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Abstract
Recent years have seen the application of the concept of uidisation extended to dierent kinds of industrial processes. This technol-
ogy now plays a central role in the chemical and petrochemical industries, in power generation and in mineral processing and metallurgy.
The current research is directed towards gas-phase extraction of metals because of the high yield of recovery that can potentially be
achieved. This process achieves the extraction of metals by using a volatile organic reagent, which passes through the feed material
and reacts selectively with the metal to be extracted. The product is a volatile metal complex, which is removed from the residual gangue
by a carrier gas.
The results showed that the procedure could be successfully applied to recover aluminium, chromium, vanadium and iron with acet-
ylacetone from their respective solid oxides in a uidised bed. The percentage recovery ranged from 75.2% for iron to 48.2% for chro-
mium. Kinetic investigations were performed to estimate the activation energy required for each reaction. The recovery of the metals
depended on the temperature and reaction time.
2005 Elsevier Ltd. All rights reserved.
0892-6875/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.08.002
J.H. Potgieter et al. / Minerals Engineering 19 (2006) 140146 141
able metals, except blast furnace slag. By applying mineral Carrier Gas
Extractant
processing technologies, such as crushing, grinding, mag- (N2)
netic separation, otation and leaching or roasting, it is
possible to recover metals such as Fe, Cr, Cu, Al, Pb, Volatilisation of extractant and
mixing with carrier gas
Zn, Co, Ni, Nb, Ta, Au, and Ag from these various slags
Extractant recycle
(Basir and Rabah, 1999). Gaseous Extractant
The conventional method for disposal of slags is dump-
ing. The continued dumping of slags not only occupies Extraction of metal
(gas-solid reaction)
large areas of land, but also wastes resources and can have
a harmful impact on the environment due to potential Volatile extract
water pollution. It is therefore desirable to recover metals
Recovery of
from slags and utilise the slags, for example in building metal
or other construction applications. Several methods have
been proposed for the treatment of waste from the ferro-
alloys industry (Cohen et al., 1997; Salamon, 1995). Tradi- Metal
tionally the recovering processes of metals can be classied
Fig. 1. Process ow sheet for the vapour phase extraction of metal from
in following categories: pyrometallurgy, hydrometallurgy, slag.
solvent extraction and ion-exchange.
Current research is now starting to focus on gas phase
extraction because of the high yield of metal recovery with moved from the residual gangue by a carrier gas ow
the advantage that the extractant can be continuously and condensation (see Fig. 1). Under specic conditions,
regenerated (Allimann et al., 2001). This process can this volatile metal complex can be reduced after condensa-
achieve the extraction of heavy metal contaminants from tion of the vapour phase to the metallic product and the or-
several matrices (low grade ore, soil, sediment, spent cata- ganic reagent. The latter can then be recycled for re-use in
lysts, slags, industrials wastes, etc.) by using a volatile or- the process (Allimann et al., 2001). The ow sheet of the
ganic reagent, which passes through the feed material and process used is shown in Fig. 1.
reacts selectively with the metal to form an extractable vol-
atile complex (Allimann et al., 2001). 2.2. Measurements
A French engineer, Eugene Houdry, rst discovered and
designed a uidised solids process that has formed the 2.2.1. Preparation of the standards
foundation of all subsequent developments in this eld Calibration standards for the UVVis spectrophotometry
(Jehning et al., 1980). The high proportion of the elements analysis were prepared from synthesized metal acetylacetone
cited above in slag and their important use in the metallur- complexes (Hon et al., 1965; Earley and Cannon, 1966;
gical eld led to this investigation of an alternative way of Brown, 1978; Chaudhuri and Ghosh, 1983; Stary and Hlad-
recovering those valuable metals. This is done by treating ky, 1963). Stock solutions containing 450, 2000, 1000 and
the materials with a b-diketone (2,4-pentanedione) as a 6000 mg L1 of chromium-, aluminium-, vanadium oxy-
complexing agent, and extracting the metals through and ferric acetylacetone complexes, respectively were pre-
gas phase extraction in a uidised bed reactor. All the pared in absolute ethanol. Dilutions ranging from a 100
parameters that can usually inuence such a process, to 0.1 suced for the construction of calibration curves.
such as temperature, total reaction time and the kinetics The wavelength of maximum absorbance for each com-
of the processes were investigated and are described in this plex was selected by scanning a solution of the relevant
paper. metal complex over a range of wavelengths from 200 to
800 nm. A series of standards were measured at this wave-
length to construct a calibration curve of the concentration
2. Experimental of the compound against its absorbance. After each exper-
iment the absorbance of the metal complex analysed was
2.1. Apparatus and description of the process ow sheet read from the calibration curve and the concentration
determined.
A laboratory scale glass uidised bed reactor system of
500 mm long and 15 mm in diameter was designed. The 2.2.2. Procedure for the recovery of metals
uidised bed also contained a vessel (reactor 1) of Reactor 2 was charged with 12 g of the relevant pure
250 mL which carried the liquid extractant, coupled to a metallic oxide (Cr2O3, Al2O3, V2O5, and Fe2O3, respec-
tube with a coarse glass frit (reactor 2). The uidised bed tively) after mixing it with 50 g of silica. Reactor 1 was
column had three outlets for thermocouples to measure heated to a temperature (T1) of 140 C, allowing the
the temperature distribution in the reactor. extractant to vaporise into reactor 2 where the reaction
The product of the gas phase extraction process in the with the particular oxide could occur at dierent tempera-
uidised bed reactor is a volatile metal complex. It is re- tures ranging from 150 C to 220 C. Each temperature was
142 J.H. Potgieter et al. / Minerals Engineering 19 (2006) 140146
Recovery [%]
complex were diluted to 250 ml with absolute ethanol and 50.0 190 C
200 C
analysed by UVVis spectrophotometry to subsequently 210 C
40.0
calculate each respective metal concentration. 220 C
30.0
2.2.3. Recovery study 20.0
All experiments were carried out in batch mode for sim-
10.0
plicity and reliability (Curckovic et al., 2001). The batch
experiments were run at dierent temperatures and reac- 0.0
0 50 100 150 200
tion times. The concentration of the acetylacetone, the
Time [min]
quantity of feed material, the gas ow rate and the mass
of silica were kept constant for each experiment to ensure Fig. 2. Eect of time on the recovery of aluminium at various
reproducibility. temperatures.
The recovery for each metal was calculated from the
determined concentration. The theoretical and actual
recovery was calculated using the following equations: 100 min. A recovery of 63.7% was achieved after 90 min
and remained at 63.7% after 105 min at temperatures of
Rthe C=F 100 1
180 C or higher. The results also show that no further var-
Rreal Rthe K=100 2 iation in recovery occurs when the reaction time is in-
where C is the quantity in g of the element in the extracted creased for longer than 105 min.
solution at a given temperature and time; F is the quantity The extraction of aluminium also increases with increas-
in g of the element in the feed material; K is the coecient ing temperature. It can be seen that the recovery improves
of recovery when preparing the complexes (i.e. actual yield/ substantially from 160 C to 180 C when sucient time is
theoretical yield). allowed, e.g. only 31.4% of the available aluminium is ex-
In this work the order of the extraction process for Al, tracted after 105 min of reaction at 160 C, while 63.7%
Cr, V and Fe was determined using kinetic models based is extracted at 180 C and 65.7% at 200 C in the same
on chemical analogy. The integral method was used (Fog- time. The results obtained showed that an increase of tem-
ler, 1986) to estimate the reaction order and integrate the perature after 180 C did not aect the recovery to any
dierential equation used to model the batch system. If great extent, regardless of the time allowed for extraction.
the assumed order is correct, the appropriate plot (deter- Chris et al. (2000) used thermal treatment to reduce the
mined from this integration) of concentration-time should metal content of y ash. This was achieved by vaporizing
be linear. This method evaluates the specic reaction rate the volatile aluminium from municipal solid waste
constant at dierent temperatures in order to determine (MSW). For that reason the authors of this study used pure
the activation energy. The order of the extraction process Al2O3 to simulate the relevant constituent in the y ash and
was evaluated for rst order and second order reaction found that the equilibrium time needed was longer than
kinetics according to the following well-known equations: 90 min, as is illustrated in Fig. 2. This result concurs with
that obtained by Allimann et al. (2001). These latter
C0 authors conducted experiments on the purication of y
ln kt 3
C ash using the Servo Process, which involves the extraction
1 1 of heavy metals using a volatile chelating extraction re-
kt 4 agent that is selective for the chosen metals. The dierence
C C0
in equilibrium time between their work, which was 120 min
where C0 is the initial concentration, C is the nal concen- and the values obtained in the current work, may be due to
tration, k is the rate constant, t is the time in seconds. the dierence in experimental conditions, the extractant
and the type of material used.
3. Results and discussion
3.2. Recovery of chromium
3.1. Recovery of aluminium
The recovery of chromium increased with increasing
Fig. 2 shows the eect of reaction time at dierent tem- time and reached 48.2% after 150 min at a temperature of
peratures on the recovery of aluminium from the metal at least 210 C, as is shown in Fig. 3. A further increase
oxide by forming the acetylacetone complex (Al(acac)3). in time to 150 min did not have any large eect on the
Results show that the recovery of aluminium increases with recovery process, regardless of the temperature at which
increasing time, but reaches a maximum after about the extraction was conducted.
J.H. Potgieter et al. / Minerals Engineering 19 (2006) 140146 143
190 C can also be seen that the recovery of vanadium does not de-
40.0 200 C pend on temperature to the same extent it does on time.
210 C
30.0 220 C
While the % recovery of vanadium only increases from
about 61% at 160 C to 66% at 220 C, there is an increase
20.0 of more then 50% in the percentage recovery from 30 min
10.0 to 120 min.
The results obtained here indicate that gas phase extrac-
0.0 tion of vanadium presents a viable opportunity for the
0 50 100 150 200
treatment of such wastes. The recovery of vanadium from
Time [min]
ferro-alloy waste originating from the treatment of various
Fig. 3. Eect of time on the recovery of chromium at various primary and secondary materials constitutes a challenging
temperatures. problem in the valuable metals rening industry, and the
results obtained in this investigation oer a potential way
The eect of temperature on chromium recovery by of achieving good recoveries.
acetylacetone was not as pronounced as in the case of alu-
minium. Beyond 210 C the maximum recovery seems to 3.4. Recovery of iron
stay constant with any particular reaction time employed
in the extraction process. The eect of time on the recovery of iron was studied at
The results correlate well with the work of Das et al. dierent temperatures in the range from 150 to 200 C and
(1997) who found that 180 min was needed for a recovery time intervals varying from 30 to 120 min. The results are
of 57% of chromium. Gordon and Chi-Ming (1998) studied presented in Fig. 5. It was found that the recovery of iron
the extraction ability and recovery of heavy metals by elec- with acetylacetone increases rapidly with time and reaches
trolysis from municipal incinerator y ash. Although a dif- saturation within 45 min, except at the two lowest reaction
ferent technique was used, the authors found that for temperatures. This eect can be explained by the fact that
maximum recovery of chromium to be achieved, a time iron reacts very strongly with any beta-diketone (Allimann
of 180 min were required, which is similar to the ndings et al., 2001).
of this work. Fig. 5 shows that as the temperature was raised, the
recoveries of iron improved. The maximum iron is recov-
3.3. Recovery of vanadium ered at 180 C within 45 min. Raising the temperature up
to 210 C does not improve the recoveries any further.
The eect of time on the recovery of vanadium from the Thus, 180 C seems to be the optimal temperature. During
vanadium oxide at dierent times was studied in the time the rst 30 min an almost linear increase in the percentage
range of 30180 min. The recovery of vanadium increased recovery of iron as the temperature increases, is apparent.
rapidly with time as shown in Fig. 4 and reached an opti- Extrapolation of the percentage recovery at 150 and
mum value in about 120 min. 160 C during the initial part of the reaction seems to
70.0
80.0
60.0
70.0
50.0
60.0
Recovery [%]
Recovery [%]
Table 2
Optimum conditions for maximum recovery of Al, Cr, V and Fe
Elements Optimum condition for maximum Maximum recovery Activation energy Type of reaction control
recovery (%) (kJ mol1)
Temperature (C) Time (min)
Al 190 105 63.7 27.7 Surface reaction
Cr 210 150 48.2 23.1 Surface reaction
V 190 120 63.0 4.96 Diusion control
Fe 180 45 75.2 181.3 Chemical reaction
Table 3
A comparison of the percentage recovery of Cr, Al, V and Fe
Methods Conditions Elements Recovery (%) References
Acid extraction 100 C/40 h Cr 5.7 Cohen et al. (1997)
Fe 65.0
Gravity separation Cr 11.5 Khan et al. (2001)
Cr 3.0 Choudhury et al. (1996)
Fe 8.0 Das et al. (1997), Liu (1991)
BFS 1600 C Fe 55.0 Huang and Wang (2001)
Servo process 130235 C Cr 13.6 Allimann et al. (2001)
2 h max V 18.6
Fe 18.7
Gas phase 180 C/105 min Al 63.7 This work
210 C/150 min Cr 48.2
190 C/120 min V 63.0
180 C/45 min Fe 75.2
J.H. Potgieter et al. / Minerals Engineering 19 (2006) 140146 145
Jehning, C.E., Cambeli, D.L., Martin, H.Z., 1980. Fluidization, third ed. Salamon, M., 1995. Milestone for alloy-slag separation. MINTEK
Plenum Press, New York. Bulletin (South Africa) 86, 2.
Khan, S.A., Ray, G., Sinha, M.K., Rao, P.V.T., 2001. Recovery of charge Sievers, R.L., Moisier, R.W., 1965. Gas Chromatography of Metal
chrome from mixed metal and granulated slag. Tata Search (India) 4, Chelates. Aerospace Research Laboratories, Pergamon Press, Oxford,
115118. London, p. 163.
Liu, S., 1991. The methods for steel slag processing. Steel Making 5, 590 Stary, J., Hladky, E., 1963. Systematic study of the solvent extraction of
609. metal -diketonates. Analytica Chimica Acta 28, 227.
MINTEK-Annual Review, 1999. Ferrous metals. <http://www.min- Terkel, R., 1974. Principles of Extractive Metallurgy, Material Science
tek.co.za/pubs/ar99/ferrous,htm> (accessed 27/05/02). Engineering Series. McGraw-Hill, USA.