Beruflich Dokumente
Kultur Dokumente
a r t i c l e i n f o a b s t r a c t
Keywords: Sediment sampled from Taichung Harbor was mixed with local reservoir sediment at different weight
Sintering ratios to prepare lightweight aggregate at 1050, 1100, and 1150 °C. A pressure of 3000 or 5000 psi was
Bloating process used to shape the powder mixtures into pellets before the heating processes. The results indicate that
Sediment recycling
the leaching levels of trace metals from the lightweight aggregate samples are considerably reduced to
Lightweight aggregate
levels less than Taiwan Environmental Protection Administration regulatory limits. Increasing final pro-
Fe K-edge XANES
cess temperature tends to reduce the bulk density and crushing intensity of lightweight aggregate with a
concomitant increase in water sorption capability. Lightweight aggregate with the lowest bulk density,
0.49 g cm 3 for the 5000 psi sample, was obtained with the heating process to 1150 °C. Based on the
X-ray absorption near edge structure results, FeSO4 decomposition with a concomitant release of SOx
(x = 2, 3) is suggested to play an important role for the bloating process in present study.
Ó 2008 Elsevier Ltd. All rights reserved.
0025-326X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2008.03.033
868 Y.-L. Wei et al. / Marine Pollution Bulletin 57 (2008) 867–872
the sintering and vesicant processes. Molecular environmental sci- cesses at 1050–1150 °C, the dense pellets needed to experience a
ence with XAS technique has emerged to provide information de-volatile pretreatment process at much lower temperature than
needed for a long-term solution of environmental remediation 1050–1150 °C. The de-volatile (preheating) process at 500 °C,
and waste management (US DOE, 1995). An XAS spectrum, includ- determined with a thermogravimetric analyzer, is intended to
ing X-ray absorption near edge structure (XANES) and extended X- drive out most organic components in order to avoid blasting the
ray absorption fine structure (EXAFS), is capable of revealing speci- pellet into small pieces, while being subjected to the subsequent
ation, distribution, form transformations, and mobility of target 1050–1150 °C heating process for 18 min. The sintering duration
metal (US DOE, 1995). The aim of this study is to study the feasibil- was determined to be 18 min, because we found that such duration
ity of recycling sediment from Taichung Harbor of Taiwan as a raw could lead to satisfactory sintering thickness, approximately 1 mm.
material for manufacturing LWA and to apply XAS technique to Approximately, this time duration is also being used by a local
investigate the change of Fe speciation prior to and after the sinter- plant to generate light aggregate from the same reservoir sediment
ing and vesicant processes. employed in our study. For the de-volatile process, the dense pel-
lets were gradually heated from room temperature to 500 °C in
2. Experimental methods 2 min and, subsequently, the temperature was held at 500 °C for
another 2 min under atmospheric environment in a temperature-
The experimental flowchart is depicted in Fig. 1. Two sediments programmed electric furnace to drive out most organics. The de-
were sampled: one from Taichung Harbor of Taiwan and the other volatile pellets were then discharged and ready for the sintering
from a local reservoir. The reservoir sediment has been well stud- and vesicant processes. They were placed in alumina crucibles
ied and it is regarded as a satisfactory raw material for commer- and introduced into the furnace that has already reached a pre-
cially manufacturing LWA. The reservoir sediment used in this set temperature (i.e., 1050, 1100, and 1150 °C), and stayed inside
study is intended for comparison with the harbor sediment. Prior the furnace for 18 min.
to forming the pellet by the use of a pressure shaping method, After the 1050–1150 °C process, the bulk density of LWA sam-
the sediment sampled from Taichung Harbor was thoroughly ples was measured based on Archimedes Principle (Cheeseman
end-to-end mixed with the local reservoir sediment at five differ- et al., 2005). Note that the sizes of all LWA samples were measured
ent weight ratios (100:0, 80:20, 60:40, 40:60, 20:80, and 0:100) by immersing them into water by using a very slim metal wire to
in a mixer which rotated at a speed of 30 rpm for 24 h. Pre- suppress them downward. Because the difference in percent
weighed amount of the sediment mixture was then loaded into a weight loss after sintering is negligible (only approximately 1%),
stainless-steel holder, and pressurized into a disk-like dense pellet the size of the LWA sample is inversely proportional to the bulk
by the use of a pressure shaping machine which is equipped with a density. The sizes of the LWA samples are in the 6.0–15.4 cm3
pressure gauge. Two different pressures, 3000 and 5000 psi, were range. Water absorption capacity for the LWA samples was deter-
applied to the sediment mixtures to shape them into dense pellets. mined according to a method formulated by Taiwan government
The sizes of the dense pellets (8.00 g in weight) shaped with 3000 (Taiwan CNS, 1993). The basic principle behind the water absorp-
and 5000 psi are 4.1 and 3.6 cm3, respectively. To successfully pre- tion capacity is to determine the amount of water absorbed by
pare lightweight aggregate through sintering and vesicant pro- LWA in 24 h (Taiwan CNS, 1993). The capability of the LWA sam-
ples against crushing was estimated with an auto-compressor de-
vice equipped with a microprocessor-control console. Pb toxicity
characteristic leaching procedure (TCLP) concentrations in all sam-
Raw sediments ples were determined with a flame atomic absorbance spectrome-
ter (FAAS) based on the method formulated by US EPA (US EPA,
1992). The calibration curves have Pb concentration span 1.00–
o 10.0 mg L 1 with the correlation coefficient >0.9995.
Dried at 105 C
All Fe K-edge XAS spectra were recorded on the wiggler C (BL-
17C) beam-line at the National Synchrotron Radiation Research
Characterization Center (NSRRC) of Taiwan. During the XAS experimentation, the
Ground to < 50mesh facility had storage energy 1.5 GeV, an electric current 120–
of raw materials
220 mA, and the energy spanning was 4–15 keV for the monochro-
with various mator. The K-edge jump for Fe is 7112 eV. All XAS spectra from
Mixed at different proportions reference compounds (Fe metal, Fe(OH)3, Fe2O3, Fe3O4, FeO, and
instruments
FeSO4) were recorded in transmittance mode at room temperature;
while the XAS spectra from lightweight aggregate samples and
Shaped at 3000 and 5000 psi sediment were all recorded in fluorescence mode. Data reduction
was carried out using WinXAS software (Ressler, 1998).
o
Pretreated at 500 C for 2 minutes
3. Results and discussion
Table 1
Chemical compositions of harbor and reservoir sediments 100 100
Element Reservoir sediment Harbor sediment
Sia 31.53% 28.90% 80 80
Al 7.67% 7.57%
Fractional Weight Percentage
Fe 4.32% 4.05%
60 60
90
0
7
4
49
0
2
59
29
<
-7
00
11
-1
20 0.84 0.35 0.20
9-
-2
7-
2-
53
74
0-
14
29
90
40 0.65 0.36 0.23
59
11
60 0.55 0.29 0.10
Particle Size (μm)
80 0.51 0.22 0.22
100 0.28 0.26 0.18
Fig. 2. Particle size distribution of sediments sampled from a local reservoir (top
5000 0 0.12 ND ND panel) and Taichung Harbor (bottom) in Taiwan.
20 0.13 ND ND
40 ND ND ND
60 ND ND ND
80 ND ND ND
10
100 0.13 ND ND
3000 psi
1
ND: <0.092 mg L .
9 1050 oC
1100 oC
officially enforced in Taiwan is 5.0 mg L 1 that can be translated to 1150 oC
8
100 mg kg 1 sample according to the TCLP procedure (US EPA,
1992). The Pb TCLP concentrations from all LWA samples meet
the regulatory limit. Other trace metals regulated by Taiwan EPA
in terms of TCLP concentration are Hg, As, Cd, Cu, and Cr. Table 1 7
Weight Loss (%)
shows that, for Hg, As, Cd, Cu, and Cr, the contents of each trace
metal in the raw sediments are lower than their regulatory limits
enforced by Taiwan EPA. Thus the TCLP test of these trace metals 10
6
from all LWA samples is not performed.
Fig. 2 shows that particle size distribution of harbor sediment is 5000 psi
slightly coarser than the reservoir sediment. The <2 lm fraction is 9 1050 oC
approximately 37–38% for both sediments. However, the total res-
o
ervoir sediment is finer in size. Finer particle size is responsible for 1100 C
easier occurrence of sintering reaction to form glassy shell (sur- 1150 oC
face) to encapsulate the gases evolved during the subsequently oc- 8
curred bloating reaction. Fig. 3 presents the weight loss percentage
of the specimen after the 1050–1150 °C sintering processes. The
weight loss for all samples is in the 6–8% range. This observation 7
is slightly greater than the LOI listed in Table 1, because the LOI
was determined at 900 °C, that is lower than the temperatures
used for the sintering and bloating processes. 6
Fig. 4 depicts the bulk density of the LWA samples prepared 0 20 40 60 80 100
from sediment mixtures of different weight ratios and different
Fraction of Reservoir Sediment (%)
formation pressures. The LWA bulk density always decreases with
increasing final temperature. Their bulk density is about 0.49– Fig. 3. Weight loss of lightweight aggregates after sintering at 1050, 1100, and
1.26 g cm 3. LWA with the lowest bulk density was obtained by 1150 °C.
870 Y.-L. Wei et al. / Marine Pollution Bulletin 57 (2008) 867–872
the processes at 1150 °C: 0.49 and 0.69 g cm 3 for the 5000- and
3000 psi samples, respectively. It is noted that the generally
acceptable bulk density of LWA is <2.0 g cm 3 and LWA with dif- 16
ferent bulk density has various practical applications. This figure 3000 psi
shows that the LWA bulk density generally decreases with increas- 14
1050 oC
ing fraction of reservoir sediment, because the average particle size
12 1100 oC
of the reservoir sediment is smaller than the harbor sediment; in
other words, the pellets containing more fraction of reservoir sed- 1150 oC
10
iment are more closely packed. This would favor encapsulation of
Water Absorption Capacity (%)
the gases produced during the bloating process, leading to less bulk
8
density; however such trend is not observed for the results associ-
ated with 3000 psi and 1050 °C (see the upmost curve in Fig. 4). To 6
explain this exceptional observation, we suggest that the benefit of
finer particle size for easier sintering might have been offset by 4
both lower shaping pressure (3000 psi) and the richer Si + Al + Ca
content in the reservoir sediment (see Table 1). Note that SiO2, 16
Al2O3, and CaO all have relatively high melting point, consequently
5000 psi
greater content of these constituents would result in slower sinter- 14
1050 oC
ing reaction; thereby the gases generated by the bloating reaction
have more opportunity to slip out to the atmosphere through the 12 1100 oC
still-open interparticle space. 1150 oC
The effect of pellet shaping pressure on the LWA bulk density is 10
also indicated in Fig. 4. A general trend of decreasing bulk density
8
with increased shaping pressure is observed. This trend can be ex-
plained in a simple way by the fact that particles closer to each
6
other are easier to be brought together and sintered at elevated
temperature. Thus, the pellets shaped with greater shaping pres- 4
sure would take less time to form the sintered layer (i.e., the shell)
which is glassy and considerably smooth. Once the shell is formed, 0 20 40 60 80 100
the gases generated during the subsequent vesicant process would
Fraction of Reservir Sediment (%)
expand the shell dimension and the core region becomes porous
with the gases caught inside, resulting in less density of the light Fig. 5. Water absorption capacity of lightweight aggregates prepared with sintering
aggregate. at 1050, 1100, and 1150 °C.
Y.-L. Wei et al. / Marine Pollution Bulletin 57 (2008) 867–872 871
3500 2.0
105 oC raw sediment
1.5
3000 psi 1.0
3000
1050 oC
o 0.5
1100 C
2500 0.0
2.0
1050 oC-core
1.5
0.5
1500 0.0
2.0
1050 oC-shell
1.5
1000
1.0
5000 psi
0.5
3000
0.0
2.0
1150 oC-core
2500 1.5
1.0
2000 0.5
0.0
2.0
1500 1050 oC 1150 oC-shell
1.5
1100 oC
1.0
1000 0.5
0 20 40 60 80 100
0.0
Amount of Reservoir Sediment (%) 7.12 7.14 7.16 7.18 7.12 7.14 7.16 7.18
Fig. 6. Crushing intensity of lightweight aggregates prepared with sintering at 1050 Photon Engergy (keV)
and 1100 °C.
Fig. 7. XANES spectra (left) and their corresponding first-derivative spectra (right)
from harbor sediment and lightweight aggregates prepared with sintering at 1050
ature (1100 °C) results in less crushing intensity, which is sug- and 1150 °C. The vertical dotted lines running through each panels are intended for
easier comparison among various samples.
gested to be due to the rigorous bloating process at 1100 °C, there-
by providing the vesicant gases with enough energy to escape to
the atmosphere by tunneling through the sintered shell with some
tiny pores left behind on the glassy surface. In addition, because 2.0
Normalized Absorption (Arbitary Unit)
the crushing intensities for all 1150 °C LWA samples are less than harbor sediment
the minimum detection limit of the auto-compressor device,
166 psi, therefore being excluded from Fig. 6. Despite the consider- 1.5
ably lower crushing intensity for the 1150 °C LWA samples than all
samples manufactured at 1050 and 1100 °C (i.e., 1727–3046 psi),
the 1150 °C LWA samples, when properly incorporated into ce-
1.0
ment, may be able to effectively reduce the total density of the ce-
ment specimen while still retaining reasonable crushing strength
for the LWA-incorporated cement specimen because the strength
may be contributed by cement. 0.5
Fig. 7 presents the Fe K-edge XANES spectra from the LWA sam- Fe2O3 36.8 % Fe3O4 30.1 %
ples prepared from harbor sediment (not containing reservoir sed- FeO 13.4 % FeSO4 19.7 %
iment). Each LWA sample was divided into two parts: shell and 0.0
core regions. The shell region corresponds to the glassy surface,
and the core region represents the bloating part. The main edge
7.12 7.14 7.16 7.18
peak (as indicated by the arrow in each panel) in the XANES spec-
tra from all LWA samples, except the 1050 °C-core, shifts toward
Photon Engergy (keV)
greater photon energy, indicating an increase in average oxidation Fig. 8. Results from simulation of XANES spectrum for harbor sediment.
state of Fe. This is in contrast to the generally accepted mechanism
that during the vesicant process, the average oxidation state of Fe
decreases due to the transformation of Fe2O3 into Fe3O4, FeO, and the sintering and bloating processes, we suggest that FeSO4 decom-
O2. Fig. 8 shows the results based on the simulation of XANES spec- position with a concomitant release of SOx might have played an
trum from raw harbor sediment using WinXAS program (Ressler, important role for the bloating process in present study. Noted that
1998). The Fe speciation in raw harbor sediment consists of this study also attempted to simulate other XANES spectra for
36.8% Fe2O3, 30.1% Fe3O4, 13.4% FeO, and 19.7% FeSO4. As indicated obtaining Fe speciation in LWA samples, however it is unsuccessful
in Fig. 7, the average oxidation state of Fe tends to increase after due to the unavailability of a complete set of Fe reference
872 Y.-L. Wei et al. / Marine Pollution Bulletin 57 (2008) 867–872