Communications
4 Outlook
The employment of bioadsorptive carriers possesses some
advantages compared to the conventional soil washing tech-
nology with respect to ecological as well as economic aspects.
During the conventional soil washing process, up to 20 % of
the soil (the small-sized particle fraction) has to be disposed as a
highly contaminated hazardous waste. The accumulation of the
pollutants to the small-sized particle fraction can be prevented
to a largeextent by the addition of bioadsorptive carriers during
the soil washing procedure. This way the only low-contami-
nated small-sized particle fraction can be added to the washed
soil at the end of the treatment. The generated product is thus
very similar to the natural soil structure. Furthermore, the
proposed procedure opens the possibility to treat soils with
high small-sized particle shares also. The limits of the process
must, however, be determined in further investigations.
Since a portion of the microorganisms introduced into the
soil during treatment remained in the cleaned soil, a complete
decontamination during the soil washing process was not
required in most cases. The elimination of the remaining
pollutants occurred during a following microbial degradation
period within the soil.
The microorganisms used can be optimized for a given
purpose by immobilization at a suitable support and by
cultivation in the soil washing waterused or in synthetic sewage.
During the regeneration, the loaded carriers and the water
from the washing process were decontaminated and could be
reused. In some cases the addition of nutrients, such as
ammonia or phosphate, was necessary. So, considerable
amounts of the water from the soil washing process, which is
cleaned up presently with costly combinations of different
procedures, could be recycled. First attempts to the biotech-
nological treatment of phenol-containing water were imple-
mented successfully at the plant of the RST Recycling
Sanierung Thale.
Since the biological regeneration of the carriers and the
washing water is relatively inexpensive, the proposed proce-
dure can contribute to a significant reduction of the
expenditures compared to the conventional process. With
respect to the carrier prices, for soils containing 20 % small-
sized particles a cost-neutral use of the proposed method is
given for prices below 100 DM/t carrier. According to our
findings, the carriers could be reused up to 10 times. So it
would be possible to use also more expensive specialized
products, which can be adapted to the respective purpose.
Received: November 9, 1999 [K 2479]
References
[1] Beudert, G.; Kuebler, P.; Schmid, K.; Hahn, H. H., Versuche zur
Bodenwäsche einschlieûlich biologischer Behandlung der hierbei anfal-
lenden Feinkornfraktion (Investigations for the soil washing process
including the biological treatment of the small-sized particle fraction),
Kluwer Academic Publishers, London 1993, pp. 1405±1406.
Chem. Eng. Technol. 23 (2000) 10, Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000
[2] Elias, F.; Wiesmann, U., Biologische Behandlung von Reststoffen der
Bodenwäsche in einer 4-stufigen Rührreakatorkaskade im Labormaûstab
(Biological treatment of byproducts from the soil washing process in a
four-step activated sludge reactor), Altlastenspektrum 4 (1995) 3, pp. 148±
115.
[3] Gatchett, A.; Banerjee, P., Evaluation of the BioGenesis Soil Washing
Technology, J.Hazardous Materials 40 (1995) 2, pp. 165±117.
[4] Haase, B.; Tjarks, G., Modellversuche zur mikrobiologischen Behandlung
PAK-kontaminierter Waschrückstände (Model experiments to the
microbial treatment of PAH-contaminated byproducts from the soil
washing process), TerraTech 3 (1994) 3, pp. 26±27.
[5] Hughes, J. B.; Beckles, D. M.; Chandra, S. D.; Ward, C. H., Utilization of
Bioremediation Processes for the Treatment of PAH-contaminated
Sediments, J. Ind. Microbiol. Biotechnol. 18 (1997) 2/3, pp. 152±160.
[6] Jafvert, Ch. T., Sediment- and Saturated-Soil-Associated Reactions
Involving an Anionic Surfactant (Dodecylsulfate) ± 2nd Partition of
PAH Compounds Among Phases, Environm. Sci. Technol. 25 (1991) 6, pp.
1039±1045.
[7] Martienssen, M., Verfahren zur mechanisch-mikrobiologischen Reini-
gung kontaminierter Böden (A technology for the combined mechanical
and biological treatment of contaminated soil), DE 197 44 376 (1997).
[8] Portier, R.; Bianchini, M.; Fujisaki, K.; Henry, C.; McMillin, D., Vergleich
der Effektivität autochthoner Mikroorganismen und kommerziell ver-
fügbarer Kulturen für die Biotransformation toxischer Stoffe bei der In-
situ-Sanierung eines verlassenen Industriestandortes (Comparison of the
effectiveness of autochtonic and comercially available cultures for the
biotransformation of toxic substances during in-situ remediation of an
industrial site), Schriftenreihe des Vereins für Wasser-, Boden- und
Lufthygiene 80 (1988) pp. 273±292.
[9] Reinert, G.; Schuster, E.; Schneider, M.; Bryniok, D., Biologische
Reinigung von Bodenwaschschlämmen: Neue Perspektiven durch eine
Verfahrensinnovation (Biological treatment of sludges from the soil
washing process), TerraTech 5 (1996) 3, pp 55±57.
[10] Schmid, K.; Hahn, H. H., Entwicklung eines Verfahrens zur biologischen
Behandlung von Feinkornextrakten aus der Bodenwäsche bei Kohlen-
wasserstoff-Altlasten (Investigation of a technology for the biological
treatment of fine-grain extracts from the soil washing process),
Altlastenspektrum 4 (1995) 2, pp. 94±101.
This paper was also published in German in Chem. Ing. Tech. 71 (1999) No. 6, pp.
624±628.
_______________________
Optimization of the Comminution
of Metallurgical Grade (MG) Silicon
in a Vibration Mill
By AndrØ Mecklenburg, Ulrich Kunz and Ulrich Hoffmann*
The field of reactive grinding has gained increasing
attention in recent years. Mechanical activation through
mechanical stress allows chemical reactions to run faster and
at lower temperatures. These effects could be obtained with
the reaction of solids with a gas and with reactions of two or
even more solids with each other. The comminution behavior
of MG silicon in a vibration mill with variation of frequency,
vibrational amplitude, and size and form of the grinding balls
was investigated. Particle size distributions of the grinding
experiments was measured and plotted. It could be shown that
±
[*] Dipl. -Ing. A. Mecklenburg, PD Dr. -Ing. habil U. Kunz, Prof. Dr. -Ing.
habil U. Hoffmann, Institut für Chemische Verfahrenstechnik, Technische
Universität Clausthal, Leibnizstr 17, 38678 Clausthal-Zellerfeld, Ger-
many.
0930-7516/00/1010-0863
0930-7516/00/1010-0863 $$ 17.50+.50/0
17.50+.50/0 863
 Communications

vibrational amplitude and the size of the grinding balls are of
decisive importance for the success of the comminution. It is
advantageous to divide the reaction chamber into at least two
compartments with different grinding ball diameters (grad-
ing).
and form of the grinding balls dK1). Moreover, the fractional
filling of grinding balls jK and the fractional filling of the solid
jG are also important.
3 Experimental

1 Introduction Fig. 1 gives a general view of the vibration mill used at the
Institute for Chemical Process Engineering (ICVT). It
In recent years the combination of basic process engineer- consists of a reaction chamber, the vibration frame, and a
ing operations into one step has been of great interest to the system of four unbalance disks driven over two shafts by an
chemical industry. An excellent example is the field of reactive asynchronous motor. Accelerations up to 60g are possible. As
grinding. Application fields for this technology are found prototypical processes, a solid-liquid (Grignard compounds
mainly in small and medium sized companies, where a [4]) and a solid-gas reaction system (formation of chlorinated
multitude of different heterogeneous reactions are carried silanes [5,6]) were examined on the laboratory scale so far.
out. Most of these reactions and processes create products Although the main attention was directed towards the
with a large increase in value. chemical reaction, a closer investigation of the parameters
The main purposes of a reaction mill are first the abrasion of relevant for the comminution was not made.
product layers and inactive by-products, second the comminu-
tion of the reactants (surface enlargement) and products, third
the mechanical activation of the reactants and fourth the
addition of energy to the reaction chamber. In principle, the
following reaction systems are possible:
l Gas-solid reactions
l Liquid-solid reactions
l Solid-solid reactions Figure 1. Principle sketch of the reaction mill used at the ICVT (cut through the
reaction chamber).
The term ªmechanochemistryº or ªmechanical activationº
summarizes all chemical changes caused by intense mechani-
The subject of the examinations presented here is the
cal strain, such as pressure, tension, impact or friction [1]. With
comminution of metalurgical grade (MG) silicon. It contains
mechanical activation of solids, the following chemical
about 90 % silicon with 5-7 % iron (Fe) as the main impurity.
reaction can take place at significantly lower temperatures.
MG silicon shows a very brittle behavior (Mohs hardness
These effects could be obtained with reactions of solids with a
about 6.5). For a quick conversion of MG silicon to
gas and at the reaction of two or even more solids with each
chlorosilanes, it is important to reach particle sizes of 20 mm
other. A higher reaction rate and efficiency are also of great
as fast as possible. Besides an increased particle surface,
advantage. Nevertheless the lack of construction data make
improved mechanical activation due to the higher portion of
intense experimental investigations necessary.
plastic deformation is achieved.
Small notches or cracks can cause a breaking event in a
particle. Because of the strong decrease of such flaws under
2 Theory continuous communtion a plastic deformation of only very
small particles is possible. This so-called ªmicroplastificationº
Vibration mills are characterized by a high energy density.
determines the lower boundary of comminution (0.02 to 0.05
Therefore, a very fine grinding product can be achieved [2].
mm for brittle materials). The grinding results depend on the
The solid is strained first by pressure and second by impact.
starting particle size x0, due to the inverse proportionality of the
The reaction chamber is filled with multiple layers of particles
energy efficiency EA to the particle size (Bond and Rittinger).
between the grinding balls. Moreover, we have the lateral
limitation of the individual space of a single particle by the DS 1
EA ˆ ˆ (1)
presence of neighboring particles. According to the coordina- Wm x0
tion number, which is the number of particles surrounding the
In addition to high vibrational amplitudes, a high vibration
investigated particle bed, very different types of strain of the
frequency between 1000 and 3000 1/min is necessary.
particles in the examined particle bed are obtained. During
Although the fractional filling of the grinding balls should
the comminution process, the number of strain attack points
be set to 65±80 %, it was held at 50 % in these first test series to
plays a very important role. Therefore, the structure of the
gain comparability to earlier experiments. The fractional
packing of the particles is essential to the comminution
filling of the solid was also set to 50 %.
process [3].
Parameters influencing the grinding result are number of ±
revolutions (frequency) w, amplitude of vibration A and size 1) List of symbols at the end of the paper.

864 Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0930-7516/00/1010-0864 $ 17.50+.50/0 Chem. Eng. Technol. 23 (2000) 10

Following the theory of Bachmann, the entire filling of the
reaction chamber is assumed as one plastic mass point. A so-
called statistical resonance exists where the comminution is
most efficient. The needed frequency is calculated as follows:
a p

ˆ 1 ‡ p2
k2 †
g
a = A ´ x2 = A ´ (2 ´ p ´ n) 2
The relation a/g is the Froude number. Adjustments for the
amplitude and the frequency used in this test series are given
in Tab. 1. These values were calculated applying the method of
statistical resonance.
Table 1. Investigation plan including additional attempts of the fine particle
mass achieved at a griding time of 540 s.
Before milling, the grinding balls were put into the feed.
Polished stainless steel balls with diameters of 3, 5 and 10 mm
were used. In addition, cylindrical grinding pellets (Cylpebs
CHILLARD) from Doering GmbH with a nominal diameter
of 8 mm were used.
The comminution experiments (Nos. 1 to 8) and the
additional experiments (Nos. 9 to 14) are given in Tab. 1.
The particle size of the solid feed was 800 to 1000 mm. The
comminution time for each single experiment was set at
9 minutes. Thereafter, the particle size distributions of the
grinding experiments were measured (core particles,
63±1000 mm: R5 wet sieving analyzation; fine particles,
22±62 mm: Laser diffraction spectrometer, very fine particles,
Chem. Eng. Technol. 23 (2000) 10, Ó WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000
Communications
< 22 mm: laser diffraction spectrometer) and plotted with the
help of Q3(x) distributions.
4 Results
(2)
4.1 Core Particles (63 m < x < 1000 lm)
(3) The analytical results of all experiments for the core particle
area with respect to the fine particles obtained during grinding
are given in Tab. 1. Because a vibration frequency of 1867
1/min was more suitable in cases of even amplitude, a
comparison of the grinding results for this frequency at an
amplitude of 3.4 mm will follow. The results for the core
particle area are shown in Fig. 2. The use of 3 mm grinding balls
results in 82.7 % with the size x > 630 mm. The reason for this
poor result is the low kinetic energy of these small balls, which
cannot overcome the necessary breakage work.
Figure 2. Comparison of the rough comminution (x > 63 mm) using different
griding bodies for 1867 1/min and 3.4 mm amplitude, determined by R5 sieving
analysis.
Using 5 mm grinding balls, a high proportion of the particle
bed is ground to particle sizes  250 mm. Because of their
relatively high single mass, those grinding balls are in a greater
position to overcome the breakage work (particularly the core
particles).
Similar upward curved characteristics for the Q3(x)
distributions were obtained using 10 mm grinding balls and
8 mm Cylpebs. However, substantially higher proportions of
fine particles were obtained compared to the grinding balls
described above (10 mm balls: 40.8 %, Cylpebs 63.22 %)
In view of effective comminution with a fast increase of the
surface of the particle bed, 8 mm Cylpebs are preferred above
10 mm grinding balls. With the effect of the so-called point-
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 Communications

surface-line strain, these cylpebs are superior in the investi-

gated core particle area.

4.2 Fine (22 lm < x < 63 lm) and Very Fine Particle Area
(x < 22 lm)

In Fig. 3, the Q3(x) distributions of the fine particles are

shown and compared (1867 1/min; 3.4 mm).

Figure 4. Fine mass proportion x< 63 mm projected onto a plane at 1867 1/min.

Figure 3. Comparison of fine comminution of 3 (pro14_11), 5 (pro3_11), and

10mm (pro7_11) grinding balls and 8mm (pro9_11) Cylpebs by distribution
curves, determined by laser diffraction spectroscopy.

Obviously particle sizes between 5 to 20 mm were not

obtained using 3 mm grinding balls. The 10 mm balls and the
Cylpebs lead to much better results. However, the best results Figure 5. Very fine mass proportion x < 21 mm projected onto a plane at 1867
for the comminution of very fine particles were obtained with 1/min.
5 mm grinding balls. Here a regular distribution down to very
small particle sizes was obtained. In Tab. 2 and Figs. 4 and 5 Table 2. Proportion of very fine particle mass achieved.
fine and very fine proportions (mass percent) at different
amplitudes and grinding bodies are given. By projection onto
the plane level it could be seen which areas within the surface
stretched by the amplitude and the grinding body diameter
high fine and very fine proportions were obtained.
Therefore, achievement of high fineness of over 60 %
related to the total grinding mass becomes only possible
within a narrow, diagonally wedge-shaped area. For higher
amplitudes, this area tapers. With amplitudes larger than
5.7 mm, it is necessary to adapt the grinding body diameters
exactly to the grinding mass and the adjusted amplitude.
Since mechanically activatable particles are preferentially
available in the range from 1 to 20 mm, the proportion of very
fine particles in this fraction on the total grinding mass is
interesting for the execution of the grinding process and
reaction.
Also with the proportion of very fine particles (Fig. 5)
(similar to the fine particle proportion), an increase with
higher vibration amplitudes and larger grinding ball diameters
has to be determined. However, the area of the maximum
proportion of very fine particles is uniquely assigned for the
grinding ball diameter 10 mm in the right upper diagram
corner at maximum amplitude.
With the 3.4 mm amplitude, however, 8 mm Cylpebs
achieved better comminution results. Since in our experi-

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 Communications

mental setup the reaction chamber is undivided, it is important Within the area of very fine particles, 5 mm grinding balls
to use the larger grinding bodies indicated above. However, if possess crucial advantages. They produce the highest propor-
a possibility for a precomminution of the feed exists, 5 mm tion of fine, mechanically activatable particles. A reaction
grinding balls are best suitable for very fine comminution and chamber with at least two reaction compartments (grading) is
mechanical activation, see, e.g., experiment 3: Although only desired.
8.34 % fine particles were produced, 5.06 % of the feed mass The results of these investigations were used in the
was already smaller than the required 22 mm. This corresponds construction of an improved vibration mill.
also to the thesis that smaller grinding bodies cut up the
grinding mass more finely.
Because of the reasons mentioned above, it is reasonable to Acknowledgments
carry out this process as a multi-level comminution:
l The reaction chamber must be divided in the axial direction The authors thank the AIF for the partial promotion of the
into at least two grinding compartments with different project (No. 11193 N/2).
grinding body sizes (grading) Received: March 2, 2000 [K 2602]
l At the beginning the core feed can be cut down to the lower
core particle size area in the first grinding compartment by
the using larger, laminar grinding milling bodies, such as Symbols used
8 mm Cylpebs.
l Particles below a size of, for example 100 mm, arrive through A [m] vibration amplitude
a sieving partition wall into the second grinding compart- dK [m] diameter of the grinding balls
ment, where 5 mm balls are responsible for further grinding EA [m2g/J] energy efficiency
of the precomminuted and already partly reacted feed. Here k [±] parameter
comminution down to the very fine particle size (x < 22 mm) m [kg] mass
area takes place, and intensified mechanical activation n [1/min] number of revolutions
occurs. Q3(x) [±] mass distribution
l Another advantage is that the fine particles produced can be S [m2] particle surface area
taken off from the reaction chamber. They do not obstruct t [s] time
the core grinding by the so-called softening effect. W [J] comminution work
X [mm] particle size
j [%] fraction of filling
5 Conclusion

The comminution behavior of (MG) silicon 90 in a vibration References

mill was examined. Grinding balls (3; 5 and 10 mm) as well as
cylindrical grinding bodies with a nominal diameter of 8 mm [1] Bernotat, S.; Schönert, K., Ullmann's Encyclopedia of Industrial
Chemistry, Sixth Edition, 1999 Electronic Release.
were used. The objective was optimally adapting the geometry
[2] Höffl, K., Freiberger Forschungshefte A750, Deutscher Verlag für
of the grinding bodies, the amplitude and the frequency to the Grundstoffindustrie, Leipzig 1988, pp. 8±25.
feed: [3] Stieû, M., Mechanische Verfahrenstechnik, Band 2, Springer Verlag 1994,
pp.303±306.
Vibration amplitudes under 3.4 mm are not highly effective. [4] Veit, M., Chem. -Ing. -Tech. 68 (1996) pp. 1279-1282.
With an amplitude of 3.4 mm, the quantity of fine particle [5] Bade, S.; Hoffmann, U., Chemical Engineering Communications 143
produced (x < 63 mm) rises precipitously. (1996) pp. 169-193.
[6] Bade, S.; Hoffmann, U., Chem. -Ing. -Technik 66 (1994) pp. 66±69.
At higher amplitudes (5.7 mm) the fineness produced
decreases again. This paper was also published in German in Chem. Ing. Tech. 72 (2000) No. 3, pp.
The 8 mm Cylpebs achieve the highest fine particle 264±268.
proportion as a function of the vibration amplitude cylindrical.

_______________________

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