perature window.
At 325 °C, the net formation on the CAS matrix and
alumina were in agreement; those on silica were lower by
(6) Ghorishi, S. B.; Altwicker, E. R. Chemosphere 1996, 32, 133-144.
(
(
(
7) Ross, B. J.; Naikwadi, K. P.; Karasek, F. W. Organohalogen Compd.
990, 3, 147-151.
8) Hell, K.; Altwicker, E. R.; Stieglitz, L.; Addink, R. Organohalogen
Compd. 1998, 36, 53-58.
9) Nestrick, T. J.; Lamparski, L. L.; Crummett, W. B. Chemosphere
1987, 16(4), 777-790.
1
∼
1/ 4. At 400°, a 4-fold increase in amount was observed on
the silica supported sample from its value at 325 °C, which,
however, was more than eight times less than the formation
in the presence of the CAS matrix.
(10) Altwicker, E. R.; Konduri, R. K. N. V.; Lin, C.; Milligan, M. S.
Chemosphere 1992, 25(12), 1935-1944.
11) Ghorishi, S. B.; Altwicker, E. R. Environ. Sci. Technol. 1995, 29,
It is evident that the time and temperature history of the
support matrix could be very important in determining the
reactivity of the sample. The CAS matrix gave an aqueous
slurry with pH 8.4. For comparison, the water slurry pHs of
alumina, silica, and synthetic CAS solids were 5.8, neutral,
and 12.4, respectively. Some physical properties of the CAS
batch used for this work were determined directly in the
laboratory or furnished by MMT. The average particle size
was 1 µm. The average range of particle diameters of the
acidic alumina and silica were 50-200 and 70-150 µm,
respectively (i.e., more than 1-2 orders of magnitude greater
than CAS). In light of the inhibitory nature reported for
calcium oxide (59), the dechlorination/ destruction on alu-
mina (57), and the agreement observed in this present work,
it is clear that the in situ formed support matrix (an apparently
intimate mixture of these three compounds) exhibits prop-
erties different from a matrix prepared by physically com-
bining the individual components.
(
(
1
156-1162.
12) Stieglitz, L.; Zwick, G.; Beck, J.; Roth, W.; Vogg, H. Chemosphere
989, 18(1-6), 1219-1226.
1
(13) Stieglitz, L. Environ. Eng. Sci. 1998, 15(1), 5-18.
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Technol. 1987, 21, 1085-1088.
(
15) Addink, R.; Altwicker, E. R. Organohalogen Compd. 1997, 31,
86-491.
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990, 8, 203-214.
4
(
1
(17) Luijk, R.; Akkerman, D.; Slot, P.; Olie, K.; Kapteijn, F. Environ.
Sci. Technol. 1994, 28(2), 312-321.
(
(
(
18) Addink, R.; Altwicker, E. R. Environ. Eng. Sci. 1998, 15(1), 19-
7.
19) Beard, A.; Naikwadi, K. P.; Karasek, F. W. Environ. Sci. Technol.
993, 27(8), 1505-1511.
2
1
20) Stieglitz, L.; Vogg, H.; Zwick, G.; Beck, J.; Bautz, H. Chemosphere
1991, 23(8-10), 1255-1264.
(21) Xhrouet, C.; Pirard, C.; De Pauw, E. Environ. Sci. Technol. 2001,
5(8), 1616-1623.
3
A direct comparison between PCDD/ F formation with
copper (II) chloride, copper (I) chloride, and iron(II) chloride
in the present CBB/ CAS matrix at their respective reported
maximum net formation temperatures (275 °C for the copper
chlorides and 400 °C for iron chloride) was performed. The
copper(II) chloride containing samples produced approxi-
mately 5 times more total PCDD/ F than the iron(II) chloride
mixtures in the 2% oxygen atmosphere over 60 min at
equivalent metal concentrations (0-5 wt % metal). Mixtures
with iron(II) chloride were slightly more active (1.2-1.5 times)
in producing PCDD/ F over this metal concentration range
than those samples containing copper(I) chloride. It should
be noted that the concentrations of iron in MSWI has been
reported as being 10-100 times greater than those of copper,
thus perhaps counterbalancing iron’s slightly lower pro-
pensity to promote PCDD/ F formation in such. In iron ore
sintering fly ash, iron concentrations of nearly 50% have been
reported (21). Synergistic activity between copper and iron
chlorides and the modeling of these systems has been
reported (25) and will be the subject of forthcoming papers.
(
(
22) Brenner, K. S. Toxicol. Environ. Chem. 1995, 47, 7-14.
23) Nagel, C.; Chanenchuk, C.; Wong, E.; Bach, R. Environ. Sci.
Technol. 1996, 30, 2155-2167.
(
24) Ryan, S. P.; Altwicker, E. R. Chemosphere 2000, 40, 1009-1014.
(25) Ryan, S. P., Ph. D. Thesis, Rensselaer Polytechnic Institute, 2001.
(26) Van Dell, R. D.; Mahle, N. H.; Hixon, E. M. Comb. Sci. Technol.
1
994, 101, 261-283.
27) Addink, R.; Altwicker, E. R. Organohalogen Compd. 1999, 41,
9-72.
(
6
(
(
28) Schafer, V. H. Z. Anorg. Chemie 1949, 260, 279-294.
29) Schafer, V. H. Z. Anal. Chemie 1949, 129, 222-229.
(30) Saeki, Y.; Matsuzaki, R.; Fujiwara, S. Bull. Chem.l Soc. Jpn. 1978,
51(12), 3527-3529.
(
(
31) Xun, Y. Ph. D. Thesis, Rensselaer Polytechnic Institute, 1999.
32) Kanungo, S. B.; Mishra, S. K. J. Therm. Anal. 1996, 46, 1487-
1
500.
(
33) Mul, G.; Kapteijn, F.; Doornkamp, C.; Moulijn, J. A. J. Catal.
998, 179, 258-266.
1
(34) Mul, G.; Kapteijn, F.; Moulijn, J. A. Appl. Catal., B 1997, 12,
33-47.
(
(
(
(
(
(
35) Collina, E.; Lasagni, M.; Tettamanti, M.; Pitea, D. Environ. Sci.
Technol. 2000, 34(1), 137-142.
36) Lasagni, M.; Collina, E.; Tettamanti, M.; Pitea, D. Environ. Sci.
Technol. 2000, 34, 130-136.
37) Milligan, M. S.; Altwicker, E. R. Environ. Sci. Technol. 1993, 27(8),
1595-1601.
38) Stieglitz, L.; Eichberger, M.; Schleihauf, J.; Beck, J.; Zwick, G.;
Will, R. Chemosphere 1993, 27(1-3), 343-350.
39) Talbot, S.; Altwicker, E. R.; Espourteille, F. Organohalogen
Compd. 1996, 27, 36-41.
Acknowledgments
The authors thank Molten Metals Technologies, Inc., Walth-
am, MA for providing initial funding and motivation for this
work. Support from the Mid-Atlantic States Section of the
A&WMA in the form of an Air Pollution Educational Research
Grant (APERG) awarded to S.R. in 1999 is greatly appreciated.
The DSC and AOX analysis was performed under the direction
of Dr. L. Stieglitz at the Forschungszentrum Karlsruhe
40) Addink, R.; Espourteille, F.; Altwicker, E. R. Organohalogen
Compd. 1996, 27, 20-25.
(41) Hell, K.; Stieglitz, L.; Dinjus, E. Environ. Sci. Technol. 2001, 35(19),
892-3898.
(
3
(
Germany). The collaboration with and assistance of his
42) Wikstr o¨ m, E.; Ryan, S. P.; Touati, A.; Tabor, D.; Gullett, B. K. The
Origin of Carbon in Polychlorinated Dioxins and Furans Formed
during Sooting Combustion, submitted Environ. Sci. Technol.,
2003.
group, including K. Hell, M. Lenzer, P. Weber, J. Wilhelm,
and R. Will is greatly appreciated. The stay of S.R. at FZK in
the summer of 1998 was funded by a dissertation enhance-
ment award from the National Science Foundation, for which
the authors are grateful. The authors also express their
appreciation to R. Addink for many useful discussions.
(43) Blaha, J.; Hagenmaier, H. Organohalogen Compd. 1995, 23, 403-
4
06.
(
(
(
44) Weber, R.; Sakurai, T. Organohalogen Compd. 2002, 59, 49-52.
45) Milligan, M. S.; Altwicker, E. R. Carbon 1993, 31(6), 977-986.
46) Palot a´ s, A.; Rainey, L.; Sarofim, A.; Vander Sande, J.; Ciambelli,
P. Energy Fuels 1996, 10, 254-259.
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