AISTech 2019 — Proceedings of the Iron & Steel Technology Conference

6–9 May 2019, Pittsburgh, Pa., USA

DOI 10.1000.377.112

Pyrophoric Dust Formation During Vacuum Degassing: Uncovering the Determining Factors

M. Vidonis1, F. Gandin1, H. Koblenzer1

1
Danieli & C. Officine Meccaniche
Via Nazionale 41, Buttrio (UD), Italy, 33042
Phone: +39 0432 195 5535
Email: m.vidonis@danieli.it

Keywords: Vacuum Degassing, Pyrophoric Dust, Mechanical Vacuum Pumps, Magnesium Oxide, Opex

INTRODUCTION
In recent years, the production of special steels in modern Vacuum Degassing (VD) plants has seen an ever-increasing
adoption of Mechanical Vacuum Pumps (MVP) over Steam Ejector (SE) pumps. MVP-based plants were previously shown
by our group1 to perform better than their SE counterparts in flexibility, serviceability and operating costs assessment, while
being able to guarantee the same final steel quality and process times.
VD plants driven by Mechanical Vacuum Pumps are characterized by production, during the process, of dry dust which can
occasionally show pyrophoric properties. Sudden dust ignition poses a risk for personnel and equipment, delays in production
and loss of productivity.
This is a well-known problem, but little data is available to determine its root causes. Our study, carried out collecting and
analyzing dust samples in ABS, Italy, highlighted some of the parameters that play a major role in the formation of
pyrophoric dust during the vacuum degassing treatment.
The product mix in ABS includes carbon steel, medium alloyed and high alloyed steel grades, with an annual productivity of
approximately 1.4M ton of liquid steel. The plant comprises 2 VD stations, as 100% of the product mix requires to be
vacuum degassed. Continuous production of both Vacuum Degassing plants means that any delay caused by dust
pyrophoricity has the potential to affect negatively the production of the melt shop. Nowadays filter bags are replaced once a
year in each VD as a preventive maintenance, the result of the focus placed on the optimization of filter cleaning and filter
dust management.
The high number of VD-treated heats and the wide spectrum of steel grades place ABS in a unique position to study the
phenomenon of dust produced during the vacuum treatment.

EXPERIMENTAL PROCEDURE AND PLANT DESCRIPTION

All data in the present work was gathered from several heats followed in both VD1 and VD2 plants of ABS, Italy. A filter
dust sample of each heat was collected. To avoid contamination with the dust from previous heats, sampling was carried out
during dust discharge from the filter at the end of each heat. A steel cup made for this purpose was used. This was done to
guarantee that each measurement and observation in the study was representative of the heat that produced that dust before it
was mixed in the collection bin, so that it could be related to all other process parameters. Immediately after sampling, dust
temperature was measured by means of a K-type thermocouple and recorded (see Figure 1). Each sample was then cooled
down to room temperature and stored for later analysis.
This procedure allowed overcoming the main drawback in all previous observations, that is, the difficulty in determining the
factors involved in dust pyrophoricity by observing the behavior of a mix of dusts collected through several heats.
All samples were analyzed at the melt shop laboratory after complete oxidation. The chemical composition was determined
by means of X-Ray fluorescence and High Temperature Combustion (LECO).
All relevant data from different sources (direct measurements, Level 2 and 3 automation, Quality laboratory) was collected
and gathered in a database for statistical analysis.

© 2019 by the Association for Iron & Steel Technology. 1091

 Figure 1. Measurement of the temperature of sampled dust during oxidation.
Figure 2 reports a sketch representing a typical Vacuum Degassing plant layout equipped with Mechanical Vacuum Pumps.
The system includes the following main equipment:
• Vacuum tank(s)
• Dust Separator
• Main Shut-Off Valve (MSOV) with Main By-Pass Valve (MBPV)
• Textile Filter(s)
• Mechanical Vacuum Pumps (MVP), each isolated by a skid valve
• Pressure transmitters, marked as PT1 and PT2
• Online Dust Detector (DD).
The plant is divided in the Tank side and Filter side by the Main Shut-Off Valve.

PT1
Main Valve

PT2
Textile
Filter
DD

Skid 
Valves
Dust
Separator

Vacuum tank Dust  Filter Mechanical 

Separator Pumps

Figure 2. Representation of a typical Vacuum Degassing plant with mechanical pumps.

The main features and advantages offered by innovations introduced in this equipment (such as Main By-Pass Valve and
Dust Detector) have been discussed previously1.
Hot fumes coming from the tank pass through the Dust Separator, a water-cooled cyclone where coarser-grain dust is
collected and gases temperature is reduced. The finer dust is collected at the textile filter, while clean gases can safely pass
through the pumps.
Experience shows that most of the pyrophoric dust is collected from the textile filter. The amount of dust produced during
one VD treatment is approximately 0.1-0.2 kg/t, while it can be up to 20 times higher for the VOD process.

1092 © 2019 by the Association for Iron & Steel Technology.

 RESULTS AND DISCUSSION

Pyrophoric Dust
The fine, dry dust that is collected from the VD textile filter is generated by evaporation and entrainment of steel and slag
during the vacuum treatment in the tank environment. Fumes are cooled down during transport through the suction line and
the water-cooled dust separator and are then filtered in vacuum. An inert atmosphere is kept inside the textile filter volume
always. Therefore, the cycle of discharge from the Dust Separator and filter is the moment when the VD dust first makes
contact with air-borne Oxygen. Experience shows that in this event dust can often show a pyrophoric behavior, igniting
spontaneously and sometimes giving rise to a sudden and violent oxidation. This occurrence is quite unpredictable in nature,
and so far, no methods are available to predict the behavior of the dust produced in a particular heat, sequence or production
campaign.
Pyrophoricity is a major problem for dust handling and disposal. In the discharge bin, oxidation of pyrophoric dust stops
when the superficial layer is fully oxidized, as air can hardly penetrate through the fine dust: As a result, most pyrophoric
dust collected remains reactive under a protective oxidized layer. During disposal, even several hours after collection, any
movement that exposes the underlying dust to air triggers immediately a potentially dangerous exothermic reaction (Figure
3).

Figure 3. Dust bin with pyrophoric dust. Still reactive dust rests below a superficial oxidized layer.
All dust collected from the textile filter must be completely oxidized before a safe disposal. This is true especially when
industrial vacuum cleaning trucks are used for dust disposal from the collection bins: Since these devices are not designed for
high temperature materials, pyrophoric dust can seriously damage them if it reacts during suction. The need of oxidizing and
cooling down pyrophoric dust can greatly delay disposal operations.

Types of Dust
In this study, 3 different types of dust were identified (see Figure 4):
• Type 1: Cold dust, with a measured temperature slightly above room temperature (approx. 30 – 50°C). This dust did
not show reactivity when mixed with air.
• Type 2: pyrophoric dust that oxidizes and becomes red hot when in contact with air. Measured temperatures were in
the range of 400 – 500°C. The oxidation reaction of material exposed to air proceeds quickly (< 1 second) and
generates no fumes.
• Type 3: pyrophoric dust like Type 2, but characterized by a high production of white smoke during oxidation. The
oxidation reaction proceeds more slowly compared to Type 2.

© 2019 by the Association for Iron & Steel Technology. 1093

 Figure 4. Types of VD dust. Type 1, non-reactive (left), Type 2, pyrophoric (center) and Type 3, pyrophoric with smoke
production (right).
The graph below (Figure 5) reports the average temperatures reached by each kind of dust, as measured with a thermocouple
just after discharge from the textile filter. All dust samples were then let oxidize and cool down completely for storage and
analysis.

Type 1
600.00
Type 2
Type 3
500.00

400.00
Dust T (°C)

300.00

200.00

100.00

.00
Dust Type

Figure 5. Average dust temperature of different dust types, measured at discharge from the textile filter.
All dust samples were analyzed to identify chemical differences that would explain the different behavior of the three kinds
of dust show upon contact with air. The chemical composition was determined for each dust sample by means of X-Ray
spectrometry and LECO analysis: The average composition for each type of dust is reported in Table 1 below.

Table 1. Average composition of VD dust sample collected during the present work.
Dust type %MgO %MnO %C %Fe2O3 %ZnO %PbO %CaO %Al2O3 %SiO2 %P2O5 %SO3 Others SUM
1 40,1 37,9 3,2 6,3 6,4 1,20 0,91 0,05 0,14 0,07 1,48 2,32 100,0
2 43,3 37,2 1,0 5,7 6,4 1,20 1,22 0,05 0,20 0,09 1,44 2,22 100,0
3 39,3 36,0 4,6 6,8 7,4 0,87 0,86 0,08 0,21 0,08 1,28 2,50 100,0

The exothermic reaction observed in the dust is the oxidation of elements still present in metallic form. The table shows that
MgO and MnO make up for approximately 80% of a dust sample: The formation of these oxides is thus the most likely cause
of the observed phenomenon.
Nevertheless, there is no significant difference in the content of these oxides for the 3 types of dust. In fact, as highlighted by
the chart of Figure 6, all dust types have essentially the same composition, with the exception of Carbon content. There is a
marked difference in the amount of C present, on average, in Type 2 and Type 3 dusts, while both fall in the quite wide
distribution of C in cold dust. The different amount of Carbon could explain the difference in reaction speed and in

1094 © 2019 by the Association for Iron & Steel Technology.

production of smoke of the two types of pyrophoric dust: When present in relatively high quantity, C would take part in the
oxidation reactions, changing their paths and thus the observed speed and products.

50.00
Type 1
45.00 Type 2

40.00 Type 3
Compound Content (%)
35.00

30.00

25.00

20.00

15.00

10.00

5.00

.00
MgO C MnO Fe2O3 ZnO

Figure 6. Average content of the main compounds in different types of dust.

Measurements and observations of VD dust of each heat followed during this study were correlated with melt shop process
data (EAF, LF and VD) from the melt shop production database. This analysis highlighted some parameters that appear to be
related to the formation of pyrophoric dust.

Steel Temperature
The chart of Figure 7 reports the VD dust temperature as a function of the steel temperature measured at VD inlet and
immediately at the end of the vacuum treatment. Data shows that high dust temperatures cluster at higher values of steel
temperature: Pyrophoric dust was produced only when the starting VD temperature was above approximately 1650°C or with
a steel temperature of 1595°C or higher after vacuum.

600.00
VD Inlet
500.00
End of
Dust Temperature (°C)

Vacuum
400.00

300.00

200.00

100.00

.00
1525 1550 1575 1600 1625 1650 1675 1700

Steel Temperature (°C)

Figure 7. VD dust temperature vs. steel temperature measured at VD inlet (red triangles) and after vacuum (blue open
circles). Pyrophoric dust was observed only for heats starting the process with more than 1650°C and ending the vacuum
process with more than 1595°C

© 2019 by the Association for Iron & Steel Technology. 1095

Similar clusters can be observed also for steel superheat temperature over liquidus, a more commonly used parameter in melt
shop process control. Figure 8 reports superheat temperatures at VD inlet and immediately after vacuum. Pyrophoric
behavior of dust was encountered only in heats starting the vacuum process with a superheat temperature of 160°C or higher,
and heats ending vacuum with a superheat of 90°C or higher. As could be expected, there is less variability in superheat
temperature at departure from VD (data not shown): Since this is a fundamental parameter in controlling the casting process,
all activities after degassing are aimed at achieving the correct superheat.

600.00

500.00 VD Inlet
Dust Temperature (°C)

End of Vacuum
400.00

300.00

200.00

100.00

.00
.0 25.0 50.0 75.0 100.0 125.0 150.0 175.0 200.0

Steel Superheat Temperature (°C)

Figure 8. Steel superheat temperatures: VD inlet (red triangles) and after vacuum (blue open circles). Pyrophoric dust was
observed for VD inlet superheat > 160°C and vacuum end superheat > 90°C.

Ladle Life
During treatments, ladle wear lining is worn out by a combined effect of temperature, chemical attack, and erosion by the
agitation of liquid steel and slag. The most common type of wear lining bricks in the production of special steels is carbon-
bonded magnesite.
The chart of Figure 9 shows the average ladle refractory life for each dust type. Data shows that, while no difference is
evident between Type 1 and 2 dusts in terms of number of heats, Type 3 dust seems to be associated with newly lined ladles.
Dust composition analysis showed (see Figure 6) that Type 2 and Type 3 dusts differ mainly in their Carbon content: A
possible correlation between the two observations would suggest the higher %C found in dusts of Type 3 being originated
from graphite removed from refractory bricks during the first few heats in the life of ladle refractory.

Type 1
70.00
Type 2
60.00 Type 3

50.00
Ladle life (heats)

40.00

30.00

20.00

10.00

.00
Dust Type

Figure 9. Average number of heats treated in the ladle of the observed heats, for each kind of dust produced.

1096 © 2019 by the Association for Iron & Steel Technology.

Slag Fluidity During Vacuum Treatment
Bauxite and lime additions are usually carried out to modify slag viscosity and chemistry to correct its properties and
optimize its interaction with steel. A correction of slag viscosity is often required during the vacuum treatment to guarantee
an intimate mixing of steel and slag, which promotes further Sulfur removal and inclusions capture.
The graph of Figure 10 shows average flux additions during vacuum treatment. Data shows that bauxite additions were on
average lower during heats that produced pyrophoric dust (approx. 40-50 kg) compared to cold dust (on average, 90 kg). This
would suggest that a lower slag viscosity since the beginning of the vacuum process could be linked with the generation of
pyrophoric dusts. No significant difference was observed in lime additions between the three kinds of dust.

Type 1
160.00
Type 2
140.00 Type 3

120.00
Flux Addition (kg)

100.00

80.00

60.00

40.00

20.00

.00
Bauxite CaO

Figure 10. Average additions of bauxite and lime during the vacuum treatment for each kind of dust. Bauxite additions were
relatively lower for Type 2 and 3 dusts compared to Type 1. No significant difference was observed in lime additions for the
three types of dust.

Steel Composition
Steel grade and composition is generally believed to play an important role in the generation of pyrophoric dusts. Hypotheses
are sometimes advanced on the correlation between the C, Si and Mn content of steel and the occurrence of pyrophoric dust.
The graphs of Figure 11 report the measured dust temperature against the content of Carbon, Manganese, Chromium, Silicon
and Aluminum in final steel composition. Data shows that high dust temperatures were measured across the whole range of
steel composition. Based on these observations, there is no evidence that steel composition affects the state of oxidation of
VD fumes during vacuum treatment.

© 2019 by the Association for Iron & Steel Technology. 1097

 A B
600.00
600.00

500.00
Dust Temperature (°C)

500.00

Dust Temperature (°C)

400.00
400.00

300.00 300.00

200.00 200.00

100.00 100.00

.00 .00
.000 .2000 .4000 .6000 .8000 1.000 1.2000 .000 .2000 .4000 .6000 .8000 1.000 1.2000 1.4000 1.6000
%C %Mn

C D
600.00 600.00

500.00 500.00

Dust Temperature (°C)

Dust Temperature (°C)

400.00 400.00

300.00 300.00

200.00 200.00

100.00 100.00

.00 .00
.000 .25000 .5000 .75000 1.000 1.25000 1.5000 1.75000 2.000 .000 .1000 .2000 .3000 .4000 .5000 .6000 .7000
%Si
%Cr

E
600.00

500.00
Dust Temperature (°C)

400.00

300.00

200.00

100.00

.00
.000 .01000 .02000 .03000 .04000 .05000
%Al

Figure 11. Dust temperature as a function of average final steel composition. A: %C; B: %Mn; C: %Cr; D: %Si; E: %Al.
There is no evidence of steel composition influencing the formation of pyrophoric dust.

Ellingham Diagram
As discussed earlier, the different behavior shown by dusts when exposed to Oxygen is likely based on the extent of their
oxidized or reduced state. Additionally, our results show that steel temperature during the vacuum process plays a major role
in determining whether dust shows a pyrophoric behavior.
The equilibrium of a mix of oxides can be studied with the Ellingham diagram, which represents the free energy of formation
of different oxides as a function of temperature. The diagram shows that the curves representing the formation of MgO and
Al2O3 cross at 1550°C: Above this temperature, Al oxidation becomes energetically more favored than Mg, so metallic Al,
when present, would be able to reduce MgO to form alumina and metallic Mg.
The graph of Figure 12 reports the measured dust temperature as a function of steel temperature at the end of vacuum, along
with the curves of oxidation of Mg and Al from the Ellingham diagram. In the graph, the point of change between the
equilibria of the two oxides is close to the temperature at which pyrophoric dust starts to appear. If the measured steel
temperature is representative also of slag temperature, data shows that in some heats the temperature during the whole
vacuum process would allow, from a thermodynamic point of view, the presence of metallic Magnesium.

1098 © 2019 by the Association for Iron & Steel Technology.

 600 -500
End of Vacuum
-550

Formation Free Energy ΔG (kJ)

500
Mg Oxidation -600

Dust Temperature (°C)

Energy
-650
400
-700
300 -750
-800
200
-850
-900
100
-950
00 -1000
1000 1200 1400 1600 1800
Steel Temperature (°C)

Figure 12. Dust temperature (blue dots) and free energy of formation of Al2O3 (red dashed line) and MgO (blue solid line) as
a function of steel temperature at the end of vacuum. The two lines cross approximately at the temperature where pyrophoric
dust starts to appear.
Oxidation equilibria in slag and fumes during vacuum treatment can explain the presence of metallic elements in fumes. The
high presence of MgO in dust and the change in the equilibrium of MgO formation at process temperatures are an indication
that a higher presence of metallic Mg in dust could be the cause for pyrophoricity.
In general, data indicates that heats that were vacuum treated at temperatures where the formation of metallic Mg is favored
seem to be more likely to produce pyrophoric dusts.

CONCLUSIONS
Pyrophoric dust represents arguably the most challenging aspect for VD plants with Mechanical Pumps. Possible safety risks
for personnel and equipment, delays in dust disposal and, in some cases, loss of productivity are the major concerns caused
by oxidation of dust.
The purpose of this work was to investigate which parameters of the steel production process are involved in the formation of
pyrophoric dust. Dust samples were collected at discharge from the VD filter and dust temperature during oxidation was used
as a measurement of pyrophoricity. Production data was collected for each heat and analyzed to find correlations with the
observed dust behavior.
Based on on-site observations, 3 types of dust were identified: Type 1 dust appears cold and non-reactive and has an average
temperature of approx. 40°C. Type 2 and 3 dusts are both pyrophoric and reach on average 430°C during oxidation. The two
types differ in composition, reaction rate and products: Type 3 dust has a higher C content (on average, 4.6% as opposed to
1%), oxidizes slowly and produces a large amount of smoke during combustion. The difference could be explained with
Carbon taking part to the oxidation reactions, modifying the overall paths and products. Aside from Carbon content, all types
of dust have essentially the same oxides composition after the reaction.
Analysis of collected data showed that the most relevant parameters in the formation of pyrophoric dust are steel temperature,
ladle life and slag fluidity during the vacuum treatment. Dust pyrophoricity was observed only for heats in which the steel
started the vacuum treatment at 1650°C or higher, or finished the treatment above 1595°C. It is proposed that steel and slag
temperature influences oxidation equilibria and thus the content of metallic particles in fumes.
Ladle life played a role in the formation of Type 3 dust, which was observed only with ladles that had been employed for less
than 10 heats. Ladle wearing rate is known to be higher in newly-lined ladles, which could explain the higher C content in
dust. Additions of slag builders at VD were also related to pyrophoric dust occurrence, which was only formed in heats with
low bauxite additions (40-50kg compared to an average of 90kg in Type 1 dust). This suggests that slag viscosity in these
heats was relatively low from the beginning of the vacuum treatment, a condition that can be more aggressive on the
refractory. These results support the hypothesis that MgO-C bricks could be the main source of Magnesium and graphite
found in fumes dust. Refractory wearing thus seems another determining factor in pyrophoricity.

© 2019 by the Association for Iron & Steel Technology. 1099

Contrary to the common understanding that certain steel grades are associated with the production of pyrophoric dust, no
evidence was found to support this hypothesis. In fact, pyrophoric dust was found across the whole range of steel
composition in the population analyzed.
Results obtained also suggested a possible mechanism to explain the formation of pyrophoric dust. Since all kinds of dust
have approximately the same composition after oxidation, the main difference lies in the extent of oxidation of its
components when dust first makes contact with Oxygen. The role of steel temperature during vacuum can be explained by
analyzing the Ellingham diagram: heats with a higher steel temperature at VD inlet spend on average more time in a
temperature range where the formation of metallic Mg is favored. This would suggest that the dust generated could contain a
higher amount of Mg, which would then oxidize to MgO when in contact with air. Similar considerations could be done for
the oxidation equilibria of all dust components, as the fumes that originate from the ladle in the vacuum tank span all
temperatures, from more than 1600°C in the slag to room temperature in the textile filter.
Our results allowed shedding some light on the issue of the formation of pyrophoric dust in VD plants. Data gave an
indication regarding which parameters seem to play a role in this process and which, on the other hand, show no correlation.
This will allow focusing further studies on the right factors and carrying out the most effective corrective actions.
Additionally, this information could be useful in predicting when pyrophoric dust is most likely to occur, based on readily
available process data. Such indication could then be used, for example, for a better organization of dust disposal operations.

ACKNOWLEDGMENTS
We would like to thank the process, production, maintenance and laboratory teams at ABS, Italy for their precious support
and contribution to this work.

REFERENCES
1. F. Gandin, H. Koblenzer, “Innovative Vacuum-Tank Degassing technologies: well-established metallurgical
performance figures achieved by using dry amechanical pumps”, AISTech 2015.

1100 © 2019 by the Association for Iron & Steel Technology.