Communications

t
Dt
~
vn
~
vt
~
x
dn
d~
t

ls
p
t

[s]
[s]
[m/s]
[m/s]
[m]
[m]
[m]
[]
[kg/m3]
[]

time
time step of the iteration
relative velocity in normal direction
relative velocity in tangential direction
position vector
displacement in normal direction
displacement in tangential direction
coefficient of sliding friction
particle density
Poisson's ratio

References

1 Introduction

[1] W. Mller, Chem. Ing. Tech. 1981, 53 (11), 831.

[2] S. E. Pratsinis, Mechanische Verfahrenstechnik I, Vorlesungsskript,
Institute of Process Engineering, ETH, Zurich 2002.
[3] K. Wieghardt, Annu. Rev. Fluid Mech. 1975, 7, 89.
[4] K. Terzaghi, R. Jelinek, Theoretische Bodenmechanik, Springer, Berlin
1954, 505.
[5] R. Hill, The Mathematical Theory of Plasticity, Clarendon Press, Oxford
1950, 355.
[6] H. M. Jaeger, S. R. Nagel, R. P. Behringer, Rev. Mod. Phys. 1996, 68 (4),
1259.
[7] C. S. Campbell, Annu. Rev. Fluid Mech. 1990, 22, 57.
[8] D. G. Wang, C. S. Campbell, J. Fluid Mech. 1992, 244, 527.
[9] P. K. Haff, J. Rheol. 1986, 30 (5), 931.
[10] A. Rosato, K. J. Strandburg, F. Prinz, R. H. Swendsen, Phys. Rev. Lett.
1987, 58 (10), 1038.
[11] J. M. Ottino, D. V. Khakhar, Annu. Rev. Fluid Mech. 2000, 32, 55.
[12] D. W. Heermann, Computer Simulation Methods in Theoretical Physics,
Springer, Berlin 1990, 145.
[13] H. J. Herrmann, S. Luding, Continuum Mech. Thermodyn. 1998, 10 (4),
189.
[14] J. Novosad, G. Standart, Collect. Czech. Chem. Commun. 1965, 30 (10),
3247.
[15] S.-I. Makishima, T. Shirai, J. Chem. Eng. Japan 1967, 1 (2), 168.
[16] B. Cooker, R. M. Nedderman, Powder Technol. 1987, 50 (1), 1.
[17] S. Masiuk, Powder Technol. 1987, 51 (3), 217.
[18] Y. C. Zhou, A. B. Yu, R. L. Stewart, J. Bridgwater, Chem. Eng. Sci.
2004, 59 (6), 1343.
[19] Y. C. Zhou et al., Physica A 1999, 269 (24), 536.
[20] R. L. Stewart, J. Bridgwater, Y. C. Zhou, A. B. Yu, Chem. Eng. Sci.
2001, 56 (19), 5457.
[21] Y. Tsuji, T. Kawaguchi, T. Tanaka, Powder Technol. 1993, 77 (1), 79.

______________________
Explosions Limits of H2S/CO2/air and
H2S/N2/air
By Robert Pahl and Kai Holtappels*
For the evaluation of the dangers of explosions, which can
take place while handling H2S, only literature values exist,
which had not been determined according to actual standard
methods. Therefore the explosion limits of the two ternary
gas systems H2S/CO2/air and H2S/N2/air were determined at
20 C and 1 bar(a) according to the bomb method of the new
European standard EN 1839. A comparison of these mea
[*]

746

sured values with the literature values results in a clear expansion of the explosion range for both gas systems. Thus
the explosion limits for H2S/air were found at 3.9 mol-%
(LEL) and 49.8 mol-% (UEL) in relation to literature values
of 4.3 mol-% and 45.5 mol-%. Adding CO2 or N2 to the gas
systems in particular the UEL was found at higher amounts
of H2S than reported in the literature. Hence the LOC values are smaller. For the system H2S/CO2/air a LOC value of
10.5 mol-% (literature value: 12.1 mol-%), for H2S/N2/air
9.1 mol-% (literature value: 10.8 mol-%) was determined.

Dipl.-Ing. R. Pahl, Dr. K. Holtappels (kai.holtappels@bam.de), Bundesanstalt fr Materialforschung BAM, II.1 Gase, Gasanlagen, Unter den
Eichen 87, D-12205 Berlin, Germany.
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

One of the most technical important sulfur compounds is

hydrogen sulfide (H2S). H2S is a colourless, reactive, flammable and toxic gas, which smells like foul eggs [1]. Among
other things hydrogen sulfide is a reduction product of organic substances, which contain sulfur.
For the use of hydrogen sulfide it is strongly recommended to carry out safety evaluations in order to prevent
dangerous situations. In most cases only the toxicity of the
gas is considered. In a concentrate form breathing in H2S
has a quick deadly effect by means of paralysis of the breathing centre. The smell is perceptible in a concentration of
0.025 ppm (threshold of smell). The awareness of the smell
decreases very quickly and disappears nearly till a rest after
a short time because the smell receptors are narcotized.
Through there the danger exists that hydrogen sulfide will
be breathed in unnoticed. The maximum allowed working
place concentration is mentioned in the literature with a value of 10 ppm [1].
In chemical processes clearly higher H2S-concentrations
are used or arise during the process. In this case the detailed
knowledge of the lower respectively the upper explosion
limit (LEL and UEL) is necessary for a safety evaluation.
Usually such safety characteristics like the explosion limits
are available in several tables and databases, for example
the database CHEMSAFE [3]. In case of the hydrogen sulfide only elder literature values of Coward and Jones [4] exist, which are not measured after a standard procedure like
the present state-of-the-art. Therefore the explosion limits
of both gas systems should be determined again after the
bomb method of the new European Norm EN 1839 [5].

2 Experimental Section
The explosion limits of both ternary gas systems H2S/CO2/
air and H2S/N2/air were determined according to the bomb
method of the new European Norm EN 1839. In Fig. 1 the
experimental setup is shown schematically.
The mixture production was executed according to the
partial pressure method. The mixtures were produced directly in the ignition vessel (spherical high-grade steel
autoclave, V = 14 dm3). Therefore the ignition vessel was
evacuated and then the individual components were dosed
DOI: 10.1002/ceat.200500066

Chem. Eng. Technol. 2005, 28, No. 7

Communications

TIR
201
ERY
301

I,U
PIR
101

pressurized air
CO2
H2S

EL.

H 2O

TIC
202

Figure 1. Experimental setup for the determination of the explosion limits of

H2S/inert gas/air mixtures at initial conditions of p0 = 1 bar (a) and 20 C according to EN 1839 (B).

trodes at a distance of 5 mm, holding a copper nickel wire (d

= 0.12 mm) on its ends, located in the middle of the vessel.
The ignition energy was provided by a 1.5 kVA/230 V insulating transformer, which was connected to the igniter by an
electronic control unit. For the ignition a part of a half wave
of the mains was switched to the wire. The wire melted and
an electric arc burns between the electrodes for a time extending maximally to a half period of the supply voltage
(0.01 s). By setting the duration of the burning arc it was
possible to change the ignition energy between values of 2 J
up to 90 J. By measuring the voltage/time and the current/
time histories the ignition energy was determined at each
ignition. The electric arc has a high energy density at a relative large surface and is very effective for ignition of gases
and gas mixtures. This ignition source is recommended in
the new European standard EN 1839 [5]. Corresponding to
the standard ignition energies from 10 J to 20 J were taken
for determination of explosion limits in the gas systems.

according to their partial pressures, which were calculated

before. A real gas correction was not executed because a
nearly ideal behavior was presupposed at the maximal mixture end pressure of 1.0 bar (a). The partial pressures as
well as the mixture end pressure was measured by means
3 Results and Discussion
of a piezoresistive pressure transducer (company Keller,
type PAA-10, measuring area from 0 bar (a) up to
The explosion limits, which were experimentally deter2 bar (a), dissolving 0.0002 bar, precision 0.5 %), which was
mined according to EN 1839 method B, are shown in Fig. 2
calibrated with a precision manometer of the company
and Fig. 3. For a comparison the literature values are also
Wallace & Thiernan, class 0.066, before. The mixture was
plotted in these figures. For both gas systems the new explohomogenized with a magnet stirrer. After production of the
sion limits differ from the literature values.
mixture it was ignited when the stirrer was switched of and
The lower explosion limit (LEL) for H2S/air mixtures
the mixture was stagnating. The used pressure transducer
was determined at nearly the same H2S concentration
was also taken for the measurement of the pressure/time
(LELEN 1839 = 3.9 mol-%; LELliterature = 4.3 mol-%). The
histories in the autoclave after the ignition. The pressure
upper explosion limit (UEL) for H2S/air mixtures was found
signals were recorded by a personal computer with installed
A/D-converter-card (company KeithH2S
ley, type DAS 1402). The pressure/
0
time histories were saved in a digita100
lized form and the explosion pres10
Coward/Jones [4]
sures were determined from these di90
BAM
gitalized curves by the use of special
20
software (BAM-development). Cri80
terion for an ignition was a pressure
30
70
increase greater than 5 % after the
40
ignition. The content of hydrogen
60
sulfide in the test mixture was varied
50
CO2
H2S
step by step till the lower (LEL) re50
spectively upper explosion limit
in mol-%
60 in mol-%
(UEL) was determined. The step dis40
tance was 0.2 mol-% hydrogen sul70
fide. The explosion limit is defined as
30
80 MXC = 14.4 Mol-%
the concentration of hydrogen sulLAI = 50.2 Mol-%
20
fide where just no ignition takes
(LOC = 10.5 Mol-%)
90
place. For the validation four repeti10
tion tests were carried out at the ex100
plosion limit.
0
Luft
As ignition source an exploding
100 90 80 70 60 50 40 30 20 10 0 CO2
wire igniter was used, fired by help
air in mol-%
of special electronic equipment. The
Figure 2. Experimental determined explosion limits (EN 1839 "B") and literature values (Coward and
Jones) of H2S/CO2/air at 1 bar (a) and 20 C.
igniter consisted of two isolated elecChem. Eng. Technol. 2005, 28, No. 7

http://www.cet-journal.de

 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

747

Communications

H2S
0
100
90
80

Coward/Jones [4]
BAM

10
20
30

70

40

60

50

H2S
50
in mol-%
40

N2
in
mol-%
60
70

30

80

20

LAI = 43.5 Mol-%

(LOC = 9.1 Mol-%)

10
0

Luft

90
100

100 90

80

70

60

50 40 30
air in mol-%

20

at a clearly higher H2S concentration. According to EN 1839

the UEL was determined at a H2S concentration of
49.8 mol-% while in the literature a value of only
45.5 mol-% was reported. Adding an inert gas CO2 (see
Fig. 2) or N2 (see Fig. 3) to the system the upper explosion
limits were determined at higher H2S concentrations, so that
the explosion ranges became much broader than reported in
the literature.
The reason for the differences especially at the UEL is
to find in the different determination procedures. Coward/
Jones executed the determination of the explosion limits in a
comparatively small ignition vessel (glass pipe with small interior diameter). In such an ignition vessel wall influences, in
particularly heat loss of the system at the vessel wall, can not
be excluded. This results in a smaller explosion range than in
case of the determination in spherical ignition vessels with a
volume bigger than 5 dm3 [6].
There are some other safety related properties, which can
be deduced from the triangular explosion diagrams in Fig. 2
and Fig. 3 [7], for example:
The maximum permissible amount of combustible
(MXC): This characteristic is the maximum permissible
amount of combustible gas in nitrogen, at which this combustible/nitrogen mixture is not flammable in any mixture
with air, measured under defined conditions.
The maximum oxidizer content (MOC): This characteristic is the maximum oxidizer content, at which no explosive
mixtures can be created by adding more combustible. If
the oxidizer is air and the maximum oxidizer content is related to the oxygen content of air, the MOC value is
equivalent to the limiting oxygen concentration (LOC). In
practice the limiting air concentration (LAI) will mostly
748

MXC = 8.9 Mol-%

10

0 N2

Figure 3. Experimental determined explosion

limits (EN 1839 B) and literature values
(Coward and Jones) of H2S/N2/air at 1 bar (a)
and 20 C.

be determined. The LOC-value is then calculated according to LOC = 0.209 LAI.

Both above mentioned values as well as the necessary tangents for the determination of these values are shown in
Fig. 2 and Fig. 3. The maximum permissible amount of combustible for a H2S/CO2/air system was determined at
MXC = 14.4 mol-% H2S and the maximum oxidizer content
at MOC = 10.5 mol-% O2. For the system H2S/N2/air a
MXC-value of 8.9 mol-% H2S and a LOC-value of
9.1 mol-% O2 was found. The values determined by the use
of the literature values would show lower MXC-values and
higher MOC-values. Especially the use of these MOC-values
is serious for safety evaluations.
Due to the significance of the determined safety characteristics in particular only the latest determined values shall be
used for safety evaluations. They correspond to the present
state of technology and will be recorded in the database
CHEMSAFE.
Received: February 21, 2005 [CET 0066]

Literature
[1]
[2]
[3]
[4]
[5]
[6]

 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Sorbe Sicherheitstechnische Kenndaten chemischer Stoffe, ecomed

Verlagsgesellschaft AG & Co. KG, Landsberg 2002, Ausgabe 06.
TRGS 900 Grenzwerte in der Luft am Arbeitsplatz Luftgrenzwerte,
Ausgabe Oktober 2000 (BArbBl. Nr. 10/2000).
CHEMSAFE Database for safety charcteristics, DECHEMA, BAM
und PTB, Frankfurt/M, Version 1.4.5.0.1, 2004.
H. F. Coward, G. W. Jones, Limits of Flammability of gases and vapours,
Bureau of Mines Bulletin 503, U.S. Government Printing Office,
Washington 1952.
EN 1839, Determination of Explosion Limits of Gases and Vapours,
Beuth Verlag GmbH, Berlin 2003.
M. Hattwig, H. Steen, Handbook of Explosion Prevention and
Protection, Wiley-VCH, Weinheim 2004.

http://www.cet-journal.de

Chem. Eng. Technol. 2005, 28, No. 7

Communications
[7]

M. Molnarne, T. Schendler, V. Schrder, Sicherheitstechnische Kenngren, Band 2, Explosionsbereiche von Gasgemischen, Wirtschaftsverlag NW, Bremerhaven 2003.

This paper was also published in German in Chem. Ing. Tech. 2004, 76 (10), 1558.

______________________
A Modular Microreactor for Mixed Acid
Nitration
By Lder Henke and Hansjrgen Winterbauer*
A corrosion resistant microreactor made of PTFE and
Tantalum has been developed for the simulation of different
nitration reactions. The new microreactor can be easily
adapted to the conditions in an industrial plant due to the
modular type of construction, and in most cases the results
can be directly scaled up and pilot scale plants are not required. The new microreactor can be used for isothermal as
well as for adiabatic nitrations, and thermally unstable and
sensitive compounds can be produced as the whole reactor
can be operated at very low temperatures.

1 Introduction
A well known method to add nitro groups to organic compounds is the mixed acid nitration. This technology for the
production of intermediates and final products has been
applied for decades. For process optimization, extensive laboratory tests followed by tests in large scale plants were necessary in the past. Generally, the lab equipment cannot be
adapted sufficiently to large scale plant conditions. The common procedure is disadvantageous because obtained results
only give tendencies and direct scale up is difficult. Therefore, a corrosion resistant microreactor made of PTFE and
Tantalum was developed. Combining the advantages of micro reaction technology and modular type construction enables the simulation of different nitration reactions. A
screening of parameters is now possible in less time and with
fewer costs. The new microreactor can be easily adapted to
the conditions in an industrial plant due to the modular type
of construction. Additionally, it is easy to simulate the influence of changes in the equipment. In most cases the results
can be directly scaled up and pilot scale plants are not required. The number of tests at industrial scale production
plants is minimized. The new microreactor can be used for
isothermal as well as for adiabatic nitrations.

2 State of the Art

The nitration reaction using a mixture of nitric and sulfuric acid is a common method to add nitro groups to organic

[*]

Dipl.-Ing. L. Henke, Dr. H. Winterbauer (winterbauer@plinke.de), Plinke

GmbH, PO Box 21 51, D-61291 Bad Homburg, Germany.

Chem. Eng. Technol. 2005, 28, No. 7

DOI: 10.1002/ceat.200500096

intermediates and products. Process optimization in the past

has been carried out by laboratory tests followed by studies
in the field at pilot scale and finally at industrial scale plants.
The results obtained in the lab often could give only indications for the behavior of the compounds in industrial
plants because the conditions in the lab could not be adapted
sufficiently to the conditions in the plants.
A further disadvantage of the common procedure is the
requirement of huge amounts of feed compounds and the
production of waste streams or products with low quality
when testing at industrial scale. Also, the safety risk has to
be considered, especially when handling large amounts of
sensitive materials during the tests.
To avoid these disadvantages the idea was formed to develop a microreactor which enables simulation of the nitration reaction as closely as possible to industrial scale production plants. This was attained by a modular construction.
The advantage of using this reactor is the low amounts of
feed and products to be handled.
Different microreactors are already applied for screening
parameters. Scherzer describes in [1] a microreactor consisting of two parallel plates, whereby one of the plates is designed with several reaction chambers and is mounted on a
rack, and on the second plate connections for feed and product streams are provided.
H. Nobuaki presents in [2] a microreactor where a multitude of heat exchangers are located along separate micro
channels. Using this construction the temperature along the
micro channels can be controlled within a small range.
Bowen [3] described a microreactor using micro structured plate type distribution units which are connected via
pipes. The feed products are mixed in the distribution units
and the reaction mixture is then cooled down or alternatively heated up. In the first distribution unit the reaction
mixture is distributed in different channels and the streams
are then remixed in the following distribution unit.
All microreactors which are currently applied have in
common the disadvantage of a complicated construction.
This complicated construction ensures an optimized mixing
and heat transfer, but the structures are only available in selected materials like carbon steel, stainless steel, graphite,
glass, silicon, etc. These reactors are restricted in use, especially for applications in highly corrosive environments, like
mixed nitration acids at high pressure.

3 Microreactor Development
The targeted microreactor has to be resistant against
mixed nitration acid and organic compounds. Additionally,
the variation of mixing devices, reaction chambers, heat exchanges, etc. should be easy. This is achieved using PTFEcomponents which are connected via PTFE-tubes. The
PTFE-components have a thread with related nuts. The
tubes are put in and are fixed by tightening the nuts. No gaskets are required because the covering part of the PTFE 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

749