Private :

Melatener Strae 103

52074 Aachen, Germany
Tel.: + 49 (0) 241 872131
URL: http://www.hochofen.com

Heinrich Wilhelm Gudenau

Univ.-Prof. Dr.-Ing. Dipl.-Wirtsch.-Ing.

Office:
RWTH Aachen University
Dept. of ferrous metallurgy
Intzestrae 1
52072 Aachen, Germany
Tel.: +49 (0) 241 8095788
Fax.: +49 (0) 241 8092368
e-mail: gudenau@iehk.rwth-aachen.de
URL: http://www.iehk.rwth-aachen.de

Mr. L. Capogrosso
RIVA Group
ILVA S.P.A.
Via Appia Km 648
I-74100 Taranto/ Italy

Consulting Project

Taranto Dioxin Sinter Plant Emission

Part I

2
1.

Introduction

At the visit of the Taranto Plant in October 2005 with a lecture and discussion the
sinter plant was shown to the contractor. Further information especially
by the visit of Mr. Quaranta and Mr. Di Tursi at 01.09.2006 in Aachen
were given and discussed.
According to the letters to Mr. Capogrosso at the 12.09.2006 and 05.06.2007 the
contract of consult service was fixed with an annex.
The final report has the following table of contents:

Table of Contents
1.

Introduction

2.

Dioxin
-

3.

Review
-

4.

Problems at Seveso (Italy), Start of Research about Dioxin

Primary Sources
Secondary Sources
Dioxin at Iron and Steel Industry
First Published Results

Iron Ore Sinter Process

-

5.

Different Kinds of Dioxins and Furans

Structures of PCDD and PCDF
Chemical and Physical Properties
Formation Mechanism
Toxic Equivalency Factors
Aims and Limits

Definition
Sinter Strand
Heat Transport
Charged Materials

Experiments in a Sintering Pan

- Experimental Apparatus at Institute of Ferrous Metallurgy in Aachen
- Results and Discussions of Experiments in a Sintering Pan

6.

Measurement in Sinter Plants

- Influence of Filter-Systems
- Influence of Different Sintermaterials
- Results of Dioxinemissions over the Length of the Sinter Strand

7.

Proposals of Dioxin Minimizing by Technological Changes

-

8.

Air Fine
EOS
LEEP
Partly Offgas Recycling
Eposint
Bag filter
Injection of pulverized coke breeze
Effect of Additives on the Dioxinemission in a Sinter Pan

Prediscussion of the Report Part I

4
2.
-

Dioxin
Different Kinds of Furans and Dioxins

The polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans

(PCDF) are in general incorrectly summarized as dioxins. The chemist assigns the
dioxins to the group of cyclic halogenated aromatic ether. Typical characteristic of the
dioxin compounds is the connection of two carbon atoms by an oxygen bridge. For
PCDDs, the carbon atoms are connected by a pair of oxygen atoms. PCDFs are
connected via a single oxygen atom. /1-3/
Group of dioxins and furans with analogue structure:
Cyclical ether (furan)
- chlorine-benzofuran
- chlorine-dibenzofuran (PCDF)
- chlorine-benzoaphthofuran
- chlorine-dinaphtofuran
- chlorine-phenyldibenzofuran
Cyclical diether (dioxin)
- chlorine-benzodioxin
- chlorine-dibenzodioxin (PCDD)
- chlorine-benzoaphthodioxin
- chlorine-diaphtodioxin
- chlorine-phenyldibenzodioxin
-

Structures of PCDD and PCDF

The basic structure of dibenzodioxins and furans are based on two benzene rings.
The benzene rings are missing two hydrogen atoms each, so the carbon atoms can
be connected to each other directly with one oxygen bridge (furans) or with two
oxygen bridges (dioxins), see Fig. 1.

5
Mono or polychlorinated dibenzodioxins and furans are nascented by the
substitution of the hydrogen atom at the positions 1,2,3,4,5,6,7,8 and/or 9 by chlorine
atoms.
The number of the chlorine atoms in the molecule is shown by the prefix mono (1) to
octa (8). Also characterizing beside the number is the position of the chlorine atoms
to each other (isomers).

Fig. 1: Structural formula of dibenzodioxins and dibenzofurans

Compounds with different chlorination degrees are called congeners. There are 210
different congeners together, 75 congeners of dibenzodioxins and 135 of
dibenzofurans, see Table 1.

Table 1: Composition of chlorinated dibenzodioxins and dibenzofurans

6
The toxicological properties of the mono to tri- CDD/F are under dosed, so the used
term polychlorinated dibenzodioxins/ -furans mostly contains only the homologous
series tetra to octa.
Congeners with chlorine substituents in the 2,3,7,8- position are called 2,3,7,8class and their toxicological properties should be underlined. The so called
Seveso- poison the most toxical of the 210 congeners should be pointed out as a
special example, see Fig. 2. /14,15/

Fig. 2: Structural formula of 2,3,7,8- Tetrachlorodibenzodioxin

The more formal notation of technical literatures dibenzo-p-dioxins or
dibenzoparadioxin are pointing out the symmetric position of the oxygen atoms in the
structure of the dibenzodioxins.
Beside chlorine other halogens like bromine, iodine or fluorine and their mixtures also
can be used as substitution atoms. Analogous to the polychlorinated dibenzodioxins/
-furans is the chemical structure and the nomenclature of the ploybrominated,
-iodinated and fluorinated dibenzodioxins /-furans constructed. Also there is an equal
toxicological level supposed, the report would not going into details of this
compounds.
-

Chemical and Physical Properties

The studies on the chemical and physical properties of dioxins are not completed;
there are only exact facts of the well known compounds. Isomers of different
homologous series have very different properties. The melting point of 2,3Dichlorodibenzodioxin is about 89C and 332C for octadibenzodioxin. Even in the
same homologous series with similar chemical and physical properties exist big
varieties in toxicity.

7
PCDD and PCDF are almost leach- and base-insoluble and have a low volatility
under normal air pressure. On the other side they are lipophilic and concentrate in
animal and human adipose tissues. Water and fat solubility as well as vapour
pressure have following attitudes depend on the rate of chlorination:
-

The water solubility decreases strictly logarithmical when the rate of

chlorination increases. And is general very low between 1 g/l and 7,4* 10

g/l.
-

The fat solubility increases at higher rate of chlorination and is about 4

dimensions higher than the water solubility.

The vapour pressure of PCDD and PCDF shows a downward drift at higher
rate of chlorination, it decreases about a factor of 8 for each substituted
chlorine.

The important physical properties of 2,3,7,8- Tetrachlorodibenzodioxin, see Table 2:

physical propertie
molecular weight
melting point
vapour presure
critical presure
critical temperature
critical volume
boiling point
solubility in:
water
methanol
xylene
chlorobenzene
partition coefficient:
n-octanol/ water
soil/ water
biota/ water

value
321,97
303-305
4,5
23,42
661,3
763
440

unit
g/mol
C
MPa (25C)
atm
C
cm/g mol
C

0,2
10
3580
720

g/l
mg/l
mg/l
mg/l

1,4* 10 7
1,0* 10 7
2000-3000

Table 2: physical properties of 2,3,7,8-TCDD

8
The change of the state of aggregation of PCDD/F depending on the temperature is
very important for the filtering. PCDD/F are emitted depending on the kind of facility,
waste heat utilization and purification of waste gases at a temperature of 60C to
400C. On the way to chimney the exhaust gas cools down, condenses and will be
absorbed by dust and sooty particle. Studies have resulted that with waste gases
with temperatures above 300C PCDD/F are mostly (>80%) gaseous, but if the
temperature is under70C they are sorbed by dust particle (>90%).

Formation Mechanism

Polychlorinated dibenzodioxins and furans are man-made matters, as a byproduct

of the industrial production of trichlorinephenol and benzene or as combustion
product.
Formation mechanism of PCDD and PCDF can be split up in:
- Condensation reaction
- Substitution reaction
- Radical reaction
- de novo synthesis
The condensation reaction is one of the classic formation mechanisms. It is the
condensation of two chlorophenolmolecule. Phenolic compounds adsorbed on the fly
ash surface are chlorinated to form the dioxin precursor, and the dioxin is formed as
a product from the breakdown and molecular rearrangement of the precursor.
Figure 3 shows the formation of 2,3,7,8-TCDD by sodium salt of 2,4,5-trichlorophenol
as a example for condensation reaction. This kind of reaction prefers less than
350C.

Fig. 3: Condensation reaction

The substitution of hydrogen from none- or single halogenated dibenzodioxins and

furans by chlorine forms the polychlorinated dibenzodioxins. The substitution prefers
the 2,3,7,8-position at the chlorination with the present of a metalchlorid catalyst.
The dechlorination e.g. of OCDD with the present of metal at higher temperature into
TCDD and the dechlorination with UV-light are also counted as substitution reactions.
Radical reactions are another important formation mechanism of PCDD and PCDF.
At this reaction organic precursors combust with chlorine compounds at 300C to
600C.
The de novo synthesis occurs at a temperature of 300 450C as formation of dioxin
and furan compounds form nonchlorinated materials with the present of chlorine
compounds and carbon, supported by catalytic reactions with metal. Like the
DEACON reaction the important start reaction is the formation of chlorine from
cooper and other metal chloride with oxygen.
The de novo reaction is characterized by his long reaction time. At flue gas cleaning
formation of PCDD/F is possible because the fly ash stays many hours in the electric
filter.
The standard dioxin formation takes place at 400 to 800C. Above 800C the
pyrolysis (thermal decomposition) and the reaction with oxygen start. At the cool
down process dioxins can be formed by the de novo reaction. This opposite reactions
leads to the typical dependence of dioxin on the temperature (Fig. 4).
The formation velocity shows a saturation curve and the decomposition velocity are
proportional to the temperature.

10

Fig. 4: Dioxin Concentration

Also there are many assays and theories about the formation mechanism the exact
formation mechanism is still partly unknown. It is unsettled when chlorine and oxygen
enter the molecule or how important catalytic effects are at the combustion.
-

Toxic Equivalency Factors

One of the main questions at the rating of dioxins and furans is the toxicity and
specially the effectiveness on human. To rate the toxical potential of PCDD and
PCDF toxic equivalency factors were introduced. The toxic equivalency factors show
the toxicity of a special compound in relation to the most toxic substance 2,3,7,8TCDD (Table 3).

Table 3: International toxic equivalency factor

11

TEF is an international NATO CCMS-Code replacing the old common national

factors. The TEF divided all PCDD/PCDF congeners into their respective homologue
groups and assigned to each group a toxicity factor relative to TCDD. These
numerical factors could then be applied to transform various concentrations of
PCDDs and PCDFs into equivalent concentrations of 2,3,7,8-TCDD. The
concentration of PCDDs and PCDFs would be analytically determined, the
concentration of each congener would be multiplied by its respective TEF value, and
all the products would be summed to give a single 2,3,7,8-TCDD equivalent.
For example in an alloy are 2000 fg octadibenzodioxin. With the equivalency factor of
0,001 you get 2000 fg * 0,001 = 2 fg, that means the OCDD has a toxic effect equal
to 2 fg of 2,3,7,8-TCDD.
The toxic equivalency factor does not contain conclusions of cancer risk.
Carcinogenic effects of 2,3,7,8-TCDD could be detected in animal experiments, for
other compounds are only insufficient assays.
-

Aims and Limits

To find a toxic limit for dioxins depends on the effect on human organism. There is no
clear line between the appearance and missing of unhealthy effects. The bandwidth
is influenced by age, initial level of pollution and state of health. /5/
The first German standard regulation about emission control of polychlorinated
dibenzodioxin and furans was published on 23.11.1990 (17. BImSchV). This
regulation contains many requirements about the formation of dioxins and furans and
emission. The core is the emission limit of 0,1 ng TE/ m 3 , in the most cases only
reachable with special filtering systems. Operators of old facilities have to keep these
conditions since December 1996. To control these regulations sampling and
analyzing of samples are standardised, too.
The European Union published on August 3 rd, 1993 a guide line for combustion of
dangerous waste. The published requirements are similar to the 17. BImSchV in
Germany. The limit of 0,1 ng TE/ m 3 for dioxins and furans have been taken over.

12
3.

Review
- Problems at Seveso (Italy), Start of Research about Dioxin

In literature it was mentioned that already 1963 dioxin cloudes escaped after an
explosion in a plant near Amsterdam four people died and 50 more suffered with
score health problems /1/.
After the accident at Seveso (Italy) in 1976 intensive research started about dioxin /210/, although no human fatalities or defects occured /1/.
Soon it was found that in the waste-gases of waste-incinerators tracers of dioxins
were measured.
In the following years in different waste gases of chemical and thermal processes
dioxin were found, furthermore unwanted burning processes and fires.
The detection limit was possible to be lowered. More and more knowledge was
added to the origin of PCCD and PCDF in the environment. It was noticed that
dioxins are not only a problem of waste gases but it went in waters and grounds. It
was also a problem in dusts slags and activated carbon of filter processes.
It became useful to divide between primary and secondary sources; the primary are
formed in actuel processes and processes the secondary are based on dioxins,
which are brought into the environment on different ways becaming dangerous for
human beings.
-

Primary Sources

Waste-incinerators, heating of houses and motor vehicles were first tested and it was
soon mentioned that their gases are harmful but a lot of different sources were soon
detected and registered /1,11/.
The German law (17. BimSchV) prescribed a limit of 0,1 ng TE/m 3 in the waste gas
and this should be reached until 1996 that means e.g. all waste incinerators
needed special filters.

13
In the thesis of R. Ptz /2/ a lot of problems in the first years of dioxin-research were
discussed were shown.
Special-waste incinerators with rotary kilns soon became clean and the wastes of
clinics had to be burnt in special furnaces.
The burning of natural gas, oil and hardcoal in houses were found not to be as
harmful as first suggested, but burning of wood and special treated wood are still
problematic.
Since prohibiting (in Germany in 1992) of using Scavengar-containing leaded
gasoline the problem seemed to be solved but the year by year increasing number of
motor vehicles brought new problems.
Industry was first spared out, for the ceramic industry e.g. brought results nearly to
0,1 ng TE/m3.
Here are only some hints repeated /12/: Copper Recovery: Depending on the type of
furnace and the input materials, operating conditions and gas cleaning systems used,
PCDD/PCDF concentrations in the off-gases may vary considerable. Most of the
results obtained from industrial scale facilities in Germany were in the range of 1 to 2
ng TEQ/m3. Fabric filters are normaly used for flue gas cleaning, a few plants are
equipped with an afterburner.
Aluminium Remelting Plants: Most processes for generation of secondary aluminium
use a rotary kiln. Concentrations measured showed a wide range of emission values
(0.15-13.4 ng TEQ/m3 for Al remelting plants; 0.02-21.5 as an average from 30 Al
smelters). Very low levels were found in the flue gases of foundries (0.1 ng TEQ/m 3).
The arithmetic mean stands at about 4.4 ng TEQ/m 3 and the total emissions from
aluminium melting plants in Germany are estimated to be approximately 25 g TEQ
per year.
Single measurements from reprocessing of lead from accumulators (contamination
almost unavoldable) gave dioxin concentrations from 0.02 to more than 1 ng TEQ/m 3.
- Secondary Sources
The slag of copper production e.g. at Marsberg showed such high contents, that this
material was not any longer usable for playgrounds.

14
Also dusts and acivited carbon of filters and slags of the non-ferrous industry was
surprisingly high.
- Dioxin in Iron and Steel-Industry
In the following Fig. 5 the routes of the steelproduction are shown.
In the world nearly 60,6% of steel is produced in the traditional route with blast
furnace and the connected oxigen converter. 34,9% is produced by melting of scrap,
which was before it became to scrap also was produced by the blast furnace/oxigenconverter route. Only 4,3% of the worldwide steelproduction went the way via sponge
iron by the direct reduction route and the smelting-reduction route is only 0,2% /13/.
On the right side of Fig. 5 scrap-melting is marked. The autothermic oxigen converter
route needs colling scrap but the scrap amount is to large and therefore the
allothermic route with scrap melting in a EAF is needed.

15

Fig. 5: Routes of Steel Production /14-16/

16
-

First Published Results

Before starting with results the paper about sources of PCDD/PCDF and impact on
the environment by Fiedler (1994) is mentioned /6/: The state of Northrhine
Westfalia (Germany) has initiated a program to evaluate 42 priority industrial facilities
with potentially relevant dioxin emissions to the air. The program includes analyses of
gaseous emissions from remelting plantes and foundries (total of 28 plants), plants
for wood combustion (5 plants), for melting, sintering, raw-iron and non-ferrous-raw
material manufacturing, chipboard manufacture and manufacture of compounds
using chemical processes with chlorine involved (wood preservatives, distillation of
waste oil, bleaching of cotton and threads). So far, dioxin emission > 0.1 ng l-TEQ/m 3
were found for most of the plants investigated. However, facilities with emissions > 1
ng l-TEQ/m3 were identified, too (Table 4).

Table 4: First results of the dioxin program in Nordrhine Westfalia Plants with
emissions more than 1 ng l-TEQ/m3 (mean value of three measurements)
In detail more results of the iron and steel industry are given /2/:
(The iron ore sintering will be discussed at the end of this chapter).
Pig iron is produced in blast furnaces by reduction atmosphere, that means the
possibility of formation of dioxins is small and therefore a few tests are done only at
blast furnaces itself.
The chance of dioxin formation seems to be possible in the blast furnace cast
house, but Table 5 shows low values /2/.

17
Facility/
Offgas cleaning

Capacity

Offgas flow
[Nm/h]

Blast furnace
(cast house
dedusting)/ Wet-EFilter
Blast furnace
(cast house
dedusting)/
Baghouse Filter

600t/d

91.400

9000t/d

700.000

PCDD/F
Concentration
[ng TE/m]
0,002
0,004
0,0015
0,0036
0,0022

Table 5: Dioxinemission at blast furnace cast house

Furthermore cowpers showed emissions of only 0.032 ng TE/m 3 see table 6.
Facility/
Offgas cleaning

Capacity

Offgas flow
[Nm/h]

Blast furnace
(cowper)/ N.N.

600t/d

70.000

Blast furnace
(cowper)/
1 seperator
2 whirler 2 scrubber

9000t/d

329.200

PCDD/F
Concentration
[ng TE/m]
0,03
0,029
0,004
0,037
0,038
0,021

Table 6: Dioxin emission at blast furnace-cowper

In the first route blast furnace O 2-converter beside in the blast furnace and in the
O2-converter there were no relevant dioxin contents measured. In the converters
usually 20% scrap is charged as cooling material. Even in this case table 7 gives
reasonable results.
Facility/
Offgas cleaning

Charge

Comment

Offgas flow
[Nm/h]

Converter/
Baghousefilter

Pig Iron

Converter/
E- Filter

Scrap Iron

Primary
Dedust

165.000

0,026
0,045
0,04

Converter/
Baghousefilter

Scrap Steel

Secondery
dedust

912.068

0,024
0,042
0,063

570.000

Table 7: Some dioxin emissions at O2-converters

PCDD/F
Concentration
[ng TE/m]
0,032
0,033
0,042

18
Electric arc furnaces showed different results. Especially scrap-preheating gase e.g.
9.2 ng TE/m3 see table 8. This kind of scrap preheating is since 1994 no longer
allowed.
Facility/
Off gas cleaning

Charge

Comment

Offgas flow
[Nm/h]

E- Arc Furnace/
Baghousefilter

60% Clean
Scrap, 40%
Dirty Scrap

without
Preheating,
with
Preheating

68.000

E- Arc Furnace
including e.g.
Quenching

Shredder
Scrap, Scrap
Steel,
Splinters

1.040.000

1.100.000

PCDD/F
Concentration
[ng TE/m]
0,7
2,3
5,6
9,2
0,267
0,159
0,236
0,13
0,104

Table 8: Some dioxin-emissions at Electric-arc-furnaces

Interesting was the fact, that scrap with impurities like oil containing grinding material
or dirty oil-barrels were problematic.

19
4.

Iron Ore Sinter Process

- Definition
This chapter will be not a course-book about iron ore sintering; only the main
foundamentals will be given especialy in connection with dioxin problems. The real
treative are given e.g. in the lecture book about iron making at the RWTH Aachen /
18/ an for e-learning /19/ and about iron ore sintering /20/. The main background was
given e.g. by Cappel/Wendeborn /21/.
Sintering may be defined as the agglomeration of fine mineral particles into a porous
mass by incipient fusion caused by heat produced by combustion within the mass
itself. In regard to the Ferrous Metallurgy the agglomeration of fine ferrous
compounds, like fine ores as well as blast furnace dust (flue dust), remmants of the
steel works, mill scale and dusts from electrostatic precipitators, is called the iron ore
sintering process. Thereby the compounds are heated up, a melting is not taking
place, but a partial liquefaction is fulfilled. On account of the melting below the
surface, the liquefaction, just as the formation of slag a strengthening is obtained, the
liquid phases are caked together with the down-cooling. The most important quality
pretensions of sinter products are high resistance against mechnical stress under
blast furnace reduction conditions, good reducibility, and uniformity of the size
distribution as well as a high Fe-content of the product /18-21/.
The iron-bearing constituents are iron ore concentrate, fine ores (fraction less than 810 mm, incl. about 70% > 0.2 mm), flue dust, recycled materials (mill scale
precipitator dust, pyrites etc.). Hematite and magnetite ores can be used for sintering.
Sinter process using magnetite ores requires lower (less) fuel consumption because
of lower heat demand. Sintering using 100% finely pulverized concentrates in charge
ore component is known. Share of recycled sinter fines makes up about 20-30% of
sinter mixture /20/.
Coke breeze is the most common solid fuel (fraction less than 3 mm), but coal and
other carbonaceous materials are also used. The fuel should have low content of
volatile matter, ash and sulphur, high calorific value and ignition temperature, low rate
of fraction < 0.5 mm.

20
Limestone, burnt lime, dolomite or dunite or olivine (fraction less than 3 mm) is used
as flux. Flux maintains not only a needed volume and chemical composition of slag in
a blast furnace, an increase in the sinter reducibility but also (especially burnt lime)
an increase in sinter production.
Water (5-9% of sinter mixture) is needed for agglomerating.
-

Sinter Strand

The schematic representation of a sinter strand is shown in Fig. 6:

Fig. 6: Sinter strand

Fig. 7: Sinter plant

21
Compared with a sinter plant it is obvious, that there are more facilities and
equipments, which can influence the quality of sinter but also the composition of the
waste gas: the materials and the delivering to the plant, the homogenization in
blanching beds, transportation by belt conveyors to the bins, where flux, coke breeze
and e.g. recycled sinter fines are added, conditioning with water in a mixing and
pelletizing drum; furthermore the charging system, the ignition by an ignition hood,
the sucking-system and the discharging the crusher and the cooling system see
Fig. 7.
-

Heat Transport

The sintering process is described as a non-stationary bed-reactor being flown

through by the parallel-flow-process. Fig. 8 shows the most important thermal and
chemical reactions.

Fig. 8: Thermal and chemical processes in the sinter bed

22
The lower layer of the sinter bed (G) is heated to 100C by the hot process gas
leaving the layers. This zone is followed by the drying zone (F). After the drying of the
sinter mix dehydration (E) is taking place from 300 to 800C, the expulsion of carbon
dioxide and reduction follows (D). From 900C starts the ignition of the fuel. The
burning of the fuel heats up the sinter bed to 1250-1350C. The range between the
ignition of the fuel and the maximum temperature is called flame- and sintering zone
(C). The maximum temperature depends on the composition othe sinter mix and the
content of coke breeze. After the burning- and sintering zone the sinter is reoxydated
(B) and cool by the gas stream (A).
This ideal sinter-peak, which is discussed in literature very often, is influenced by
different factors e.g. the changing of coke-breeze to charcoal: in this case a good
sinter quality cannot be expected, for the optimal sinter temperature of 1350C is not
reached by charcoal this has naturally an influence on the waste gas, too see Fig.
9 /18,21/.

23

Fig. 9: Temperature with different

fuels: charcoal (Holzkohle)
and cokebreeze (Koks)

Fig. 10: Temperature-time by sintering of

Labrador with 40% returned fines
and 6,5% cokebreeze

24
This ideal sinter peak will appear after half of the sintertime e.g. after 10 min. of total
20 min. and near to the ignition it will be slim and will widen to the end of the
sintertime in a sinter-pot and on a sinterstrand, see Fig. 10 /21/.
In the mixture on the sinterstrand the reaction will run from the top (ignition) to the
bottom of the sinterbed, see Fig. 11.

Fig. 11: Sinterreactiontemperature (1340C)

In the next figure see Fig. 12 it is shown that the waste gas temperature reaches
at the end 350C; the everage temperature of the waste gas is normally between
130C to 180C.
Corrosponding to the operation mode, the sintermaterial especially to the additions
the content of the waste gas may change; the highest content is normally N 2, the rest
13,5% H2O, 13% O2, 5% CO2, 1-2% CO, some NOx and SOx.
Fig. 12 shows that SO2 has a maximum of SOx at the middle of the sintermaschine
length; it is explained that the SO x of the drying and burning zone is accumulated
there and then decreases /18/.

25

Fig. 12:
Temperatur and
gas composition
on a sinterstrand

Charged Materials

In the literature mainly the influence of the charged material was discussed in con-

Fig. 13:
Influence of addition
of fine material
(Gichtstaub) on the
decreasing efficiency

26
nection with the sinterquality, reducing of fuel and e.g. the influence of fines on the
efficiency /22,23/.
Intensive was discussed, how to remove lead, zink and alcalies at a sinterstrand. It
was nearly not possible to vaporize these materials in a normal sinterprocess, only
by adding of calciumchlorid considerable amounts could be removed /24/.
An interesting possibility to solve the oil problem of mill-scale it was discussed and
researched in 1985 by Thyssen in a double sinter process: the mill-scale was only
added into the upper layer and the gasified oil was filtered in the second layer and
burnt there /27/. From the viewpoint of using mill-scale in the sinter process it was in
these days interesting, but an dioxin content was not measured.
Four years later R. Bothe showed in his thesis that the amount of recycled material
had an intensive influence on the hydrocarbons in the waste gas and on the burning
problems of filters /26/.
A foundamental research was carried out by M. Riedhammer on the influence of
moisture on the sinterprocess /27/. There are two reasonable values, one to get a
higher productivity and one to get the best sinter quality. This is interesting for the
waste gas amount and concentration.
A. Deja tested /28/ the preheating and prereduction of the sintermaterial to minimize
the solid fuel content in the mixture. He could show very interesting low fuel contents
but often combined with low sinterqualities /29/.
F. Cappel who wrote already with Wendeborn the book Sintering of Iron ores /21/
used the tests and results of Deja /28/ in the consideration of his thesis /30/. He did a
lot of tests first parallel to the sinterstrand in Dnkirchen and then changing many
parameters. Furthermore he developed a model to predict further tests but mainly to
explain his results. In Fig. 14 one of his results of his tests is compared with his
model. By these results he could predict the reactions in a sinter-bed even by
recycling of waste gas from the strand, giving hints for the EOS (Emission Optimized
Sinterprocess) of Lurgi /31/.

27

Fig. 14: Measured and calculated results: Temperature-Time of test 53

(Preheating time 38,6%, Gastemperature 600C)

28
5.

Experiments in a Sinter Pan

X. Hong was the first one, who researched since 1989 in our department about dioxin
/32-33/; he measured the influence of preheated scrap in an EAF and showed the
210 isomers and discussed e.g. their toxicity.
In 1993 our department got by the State of Northrhine Westfalia (Germany) MURL
(Ministry of Environment) the researchproject: Dioxin problems at metallurgical
processes in the steel industry concerning the sintering of iron ores.
In many discussions with other researchers and members of the goverment details
were discussed; first results were given in Brazil already in 1995 /3/.
Our department got another research project to the above one from MURL:
Possibilities of the use of plastic waste in the iron- and steelindustry /34-37/.
Some results were given in Brazil 1995, too /37/. It was explained that even by
injecting of plastic until a special amount the formation of dioxin in different furnaces
was not higher than 0.1 ng TE/m3.
A further paper was given by K. Onaka in a Seminario International: Sustainable
Development Metallurgy of Iron and Steel in Belo Horizonte, Rio de Janeiro and
Florianopolis in Brazil 2001 by comparing the results of our research and industry
with results of the iron- and steel industry in Japan /38/: Dioxin control technology in
iron and steel industry. He discussed as well results in EAF (Electrical Arc Furnaces)
and iron ore sintering.
At HKM (Httenwerke Krupp Mannesmann) A. Kfler researched and gave results of
his company in the combination with the results at Aachen in his thesis /39/.
At 26.-30.November 2006 a paper was given as a Keynote lecture in Osaka at the
ICSTI 06 with the title: Research based on international cooperation with iron ore
sintering and dioxin as an example /40/.
In the following chapter the result of these papers with the background of literature
studies will be presented.

29
- Experimental Apparatus at Institute of Ferrous Metallurgy in Aachen
The dioxin generation was investigated in our department in 1993 a sintering pan
(Fig. 15), which had been used in several research programs before see chapter 3.
Added was further active-coal filter in the gas pipe to the blower before the gas went
into the normal filter of the research lab. To measure the temperature in the
sinterlayer 5 thermocuples are installed; O 2, CO2, CO and CH4 were measured
furthermore by a beame emission analysis (FID) the total C-content in the waste gas.
The filter/cooling method was used take the gases and by the adsorption method the
content was measured by the Gesellschaft fr Arbeitsplatz und Umweltanalytik mbH
(GfA).

Fig. 15: Sintering pan of the Institute of Ferrous Metallurgy

To the base mixture which was used by industrial partner (with a raw mixture plus
4.1% cokebreeze and 24.3% returned fines) = SM I. Three different additions were
given, see Table 9:

Table 9:
Admixtures of
sample sinter

30
- Results and Discussions of Experiments in a Sintering Pan
The range of Dioxin concentrations is situated between 0.17 and 0.65 ng TEQ/m 3
(TEQ: Toxic EQuivalents) with a tendency to raise from sinter mixture SM I to SM IV,
Fig. 16.
The average value of the Dioxin emissions from the assigned base mix (SM I)
amounts to 0.185 ng TE/m 3. Under the addition of 5% mill scale with a middle oil rate
of 0.1% (SM II) the emission increases by only 22%. In the case of an additional
admixture of 1% blast furnace dust (SM III) emission increasing rate is to be
determined about further 75%. This results almost twice in relation to emission from
the base mix. With the use of 5% mill scale with an oil rate of 0.34% (SM IV) the
emission reaches to more than three times than the base value of SM I. Comparative
PCDD/F emissions for the oil rate of mill scale and the addition of blast furnace dust
could be shown through several lab tests.

Fig. 16: Dioxin emission in a sintering pan test

The tests showed that by the sintering pan results are simular to results of a
sinterstrand.
Furthermore it was postulated out of these tests that an increasing C-total amount
will show increasing PCCD/F-contents in the offgas.

31
6.

Measurements in Sintering Plants

In the same project with the sinterpan-tests, tests were done at the sinterstrand 3 of
Krupp Hoesch Stahl AG together with our Institute at RWTH Aachen.
Known were at that time different dioxin results see table. 10 /3/:

Table 10:
PCDD/F-concentrations at German
sinterstrands

Date of

Operator

County

measure

Table 11:
PCDD/F-concentrations
of sinterstrands in German neightbourcountries

12.06.1990
12.06.1990
13.06.1990
13.06.1990
10.10.1991
10.10.1991
10.10.1991
14.01.1992
16.01.1992
1994
1994
1994
1994

Concentration
[ng TE/m]

Hoogovens
Hoogovens
Hoogovens
Hoogovens
Voest-Alpine
Voest-Alpine
Voest-Alpine
Arbed S.A.
Arbed S.A.
British Steel
British Steel
British Steel
British Steel

Netherlands
Netherlands
Netherlands
Netherlands
Austria
Austria
Austria
Luxemburg
Luxemburg
UK
UK
UK
UK

3
2,5
3,4
3
2,52
1,79
2,47
0,85
2,08
0,6
1,6
3,4
1,7

32
These results of German Industry were single results (not repeated tests) out of
plants with different operating modes, different materials and different additions. Such
extreme values were not known in our neighbor countries, see table 11 /2/.
In Fig. 17 the dioxin emissions are shown at Krupp-Hoesch AG. It is obvious that the
extrem high emissions were stopped already at 1992 and in 1993 the values were
normally not higher than 3ng TE/M3 /2/.

Fig. 17: Dioxinemission at Krupp-Hoesch

These results were reached with primary measures, e.g. lower speed of the
sintermachine and by this a lower productivity and e.g. by avoiding of mill scale with
an oil content > 0,1%.
-

Influence of Filter Systems

In the following two Figures 18 and 19 electrofilter and bagfilter are compared /2/.
Though the two sinter strands were different even by changing from electrofilter to
bagfilter it was not possible to overcome all problems of the dioxin emissions.

33

Fig. 18: Measured results with electro filter

Fig. 19: Measured results with fabric filter

34
-

Influence of Different Sintermaterials

At the same time tests were done with different coke-breeze-qualities and test with
avoiding of the addition of blast furnace dusts, see Fig. 20.

Fig. 20: Different Sintermaterials

-

Results of Dioxinemissions over the Length of the Sinter Strand

The following tests were done at the Hoesch (Dortmund) Sinter Strand (150 m 2) in
cooperation of the measurement by LUA (Landesumweltamt NRW). Several different
possibilities were checked e.g. without any additions like oil containing millscale and
with millscale. Fig. 21 and 22 shows examples of the results e.g. with the bed heights
400 mm, the speed of the strand between 2.41 and 2.48 m/min and the production
was between 31.2 and 31.5 t/m2d.

35
Fig. 21: Underpressure at windboxes

Fig. 22: Temperature at windboxes

The most interesting result is given in Fig. 23. At every second windbox the PCDD/Fconcentration was measured and the other were calculated.
There is a continuous increase from windbox 3 to 11 and the main emission of
Dioxins is measured in windbox 11. The less higher values in windbox 1 compared to
windbox 3 can be due to the ignition zone. The decrease from windbox 11 to 13 is
attributed to the final sintering operation. Approximately 3/5 of the exhaust gas
stream can be classified as not critical, whereas the reamsining 2/5 need a special
waste gas cleaning in order to decrease dioxin emissions.

Fig. 23: PCDD/F-concentration over length of sinter strand (measured and

calculated)

36
The CO- and the NO-emission was nearly constant in nearly all compaigns. A
remarkable correlation between the temperature and the PCDD/F-concentration is
shown in Fig. 24. This can explain the dioxin behaviour in the sinterbed.
It should be stressed that nearly half of the windboxes show less than 0.1 ng TE/m 3.
The values of the addition e.g. of millscale or wastes can be compared with the
results of the lab-tests.

Fig. 24: PCDD/F-concentration and temperature

It is interesting that the maximum of dioxinemission and the temperature at the end of
the sinterstrand does not correlate with the SO 2 maximum, for this appears at the
middle of the length see Fig. 12 /18/. Also the theory of the presence of this SO 2
maximum will not be same, for dioxin is not solutable in water. This SO 2 maximum
was explained that the SO2 is first absorbed by the water content in the lower part of
sinterbed and then driven out, when the temperature reaches this area /18/.
In 2001 also Kansai and co-authors showed this phenomenon in their research at
sinter strands in the collaborative Japanese Research-Project (SDD-Project Japan),
see Fig. 25 /41/.

37

Fig. 25: Changes in exhaust gas temperatures and relative concentrations of

PCDD/Fs and other gases in windboxes with progressing of sintering

38
7.
-

Proposals of Dioxin Minimizing by Technological Changes

Air fine

By the author of this report a not published expertise was made about the
development of the KVA-process of Voest-Alpine-Stahl (Donawitz/Austria).
This continuously acting scrap melting process was based on the use of natural gas
and oxygen it was a flexible process of pure pig iron with coiling scrap (until 100%
motorcar-scrap) /42/. The same dioxin problems as in an EAF were expected but in
October of the same year it became obvious, that only by a large filter this aim could
be reached /43/. Filter were developed e.g. by Voest Alpine-Industrieanlagen: Air fine
to minimize the dust-out-put at electro-filter or at bagfilter to clean oven gases. By
this way the amount of Dioxin could be minimized to 0,4 ngTE /39/.
A problem by cleaning of sinter offgases by electric filters are the alkali containing
aerosols, therefore by Air fine first the solid particles were minimized and then by a
quenching and washing step difficult gases even dioxins could be treated.
In the meantime VAI is developing a dry-typ gas cleaning process /44/.
-

EOS

In the thesis of F. Cappel already 1977 /30/ many different ways of recycling of waste
gas were discussed, see e.g. Fig 26.

39
Fig 26. Recycling of waste gases of the last wind boxes
In Fig 14 measured and calculated preheatment treatment was shown and in the
thesis discussed.
While F. Cappel /30/ used these possibilities mainly to save energie, the combination
with the results by Ptz /2/ gave the new EOS-Process /31/.
In chapter 5 experiments in a sinter pan and at sinter plants about Dioxin emission
were compared.
In Fig. 27 the optimized sinter process (EOS) is shown /45/.

Fig. 27 Flow sheet of a sinter plant with EOS system

Conventional sintering uses ambient air to transport heat within the sinter bed,
requiring a high air flow rate. However, EOS takes advantage of the fact that only a
part of the oxygen in the air is consumed for coke combustion. Therefore a part
stream of the offgas is recycled via the hood, enriched with ambient air to an oxygen
content of 1314% and used as intake process air. This reduces off-gas volumes by
about 4050% without affecting the sintering process.
The process was developed in 1994 by Outotec (the former Lurgi Metallurgy GmbH)
and is presently applied at all three sintering strands of Corus Ijmuiden.

40
The EOS brings an almost 50% reduction of the waste gas volume, but also 10%
reduction of the coke breeze. 75% of the Dioxins could be avoided /39/.
-

LEEP

This Low-Emission-and-Energy-optimized-Sintering-Preocess (LEEP) was developed

mainly by the doctor-thesis of A. Kfler /39/. He discussed the different possibilities of
treating the NO-content or the desulphurization. Especially he mentioned the
influence of carbon and CO and CU as catalyser on the PCDD/F formation.
Before he started to explain his equipment at Httenwerke Krupp-Mannesmann he
reported of the sinterplant No. 4 at Wakayama of Sumitomo Metals to recycle the hot
waste gases of the whole sinterbed and at Yamata by Nippon Steel where some
parts of the waste gases after ignition were brought back to the sinter layer. This
procedure was mainly used to minimize the SO 2-content.
In the Kflers thesis Cu was tested under sinter strand conditions. From discussions
and tests in different equipments it was known that Cu react at a catalyst. The
starting value was between 0.958 and 1.017 ng TE/m 3. The dioxin-emissions were
lowered to 0.431 or 0.335 ng TE/m 3 in the first step and then 0.248 and 0.265 were
reached. This became possible for the Cu-content was lowered by 20% and once
again by 20%.
For this lowering the dusts of the roomcleaning filter and from the blast furnace were
agglomerated with burned limestone and water. These agglomerates were then given
into the sintermix. With this procedure it became possible that the Cu-containing
particles remained in the sinter and were not transported into the sinter offgas and
could not react as a catalyst.
By this method it seemed to be possible to reach 0.5 ng TE/m 3 but the company
wanted to reach lower values.
Therefore quenching tests were added. The windboxes 25 to 28 were selected, for it
was known that this windbox showed the highest waste gas-temperature nearly
335C without quenching. From pretests it was known that this windbox would show
the highest dioxin emission. With the quenching the offgas-temperature was 150C.

41
Fig. 28 shows the results, the lowering of the dioxin emission reached 30-50%.

Fig. 28: Results of the quench-tests in the windboxes

The next step was the jet-injection of fine lignite coke particles (BKKS = Braun-KohleKoks-Staub), see Fig. 29 with following limitations: not too high amounts of coke
breeze to avoid explosions and the waste gas temperature should be lower than
145C.
Some tests with this procedure were already done before by Thyssen and that
knowledge was taken into consideration.

Fig. 29: Jetstream injection and absorber

42

Fig. 30 shows the results; it is interesting that by this method 50% less dioxin
emission was measured.

Fig. 30: Results of the injection- and adsorber-method

-

Partly Offgas Recycling

Fig. 31 shows the possibility of recycling a special part of the off-gas.

Fig. 31: Partly off-gas recycling

43

This method was also checked, calculated and discussed by Kfler /39/. He found
out that the PCDD/F-, the Sulfur- and the NO x-emission reached interesting low
values. By Kfler also the influence on the efficiency and quality of sinter was
checked and discussed. In Fig. 32 the recycling system at the sinter plants of HKM is
shown.

Fig. 32 LEEP waste gas recycling process at HKM

Eposint

A waste gas recycling process has been developed by Voestalpine Stahl Linz and
Siemens VAI. The Environmentally Process Optimized Sintering (Eposint) was
developed with the knowledge of the Airfine process.
In this process the gas is selectively recycled from the windboxes n the area of the
high waste gas temperature see Fig. 33. Low SO2 concentrations were reached and
Dioxions can effectively destroyed by the selective selection of the partial waste gas
stream from the burn-trough zone. To get emissions a bag filter is installed after the
electro-filter. This is called Maximized Emission Reduction of Sintering (Meros).

44

Fig. 33 Eposint waste gas recycling process at Voestalpine Stahl Linz

Bag filter

An End-of-pipe-solution for waste gas cleaning are bag filters. They have been
developed by different companies. Fig. 34 shows the process diagram of the Rogesa
Plant in Dillingen.

Fig.34
Bag filter technology at
Rogesa

45
-

Injection of pulverized coke breeze

In a report by Prof. Philp /46/ tests were done and discussed to bring down the Dioxin
emission of sinter strands; this is the state of the art.
The aim was to bring down the PCDD/F concentration < 0,1ngTEQ/m. The
demonstration was shown at the sinter strand 2 at TKS; the dates of the sinter
strand were given, further more the dates of the sinter raw mix. The qualities of
the ingnite coke breeze (BKKS=Braun-Kohle-Koks-Staub) was listed up.
Fig. 35 shows the Bloek Diagramm /46/

Fig. 35 Waste gas cleaning with adsorption stage and catalytic converter

Results which were reached e.g.:

-

it was possible to inject BKKS

increase of injected materials brings more efficiency

70% of Dioxin could be reduced

2,3,7,8-TCDD was reduced by 76%

Results were between 0,13 and 0,76 ngTEQ/m

46
-

0,1 ngTEQ/m was not reached

Effect of Additives on the Dioxin Emission in a Sintering pan

Beside the interesting papers of the effect of metallic chlorides /47/ and the
mechanism of dioxin-furans-formation at high temperatures /48/ the de novo
formation characteristics of dioxins in the dry zone of iron ore sintering bed was
studied /49/, where e.g. the following conclusions are valuable that the addition of
CuCl2 and CuO to the sinter mixture led to a significant increase in the total about of
dioxins. In particular, CuCl2 accelerated dioxin formation at a greater rate than CuO.
The homologue distribution of PCDD/Fs shifted to higher versions and that the dioxin
formation from the sinter mixture was influenced by temperature, presence of
chlorine compounds, catalyst and carbonaceous materials in the sintering bed or
gas.
In the paper about the effect of additives it was shown that the sintering pan tests
like Ptz /2,3,7/ - see Fig. 15 and 16 can give results, that can be used to explain
results at sinter strands /50/.
Fig. 36 shows the effect of additives in different series and the authors stated that the
details had not been classified.

Fig. 36:
Effect of additives
on PCDD/Fs
formation.
(Anth: anthracite)

47
8.

Prediscussion of the Report Part I

In this report at first the literature about dioxin was taken in consideration, which was
selected and discussed in the Phd-thesises at our University by X. Hong, R. Ptz, G.
Schwanekamp and A. Kfler, furthermore the discussed results of their publications.
Onaka (DAIDO-Steel, Japan), who researched in our University, gave interesting
discussions about the Japanese research and publications.
In chapter 1 dioxin is introduced. Dioxins and furans can from 210 congeners. They
consists of two benzene-rings combined by two oxygen atoms = dioxins or by one
oxygen atom = furans and they have Cl-atoms at different position.
The most toxic one with 2,3,7,8 Cl-positions is called Seveso poison with the
highest toxic equivalency factor = 1. This one has e.g. nearly no solubility in water.
The dioxins are mainly formed in a middle temperature of 400C to 800C and
destroyed by higher temperature, but they can be reformed again by de novo
synthesis by slowly cooling down.
In chapter 2 a review is given and shown that after the Seveso accident in Italy a lot
of research started e.g. in Germany. In this report the research about iron-ore
sintering is stressed including results of electro-arc- and shaft-furnaces that means
in iron metallurgy. Results e.g. with reactions as a poison to plants, animals and
human beings are not discussed.
In chapter 3 the iron ore sinter process is explained with its definition and the typical
sinter strand. The heat transport with the moving of the sinter-temperature-peak
from the top of the sinterbed to the bottom. The importance of the sinter temperature
of 1350C is discussed and the quality of the offgas is explained.
In chapter 4 experiments in a sintering pan in an apparatus at the Institute of Ferrous
Metallurgy is shown. Results of electric-arc- and shaft-furnace were taken in
consideration and the results were discussed with the partners at MURL and industry.
Mill scale and blast furnace dust addition gave higher emissions of dioxins.

48
In chapter 5 results of industry at sinter plants were compared with results at KruppHoesch in a combined research between Aachen University and industry. Filters
(electric and bag-) were tested and different sinter materials were used.
Interesting results were found over the length of the sinter strand with a maximum of
dioxin-emission at the end of the sinter strand parallel with the maximum of the offgas-temperature.
Some years later in Japan by the SDD-Project were found and showed the rightness
of the former results.
In the last chapter 6 dioxin minimizing possibilities of different equipments were
checked and discussed. First the Air fine process was introduced, but just a new way
of this process was published with dry typ of gas cleaning.
The EOS (Emission optimized sintering) was shown and further test-campaigns
with LEEP at HKM were added, e.g. Quenching- and Jet stream injection of active
coke breeze. Step by step these ways were discussed. The partly off-gas recycling
brought interesting low values. The clean part of the off-gas was given to the chimney
but the off-gas with dioxin were returned into the hot zone of the sinter strand.
At the end of this chapter once again tests in a sintering pan were discussed of the
SDD-project in Japan. They showed e.g. the increase of dioxins by PVD- and by
sinter strand dusts-addition.
After these global views in the next chapter the Sinter plant and the possibilities of
Taranto will be shown in short words. The first measurement results of Dioxin will be
given and technologies and the used materials are mentioned.
The following part will show the possibilities to minimize Dioxin emission without
technological changes on the strand.

49
Literatur
/1/

Dioxin-Wikipedia, the free encyclopedia

file: http://en.wikipedia.org/wiki/Dioxin

/2/

R. Ptz:
Dioxinproblematik bei metallurgischen Prozessen der Stahlindustrie am
Beispiel der Eisenerzsinterung.
(Betreuer: H.W. Gudenau, H.P. Johann, W. Dahl)
Dissertation RWTH Aachen 1996

/3/

H.W. Gudenau und R. Ptz:

Dioxin generation during the sinter process and possibilities for future elemination.
Environmental Management and New Technologies in the Iron- and Steelindustry, Belo Horizonte/Brazil, 30.11.1995

/4/

D. Schulz:
Wirkungsbezogene Richt- und Grenzwerte fr Dioxine sowie gegenwrtige
Belastung von Mensch und Umwelt in der Bundesrepublik Deutschland.
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Emissionsbegrenzung und minderung. UTECH Berlin 1994, S. 7-38

/5/

H. Hagemeier:
Polychlorierte Dibenzodioxine und polychlorierte Dibenzofurane Bestandsaufnahme und Handlungsbedarf.
VDI-Berichte 745 (1989), Band II

/6/

H. Fiedler:
Sources of PCDD/PCDF and impact on the environment.
Organologen Compounds Vol. 20, 1994, pp. 229-236

/7/

H.W. Gudenau und R. Ptz:

Stand der wissenschaftlichen Forschung zur Dioxin-Problematik bei metallurgischen Verfahren der Eisen- und Stahlindustrie.
Seminar des Informations- und Meausbildungszentrums Immissionsschutz,
Essen-IMIS, 24.08.1994

/8/

H.W. Gudenau, K.-J. Geueke und R. Ptz:

Entstehungszonen dingfest gemacht.
Umweltmagazin Mai 1995, S. 48-49

/9/

H.W. Gudenau, K.-J. Geueke und R. Ptz:

Dioxinemissionsuntersuchungen an einer Eisenerzsinteranlage beim Zusatz
verschiedener Httenreststoffe.
VDI-Seminar Thermische Behandlung von Abfllen, 30./31.05.1996

/10/

H.W. Gudenau, K.-J. Geueke und R. Ptz:

Die Eisenerzsinterung und Dioxinemissionsuntersuchungen.
VDI-Seminar Energienutzung bei der thermischen Behandlung und Einschmelzung von Reststoffen, 27./28.04.1995

50
/11/

Arbeitsgruppe des Unterausschusses Luft/Technik des Lnderausschusses

fr Immissionsschutz
Erarbeitung von Anforderungen zur Emissionsbegrenzung fr Dioxine und
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/12/

H. Fiedler, H. Frank, O. Hutzinger, W. Parzefall, A. Riss und S. Safe:

Dioxin 93
13th Intern. Symposium on Chlorinated Dioxins and Relate Compounds,
Vienna/Austria, September 1993

/13/

N.N.
Jahrbuch Stahl 2005 Verlag Stahleisen

/14/

H.W. Gudenau:
Einflu der Eisenmodifikation bei der direkten Stahlerzeugung.
Metallurgie und Werkstoffwissenschaften, Clausthal 28.04.1987

/15/

H.W. Gudenau, J. Fang, T. Hirata und U. Gebel:

Fluidized bed reduction as the prestep of smelting reduction
Steel Research 3+4 (1989), pp. 138-144

/16/

H.W. Gudenau:
Materialsammlung zur Vorlesung Vertieferfach III
Alternative Stahlerzeugung 1 Direktreduktion, 1997

/17/

H.B. Lngen:
Beitrag zum Austausch von gasfrmigen und festen Brennstoffen bei Sintern
von Eisenerzen
(Betreuer: H.W. Gudenau, W. Dahl, K.H. Mommertz)
Dissertation RWTH Aachen 1990

/18/

H. W. Gudenau:
Eisenhttenmnnische Verfahrenstechnik Vom Erz zum Stahl
Materialsammlung zum Praktikum an der RWTH Aachen, 1989

/19/

H.W. Gudenau, K. Mavrommatis und A. Babich:

Ironmaking, Lecture-Textbook, e-learning 2002
http://meveus.iehk.rwth-aachen.de

/20/

H.W. Gudenau:
Mlleraufbereitung
Materialsammlung zur Vorlesung, 1991

/21/

F. Cappel und H. Wendeborn:

Sintern von Eisenerzen
Verlag Stahleisen 1973

51
/22/

S.A. Dwiwanto:
Agglomerierter Braunkohlenfeinkoks als Sinterbrennstoff
(Betreuer: W. Wenzel und H.W. Gudenau)
Dissertation RWTH Aachen 1976

/23/

W. Wenzel, H.W. Gudenau und S.A. Dwiwanto:

Vergleichende Bewertung von Sinterbrenstoffen
Intern. Eisenhttentechnischer Kongre, Dsseldorf 1974
Band I, 1.127 und Ergnzungsband
U.D. Matzke:
Blei-, Zink- und Alkalientfernung beim Sintern von Reicherzmischungen
(Betreuer: H.W. Gudenau, W. Dahl, H.-P. Johann)
Dissertation RWTH Aachen 1987

/24/

/25/

E. Streich:
Entstehung und Beseitigung von Aerosolen im Doppelsinterproze beim Einsatz von Walzzunderschlamm
(Betreuer: H. Fian, H.W. Gudenau)
Dissertation RWTH Aachen 1989

/26/

R. Bothe:
Umweltproblematik bei der Eisenerzsinterung; Diskussion vorhandener Verfahren zur Begrenzung von Emissionen und der Konsequenzen der aktuellen
Gesetzgebung auf den Betrieb von bestehenden Anlagen
Dissertation RWTH Aachen 1993

/27/

M. Riedhammer:
Die Mischungsfeuchte als eine wesentliche Einflugre bei der Steuerung
des Sinterprozesses fr Eisenerze
(Betreuer: H.W. Gudenau, W. Dahl, K. Meyer)
Dissertation RWTH Aachen 1980

/28/

A.G. Deja:
Reduzierende Vorwrmung von Eisenerzsintermischungen bei der Saugzugsinterung
(Betreuer: W. Wenzel, H.W. Gudenau, W. Dahl)
Dissertation RWTH Aachen 1976

/29/

W. Wenzel, H.W. Gudenau und A. Deja:

Preheating of sinter mixtures
World Steel & Metalworking 78 (1978), pp. 37-40

/30/

F. Cappel:
Wrmebehandlung des Sinters mit heien Rauch- oder Prozegasen im
Anschlu an den Zndofen
(Betreuer: H.W. Gudenau, W. Dahl, K.-H. Mommertz)
Dissertation RWTH Aachen 1977

52
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H.W. Gudenau, D. Schlebusch, F. Cappel, N. Magedanz und H. Weisel:

EOS-Emission-Optimized-Sintering: Ein neues Verfahren zur Verbesserung
des Umweltschutzes beim Sintern von Eisenerzen
Wissenschaft und Umwelt 4/1992, S. 313-318

/32/

X. Hong:
Simulation und Optimierung der Schrottvorwrmung fr anschlieende
Schrottschmelzverfahren
(Betreuer: H.W. Gudenau, W. Dahl, T. Yang)
Dissertation RWTH Aachen 1992

/33/

X. Hong und H.W. Gudenau:

Dioxinproblematik und Mglichkeiten der Emissionsminderung
Vortrag vor dem Stahlwerksausschu/Arbeitsausschu VDEh,
13.06.1991

/34/

G. Schwanekamp:
Einsatz von geshredderten Kunststoffreststoffen als Reduktionsmittel und/
oder Energietrger in Schmelzaggregaten der Eisen- und Stahlindustrie
(Betreuer: H.W. Gudenau, W. Dahl, H.-P. Johann)
Dissertation RWTH Aachen 1997

/35/

H.W. Gudenau, G. Schwanekamp, J. Rachner und M. Rudack:

Recycling von Kunstreststoffen im Hochofen und Kupolofen
Aachener Umwelttage Reststoffverwertung, RWTH Aachen, 9.-10.11.1995
Tagungsband S. IV 3.1

/36/

H.W. Gudenau, G. Kleinschmidt und G. Schwanekamp:

Possibilities of the use of plasticwaste in the Iron- and Steel Industry
Intern. Seminar Environmental Protection and New Technologies in the
Iron- and Steel Industry, 30.11.-01.12.1995, Belo Horizonte/Brazil,
Tagungsband S. 14

/37/

H.W. Gudenau, R. Ptz, K.-J. Geueke, G. Schwanekamp, C. Wiebe,

J.E. Becker und M. Weinberg:
Verwertung von Reststoffen in Schmelzprozessen Vorstellung verschiedener
Forschungsvorhaben des Instituts fr Eisenhttenkunde
VDI-Bildungswerk Dsseldorf, Handbuch BW 43-20-01, 27.-28.04.1995

/38/

H.W. Gudenau und K. Onaka:

Dioxin control technology in iron- and steelmaking industry
Sustainable Development Metallurgy of Iron and Steel, Seminario Intern.
April 2001, S. XVI 1-6, Florianopolis/Brazil

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A. Kfler:
konomisch optimierte und anlagentechnische Mglichkeiten zur Emissionsminderung einer Sinteranlage unter besonderer Bercksichtigung der Dioxinund Furan-Problematik
(Betreuer: H.W. Gudenau und H.P. Johann)
Dissertation RWTH Aachen 1999

53
/40/

H.W. Gudenau, D. Senk and A. Babich:

Promotion of Ironmaking Research based on International Cooperation
Keynote-Lecture beim ICSTI in Osaka/Japan 2006

/41/

Eiki Kasai, Teruhiko Aono, Yukio Tomita, Makoto Takasaki, Norihisa Shiraishi
and Shiji Kitano: Macroscopic Behaviors of Dioxins in the Iron Ore Sintering
Plants, ISIJ International, 41 (2001), 86-92

/42/

L.von Bogdandy, G. Miller, A. Moser and O. Kller:

Entwicklung und Stand des KVA-Verfahrens
BHM 134, Jahrgang 1989, Heft 7, S. 203-207

/43/

N.N.: Gefhrlicher Schrott

Management Wissen 10/89, S. 9-10

/44/

A. Fleischanderl:
Improved dry-type gas cleaning process for the treatment of sinter offgas, MPT
International 3/2006, pp. 36-40

/45/

Outotec- Sintering technologies

www.outotec.com

/46/

J.A. Philp:
Verringerung von Dioxinemissionen aus Sinteranlangen
UBA-Abschlubericht 50 441-5/217, Dec 2002

/47/

S. Kuzuhara, H. Sato, E. Kasai and T. Nakamura:

Influence of Metallic Chlorides on the Formation of PCDD/Fs during LowTemperature Oxidation of Carbon, Environ. Sci. Technol. 2003, 37, 2431-2435

/48/

Hirotoshi Kawabata, Tateo Usui, Katsukiyo Marukawa, Shigeta Hara, Toshihiro

Tanaka and Hideki Ono-Nakazato:
Mechanism of Dioxins/Furans Formation at Hiongh Temperature in
Combustion Processes, ISIJ International, Vol 43 (2003), No. 3, pp.461-467

/49/

K. Suzuki, E. Kasai, T. Aono, H. Yamazaki and K. Kawamoto:

De novo formation characteristics of dioxin in the dry zone of an iron ore
sintering bed, Chemosphere 54 (2004) 97-104

/50/

Eiki Kasai, Yozo Hosotani, Takazo Kawaguchi, Koichi Nushiro and Teruhiko
Aono:
Effect of Additives on the Dioxins Emissions in the Iron Ore Sintering Process,
ISIJ International, Vol. 41 (2001), No. 1, pp. 93-97