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87]97
Maurice Morency a,b , Holger Weiss c , Klaus Freyer d , James Bourne b,U ,
Denise Fontaine b , Raymond Mineau b , Monika Moder
¨ d , Peter Morgenstern d ,
d b
Peter Popp , Michel Preda , Hanns-Christian Treutler d , Rainer Wennrich d
a
Institute des Sciences de l’En¨ ironnement, Uni¨ ersite´ du Quebec
´ a` Montreal,
´ Quebec,
´ Canada H3C-P8
b
´
Departement des Sciences de la Terre, Uni¨ ersite´ du Quebec
´ a` Montreal,
´ Quebec,
´ Canada H3C-3P8
c
Industrial and Mining Landscapes Department, Umweltforschungszentrum, Leipzig-Halle, Germany
d
Department of Analytical Chemistry, Umweltforschungszentrum, Leipzig-Halle, Germany
Abstract
A low temperature oxidation process has been developed to separate Pb from Zn in a complexly contaminated
scrubber dust. The material consists of approx. 50% galena ŽPbS. and sphaleriterwurtzite ŽZnS., and also an
amorphous component, a variety of different silicate and carbonate phases as well as naturally-occurring radionu-
clides and oil and grease. The two-stage process consists of a grinding stage followed by placing this material into a
hydrogen peroxide solution. The resultant oxidation reaction is violently exothermic } the temperature rises
spontaneously to approx. 968C. The amount of solid phases remaining after completion of the reaction was reduced
by approx. 40% and consisted largely of insoluble lead sulphate which retained the bulk of the radionuclides. Almost
all of the zinc was placed into solution by this process as was the Cd, Re and Cu. The total PAH content of the
original Theisenschlamm Ž468 ppm. was reduced to 11.25 ppm in the residual sediment and the PCDDrPCDF
concentrations were reduced by approx. 40%. The radionuclides are almost totally concentrated in the solid phase.
The method shows considerable promise as a separation technique for very fine-grained sulphide-bearing residues.
Q 1998 Elsevier Science B.V. All rights reserved.
Keywords: Oxidation; Scrubber dust; Sulphide-bearing; Organic and inorganic phase; Liquid and solid phase
U
Corresponding author.
0048-9697r98r$ - see front matter Q 1998 Elsevier Science B.V. All rights reserved.
PII S0048-9697Ž98.00271-X
88 M. Morency et al. r The Science of the Total En¨ ironment 223 (1998) 87]97
diameter. The lower resolution of the instrument 10:1.. For PAH determination by HPLC, the sam-
is approx. 0.2 m m. The machine is coupled to an ples were then subjected to a solvent exchange
optical system which allows visual observation of Žcyclohexane., ultrasonic treatment Ž5 min., a sil-
the morphology andror the degree of agglomera- ica gel clean-up and a final solvent exchange.
tion of the particles. The measurement was made A GCrMS analysis was used to obtain additio-
in an aqueous medium which maintained the nal information concerning the categories of or-
particles in suspension using ultrasound as well as ganic substances present in the samples. Starting
a mechanical stirring device. with the sample preparation methods described
DTArTGA measurements, using a Linseis above, each sample was concentrated to a total
thermobalance with a furnace capable of heating amount of 1 ml. The complex mixtures were sepa-
up to 16008C were made to determine the ther- rated by gas chromatography using a Hewlett
mal stability of this polyphase system. Approxi- Packard HP 5890 series II instrument. A directly
mately 250 mg of material were used for the coupled mass spectrometer ŽMSD Hewlett
measurements. Packard. was used to analyze the components
The major element concentrations as well as separated by the gas chromatograph using elec-
several trace element concentrations were de- tron impact ionization of 70 eV.
termined using X-ray fluorescence analyses ŽXRF. For the determination of PCDDrPCDF a Fin-
and ICP-MSrICP-AES in order to obtain repre- nigan MAT double focussing mass spectrometer
sentative values for the different elements. including a Hewlett Packard HP 5890 series II
For XRF, two sample preparation techniques gas chromatograph was used.
were employed: Ž1. a fusion technique with lithium Two techniques of measurement are required
tetraborate during which the samples were heated in order to determine the radioactivity concentra-
tions of 210 Pb and 210 Po } alpha spectrometry
to a maximum of 9508C to assure complete disso-
for 210 Po and high resolution gamma spectrome-
lution and homogenization of the melt. The resul-
try for 210 Pb.
tant glass bead was analyzed using a Philips PW
For alpha spectrometry, the samples were first
1600 simultaneous X-ray fluorescence spectrome-
put in solution with concentrated hydrofluoric
ter; and Ž2. samples were dried in air at a temper-
acid. The solutions were then spiked with an
ature of 1058 C, ground in an agate mill, mixed
aliquot of a tracer using 209 Po. The fractions were
with a wax binder Ž20%. homogenized in agate evaporated to dryness and electrodeposited on
and pelletised at a pressure of 140 MPa. The polished steel disks for subsequent counting.
measurements were done using wave-length-dis- The gamma spectrometry data were collected
persive X-ray fluorescence spectrometry ŽSiemens using a high-purity germanium ŽHPGe. coaxial
SRS 3000.. low-energy detector, n-type, covered with a beryl-
For ICP-MS and ICP-AES, analyses the sam- lium window of 0.5 mm in thickness.
ples were prepared using an aqua regia digestion
according to DIN 38414r7. For ICP-MS analysis
ŽELAN 5000, Perkin Elmer., the samples were 3. Oxidation experiments
diluted to 1:100 and 1:1000 in doubly distilled
water. After applying pneumatic nebulization and Samples of the Theisenschlamm were ground
multi-element standard solutions, the ICP-MS re- in an attritor and dried prior to treatment with
sults were verified using the standard addition hydrogen peroxide. The grinding was done to
technique. For ICP-AES analysis ŽSpectroflame, create fresh surfaces on the constituent particles
Spectro A.I.., the digestion solution was diluted which would be more reactive. Also, the reduc-
to 1:10 and 1:100 with doubly distilled water. tion of the grain size would help to make the
Prior to determination of the organic com- reaction more complete and more exothermic.
pounds, the samples were treated by Soxhlet ex- Our standardized procedure consisted of two sep-
traction Ž12 h with a toluenermethanol ratio of arate steps } a mechanical pre-treatment phase
90 M. Morency et al. r The Science of the Total En¨ ironment 223 (1998) 87]97
Fig. 1. Composite diffractogram showing the profile for the starting material prior to reaction, Ž33A., the residual sediment after
reaction, Ž43A. as well as a diffraction profile for the sediment obtained by total evaporation of the peroxide solution Žafter the
reaction had completely terminated Ž43L..
sediment after treatment Ž43A. as well as the ing element. Distribution coefficients, Žcalculated
composition of ground Theisenschlamm Ž33A. and as: K SrL s mass of element in sedimentrmass of
the composition liquid phase after cessation of element in liquid. are also shown in Table 2 and
the reaction Ž43L.. The most important feature of provide information on the partition of the ele-
Table 2 is seen by comparing the PbrZn ratio for ments between these two respective phases.
the ground Theisenschlamm prior to treatment
with that of the sediment remaining in the con- 4.3. Impact of the peroxide treatment on the organic
tainer after treatment } in the former it is chemistry
roughly 0.75:1 whereas in the latter it is approx.
12:1. The same ratio in the liquid phase is 1:700. Results of the determination of the PAH con-
The percentage of the original mass that was put centrations using the EPA method 610 are pre-
into solution for each element was calculated by sented in Table 3. The data show that PAH
assuming 3 g of sediment remaining after treat- values in 33A are much higher than in the resid-
ment and 280 cm3 of liquid phase. These values ual sediment 43A. The total PAH concentration
are shown graphically in Fig. 2 in relationship to in the untreated material is 468.9 mgrkg, whereas
their concentrations in 33A. Results show that in the residual sediment it is 11.25 mgrkg. This
93.7% of the zinc originally present was placed represents a reduction of almost 98%.
into solution whereas the comparable figure for The results of the identification of several cate-
Pb is approx. 0.2%. In other words, the separation gories of compounds were classified into groups
of Pb from Zn is almost complete. Lead, S, Si and and are presented in Table 4. Sample 33A con-
Fe are the most important of the elements in the tains only a few low volatile components, such as
residual sediment, whereas in the liquid phase, the methyl and dimethylbenzene. The main part
the total of Zn q S is 92.6% of the total amount of the hydrocarbons is a mixture of polyaromatic
present, with Cu being an important accompany- compounds with a higher boiling point, however,
M. Morency et al. r The Science of the Total En¨ ironment 223 (1998) 87]97 93
Table 2
Composition of a typical sample of ground Theisenschlamm and the composition of the products after hydrogen peroxide treatment
Ag 520 810
Al 23 600 31 500 42.15 89 8.0
As 4080 7600 0.19 100 429.0
B 111 135 1.07 57 1.4
Ba 1670 1930
Bi 165 280
Ca 8800 2200 8.8 73 2.7
Cd 360 30 5.1 6 0.06
Co 80 35 1.12 25 0.33
Cr 890 1160 1.56 89 8.0
Cu 14 100 1215 183.5 7 0.07
Fe 30 850 43 700 1.45 100 323
Ga 78 140
Ge 31 32 0.23 60 1.5
Hg 110 130
In 23 45
K 6700 8350 27 77 3.3
Mg 2500 5200 12 82 4.6
Mn 670 580 5.82 52 1.1
Mo 600 880 0.02 100 471
Na 670 1400 4.3 78 3.5
Ni 510 360 4.57 46 0.84
Pb 122 000 182 000 3.75 100 520
Re 63 9 1 9 0.10
Stotal 113 000 39 900 1680 20 0.25
Sb 1470 2400 0.06 100 429
Se 720 320 8.4 29 0.41
Si 96 700 20 98 52
Sn 17 200 26 500
Th 2 3
Ti 5000 5580
Tl 320 290 2.18 59 1.4
U 30 32 0.12 74 2.9
Zn 163 000 15 800 2500 6 0.07
Zr 970 1135
additional alkylated homologues and partially hy- is shown in column 2 of Table 4. The high boiling
drogenated aromatics were also detected, as were temperature of the mixture has been reduced.
some hydroxyaromatics and O-heterocyclic com- The values in Table 4 clearly show the decrease
pounds, quinoline andror isoquinoline as well as in the concentration of aromatic compounds.
dibenzothiophene derivatives. The data are pre- Specifically, the quinolinerisoquinoline deriva-
sented as semi-quantitative countsrg of sample. tives are absent and their alteration products, the
The GCrMS analysis of the residual sediment aromatic amino compounds, appear.
94 M. Morency et al. r The Science of the Total En¨ ironment 223 (1998) 87]97
Fig. 2. Element distribution pattern between the solid Žleft, 43A. and liquid Žright, 43L. phases after the TSOP treatment.
The analysis of the extract of the liquid phase vant N- and S-heterocyclic compounds has been
indicates a low concentration of hydrocarbons. significantly reduced. Sample 43L contains insig-
Water soluble substances, such as ben- nificantly small quantities of hydrocarbons, pre-
zenemethanol and benzenedicarbonyl acids are dominantly alkanes, some low boiling aromatics
predominant, however, volatile compounds, such and water soluble compounds, such as phthalates.
as the xylenes are also present. It is also apparent The results of the PCDDrPCDF analyses of
that the concentration of the toxicologically rele- the two solid samples 33A and 43A are listed in
Table 3
Results of PAH measurements on ground Theisenschlamm and TSOP reaction products
Table 4
Results of GCrMS analyses of ground Theisenschlamm and TSOP reaction products
Abbre¨ iations. b.d., Below detection limit; tr., trace amounts present.
Table 2.. The radioactivity value associated with as input feedstock. Alternatively, the process may
210
Pb in sample 33A prior to reaction and in the provide an initial treatment of such material which
sediment Ž43A. were determined to be 22.1" 0.6 would require further processing prior to obtain-
kBqrkg and 27.1 " 0.9 kBqrkg, respectively ing a suitable product.
whereas the value for the liquid phase was less It is important to emphasize the flexibility of
than the detection limit of 4 Bqrl. Mass balance this technique. As it is a chemical treatment, it is
calculations indicate that virtually all of the 210 Pb most suitable for very fine-grained material. It is
and 210 Po is concentrated in the sediment Ži.e. in not influenced by the chemical composition of the
the lead sulphate phase., after treatment. The mixture, however, it is influenced by the possible
total radioactivity value for the liquid phase is presence of external oxide coatings on the surface
- 4.2 Bqrl. of the particles. Conventional hydrometallurgical
and pyrometallurgical methods require significant
6. Discussion capital investment which would not be economi-
cally feasible considering the relatively small
The partition coefficients shown in Tables 2 amount of material to be treated ŽLeipner et al.,
and 3 clearly indicate that certain elements or 1991; Lorenz et al., 1992..
organic compounds are preferentially concen-
trated in either the liquid or solid phases after the 7. Conclusions
oxidation described above. In particular, the Zn,
Cd, Cu and Re partition strongly into the liquid
phase whereas the solid phase contains almost all 1. Hydrogen peroxide is an excellent oxidising
the As, Sb, Fe, Mo, Pb, Žincluding 210 Pb and agent for the Theisenschlamm. It caused the
210
Po. and a high proportion of the Al, Cr, and Si near complete separation of the Zn from the
Ž) 89%.. Of the 24 elements evaluated, 11 of Pb, yielding a hydrated zinc sulphate that
them were concentrated Žmore than 75% of the could potentially be used in an electrolytic
original mass present. in the sediment whereas process for zinc products and a lead sulphate
another four elements were more than 75% con- which could be used in lead smelting.
centrated in the liquid phase. Those elements 2. The elements considered can be divided into
normally present in silicates, such as Al, Mg, Na, three groups: those with a solidrliquid parti-
K and Fe Žand Si. are concentrated in the resid- tion coefficient - 1:3 ŽZn, Cu, Cd, Re.; and
ual sediment since silicates are normally not able those with a solidrliquid partition coefficient
to be attacked by hydrogen peroxide. The chemi- ) 3:1 ŽPb, As, Sb, Mo, Fe, Si, Na, Cr, Mg, K,
cal separation between Pb and Zn is related to Al. with the remainder ŽU, Ca, Ge, B, Tl, Mn,
the different solubility constants for ZnSO4 and Ni, Co and Se. being present in subequal
PbSO4 . It is therefore clear that this simple amounts in both liquid and residue.
method can be used as a first order procedure for 3. The small amount of Zn remaining in the
the separation of complex mixtures of residual solid residue after treatment does not appear
sulphides and silicates into two fractions, each of to be accessible at the grain size at which the
very different chemical composition. experiments were conducted.
Such a treatment may have considerable poten- 4. The 210 Pb is strongly associated with the solid
tial application in remediation projects, particu- phase Ži.e. lead sulphate. as is the 210 Po.
larly for very fine-grained material. In the case of 5. The peroxide treatment reduces the concen-
the Theisenschlamm, lead, zinc and sulphur are tration of PAH in the solid residue by almost
the most important components. Depending on 98% and the PCDDrPCDF concentrations
the technical specifications required by different by approx. 40%.
industries, the separation of the Zn from the Pb 6. After peroxide treatment, the liquid phase
described here may by itself generate an contains insignificantly small quantities of hy-
economically useful product which could be used drocarbons, predominantly alkanes, some low
M. Morency et al. r The Science of the Total En¨ ironment 223 (1998) 87]97 97
boiling aromatics and water soluble com- Leipner K, Korb J, Hein K. Technisch-wissenschaftliche be-
pounds, such as phthalates. trachtungen zur verarbeitung von mansfelder Theisen-
schlamm Žflugstaub.. Erzmetall 1991;44:560]565.
Leipner K. Verhalten der Hauptbestandteile der Mansfelder
Theisenschlamms bei dessen pyrometallurgis cher Ver ar-
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