenol A (TBBPA) contained in this type
Received in revised form 21 March 2012 of plastic was tentatively subjected to solvothermal treatment so as to obtain bromine-free plastic.
Accepted 12 April 2012
Methanol, ethanol and isopropanol were examined as solvents for solvothermal treatment and it was
Available online 20 April 2012
found that methanol was the optimal solvent for TBBPA removal. The optimum temperature, time and
liquid to solid ratio for solvothermal treatment to remove TBBPA were 90 ◦ C, 2 h and 15:1, respectively.
Keywords:
After the treatment with various alcohol solvents, it was found that TBBPA was finally transferred into
WEEE
Brominated flame retardant
the solvents and bromine in the extract was debrominated catalyzed by metallic copper. Bisphenol A and
Solvothermal process cuprous bromide were the main products after debromination. The morphology and FTIR properties
Debromination of the plastic were generally unchanged after the solvothermal treatment indicating that the struc-
ture of the plastic maintained after the process. This work provides a clean and applicable process for
BFRs-containing plastic disposal.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction plastic and following destruction of BFRs is imperative to reduce

such negative environmental effects.
With the market expansion of electrical and electronic (E&E) A promising way of removing BFRs from E&E plastic is supercrit-
equipment during the last two decades, around 20–50 million ical carbon dioxide (Sc-CO2 ) extraction, in which harmless plastic
tons of waste electrical and electronic equipment (WEEE) are gen- as well as high-priced BFRs were recycled [12]. Further studies [13]
erated worldwide every year [1]. Generally, WEEE contains 18% indicated that the removal efficiency of BFRs by solvent extraction
styrenic polymers such as acrylonitrile–butadiene–styrene (ABS), was better than that of Sc-CO2 modified with solvents. Recently, we
high impact polystyrene (HIPS) and polystyrene (PS) [2]. In view of have revealed that solvothermal process was a powerful method
the growing interest in the sustainable use of resources, recycle use to remove organic pollutants from soil matrix [14]. As a conse-
of E&E waste plastic is becoming more and more important, espe- quence, we applied this technique to the removal of BFRs from
cially since European commission published the directive on WEEE, E&E waste plastic. As for dehalogenation of aromatic halides, a
which has set high recycling targets for E&E waste plastic [3,4]. few methods using metals (Fe, Ni, Zn, etc.) were developed thus
Moreover, it should be noted that high concentration of bromi- far [15–20]. Among these studies, it was discovered that metallic
nated flame retardants (BFRs), mainly polybrominated diphenyl calcium in ethanol was highly effective at ambient temperature
ether (PBDE) and tetrabromobisphenol A (TBBPA) [5,6], were added [15,16]. Moreover, copper has been extensively studied due to pos-
to plastic matrices during the manufacture of E&E equipment to sible Ullmann reactions (i.e. coupling of aryl halides with copper)
increase the fire resistance of the product. Owing to the lipophilic [17–20]. Meanwhile, zinc dust/sodium hydroxide/ammonium for-
and bioaccumulative nature of these BFRs [7], the recovery of E&E mate system is highly effective for the debromination of TBBPA
waste plastic has further become a challenging task for decades. to bisphenol A [21]. Therefore, we also combined these meth-
Various technologies, including landfills [8], incineration [9], ods to conduct the debromination of BFRs. To our knowledge,
pyrolysis [10] and mechanical recycling [11] have been developed there is no report regarding application of solvothermal proce-
for disposal of E&E waste plastic. However, among these tech- dure for the removal and debromination of BFRs from E&E waste
niques, contamination by harmful bromine-containing compounds plastic.
is inevitable [8–11]. Elimination of BFRs before recycling E&E waste The primary objective of this study was to evaluate the effective-
ness of solvothermal procedure for the removal of BFRs from E&E
waste plastic. Effects of various conditions on BFRs removal effi-
ciency were evaluated, and a suitable procedure for debromination
∗ Corresponding author. Tel.: +86 10 62849515; fax: +86 10 62849515.
of BFRs in organic solvent was also established.
E-mail address: [email protected] (F.-S. Zhang).

0304-3894/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
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194 C.-C. Zhang, F.-S. Zhang / Journal of Hazardous Materials 221–222 (2012) 193–198

2. Experimental stainless steel capsule. The bomb was assembled and purged with
oxygen for 1 min. The bomb was then immersed in a water bath at
2.1. Materials room temperature, ignited by an electric discharge and kept in the
water bath for 30 min. After the pressure of the bomb was reduced,
Waste computer housing plastic was supplied by HuaXing Envi- the sample capsule and the interior of the bomb were rinsed with
ronment Protection Co. Ltd. The plastic, which was ABS resin with Milli-Q water and collected in a 100 mL volumetric flask. The sam-
TBBPA as additive flame retardant, was cut into small pieces and ple solution was filtered through a 0.45 ␮m membrane filter before
ground to 14–20 mesh by a grinder under cooling with liquid IC analysis. IC analysis was performed using an ion chromatograph
nitrogen. HPLC grade acetone, methanol, ethanol and isopropanol (ICS-2000, Dionex, USA) with an IonPac AS18 (4 mm × 250 mm)
were purchased from J&K Chemical Ltd., USA. Standard stock solu- analytical column and IonPac AG18 (4 mm × 50 mm) guard col-
tion of bromine ion (1000 mg/L) was purchased from the National umn, coupled to an ASRS-300 4 mm suppressor. Hydroxide eluent
Research Center for Certified Reference Materials of China and gradients were generated online using EGC II KOH cartridge. A con-
TBBPA (≥97% purity) was supplied by ACROS Ltd., USA. Anhydrous tinuously regenerated anion trap column (CR-ATC) was installed
sodium sulfate (Na2 SO4 ) and copper powder (200 mesh) were ana- at the EGC eluent outlet. The optimized hydroxide eluent gradi-
lytical reagents from domestic manufacturers. ent was: 0–7 min: 12 mM isocratic; 7–8 min: gradient from 12 to
40 mM; 8–15 min: 40 mM isocratic; 15–20 min: 12 mM isocratic.
2.2. Experimental procedures As for the identification of bromine in the spent copper powder,
spent copper powder (0.50 g) was stirred in 10 mL of 0.1 M HNO3
A series of reactors consisted of 100 mL Teflon interiors and for 24 h. On the termination of the reaction, the mixture was sep-
stainless exteriors were employed for the solvothermal experi- arated by centrifugation (10,000 g, 10 min, TG16-WS, China). The
ments. In a typical run, a certain amount of organic solvent and obtained solution was used in Mohr’s titration [15] after adjusting
weighed plastic were introduced into a reactor and the reactor pH to 6.5–10.5 with 1 M NaHCO3 .
was sealed. The reactor was then placed into an oven, raised to the TBBPA in solvent phase was analyzed by an Agilent 7890A gas
desired temperature and held for a specified time. On the termina- chromatograph equipped with an Agilent 5975 C mass spectrom-
tion of the reaction, the mixture was separated by centrifugation etry detector and a HP-5 capillary column (USA). High purity He
(10,000 g, 10 min, TG16-WS, China). The solid phase was allowed was used as carrier gas with a flow rate of 1 mL/min. The column
to air-dry overnight, followed by oxygen bomb combustion and ion temperature of chromatographic analysis was programmed as fol-
chromatography (IC) analysis to determine the bromine content in lows: the initial oven temperature was set at 50 ◦ C and ramped to
the solid phase. The solvent phase was first evaporated on the vac- 150 ◦ C at 20 ◦ C/min, then to 180 ◦ C at 10 ◦ C/min, finally to 280 ◦ C at
uum rotary evaporator for solvent substitution with acetone and 3 ◦ C/min hold for 2 min. HPLC analysis was accomplished by Agilent
then dehydrated by anhydrous sodium sulfate. After concentrated, 1200 (USA) with a C18 reversed-phase column (150 mm × 4.6 mm,
the solvent phase was transferred to Kuderna–Danish (K–D) con- 5 ␮m particles, Agilent, USA), a diode array detector and an auto
centrator and evaporated to 1 mL under a stream of nitrogen flow sampler controlling under a Chemstation data acquisition sys-
for gas chromatography–mass (GC/MS) analysis of TBBPA. tem. The measurement was performed in a methanol/water = 85:15
There solvents, i.e. methanol, ethanol and isopropanol were (v/v) as mobile phase with a flow rate of 1 mL/min and a detec-
examined to compare their solvothermal removal efficiency for tion wavelength of 230 nm. The type of plastic was identified by
TBBPA. The temperature varied from 50 ◦ C to 170 ◦ C at constant in situ Fourier transform infrared (FTIR) spectrometer (BrukerTen-
time and liquid to solid ratio, the treating time varied from 0.5 h sor27). XRD analysis was carried out using Philips PW 1700 X-ray
to 15 h at constant temperature and liquid to solid ratio, and the diffractometer.
liquid to solid ratio varied from 5:1 to 20:1 (mL/g) at constant tem- Procedure blanks were run to determine background levels.
perature and time were performed to optimize the parameters of Blank levels for the solvothermal procedure were typically ≤3% of
solvothermal process to remove TBBPA. the concentrations of TBBPA in the samples. The presented concen-
Since it is hard to separate copper and plastic if they were com- trations were corrected accordingly. Bromine ion was not detected
bined and this is unfavorable for recycle use of copper and plastic, in blank test for oxygen bomb combustion. Each experiment was
only the solvent extract and copper powder were combined for carried out in triplicate for parallel test, and average values with
possible debromination of TBBPA. In this section, methanol extract standard errors were reported.
(15 mL) and copper powder (0.50 g) were introduced to the 100 mL
Teflon interior placed inside the stainless exterior. The reactor was
sealed, placed into the oven, and the temperature was increased 3. Results and discussion
to 150 ◦ C and maintained for 10 h. After cooling to room tempera-
ture, the mixture was separated by centrifugation (10,000 g, 10 min, 3.1. Characterization of the solvothermal products
TG16-WS, China). The spent copper powder was allowed to air-
dry and subjected to X-ray diffraction (XRD) analysis. The liquid The chromatogram of solvent phase by solvothermal treatment
product was subjected to GC/MS and high performance liquid chro- reveals TBBPA was the major component of extract in all cases
matography (HPLC) analysis after solvent substitution and sodium (Fig. 1), followed by corresponding hexadecanoic esters and octade-
sulfate dehydration. This mixture of methanol extract (15 mL) and canoic esters. As shown in Fig. 1(a)–(c), ethyl ester, methyl ester and
copper powder (0.50 g) was also stirred at room temperature for isopropyl ester of hexadecanoic acid and octadecanoic acid were
24 h and compared with the above results. formed respectively with ethanol, methanol and isopropanol as sol-
vents, which means a small amount of alcohol solvents participated
2.3. Analytical procedures the reaction. These products were not observed under milder con-
ditions such as lower temperature and less time (Fig. 1(d) and (e)).
The oxygen bomb combustion-IC was applied for the analysis of Five TBBPA calibration solutions were prepared for the quantifi-
bromine content in raw plastic and solid phase after solvothermal cation and the corresponding bromine contents were calculated
treatment [22,23]. In a typical run, 10 mL Milli-Q water (Millipore, according to the chemical formula of TBBPA.
USA) was transferred to the bomb with moistening of its inner sur- Oxygen bomb combustion-IC analysis of raw plastic indicated
face. Accurately weighed solid sample (0.2–0.5 g) was placed into a that the bromine content accounted for 7.45% of the total plastic
 C.-C. Zhang, F.-S. Zhang / Journal of Hazardous Materials 221–222 (2012) 193–198 195

Fig. 1. GC/MS chromatograms of the solvothermal extracts. Solvents, temperature, time and liquid to solid ratio conditions: (a) ethanol, 150 ◦ C, 10 h, 15:1; (b) methanol,
150 ◦ C, 10 h, 15:1; (c) isopropanol, 150 ◦ C, 10 h, 15:1; (d) isopropanol, 50 ◦ C, 10 h, 15:1; (e) isopropanol, 150 ◦ C, 30 min, 15:1.

(wt.%). After solvothermal treatment at 90 ◦ C for 2 h, the residue methanol is considered as superior solvent because of the mini-
amount of bromine in the plastic was reduced to 1.87% (wt.%). Fur- mum loss of bromine. Accordingly, it is necessary to determine the
ther treatment under the same condition showed that no bromine optimal solvent for maximum recovery and minimum loss of BFRs,
was detected in the plastic. This result confirmed the feasibility of as also demonstrated by Bandh et al. [29].
solvothermal procedure for TBBPA removal from E&E waste plastic. Fig. 3 shows that bromine in solvent increased with tempera-
ture below 90 ◦ C and then basically kept constant in a certain range
at higher temperature (90–170 ◦ C). This implies that certain inter-
3.2. Optimization of solvothermal procedure
molecular bonds between TBBPA and plastic can easily be broken
at higher temperatures, and this is probably the decisive advantage
The solvent property plays a critical role in solvothermal treat-
of solvothermal procedure. Meanwhile, certain temperature range
ment of additive BFRs from plastic. The solvent should have high
(>90 ◦ C) cannot promote the further removal of TBBPA remarkably
affinity for both BFRs and the plastic, inducing certain swelling
(Fig. 3). According to previous reports [2,24], diffusion rates of BFRs,
effects in the plastic but without causing dissolution of plastic, as
both in the plastic core and in the boundary layer around the plas-
also demonstrated by previous studies [2,24]. Meanwhile, the use
tic surface were higher at elevated temperatures. The solubility of
of hazardous solvents should also be avoided. Alcohol solvents such
BFRs in the solvent and the mass transfer from the boundary layer
as methanol, ethanol and isopropanol were thus considered. As can
be seen from Fig. 2, all of the selected solvents achieved high TBBPA
removal efficiency. Previous reports [24,25] have also indicated
that alcohol solvents, which may not perform as good extraction
solvent at moderate pressure and temperature, can be efficiently
employed for accelerated solvent extraction. The bromine con-
tents in the solid phase were 19.3%, 17.8% and 17.0% of total
bromine respectively with methanol, ethanol and isopropanol as
solvents. This indicated that there was no significant difference in
the removal efficiency of TBBPA between these solvents. Further-
more, the loss of bromine content was calculated by subtracting
the bromine content of solid phase and solvent phase from the ini-
tial bromine content of raw plastic. It should be noted that there
were 2.4%, 29.8% and 12.2% losses of bromine in methanol, ethanol
and isopropanol respectively. According to previous reports, these
different losses of bromine could be attributed to the different
polarities of the solvents [2] and the solubility of TBBPA in the sol-
vents [26–28]. Previous studies have also indicated that the storage
of hexabromocyclododecane in n-hexane, isooctane and acetoni-
trile resulted in loss of hexabromocyclododecane [26–28]. All of
these findings indicated that the loss of hexabromocyclododecane
in solvent was attributed to glass absorbance due to the low solu- Fig. 2. Effect of solvent type on Br distribution. Conditions: temperature 150 ◦ C;
bility of hexabromocyclododecane in these solvents. In this study, time 10 h; liquid to solid ratio 15:1.
196 C.-C. Zhang, F.-S. Zhang / Journal of Hazardous Materials 221–222 (2012) 193–198

Fig. 3. Effect of temperature on Br distribution. Conditions: solvent isopropanol;

time 10 h; liquid to solid ratio 15:1. Fig. 5. Effect of liquid to solid ratio on Br distribution. Conditions: solvent iso-
propanol; temperature 150 ◦ C; time 10 h.

to the solvent were enhanced at increased temperatures [2,24].

Moreover, the swelling ratio between the plastic and the solvent polarity of BFRs. The temperature and time were the most signif-
was also influenced by temperature [2,24]. Thus, temperature plays icant factors for extraction process. Meanwhile, other conditions
an essential role in the extraction process. By contrast, the residue such as solvent and particle size had no significant effects on BFRs
amount of bromine in the solid phase decreased rapidly with a dras- removal as discussed for microwave-assisted extraction [2,31].
tic drop at lower temperature (50–90 ◦ C) and then remained almost
the same below 170 ◦ C. In this case, 90 ◦ C is considered as optimal 3.3. Advantages of the solvothermal process
temperature with the lowest remaining of bromine in plastic after
solvothermal treatment. Compared with conventional extraction processes, solvother-
As demonstrated in Fig. 4, the effect of time on bromine dis- mal procedure consumes less solvent, shortens extraction time,
tribution had similar trend with the temperature. The bromine in shows better applicability and broadens the range of solvent type,
solvent increased as the prolonging of time till about 2 h and then as also demonstrated by Lou et al. for accelerated solvent extrac-
remained basically unchanged. The residue amount of bromine in tion [24]. In previous reports [13], toluene has been extensively
plastic achieved lowest after 2 h treatment. It also should be noted examined as an efficient solvent in conventional extraction pro-
that, the bromine in solid phase decreased rapidly initially and then cesses to remove BFRs from waste plastic. However, toluene is a
varied in a certain range as the increase of liquid to solid ratio kind of highly toxic chemical, thus alcohol solvents obviously show
(Fig. 5). The lowest remaining of bromine in plastic was achieved superiority over toluene.
till the liquid to solid ratio was 15:1. Under this condition, a period Similar to the process of accelerated solvent extraction [24],
of 2 h and a liquid to solid ratio of 15:1 were adequate to obtain the superior removal performance of solvothermal procedure was
maximum removal efficiency. attributed to the enhanced temperature and slightly higher pres-
The foregoing results were in accordance with previous reports sure as compared to conventional extraction processes. In the
[2,25,30,31], which suggested that the extraction efficiency was solvothermal procedure, BFRs are extracted at temperatures above
conditioned by the plastic, as well as the molecular weight and the boiling point of solvents. Contrarily, in conventional extraction
processes such as Soxhlet, the temperature is limited by the boiling

Fig. 6. FTIR spectra of the residues after solvothermal treatments by (a) no solvent,
Fig. 4. Effect of time on Br distribution. Conditions: solvent isopropanol; tempera- (b) ethanol, (c) methanol, (d) isopropanol; conditions: temperature 150 ◦ C; time
ture 150 ◦ C; liquid to solid ratio 15:1. 10 h; liquid to solid ratio 15:1.
 C.-C. Zhang, F.-S. Zhang / Journal of Hazardous Materials 221–222 (2012) 193–198 197

Fig. 7. Morphology of the plastic before and after solvothermal treatment. Conditions: solvent isopropanol; temperature 90 ◦ C; time 2 h; liquid to solid ratio 15:1.

point of solvents. Since the kinetics of mass transfer are greatly

improved at elevated temperature, a poor solvent in conventional
extraction can thus be a good solvent in solvothermal process at
higher temperatures. Although pressure had no effect on the accel-
erated solvent extraction [24], the role of pressure was important
in that a slight higher pressure kept the solvent in the liquid phase
at a high temperature as described by Gan et al. [32] for accelerated
solvent extraction.
Obviously, as a practical technique to remove BFRs from plastic,
solvothermal procedure must not significantly affect structure of
the plastic. As shown in FTIR spectra of raw plastic (Fig. 6), the broad
band in the region 2800–3000 cm−1 are assigned to vibrations of
saturated C–H or CH2 ; the band at 3000–3100 cm−1 correspond to
aryl-H stretching. The strong peak at 1604 cm−1 is attributed to
vibration of styryl (C C aromatic), and the peaks at 964 cm−1 and
2239 cm−1 are respectively assigned to the vibration of butadienyl
and nitrile group [13]. This result confirms that the sample is typ-
ical ABS resin. Fig. 6 further indicates that similar profiles were
obtained before and after solvothermal treatment except that the Fig. 8. GC/MS chromatograms of the extracts after reaction with (a) no copper; (b)
copper stirred at room temperature; (c) copper heated at 150 ◦ C.
peaks were slightly sharper after treatment. Additionally, the mor-
phology of plastic (Fig. 7) was almost the same before and after
treatment except for slight agglomeration of plastic. Since halogen- [21,33,34]. The XRD pattern of spent metallic copper is described
free plastic were valuable resources for recovery of energy and in Fig. 9. The three peaks, which appeared at 43.29 (main peak),
chemical feed-stocks, solvothermal procedure is of great superior- 50.42 and 74.16◦ , correspond to copper diffraction peaks. The char-
ity for safety disposal of plastic especially by virtue of less damaged acteristic peak of cuprous bromide (CuBr) was clearly observed,
structure. indicating that bromine was mainly in the form of cuprous bro-
mide. The identification of bromine in the spent copper powder
3.4. Debromination of TBBPA in the presence of copper was also confirmed by Mohr’s titration method. According to previ-

According to the GC–MS profiles (Fig. 8), copper powder has

significant effects on the debromination of TBBPA in methanol.
TBBPA residue was less than 12.3% after the reaction stirred at
room temperature with metallic copper, and was not detected after
reaction with metallic copper in solvothermal reactor at 150 ◦ C. It
means that metallic copper in alcohol solvents is highly effective
for the debromination of TBBPA. This is consistent with previous
reports [15,16], which demonstrated that the dechlorination of
polychlorinated biphenyls easily took place by a simple stirring
procedure at room temperature for 24 h using metallic calcium in
ethanol. Luo et al. [33,34] also described the degradation behavior
of TBBPA in Fe–Ag suspension solutions under ultrasonic radia-
tion and revealed that TBBPA was completely degraded over Fe–Ag
nanoparticles. The HPLC analysis further shows that no TBBPA peak
was observed after reaction in solvothermal reactor. The presence
of metallic copper is thus an efficient and environmental-friendly
method for complete debromination of TBBPA in alcohol solvents.
Meanwhile, HPLC profiles imply that bisphenol A was the
main debromination product, in accordance with previous reports Fig. 9. XRD pattern of spent copper powder.
198 C.-C. Zhang, F.-S. Zhang / Journal of Hazardous Materials 221–222 (2012) 193–198

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