Flue Gas and Fly Ash

FLUE GAS AND FLY ASH
Proceedings of a contractors meeting organized by the Commission of the European

Communities, Directorate-General for Science, Research and Development, held in
Brussels, Belgium, 16 June 1988.
FLUE GAS AND FLY ASH
Edited by
P.F.SENS and J.K.WILKINSON
Commission of the European
Communities, Brussels, Belgium
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British Library Cataloguing in Publication Data
Flue gas and fly ash.
1. Industrial waste materials. Treatment & disposal
I. Sens, P.F. II. Wilkinson, J.K. (James Keith), 1933
III. Commission of the European Communities, Directorate-General for Science,
Research and Development
628.54
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PREFACE
The present volume represents the third publication from the energy R&D programme
Utilization of Solid Fuels, performed under the supervision of Directorate-General XII
for Science, Research and Development of the Commission of the European
Communities. This programme started with a call for proposals for R&D projects in
March 1985 and, at present, 66 projects are in progress. Some of them are now
approaching termination, others will continue into 1989 and even 1990, although 1988 is
formally the last year of the current energy R&D programme.
The Utilization of Solid Fuels programme addresses the following issues:
-
fluidized bed combustion

coal/water mixtures
burner development
solid fuels in integrated cycles
environmental aspects
transportation and handling
basic studies of solid fuel combustion and properties.
On June 16, 1988, a contractors meeting was held concerning the subject of
environmental aspects, in particular dealing with flue gas and fly ash. This book contains
the reports of this meeting.
The meeting provided a forum for interesting discussions and exchange of views and
experience.
At the end of the book, some conclusions are given as well as some directions for
future work.
This is of special interest now because of discussions, taking place at this moment,
concerning the contents of the next energy R&D programme, to start in January 1989.
P.P.SENS
This page intentionally left blank.
CONTENTS
Preface
Session I:
Flue gas treatment
Contract n EN3F0054NL (GDF) Catalytic nox reduction
G.TUENTER, H.G.P.MULLER and L.J.M.SNEPVANGERS, Netherlands
Energy Research Foundation, Dept of Chemistry and Materials Science
Contract n EN3F0069IRL Improved gas filtration systems for control of
solid fuel particulate emissions
P.CROMWELL, A.DOYLE, A.D.KENNEDY and K.OROURKE,
EOLAS, The Irish Science & Technology Agency
Contract n EN3F0055D Development of a process for removal of SO2
and NOx from flue gas using brown coal coke
U.LENZ, H.P.PAEFFGEN and E.WOLFRUM, Rheinische
Braunkohlenwerke AG, VF1 Coal Chemistry
Contract n EN3F0014NL (GDF) Regenerative desulfurization in
fluidized bed combustion of coal
C.M.VAN DEN BLEEK and P.J.VAN DEN BERG, Delft University of
Technology
Contract n EN3F0056NL Development of a regenerative sulfur dioxide
system
B.KAMPHUIS and U.SPITSBERGEN, University of Twente
Contract n EN3F0028NL Closed loop controlled integrated hot gas
clean-up
J.ANDRIES, Delft University of Technology
Contract n EN3F0035F (CD) Electromulticyclone for coal burner
exhaust gas cleaning
J.N.DUMONT, P.AULARD, J.VENDEL and M.RAMEL, Bertin & Cie
Contract n EN3F0073F Development of a dust separator for hot gas
clean-up
J.TAILLET and R.RENNHACK, ECOPOL
Contract n EN3F0070I Pulse power techniques for flue gas treatment
G.DINELLI, ENEL Italian Electricity Board
vi
17
23
36
54
68
85
95
105
Session II:
Fly ash properties, re-use and disposal
Contract n EN3F0052NL Contract n EN3F0053D Characterisation
of fly ash from fluidised bed combustors with regard to its utilisation and
safe disposal
A.J.GAY, The Netherlands Organization for Applied Research TNO and
J.FRIGGE, Bergbau-Forschung GmbH
Contract n EN3F0031NL Adsorption and desorption phenomena of
polycyclic aromatic hydrocarbons on fly ash
L.J.M.RODENBURG, TNO Division of Technology for Society
Contract n EN3F0030D Adsorption and desorption phenomena of
polycyclic aromatic hydrocarbons on fly ash
K.KLEMM and K.G.LIPHARD, Bergbau-Forschung GmbH
Contract n EN3F0032NL Contract n EN3F0033DK Waste/soil
interaction studiesthe leaching of molybdenum from pulverized coal ash
H.A.VAN DER SLOOT and G.J.DE GROOT, Netherlands Energy
Research Foundation O.HJELMAR, Water Quality Institute
Contract n EN3F0071F (CD) Handling and conditioning of fluidized
bed and pulverized coal boilers fly-ash for landfill disposal and re-use
J.BLONDIN, CERCHAR
Contract n EN3F0057IRL The utilisation of P.F.A. (pulverised fuel ash)
as a filler in rigid polyurethane insulation foams
P.SHEEHAN, P.OSULLIVAN and T.HAMM, Polycomp Ltd.
Conclusions and recommendations for future work
List of participants
Index of authors
123
140
146
156
181
184
193
195
199
Session I:
Flue gas treatment
Catalytic nox reduction
Improved gas filtration systems for control of solid fuel particulate emissions
Development of a process for removal of SO2 and NOx from flue gas using
brown coal coke
Regenerative desulfurization in fluidized bed combustion of coal
Development of a regenerative sulfur dioxide system
Closed loop controlled integrated hot gas clean-up
Electromulticyclone for coal burner exhaust gas cleaning
Development of a dust separator for hot gas clean-up
Pulse power techniques for flue gas treatment
CATALYTIC NOX REDUCTION

G.TUENTER, H.G.P.MULLER and L.J.M.SNEPVANGERS*
Contract number :
Duration :
Total budget :
Head of project :
Contractor :
Address :
*Present adress :
EN3F0054NL (GDF)
24 months 1 Jan. 198731 Dec. 1988
f1 525.000, CEC contribution: f1 262.500,
ir. G.Tuenter, Netherlands Energy Research Foundation
Netherlands Energy Research Foundation
Department of Chemistry and Materials Science
P.O.Box 1
1755 ZG PETTEN
The Netherlands
Hoogovens Ymuiden B.V.
P.O. Box 10000
1970 CA YMUIDEN
Summary
The aim of the project is to evaluate the perspective of a modified selective catalytic
reduction process to reduce NOx emissions from flue gas. In a previous study the activity
of the equimolar NO/NO2 reduction was found to be higher then the NO reduction. The
modified process is based on the equimolar NO/NO2 reduction. NO being the
predominant NOx component in flue gas from stationary sources, must then be partly
oxidized to NO2. A desk study is carried out to review the literature on methods for flue
gas composition modification with respect to the NO/NO2 ratio. The evaluation of the
modified SCR process also requires more knowledge about the increase in catalytic
activity of the equimolar NO/NO2 reduction as compared to the NO reduction and about
the effect of catalyst composition on the reaction rate. In order to investigate these
aspects, an experimental programme is carried out, using four different catalyst materials;
two commercial preparations and two self-prepared vanadium-titaniumdioxide catalysts.
The results of activity measurements for NO, NO2 and the equimolar NO/NO2 reduction
are reported, under conditions relevant for large scale applications. From these results
some preliminary conclusions can be drawn with respect to the perspective of the
modified process.
Flue gas and fly ash
1.INTRODUCTION
In most nations within the European Community, SOx and NOx emissions from
stationary combustion must be minimized to meet environmental requirements. SOx is
normally removed by tail-end flue gas treatment systems. The NOx levels can be reduced
considerably by combustion modification, which is at present the most attractive method,
with, however, a minimum achievable level of NOx concentration. Further reduction is
possible using the selective catalytic reduction (SCR) process, a proven commercial
process to reduce the residual NOx with NH2. SCR has a high removal efficiency of 80
90%, but still suffers from various disadvantages in terms of high cost and fly ash
contamination. Research efforts have been concentrated mainly on the development of
improved and/or cheaper catalysts to overcome these difficulties. Only perfunctory
attention has been given to modifying the SCR process. An earlier investigation at ECN
demonstrated that on a commercial grade deNOx catalyst, the equimolar reduction of
NOx ([NO]/[NO2]=1) was much faster than in cases of either pure NO or pure NO2 [1, 2].
NO however, being the predominant NOx component in flue gases, must be partly
oxidized to NO2 prior to entering the catalytic reactor. The flow schemes of a
conventional SCR process and a modified SCR process are shown in the following
figure.
Figure 1. Flow-scheme of the conventional and modified SCR

process.
The observed acceleration of the reaction rate between the equimolar NO and NH
x
3
has commercial potential i.e. capital investment and annual cost for the SCR unit can be
decreased. The main objective of the proposed research work is to evaluate the
perspective of the modified process with respect to the conventional SCR process. This
evaluation requires more knowledge about:
- The catalytic activity, i.e. rate of the equimolar reduction under flue gas conditions.
- The effect of catalyst composition and geometry on the reaction rate.
- Possibilities of modifying the flue gas composition with respect to the NOx
component (oxidation of 50% of the NO).
2.EXPERIMENTAL SECTION
Catalyst materials
Four different catalysts are studied; two commercial preparations (VTT, TT) and two
self-prepared vanadium-titaniumdioxide samples (V/TiO2 and V08). The preparation
procedure of the self-prepared samples is described by van Hengstum [4]. Elemental
composition of the catalysts were measured by neutron activation analysis (INAA).
Nitrogen adsorption was used for surface area measurements. Elemental composition and
surface area (SBET) of the materials are given in table 1.
Table 1. Properties of TiO2 supported catalysts.

no.
VTT
TT
V08
V/TiO2
active component (s)

V (2.7 wt%),
V (0.63 wt%)
V (1.7 wt%)
W (6.5 wt%)
W (9.9 wt%)
SBET(m2.g-1)
29
86
46
50
The catalysts were also characterized by Temperature Programmed Reduction (TPR).

TPR is a very useful technique to study the reducing behaviour of oxide materials. In a
TPR profile the H2 consumption rate by the oxide is plotted against the reaction
temperature. The apparatus is described elsewhere [5].
Apparatus and procedure for activity measurements
The activity measurements are carried out to determine the rate of equimolar reduction as
a function of temperature, reactant concentration and catalyst composition. The NOx
reduction with NH3 is performed in a conventional fixed-bed, plug-flow reactor. A
schematic diagram of the apparatus is shown in figure 2.
Figure 2. Schematic diagram of the experimental apparatus
The manifold, tubing and reactor, as well as the scrubber for removal of unreacted
NH3, is heated in a thermostated oven, controlled at 150C. The flow rate of the reactant
gases is adjusted and controlled by mass flow controllers (MFC), which enables the
fixation of the total flow rate at a constant value within 2%. The reactor is heated by an
electric oven with controller and designed to maintain a uniform bed temperature.
NO and NO2 are measured by an NOx monitor, based on the chemiluminiscence
principle, after diluting the gasmixture (ratio 1:200). NO and NO2 are analyzed after
removal of NH3 by passing the mixture through a phosphoric acid scrubber. NH3 and
N2O are determined in-situ at elevated temperatures by infrared spectroscopy.
The standard conditions at which the NOx conversion level is measured as a function
of the catalyst temperature is given in table 2.
Table 2. Standard conditions.

feed composition:
flow (cm3.s-1 STP)

catalyst (g)
grainsize (mm)
NO
: 01000 ppmv
NO2
: 01000 ppmv
NH3
: 02000 ppmv
: 2.0 vol.%
O2
balance N2
: 16.7
: 0.200
: 0.10.3
An activity curve of a catalyst is obtained by plotting the NOx conversion level against
temperature. Ranking of different catalysts is then possible by comparing these curves.
3.RESULTS
a.Reduction behaviour
The TPR profiles of the catalysts are shown in figure 3.
Figure 3. TPR profiles of the catalysts.
The values in this figure corresponds to the relative amount of H2 consumed.

As shown in this figure, reduction of supported V2O5 and WO3 takes place between
300C and 600C. The self-prepared low-loaded vanadium catalysts V08 and V/TiO2 are
reduced more easily then VTT and TT.
b.NO reduction with NH3
The activity of the catalysts in the NO reduction with NH3 are shown in figure 4.
Figure 4. Activity of VTT, TT, V/TiO2 and V08 in the NO

reduction.
From figure 4 it is apparent that the activity of the vanadiumoxide-containing catalysts

(VTT, V/TiO2 and V08) is much greater then the tungsten catalyst (TT). It is also shown
that the activity of the vanadium catalysts decreases in the order:
The activity curves of VTT, V/TiO2 and V08 demonstrate a maximum in the NO
reduction-curve.
In order to study the NO reduction rate as a function of the reactant concentrations NO
and NH3 a series of experiments were carried out in which the NO conversion level was
measured with different levels of inlet reactant concentations. The experimental data are
then correlated by minimizing the sum of squares of the difference between experimental
and calculated rate constants by means of a Nelder Mead optimalization procedure, using
the power law rate expression
(equation 1)
the Arrhenius equation
(equation 2)
and the steady-state material balance equation for the integral flow reactor [1].
The calculated results of this procedure for the reaction-orders m and n, ko and E are
summarized in table 3.
Table 3. Results of numerical calculation for m, n, ko and E for NO reduction.

catalyst
reaction order
preexp. constant
activation energy
m
n
ko
E (kJ.mol1)
VTT
0.6
0.2
2.0*10E4
522
V08
0.8
0.0
8.4*10E5
552
c.NO2reduction and NO/NO2reduction
The conversion level of the NO2 and NO/NO2 reduction was also measured as a function
of temperature over VTT, TT, V/TiO2 and V08. The order of activity for these reactions
was the same as observed for the NO reduction, thus
In table 4, the results of the numerical optimalization procedure are summarized for the
NO2 and NO/NO2 reduction over VTT and V08.
Table 4. Results of numerical calculation for m, n, ko and E in NO2 and NO/NO2

reduction.
catalyst
reaction order
pre-exp. constant
activation energy
m
n
ko
E (kJ.mol1)
NO2
VTT 0.4
0.5
3.7*10E6
534
V08 0.6
0.1
1.6*10E6
632
NO/NO2 V08 0.9
0.1
6.2*10E6
532
Using equation 1 and 2 and substitution of the values for m, n, ko and E, the reaction
rate r (mole.kg1.s1) can be calculated as a function of [NO], [NO2], [NH3] and reaction
temperature. From these calculations, a quantitative comparison is possible between the
reaction rate of the NO and the equimolar NO/NO2 reduction. A more qualitative
comparison is based on the conversion levels for the NO, NO2 and NO/NO2. A typical
example is shown in figure 5. in which the conversion levels are shown over V/TiO2
catalyst.
10
Figure 5. NO, NO2 and NO/NO2 conversion over V/TiO2.
From this figure it is clear that the rate of the equimolar NO/NO2 reduction is much
faster than either the NO reduction and NO2 reduction. This result confirms the results
reported in an earlier investigation over the commercial VTT catalyst [1, 2]. The results
for the equimolar NO/NO2 reduction shown in this figure also demonstrate that NO and
NO2 reacts 1:1, even at conversion values as high as 95%. This observation is confirmed
for all catalysts reported in this study.
4.DISCUSSION
a.Reduction measurements
The temperature at which a maximum in the TPR profile is observed (Tmax) increases
with increasing V-content. Thus the interaction between the TiO2 support and vanadiumspecies decreases Tmax, because the bond-strength between vanadium and oxygen is
decreased. Consequently, by increasing the vanadium-loading, the structure and
performance of the supported vanadiumoxide will tend towards the bulk oxide.
According to Bosch et al. [5], bulk V2O5 reduces at temperatures >650C, which is in
agreement with our results. Comparing the TPR profiles of VTT and TT, we can
conclude that the resolution of the TPR apparatus is apparently insufficient to resolve the
maxima of the reduction rate of the active components V2O5 and WO3. The broad peak
of the VTT profile can be explained by assuming that the peak results from a consecutive
reduction of V2O5 and WO3. The V2O5 reduction then, has a maximum rate at
approximately 460c, while WO3 has a maximum at 580C.
The amount of H2 consumed i.e. the surface of the peak, is a measure for the oxidation
state of catalysts before and after the reduction. Preliminary calculations have shown that
11
vanadium and tungsten are fully oxidized for fresh catalysts. After the TPR profile has
been recorded, the active components seem to be completely reduced to its metallic state.
b.NO reduction
The order of activity of the vanadium-containing catalysts
is the same as the order of the vanadium content. From the evaluation of the kinetic data
presented in table 3, the reaction rate can be calculated per mole vanadium. This
calculation is carried out at 230C, a temperature at which side reactions (oxidation of
NH3) are of minor importance. The results of the calculation of turnover numbers (TN)
are shown in table 5.
Table 5. Calculation of TN (T=230C).

catalyst
V-content
Reaction rate
(wt%)
(mole NO. kg1.s1)
VTT
2.7
12.9*10E4
V/TiO2
1.7
7.4*10E4
V08
0.63
3.2*10E4
TN
(mole NO. mole v1.s1)
2.4*10E-3
2.2*10E3
2.6*10E3
The TN of the NO reduction is constant within experimental error. This is a very

strong indication that the same active sites are present on these catalyst and the active
sites are connected with the vanadium compound. Tungsten, present in large amounts on
the commercial deNOx catalysts has no influence on the activity in the NO reduction.
The indication that the same active sites are present on these catalysts is also fortified
by the calculated activation energy of the NO reduction. The activation energy is a
measure for the potential energy barrier for a given reaction. Thus the same activation
energy (table 3) is an indication that the adsorbed species and transition states of the
intermediates are reacting according to the same reactionroute.
The maximum in the NO conversion curve cannot be explained only by taking the
dominant reaction (reaction 1) into consideration.
An explanation is given in terms of a side reaction, the NH3 oxidation, which becomes
favourable at higher temperatures. Oxidation of NH3 can be written as:
According to reaction 2, NH3 is consumed, while NO, a reactant in reaction 1, is
12
produced.
Oxidation of NH3 in the absence of NO was measured independently over V08. The
result is shown in figure 6. In this figure it is shown that a significant amount of NH3 is
oxidized at temperatures >300C. The amount of NO and N2O formed as products from
NH3 oxidation is also shown in this figure.
Figure 6. NH3 oxidation over V08 catalyst.
The result of the NH3 oxidation is that the NH3/NO ratio will change from 1 at lower
temperatures, to a value >1 at higher temperatures. In fact, this is what has been observed
for vanadium-containing catalysts at temperatures >300C.
c.NO2reduction and NO/NO2reduction
From the kinetic data given in table 3 and 4, a quantitative comparison can be made
between the NO reduction, the dominant reaction in a conventional SCR process, and the
NO/NO2 reduction, the most important reaction in the modified process. This
quantification is one of the most important aspects of this study and essential for further
evaluation of the modified process.
Typical flue gas conditions before the SCR reactor are 200800 ppm NOx, NH3/NOx
ratios of 0.80.9 and inlettemperatures in the range of 200350C.
From equation 1 and 2, and substitution of the kinetic data reported in table 3 and 4, it
can be calculated that at 250C and 400 ppm NO, the NO/NO2 reduction rate is
approximately 10 times faster then the NO reduction. Because the same activation energy
is measured for both reactions, this value is applicable for the entire temperature range
under consideration.
In view of the equivalence in performance between the model V08 catalyst and the
commercial VTT catalyst, the calculated difference in reaction rates for the V08 catalyst
can be extrapolated to the commercial VTT catalyst. This implies that the maximum
13
amount of catalyst material in the SCR reactor can be reduced by a factor 10. However, it
should be pointed out that this factor is reduced by mass transfer problems, which
frequently occur in large scale applications. The significance of transfer problems are
dependent on geometric factors as well as reaction conditions. Thus, quantification of the
effect of transport phenomena on the reduction of catalyst materials is virtually
impossible and is beyond the scope of this study.
5.EVALUATION OF THE MODIFIED PROCESS

A preliminary evaluation of the perspective of the modified SCR process will be given in
this report. The evaluation includes an estimation of the costs of the flue gas NOx
modification, preceding the SCR process.
A review of possibilities for flue gas modification has been given elsewhere [3].
Summarizing we can conclude that there are two possibilities of modifying the NO/NO2
ratio in flue gases; NO oxidation and NO2 addition. NO2 addition is unattractive due to
the increase in operational costs. NH3 consumption is at least three times higher as
compared to the conventional SCR process. Catalytic oxidation of NO is potentially the
most attractive method, but this technique is still under development. NO oxidation by
ozonisation and chlorination are proven techniques and commercially applied. However,
chlorination causes additional environmental problems and will therefore not be included
in this study. Thus, at present only ozonisation can be considered for flue gas
modification.
BBC Brown Boveri BV has made an estimation of investment cost and operating cost
for an ozone generation plant on bases of a 700 MW boiler, containing 500 ppm NOx in
the off gas. The investment cost adds to about 2.0*10E7 ECU (excluding reactor for flue
gas and ozone) and operating costs to 2.6*10E6 ECU/year (boiler utilization 6130
h/year).
Besides information on ozone generation, estimation of the costs of a modified proces
assumes also knowledge about the potential reduction of catalyst costs. From the kinetic
data it was concluded that the maximum reduction of the quantity of the catalyst
necessary is about 10. However, in most cases this factor will be reduced by mass
transfer effects in large scale applications. In the cost estimations, two factors have been
used for the reduction of the quantity of catalyst material: 10 (theoretical maximum
reduction) and 2.
J.Ando has given an estimation of SCR cost for new power plants (conventional dry
bottom boiler), based on a 700 MW coal fired boiler and a boiler utilization of 6100
h/year [6].
The cost estimations for the different options have been summarized in table 6.
14
Table 6. Cost estimations for the conventional and modified SCR process.
conventional
modified (A)
modified (B)
[6]
(cat.
(cat red.=50%)
reduction=90%)
Investment cost
(*10E5 ECU)
-catalyst (A)
219
22
110
-ozone (B1)
200
200
-other (B2)
90
90
90
Annual cost
(* 10E4 ECU)
-fixed cost
444
747
835
(0.1A+0.25B1+0.25B2)
-catalyst (A/life)
730
73
365
-power
85
349
349
-NH3
275
275
275
-other
60
60
60
total
1594
1504
1884
(excl. ozone reactor)
(excl. ozone
reactor)
From the estimations given in table 6, it is obvious that even in case of a 90%
reduction of catalyst materials in the SCR reactor, the annual cost of the modified process
is approximately the same as for the conventional process. The most important costfactor in the modified process is the ozone generation plant, even if the ozone-flue gas
reactor is not accounted for. From these preliminary calculations we can conclude that
unless the cost of the flue gas NOx composition modification process is significantly
reduced, a modified SCR process will not be feasible.
6.CONCLUSIONS
- TiO2 supported V2O5 is more easily reduced to metallic vanadium then bulk V2O5,
due to the interaction between the support and the active component. This
interaction between support and active component has no influence on the activity
of the catalysts in the NOx reduction.
The
activity in the NOx reduction over the catalysts included in this study, decreases
in the following order:
15
The reaction rate is proportional with the vanadium content, thus vanadium is the
active component in the comercial VTT catalyst. The observed values for the
activation energy for the NO and NO/NO2 reduction (table 3 and 4) indicates that
the same active sites are present in the vanadium containing catalysts VTT, V/TiO2
and V08.
- Comparing the equimolar NO/NO2 reduction rate with the rate of NO reduction and
NO2 reduction, results in the following order:
This result is in agreement with the results reported in a previous study [1, 2] The
reaction rate of the equimolar NO/NO2 reduction is approximately 10 times larger
then the reaction rate of the NO reduction over the V08 catalyst. This implies that
for large scale applications, theoretically, the amount of catalyst necessary for the
modified process is reduced with a factor of 10, as compared to the conventional
SCR process.
- Preliminary cost estimations of the modified SCR process and the costs of the
conventional SCR process given by J.Ando [6], demonstrate that even in case of a
90% cost reduction of the catalyst in the SCR reactor, the modified process is hardly
feasible. Investment and operating cost for the ozone generation plant attributes
significantly to the annual total cost of the modified process. Development of less
expensive processes for flue gas composition modification with respect to the NO2
component, e.g. catalytic oxidation of NO, is an essential step towards the
introduction of a commercially attractive modified SCR process.
16
REFERENCES
(1)TUENTER, G., van LEEUWEN, W.F., SNEPVANGERS, L.J.M., Ind. Eng. Chem.
Prod. Res. Dev., 25, 633, 1986.
(2)TUENTER, G., SNEPVANGERS, L.J.M., Proc. 20th Swedish Symp. on Catalysis,
Oct.87, Lund, Sweden.
(3)SNEPVANGERS, L.J.M., MULLER, H.G.P., TUENTER, G., Periodic Report jan.
87- dec. 87, ECN8814, jan. 88, Petten.
(4)van HENGSTUM, thesis 1984, University of Twente.
(5)BOSCH, H., KIP, B.J., van OMMEN, J.G., Ceilings, P.J., J. Chem. Soc. Far. Trans.,
80, 2479, 1984.
(6)ANDO, J., Contractor Report, EPA/600/785/040, Sept. 1985.
IMPROVED GAS FILTRATION SYSTEMS

FOR CONTROL OF SOLID FUEL
PARTICULATE EMISSIONS
Authors :
P.CROMWELL, A.DOYLE, A.D.KENNEDY, K.OROURKE
Contract number: EN3F0069IRL
Duration:
24 months 1 August 198731 July 1989
140,000 CEC contribution: 70,000
Total budget:
Head of project: Dr. A.D.Kennedy, Materials Technology Department
Contractor:
Eolas, The Irish Science & Technology Agency
Address:
Glasnevin
Dublin 9
Ireland
Summary
A theoretical analysis of the problems associated with the filtration and rapid combustion
of carbonaceous smoke in systems which can tolerate only extremely low resistance to
gas flow was carried out.
Discussions were held with a range of commercial suppliers. A number of potentially
suitable filters were identified, some of these have been acquired, others will be acquired
in the near future.
Two pilot test installations and all of the associated instrumentation were
commissioned. Pilot installation No. 1 is an open type system and installation No. 2 is a
closed type system. The most appropriate smoke emissions measuring equipment was
identified and fabricated. This latter equipment has now been commissioned.
The relevant operating characteristics of the pilot systems (gas flows, temperatures,
etc.) were determined for three typical solid fuel typeshigh volatile coal (Texan
coal), medium volatile coal (Polish coal) and peat briquettes. Preliminary trials with
some filter systems in place have been carried out.
1.INTRODUCTION
In the combustion of bituminous solid fuels in large scale combustion systems smoke
emissions are not normally a serious problem. Conditions are such that near total
combustion of carbonaceous material occurs. Also there is available well developed (but
expensive) technology for the filtration/entrapment/collection of non-combustible
18
particulates, e.g. electrostatic precipitators, etc.

For small combustion systems, however, this is not so. Combustion is often incomplete
and no satisfactory inexpensive technology exists for particulate emissions control.
Within the solid-fuel and energy industrial sectors the two usual approaches to
resolving this problem are:
- improved appliance design to minimise smoke emissions, and
- changing from smoking to smokeless fuels.
While fully accepting the validity of these approaches we have adopted a different
approach in this projectto attempt to remove smoke particulates by gas filtration and/or
catalysis. Small solid fuel combustion systems can only tolerate extremely small
resistance to the flow of flue gases. Hence any filters we use will be operating very close
to the limit of what is practical.
The project which commenced in August 87 is centred around 2 pilot test installations
(an open and a closed fire) and involves the testing of candidate filters either
obtained commercially or by in-house development/modification.
The project is multi-disciplinary requiring inputs from gas filtration technology, energy
technology, materials technology and catalyst technology
2.OBJECTIVES
In the case of small combustion units, both open type and closed type, using peat or
bituminous coal as fuel;
(A) to design and test gas filters which will:
-
provide little or no impedance to the flow of flue gases

effectively remove at least 50% of the suspended particulates
be relatively inexpensive (costing, say <IR30 per unit)
be capable of periodic regeneration by heat treatment (to remove combustible
material) so that their useful life would be at least one heating season.
(B) to design and test filter catalysts which would perform as in (A) above but
additionally would combust at least 50% of the unburnt gaseous hydrocarbons
(including polyaromatic hydrocarbons, PAH) contained in the typical flue gases
from these combustion units. The objective here will be to achieve a cost of
<IR50 per filtercatalyst unit, while meeting the above performance
characteristics.
For the period under review (Aug. 87May 88) the partial objectives were:
- to commission 2 pilot test installations with appropriate measuring instrumentation;
- to carry out baseline studies of the relevant operational characteristics of these test
installations using three typical solid fuels;
- to obtain samples of potentially suitable filter materials and begin testing them in the
Improved gas filtration systems for control of solid fuel
19
pilot test rigs.
3.DESCRIPTION OF TEST INSTALLATIONS

The open fire (test rig No. 1) was 400 mm wide580 mm high dry back fireplace
incorporating a stool bottom grate of the type used by the UK authorities for testing the
radiation output of coals and using a conventional firefront. It was served by means of a
flue 220 mm square terminating at 4.6 mm height, at which point dilution air is drawn
into a metal flue duct for exhaust via a variable speed fan. This enables standardised test
conditions to be operated for repeatability purposes.
The closed appliance selected (test rig No. 2) was a Hydrostove model manufactured
by Grant Engineering Ltd., Birr, Co. Offaly, Ireland. This is a glass-fronted appliance
with an approximately cubic firebox, a secondary air inlet and thermostatic control.
Products of combustion are diverted around a baffle plate before exiting.
Test instrumentation was as follows:
o Thermocouples (K type) for temperature measurements generally i.e. ambient,
front of fire (shielded by aluminium sheeting), fire bed, flue inlet passageways, flue
gas (at various heights).
o Inclined manometer for flue gas velocity.
o Hot wire anemometer for air inlet velocity.
o Bacharach draught gauge for draught.
o Bacharach smoke pump for smoke density indication (qualitative).
o BCURA radiometer cage for radiation heat output.
o British Standard pumped water mixing circuit for determining heat output from
closed stove boiler.
Temperatures were recorded on a multi-channel Leeds and Northrup chart recorder.
For quantitative measurement of particulate emissions we used the Dichotomous
Gravimetric Sampler (DGS) designed by Warren Spring Laboratory, UK. This consists
essentially of an electrically heated single plate impactor for collecting larger particles in
series with a small filter for collecting the remaining particles. It can be used
isokinetically or anisokinetically and has a choice of inlet nozzles and orifice plates
depending on flow rate and particle size.
It was selected mainly on grounds of convenience and versability. The design and
drawings were acquired and fabrication of two such devices in the EOLAS mechanical
workshop was completed in March 1988.
The apparatus was commissioned using our open fire test installation during April 88.
The nozzle was located in the geometric centre of the flue at a height of ~4.6 m from the
fire. Sampling rates were controlled by a pump, critical orifice and gas flowmeter which
were connected in series to the sampler via a dessicant train. Typical sampling flowrates
were ~6 litres/min. which corresponds to ~0.1% of total volumetric flue gas flowrates.
The frequency of changing the sampling filters varied from 20 min. to ~2 hrs. depending
on fire conditions.
20
4.GAS FILTER SYSTEMS USED

The following severe technical constraints apply to this task:
- the combustion units can tolerate only extremely low pressure drops (especially the
open fire where the maximum pressure drop arising from the introduction of a filter
must be less than ~5 Pa);
- once even small quantities of smoke begin to be deposited on a filter, gas flow
impedence increases very rapidly;
- although the smoke particulates are almost totally carbonaceous, the temperature at
which in situ filter regeneration by combustion of the filtered smoke is sufficiently
rapid to prevent blockage of the gas flow is probably>500 C, (in the presence of a
catalyst this temperature may be lowerperhaps 300400 C).
Because of these constraints most commercially available smoke and dust filters are not
suitable for this application. We have concentrated to date on using a very low density
ceramic fibrous mat with the following characteristics:
Supplier:
Chemical Composition
Bulk Density
Nominal Thickness
Physical Texture of Mat
: Quartz et Silice (Paris)

: 99.9% SiO2
: 17kg/m3
: 5 mm (as received)
: Felt
In use this was delaminated to a nominal thickness of 12 mm and for physical support
was sandwiched between 2 sheets of stainless steel mesh which also acted as a heat
conductor.
For most tests carried out to date the filter unit assembled as above was shaped to fit
horizontally into the open fireplace at heights of between 715 cm. above the fuel bed. It
was supported on a specially designed 2kw electric element which acted as a source of
secondary heating and maintained the mat temperature generally in the range 250C700
C depending on fire conditions.
We have also acquired some samples of ceramic foam filters of very high gas
permeability and we are currently attempting to acquire some ceramic honeycomb
catalysts of the type used in certain wood stoves and related applications. We plan to try
out these later.
5.RESULTS OBTAINED TO DATE

Most work to date has been carried out on a medium volatile coal Polish coal and on
peat briquettes. TABLE I gives average values for the main relevant operating conditions
of the two test rigs.
Improved gas filtration systems for control of solid fuel
21
TABLE IPILOT TEST RIGS

Relevant Operating Characteristics
TEST
DRAUGHT
FLUE GAS
FLUE GAS
RIG
(AVERAGE,
VELOCITY
TEMPERATURE
Pa)
(AVERAGE, M/S)
(AVERAGE C)
Open
Type:
4.6
2.35
60
Closed
28.4
1.1
340
Type:
In reality these values range between wide limits depending on fire conditions. As
expected the closed fire has higher draught, higher flue gas temperature and lower flue
gas velocity than the open fire.
TABLE II summarises results obtained to date on the open fire with Polish coal as fuel.
Tests P7, P8 and P9 were without any filter in place and constitute baseline data.
Although some significant variations are observed, the values for total smoke emissions
fall within a spread of 20% of the average value for the 3 tests. For the moment we
accept this as the limits of reproducibility obtainable with this system. Tests P10 and P11
were done with the heated ceramic fibre filter mat in place. There is some improvement
in smoke levels, particularly for the ignition cycle of test P11.
TABLE II
Particulate Emissions: Polish Coal: Open Fire
Test No.
Ignition Cycle
Refuel Cycle
1st. hr. 2nd. hr. Cleanburn 1st. hr. 2nd. hr. Overall Average
(g)
(g)
(g)
(g)
(g)
(g/h)
P7
84.2
41.5
1.2
43.7
0.8
29.4
P8
85.7
22.7
0.7
62.3
1.7
22.5
P9
67.6
13.3
6.0
32.1
1.8
21.3
P10
68.1
15.2
0.5
23.8
1.2
18.2
P11
40.6
1.3
1.2
n.m.
n.m.
n.m.=not measured
TABLE III gives corresponding values for two tests done with peat briquettes as fuel.
B2 is a test without a filter and B3 again has a heated ceramic fibre filter mat in place.
22
TABLE III
Particulate Emissions: Peat Briquettes: Open Fire
Test No.
B2
B3
Ignition Cycle
Refuel Cycle
1st
2nd
3rd
1st
2nd
3rd
Overall Average
20 mins 20 mins 20 mins 20 mins 20 mins 20 mins
(R/h)
(g)
(g)
(g)
(g)
(g)
(g)
12.6
6.0
1.7
19.8
0.8
0.1
20.8
11.6
6.3
0.8
10.5
0.5
0.2
14.9
On the basis of these initial results we can tentatively say that reductions of the order
of 2030% of overall smoke emissions are possible by using this type of filter system
with secondary heating.
6.CONCLUSIONS TO DATE/FUTURE WORK

In the case of the open fire it does not seem possible to have rapid in situ filter
regeneration so as to prevent blockage by smoke deposition, without the use of secondary
heating.
With the use of secondary heating of a highly porous ceramic fibre filter some
reduction (~2030%) of smoke levels is possible for both coal and peat.
At the moment we are not optimistic that this could from the basis of a viable, efficient
filter system for open fires.
For the remainder of this project we will concentrate mostly on the closed fire heater
where higher available pressure drops, and higher temperatures close to the fuel bed
should offer improved prospects of success.
DEVELOPMENT OF A PROCESS FOR

REMOVAL OF SO2AND NOxFROM FLUE
GAS USING BROWN COAL COKE
Authors :
U.LENZ, H.P.PAEFFGEN and E.WOLFRUM
Contract
EN3F0055D
number :
Duration :
30 months 1 September 198628 February 1989
Total budget : ECU 973757 CEC contribution: ECU 486878
Head of project : Dr. H.J.SCHARF
Contractor :
RHEINISCHE BRAUNKOHLENWERKE AG VF1, Coal
Chemistry
Address :
Postfach 41 08 40
D5000 KOELN 1
Summary
The object of the research project is to confirm and extend in systematic laboratory tests
the results thus far obtained with the use of brown coal coke for removing NOx and SO2
from flue gases. It has been proved that brown coal coke is an efficient adsorber/catalyst
for dry flue gas cleaning.
The removal of NOx and SO2 largely depends on the residence time of the flue gas in
the coke fill and on its moisture content. NOx removal requires residence times of 15 to
20 seconds (referred to an empty pipe). The investigations in the field of SO2 removal
were performed with a residence time of 8 seconds which led to a maximum SO2
adsorption of approx. 20% wt. A rise in flue gas moisture reduces the cokes NOx
removal efficiency while it increases the SO2 removal rate.
Possible applications of brown coal coke are seen in small generating units and in large
power plants where desulfurization facilities have already been installed. In the former
case brown coal coke can be used for complete desulfurization and for NOx removal, in
the latter one, however, it serves the purposes of residual desulfurization and NOx
removal. Brown coal cokes big price advantage over other activated cokes, e.g. those
produced from hard coal, makes an expensive regeneration of the laden coke superfluous.
It can be used as a fuel with a high heating value in power plants equipped with flue gas
desulfurization facilities or as a valuable sulfur-containing material in other appropriate
plants.
24
1.Introduction, state of the art

It has been proved that hard coal-derived activated coke can successfully be used as an
adsorber/catalyst for a combined SO2 and NOx removal from flue gases. In West
Germany, this process has been put to commercial use for the first time in the Arzberg
power plant (Upper Franconia). Still, an adverse factor is constituted by the high costs
involved in producing activated coke from hard coal which calls for a regeneration of the
laden coke with high technical expenditure to make it suitable for multiple use. This
largely restricts the chances of marketing the product.
Preliminary laboratory and bench-scale tests have shown that the desulfurization
properties of commercial brown coal coke are quite comparable with those of hard coalbased activated coke; in addition, it has been discovered that brown coal coke has
catalytic properties for NOx removal as well. It is particularly incentive to investigate in
detail the suitability of brown coal coke for the applications mentioned above since the
cost of commercial brown coal coke is far lower than that of activated coke produced
from hard coal.
Due to the low price the laden coke must not be regenerated like activated carbons, but
can be used e.g. as a fuel. Possible fields of application are e.g. in power plants with
downstream desulfurization facilities, where the laden coke is used as a supplementary
fuel, as well as in cement works or sulfate decomposition plants interested in feedstocks
with a high heating value and/or a high S content.
Nevertheless the recycling of the regenerated coke is as well possible if it leads to a
cost advantage.
2.Characterization of brown coal coke produced in rotary hearthfurnaces

Brown coal coke is produced from predried granular brown coal using the so-called
Salem-Lurgi rotary hearth furnace process. Fig. 1 provides an outside view of a rotary
hearth furnace, Fig. 2 shows its mode of operation.
Fig. 1
26
Fig. 2
The coal/coke has a residence time of some 45 minutes in the hearth furnace, the
maximum coking temperature is 950C. A crucial factor to the easy handling of the coke
later on is the ageing treatment to which the coke is subjected at the furnace discharge.
At present, brown coal coke is produced in two rotary hearth furnaces with an annual
output of some 105,000 metric tons each which are integrated into the Fortuna-Nord
upgrading plant located at Niederauem near Bergheim.
Fig. 3 lists the analysis reference values of brown coal coke.
Development of a process for removal of so2
27
Fig. 3
Brown coal coke Is produced in three different grain sizes, viz. fine coke in the 1.25 to
5 mm grain size range, extra-fine coke of 0 to 1.5 mm, and pulverized coke of <0.4 mm.
The cokes residual moisture content is max. 1% wt.
The coke ready for dispatch contains approx. 3% wt of volatiles most of which are socalled secondary volatiles which form only during the cooling process when the hot coke
28
(approx. 900C) reacts with oxygen. The major part of these volatiles is CO2 rather than
combustible matter.
The coke has an extremely low sulfur content of only 0.45% wt; its reactivity and
resistivity are high in comparison with other carbon carriers.
Approx. 9% wt of ash is contained in the coke. The ash can be characterized as
typically alkaline since it contains more than 40% wt of CaO and has high iron and
magnesium portions, but low silicon and aluminium percentages.
Without requiring any after-treatment, the coke has a specific surface of 250 to 350
m2/g. Fig. 4 shows the relevant pore radii distribution. It can be seen that the maximum
values are obtained in the macropore and submicropore sections.
Fig. 4
3.Laboratory test apparatus
A laboratory test apparatus was set up for carrying out systematic research into the
removal of NOx and SO2 from flue gases by the use of brown coal coke. Fig. 5 shows a
photo taken of the test apparatus.
29
Fig. 5
The test apparatus comprises a synthetic flue gas generator, a gas preheater, a reactor
receiving the coke fill, and a gas analyzer.
The flue gas generator allows the concentrations of the flue gas components to be
varied with great precision over a wide range.
For NOx separation, NH3 can be added to the reactor.
The reactor was designed for a gas flow volume of 1 m3/h (STP). With aim thick coke
fill, a residence time of 8 seconds (empty pipe, STP) is obtained. The superficial gas
velocity of 0.12 m/sec. (STP) is comparable to that of commercial flue gas cleaning
facilities.
Reactor heating allows the cokes properties to be examined at higher temperatures as
well. The continuous gas analyzer recording the O2, CO, CO2, SO2, NO and NOx
contents of the gas permits a largely automatic operation of the test apparatus.
4.NOxremoval by the use of brown coal coke

For the investigations of NOx removal, ammonia was added as a reducing agent in a 0.8
to 1 molecular ratio to the simulated flue gas and the catalytic conversion on the coke
surface was observed by means of so-called breakthrough curves.
Fig. 6 shows the catalytic reactions taking place on the coke surface and, in addition,
gives an example of a NO breakthrough curve.
30
MECHANISM
- Adsorption of NOx and NH3
- Catalytic conversion into N2 and H2O
- Formation of nitrite and nitrate (secondary reaction)
REACTION EQUATIONS
Fig. 6
Based on an input concentration of 330 mg of NO per m3 (mf), the NO output
concentration amounts to approx. 150 mg/m3 (mf); this corresponds to a NOx removal
rate of about 55%. Prior ash removal from the brown coal coke by treating it with various
acids or acid mixtures leads to a considerable increase in the NOx removal efficiency, viz.
to as much as approx. 70% in this case.
In another test phase, parameters such as residence time, temperature, H2O vapour
content, and NO concentration of the flue gas were varied in order to study their effects
on the cokes NOx removal efficiency.
31
To sum up, it can be stated that the NOx removal rate improves with increasing
residence times; 15 to 20 seconds should be obtained. The optimum temperature for NOx
removal ranges between 80 and 100C. Fig. 7 shows the influences of H2O vapour and
NO on the removal of NOx.
Fig. 7
It is possible to conclude from the tests results obtained upto how the NOx removal rate
for various H2O vapour portions and NO input concentrations. The Figure shows that
NOx removal decreases with rising H2O vapour portions. Consequently, high NOx
removal rates can be attained in hard coal-fired power plants where the flue gas emissions
contain only low H2O vapour portions. The results are not so favourable for the removal
of NOx from flue gases downstream of brown coal-fired power plants since the H2O
content of these flue gases, due to the higher H2O and H2 portions contained in the
feedstock, exceeds by far that of hard coal flue gases.
Subsequent investigations of the cokes used for NOx removal have shown that the
cokes were laden with up to 3% wt of NO3-. To judge any possible safety hazards
associated with this NO3- load, the ignition behaviour of the cokes was determined. The
results obtained have proved that the reactivity of NO3-laden coke is not higher than
that of fresh one.
32
5.SO2removal by the use of brown coal coke

The SO2 removal tests were conducted with a superficial gas velocity of 0.12 m/sec.
(STP) which is typical of large-scale plants.
Fig. 8 gives a brief description of the reaction mechanism initiated by the use of rotary
hearth furnace coke for desulfurization and, in addition, shows some SO2 breakthrough
curves as an example.
MECHANISM
- Adsorption of SO2. O2. and H2O
- Catalytic conversion into SO3
- Formation of H2SO4
Fig. 8
33
Tests made so far in the 80 to 140C range in order to determine the dependence of SO2
removal on temperature have shown that with increasing temperatures there is a marked
decrease in the amount of SO2 adsorbed until the first breakthrough.
Since the composition of real flue gases is subject to great fluctuations, it was decided
to vary the SO2 input concentration and H2O vapour portion in the tests. The threedimensional diagram in Fig. 9 shows the effects of these two parameters in the reaction
temperature range of 100 to 140C.
Fig. 9
It is obvious that SO2 adsorption increases with rising H2O vapour portions (partial
pressure).
In order to establish the so-called mass transfer curve, two tests were conducted in
which the coke fill was taken out of the reactor in individual layers after SO2
breakthrough. Then, analyses were made of the average S load of the individual layers
(Fig. 10).
34
Fig. 10
On the basis of the flow direction, the first coke layer has a maximum SO2 load of 20%
wt. In both tests the load of the individual layers decreases almost linearly towards the
final layer of the coke fill.
6.Outlook
Fig. 11 summarizes the major results thus far obtained and provides an outlook for future
investigations.
35
Fig. 11
The results available so far have shown that the removal of both NOx and SO2 by
means of brown coal coke largely depends on the moisture contained in the flue gas. That
is why further tests will be directed to the influence of this parameter. In addition, other
parameters will be investigated which may have an influence on the removal of SO2 and
NOx.
Another task for the future is the detailed investigation of the suitability of rotary
hearth furnace coke from brown coal for cleaning waste gases from other production
processes.
REGENERATIVE DESULFURIZATION IN
FLUIDIZED BED COMBUSTION OF COAL
Authors :
Contract number :
Duration :
Total budget :
Head of project :
Contractor :
Address :
C.M.VAN DEN BLEEK, P.J.VAN DEN BERG

EN3F-0014-NL (GDF)
36 months April 1, 1986March 31, 1989
Dfl. 3 797 000 CEC contribution 48% (max. Dfl. 1 772 000)
until June 30, 1988 : P.J.van den Berg
from July 1, 1988 : C.M.van den Bleek
Delft University of Technology
Julianalaan 134, 2600 AA Delft
The Netherlands
Summary
New legislature will make regenerative desulfurization during FBC inevitable in the near
future. The sulfur route in such a process is being studied now at Delft University of
Technology. In the sulfur release step the mechanism of the combustion and
decomposition of pyrite has been elucidated. A model is developed to describe the sulfur
release pattern. To obtain an efficient sulfur capture a good particle mixing without
segregation is necessary for an optimum contact between gaseous sulfur species released
and sorbent material. A model is derived which sufficiently can describe the segregation
of sorbent, coal and ash particles and can be used to calculate the conditions to avoid it. A
regenerative sorbent is being developed. Its preparation is based on the sol-gel method,
producing strong particles which show a low attrition rate, a sufficient sulfation
behaviour and a promising regenerability at only 900C. Finally a simple SUlfur
REtention (SURE) model was set up which can be used as a diagnostic tool for analysis
of existing combustors as well as a predictive tool for analysis of plants under
construction or design, also at low oxygen concentration as met at substoichiometric
firing conditions. All models presented do not contain any fit parameters; all parameters
can be calculated from generally accepted literature data or can be easily measured or
controlled.
1.INTRODUCTION
The emission problem is one of the main reasons preventing a general introduction of
Regenerative desulfurization in fluidized bed
37
fluidized bed combustion of coal. Both gaseous and solid emissions are still not yet under
control completely. This is partly caused by a legislation becoming more severe time and
again, e.g. earlier NOx emission standards could be easily met by a fluid bed combustor;
the present required emission level, however, makes extra measures like e.g. stagewise
combustion necessary.
A somewhat similar situation can be expected with respect to the sulfur retention.
Sulfur capture can be performed easily in a fluid bed combustor by feeding lime together
with the sulfur containing coal. However, from an environmental point of view it will
become more and more unacceptable in the near future to landfill or seadump spent
sorbent. So the development of a regenerable sorbent is needed to keep a good
perspective for the FBC- technique.
In the Delft EC-project EN3F0014NL (GDF) the sulfur route in such a regenerative
process is studied. Originating from the sulfur content of the coal volatiles and the coal
matrix, sulfur is released and converted into SO2. Depending on fluid bed hydrodynamics
like e.g. mass transfer, particle mixing and segregation, SO2 is transported to the sorbent
particles. There it is captured and converted into sulfate. The converted sorbent is
removed from the system together with ash. In the regenerator the sulfur is recovered
from the sorbent at a concentration sufficiently high for further use; the regenerated
sorbent is fedback to the combustor. This route is summarized in Fig. 1. According to this
Fig. 1. Delft Regenerative Desulfurization Project.

figure the following research subjects are treated in the Delft project : (i) Sulfur release
during coal combustion, (ii) Fluidized bed hydrodynamics, (iii) Development of a
38
regenerative sorbent, (iv) Sulfur capture and sorbent optimization, (v) Sorbent
regeneration and (vi) Process setup. The results so far are reported here.
2.SULFUR RELEASE
In a combustor the release of sulfur is not uniformly throughout the bed: it may vary with
the radial and axial bed position caused by the fact that the devolatilization time of a coal
batch added to a fluid bed is in general less than 20% of the total burnout time and
consequently in the same order as the particle mixing time (1020 sec.). This implies that
the volatiles-sulfur is released predominantly around the coal feed points, while the
char-sulfur is released throughout the bed. This phenomenon has consequences for the
combustor design and operation e.g. the position of sorbent feed and removal, the pitch of
the heat exchanger pipes etc.
For that reason FBC and TGA sulfur release experiments were performed from which
the distribution of coal-sulfur is determined as well as the sulfur release pattern and the
average sulfur release rate during volatiles and char combustion. A non-steady fluid bed
sulfur release model has been developed to explain and predict the measured phenomena.
2.1Sulfur in Coal
Coal contains pyritic, organic and sulfate sulfur. Pyrite (FeS2) in coal occurs
predominantly as microscopic grains and aggregates of micron-size crystals which are
intimately combined with the coal. Based on literature e.g. (1) and own experiments the
decomposition and combustion of pyrite was elucidated. A general reaction scheme of
pyrite in coal (see Fig. 2.) was presented (2, 3). The distribution parameter x in Fe2O3x
(SO4) was calculated based on this scheme and related to the ratio between the weight of
inert material and the weight of FeS2 and FeS in the sample (see Fig. 3. (2)).
Organic sulfur in coal is present in many different sulfur containing functional groups.
Only divalent sulfur is found; the most importants compounds are thiophenes, aryl-,
cyclic-, alifatic sulfides and aryl- and alifatic thiols.
39
Fig. 2. The reaction mechanise of pyrite in coal.
Fig. 3. The distribution parameterp x in Fe2O3x(SO4)x as function of the ratio

between the wt% inert material and the wt% FeS2+Fes in the
sample.
Sulfate sulfur (CaSO4) can react with SiO2 which is present in the coal ash to form
silicates and SO2. It was found (2) that this reaction is only important at temperatures
40
above 980 C, so far above the normal operating temperature of the combustor.
2.2.Sulfur from Coal
From TGA experiments it was observed (2, 3) that the coal sulfur release pattern
generally is strongly effected by the sulfur composition of the coal as well as by the
combustion temperature and the coal combustion rate. All organic sulfur is released
during coal devolitalization, while pyritic sulfur is predominantly released during char
combustion. However, at high combustion rates (by using oxygen instead of air) all sulfur
is released just in one peak, making the appearence of different peaks in the sulfur release
profile of a coal sample during FBC (at even higher burnout times) most doubtful. This
was confirmed during FBC experiments (4) where roughly half of the char-sulfur was
already released during or directly after devolitalization.
To be able to predict sulfur release patterns a non-steady sulfur release model has been
developed (4) which is based upon diffusion controlled devolitalization, second order
volatiles combustion and shrinking particle char combustion; further coal particle and
bed heat up and fluid dynamic behaviour like segregation, slugging and bed expansion
are taken into account. The model contains no fit parameters; most of the variables are
based on literature correlations; the gas transfer parameters like Sherwood number and
bubble-dense phase transfer coefficient have been obtained from coal burnout
experiments. In Fig. 4 a result of such a calculation is shown together with the results of a
quadruple experiment. The agreement between the calculated and the measured curves is
good.
Fig. 4. Sulfur release (2.5 g 515 US 38; 2.232 mm; 0.78 m/s) (
measured; -----model)
3.FLUID BED HYDRODYNAMICS

The particles applied in FBC are B- or D-type of powders according to the classification
scheme of Geldart (5). They differ significantly in size and density; coal ash: d700 m,
2600 kg/m3; coal: d16 mm, 8001400 kg/m3; regenerative alimina based
sorbent/limestone/dolomite: d300 m5 mm, 12002700 kg/m3.
It will be clear that a good mixing during FBC has to be accomplished: (i) to derive an
41
optimum contact between the gaseous sulfur species released from volatiles and char
combustion and the sorbent material in order to obtain an efficient sulfur capture, and (ii)
to avoid defluidization of the particles. This latter phenomenon is caused by variation of
the minimum fluidization velocity along the bed height due to segregation. In general it
happens in a region just above the distributor (6). and must be avoided, because: (i) it
enhances coking, sintering and clinkering of the ash (7), and (ii) it will decrease the coal
combustion efficiency as well as the level of sulfur retention, and (iii) it can shorten the
lifetime of the applied regenerative sorbent material. A complicating factor is further that
the rate and extent of sorbent segregation will change as a function of time due to the
sulfur-uptake (8).
So it is obvious that in FBC the rate and extent of segregation have to be well known in
order to select the proper bed dimensions ((hydraulic) bed diameter) and the correct
operating conditions (superficial gas velocity).
3.1.Fluidization Behaviour during FBC
In general the fluidization behaviour of FBC-large-particle systems is characterized as
slow bubbling: the bubble rise velocity is smaller than the interstitial velocity; the
transition zone between the slow bubble void and the dense phase is not well defined and
particles can rain through the voids.
However, the fluidization behaviour in a FBC combustor is also influenced by the
closely packed internals as heat exchanger tubes. The space surrounded by the convex
side of the tubes may be regarded as a system of small parallel fluidized beds with a
hydraulic bed diameter of about 5 to 30 cm. The solids exchange between the parallel
sections is low (9) and a good vertical mixing takes place with horizontal tubes
positioned in line (10) or with vertical pipes. The fluidization is mostly of the slugging
type and shows remarkable agreement with the mode of fluidization in relatively small
diameter fluid beds (11).
3.2.Segregation/Slugging Experiments
Slugging, particle mixing and segregation have been investigated using two experimental
techniques: abrupt defluidization and radioactive labeling of a sorbent particle.
Slugging was characterized using the dimensionless slug parameters a and b, related to
the slug type and slug spacing respectively. It was concluded (12) that e.g. square nosed
slugging is occurring at ratios of bed height at minimum fluidization and bed diameter
(Hmf/D) higher than 4. It could be concluded that at these ratios b is about 0.80.9,
meaning that the average length of a particle slug equals about 8090 % of the bed height
at minimum fluidization. This implies that, in general, only one particle slug is present in
the bed.
It was observed (12) that the extent of segregation is increasing at increasing Hmf/D
ratio, at smaller bed diameters (see Fig. 5) and at decreasing superficial velocities (Fig.
6). From these experiments it can be expected that segregation will disappear above a
certain critical bed diameter.
42
Fig. 5. Influence of bed diameter on extent of segregation.
(Mixture I; Hmf/D2; UOUmf0.30 m/s)
Fig. 6. The extent of segregation S as a function of the superficial gas velocity

at 850 C: a comparison between model and experiment.
(Hmf/D2.1 []; Umf0.38 m/s; D10 cm)

By means of radioactive tracer measurements it was shown (13, 14) that in a slugging
fluidized bed two differently fluidized regions are present: one above and one below the
position of the bed height at minimum fluidization. The influence of axial position,
superficial gas velocity and Hmf/D was investigated on particle velocity and particle
presence probability (Fig. 7).
43
Fig. 7. Model fit of the normalized presence probability in case of

experimental set 2.5: UO1.4 m/s; Hmf/D3.85 []; zH0.37 []
3.3.Segregation/Slugging Model
A general model to describe particle motion in slugging gas fluidized beds has been
developed (13), based upon the following assumptions.
First, it is assumed that a slugging bed consists of two layers. Based on the
experimental observations it is assumed that the boundary between these two layers is
situated at h/Hmf1. In each layer solids move upwards and downwards caused by
convective, dispersive and segregative solids flows. These solids flows are caused by
different forces on the solids, which are predominantly the drag force, the gravity force
and buoyancy.
Secondly, it is assumed that in each layer the upward and downward solids velocities
as well as the axial solids dispersion coefficient are constant and do not change as a
function of the bed height. The only change is observed at the boundary between the two
layers in the bed.
Finally, it is assumed that the distribution of the solids over the particle and the gas
slug is no function of the bed height. This implies that the volume fractions of solids in
respectively the particle slug and the gas slug are the same in both bed layers.
A schematical representation of the model is given in Fig. 8. Based upon this model a
comparison is made between the calculated and the measured presence probabilities. The
results are in good agreement (Fig. 7). Using a simplified version of the model and the
measured values of the distribution parameter from the radioactive tracer experiments
(describing the distribution of the segregative particles over gas and solid slugs) the
segregation profiles in the abrupt defluidization experiments were calculated without any
fitting and compared with the segregation profiles actually measured. The agreement is
good as is shown in Fig. 9.
44
Fig. 8. A schematical representation of the general model for particle motion

in a slugging gas fluidized bed.
Fig. 9. Segregation model vs experiment.
The calculated dependency on the superficial gas velocity is shown in Figure 6

together with the experimental values; the dependency on D, resulting in a calculated
value of the critical bed diameter of 23 cm (see Fig. 5) is in good agreement with the
experiments.
45
4.REGENERATIVE SORBENT DEVELOPMENT

Traditionally limestone and dolomite are used as SO2 sorbents in fluidized bed
combustion of coal. However, for regenerative purposes these materials are not
appropriate for two reasons: (i) attrition followed by elutriation brings about
unacceptably large losses and (ii) very high temperatures (up to 1100 C) are needed
during regeneration to prevent CaS formation. This is uneconomical and might also cause
deactivation of the sorbent. Therefore the two main research objectives are (i) improving
of the attrition resistance and (ii) decreasing of the CaS formation (regeneration
temperature) while keeping constant or even improving sulfation behaviour.
From literature e.g. (15) it is known that two types of material can be used as a
regenerable sorbent. (i) The titanates of calcium and barium show a good regeneration
and a fast sulfatation behaviour without deactivation. (ii) On the other hand CaO on
alumina gives a very stong sorbent with a sulfation and regeneration behaviour
comparable to limestone and dolomite.
Besides the type of material also a production process has to be selected. The process
strongly influences the suitabilty of the product as a sorbent since it effects texture
(structure of the voids), chemical composition and structure, strength and outer shape of
the particles. Furthermore the cost price is of importance.
4.1.Preparation Methods
In the original set up of the project it was meant to prepare the regenerative sorbent by
traditional methods like pelletizing, extrusion and agglomeration. During the course of
the project the socalled sol-gel method (16, 17), a very promising way of preparing strong
spherical particles in catalyst preparation, was adapted for sorbent production. An
alumina containing sol (a semi-stable dispersion of AlOOH in diluted nitric acid) is
dropped into an ammonia solution passing through an oil layer. This layer enables the
drops to spherulise and the ammonia causes the sol to gelate, thus forming rigid spheres
with a large void volume. When a calcium salt is added to the ammonia solution,
impregnation of these spheres can be performed in the same step. This method is
expected to produce strong spheres with a high pore volume. However, it is a more
expensive method.
The sol-gel method was applied using direct impregnation with Ca (NO3)2, starting
from AlOOH (PURAL SB 70 from CONDEA, Brunsbuettel,FRG). Next to the sol-gel
method some more traditional preparation routes were investigated, like (i) impregnation
of TiO2 powder (Degussa) with calcium or barium salts followed by peletization, (ii)
impregnation with Ca(NO3)2 of several types of alumina pellets (AKZO, Amsterdam,
The Netherlands) and (iii) wet agglomeration of alumina powder (AKZO), calciumaluminate cement (ALCOA, Rosenburg, The Netherlands) or AlOOH powder
(CONDEA).
46
4.2.Attrition Behaviour
Attrition and elutriation were tested in a fluidized bed (ID 5 cm) at room temperature
using air (1 m/s) and starting with approximely 150 g sorbent. Weight changes were
monitored. After a few days a steady attrition rate was reached, expressed as the relative
weight loss per unit time a (kg/(kg.h)). The results are mentioned in Table 1 together with
crushing strength test results and some other relevant features.
The sol-gel method show very promising results. Although the spheres consist of alumina, a mechanically weak alumina crystal structure, they are strong and still have a
high pore volume.
4.3TGA Experiments
Sorbent screening was performed in the TGA equipment using a standard test procedure,
the so called SRO-test. It consists of :
SULFATION: 850 C; 0.5 vol% SO2/air; 100 ml/min; 2.5 hours.
REGENERATION: 900 C; 10 vol% H2/N2; 100 ml/min; until completion.
OXIDATION: 850 C; air; 100 ml/min; until completion.
4.3.1Sulfation behaviour.
From the recorded weight changes during the sulfation part of the tests the conversion of
the CaO-content of the sorbent can be calculated. These are mentioned in Table 2,
together with the CaO loads of the fresh sorbent and the initial sulfation rates.
TABLE 1: RESULTS OF ATTRITION TESTS
sample
alumina pellets
alumina pellets
impregn. -alumina pell.
shape
cylinder
cylinder
cylinder
sol-gel spheres
agglomerates (A100H)
agglomer. (Ca-Al cement)
sphere
sphere
sphere
pV1
F2
104.3
1.02 6020
4.71
0.48 12030
2.15
155
2.42
CaAlxOy4 0.36
-Al2O3 0.64
60
0.65
30
5.78
-Al2O3 0.67
20
CaAlxOy 0.48
material
-Al2O3
-Al2O3
1 pV: pore volume measured by water intrusion (ml/g);

2 F: crushing force determined on a Schleuniger 2E/205 (N);
3 : attrition rate (kg/(kg.h));
4 CaAl O : general code for compounds of CaO.xAl O .
x y
2 3
TABLE 2: RESULTS OF SULFATION TESTS

sample code2 sample description
1a
1b
2
3
4
5
sol/gel; Al2O3 as support

sol/gel; -Al2O3 as support
impregnated -Al2O3 pellets
impregnated -Al2O3 pellets
agglomerates (Ca-Al cement)
CaTiO3 -pellets
47
Ri,s
(CaO)1 conv
(%)
(w%)
(1E-3/min)
7.4 80
1.3
15.0 95
2.7
7.0 100
1.8
10.0 100
3.3
27 45
3.3
41 45
3.3
1 (CaO): CaO content determined by Atomic Absorption Spectrometry (AAS);
It will be clear that high quality sorbents with respect to sulfur capture will combine a
high calcium oxide load with a high calcium conversion and a high sulfation rate. The
sol-gel sorbent lb and the impregnated -Al2O3 pellets score relatively high.
4.3.2.Regeneration behaviour.
After regeneration at 900 C the sample is oxidized giving a weight increase according to
the reaction CaS+2O2--->CaSO4. So the amount of CaS and CaO after regeneration can
be determined. Especially temperature and type of material appear to be important factors
in determining the amount of CaS formed (18). The higher the temperature and the more
reactive the support in forming compounds with CaO, the better the selectivity of the
regeneration. General results are summarized in Table 3.
The sol-gel materials show an extremely high conversion to CaO, even at low
temperatures. This is caused by the fact that -alumina is used as a support; it is reactive
and has a large surface area giving rise to the formation of calcium aluminates; in this
way a high dispersion of CaSO4 during sulfation is ensured. During regeneration this
enhances the direct back-formation of calcium aluminates (19) instead of CaS. The
important influence of the dispersion on the regenerability is known from other processes
(20).
TABLE 3: THE RELATIVE AMOUNT OF CaO FORMED DURING REGENERATION
type of material
CaTiO3
CaO.xAl2O3 on -Al2O3 (sol-gel)
CaO.xAl2O3 on -Al2O3
CaO.xAl2O3
850 C
6570
8090
6070
2535
1000 C
95
90
90
50
48
4.3.3.Cyclic behaviour
.
By repeating the SRO-test a number of times the short term cyclic behaviour of the
samples was tested. The sol-gel materials showed an initial decrease in sulfation
efficiency and regeneration selectivity, mainly attributed to the diffusion of some CaO
from the surface into the bulk of the support. After 3 cycli the behaviour is constant. The
calcium titanates show a constant behaviour directly from the first cyclus.
4.4.Scaling-up Sorbent Manufacturing
.
Because it was overall concluded that the sol-gel made particles are very promising an
installation for the continous production of this type of sorbent was designed and built.
The design is based on a KEMA facility at Arnhem, The Netherlands. The sol-gel sorbent
produced is now being tested.
5.SULFUR CAPTURE AND SORBENT OPTIMIZATION
The main fluid bed reactor quantities that influence the degree of desulfurization in a
fluid bed combustor are respectively (2125): the sorbent residence time, the superficial
gas velocity, the stoichiometric air ratio, the bed temperature and the mean bed particle
size; the main sorbent properties of influence are respectively: the mean sorbent particle
size, the maximum sorbent CaO conversion and the sulfation kinetic rate constant. The
most important system parameter is, of course, the (Ca/S) molar ratio in the reactor feed.
One useful way to determine the mutual connection between these quantities and
properties and in what manner they influence the sulfur capture process, is by the
application of a mathematical sulfur retention model. Based on a parameter sensitivity
analysis it is generally possible to focuss in on the main parameters that influence the
sulfation process. In that way the model is used as a practical engineering tool for the
analysis of combustors in design or operation (diagnostic or screening tool). However,
the model may also be used as a predictive tool for the calculation of the required process
operating conditions in an existing FBC facility.
Research activities on emissions for fluid bed coal combustors are also more and more
concerned with the reduction of NOx emissions by means of staged (sub-stoichiometric)
combustion. However, SOx and NOx emissions are found to be strongly interrelated: in
general SOx emissions increase with a lower primary air ratio (26), while NOx emissions
increase with a higher sorbent hold-up and a lower sorbent fractional sulfation (27). So it
is also necessary to incorporate the oxygen influence in such a sulfur retention model.
5.1SURE Model Assumptions
The choice of the type of fluid-dynamical reactor model is strongly dependent on the
mode of fluidization and gas transport that is present in a fluid bed coal combustor.
49
Recently, Almstedt and Ljungstrom (28, 29) have demonstrated with capacitance and
oxygen probe measurements that the visible bubble flow rate in a FBC combustor is
much smaller than predicted by the two-phase theory of fluidization. This is a result of
the bubble growth and rise velocity being limited by the horizontal in-bed cooling tubes
giving the bed a slugging fluid dynamical character. This in turn causes a significant
amount of the gas to pass the bed as a throughflow through the bubbles (or gas slugs) and
through the dense phase between the vertically aligned bubbles. Further no variation in
the oxygen concentration due to the presence of bubbles can be seen caused by the rapid
interphase gas exchange which results in a high and even oxygen concentration
throughout the bed. Consequently, the one-phase ideally mixed gas flow model (ISTR) is
applied, which corresponds with these experimental results.
Furthermore, the solids are assumed to be ideally mixed due to the relatively high
sorbent residence time with respect to the gas residence time; particles are spherical and
of uniform size.
The coal combustion rate is assumed to be first order in the oxygen concentration and
first order in the total external reactive coal surface area.
The sorbent CaO sulfation rate is first order in the gaseous sulfur SO3 concentration
and first order in the total external reactive sorbent surface area.
The maximum sorbent conversion is smaller than unity due to deactivation phenomena
like pore plugging.
Elutriation and freeboard phenomena are not taken into account.
5.2SURE Model Calculation/Validation
Based on its mass balances the SURE model provides (2125) an analytical expression
for the molar Ca/S ratio in the reactor feed as a function of a required (e.g. by EPA
standards) level of sulfur retention, the maximum sorbent conversion and a dimensionless
model parameter. This parameter is a known function of the fluid bed operating
conditions and of the coal and sorbent properties. The components of this parameter can
either simply and independently be measured or controled or can be calculated from
generally accepted literature data.
A quantitative validation of the SURE model was carried out (31) with application of
steady state retention data that were obtained in the 4MWth coal fired fluidized bed boiler
of TNO (30) in The Netherlands (bed height about 1 m; bed cross sectional area 2.25 m2).
The results are shown in Fig. 10, where the calculated values of the Ca/S ratio (without
any fitting to the combustor data) are compared with the actual values as used in the TNO
experiments. A good agreement is obtained.
The SURE model can also easily explain (24) the observed dependency of the oxygen
concentration in the combustor outlet as a function of the excess air ratio (Fig. 11) and
the generally observed decrease of the desulfurization efficiency during
substoichiometric (staged) combustion (Fig. 12). Quantitative validation of these last
phenomena is, however, hampered by the lack of reliable data.
Sometimes an optimum in the sulfation rate (or degree of sulfur retention) as a function
of bed temperature is reported in literature (31). One explanation may be that both
sulfation and calcination occur simultaneously, which lead to an optimum temperature
50
resulting from these two opposing tendencies. However, the occurence of an optimum
can also be theoretically explained by the rate of SO3 formation in combination with the
SO3 sorbent sulfation reaction as applied in the SURE model. (Fig. 13).
Fig. 10. Comparison of the calculated SURE Ca/S ratio with the actual value
in the TNO 4 MWth FBC combustor.
Fig. 11. Oxygen concentration in combustor outlet as a function of air ratio .
The SURE model is being incorporated as the sulfur retention module in the overall
combustor model of the International Energy Agency (IEA). The first results are very
promising (32).
The use of the SURE model as a diagnostic tool for sorbent minimization is explained
in detail elsewhere (21, 22).
51
Fig. 12. Model sensitivity analysis. Sulfur retention as a function of air ratio .
Fig. 13. Temperature effect on sulfur retention.
6.ACKNOWLEDGEMENT
The research on the regenerative desulfurization process is a joint effort of the D.U.T.
Dept. of Chemical Engineering and the Dept. of Inorganic & Physical Chemistry. The
contribution of the Ph.D. students Anton Duisterwinkel, Eric-Hans Wolff and Peter
Valkenburg and of Jaap Schouten who recently obtained his doctorate is greatly
acknowledged.
7.REFERENCES
(1)Thorpe, A.N., Senftle, F.E., Alexander, C.C., Fuel63, 1984, 662.
(2)Schouten, J.C., Hakvoort, G., Valkenburg, P.J.M., Van den Bleek, C.M.,
52
Thermochimica Acta, 114, (1987), 171.

(3)Schouten, J.C., Blommaert, F.Y., Hakvoort, G., Van den Bleek, C.M., in: J.A.Moulijn,
K.A.Nater, H.A.G.Chermin (eds.), Coal Science and Technolgy 11, Elsevier,
Amsterdam, 1987, 837.
(4)Schouten, J.C., Ingwersen, M.J., Van den Bleek, C.M., in: J.A.Moulijn, K.A.Nater,
H.A.G.Chermin (eds.), Coal Science and Technolgy 11, Elsevier, Amsterdam, 1987,
841.
(5)Geldart, D., Powder Technol., 7, (1973), 285.
(6)Beeckntans, J.M., in: D.Kunii, R.Toei (eds.) Fluidization, Engineering Foundation,
New York, 1984, 177.
(7)Cooke, M.J., Napier, B.A., Parkinson, M.J., Rogers, E.A., Proc. 7th Int. Conf. on FBC,
Philadelphia, USA, vol. 11, 1982, 792
(8)Valkenburg, P.J.M., Schouten, J.C., Van den Bleek, C.M., in: K.Ostergaard,
A.Sorensen (eds.) Fluidization, Engineering Foundation, New York, 1986, 193.
(9)Chen, M.M., Chao, B.T., Liljegren, T., Proc. 4th Int.Conf. on Fluid, Japan (1983).
(10)Raven, P., Sparham, G.A., Proc. 7th Int.Conf. on FBC, Philadelphia, USA, vol. I,
1982, 275.
(11)Noordergraaf, I.W., Van Dijk, A., Van den Bleek, C.M., Powder Tecnhol., 52,
(1987), 59.
(12)Schouten, J.C., Valkenburg, P.J.M., Van den Bleek, C.M., Powder Technol., 54
(1988), 85.
(13)Schouten, J.C., Masson, H.A., Van den Bleek, C.M., The motion of particles in gas
fluidized beds, submitted for publ. in Powder Technol.
(14)Schouten, J.C., Masson, H.A., Van den Bleek, C.M., Proc. Int. Symp. on Multiphase
Flows, Hangzhou, China, August 37, 1987, 237.
(15)Newby, R.A., Keairns, D.L., Proc. 5th Int. Conf. on FBC, 1978, 680.
(16)Zelinski, B.J.J., Uhlmann, D.R., J. Phys.Chem., 45 (10), 1984, 1069.
(17)Hermans, M.E.A., Powder Metallargy Int.5 (3), 1973, 137.
(18)Hakvoort, G., Van den Bleek, C.M., Schouten, J.C., Valkenburg, P.J.M.,
Thermochimica Acta, 114, 1987, 103.
(19)Okutani, T., Furuichi, R., Ishii, T., J. Chem. Soc. Jap.9, 1975, 1485.
(20)Gerritsen, A.W., Soerawidjaja, T.H, Proc. Int. Conf. on Adv. Coal Power Plant
Technology and Hot Gas Cleaning, Dsseldorf, Dec. 24, 1987, V44
(21)Schouten, J.C.Van den Bleek, C.M., Proc. 9th Int. Conf. on FBC, vol. 1, (1987), 749.
(22)Van den Bleek, C.M.Schouten, J.C., Proc. Int. Conf. on Adv. Coal Power Plant
Technology and Hot Gas Cleaning, Dsseldorf, Dec. 24, 1987, V29
(23)Van den Bleek, C.M. and Schouten, J.C.: 9th European Conference on
Environmental Pollution, Corfu, Greece, May 1920, 1988.
(24)Schouten, J.C.Van den Bleek, C.M., The influence of oxygen stoichiometry on
desulfurization during FBC: a simple SURE modeling approach, accepted for
publication at the 10th Int. Symposium on Chemical Reaction Engineering (ISCRE
10), Basle, Aug. 29Sept. 1, 1988.
(25)Schouten, J.C., Ph.D. thesis, Delft Univ. of Technology, March 1988
(26)Valk, M., Bramer E.A. and Toissant, H.H.J., Proc. 9th Int. Conf. on FBCvol. 2, 1987,
53
784.
(27)Hirama, T., Takeuchi, H.Horio, M., Proc. 9th Int. Conf. on FBC, vol. 1, 1987, 898.
(28)Almstedt, A.-E.: Chem. Eng. Sci., 42 (3), 1987, 581.
(29)Almstedt, A.-E.Ljungstrom, E.B., Proc. 9th Int. Conf. on FBC, vol. 1, 1987, 575.
(30)Van Haasteren, A.W.M.B., T.N.O. rep. 86259, The Netherlands,April 1987
(31)Schouten, J.C., Van den Bleek, C.M., SUlfur REtention during FBC of Coal:
Experimental validation and new applications of th D.U.T. SURE modelaccepted for
publication at the 23rd Intersociety Energy Conversion Eng. Conf. (IECEC 23),
Denver, USA, July 31Aug. 5, 1988.
(32)Valkenburg, P.J.M., Schouten, J.C., Van den Bleek, C.M., IEA AFBC Meeting on
Mathematical Modeling, Palo Alto, USA, May 2, 1988.
DEVELOPMENT OF A REGENERATIVE
SULFUR DIOXIDE SYSTEM
Authors:
Contract number:
Duration:
Total budget:
Head of project:
Contractor:
Adress:
B.Kamphuis, U.Spitsbergen
EN3F-0056-NL
36 months 1 July 198630 June 1989
(HFL) 1.930.780, CEC (HFL) 1.003.095,
Dr. U.Spitsbergen
University of Twente
University of Twente
P.O. Box 217
7500 AE Enschede
The Netherlands
Summary
Regenerative sulfur dioxide sorbents based on calcium oxide and on titanium oxideto
be applied during AFBCwere synthesized by agglomeration. This technique as well as
the starting materials were selected considering technical and economical feasibilities.
The sorbents were tested by TG methods and by measurements using a laboratory-scale
AFB reactor.
Calcium oxide based sorbents were prepared having both a mechanical stability
equalling that of the hardest types of natural limestones, as tested, and a sulfur dioxide
capacity sufficient to meet environmental standards. Residual calcium sulfidethough an
unwanted productcontributes as an intermediate to the progress of regeneration
reactions. Multicycle sulfation and regeneration tests showed an optimal regeneration
behaviour below 1100C while differences of sorbent quality faded with proceeding
recycling.
Titanium oxide based sorbents were prepared with which an absorption and
regeneration cycle could be performed at a same temperature. The conversion was nearly
complete but the sulfur dioxide transport per cycle small due to the low content of active
material thusfar. The mechanical strength at high temperatures of these sorbents, as
tested, can be compared with that of the hardest natural limestones.
1.SCREENING AND SELECTION OF POSSIBLE SORBENTS
For the screening of regenerative sorbent materials for AFBC applications the following
criteria are formulated:
- the sorbent must be capable of reducing the sulfur dioxide concentration of the
55
FBC-fluegas within the emission limits,

- the sorbent must be capable of producing a relatively high sulfur dioxide
concentration during regeneration,
- the rate of absorbing and desorbing reactions must not interfere with the total
process,
- the sorbent must have a mechanical stability to allow a repetitive use,
- the sorbent must have an acceptable price/lifetime ratio for economic operation.
A feasibility study, done for the Dutch Management Office for Energy Research (PEO),
shows that the following materials will fullfill the first two criteria (1):
-
calcium oxide
calcium alluminate
barium alluminate
barium titanate
We at Twente University have decided to put our efforts in relatively inexpensive

sorbents with a relatively short lifetime. Our filosofy is that, besides problems of finding
sorbents with a long lifetime, the environment of regenerative sulfur capture processes is
very hostile for the delicate chemical composition and microstructure of the sorbent.
Byproducts of combustion or regeneration, like tar, ash or traces of heavy metals, can
ruin the favourable characteristics of the sorbent.
The first material, calcium oxide, has the disadvantage of a higher desulfation
temperature for producing an acceptable sulfur dioxide concentration during
regeneration. On the other hand it has the advantage to be generally available for a very
low price. For a high reaction rate, the third criterium, the sorbent should have a high
inner surface area, combined with an optimum micro-structure. Natural limestones can be
made to an acceptable sorbent by improving its structure. Agglomeration is a relatively
inexpensive technique capable of manufacturing limestone particles with an attainable
proper inner structure. In agglomeration small particles (particle diameter below 200 m)
are bound together with the use of water and cement. Particles with a diameter between 0,
54 cm are formed. A temperature treatment can be used to improve the strength of the
particles. It has been shown that agglomerates have a large internal volume and a large
mean pore radius (2). During the agglomeration process also chemical compounds can be
added with a positive influence on absorbing and desorbing reactions maintaining the
favourable microstructure.
The second type of sorbent in this research program is based on barium titanate. This
material has advantage of a lower regeneration temperature (1). Barium titanate is not
generally available as a raw material, so it must be synthesized. A carrier of titanium
oxide can be impregnated by a barium compound in such way that during a heat
treatment barium titanate developes. The choice of an inexpensive raw material to form
the carrier as well as the choice of the manufacturing process are of determining
importance.
56
2.CALCIUM OXIDE BASED SORBENTS

2.1.Sulfation behaviour
In first instance a comparison have been made between several commercially available
natural limestones and two of our agglomerates. These experiments are conducted in a 4
cm inner diameter electrically heated fluid bed with a modelgas containing 0.2 vol%
sulfur dioxide (see also (2)).
The following conclusions can be drawn from table I:
- our agglomerates do have a higher sulfation capacity, probably caused by the
favourable microstructural properties like surface area and internal pore volume.
- their mechanical strength can be compared with the most stable natural limestones.
Table I. Microstructure, elutriate and sulfation capacities of some natural limestones and of
Twente agglomerates.
Sorbent
As
prepared/received
Calcined*
Elutriation
Maximum
after
conversion after
calcination
90 min**
Surf .Area
%
(m2/mol)
Pore
Surf.
Pore
Vol.
Area
Vol.
3
2
(m /mol) (m /mol) (m3/mol)
Carmeuse
11 19.106
1506
0.1
0.17
2.106
Engis
Nekami
65 22.106
1663
12.1
0.36
9.106
6
121 18.10
1596
1.6
0.34
Wlfrath
2. 10 6
6
129
1590
<0.1
0.27
DuWa C
18.10
1.10 6
normal
191 31.106
328
<0.1
0.54
C.Si.3
15.106
6
6
250
1518
<0.1
0.51
C.C1.2/S
28.10
17.10
*) Calcined during 15 minutes in a fluid bed with a superficial gas velocity of 1
m/s in an atmosphere of 15% CO2 and 85% N2.
**) Sulfated in a fluid bed with a superficial gas velocity of 1 m/s in an atmoshere
of 0.2% SO2 , 2% O2, 15% CO2 and 82.8% N2.
2.2.Desulfurization behaviour
During desulfurization the following reaction takes place:
57
(1)
Preliminary complete cyclic regenerative testruns were carried out with combined TG
and SO2 analyser.
The sorbent used is C.C1.2/S, with a diameter between 0.50 and 0.85 mm. A
superficial gasvelocity of 0.17 m/s in the TG apparatus was chosen to eliminate gas phase
transport resistances during desulfurization. First the sorbent is calcined during 12
minutes at 850C in an atmoshpere of 15 vol% carbon dioxide 2 vol% oxygen and 83
vol% nitrogen. Then, during 70 minutes 2000 vol ppm sulfure dioxide is added to the
modelgas to produce a standard sulfated state of this sorbent. The conversion reached in
these 70 minutes is 0.640.01. After a purge period with nitrogen, the temperature is
raised to the regeneration temperature and the composition of the model gas is changed to
regeneration conditions. A concentration of 5 vol% hydrogen and 15 vol% carbon
dioxide in 80 vol% nitrogen is used to start with. Both, the change of mass as well as the
sulfur dioxide concentration in the offgasses are measured and recorded. The following
reactions will mainly take place during regeneration:
(2)
(3)
Under the circumstances used, the gasphase reaction of sulfur dioxide with hydrogen can
be neglected. Reaction (3) must be considered as an unwanted side-reaction, because
sulfur remains in the sorbent. This decreases the efficiency of the absorbing/desorbing
cycle. In figure 1 and 2 the results of the regeneration experiments are shown. The
conversion to calcium oxide (figure 1) was calculated with the aid of the sulfur oxide
released by the sorbent. The conversion definitions used were: mols of component i
divided by mols calcium sulfate present at the start of the regeneration. The remaining
calcium sulfate and the formed calcium sulfide were calculated by a mass balance over
the sorbent present in the TGA substracting the amount of calcium oxide formed (figure
2).
At low temperatures the conversion to calcium oxide and sulfur dioxide is low. At
850C only 14 mol % of the calcium sulfate is converted to the desired calcium oxide.
The remaining calcium sulfate reacted according to reaction (3) to form the unwanted
CaS (figure 2). Increasing the temperature improves the conversion of the desired
reaction (2). At 1000C 73 mol % is converted to calcium oxide. To reach complete
conversion to calcium oxide a higher temperature is needed.
At higher temperatures the rate of reaction increases considerably. Only 3 minutes are
needed for a complete reaction at 1000C. The residence times in the regenerator will be
short, leading to energy savings and less degradation by sintering and poisonning.
A third reaction can also take place during regeneration:
58
(4)
This reaction belongs to the category of pseudo-solid-solid reactions and contributes to

sorbent regeneration.
In Figure 3. the regeneration of an agglomerate type of sorbent, it can be seen that in
the first part of the regeneration process no calcium sulfide is being detected. Only after
the conversion of the calcium sulfate, has ceased an amount of calcium sulfide is being
formed. The behaviour is typical with a high selectivity. Selectivity is defined as the
mole-ratio between the formed calcium oxide, the desired product, and the calcium
sulfate as decomposed. A different behaviour can be observed with sorbent s with a low
selectivity like Duwa C Normal. From the start calcium sulfide is being formed, as can be
seen in Figure 4. The conversions to calcium oxide and to calcium sulfide start and
proceed simultaneously.
The results from these two types of data leads to our conclusion that the formation of
CaO is a two step mechanism. The reduction of calcium sulfate to calcium sulfide (3) is
the first step. By a consecutive reaction (4) the sulfur dioxide and the calcium oxide are
formed.
Evidence for the solid-solid reaction (4) is given by the following TG experiments: At
low temperature (850C) the sorbent is exposed to a 5 vol % hydrogen in a nitrogen
atmosphere. Under these circumstances only reaction (3) takes place. The hydrogen flow
is stopped after a calciumsulfide conversion of 0.33 is reached. Further, using pure
nitrogen the temperature is increased to 1000C. Subsequent raising of temperature above
900C results in a sorbent weight decrease as well as an increase of sulfur dioxide content
in the off-gas. Both phenomena argue reaction (4). Direct thermal decomposition of
either calcium sulfate or calcium sulfide can be excluded by experiments: no weight
changes were observed when a) a sulfated sorbent and b) pure calcium sulfide were
heated up to 1050C.
In our opinion the reaction mechanism can be described as follows: First calcium
sulfide is being formed. Depending on the temperature and the amount of calcium sulfate
available around the formed calcium sulfide the consecutive reaction between calcium
sulfate and calcium sulfide (3) takes place. Sorbents with a low calcium sulfate
concentration and a relatively high surface area, like Duwa C Normal or Carmeuse Engis
do not have a high concentration of calcium sulfate at this location for the consecutive
reaction. For this reason their selectivity is low.
The proportion between calcium sulfide being formed and calcium sulfate still present
should be optimal for a high selectivity. Reducing the rate of formation of calcium sulfide
by lowering the hydrogen pressure, has a positive effect on the selectivity.
The phenomenon of calcium sulfide formation at the end of the conversion is caused
by thelocallyabsence of calcium sulfate of this stage. The temperature is of great
importance with this reaction mechanism.
59
2.3.Duration tests
Regenerative sulfur capture is based on the cyclic absorbing and desorbing reactions of a
sorbent with sulfur dioxide. A good regenerative sorbent retains its behaviour for a large
number of cycles.
A number of sorbents has been tested for its chemical behaviour during 8 cycles in the
TGA-apparatus. The tested sorbents are:
-
C.C1.2/S
C.Si.3
Carmeuse Engis
sintered C.C1.2/S
sintered C.C.1.2+A12O3 dopes.
The following procedure is used: a batch of about 25 mg is heated to 850C in the TGA
in an atmosphere of 15% carbon dioxide and 85% nitrogen. After the calcination has
been completed, the first cycle is started. A cycle consists of a number of steps in which
the temperature and/or the gas atmosphere are changed (Table II).
A stabilizing step has been added to oxidize to calcium sulfide formed during
regeneration. Two reactions can take place during this step:
(5)
(6)
Both reactions result in a weight change and its magnitude is a measure for the calcium
sulfide formed during the regeneration. Unfortunate the ratio between reaction (5) and (6)
depends mainly on sorbent and reaction conditions, and complete conversion is seldom
reached (3). For this reason its is not a reliable method for calculating the selectivity of
the regeneration.
Depending on the presence of calcium sulfide, formed during regeneration and not
oxidized during the stabilizing step, the solid-solid reaction reaction of calcium sulfate
and calcium sulfide can take place after the sulfation. Especially when the temperature is
brought to the regeneration level, the conditions for this reaction are favourable (above
950C). Sorbents with a low selectivity during regeneration and with not a complete
conversion during stabilizing, show a considerable extend of this solid-solid reaction (4).
(4)
By this reaction sulfur dioxide is produced, and the weight of the sorbent decreases.
60
Table II. Steps within one cycle
STEP
Name
Temp.
1
sulfation
850C
2
3
4
5
purging
regeneration purging
stabilizing
8501000C 1000C
1000850C
15 CO2
Gas composition O, 2 SO2 15 CO2
5 H2
2 O2
2 O2
15 CO2
15 CO2
(vol%)
balance N2 balance N2 balance N2 balance N2 balance N2
Time (s)
3600
900
600
450
300
Only weight changes can be recorded because of the long runtime of these duration
experiments. This requires different data-analyzing techniques compared with the other
(non-duration) experiments.
An easy evaluation parameter for absorbing and desorbing phenomena is the weight
change related to the start weight. When the weight decrease during regeneration equals
the weight increase during the sulfation the sorbent is completely regenerated to calcium
oxide.
A lower weight decrease indicates two phenomena:
a) the formation of calcium sulfide;
b) the remaining of calcium sulfate, i.e. not complete conversion during regeneration.
From paragraph 2.1. it can be concluded that with agglomerates the conversion is always
nearly complete. With the assumption of complete conversion the selectivity can be
calculated from the weight changes. When 90% of the weight remains, this means a
molecular selectivity of 50%, when 98, 3% remains the selectivity is 91%.
Attention must be paid to include the calcium sulfate formed during the stabilizing step
and the already regenerated sorbent by the solid-solid reaction (3). The results of the
duration test are illustrated by an example in figure 5. All sorbents show a considerable
drop in sulfation capacity after the first cycle. Especially regeneration at 1100C causes a
decline of about 100%. This effect is mainly caused by a deteriotation of the sorbent
structure by sintering during regeneration. Although, the payload during the first cycle,
by a better selectivity at 1100C, gives a better result. But the cumulative effect of all
cycles indicate a better total result with a lower regeneration temperature. The
regeneration temperature is to be considered as an optimizing parameter. The different
sintering behaviour of sorbent causes gradually a shifting of the sorbent quality. C.Si.3
has a better first cycle, but the difference with C.C1.2/S disappears, after an increasing
number of cycles.
61
3.TITANIUM-BASED SORBENTS
3.1.Starting materials
Preparation and testing of titanium-based sorbents is started. The active part in this type
of sorbent is formed by barium-titanium compounds. In first instance attention is
focussed on sorbents consisting of a titaniumoxide carrier provided with a bariumoxide
layer. This bariumoxide layer is introduced by impregnation.
Chosen is a relatively cheap titaniumoxide powder containing iron impurities with a
mean particle size of<15 um. X-ray diffraction methods showed iron mainly in the form
of iron (II) titanate (Fe2Ti2O4) . Advantages of this material are a higher crushing
strength and a lower price. A disadvantage of this material is the reduction-oxidization of
the iron compound during the regeneration and absorption cycles. Measurements
appeared to be complicated by this side-reaction.
Because the original material is lacking a favorable microstructure, agglomeration is
applied. The agglomeration procedure corresponds to the method used for limestone. The
cement used is silicate. Batches with various amounts of cement are prepared (see table
III).
3.2.Mechanical stability
Testing of the mechanical stability of the prepared sorbents is carried out by measuring
the amount of elutriated material in a fluidized bed with an inner diameter of 4 cm.
Superficial gas velocity in the bed is 1 m/s, gas consists of pure nitrogen. A special
bottom plate is designed in order to increase the amount of attrition in the bed. Batches of
25 g are used. Elutriate is collected by a cyclone, and captured on electrostaticly charged
quartz wool kept in a flask. Tests are done at 20C (cold- elutriation) and 850C (hotelutriation) . For comparison purposes several natural limestones are also tested in this
experimental set-up. Results are given in table III.
The mechanical stability of the prepared barium- titanium sorbents depends on its
cement contents. Optimization of this amount together with the application of other
cement types will be carried out.
Table III. Cold and Hot Elutriation Tests
Name
type of
sorbent
T.Si.2
T.Si.3
T.Si.4
T.Si.5
Carmeuse
BaO.TiO2
BaO.TiO2
BaO.TiO2
BaO.TiO2
limestone
elutriation
0.5<Dp<0.85
cold
hot
68
26
9
0.1
9.6
8.0
3.2
1.2
0.0
(wt% of input 0.85<Dp<1.0

mm)
cold
hot
28
0.8
23
0.4
5
0.4
0.4
Engis
Duwa C.
Normal
Nekami
62
limestone
0.0
limestone
51
22.4
amount together with the application of other cement types will be carried out.
The difference between hot and cold elutriation is probably caused by the sintering
behaviour of the sorbent. It can be concluded that a high temperature has a beneficial
effect on the strength. Optimization can improve the results.
3.3.Sulfation/regeneration behaviour
During the sulfation and regeneration of titanium based sorbents the following reactions
takes place:
(7)
(8)
One of the main advantages of bariumtitanate as a sorbent for sulfur dioxide capture is
the possibility of regenerating at a relative low temperature at 850C, without the
formation of sulfides (3). According to thermodynamical calculations the main reactions
are (7) and (8). The presence of titaniumoxide, causing the formation of bariumtitanate,
allows energetical the lower regeneration temperature.
Sulfation and regeneration runs are carried out with the TGA apparatus as described in
2.2.
The following results are obtained from the titanium based sorbents T.Si.3, T.Si.4 and
T.Si.5 (table IV). The conversion is calculated as the molar conversion of the barium
present. For all sorbents a high conversion is achieved. An explanation can be found in
the fact of the relatively high surface areas of the titanium based sorbents and the fact of
the absence of a thick productlayer, as a consequence of the relative low amount of
bariumoxide present.
Table IV. Regeneration of titanium-based sorbents. Payload compared with calcium-based
sorbents (regeneration at 850C resp. 1000C with 5% H2)
Name
Type of sorbent
T.Si.3
T.Si.4
BaO.TiO2
BaO.TiO2
Maximum conversion
Pay-load
(mol SO2/kg sorb.)
0.97
0.85
0.20
0.22
T.Si.5
BaO.TiO2
C.C1.2/S Limestone
C.Si.3
Limestone
0.96
0.56
0.63
63
0.21
6.17
7.32
The performance of this type of sorbents compared with the practical requirements, is
bad. The pay-load, the ratio of moles sulfur dioxide transferred from absorption to
regeneration per kilo sorbent is low in contrast with the calcium based sorbents, as can be
seen from table IV. Pay-load values for calcium based sorbents are approximately 30
times higher.
To select a proper sorbent, its cyclic behaviour for a large number of absorption
desorption reactions should be considered. Therefore, duration tests for 5 cycles are
carried out with the sorbent T.Si.5. The procedure used is the same as already described.
However, an oxidizing step has been added before each sulfation to reduce the influence
of the iron-compounds. Results of these experiments are given in figure 6. Probably the
constant value of the sulfation weight increase and the regeneration weight decrease after
three cycles is due to the low regeneration temperature (850C), minimizing sintering
effects.
ACKNOWLEDGEMENTS
The support of the Commission of the European Communities made this research
possible.
Assistance in this research came from Mrs. A.W.Potma, E.H.T.M. Weltering and
H.A.Akse.
REFERENCES
(1)Kamphuis, B. and Spitsbergen, U. (1986). De haalbaarheid van Regeneratieve
Zwavelvangst. Report PEO-contract nr. 4.351, jobnr. 1.1.2
(2)Akse, H.A., Spitsbergen, U., Kamphuis, B. and Vincent, Ch.J. (1985). Het
vergelijkend Kalkonderzoek. Report PEO-contract nr. 4.351, jobnrs. 1.1.1 and 1.1.3
(3)Taylor, T.E. (1980). NOx Control through Staged Combustion in Fluidized Bed
Combustion Systems. Proceedings of the 6th International Conference on Fluidized
Bed Combustion, Atlanta.
64
Figure 1: Conversion to calcium oxide during calcium sulfate regeneration
(sorbent C.C1.2/S in 5% H2)
Figure 2: Fraction of remaining calcium sulfide as formed during calcium
sulfate regeneration
(sorbent C.C1.2/S in 5% H2)
Figure 3: Regeneration of an agglomerate
(sorbent C.C1.2/S in 5% H2 at 950 C.)
Figure 4: Regeneration of a natural limestone
(sorbent Duwa C Normal in 5% H2 at 1050 C.)
Figure 5: Sulfation/regeneration weight changes in TG during 8 cycles of a

calcium oxide based sorbent
(sorbent C.Cl.2/s in 5% H2).
Figure 6: Sulfation/regeneration weight changes in TG during 5 cycles of a

titanium oxide based sorbent
(sorbent T.Si.5 in 5% H2).
CLOSED LOOP CONTROLLED INTEGRATED

HOT GAS CLEANUP
Author :
Contract number :
Duration :
Total budget :
Head of project :
Address :
Contractor :
Address :
J.ANDRIES
EN3F-0028-NL
36 months June 1, 1986May 31, 1989
Hfl. 3.024.000 CEC contribution: Hfl. 1.094.460
Drs . J.Andries
Laboratory for Thermal Power Engineering
Rotterdamseweg 139A
2628 AL Delft
The Netherlands
Julianalaan 134
P.O. Box 5
2600 AA Delft
The Netherlands
Summary
The availability of hot gas clean up systems which can meet environmental regulations
and protect other system components is essential for the introduction of advanced coal
conversion processes. Granular bed filtration is considered as a promising technique. This
report describes the progress in the project during the first 2 years. During the operation
of the sub pilot-scale pressurised fluidised bed combustor a number of experimental
problems were experienced. The coal feed system, the construction of the bottom part of
the first cyclone and the operating procedure were modified. The influence of operating
parameters on the elutriation of solids from the combustor and the operation of the two
high temperature cyclones has been determined. Laboratory-scale test rigs which are used
for the development of on-line, in-situ particulate measurement systems, recycle cyclones
and electrostatic enhancement of granular bed filtration have been designed and built.
Measuring instruments for the determination of electrostatic-, flow- and sintering
properties of ash and filter materials at high temperatures and the in-situ charge of
particulates in the exhaust of a PFB combustor are under development and some
preliminary results have been obtained.
1.INTRODUCTION
The availability of hot gas clean up systems which can meet environmental requirements
Closed loop controlled integrated hot gas cleanup
69
and protect the gasturbine and other system components at changing conditions (plant
start-up, shut-down and turndown) will enable the introduction of energy-efficient and
environmentally acceptable advanced coal-conversion processes (PFBC, coal gasification
and direct coal-fired gasturbines) and improved or new high temperature processes in the
process industry.
Conventional filter systems can not meet the requirements at high temperatures (>850
C) and pressures (>10 bar) and advanced filter systems are not available at this moment.
In June 1986 an EC sponsored research and development project on hot gas clean up
has been started, which is aimed at the development, construction and operation of a gas
cleaning system at a temperature of 850 C and a pressure of 10 bar. As the test bed an
experimental pressurised fluidised bed combustor is used, which has a thermal output of
1.6 MW.
The philosophy of the project is that advanced gas cleaning equipment should be
continuously monitored and controlled. The dust loading presented to the equipment
varies enormously during a continuous process and optimal performance coupled with
certainty can only be obtained with an instrumented and controlled plant.
The main objectives of the program are:
o characterization of the hot gas stream at different points of the installation using
advanced in-situ, on-line instrumentation,
o the investigation of the performance of high temperature gas cleaning equipment
(cyclones, granular bed filters),
o the investigation of electrostatic enhancement of hot gas clean up processes,
o the investigation of fluidic elements to control hot dust laden gas streams,
o the design and construction of a closed-loop controlled hot gas clean up system.
The final aim of the program is to proof the concept of a closed loop controlled integrated
hot gas clean up system at sub-pilot scale in the exhaust of a pressurised fluidised bed
combustor.
In order to achieve this aim the following subsystems will be developed:
o reliable on-line instrumentation for the characterization of hot coal-derived gas
streams (solid and gaseous components) which can be used for the determination
and real-time monitoring of the performance of hot gas clean up systems,
o a hot gas clean up system which is suitable for controlled operation. At this moment
granular bed filtration is considerd as the most promising technique because of the
relatively easy control of the composition of the bed material and the possibility for
electrostatic enhancement of the filter performance,
o a system to control the operation of the hot gas clean up device in order to obtain an
optimal system performance at changing conditions (electrostatic enhancement, and
switching of hot gas streams using power fluidics).
The systems will be developed and tested in the exhaust of the pressurised fluidised bed
combustor of the Laboratory for Thermal Power Engineering in Delft.
Experimentally, the programme is being carried out in a dual fashion. Prototype
equipment is being installed on the fluidised bed test rig which uses the best available
70
technology of the present time. This part of the programme subjects the system to real
and difficult conditions and defines what now is possible, the state of the art.
At the same time a number of ancillary experiments are being carried out under
simpler or ideal conditions in order to expedite the development of the equipment designs
in some novel ways, either improvements of the existing system or components which are
not yet available.
The program will run until June 1989 and is executed by the Laboratory for Thermal
Power Engineering in cooperation with the Laboratory for Particle Technology and TNO.
2.HIGH TEMPERATURE, HIGH PRESSURE TEST FACILITY
2.1The combustor
Since the beginning of the research program on pressurised fluidised bed combustion
there have been 3 versions of the combustor which are described in (1). The latest version
of the combustor, which was commissioned in 1984, is shown in figure 1, the main
design data are given in table 1. A more detailed description is given in (1), (2), (3) and
(4).
Compressed air produced by two high pressure compressors of the nearby Laboratory
for Aero- and Hydrodynamics, is supplied to the combustor by a control valve and enters
the bed through a nozzle type air distributor, after it has been preheated in the annulus
between the pressure vessel and the heat resistant inner vessel. At pressurised conditions
the pressure and the fluidisation velocity are controlled by respectively the inletand the
outlet control valve.
The vertical in-bed heat exchanger and the pressure vessel cooling system are part of a
closed circuit filled with demineralized water. The heat release is adjusted by varying the
bed content and hence the cooling surface immersed in the bed.
Coal and gas can be supplied to the combustor respectively via the top and the bottom
of the bed. The combustor can also burn light oil, which is supplied through atomizers
placed inside the distributor plate nozzles By means of three solid feed systems, each
using a screw feeder, coal, inert bed material and sorbent material are fed pneumatically
downwards into the combustor through a common vertical feed pipe. By a pressure lock
system the pressurised storage bunkers are periodically filled from atmospheric ones.
The solids feed pipe, which enters the combustor vessel above the bed surface, initially
ended immediately after entering the inner vessel but it was later extended vertically to
0.2 m above the air distributor plate. In the third quarter of this year a new feed system
will be installed which will inject the solids pneumatically upwards through the air
distributor plate into the combustor.
The latest version of the combustor uses a nozzle type air distributor. In every nozzle
an atomizer is mounted to supply natural gas or oil to the fluidisation air. The freeboard
region is heavily insulated and free of internals to enable unobstructed experiments on
freeboard phenomena.
Due to limitations of the air supply, the installation can be used only two days a week.
This means that the installation has to be started up in the morning, runs for about 8 hours
71
and is shut down at the end of the day. An independent air supply, enabling longer test
runs, will be installed later this year.
Table 1: Main design data of the combustor
MAIN DESIGN DATA

Bed diameter
Static bed height
Freeboard height
Operating pressure
Fluidisation velocity
Air distributor
Heat exchanger
0.49 m
0.31.5 m
2.63.8 m
0.11.0 MPa
0.81.8 m/s
nozzle plate
water cooled,
vertical pipes
1.6 MW
Maximum thermal capacity

Table 2: Main properties of the coals
MAIN PROPERTIES OF THE COALS

(approximate analysis, dry)
anthracite
Colombian
Polish
ash
(%)
3.6
11.2
8.4
(%)
8.5
35.2
28.9
volatiles
(%)
87.9
53.6
62.7
fixed carbon
(MJ/kg)
34.4
29.5
28.0
higher heating value
2.2Hot gas clean up system
During 1986 the test rig has been extensively modified. A sketch of the installation
including the granular bed filter is given in figure 2.
The original water-cooled cyclone has been replaced by two standard high efficiency,
high temperature cyclones. The design of the cyclones is based on standard, textbook,
design rules.
The cyclones, made of a heat resistant metal alloy, are installed in two identical
pressure vessels. The space between the outside wall of the cyclones and the pressure
vessel wall is filled with heat insulating material (kao wool type material). The diameter
of the first cyclone is 0.3 m, the diameter of the second cyclone is 0.2 m.
After the first series of experiments, which ended in June 1987, an air cooling system
for the bottom part of the cyclone has been installed to keep the wall temperature at a
reasonable level (figure 3). The heated air coming out of the cyclone cooling system was
originally directly used as transport air for the coal feed system. After it became clear that
the temperature in the coal feed pipe became so high that under certain operating
conditions the coal started to burn in the feed pipe, the air was cooled down before being
used as transport air for the solids feed system. The hot gas ducting consists of two
72
concentric pipes. The outer one serves as the pressure containment. The inner pipe has a
diameter of 0.1 m and the space between this pipe and the outer one, which has a
diameter of 0.5 m, is filled with a kao-wool type heat insulating material. The cyclones
and the inner duct are made of Thermax 4742 (DIN 1.4742) heat resistant steel.
The solids captured by the first cyclone are periodically removed and weighed by an
automatically controlled ash removal system and can be reintroduced discontinuously
into the solids feed system (figure 3) . The solids captured by the second cyclone are
currently removed by a manually controlled lock hopper system. An automatically
controlled ash removal system, similar to the one used for the first cyclone, will be
installed in the second quarter of this year.
Arrangements have been made to enable the installation of a fixed granular bed filter
after the two cyclones in the third quarter of this year. At the same moment isokinetic
sampling systems will be installed in the in-and outlet of the granular bed filter. The
filter, which has a diameter of 0.4 m, will be able to clean a variable part (1075 %) of
the exhaust gas stream. It will be used to study the influence of several parameters (filter
velocity, fly ash composition, electrostatic charging and polarization) on the collection
processes.
The fixed granular bed filter will be replaced by a moving granular bed filter in the
beginning of 1989.
2.3Emission measurements
The modified installation was started up for the first time in January 1987. The main
purpose of the test program, which was started then, was to assess the influence of
operating parameters on the elutriation of solids from the combustor and to determine the
effectiveness of the two high temperature cyclones. Due to operational problems, which
will be described later, this part of the project took considerable more time than planned
and was completed in April 1988.
Up till now three different types of coal have been used. The main properties are given
in table 2. All experiments up till now used a sand bed. The diameter of the bed material
is 850 micron.
2.3.1Experiments without cyclone cooling
During these experiments the first cyclone was uncooled. The operating conditions are
given in table 3.
All experiments, except one, used anthracite. During one of the last tests a Colombian
coal was burnt for a number of hours.
The first experiment with the high temperature cyclones showed that the combustion of
carbon-containing fly ash in the bottom part of the first cyclone caused an unacceptable
rise of the wall temperature. This resulted in melting of the bottom part of the first
cyclone after the coal feed was stopped at the end of the first experiment.
After implementing a number of modifications in order to improve the thermal
behaviour of the first cyclone, experiments were done with low excess air levels but this
resulted in high elutriation rates of unburnt carbon, which counteracted the beneficial
73
effect of low oxygen levels on the temperature rise of wall of the first cyclone. The low
excess air levels resulted in low NO and high SO2 and CO outlet concentrations.
At higher excess air levels the elutriation of unburnt carbon decreased substantially
having a beneficial effect on the wall temperature of the bottom part of the first cyclone.
The use of high volatile coals (Colombian and Polish) instead of anthracite increased the
range in which the installation could be operated without endangering the structural
integrity of the first cyclone.
The size distributions of the fly ash captured by the first cyclone using anthracite and
the Colombian high volatile coal are shown in figures 4 and 5. The fly ash from the high
volatile coal is clearly much smaller than the fly ash from the anthracite.
At higher combustion intensities (pressures above 6 bar) the wall temperature of the
first cyclone still rose to unacceptable levels. Therefore it was decided to install a cooling
system for the bottom part of the first cyclone using the coal feed transportation air.
2.3.2Experiments with cyclone cooling
After installation of the cyclone cooling system and some other modifications a second
series of experiments was started, which ran until the end of April 1988. The operating
conditions of the first series of experiments are given in table 4. All experiments are done
with a Polish high volatile coal. An example of the operating conditions and emission
data is given in figure 6. The graphs represent data which were sampled every minute.
The gas analysis graph is based on bidirectionally smoothed data.
The cooling of the bottom part of the first cyclone causes a flue gas temperature drop
of about 50 C in the first cyclone. The heated air from the cyclone cooling system,
which has a temperature of about 200 C was originally directly used as coal feed
transportation air. Heat transfer from the freeboard and the fluidised bed to the air in the
coal feed pipe increased the temperature to 500 C at the end of the coal feed pipe. To
avoid burning of the coal in the feed pipe the coal feed air is cooled to 60 C before it
enters the coal feed pipe. The temperature of the air leaving the end of the coal feed pipe
is approximately 300 C, which means that devolatilization of the high volatile coal starts
already in the coal feed pipe. To avoid future problems caused by this premature
devolatilization a new coal feed system, which injects the coal pneumatically upwards
through the air distributor plate into the combustor will be installed in the third quarter of
this year.
Table 3. Operating conditions (uncooled cyclone)
date
870402
870402
870402
870402
pres flui bed coal bed O2 CO NO SO2 catch carbo catch carbo
velo con supp temp
cyc11 cyc11 cyc12 cyc12
bar m/s kg kg/h C % % ppm ppm kg/h % kg/h %
4.0 0.93 145 66 910 1.4 0.16 57 1000 10.2
74 0.29
17
4.0 1.00 145 66 895 2.6 0.21 81 924 9.2
0.22
4.3 1.00 145 66 925 3.0 0.18 101 915 8.2

0.29
4.5 1.00 145 66 915 3.8 0.02 91 883 7.7

74 0.34
11 *
74
870407 4.5 1.00 145 75 912 2.2 0.20 69 982 10.1

69 0.29
870407 4.5 1.05 145 75 903 2.7 0.16 76 938 9.6
0.26
870407 4.5 1.05 145 70 885 3.6 0.16 88 900 10.2
0.21
870407 4.5 0.90 145 72 880 2.3 0.21 67 947 7.8
0.19
870407 4.5 0.90 145 70 905 2.3 0.03 68 947 8.9
77 0.30
870407 5.0 0.90 145 70 935 2.4 0.15 88 938 7.3
69 0.16
870409 5.5 0.90 155 73 875 3.8 0.14 92
7.3
0.28
870409 6.0 0.80 176 83 885 1.4 0.10 57
7.7
62 0.23
870409 6.0 0.85 176 83 885 2.7 0.01 47
7.4
0.26
870409 6.0 0.80 176 79 850 2.2 0.09 78
7.0
0.24
870409 6.0 0.80 186 83 850 2.8 0.02 46
7.3
0.23
870414 5.0 1.00 160 88 855 3.0 0.14 83
10.2
66 0.29
870414 5.0 1.00 170 87 855 2.3 0.09 66
11.0
0.38
870414 6.0 0.95 190 89 870 3.0 0.03 78
10.6
0.35
870416 5.0 1.00 160 84 885 2.0 0.10 67
7.7
67 0.18
870612 5.0 1.00 161 84 860 1.5 0.10 74 547 9.9
0.07
870612 5.0 1.00 161 83 937 1.1 0.03 72 553 8.0
73 0.12
870612 5.0 1.00 161 80 895 2.5 0.05 96 477 8.0
0.06
870623 5.0 1.00 136 68 910 5.6 0.02 129 370 5.6
0.05
870623 5.0 1.00 136 68 855 6.2 0.21 124 386 6.5
87 0.07
870625 5.0 1.00 142 68 890 6.0 0.05 172 387 5.6
71 0.10
870625 5.0 0.90 149 62 880 4.3 0.05 125 283 5.8
0.33
870625 5.0 0.90 149 84 874 4.7 0.04 138 438 6.9
28 0.15
870630 6.0 1.00 165 78 880 5.3 0.08 108 281
870630 6.0 0.95 165 77 905 4.3 0.06 100 283
* Gas analysis after first cyclone (other experiments before first cyclone)
** Colombian coal (other experiments with anthracite)
12
11 *
9
9
*
*
7
*
3
5
**
Table 4. Operating conditions (cooled cyclone)
date
880225
880303
880308
880310
880310
880315
880315
880317
880317
pres flui bed coal bed O2 CO NO SO2 catch carbo catch carbo
velo con supp temp
cyc11 cyc11 cyc12 cyc12
bar m/s kg kg/h C % ppm ppm ppm kg/h % kg/h %
5.0 1.00 150 62 808 8.1 171 146 300 5.0
0.38
_
5.0 1.00 178 61 826 5.0 81 81 390 6.1

5.0 0.90 109 50 845 10.1 192 19? 231 3.2
_
_
_
5.0 0.80 106 47 868 9.5 227 227 237 3.0
0.31
_
0.39
5.0 0.80 106 48 846 10.0 215 215 258 3.0

5.0 1.00 109 61 849 9.4 205 205 271 4.2
0.38
6.0 0.80 109 59 845 9.6 200 200 232 3.1

0.33
4.0 1.00 92 44 852 10.1 228 228 270 3.6

0.34
_
0.35
4.0 0.90 92 45 851 9.9 236 236 242 3.2
75
During the last part of this test period the solids recirculation system has been tested
for a longer period of time and the influence of the addition of sorbent material
(dolomite) on gaseous and particulate emissions has been determined with and without
solids recirculation.
The size distribution and chemical composition of the fly ash captured by the two
cyclones are currently determined. The results of these analyses and a more detailed
discussion of the gaseous emission measurements will be given in the next progress
report.
3ANCILLARY EXPERIMENTS
3.1Development of on-line measurement systems
The design and construction of an atmospheric high temperature test rig, which will be
used for development and testing of on-line particulate measurement instruments have
been delayed but the design of the test rig has recently been completed and construction
will start in July 1988.
The main design data are:
gas flow
gas temperature
dust concentration
gas velocity
pipe diameter
: 150300 Nm3/h
: 8001000 C
: 020 g/Nm3
: 1632 m/s
: 0.10 m
A forward light scattering particle counting instrument will be tested immediately after
the construction of the test rig will be completed. A second on-line measurement
instrument using fiber optics will be tested after the forward light scattering particle
counter has been installed in the high temperature, high pressure test rig.
3.2Cyclone test rig
The experimental problems with the high temperature, high pressure test rig showed that
the first high temperature cyclone which is used to separate reacting particles from the
gas stream is a critical component of the system. The coupling of gas flow, particle flow
and particle combustion presents a complicated problem which has to be solved in order
to achieve the aim of the project. More experimental and theoretical research is needed to
enable a reliable design of this essential part of many advanced coal conversion systems.
For this purpose an atmospheric test rig with a glass cyclone has been designed and
built to enable flow visualization experiments which will be used to study the influence
of underflow on the gas flow pattern and the particle trajectories in the bottom part of the
cyclone. The main design data are:
Gas flow
: 150300 Nm3/h
Inlet gas velocity

Cyclone diameter
Dust concentration
76
: 1836 m/s
: 0.15 m
: up to 15 g/Nm3
3.3High temperature electric properties of fly ash and filter material

The electrical properties of a material can be determined from the complex impedance of
a cylindrical capacitor filled with this material. Two (platinum coated) alumina cylinders
define a capacitor gap of 5 mm width and 60 mm inner diameter. The height of the
cylinders is 80 mm. The electrodes of the capacitor gap are made of platinum, which is
burned onto the alumina at 1350 C.
The test cell is placed In a cylindrical oven with a diameter of 100 mm and a height of
100 mm, heated with an electrical coil. Because fly-ash material may contain a
substantial amount of carbon the high temperature measurements are being performed in
an atmosphere of dry nitrogen.
The experimental set-up has been used to measure the conductivity of filter bed
materials (sand and alumina) and the electric properties of some fly ashes. Alumina is
shown to be better suited for an electrified granular bed filter at high temperatures than
sand.
The fraction of the fly ash from a pressurised fluidised bed combustor captured in the
first cyclone has a high carbon content and is found to be rather conducting. The fly ash
captured in the second cyclone is shown to be a dielectric material with properties similar
to that of sand. A more extensive description of the test cell and the results is given in (5).
3.4In-situ measurement of particle charge
A technique for the in-situ measurement of the electrostatic charge of fly ash particles has
been selected and preliminary measurements have been performed in order to explore
whether it can be used for in-situ measurements in the high temperature, high pressure
test rig.
A variable air flow (1.58 m3/h) with NaCl particles (diameter: 0.10.5 micron) is
produced and guided through the measuring section. The particles can be charged by a
corona charging device.
In the measuring section, a part of the gas flows between the two capacitor plates. One
of the plates, made of brass, is connected to a variable high voltage DC power supply.
The other plate consists of an insulating plate (PVC), on which sheets of brass are glued
on both sides The two central sheets are the measuring electrodes (the first upstream with
respect to the air flow, the second downstream), which can be connected to the
electrometer seperately or together (in the first case the other electrode is grounded). The
electrometer measures the current. This current is recorded on the stripchart recorder. The
other sheets on the insulating plate (the strips near the cylinder wall and the sheet on the
back side) are grounded.
Experiments showed that reentrainment of fly ash particles can influence the
measuring results and work is going on now to find a method to avoid reentrainment or a
77
method to correct for the influences of reentrainment. A suitable probe for the high
temperature, high pressure test rig will be installed in the next 6 month period.
3.5Flow properties and agglomeration behaviour
The current program at TU Delft dealing with the mechanical design (i.e. powder flow
mechanics) of a moving granular bed filter (MGFB) is tailored specifically towards
addressing the problem of granule cohesion/flowability and consists of three phases:
o development of a skeletal understanding of the mechanisms behind fly ash sintering
as well as the factors influencing such mechanisms such as interparticle load, the
presence of volatile alkalies, and time of compaction. Fly ash sintering rates,
morphology, surface chemistry, and bulk chemistry are being studied by a
combination of pressure dilatometry, XRD, XRF and SCM/EDAX,
o design and construction of a high temperature shear cell to measure granule
flowability,
o provide a conceptual design of a high temperature MGFB based on a knowledge
obtained during the two first phases and current experience of low temperature
MGFBs.
An initial study of anthracite fly ash sintering using pressure dilatometry has been
undertaken at City College (New York, NY). Degassed fly ash material from the second
cyclone provided by TNO was selected as a sample to allow comparison to available
conductivity measurements. The elongation of a small sample of ash (approx. 0.2 grams)
under a compacting load of 25 grams (sample diameter of 5 mm) is measured as a
function of temperature under a sample heating rate of 3 C/min. (See (6) for details of
the CCNY dilatometer and method.)
Since most sintering mechanisms (but not all) result in powder densification, the
temperature at which sintering is assumed to become significant (Ts) is marked by a
beginning of a contraction of the sample. The measured constant heating rate dilatometry
curve for the degassed second cyclone material indicates an initial sintering temperature
of approximately 850 C. This initial sintering temperature agrees with recent TNO
conductivity measurements of anthracite fly ash heated to 1000 C where the formation
of bond necks between ash grain leads to marked increases in overall sample
conductivity.
The sintering of fly ash would be expected to be composed a number of mechanisms
such as diffusional flow involving the oxides, low melting eutectics and glass
components contributing by viscous flow, and volatiles and alkali constituents
contributing to sintering by evaporation and condensation. It is desirable from a MGFB
design standpoint to establish at least a crude knowledge of the dominating mechanisms,
if any, since filtration design parameters such as intergranule load, gas pressure, and time
of static compaction for an intermittantly operated bed will effect each sintering
mechanism to a different degree.
78
3.6Electrostatic enhancement
A glass test rig with an electrostatically enhanced granular bed filter has been designed
and built in collaboration with the High Voltage Engineering Laboratory of the
Department of Electrical Engineering. The experiments started in January 1988.
A laser system integrated with a windtunnel circuit at the Laboratory of Chemical
Engineering will be used for the investigation of the electric mobility of small particles in
an oscillating electric field. The experiments started in January 1988.
The aim of the experiments in the two rigs will be the investigation of the effect on
filtration behaviour of the filter of fly-ash particle charging combined with an oscillating
electrical field applied to the granular bed filter. To analyse the penetration a calibrated
feed system is used in combination with a particle counting device which is based on
aerosol scattering techniques. Using this counting device before and after the granular
bed filter the influence of adjusting the electrostatical parameters will be analysed.
The following parameters will be varied:
- AC field strength
- AC frequency range
- particle charging voltage range
- granular bed material size
- granular bed material
- granular bed height range
- laden gas flow inside the rig
- flyash load of the gas
- flyash particle size
: 0 to 60 kV
: 25 to 1500 Hz
: 0 to 100 kV
: 1400 to 2000 m
2000 to 3000 m
: aluminiumoxyde
: 0 to 0.40 m
: 30 to 90 m3/s
: variable; probably 500 ppm
: d10=6m, d50=17 m
d90=42 m
The first electrical geometry to be tested is a configuration with two half-cylinder

electrodes on a cylindrical bed with an inner diameter of 0.20 m. As soon as some
indication is obtained about effective AC electric field strength and frequency ranges,
arrangements will be made for supporting the filtration experiments with laser Doppler
measurements in the wind tunnel circuit. These arrangements consist of the design of an
electrode system and an electric power source.
ACKNOWLEDGMENTS
This research is supported by the Dutch Ministry of Economic Affairs (PEO contracts
20.360110.10 and 20.360110.11), the European Community (contract EN3F-0028-NL
(GDF), TNO and Stork Boilers.
79
REFERENCES
1.J.Andries. The Delft experimental pressurized fluidized bed testfacility. Paper
presented at the second biennial PFBC power plants utility conference, June 1820,
1986, Milwaukee, Wn, USA.
2.J.Andries. Hot gas cleanup research on the Delft pressurisedfluidised bed combustion
test facility. Paper presented at the 9th international conference on fluidized bed
combustion, May 37, 1987, Boston, Ma, USA.
3.J.Andries. Hot gas cleanup research at the Delft pressurisedfluidised bed combustion
test facility. Paper presented at the International ConferenceAdvanced coal power
plant technology and hot gas cleaning, December 24, 1987, Dusseldorf, RFC.
4.D.Boersma,
und
K.R.G.Hein.
Emissionsuntersuchungen
an
einerDruckwirbelschichtfeuerung.
Paper
presented
at
the
International
ConferenceAdvanced coal power plant technology and hot gas cleaning, December
24, 1987, Dusseldorf, RFC.
5.P.de Haan, et al. Electrical characterisation of filter bedmaterial and fly ash at high
temperature. Paper presented at the third international conference on electrostatic
precipitation, October 2529, 1987, Abano, Italy
6.P.Compo, R.Pfeffer and G.I.Tardos, (1987), Powder Technology, (51), 1, p85
7.J.Andries, et al. Closed loop controlled hot gas clean up.Periodic report for the period
June 1. 1986 to November 30. 1987. Delft: Delft University of Technology, December
1987.
Figure 1: The Delft pressurised fluidised bed combustor
Figure 2: The Delft hot gas clean up test facility
Figure 3: Cyclone cooling and solids recirculation system
Figure 4: Size distribution of the fly ash captured by the first cyclone
(experiment 870625, anthracite)
Figure 5: Size distribution of the fly ash captured by the first cyclone
(experiment 870625, high volatile coal)
Figure 6: Operating conditions and emissions during experiment 880308
ELECTROMULTICYCLONE FOR COAL

BURNER EXHAUST GAS CLEANING
Authors :
J.N.DUMONT*, P.AULARD*, J.VENDEL**, M.RAMEL***
Contrat number : EN3F-0035-F (CD)
Duration :
37 months 1 October 198630 October 1989
Total budget : FF 4 800 000 CEC contribution : FF 2 400 000
Head of project : J.N.DUMONT, BERTIN et Cie
Contractor :
BERTIN et Cie
Address :
Zone industrielle des Gtines
78373 PLAISIR CEDEXFrance
* BERTIN et Cie
** COMMISSARIAT A LENERGIE ATOMIQUE
*** CERCHAR
SUMMARY
Following a former project where a tangential entry electrocyclone was built and tested,
the present project deals with the demonstration of economic and technical validity of an
electromulticyclone for coal burner exhaust gas cleaning. The first phase of the project is
being completed. A single cell of electrocyclone, adapted from a commercial
multicyclone cell, was built and tested in laboratory and industrial conditions. Electric
insulation was improved, electrode geometry optimized, and a rapping defouling device
was installed and tested. Results show that electrostatic collection efficiencies of 50% to
80% could be attained with modified cyclones where residence time would be increased.
1.INTRODUCTION
During the years 1983 to 1985, a joint research programme was pursued by the French
Commissariat lEnergie Atomigue and Bertin et Cie. During this programm, a 0, 25 m
diameter modular electrocyclone was constructed and tested. It was a tangential entry
cyclone derived from Stairmand design with a ceramic vortex finder. The gas flow was
280 m3/h. It showed promising performances, reducing by up to 80% the particle
emission, despite the good efficiency of the cyclone itself.
On the basis of these results, the objective of this new project was to demonstrate the
technical and economic viability of an electromulticyclone for coal burners. Thus the best
compromise was sought between improvement of collection efficiency and acceptable
increase of cost. For this research, the laboratory tests were performed by CEA and the
industrial tests were performed on the experimental platform of CERCHAR, at
86
Mazingarbe (France).
2.PLANNING OF THE RESEARCH
The project was divided into 2 phases :
Phase 1 (21 months), whose objectives are, on the basis of a single cell:
- to optimize the electrode geometry and voltage
- to define a new cell geometry, made from more common materials and equipped
with defouling device
- to test this second electrocyclone on a pulverized coal boiler of CERCHAR, in
Mazingarbe
- to establish a first assessment of the economic viability of the process.
Phase 2 (16 months), whose objectives are to build an electromulticyclone pilot and test
it at different operating rates, with differents coal types, for long duration runs.
3.WORK STATUS AND FURTHER PROGRESS
Phase 1 will be soon completed. Different electrode geometries were investigated, and a
dedicated electrostatic device constructed in order to facilitate electrode testing. The
electrocyclone collection efficiency is in fact directly connected with the current intensity
which can be obtained under a specified voltage. So in this device, intensity versus
voltage is measured, outside the dust collection bench. Fig. 4 shows the evolution of
current intensity for the successive types of electrode.
For the design of the new electrocyclone cell, it was decided, in a first attempt, to adapt
an existing cell of industrial multicyclone so that the increase of cost is minimized. Thus
the new electrocyclone (cell n 2) has an axial entry, and its nominal flow is about 750
m3/h.
After first tests in laboratory conditions (CEN Saclay) the cell was installed at
Mazingarbe. Different electrical problems were encountered, due to the high level of dust
loading in industrial conditions, compared to laboratory conditions. They lead to the
modification of the electric insulation. Furthermore, this allowed to lengthen the
electrode. A rapping defouling device was also tested. It worked satisfactorily. At present
time, an evaluation of manufacturing costs in series is being made.
4.ANALYSIS OF PRESENT EXPERIMENTAL RESULTS
Cyclone efficiency
As compared to the efficiency of cyclone n 1, the efficiency of the cyclone n 2 is poor.
This is explained by its axial entry, which provides a tangential entry of 10 m/s for about
700 m3/h instead of 280 m3/h for cell n 1. Thus, the residence time being shorter, the
collection is worse. However for high dust loading, efficiencies of more than 90% were
Electromulticyclone for clone burner exhaust gas cleaning
87
obtained (for particles dm 35m).

Electrocyclone efficiency
Fig. 6 and Fig. 7 show the increase of efficiency for two types of conditions, with cell n
2:
- laboratory conditions, low dust loading, dm m, with electrode n 3 (Fig. 6),
- industrial conditions, high dust loading, dm 12, 5 m with electrode n 4 and n 5.
As a reference, Fig. 2 shows collection efficiencies measured previously on cell n 1.
This electrostatic efficiency was calculated assuming that the electrocyclone behaves
like a cyclone and an electrofilter behind each other: respectively
total, centrifugal and electrostatic efficiencies.
Considering that the efficiency of the electrofilter can be described by Deutsch law, an
electrostatic migration velocity can then be deduced:
A: collection surface= DL (m2)

L: length of electrode (m)
D: cyclone diameter
We: electrostatic migration velocity (m/s)
Q: gas flow (m3/s)
This helps comparing results with different lengths of electrode and different gas
flows.
From Fig. 6 it appears that a maximum electrical efficiency e, corresponding to a
maximum migration velocity We, is obtained for gas flow around 450 m3/h.
From Fig. 7, where the gas flow is over the maximum point, it is confirmed that
optimization of electrode geometry on the basis only of current intensity (Fig. 4) leads to
optimization of electrostatic collection efficiency.
The results of We calculations are summarized in Fig. 8, for the conditions leading to
the same tangential velocity of 10 m/s in the case of cell n 1 and cell n 2. It can be
deduced from this and from Fig. 7 that the value of 0, 2 m/s which was obtained with
rather big particles (dm 12, 5 m), and over the maximum point could be exceeded
easily, in the case of fine particles.
5.PROSPECTS
Fig. 9 shows theoretical electrostatic collection efficiency, using Deutsch law, for new
designs of cyclones where the cylinder length, and thus the electrode length, would be
increased. Assuming that in such a case, the cyclone efficiency would not be modified, it
appears that:
- efficiencies of 90% could be reached with a cyclone efficiency of 80% and an
88
electrostatic efficiency of 50% corresponding for example to migration velocity of

0, 2 m/s and cyclone total length 1, 37 m instead of 0, 9 m presently;
- efficiencies of 96% could be reached with a cyclone efficiency of 90% and an
electrostatic efficiency of 60% corresponding for example to migration velocity of
0, 3 m/s and cyclone total length 1, 25 m.
If this is confirmed by experience, it will be possible to reach low emission levels (100
mg/Nm3 or even 50 mg/Nm3) in one step (electromulticyclone) or two steps
(multicyclone+electromulticyclone) depending on the initial dust loading and particle
granulometry.
REFERENCES
(1)P.W.Dietz. Electrostatically Enhanced Cyclone Separators. Powder Technology, 31
(1982)221226.
(2)R.R.Boericke, J.T.Kuo, P.W.Dietz, W.C.Giles. Electrocyclone for high temperature,
high pressure dust removal. AIAA 19th Aerospace Sciences Meeting, Jan. 1981/St
Louis
(3)W.B.Giles. Electrostatic Separation in Cyclones. Symposium on the transfert and
utilization of particulate control technology. Vol. 3 ERA. 600/779004 c, pp 291
302.
(4)F.Daniel, M.Pourprix, J.Vendel, J.Y.Deysson, J.N.Dumont. Llectrocyclone: une
technique nouvelle de prfiltration. Confrence europenne: Traitement des rejets
gazeux dans les installations nuclaires. Luxembourg. 1418 oct. 1985.
Figure 1: Cell n1
Electromulticyclone for clone burner exhaust gas cleaning
Figure 2: Collection efficiency of cell n 1
Figure 3: Laboratory bench
89
Figure 4: Electrode optimization
Figure 5: Cell n2
Figure 6: Increase of collection efficiency
Figure 7: Increase of collection efficiency
Figure 8: Evaluation of equivalent migration velocity We for a tangential

velocity of 10 m/s
Figure 9: Influence of cyclone length on theoretical electrical efficiency
DEVELOPMENT OF A DUST SEPARATOR

FOR HOT GAS CLEAN-UP
Authors :
J.TAILLET, R.RENNHACK
Contract number : EN3F-0073-F
Duration :
27 months 1st december 198728th february 1990
Total budget :
Ecu 551.743 CEC Contribution : Ecu 291.120
Scientific
Dr J.TAILLET
Director :
Contractors :
a) ECOPOL
b) Institute of Chemical Engineering, University of Paderborn
c) LURGI GmbH
Address :
a) 26 rue du Chteau des Rentiers, 75013 PARISFRANCE
b) Postfach 1621, Pohlweg 55D4790 PADERBORN FRG
c) Gwinnerstrasse 27/33D 6000 FRANKFURT AM MAIN
60, FRG
Summary
A new method for injecting electric currents in a gas stream in order to charge fine dust
particulates has been proposed and patented by ONERA (French Aerospace Research
Institute). Laboratory studies by ECOPOL, performed since 1982, have shown that the
charge collected by the fines is appreciable, and that the current can be injected in high
pressure and/or high temperature gas streams. The contract mentioned above has the
following objectives :
1 Apply in the laboratory the method to several types of dust separators (a
granular bed filter, and electrostatic precipitator, a scrubber and a fabric filter)
in order to determine the advantages of this new process.
2 Select an industrial facility at one of the plants installed by LURGI and
proceed to the necessary modifications to adapt this new type of charging
device.
3 Perform a full scale experiment, and compare the results (filtering efficiency,
clogging, pressure drop and energy requirements) to the previous performances
of the facility.
1.INTRODUCTION
A number of processes related to dust separation can take advantage of using electrostatic
charging of dust particulates to improve the overall performance of the related facility. In
96
a number of cases, the coarse particulates are removed by using a first aerodynamic stage
of dust separation constituted by a cyclone or by a pebble bed filter, and the problem
remains of extracting the fines with a good efficiency. As an example, in a scrubber or in
a granular bed filter, electrical charging of dust can help the fines to cross the boundary
layer around the water droplets or dielectric granules, and concurrently it will improve
the filtering efficiency; this effect can be increased in the latter case by a polarization of
the granular bed; in a fabric filter, charging the fines reduces the clogging and the
associated pressure drop and power consumption; we should also mention that dust
precharging is used in E.S.P. to avoid back-coronas when working with high resistivity
dusts.
If an increase of efficiency is sought in a particular facility, it could be easier and
cheaper to insert a compact charging unit in the raw gas flow between the coarse
particulates separator and the fines separator, than to install a full scale E.S.P. as the fines
separator. This can be particularly interesting if the charging unit still works correctly in
adverse conditions (high temperature and high pressure), and it can still be true even if
the performance of this unit is modest.
The present research is aimed at studying, by a series of laboratory experiments
followed by a full scale experiment on an industrial facility, the possibility of application
of a new type of particulates charger built as a compact unit, and working at ambient
pressure up to temperatures of 300 C.
The charger studied is a supersonic jet current injector which will be described in the
next paragraph. The application of such injector to particulates charging has been
patented in a number of countries (1). In order to evaluate the advantages resulting from
its utilization, four laboratory experiments will be performed:
- at Chalais Meudon (France), the filtering efficiency of a system comprised of a
charging unit followed by a polarized granular bed filter will be measured at
working temperature up to 300 C.
- at Paderborn (FRG) the unit will be used as a precharger for an E.S.P., a scrubber
and a fabric filter. The increase of filtering efficiency of the E.S.P. and of the
scrubber, and the reduction in pressure drop of the fabric filter will be evaluated.
These results will be used later for selecting the type of full scale industrial filter which,
in order to improve its performance, will be equipped with charge injectors.
2.CHARGE INJECTION METHOD
In this method, electric charge carrier are produced in one or several units. Each unit is a
small metallic cylinder (typical dimensions : length 10 cm, diameter : 3 cm) ended by a
nozzle (throat diameter : 2 mm) fitted with an axial needle-shaped electrode. The unit is
fed with air having a low percentage of humidity at a pressure ranging from 3 to 7
atmospheres. The needle is connected to a high voltage supply (5 to 10 kV). At the throat
( 2 mm in diameter), a corona discharge is produced between needle and nozzle. The
cooling resulting from the supersonic expansion of the jet produces a condensation of
water molecules onto the ions, and a fine aerosol electrically charged of ice is produced.
97
The aerosol is immediatly transferred by the jet into the raw gas stream, where after
evaporation, the ions are set free, producing the ionic space charge necessary for charging
the particulates. A typical unit can inject currents up to 100 A (with an associated mass
rate of approximately 25 kg per hour of air injected into the raw gas stream) (2)(3)(4)(5).
It should be noted that no external electrode is needed in the raw gas flow, and successful
experiments of charge injection have been carried out into raw air ducts having dielectric
walls around the injector. A sketch of the unit is shown in fig. 1.
3.TECHNICAL BACKGROUND: RESULTS OF PREVIOUS RESEARCH
The main results of previous studies related to the characteristics of this type of
precharging unit have been published in the literature (6)(7). These results show
essentially that :
a) the electric charge acquired by fine monodisperse aerosols submitted to a low
injected current is relatively significant (see fig. 2); the charge acquired by a sample
of fly ash was in analog conditions of 12 C per g.
b) the charging process is still applicable to hot gas streams (up to 600 C) and high
pressures (up to 9 atmospheres); in the latter case, a higher generating pressure
should be used (up to 40 atmospheres).
4.ECOPOL EXPERIMENT ON GRANULAR BED FILTER
This experiment is performed in a facility built for ECOPOL by ONERA at the Chalais
Meudon establishment of this Institute. This facility can supply a hot gas stream (mass
flow rate 0.5 kgs1 at a temperature up to 800 C and at pressures up to 10 atmospheres).
This stream can be seeded with various types of particulates (cement dust, fly ash). A
charging section, including a supersonic nozzle charging unit, is located upstream a
granular bed filter equipped with grid electrodes on which a high voltage can be applied.
The dust loading, the frontal velocity of the flow, the raw gas temperature, the injected
current, the polarization voltage of the bed can be easily varied; provision is also made
for changing the material and the diameter of the granules, as well as the position of the
current injector. The required temperature is obtained by joule heating of a resistive
tubing on which the gas is circulated at high pressure; the necessary power (up to 600
kW) is delivered by a ward-Leonard D.C. generator. Fig. 3 is a photograph of an early
version of this facility.
The experiment to be performed (the first preliminary trials have been started at the
end of 1987) consists essentially in measuring the filtration efficiency of the system
formed by the injector unit and the granular bed filter under various conditions and up to
a temperature of 300 C.
During the last month of 1987 and the first quarter of 1988, a granular bed filter
formed by four polarized layers of alumina beads 5 mm in diameter has been designed,
built and implemented to suppress all spurious corona discharges between high voltage
and ground electrodes; the injector unit has been modified to optimize its performance in
98
the conditions of the proposed experiment. The seeding of dust has been checked and
modified during the second quarter of 1988; a rotating plate dust injector has been found
the most convenient for fly-ash seeding, but inappropriate for cement dust: for this
particular application, fluidized bed feeding has been selected and the corresponding
device has been installed. Then, preliminary measurements of filtration efficiency have
been performed with rather rudimentary sampling systems; these measurements have
shown that it is necessary to install more sophisticated devices with provision for
avoiding dust deposition inside the tubing. The next step will be the construction of these
probes. The full set of measurements in the laboratory facility of Chalais Meudon is
expected to be achieved by the end of 1988.
5.PADERBORN EXPERIMENTS: GENERAL INFORMATION
It was agreed by the partners ECOPOL and LURGI GmbH to launch the project on
01.02.88. The initial plans, presented during the meeting in Paderborn on 29.01.88, depict
the basis of the work. A number of minor modifications were necessary for technical
reasons. The intermediate report refers to Task 1 Laboratory studies on small scale
models and describes the planning of the trials and status of the work.
The aim of the laboratory experiments is to determine the influence of an upstream
ionization unit on the dust collecting efficiency of a fabric filter, plate-type precipitator
and scrubber using the ECOPOL ionization injector.
The fabric filter and plate-type precipitator are available but must be converted for the
trials. The scrubber including water supply will be built. Further manufacturing and
installation work will be necessary for the following components : pipework, ionization
unit, heating section, dust dosing, measurement and control technique.
The trial parameters will be set as follows, taking into consideration the existing
ventilator and heating capacities :
Gas volume flow

: 8001000 m3/h
Temperature
: 2080 C
Pressure loss
: max.100 mbar
Crude cement dust (average particle size 13 m) is available.
6.PADERBORN EXPERIMENTS : PLANNING FOR THE TRIALS
Tubular fabric filter
A pulse-jet tubular fabric filter, equipped with 4 rows each with 9 tubes (Dralon
material), is available. The number of tubes (length : 2400 mm, diam. : 160 mm) is
reduced to 42 so that the air : cloth ratio is 100 m3/m2 h. Before entering the filter, the
dust loaded crude gas flows through the ionization unit (length : 1000 mm, diam. : 560
mm).
The trials should indicate to what extent electrostatic charging of the particles will
99
reduce the pressure loss in the filter or resp.extend the intervals between cleaning, at the
same loss in pressure, and thus save energy. Trials will also be run to determine whether
the dust concentration in the pure gas will be reduced.
Plate-type precipitator
A one-duct, horizontal precipitator with the field measurements 3004003600 mm is
available. By means of conversion, the field length can be divided into a 1200 mm long
ionization section and a 2400 mm long dust collecting section. The following three
configurations will be tested for the dust collecting section : discharge electrode/dust
collection plates=belt/ZT-profile (with corona discharge), pipe/ZT-profile (without
corona discharge), plate/plate (without corona discharge).
The configuration given first represents the conventional construction of a one stage
electric pricipitator. The trials are intented to show in which of the given configuration
the upstream connection of the ionization unit provides advantages with regard to the
dust collecting efficiency. One further question concerns the energy consumption of the
individual modes of operation.
Scrubber
A Venturi-scrubber with downstream cyclone for collection of the dust loaded water
drops will be built. By conversion, the ionization unit which is used for the tubular fabric
filter will be connected upstream to the Yenturi-scrubber. The throat cross-section will be
dimensioned in such a way that the max. pressure loss in the scrubber will be 85 mbar. A
second construction will be made with a larger throat cross-section. In a third variation
the unit will be run as a scrubbing tower, i.e. without constriction of the gas flow.
The trials are intended to show to what extent, in each of the three constructions, the
upstream connection of the ionization unit effectively improves the degree of dust
collection. If this is the case, a second series of trials will be run to discover the extent to
which the scrubbing water supply can be reduced with the same degree of dust collection
as obtained in the trials without the pre-ionization.
7.STATUS OF THE WORK
The planning work for the entire unit has been completed
The piping, including the gas heating section, has been mounted ready for the trials
with the tubular fabric filter and the plate-type precipitator. Work has still to be done on
the measurement and control technique and the electric equipment including the high
voltage supply.
The ionization chamber for the tubular fabric filter and the scrubber has been ready
built. There remains the installation and testing of the ionization injector.
Preparations have been made for the conversion work on the tubular fabric filter. The
additional openings in the housing for gas inlet and outlet have been made.
The conversion work on the plate-type precipitator for the first electrode configuration
100
has been completed. The ionization injector still has to be installed.

Detail engineering of the scrubber has been completed. The work has now reached the
phase where we order some of the components and manufacture other components
ourselves.
The first trials with the tubular fabric filter and plate-type precipitator are scheduled to
take place in August/September and trials with the scrubber in November.
8.REFERENCES
(1)Patents :
FRANCE
FRANCE
FRG
UK
SWITZERLAND
ITALY
SWEDEN
USA
JAPAN
n 25 06 086
n 24 83 259
n 31 21 054
n 2 079 187
n 642 870
n 1 144 568
n 81 10 33300
n 4 435 190
n 1 310 081
(14.05.82)
(29.05.80)
(30.10.86)
(03.01.85)
(15.05.84)
(29.10.86)
(26.03.87)
(01.10.85)
(26.03.86)
(2)A.MARKS, E.BARRETTO and C.K.CHU, AIAA Journal, 2, 1, 4551, (1964)

(3)B.R.WHEWELL, A.W.BRIGHT and B.MAKIN, Int. Conf. on Static Electricity,
Vienna (1970)
(4)B.R.WHEWELL and B.MAKIN, 3rd Conf. on Static Electricity, London (1971)
(5)N.J.FELICI and S.LARIGALDIE, J. of Electrostatics, 9, 5970, (1980)
(6)J.TAILLET, 2nd Int. Conf. on Electrostatic Precipitation, Kyoto (1984)
(7)J.TAILLET, N.GIBONI3rd Int. Conf. on Electrostatic Precipitation, Padova (1987)
Figure 1. Principle of the current injector.
1 humid air supply
101
2 high voltage corona needle

3 supersonic nozzle
4 injected current measurement
Figure 2. Number of elementary charges as a function of the particulate

diameter.
Pipe diameter=25 cm
Injected current=12 A
Flow velocity=1 ms1
Figure 3. Facility built by ECOPOL
Figure 4: View of the laboratory of electrostatic dust separation (University of

Paderborn)
Figure 5: View of the electrostatic plate-type precipitator (University of

Paderborn)
PULSE POWER TECHNIQUES FOR FLUE

GAS TREATMENT
Author :
Contract number :
Duration :
Total budget :
Head of project :
Contractor :
Address :
G.DINELLI
EN3F-0070-I
24 months 1 Dec. 198730 Nov. 1989
1.320.000 ECU CEC contribution: 395.000 ECU
G.Dinelli, ENEL-D.S.R., C.R.T.N.
ENEL (Italian Electricity Board)
ENELD.S.R. Via G.B.Martini, 3 I-00198-ROMA
Summary
The narrow pulse energization of the flue gas of thermal power plants appears a
promising technology for the abatement of solid particulates as well as the sulphur and
nitrogen oxides.
The research conducted on pilot installations and on a 35 MWe industrial precipitator,
has a potential for the improvement of the design and operational flexibility of the
equipment as well as for energy saving.
The results of the experiments conducted on a 10.000 Nm3/h pilot ESP have evidenced
the interest on enlarging the collection plates distance from 300 mm to 400 mm. Those
conducted on the industrial ESP has confirmed the substantial reduction of the solid
particle emissions obtainable, at an assigned specific collection surface, with the impulse
energization compared to the conventional energization.
The tests on the electrochemical oxidation of the nitrogen and sulphur oxides, carried
out with 1000 Nm3/h reactor cells, have evidenced a removal efficiency of 50 to 60% for
the nitrogen oxides and of 80 to 90% for the sulphur oxides.
1.INTRODUCTION
The aim of the research is to verify the effectiveness of narrow pulse generators in
precipitating and removing solid particulates as well as, by energizing, the sulphur and
nitrogen oxides contained in combustion gases in coal-fired power stations.
The research was proposed in the context of studies of technologies aimed at reducing
the environmental impact of thermal power stations and has the following potential
results:
- reduction in the size of electrostatic precipitators for an equivalent clean-up
efficiency;
106
- operational flexibility to cope with variations in the properties of the coal used;
- energy saving:
- simultaneous precipitation of the sulphur and nitrogen oxides by pulse energizing.
Electricity generating boards and companies will be able to use the anticipated results in
the contruction of new power stations and in retro-fitting existing plants.
The results will help establish the effectiveness of the technologies in question on an
industrial scale and the industrial feasibility of removing nitrogen and sulphur oxides
using pulse energizing techniques.
The research is conducted at the Marghera (Venice) coal-fired power station, both in
pilot installations connected in a by-pass of the main flue gas duct, as well as in a 35
MWe industrial precipitator.
The pilot installations, one for removing particulates and the other for precipitating the
oxides, are characterized by considerable operating flexibility that allow rapid changes to
the positioning of the electrodes, inside the devices.
2.EXPERIMENTAL FACILITIES
2.1Solid Particulates Removal
The Marghera power plant where the industrial demonstration of the impulse
energization is carried out consists of two 70 MWe units, each with two boilers of 35
MWe. The units are equipped with electrostatic precipitators of European design, having
high collection efficiency even with difficult particulate.
The electrostatic precipitator being used for the experiments is subdivided into two
separate chambers, each one with three electric sections in series. The discharge
electrodes of the reference chamber are flat serrated strips, while those of the
experimental chamber, are 5 mm diameter round wires. The gas passage width of the
experimental chamber may be varied between 300 and 500 mm; other design
characteristics of the electrostatic precipitator are reported in Table I.
Conventional power sets have been installed on the electric sections of the reference
chamber, while the electrical sections of the experimental chamber have been equipped
with both conventional and impulse power sets installed in separate cubicles and
connected to the electrical sections by high voltage bus ducts.
A general lay-out of the electrostatic precipitators installed in the power station in
given in Fig. 1. Flue gas velocity and particle concentration measurements are foreseen in
the gas ducts both at the inlet and at the outlet of the precipitator; opacity and particle size
distribution measurements are also foreseen in the outlet ducts, while the particle
resistivity measurements are carried out in the diffusion caps, where the gas velocity is
reduced to about 1.5 m/s.
Furthermore a pilot unit has been designed and installed in slipstream with the main
gas flow to ensure preliminary performance data, with short time investigations,
regarding:
- preliminary definition of the best electrode geometry associated with the
107
conventional and the impulse energization system;

- preliminary definition of the best rapping system operation as a function of the fly
ash characteristics;
- verification of the effectiveness of the gas conditioning system.
The pilot ESP, Fig. 2, has two electric fields in series each 5 m long and 3.75 m high. The
plate spacing can be changed from 300 mm (4 channels) to 600 mm (2 channels). Other
design characteristics are summarized in Table II.
To collect the fine ash at the outlet of the pilot ESP a baghouse has been installed.
The monitoring of the pilot unit includes several measurements and analysis of most
electrical and thermodynamic quantities.
2.2NOx and SO2Removal
A test rig has been installed at Marghera in slipstream from the main flue gas duct of a 35
MWe boiler. The reactor is alike an electrostatic precipitator formed by two gas ducts
with 200 mm width, in the center line of which a number of emitting wires, 3 mm in
diameter, are vertically placed.
The gas is drawn downstream of the electrostatic precipitator for reducing the
particulate content. In Fig. 3 the layout of the test rig is sketched; first the temperature
and gas concentration is measured, then a heat exchanger allows a temperature control of
the flue gas in the range 80 to 120C. Downstream of the heat exchanger and upstream of
the reactor a second measurement of the relevant gas components concentrations is
performed and ammonia in injected
Downstream of the reactor the temperature and the gas flow is measured and the
chemical analysis of the gas is performed concerning the concentration of the relevant
components; furthermore an isokinetic sampling is performed: the particles with a
diameter greater than 0.05 m are collected on a membrane filter and successively
analyzed; all the remaining soluble substances are taken off by means of a series of
distilled water filled impingers and also analyzed.
3.DESIGN CHARACTERISTICS OF THE IMPULSE POWER SETS
3.1Microsecond Pulse Voltage Generators
The impulse power supplies installed in the 35 MWe electrostatic precipitator have been
designed to reach the high voltage levels necessary to the 500 mm spacing between the
collecting electrodes that may be set in the experimental chamber. Therefore they are to
be considered, in a strict sense, as prototypes with dimensions and weight which are, for
this reason, larger than those that would be required for the usual 300 mm collection
plates spacing. Moreover the impulse duration is settable at 60, 120 and 250
microseconds so that, as the impulses are obtained by means of a resonant circuit,
additional coils have been used with a further increase in dimensions and weight.
The complete design characteristics of the impulse power sets are reported in Table III.
108
Two different technologies have been applied: one of them is based on impulses obtained
directly at high voltage; the other one obtains the impulses at a relatively low voltage and
their amplitude is then increased to the operating value by means of an impulse
transformer.
Two impulse power sets have been installed also in the pilot ESP; the main design data
of such power sets are given in Table IV.
3.2Nanosecond Pulse Voltage Generators
The fast rising voltage pulses are obtained with the electrical circuit schematically
illustrated in Fig. 4. The voltage pulse front is about 100 ns while its total duration is in
the order of a few microseconds. The frequency of the pulses, determined by the
frequency of the power supply, is 50 Hz.
A second arrangement for the pulse generator, shown in Fig. 5, makes use of a tyratorn
triggered at assigned time intervals thus producing impulse at several frequences up to
300 Hz. In this case the rise time of the voltage pulses, on a suitable resistance load
simulating the power absorbed by the corona discharge, is about 150 ns and the pulse
duration, that depends on the corona, is generally in the order of one microsecond
4.RESULTS
4.1Pilot ESP
A first experimental campaign has been carried out to verify the efficiency trend versus
the plate spacing and at same time to set up the equipment and the test procedures.
During the preliminary tests conventional power supplies and serrated strip emitting
electrodes have been used.
The tests were performed with the plates spaced at 300, 400 and 500 mm at gas flow
rate of 8000 Nm3/h and gas temperature of 165C, the 35 MWe unit was burning South
African/TCOA coal; under these conditions the fly ash resistivity was approximately 2.5
1012 ohm.cm.
During all of the tests the power supplies were regulated in order to have no more than
15 spark/minute. The plots of V-i curves represented in Fig. 6 show clear indications of
back corona.
The collection efficiency for 300, 400 and 500 mm plate spacings, evaluated from the
weights of the dust collected in the hoppers, is reported in Table V.
On the average the collection efficiencies, measured using standard EPA method, were
approximatly 98.5% for the 300 mm as well as for the 400 mm plate spacings and 97.5%
for the 500 mm plate spacing.
4.2Industrial ESP
The most important results of the tests performed at the industrial ESP facility consist in
the trends of outlet particle concentration, collection efficiency and energy consumption
109
of the power sets that are reported in Table VI.

On the basis of these results the following remarks may be drawn.
- When conventional energization is used, there is no significant difference in the
particle concentration at the outlet of the two chambers of the ESP, while the energy
consumption on the experimental chamber (where round wires are used) is about
60% with respect to the reference chamber (flat serrated strips).
- When impulse energization is used, the particle concentration at the outlet of the
experimental chamber dramatically drops to about 15% of the value in the reference
chamber, in any case below the design value of 50mg/Nm3. The energy
consumption with the impulse power sets is about 20% of that required with the
conventional power supplies.
4.3NOx/SO2Reactor TR-1000/1
The NOx/SO2 removal tests were carried out using two different reactors: TR-1000/1 and
TR-1000/2, having the main characteristics reported in Table VII. In the former case the
energized flue gas had the following composition:
- CO2=12.2%;
- H2O=8%;
- O2=6.2%;
- N2=77.6%;
- NOx=430550 ppmv;
- SO2=360500 ppmv;
- solid particulate=150 mg/Nm3.
The temperature in the reactor was kept at about 100C.
In the flue gas ammonia was injected at a concentration of 1000 ppmv which
corresponds to a molar ratio of 0.67 with respect to the sulphur and nitrogen oxides
content.
The tests were carried out with a gas flow rate of 600 Nm3/h, the velocity being about
0.4 m/s and the resident time about 3.7 seconds.
It has been remarked that the corona streamers starting from the emitting wires
propagate toward the plates within an angle of about 25; consequently the corona
activated volume is equivalent to about 1/10 of the total reactor volume.
4.3.1SO2removal
The SO2 removal occurs first as consequence of a thermochemical reaction with
ammonia; the energization influences the process as it increases the size of the produced
ammonia sulphate particles.
In Fig. 7 the outlet SO2 concentration and the corresponding removal efficiency are
110
plotted versus the ammonia injection rate. With an ammonia injection rate corresponding
to a concentration of 1000 ppmv the measured removal efficiency was 75% at 100C and
90% at 70C. In absence of ammonia injection the removal rate due to a flue gas
energization of 6 Wh/Nm3 was 12%.
4.3.2NOXremoval
The removal efficiency of nitrogen oxides as function of the energy transferred to the gas
is plotted in fig. 8. The results obtained suggest a possible saturation phenomenon in the
removal of NOX. That could in principle depend on the high value of power per impulse
or of the energy density.
In order to verify such hypothesis a second reactor TR-1000/2 was set up, having a
larger volume and a lower spacing between the emitting wires in order to produce a
larger corona volume and thus a lower density of the energy given to the gas.
4.4NOx/SO2Reactor TR-1000/2
The flue gas during the second test period, using a modified reactor TR-1000/2, had a
slightly different composition, namely:
CO2=13%;
H2O=8%;
O2=6%;
N2=73%;
NOx=300550 ppmv;
SO2=450 ppmv;
solid particulate=150 mg/Nm3.
The temperature in the reactor was kept, as during the first test period, at about 100C
and also the ammonia injection was kept at the same concentration of 1000 ppmv which
corresponds, in this case, to a molar ratio of 0.77 with respect to the sulphur and nitrogen
oxides content.
The gas flow rate was 600 Nm3/h and 470 Nm3/h with corresponding velocities of 0.4
and 0.3 m/s respectively; the resident times were 5.4 and 6.9 seconds respectively.
The corona active volume was 0.16 m3, thus almost the double than that of the first
reactor TR1000/1.
4.4.1SO2removal
In presence of ammonia injection the removal of SO2 was obviously the same as with the
previous reactor; however in absence of ammonia the removal of SO2 was 29% at an
energy input to the gas of 13.5 Wh/Nm3.
111
4.4.2NOxremoval
In order to assess the influence of the initial concentration on the removal efficiency, tests
were carried out with NOx initial concentration of 300, 400 and 550 ppmv.
The results are plotted in Fig. 8 and 9. In Fig. 8 it is evident the increase in
performance with respect to the previous reactor TR1000/1. For instance with an inlet
concentration of NOx of 500 ppmv, a removal efficiency of 50% has been attained with
an energy input of 13.5 Wh/Nm3. Larger efficiencies, in excess of 60%, were attained
with lower inlet concentrations, Fig. 9.
5.DIRECTIONS FOR FUTURE R. & D
.
5.1Pilot ESP
The first series of test has demonstrated that the design and the installation on the pilot
ESP fulfil all the specified requirements. The experimental data, although need to be
confirmed, indicate that the overall collection efficiency change very little when the plate
spacing is increased from 300 mm to 400 mm. The next test program will consist on a
preliminary definition of the best electrodes geometry associated with conventional and
impulse energization systems.
5.2Industrial ESP
The tests carried out in the frame of the industrial demonstration programme of the
impulse energization of electrostatic precipitators, have shown a considerable decrease
both in particulate emissions (about 85%) and in energy consumption (about 80%) with
the impulse energization compared to the conventional energization.
Other tests are in programme with coals of different characteristics and with different
operating conditions of the power unit to assess the range of benefits obtainable for
specific applications.
5.3Simultaneous DeNOx/DeSO2
Based on the present knowledge from the experimental results, an evaluation has been
performed on the feasibility of an industrial application of the electrostatic technology for
the removal of NOx and SO2 from the flue gas of a large power station. The conditions at
which the technology appears competitive with respect to the conventional technologies
seem to be:
- a removal efficiency of NOx between 60% and 70%;
- a removal efficiency of SO2 in the order of 80%;
- an electric energy consumption in the order of 15 Wh/Nm3 corresponding to a
power demand of about 6% of the generated power.
112
It is evident that the energy consumption represents a significant parameter for the
possible application in large power plants. The experimental investigations have put in
evidence the great importance of the optimization of the reactor design and of the
appropriate matching of the pulse power supply to the electrode structure.
These topics, together with the influence of voltage polarity, will be further
investigated. A side research will be pursued on the electrostatic captability of the solid
particles originated from the process.
Tab. IDesign characteristics of the electrostatic precipitator used for impulse energization tests
Coal rate (1)

t/h
16
3
Flue gas flow rate
175000
Nm /h
Flue gas specific weight
1.32
kg/Nm3
Flue gas temperature
C
155
Flue gas pressure at ESP inlet
mmH2O
150
Inlet particle concentration (1)
1016
g/Nm3
Collection efficiency
%
99.6
casing length
m
20.9
Casing width
m
9.5
Casing height
m
15
Hopper height
m
6
Parallel chambers
Nr
2
Electric fields in series
Nr
3
Electric sections
Nr
6
Gas passages per chamber (2)
Nr
14
Gas passage width (2)
mm
300
Active length
m
15
Length over height ratio
1.15
Residence time
S
21.4
Collection electrodes height
m
13
Collection electrodes width
m
0.5
Collection area (per section)
1820
m2
2
Total collection area
10920
m
2
3
Specific collection area
140
m /(m /s)
(1) The design characteristics of coal are similar to a South African coal.
(2) In one of the two chambers the gas passage width may be increased from 300
to 500 mm; the number of gas passages consequently decreases from 14 to 8.
113
Tab. IIPilot ESP design parameters
Gas flow
Gas temperature
Gas velocity
Aspect ratio
Number of el. field in series
Number of parallel channels
Collection plates spacing
Collection surface
Specific collection surface
H.V. electrical energization
m3/h
C
m/s
mm
m2
2
m /m3/s
850020000
<180
0.61.5
2.8
2
4322
300400500600
288216144144
104786252
d.c. and impulse
Tab. IIIDesign data of the impulse power sets for 35 MWe ESP
Base voltage amplitude

Impulse voltage amplitude
Maximum peak voltage
Average current associated with the base voltage
Average current associated with the impulses
Impulse duration
Impulse frequency
kV
0 to 60
kV 0 to 120
kV
180
mA
300
mA
400
s 60 to 250
Hz 20 to 500
Tab. IVPilot ESP power supplies design data
Conventional Power Sets:

Apparent power input
High voltage:
peak value at no-load condition
mean value at full load
d.c. current mean value
Power control device type
Pulse Power Sets:
Base voltage section:
apparent power input
d.c. voltage
d.c. current (mean value)
Pulse voltage section:
apparent power input
impulse amplitude
current (mean value)
impulse duration
impulse frequency
kVA
12
kV
kV
mA
150
87
75
SCR
kVA
kV
mA
2.5
560
30
kVA
kV
mA
s
Hz
3.2
0120
40
60
20500
114
Table VPilot ESPPreliminary performance data (Coal: South Afr./TCOADust resistivity:

12.51012 ohm-on)
TEST PLATE TEMPERATURE GAS

INLET DUST
OUTLET DUS
NR. SPACING
C
FLOW CONCENTRATION CONCENTRATI
mm
g/Nm3
mg/Nm3
Nm3/h
1
300
170
8300
16.0
309
2
168
8300
20.8
180
3
170
7500
16.7
258
4
162
7350
18.2
260
5
162
7350
18.2
251
6
400
163
8800
14.7
270
7
158
8000
11.8
214
8
158
8000
17.7
207
9
500
164
8000
17.7
440
10
167
7800
16.0
520
11
167
7940
17.6
527
12
164
8500
15.9
461
Table VIImpulse energization tests summary
COAL
ESP
Electrical input
Setting
(kW)
(C)
(I)
(A)
59
10
Collection
Outlet dust load
efficiency (%)
(mg/Nm3)
(C)
(I)
(C)
(I)
97.3
99.6
330
45
S.A.AMCOAL
S.A.(A)
52
10
98.0
GEN.MIN.
S.A.-TCOA
(A)
42
9
98.5
U.S. A. -Mix
(B)
22
7
99.2
2
3
(A): 3 Series Electric Fields; SCA135 m /m /s
(B): 2 Series Electric Fields; SCA=90 m2/m3/s
(C): Conventional power supply
(I): Impulse power supply
99.7
170
20
99.8
99.6
145
50
25
20
Table VIIMain characteristics of the test reactors for simultaneous DeNOx and DeSO2
Overall length
Total volume
Number of gas ducts
Duct width
(m)
(m3)
(mm)
TR-1000/1
TR-1000/2
1.40
1.50
0.84
1.20
2
2
200
200
Total plate surface

Total number of emitting wires
Distance between emitting wires
Emitting wire length
Emitting wire diameter
(m2)
(mm)
(m)
(mm)
115
8.4
14
200
1.5
3
Fig. 1Electrostatic precipitators lay-out at Marghera power station
Fig. 2Pilot ESP mechanical design
12
20
150
2.0
3
Fig. 3General layout and measurement system for DeNOx and DeSO2 tests
Fig. 4Narrow pulse power supply circuit
Fig. 5Narrow pulse generator
Fig. 6V-i curves vs collection plate spacing with flue gas
Fig. 7SO2 removal vs NH3 concentration
Fig. 8NOx removal efficiency vs dose
Fig. 9NOx removal efficiency vs dose for different initial concentrations

(reactor cell TR1000/2)
Session II:
Fly ash properties, re-use and
disposal
Characterisation of fly ash from fluidised bed combustors with regard to its
utilisation and safe disposal State of the art report for the period 1 July 1986 to
31 May 1988
Adsorption and desorption phenomena of polycyclic aromatic hydrocarbons
on fly ash
Waste/soil interaction studiesthe leaching of molybdenum from pulverized
coal ash
Handling and conditioning of fluidized bed and pulverized coal boilers fly-ash
for landfill disposal and re-use
The utilisation of P.F.A. (pulverised fuel ash) as a filler in rigid polyurethane
insulation foams
CHARACTERISATION OF FLY ASH FROM

FLUIDISED BED COMBUSTORS WITH
REGARD TO ITS UTILISATION AND SAFE
DISPOSAL
STATE OF THE ART REPORT FOR THE PERIOD
1 JULY 1986 TO 31 MAY 1988
Authors :
Contract
numbers :
Duration :
Total budget :
A.J.GAY, J.FRIGGE
EN3F-0052-NL
EN3F-0053-D
f 800 000 CEC contribution: f 400 000
DM 1 041 000 DM 520 500
Heads of project : A.J.Gay
J.Frigge
Contractors :
The Netherlands Organization for Applied Research TNO;
Bergbau-Forschung GmbH
Addresses :
PO Box 217, 2600 AE Delft, The Netherlands;
Franz-Fischer-Weg 61, 4300 Essen 13, Federal Republic of
Germany
Summary
The growing use of fluidised bed combustion (FBC) for generation of electrical power
and heat results in a large increase of the amount of residues (fly ash and spent sorbent).
These solid residues have very different properties from those of fly ash from
conventional power plants. Therefore the characterisation of the FBC residues, with
respect to their safe disposal and to their eventual utilisation, is of prime importance.
Tests giving a realistic approach to the study of leaching behaviour of the residues are
described. Results of analysis (carbon, sulphur, major- and trace-elements) are discussed,
Morphology, particle size distribution and enrichment effects on single particles are dealt
with. A method for the comparison of the results of different leaching tests is presented.
1.INTRODUCTION
The formation of fly ash, the concentration and distribution of the main and trace
124
elements in or on fly ash particles, and, consequently, the properties of the fly ash,
depend strongly on the kind of the combustion process.
The two processes most widely used in coal fired power plants are the pulverised coal
combustion (PCC) and the fluidised bed combustion (FBC). Most of the residues (fly
ash) from PCC power plants can be recycled and the products be used for example in the
cement industry, in road construction, etc. In the last decade FBC power and heat
generating stations have become more and more attractive because of their reduced
production of SO2 and NOx as compared to PCC plants. This is due to lower
temperatures (up to 950 C) and the addition of sorbents which bind SO2. The FBC
power plant residues differ thus considerably from those originating from PCC plants, as
well as differing between those from individual combustors. Therefore up till now a
large-scale application of such residues has not been possible. Consequently, the only
way to dispose of them is by dumping. Unfortunately there exist only very few reliable
data concerning the long-term behaviour of FBC residues in a dump. Certainly using only
the test described in (1) would lead to totally false characterisation of these materials
because it does not consider the chemical long-term effects in a dump. However, taken
into account the large amounts of residues in question (approx. 60,000 tons per year in
West-Germany alone) a false characterisation of dumped material would lead to
considerable economical and ecological losses. A careless disposal of environmentally
harmful substances in a normal dump would lead to environmental damage. Repairing
such a damage would lead eventually to higher costs than would have been required if the
residue were disposed in a special dump in the first place. On the other hand disposal of
harmles material in special waste dumps for unspecified safety reasons would result in
unnecessarily high disposal costs which might even hinder the proliferation of FBC
technology which can be described as non-polluting. Besides, special dump sites are rare
and should therefore be reserved for proven harmful substances and not unnecessarily
used. Therefore it is of great importance to develop methods that are more practiceoriented in order to be able to characterise better the FBC residues with respect to their
long-term behaviour in a dump, or with respect to their applications as for instance
mortar additive, raw material for light-weight insulating bricks, additive in brick making,
etc.
2.SCOPE OF THE PROJECT
This project, operated jointly by TNO in the Netherlands & Bergbau-Forschung (BF) in
Ger many, aims to provide an insight into the nature, composition and properties of fly
ash originating from the combustion of coal in fluidised bed combustors. The project is
based on three main lines of research:
i) Analysis (physical, chemical and surface) of fly ash samples taken at various
positions in the fluidised bed combustor and, wherever necessary, size separated
into fractions.
ii) Short-term leaching tests and the analysis of leachates, according to established
standard procedure (2).
Characterisation of fly ash from fluidised bed combustors
125
iii) Long-term leaching and analysis of leachates of large (34 m3) fly ash samples in
conditions closely resembling the natural ones (3, 4).
Research mentioned under i) is carried out by TNO, tests mentioned under ii) and iii) by
BF, which also carries out the chemical and mineralogical analyses of coal and
supplementary chemical analyses of fly ash.
These tests aim at the interpretation and prediction of the long-term bevhaviour of the
fly ash in a dump. The influence of the input materials and of the operating conditions in
the power plant on the re-cycling and dump behaviour are also investigated with view to
process optimisation.
The project comprises the study of fly ash originating from the TNO 4 MW
Atmospheric Fluidised Bed Boiler (AFBB) burning three sorts of steam coal with and
without recirculation of the fly ash, and of fly ash from two commercially operated
installations (Lurgi Circulating Fluidised Bed of the Stadtwerke Duisburg AG in
Duisburg, Federal Republic of Germany and Stork 50 MW AFBB of AZC at Hengelo,
the Netherlands.
3.MATERIALS
3.1Operational data
The detailed description of the TNO 4 MW Atmospheric Fluidised Bed Boiler (AFBB)
test facility is published elsewhere (5). The diagram of the AFBB with sampling points
(SP) is presented in Fig. 1.
The data concerning the runs discussed in the present report are presented in Table 1.
3.2Coals and sorbent
The following coals were burnt in the AFBB:
i) Polish (batch codes PL5 and PL8)
ii) US (Virginia) (batch code VA2)
iii) Colombian (batch code CO1)
Sorbent used in all runs was Carmeuse Engis limestone, 1.52.5 mm.
3.3Fly ash
The carry-over (SP1) was sampled with a variable nozzle dust sampler. The cyclone ash
was tapped off at SP2. Samples of the fly ash entering the bag filter (SP3) were taken
with a Goldschmidt sampler. This was done to find out if there were any changes during
its residence in the bag house. Samples of fly ash from the bag filter (SP4) were tapped
off from the bag house outlet. Sampling at SP5 with the available high volume sampler
was unsuccessful because of contaminations. Attempts to sample in the stack (SP6) had
also to be abandoned, due to the shortage of instrumentation and manpower. At any rate
these two sampling points (SP5 and SP6), providing very small quantities of paniculate
126
matter emitted to the atmosphere, were regarded as of secondary importance; the main
subject of the present research being the captured combustion residue. This materi-
Figure 1 Diagram of the AFBB with sampling points (SP).
al was collected at SP7 and consisted of the fly ash from the bag filter with a small
admixture of the cyclone ash (ca. 10:1). It was used as received for chemical analysis,
the short- and long-term leaching tests, and was separated into fractions with a cross-flow
jet classifier (6) at the Institut fr Mechanische Verfahrenstechnik, T.U.Clausthal,
Clausthal-Zellerfeld, FRG, for the study of elemental concentrations vs. particle size.
Particle size in these fractions was determined with the Sympatec Helos instrument
giving equivalent diffracted light diameter (dj). Particle size in other samples was
determined by a method described elsewhere (7), giving perimeter diameter (dc).
4.METHODS OF ANALYSIS
Carbon: modified Pregl method; CHN-Automat 2408, Perkin-Elmer.
Sulphur: empty tube combustion, colorimetric titration (8).
Major elements; Scanning Electron Microscopy/Energy Dispersive X-Ray (SEM/EDS)
analysis (Camscan 4DV/Tracor TN 5500) (7); X-ray Fluorescence (XRF) analysis,
melting technique (Siemens SRS 300).
Trace elements: Solutions obtained after digesting samples of about 0.2 g were
analysed using either Atomic Absorption Spectrometry (AAS) with graphite furnace
atomisation (Perkin-Elmer 4000, HGA 500), or flame atomisation (Varian Techtron), or
127
Atomic Emission Spectrometry with microwave-induced plasma atomisation (MIP-AES)

(TNO-design), or inductively-coupled plasma atomisation (ICP-AES)(Kontron ASS 80),
depending on the element and its concentration.
For the Instrumental Neutron Activation Analysis (INAA), samples of about 0.2 g
were irradiated with thermal neutrons and counted with a Ge-detector coupled to a 3072
channel analyser. The gamma-ray spectra were analysed using a single comparator (Zn)
method. At the BF samples of about 0.3 g were analysed after wet decomposition (PTFE
vessels, pressure bombs) (9). Solutions were analysed with the help of electro-thermal
Zeeman AAS (Z 3030, Perkin-Elmer) and mass Spectrometry with inductively coupled
plasma atomisation (ICP-MS) (PlasmaQuad, VG).
Surface analysis: Fly ash samples were analysed using Secondary Ion Mass
Spectrometry (SIMS) in a VG SIMSLAB instrument at the Surface Analysis Service,
Dept. of Chemistry, UMIST, Manchester, England.
Table 1 Operational data for the AFBB
RUN NO
COAL
MODE*
TEMPERATURE
max
C
min
C
FLUID VELOCITY
bed
m/s
freeboard
m/s
AIR FACTOR
bed
freeboard
BED HEIGHT
cm
COAL FLOW
bed 1
kg/hr
bed 2
kg/hr
SORBENT FLOW
bed 1
kg/hr
bed 2
kg/hr
Ca/S
molar
S-RETENTION
%
CYCLONE DUST
FLOW
kg/hr
UNBURNT C
%
UNBURNT C**
%
BAG FILTER DUST
FLOW
kg/hr
180
PL5
R
195
PL8
R
208
VA2
NR
210
VA2
R
217
CO1
NR
219
CO1
R
877efb 845b1 845b1 950efb 845b1 876efb

247f 235f
212f
254f
208f
249f
2.07
2.09
2.05
2.05
2.40
2.40
2.47
2.47
2.25
2.25
2.20
2.20
1.31
0
107
1.23
0
102
1.22
0
106
1.27
0
107
1.25
0
105
1.25
0
105
200
200
210
215
232
224
227
256
257
256
250
248
20
0
2.0
59
18
0
1.8
63
0
36
1.7
?
0
38
1.8
75
51
0
4.3
76
18
0
1.6
68
860
10.6
14.8
490 ca.130
19.7
59.9
20.0
68.2
250
280
ca.25
? ca.100 ca.800
?
38.6
15.0
32.8
34.9
13.8
?
ca.10 ca.120
UNBURNT C
%
3.7
8.4
UNBURNT C**
%
4.9
8.5
FLY ASH COLLECTED
[SP7]
kg/hr
51
54
UNBURNT C
%
9.3
15.7
UNBURNT C**
%
11.1
15.9
* RRecirculated NRNot Recirculated
** own analysis
efb end freeboard
b1 bed 1
f bag filter
128
13.8
14.1
8.6
8.3
21.1
22.3
6.0
6.1
158
52.7
47.3
78
21.7
22.2
112
30.5
35.2
64
13.8
13.9
Leaching properties: Shaking test (2), column test (10) and large-scale lysimeter test
(4) were used to measure the leaching behaviour. The effluents were analysed using
Zeeman AAS, ICP-MS, ion chromatography (Dionex Autoion 400) and photometric
tests. Besides, pH values and electrical conductivity were measured.
5.RESULTS AND DISCUSSION
The preliminary results from runs with the Polish coal were published earlier (11).
Concentrations of trace elements in that paper were expressed as as received analytical
results. Because of the high and variable carbon contents in samples from different SPs,
as well as in the fractionated material, the concentrations of the trace elements in the
present report are adjusted using the formula:
[1]
where: Cbbulk concentration of the element

c*bconcentration of the elements as determined,
cccarbon content in the analysed sample (in wt%).
Since the trends in the behaviour of the trace elements are the subject of the present
study, rather than the differences between individual trace elements, whether in relation
to the SP, particle size or surface enrichment, the adjusted bulk concentrations are
preferred to the enrichment factors (EF) used in some earlier papers.
5.1Morphology
The morphology of fly ash from all sampling points shows the high degree of
inhomogeneity common to most samples of fly ash from fluidised bed combustors. An
example is given in Fig. 2. The three principal species are the fine, irregularly shaped
particles of fly ash, char particles in various stages of burn-out and large particles of spent
129
sorbent. Other, morphologically interesting species are the carbonaceous cenospheres

(Fig. 3) and fine, spherical calcium-rich particles (Fig. 4).
The formation of carbonaceous cenospheres and thus their abundance depends strongly
on the maceral composition of the coal and on the combustion conditions (12, 13).
The origin of the Ca-rich spheres is not clear. They are not spent sorbent particles since
the EDS spectra show no sulphur peak.
Fig. 2 SEM micrograph of carry-over (VA2 coal, SP1).
5.2Concentration vs. sampling point

The concentrations of selected elements in fly ash from different sampling points are
given in Table 2 for runs with recirculation and in Table 3 for runs without recirculation.
At this stage of the research it should be noted that for runs with recirculation (Table
2):
i) carbon shows an entirely different behaviour in the run with CO1 coal,
ii) carbon contents at SP2 and SP7 in the run with VA2 coal are much higher than in
the other runs,
Fig. 3. SEM micrograph of a carbonaceous cenosphere (PL8 coal, SP4).
Fig. 4 SEM micrograph of a Ca-rich particle (PL5 coal, SP7).
131
iii) the very high Ca concentration at SP1 in the run with VA2 coal can be probably
explained by the much higher sorbent flow in that run (see Table 1),
iv) trace elements are accumulated chiefly in the fine fly ash entering the bag filter
and captured there, however, Mn in samples from PL8 and VA2 shows a different
trend,
v) some deviant concentrations (eg. Cu SP3 PL8 or Cr in all SPs PL8) reflect
contaminations of the sample with corrosion/erosion products from the steel parts
of the installation,
vi) significant concentration differences of trace elements are found in the material
entering the bag filter (SP3) and captured there (SP4),
vii) most of the trace elements in samples from CO1 do not reflect the trend mentioned
in vi).
Runs with no recirculation (Table 3) yield obviously samples with much higher carbon
concentrations. Most trace elements do not show the trend mentioned in vi).
Table 2 Concentration vs. SP for runs with recirculation
dc
(m)
coal
%
C
S
%
Al
Ca
Fe
Si
ppm
As
Ce
Co
Cr
Cu
Mn
Ni
Pb
Th
V
Zn
SP1
SP2
SP3
SP4
SP7
20.0 37.7 22.6 17.6 16.2 14.7 2.6 2.6 1.8 2.6 1.8 1.7 11.0 15.3 12.1
PL8 VA2 CO1 PL8 VA2 CO1 PL8 VA2 CO1 PL8 VA2 CO1 PL8 VA2 CO1
17.4 17.8 15.2 20.0 32.8 13.8
2.7 5.5 3.1 2.7 4.2 3.6
3.4 6.8 6.7 8.5 8.3 6.1 15.9 22.2 13.9

2.9 2.5 1.6 2.5 2.4 1.6 2.6 4.0 2.6
8.2
14.2
8.6
15.0
6.8 8.0 9.4

29.0 12.0 12.0
5.8 6.6 6.6
9.1 20.0 16.8
10.0 8.4 11.3 13.2 10.2 11.3

13.6 8.3 9.6 9.2 5.1 9.8
6.5 6.6 6.3 6.3 7.2 6.7
14.6 22.7 18.7 18.2 23.5 18.2
13.1 10.8 10.7

10.1 5.2 10.2
6.5 7.6 6.8
17.5 23.0 18.0
18
108
28
784
93
895
112
31
13
185
139
30 20 20 43 20 62 79 23 57 82
51 54 104 89 52 220 181 103 199 166
35 11 30 64 11 97 123 20 89 122
81 80 690 147 91 402 239 179 203 187
90 32 96 125 42 1303 232 87 231 217
631 187 976 458 206 951 1148 272 932 1287
139 55 122 211 43 418 452 84 336 424
52 11 96 89 11 287 248 37 215 237
6.1 7.5 13 11 7.5 34 23 14 32 21
289 147 214 473 146 648 991 312 526 1090
162 87 165 221 88 309 284 119 282 337
24
104
21
134
73
278
80
34
15
302
NA
11.6 8.7
12.8 8.8
6.0 8.6
15.5 21.6
32 57
131 121
45 84
579 132
134 127
982 1434
182 238
107 109
18 6.4
398 509
178 205
20
66
15
100
37
206
39
NA
9.4
189
118
132
Table 3 Concentration vs. SP for runs with no circulation
dc
SP1
(m)
62.9 26.7
coal
VA2 CO1
%
C
49.4 24.7
S
2.9
2.7
%
Al
10.1
6.8
Ca
14.7 22.5
Fe
6.0
5.5
Si
13.4 14.9
ppm
As
32
16
Ce
65
50
Co
44
12
Cr
136
73
Cu
105
38
Mn
1326 171
Ni
209
38
Pb
89
13
Th
7.6
6.6
V
360 117
Zn
238 NA
NA=Not Available
SP2
35.1 16.5
VA2 CO1
SP3
2.9
1.7
VA2 CO1
SP4
2.1
2.6
VA2 CO1
SP7
29.4 17.6
VA2 CO1
68.2
1.4
34.9
2.4
22.4
2.1
19.0
2.0
14.1
1.4
22.3
1.7
47.3
1.9
35.2
1.7
10.8
9.6
7.3
15.6
8.4
13.3
5.1
20.3
13.3
7.7
5.4
19.2
9.9
8.6
7.8
21.1
15.1
4.5
6.3
20.6
9.3
6.8
7.7
20.5
12.5
7.0
6.5
17.8
8.4
14.3
6.1
18.3
43
96
69
167
497
1830
308
97
14
563
187
13
66
15
94
43
237
28
16
9.1
170
NA
85
154
98
216
470
1128
435
225
19
782
228
33
93
22
172
70
272
70
33
13
284
116
83
194
135
248
229
1234
563
258
25
1000
279
31
103
26
151
98
319
90
35
14
346
NA
48
100
64
568
138
1632
256
112
12
546
262
19
62
15
105
45
241
69
18
9.0
181
NA
5.3Concentration vs. particle size

The concentractions of the elements in fly ash from SP7, size-separated into fractions, are
given in Tables 4 and 5 for runs with recirculation and in Table 6 for the run without
recirculation.
Carbon shows the highest concentration in fractions of about 25 m size. Calcium
(originating mostly from the sorbent) is accumulated in the coarse fractions wherein Si
and Al (typical components of fly ash) are depleted. The much steeper increase in Ca and
its much higher final concentrations in samples from runs with VA2 coal as compared to
that with PL5 coal can be explained by the higher sorbent flow in the former (see Table
1).
All trace elements (volatile, non-volatile and intermediate) show the inverse
concentrationparticle size dependence, more pronounced in the material from runs with
recirculation. One notable exception among the trace elements is Mn which shows a
direct concentrationparticle size dependence in the material from runs with
recirculation and no dependence in the run without recirculation.
133
Table 4 Concentration vs. particle size in fractions of fly ash from SP7.
(Run with PL5 coal; recirculated)
Fraction
dl (m)
SS2
2.6
C
S
Al
Ca
Fe
Si
6.6
1.7
14.7
8.1
4.3
18.7
As
Ce
Co
Cr
Cu
Mn
Ni
Pb
Th
V
Zn
24
240
91
200
420
740
280
160
34
690
250
SS4
6.0
wt%
18.7
2.0
13.8
8.3
4.9
18.1
ppm
23
200
79
190
310
840
220
130
30
600
220
SS6
22.5
SS8
44.4
SS11
60.3
22.1
3.1
11.8
10.6
5.7
15.9
9.9
3.4
10.2
13.8
5.5
14.9
7.4
3.0
9.2
16.1
7.2
12.9
15
120
42
140
230
1050
140
83
18
180
160
13
100
35
120
200
1290
110
88
15
240
160
13
100
37
110
210
1500
110
77
15
220
200
(Run with VA2 coal; recirculated)
Fraction
dl (m)
SS1
3.5
SS3
4.0
C
S
Al
Ca
Fe
Si
15.4
2.2
14.1
8.9
5.2
19.0
16.6
2.5
12.9
10.7
5.8
17.4
As
Ce
Co
Cr
Cu
72
160
120
180
280
78
170
120
190
260
SS5
25.4
wt%
45.8
3.2
8.2
16.9
7.4
12.4
ppm
44
73
64
170
180
SS7
44.0
SS8
63.7
SS10
74.9
32.0
5.5
6.9
21.9
6.7
9.4
20.3
5.9
5.5
26.7
6.7
7.7
13.3
6.2
5.6
29.0
6.3
6.6
37
56
48
200
130
29
46
38
330
110
29
41
33
90
100
Mn
Ni
Pb
Th
V
Zn
1180
410
240
23
980
290
1120
370
210
22
920
340
134
1470
270
100
10
510
310
2640
160
54
7
500
210
390
130
44
5
120
230
1790
120
44
4
230
200
SS6
47.4
SS8
69.7
SS9
83.3
58.2
2.5
7.6
14.4
10.6
11.5
39.0
3.6
6.0
25.6
7.8
8.0
40.3
3.1
5.4
27.1
9.1
7.7
35
73
59
200
240
3830
240
69
9
400
310
26
59
40
180
230
3330
140
87
7
300
780
28
61
38
220
290
2430
150
74
7
330
290
(Run with VA2 coal; not recirculated)
Fraction
dl (m)
SS2
5.4
SS3
8.5
C
S
Al
Ca
F
Si
31.7
1.6
14.2
5.0
5.1
21.1
44.2
1.5
13.1
5.8
5.4
19.6
As
Ce
Co
Cr
Cu
Mn
Ni
Pb
Th
V
Zn
73
150
91
220
610
2010
370
210
20
870
260
69
130
79
210
430
1260
360
180
15
770
240
SS4
26.3
wt%
63.9
1.4
6.3
8.3
7.0
16.4
ppm
40
78
65
170
270
1270
220
86
12
570
210
5.4Surface analysis
The quantitative results of the surface analysis obtained so far will be published
elsewhere (14).
The thickness of the surface layer formed by condensation of volatile elements on the
particles surface depends on such factors as the residence time of the particles in the
combustion zone, their cooling rates, etc. and is not necessarily equal for small and large
particles. After the formation of the first molecular layers inward penetration by diffusion
into the fly ash is likely to occur, giving raise to a concentration gradient.
The analytically determined bulk concentration (cb) consists of two contributions: the
matrix concentration (cm), i.e. the concentration in the particle before condensation
135
occurs, and the surface concentration (cs), i.e. the concentration in the surface layer. The
contribution of the latter is small for very large particles and in such a case the bulk
concentration approaches the matrix concentration. Assuming that the particles and the
surface layers have equal densities and that the thickness of the surface layer is much
smaller than the particle radius the bulk concentration of the elements can be described
by:
[2]
where r is the particle radius and t the thickness of the surface layer. The dependence of
the bulk concentration upon the particle size gives the value of tcs as the slope of the cb
vs. 1/r plot, as well as the value of cm. When after a prolonged period the SIMS signal
remains constant it can be assumed that the surface layer has been sputtered off; the
resulting SIMS level is identified as cm, a value that is available from the size dependent
concentration measurements. Therefore, when the sputter rate is known the thickness of
the surface layer and also the surface concentration are experimentally available.
An examination of the SIMS profiles for similar fractions from the two runs with VA2
coal shows that some of the elements are enriched to a different degree at the surface of
the fly ash particles.
The surface enrichment for the three elements (As, Cu, V) is summarised in Table 7,
giving an enrichment factor, expressed as a percentage based on bulk levels, and
calculated depths over which the enrichment is observed. Arsenic has a similar level of
enrichment for both the recirculated and non-recirculated material. However, the
thickness of the As layer in the recirculated material is three times that of the nonrecirculated. This indicates that As probably diffuses into the matrix during the much
longer residence in the hot zone in the run with recirculation. For the other elements the
layer thickness remains at a similar level but there is an appreciable difference in the
level of surface enrichment.
Table 7 Enrichment depths and percentages (VA2 coal) (14)
Run with no circulation

Fraction size 26.3 m
Element
Depth
%*
As
16
370
Cu
15
256
V
15
330
* Bulk concentration levels taken as 100%.
Run with circulation

Fraction size 25.4 m
Depth
%*
48
380
20
158
16
143
5.5Environmental hazards of dumped material

Two questions are important to describe the long-term behaviour of a dumped material
136
and the environmental hazards caused by this material:

i) Which components can be tolerated for a long-term disposal, at what concentrations
and as what compounds?
ii) Which components get into the biosphere, at what concentrations and in what total
amounts, as what chemical compounds, and in what periods of time?
In the Federal Republic of Germany, the procedure is as follows: Guiding- and/or
threshold values are listed in guidelines (for instance (1)). This permits a classification of
materials to be dumped. For this classification the substances are leached in a shaking test
conforming to DIN 38414 S4 (2). The leachates are tested and analysed for about 40
properties and elements. The results are compared with the guiding values and the
materials are classified accordingly into one of 5 or 6 different dump classes.
The shaking test described in (2) does not, however, reflect the reality since neither the
permeability of the dumped material, nor the chemical, physical, and microbial long-term
effects, nor various effects depending on different weather conditions, are taken into
account. Besides the guiding values relating to this test cannot be used for results of other
tests.
In the BF, a long-term test with large-scale lysimeters (Fig. 5) was developed which
permits a practice-oriented leaching of dumped materials. These lysimeters are
cylindrical containers, made of inert poly-propylene, 2 m high with a cross-section of 2
m2. They are filled to a height of 0.5 m with gravel of graduated grain sizes. The effluent
from the peripheral and central areas can be collected separately at the bottom of the
lysimeter. It should be stressed that the central area is not disturbed by wall effects and is
regarded as a realistic model of a disposal site. The lysimeters are surrounded by soil to
prevent lateral climatic influences on the dumped material and are exposed only to the
natural rainfall.
The effluents are collected once per month and the amount of effluent is measured.
Concentrations of anion and trace elements, as well as some physical properties are
determined. Plots of these results vs. time are used to correlate them to climatic
conditions (amount of rain) and seasonal effects (microbial activity) (4).
For all FBC fly ash samples investigated in lysimeters up till now, very small amounts
of effluents have been produced. Evidently more than one year is needed before effluent
from a largescale lysimeter can be collected. The reason of the low permeability is the
formation of ettringtte. The needle-like crystals (Fig. 6), grown in the intergranular
spaces lead to a monolithisation effect. This is typical for all FBC fly ash samples
containing free CaO.
To compare different leaching methods the results should be plotted not against time
but in such a way that the x-axis represents the quotient of the total quantity of effluent
produced during the test period and the quantity of the solid material leached out, and the
y-axis represents the load, i.e. the total mass of a component in the effluent in relation to
the quantity of solid material leached out (15, 16).
Leachates from samples TNO 1 and TNO 2 (Runs 180 and 210, resp.; see Table 1)
obtained in laboratory tests have initial pH values of 12 to 13. In large-scale and smallscale lysimeter tests, pH values start at 4.5 (sample TNO 1) and rise to about 810.
137
Effluents from sample TNO 2 show pH values of 12 to 13 without change in all tests.
Summing up:
For the FBC residues tested by using the laboratory tests (shaking and column) and the
lysimeter test, and applying the evaluation method described above, the results are as
follows:
Fig. 5 Schematic drawing of a BF large-scale lysimeter.
138
Fig. 6 SEM micrograph of ettringite crystals. Bar=10 m
- In a shaking test samples from the TNO AFBB give off effluents which would not
allow disposal in a normal dump class 2 or 3, due to high pH value and high anion
contents.
- In the column test a certain self-hardening occurs.
- In the lysimeters a monolithisation takes place and no effluent has been released in
the first one or two years of testing. This effect is due to the formation of ettringite
(Fig. 6).
This means that the environmental hazard posed by these FBC residues is quite small and
cannot be evaluated properly using shaking or column tests only.
REFERENCES
(1)Entwurf einer Richtlinie ber die Untersuchung und Beurteilung von Abfllen Teil 2,
LWA, NRW, Dsseldorf, June 1987.
(2)DIN 38 414 S4, October 1984.
(3)EP 0173 971 A2: Auffangbehalter fr Versickerungsmesser.
(4)FRIGGE, J., Lysimeteruntersuchungen zur Beurteilung des Deponieverhaltens von
Kraftwerksnebenprodukten. VGB Kraftwerkstechnik, 68, 143150, 1988.
139
(5)TEMMINK, H.M.G. and MEULINK, J., Operating experiences with the TNO 2M X 1
M atmospheric fluid bed boiler facility. Proc. 3rd European Coal Utilisation Conf.,
Oct. 1113, 1983, Amsterdam, Vol. 2, 99123.
(6)LESCHONSKI, K., Classification of Particles in Gases, IFPRI-report,Clausthal, 1981.
(7)GAY, A.J. et al., A convenient method combining the morphological and chemical
analysis of coal fly ash with particle size determination. Proc. 2nd Int. AshTech 84,
Sep. 1621, 1984, London, 912.
(8)ROTSCHEID, G.J. et al., Investigation Into the Applicability of a Method Derived
From MicroElement Analysis to the Determination of the Total Sulphur Content of
Coal Products. TNO-report 83/045/1207/10298/GR/CK, 1983.
(9)Bergbau Betriebsblatt, BB 22 022, Pt. 2, May, 1985.
(10)G 8707 159.2. Vorrichtung zur inversen Sulenelution.
(11)GAY, A.J. et al., Characterisation of fly ash from fluidised bed combustion of coal.
COAL 87, Proc. 6th Int. Conf. Coal Technol. Economics, London, 611 June 1987,
6375.
(12)GAY, A.J., et al., Formation of carbonaceous cenospheres during fluidized-bed
combustion of bitumous coals. Fuel, 62, (10), 12241226, 1983.
(13)GAY, A.J., et al., Studies of carbonaceous cenospheres from fluidised-bed
combustors. Sci. Total Environ., 36, 239246, 1984.
(14)GAY, A.J., et al., The use of secondary ion mass spectroscopy (SIMS) in the study of
toxic trace elements on FBC fly ash particles. Proc. 1988 MAS/EMSA Annual
Meeting, Milwaukee, WI, Aug. 712, 1988, to be published.
(15)FRIGGE, J., Beurteilung des Deponieverhaltens von Kraftwerks-Nebenprodukten.
Gewsser-schutz-Wasser-Abwasser, 99, 227246, 1987.
(16)FRIGGE, J., Prufung des DeponieverhaltensWie praxisnah sind Labortests?
Gewsser-schutz-Wasser-Abwasser, to be published.
ADSORPTION AND DESQRPTIQN

PHENOMENA OF POLYCYCLIC AROMATIC
HYDROCARBONS ON FLY ASH
Author :
Contract
number :
Duration :
Total Budget :
Head of
project :
Contractor :
Address:
Dr L.J.M.Rodenburg
EN3F-0031-NL
43 months 1 June 198631 December 1989
Dfl. 724.000 CEC contribution: Dfl. 362.000
Dr L.J.M.Rodenburg
TNO Division of Technology for Society
TNO Division of Technology for Society P.O. Box 217
2600 AE Delft The Netherlands
SUMMARY
In this paper the results of vacuum sublimation experiments are presented and discussed.
Vacuum sublimation experiments show that only low concentrations of PAH can be
detected in six of the seven fly ashes under investigation. Sublimation at high temperature
(175C) leads to a decrease of the extraction efficiency in comparison with sublimation at
60 or even at 30C. Although the cause of this effect has not been investigated, it is
probable that chemical conversion of the PAH on the fly ash surface gives rise to this
phenomenon. The fly ash with considerable amounts of PAH deviates from this
behaviour, i.e. the collected amounts of PAH are higher at 175C than at 60 or 30C.
1.INTRODUCTION
The analysis of polycyclic aromatic hydrocarbons (PAH) is of utter importance in
environmental research. It is known from the literature that extraction of PAH from
environmental samples is generally incomplete, so that uncertainty remains about the
absolute amounts of PAH in these samples. It is, therefore, necessary to develop and
evaluate techniques suitable for the isolation of adsorbed PAH for analytical purposes.
To assess the feasibility of reduction of PAH emissions by temperature-assisted
adsorption of PAH on fly ash in the bag-filter house of coal-fired installations, it is
necessary to gain an insight into the adsorption behaviour of PAH on fly ash. Insufficient
knowledge of this behaviour is available from the literature.
The project thus has two main objects:
Adsorption and desrptiqn phenomena
141
1. Extraction of PAH from fly ash for analytical purposes;

2. Study of the adsorption behaviour of PAH on fly ash.
1.1EXTRACTION OF PAH
For analytical purposes it is necessary to develop methods for the extraction of PAH from
fly ash in the highest possible yield. Several extraction techniques will therefore be
compared to establish which extraction method(s) is (are) most suitable for fly ashes.
This part of the research programme is performed in cooperation with BergbauForschung GmbH (Essen, FRG). The work performed by Bergbau-Forschung is reported
in a separate paper.
The following extraction techniques are under investigation:
a.
b.
c.
d.
e.
ultrasonic extraction
Soxhlet extraction
liquid extraction
vacuum sublimation
supercritical CO2 extraction
Extraction methods ac will be performed by Bergbau-Forschung, and methods d and e

by TNO.
The ashes under investigation originate from small coal-fired installations (2.44.5
MW). All ashes are pure bag filter ashes, with the exception that one ash is a mixture of
cyclone and bag filter ash.
1.2ADSORPTION OF PAH ON FLY ASH
Reduction of PAH emissions by coal-fired installations may be achieved by adsorption of
PAH on fly ash in the bag filter house of such installations. To study the gaseous
adsorptive behaviour of PAH on fly ash, PAH has to be generated in the gas phase. For
the exposure of fly ash to the stream of gaseous PAH, a so-called shallow-bed
apparatus had to be built. Detection of PAH concentration in the gas phase is difficult,
owing to their low vapour pressures and resulting low concentrations. PAH
concentrations can be measured by fluorescence analysis of the air stream, or by
determining the absolute amounts in air samples collected batch-wise. Both methods are
being investigated for application in the experimental set-up.
The results presented here deal with vacuum sublimation only.
The extremely low vapour pressures of PAH, e.g. pyrene has a vapour pressure of 2.A
106 mm Hg at room temperature, made it necessary to construct a sublimation apparatus
in which the impinger can be cooled with boiling nitrogen (77 K),Figure 1. The effect is
that the PAH are condensed far more efficiently on the impinger than with water as the
142
coolant. The fly ash is heated on a water or an oil bath. To test the apparatus fly ash
spiked with pyrene was submitted to vacuum sublimation in several experiments. In table
I the results of these experiments are given. It can be concluded from these data that the
recovery of pyrene is good, i.e. up to 97%, and that the experiments give reproducible
results (10%).
Table I Results of tests with the vacuum sublimation apparatus. Fly ash spiked with pyrene was
used in these experiments.
experiment
1
2
3
4
time (min)
30
30
60
60
temp (C)
40
60
60
60
p (mm Hg)
0.10
0.15
0.15
0.10
recovery (%)
16
52
97
89
Figure 1. Vacuum simulation apparatus.
Vacuum sublimation experiments with the fly ashes have been performed at
temperatures of 20, 30, 60, and 175C, at pressures of 0.020.05 mm Hg. The samples
obtained have been analyzed for 15 PAH. From the data given in Tabel II (in which the
Zevenhuizen ash is typical for all fly ashes with the except of the De Lier ash) we
can deduce the following. PAH contents of the ashes are low and in most cases only PAH
of low molecular mass can be detected, i.e. phenanthrene, anthracene, fluoranthene, and
pyrene. Remarkable is the fact that sublimation at high temperature (175C) does not lead
to higher yields of recovered PAH. In fact, there seems to be an optimum in yield in the
temperature range of 30 to 60C (Figure 2). The decreasing amounts of PAH at high
temperature can be explained by the fact that PAH are chemically activated when
Adsorption and desrptiqn phenomena
143
adsorbed on fly ash, as is known from the literature [1]. Experiments have been
performed in our laboratory in which it was shown that pyrene reacts readily, even at
room temperature, when adsorbed on fly ash [2]. The fact that the fly ashes under
investigation have been collected in 1984 could mean that aging of the ashes has led to
the low PAH content which we now observe.
The De Lier ash is completely different from all other ashes. Not only is the PAH
content much higher, the amounts of collected PAH increase with increasing temperature.
At 175C the largest quantity of PAH is collected (Figure 3). This could mean that the
surface of the fly ash does not activate the PAH.
3.CONCLUSION
The apparatus for the vacuum sublimation experiments serves well for its purpose, as was
shown in tests with spiked fly ash, in which pyrene was recovered up to 97%.
The fly ashes contain low quantities of PAH, except for the De Lier ash. At high
temperature (175C) the recovered amounts of PAH decrease dramatically, probably due
to chemical conversions. In the case of De Lier ash, it is found that the amount of
recovered PAH increases with increasing temperature. No decrease at 175C can be seen.
It must therefore be concluded that the De Lier ash differs completely from all the
other ashes.
The aging of the fly ash samples may cause underestimation of the quantities of PAH
initially adsorbed on the ash.
Table II. HPLC analysis of vacuum sublimation samples of De Lier and Zevenhuizen fly ash.
Analysis is performed with a reversed phase column and with fluorescence detection at
>385 nm (exc 254 nm).
Component
De Lier ng/g
Zevenhuizen ng/g
20C 30C 60C 175C 20C 30C 60C 175C
Phenanthrene
120.4 27.4 462.0 2500 21.3 20.8 37.4
2.6
Anthracene
2.6 0.8
8.5 >320 2.1 2.0 2.0
0.1
Fluoranthene
42.1 14.1 161.7 >4100 11.4 9.4 24.5
1.7
Pyrene
<19.8 <19.1 <44.7 1400 <16.3 <15.4 14.3
0.6
<5.4 <44.8 <207.9
<38.3 <36.2 <36.7 <4.0
Trifenylene
Benzo [a] anthracene
14.6 <8.3 62.4 1600 < 7.1 <6.7 <6.8 <0.8
35.3 <28.2 154.0 1900 <24.1 <22.8 <23.1 <2.0
Chrysene
<48.2 <46.5 184.8 2200 <39.8 <37.5 <38.1 <4.2
Benzo[e]pyrene
<1.7 <1.7 <7.7 130 <1.4 <1.3 <1.4 <0.2
Perylene
Benzo[b]fluoranthene
34.4 9.1 146.3 >2000 <2.8 <2.7 <2.7 <0.4
Benzo[k]fluoranthene
13.8 4.2 59.3 >830 <0.7 <0.7 <0.7 <0.2
Benzo[a]pyrene
13.8 5.0 62.4 700 <3.6 <3.4 <3.4 <0.3
<33.5 <32.4 238.7 1100 <27.7 <26.1 <26.5 <3.5
Benzo [ghi] pery lene
45.6 11.6 200.2 1300 < 6.4 <6.0 <6.1 <1.2
Indeno [1, 2, 3cd] pyrene
Anthanthrene
3.4 < 3.3 14.6
47 <2.8 <2.7 <2.7 <0.5
144
4.FUTURE WORK
In the remaining period of the project, supercritical CO2 extraction experiments will be
performed. For this work a supercritical CO2 extractor has been bought, which operates
at pressures ranging from 75 to 325 bar and at temperatures ranging from 35 to 90C.
When all extraction experiments have been performed, the results will be evaluated
together with the results obtained by Bergbau-Forschung. As a result it will be possible to
tell what extraction method(s) is (are) most preferred for the quantitative extraction of
PAH from fly ash samples.
In order to investigate whether PAH emissions from small coal-fired installations can
be reduced, adsorption experiments will be carried out. To determine the concentration of
PAH in the gas stream, a direct, continuous method, by means of fluorescence detection,
will be developed. If this method causes too much technical problems, the concentration
will be determined by measuring absolute amounts of PAH by batchwise collection from
the gas stream. After exposing the ash to gaseous PAH, the PAH content of the ash will
be determined by extracting the ash. The extraction method which has been proved to be
the best for extracting fly ash in the first part of the project will be applied in this part of
the research project.
5.LITERATURE
[1]Daisey, J.L. and P.R.Boone, Rates and products of reaction of benzo[a]pyrene
adsorbed on various particles, APCA, 79th Annual Meeting, 8677.3, 1986.
[2]Rodenburg, L.J.M., Verlaagde recovery van PAK van vliegas door verwarming
(Decreased recovery of PAH from fly ash due to heating), MT-TNO report R
88/148, 1988.
Figure 2. Amounts of some PAH found in Zevenhuizen fly ash by vacuum

destination.
Figure 3. Amounts of some PAH found in De Lier fly ash by vacuum

destillation.
ADSORPTION AND DESORPTIQN

PHENOMENA OF POLYCYCLIC AROMATIC
HYDROCARBONS ON FLY ASH
Authors :
Contract number :
Duration :
Total budget :
Head of project :
Contractor :
Address :
K.KLEMM and K.G.LIPHARD

EN3F0030D
ECU 215658 CEC contribution: ECU 107829
Dr. W.LIPHARD
BERGBAU FORSCHUNG GmbH
Franz-Fischer-Weg 61
D4300 ESSEN 13
Summary
Previous research in this project dealt mainly with soxhlet extraction in general and
related work as purification of solvents and extracts, testing several solvents in terms of
extraction power to PAH, stability at boiling point and selectivity. Previously used
solvents were methanol, dichloro-methane, trichloromethane, tetrachloromethane,
cyclohexane, benzene, toluene, all xylenes, mesitylene, tetralin, tetrahydrofuran and
acetic acid.
Additional investigations to separate PAH from fly ash as ultrasonic extraction and
sublimation have been applied. The special refractory desorptivity of PAH from fly ash,
derived from fluidized bed combustion, made it necessary to get some more information
about the surface structure. For this reason the fly ash was investigated by electron
microscopy. To improve contact to solvents, crushing by the pressure drop method has
been performed.
1Materials
All investigations were carried out on fly ash from the FBC in Apeldoorn. The PAH
content of this FBC fly ash is typically low and shows the special refractory desorptivity
for PAH. It is assumed, that most results acquired from Apeldoorn samples are
transferable to other FBC fly ashes of different origin. The sample has already been
characterized in terms of elemental and mineralogical composition. Moreover, the
understanding of sorption phenomena needs the consideration and detailed knowledge of
special properties as carbon content, surface area and particle size.
Adsorption and desorptiqn phenomena
147
1.1Surface investigations
Since the particle surface is of some importance for its adsorption behaviour, it has been
investigated by electron microscopy. The aim of the investigations with the stereoscan
was, to get an idea of shape, porosity and agglomeration of the particles.
It was found, that no sintering occures and only particles with porous surface are
received. The combustion temperatures of fluidized bed combustors are too low for the
formation of cenospheres with a smooth surface. The photographs in the appendix show a
porous surface with some typical structures of fly coke. These particles are suspected to
be responsible for the powerful adsorption behaviour of PAH, as it is published in the
recent literature [1]. Elemental analysis of the Apeldoorn fly ash gave a carbon content of
about 15%, which is to some extent from unburnt coke. Isolation or enrichment of coke
particles will be object of further investigations to confirm this assumption.
1.2Particle size reduction and measurement
Further investigations were carried out, to ground the fly ash for improved contact
between sample and solvent for extraction. To reduce the particle size, the fly ash was
ground with a mortar and a swing mill. More selective fragmentation was expected from
a pressure-drop apparatus, where the fly ash was abrupt expanded from 180 bar nitrogen
pressure to about 1 bar. The sudden expansion leads to the cracking of all open pores
which were filled with compressed gas. In cases where a large porous system increases
the surface and adsorption of organic compounds, respectively, this method should
prepare the sample for more effective extraction with organic solvents. The particle size
distribution of untreated fly ash and the efficiency of grounding was screened with a laser
optical particle sizer. From the particle size analysis it is evident, that it was not possible
to achieve any cracking of the TNO 3 ash by the pressure drop method. It is supposed,
that the porous system which was observed with electron microscopy is just superficial.
2Analysis
2.1HPLC
Because of its better selectivity towards aromatic compounds, the separations were
carried out on a HPLC-apparatus combined with ultraviolet detection. The HPLC is run
with a C 18 column and H2O/MeOH gradient at 40C. The identification and
quantification of compounds is performed by running an individually designed
calibration mixture as shown in figure 1. Table 1 shows a listing of substances and peak
numbers of the calibration mixture in order of retention time.
2.2GC/FID and GC/MS
The advantage of higher sensitivity in GC/FID analysis is lost, since a wide variety of
non aromatic compounds in the extracts cause interferences in FID detection.
148
Purification on an open tubular column with silicagel and Sephadex LH 20 gave

irreproducible losses in the first experiments. For the evaluation of possible errors during
an analytical procedure it is unsuitable to involve a clean up step with uncomplete
recovery from the beginning. For this reason, purification of samples will be a part of the
investigations later in this project.
Therefore it is intended to use a GC with a mass selective detector in future
investigations. Recent activities dealt with preliminary gas chromatography/mass
spectrometry investigations in the multiple ion detection mode. MID is a very
sophisticated method for combined qualitative characterization and sensitive
determination of organic compounds. Due to its selectivity for exact molecular masses it
provides a reasonable signal to noise ratio without preceding sample clean up.
3Sample Extraction
3.1Soxhlet-Extraction
The above mentioned peculiarity of FBC fly ash requires striking extraction methods
combined with very sensitive analytical detection. Objects of the investigations were
ultrasonic extraction and soxhlet extraction with different solvents. Best results but still
incomplete recoveries are received with soxhlet extraction. The findings vary with the
different solvents and extraction times. The following solvents have been used :
methanol, dichloro-methane, trichloromethane, tetrachloromethane, cyclohexane,
benzene, toluene, all xylenes, mesitylene, tetralin, tetrahydrofuran and acetic acid.
All solvents do not have striking extraction power for the low loadings of PAH on
FBC fly ash. From all solvents, used in soxhlet extraction it can be established so far, that
extraction power increases with boiling temperature and aromaticity. Xylenes with
boiling points of about 140C gave the best results for most of the investigated PAH, but
need lavish purification. It is very important, that xylenes may cause systematic errors
due to formation of traces of polycyclic aromatic compounds even in the pure solvent as
a result of heat treatment. These compounds create interferences, either because they are
identical to, or they have similar retention data as some PAH which are object of the
investigations in this project. Figure 2 shows the enlarged chromatogram of vacuumdistilled pxylene. The peaks of newly formed compounds can be seen in the
chromatogram in figure 3. Here the pure solvent was boiled in a soxhlet apparatus for 16
hours without a sample.
The extracts from mesitylene-, tetralin- and tetrahydrofuran- soxhlet-extractions were
slightly polymerized so that evaporation of the solvent was difficult. The chromatograms
showed unresolved peaks in important retention areas due to this polymerization or
formation of derivatives. Therefore it is partly impossible to determine certain PAH. On
the other hand, the recovery of PAH with longer retention times, where no such
interferences were observed, are higher than in toluene extraction. It was assumed that
high boiling solvents provide an improved solubility and mass transfer, despite the fact,
that they may cause systematic errors when kept at high temperatures for a couple of
hours. The effect of polymerization to an oily product is shown for tetralin in figure 4.
Adsorption and desorptiqn phenomena
149
Acetic acid is a reasonable solvent which doesn't cause interferences. Its solvent
strength for PAH is comparable to the low boiling chlorinated hydrocarbons. An
important disadvantage of acetic acid is the formation of salts from the mineral part of the
fly ash. After evaporation of the solvent a salt residue remains, which has to be isolated
from the organic part by water extraction. Since it is unsuitable to have too many steps of
sample preparation in trace analysis, extraction with acetic acid is not recommended. It
was found that water is contaminated with PAH in a way that it might affect the
determination without further purification by preextraction.
The results of all soxhlet extractions were always compared in parallel runs with
toluene. The time for the extractions was fixed to 16 hours with normalized conditions.
3.2Ultrasonic extraction
The extractions were first carried out at room temperature with distilled toluene. To avoid
a sorption-desorption equilibrium in the solvent/sample suspension, fresh solvent was
added after removing half the volume of the extract. The sample was kept in a precleaned
soxhlet extraction tube. The results of ultrasonic extraction at about 22 C were very poor
compared to soxhlet extraction. Additionally, the porous material of the tube released
particulate matter of small particle size into the extract and made additional filtering
necessary.
Results from ultrasonic extraction at different temperatures between 40C and 95C
are not longer valid as they were reported earlier. Further investigations showed, that
softeners or other compounds were released from the plastic material of filters for organic
solutions at the high solvent temperatures. These compounds interfere with PAH in
HPLC-analysis. From this state of affairs, it is necessary to continue the work in this area,
carefully screening artifacts, deriving from used materials and reagents.
4Future Work
For the evaluation of the importance of carbon content on the adsorption behaviour, we
will separate a sample into several size fractions, in order to preconcentrate the fly coke.
It was found, however, that many carbon particles are larger than any other component of
the apeldoorn fly ash TNO 3. So, the fraction of particles>180 m mostly contains
unburnt carbon particles. Separation and analysis of this fraction, after spiking the fly ash,
may answer the question of preferred adsorption of PAH onto carbon.
Future work will deal with other extraction methods prior to soxhlet extraction, since a
wide variety of solvents has been used with minor success.
To avoid the formation of artifacts, using solvents at high temperatures, it is intended
to carry out some more investigations concerning sublimation. Here, some experiments
have been carried out to examine optimum parameters in terms of temperature an vacuum
range.
In mass spectrometry, the same MID-technique as used in GC/MS analysis will be
applied to the solid sample during temperature controlled desorption from the sample
inlet of the mass spectrometer. This will gain some information about properties
150
concerning thermal sublimation of PAH from fly ash. On the other hand, this method will
be applied to the fly ash, to get a reference procedure for the PAH determination by
extraction in general, since it might be an instrument to compare fly ashes before and
after removal of organic compounds by extraction or sublimation.
Organic compounds are desorbed temperature programed, directly from fly ash in the
mass spectrometer with on-line detection. The required amount of sample is very low,
which improves heat transfer and diffusion of organic compounds through the sample.
The mass spectrometer provides very low pressure and sensitive detection. Results of this
method are thermograms, which show the desorption behaviour of certain masses.
Furthermore, it should be possible to get quantitative information when te reproducibility
is sufficient and NBS-standards are used additionally.
5References
[1]Griest, W.H.; Tomkins, B.A.Sci. Total. Environ. 1984,36, 209
APPENDIX
Fly Ash Apeldoorn 960x
Fly Ash Apeldoorn 1760x
Fig. 1
Table 1
Fluoranthene
Pyrene
Triphenylen
Cyclopenta [cd] pyrene
Benz [a] anthracene
Chrysene
Benzo[b]naphto[2 , 1-d]thiophene
Benzo [e] pyrene
Benzo[b]fluoranthene
Benzo[k]fluoranthene
Benzo[a]pyrene
Dibenz[ah]anthracene
Benzo[ghi]perylene
Indeno [1, 2, 3 -cd] pyrene
Indeno [1, 2, 3 -cd]fluoranthene (int. standard)
Anthanthrene
Coronene
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Fig. 2
Fig. 3
Fig. 4
1Fluoranthene
2Pyrene
3Triphenylen
4Cyclopenta [cd] pyrene
25.84 ng.g1
38.23 ng.g1
4.58 ng.g1
0.00 ng.g1
5Benz [a] anthracene

6Chrysene
7Benzo[b]naphto[2, 1-d]thiophene
8Benzo [e] pyrene
9Benzo [b] fluoranthene
10Benzo [k] fluoranthene
11Benzo [a] pyrene
12Dibenz [ah] anthracene
13Benzo [ghi] perylene
14Indeno [1, 2, 3 -cd] pyrene
15Indeno [1, 2, 3 -cd] fluoranthene (int. standard)
16Anthanthrene
17Coronene
Concentration of PAH on FBC Fly Ash from Apeldoorn.
6.26 ng.g1
10.09 ng.g1
10.73 ng.g1
7.00 ng.g1
5.15 ng.g1
3.10 ng.g1
3.39 ng.g1
1.23 ng.g1
3.93 ng.g-1
1.73 ng.g1
2.23 ng.g1
3.74 ng.g-1
WASTE/SOIL INTERACTION STUDIESTHE

LEACHING OF MOLYBDENUM FROM
PULVERIZED COAL ASH
Authors :
Contract
numbers :
Duration :
Total budget :
H.A.van der Sloot, O.Hjelmar, G.J.de Groot

EN3F-0032-NL and EN3F-0033-DK

ECN f. 480.000,CEC contribution: f. 240.000,
VKI DKr 2.420.000,DKr 1.210.000,
Head of Project : Dr. H.A.van der Sloot, Netherlands Energy Research
Foundation
Dr. O.Hjelmar, Water Quality Institute
Contractor :
Water Quality Institute
Netherlands Energy Research Foundation,
Address :
P.O. Box 1, 1755 ZG Petten, The Netherlands
Water Quality Institute,
Agern allee 11, DK-2970 Hrsholm, Denmark
Summary
In this work the leaching of molybdenum from pulverized coal ash addressed to illustrate
the similarities between a number of leach testprocedures. It highlights the usefulness of
the different methods in obtaining information to assess the release and fate potentially
hazardous components from waste materials in the soil system. For this purpose, column
leaching tests, batch extraction procedures, lysimeter measurements, diffusion
measurements, measurements of the interaction at the waste/soil interface and migration
measurements at low percolation rates have been carried out. The combined information
from these methods leads to a more detailed insight into the factors relevant to the impact
assessment of undesirable components from combustion residues. The sequence of
diffusion, interface interaction and migration measurements using radiotracers yields
valuable information about the behaviour of the stable elements, which is difficult to gain
from conventional techniques. The simplicity of the procedure and the versatility in
studying the influence of variations in relevant parameters (e.g. pH, complexing capacity,
redox) offers a great potential in tackling the complex phenomena occuring in waste/soil
systems.
Waste/soil interaction studies
157
1.INTRODUCTION
Assessment of the environmental impact of combustion residues resulting from a more
extensive use of fossil fuels for energy generation requires detailed information regarding
the leachability of potentially hazardous components under a wide variety of site specific
applications and disposal conditions. Leachability studies on combustion residues have
generally not been very systematic. Numerous test procedures have been applied, but
they are seldom comparable due to widely varying experimental conditions. For a given
component, leaching percentages may vary over orders of magnitude depending on the
experimental set-up. The pH has been found to be a very important factor, as a relatively
small change in pH may lead to orders of magnitude change in concentration [1, 2, 3].
Leaching tests designed to give information on leachability under natural conditions in
the environment should therefore not be based on extractions with strong mineral acids,
strong complexing agents and the like, since there are no means to relate the test results
to actual environmental conditions .
In The Netherlands a test procedure for combustion residues has been proposed and
standardized. It consists of a combination of a column test and a serial batch test, in
which the material is allowed to dictate the leachate composition [4]. This combination
will give information on the leachate composition as a function of time and/or percolate
production, thus yielding information on a wide variety of field conditions.
Combustion residues are used in construction materials and in stabilization products.
The leaching characteristics of products containing combustion residues have been
studied and a test procedure for obtaining effective diffusion coefficients, is available [5,
6]. This procedure evaluates intrinsic properties by tank leaching experiments and allows
for translation to other conditions than those strictly pertaining to the experimental set-up.
Since leaching of waste forms is often diffusion controlled, results from tank leaching
studies have been compared with diffusion measurements on crushed waste forms [6].
This led to a good agreement in the case of molybdate mobility in a stabilized, pulverized
coal ash/gypsum product. Here we will restrict ourselves to fine granular solids.
To be able to relate laboratory leach tests to field situations and in particular for an
assessment of long term effects more information is needed on the chemical forms
present in the leachate and the solid phase. This information can not be derived from
leach tests. Chemical interactions may be too slow to be observed in leaching tests of
short duration, but may prove very important under conditions of extremely low
percolation rate in the field. An example may be the behaviour of Cr, which is released
from pulverized coal ash in the form of chromate mainly, as was observed in shake tests.
Trivalent chromium is effectively retained in pulverized coal ash and the reduction of
chromate to trivalent chromium is slow. Consequently, all chromate is slowly converted
to the trivalent form, thus explaining the low dissolved Cr in percolate from a compacted
coal ash dumpsite [7].
More detailed information on speciation can be obtained by tracer mobility
measurements, which have been used in radionuclide migration studies [8, 9]. These
methods have to our knowledge not been applied to waste materials before. In the
158
radionuclide migration studies attention is focussed on actinides and fission products [9].
In soils the main emphasis has been on the mobility of nutrients from fertilizers. In the
case of combustion residues elements like As, Sb, Se, Mo, W, and V, which are released
as anionic species, are most important. Leachability data on these elements are limited
and information on the behaviour in the soil is poor [10, 11, 12]. When information on
their behaviour in the soil system is available, it is seldom applicable, as the percolate
composition from combustion residues may alter the properties of the soil to such an
extent, that the retardation of a given element may change drastically. Data on the
changing properties of the soil system as a result of the percolate composition are needed
to properly model the transport of potentially hazardous components from waste disposal
sites or waste containing products.
A wide variety of materials and many potentially hazardous components can be tested
with the diffusion tube procedure. An advantage of this procedure is that processes are
studied under conditions that closely resemble the actual situation in the field in terms of
porewater composition, realistic concentrations of target components, interaction of
components of interest, liquid/solid ratio. In addition, the chemical form of the tracer can
be changed and alterations in the chemical environment (e.g. redox status, pH, capacity
of complex formation) can be studied. The waste/soil interface can be studied by
combining waste and soil in one diffusion tube and measuring the transport of tracer from
the waste into the soil. The same approach has been proven feasible with convective flow
across the interface.
This paper aims to establish a relationship between laboratory leaching tests and field
conditions by comparing laboratory test results (ECN.Petten) with those obtained from
large scale lysimeters by the Water Quality Institute (VKI, Copenhagen, Denmark). It
will focus on the leachability of molybdenum from pulverized coal ash as an example of:
1. the systematic behaviour of leaching
2. the interaction of molybdenum from pulverized coal ash with different soil types
under both static conditions and with convective flow
3. the speciation of molybdenum and
4. the relationship between laboratory experiments and field data.
2.MATERIALS AND METHODS
2.1.Materials
The pulverized coal ashes used in this study were obtained from Dutch and Danish coal
fired installations. According to an earlier proposed classification acidic, neutral and
alkaline reacting ashes were selected for specific purposes [1]. Some of the data
presented in this paper refer to ashes collected in an earlier study on the classification of
coal ashes [13]. The soil samplesclay, sand and peatwere collected from the C
horizon in the Netherlands by STIBOKA, Wageningen. More detailed information on the
sample origin and properties is given in ref. [14]. In this paper only data relevant to
molybdenum behaviour will be presented. In table I the molybdenum content of the
159
materials studied are given.

Table I. The molybdenum content of the materials studied.
Material
Pulverized coal
ash 50 (acidic)
Pulverized coal
ash 44 (neutral)
Pulverized coal
ash PCA-N (neutral)
Pulverized coal
ash 9 (alkaline)
Pulverized coal
ash VKI (alkaline)
Mo (mg/kg) Material
23.5
Clay
Mo (mg/kg)
<1
15
Sand
<1
20
Peat
<1
3.3
Pulverized coal
ash HF1 (neutral)
Pulverized coal
ash BF2 (alkaline)
18
14
6.4
2.2.Methods
2.2.1.Leach tests
For fine grained materials, like pulverized coal ash, a standard Dutch protocol [4] has
been applied. It consists of a column test up to a liquid/solid ratio (LS) of 10 and a serial
batch test of five successive extractions at LS=20 on the same sample. This procedure
results in a concentration variation with the liquid/solid ratio, which is related to a time
scale through the percolation rate.
In a number of cases batch extractions have been carried out to characterize the
variation of the leachate concentration with pH, LS and contact time. Details on these
experiments are given in ref.[13] and [15]. The leachable fraction is assessed by
extracting the sample at a liquid/solid ratio of 100 at a constant pH of 4 [4].
2.2.2.Lysimeter experiments
The EEC contract work includes the continuation of several large scale lysimeter
experiments at the Water Quality Institute, in which pulverized coal ashes and flue gas
desulfurization products are exposed to rainwater infiltration. The percolate is collected
through drains at the bottom of the lysimeters. These experiments now running for 6
years allow for a comparison between laboratory and field conditions in the short term
(LS=12, at present). Detailed information on the construction, collection scheme,
analyses of percolates, and interpretation of the first 3 years of data collection is given in
ref. [16]. For comparison field data on actual ash disposal sites [17] and ash applications
[18] are given.
2.2.3.Diffusion and migration measurements
As part of the EEC contract work a procedure for the measurement of (trace) element
160
diffusion in waste materials, soils and sediments was modified from a similar procedure
used in radionuclide migration studies [19]. Several options were developed:
- Self-diffusion type measurements. A radiotracer of a specific form is chemical
mixed with a solid and the diffusion into the non-labelled segment of the same
material is measured. The procedure yields information on matrix restriction caused
by pore structure and water content when a non-reactive component is introduced
(Na-22, Cl-38 and H-3). For reactive species it will yield information on the
distribution ratio between liquid and solid phase, which can be expressed as a
retardation factor. By introducing components of interest in different chemical
forms the mobilities of these different species in a given matrix can be determined.
Analysis of diffusion profiles may result in identification of more then one species.
- Interface reactions. The behaviour of components at the multigradient interface
between two different materials can be observed by using radiotracers. In addition
quantitative information can be obtained from these measurements and compared
with the diffusion in homogeneous systems. The phenomena at interfaces often
involve precipitation reactions.
- Migration. The same approach as applied for the observation of interface reactions
has been modified to study the influence of convective flow on the migration of
components of interest. These miniature column experiments yield the normal
information obtained from column experiments by measuring the variation in
percolate composition. In addition information on the distribution of a component
over the interface is obtained by slicing the tube contents in thin slices. Since the
element added as a tracer is present in the waste in concentrations exceeding by far
the concentration in the soil, the activity profile is a direct measure of the behaviour
of the species of interest.
In figure 1 the different procedures are schematically shown. In all cases the diffusion
tube contents are sliced into thin slices and transferred to counting vials to measure the
activity profile resulting from diffusion or migration of the radiotracer [14]. The
procedure has been simplified to allow large numbers of experiments under a variety of
conditions to be performed.
The consistence of the wetted material must be such that no water transport occurs in
the diffusion tube, when the paste is introduced. The consistence of the paste is closely
related to the size distribution of the material and may vary substantially from one
material to another.
An interface marker (Tm-170) has been introduced to allow unequivocal determination
of the position of the interface after a given contact time. The mobility of Thulium is
negligible in most systems studied.
The activity distribution over the diffusion tube is plotted against distance from the end
of the tube. By plotting the natural logarithm of the activity per mm, against the square of
the distance to the interface deviations from theoretical behaviour can be observed. An
example is given in figure 2, showing the agreement of Na-22 diffusion in pulverized
coal ash with theoretical behaviour and the influence of speciation and chemical reaction
on the diffusion of Selenium species. The Se-75 tracer consists of 95% selenite and 5%
161
selenate. The diffusion of selenate is unaffected by the ash matrix, whereas selenite is
partly rendered immobile in the ash matrix (66%) and partly retarded relative to
restriction by the porous matrix. The restriction factor is obtained from the difference
between the effective diffusion coefficients of a non-interacting species and its diffusivity
in water [20]. Selenite definitely interacts with the fly ash matrix. At present the chemical
forms involved are not known. In this work we have chosen molybdenum, since it is
present only as molybdate ion under most conditions of practical interest. It is thus easily
labelled and traced.
To put the information obtained in this work in perspective, some data pertaining to
molybdate leaching from pulverized coal ash obtained in earlier studies will be discussed.
3.1.Variation of Mo leaching with time and liquid/solid ratio (LS)
In batch extractions of a neutral reacting pulverized coal ash at liquid/solid ratios ranging
from 1 to 1000, and contact times varying from 0.5 hours up to 50 hours, the molybdate
concentration was measured in the extracts [15]. The results of these measurements are
shown in figure 3. The data clearly show that in batch extractions equilibrium is
established within 24 hours.
3.2.Variation of Mo leaching as a function of pH and liquid/solid ratio
In a classification study of pulverized coal ash, in which 50 ashes obtained from Dutch,
German and Belgian power plants were subjected to leaching experiments, it was found
that the major element composition caused a leachate pH ranging from 4 to 12.5. By
carrying out batch extractions at LS values ranging from 2 to 500 on all individual ash
samples molybdate concentrations were obtained as a function of pH and LS. In figure 4
the results of these experiments are presented. A maximum in the leachability of
molybdate at neutral pH is apparent. Similar observations were made on the leaching
behaviour of other elements occurring as anionic species in solution [13]. In an extensive
study on ash leachability [21] the phases controlling Mo leachability were identified as
MoO3(s) and CaMoO4. In figure 5 the molybdate concentration is given as a function of
pH for an LS ratio of 5. The solubility limits dictated by the chemical phases mentioned
are included.
The solubility product of CaMoO4 pKso=7.38 [22]. In the pH range 5 to 10 the Ca
concentration is relatively constant 8.103 mol/l, most probably governed by the CaSO4
solubility product [15]. At high pH the Ca concentration increases almost by a factor of
four [13] resulting in a corresponding decrease of the molybdate concentration. At pH
12.5 the Ca concentration may be as high as 3.102 mol/1. The activity coefficients
calculated from the major elements in solution in the pH range 5 to 10 and at pH 12.5 are
0.4l and 0.29 respectively. The associated molybdenum solubility limits based on these
data are respectively 3100 and 1600 g Mo/1. For the MoO2(s) phase, data by Lindsay
162
[23] have been used (log[Mo]=12.10+2 pH). Solubility control by Fe2(MoO4)3 is

another possibility, as data by Titley [24] lead to the relation log[Mo] =16.4+2 pH.
According to these data indications for solubility control by the Fe2(MoO4)3 and
CaMoO4 phases are strong.
3.3.Column and serial batch test results in relation to lysimeter data
The standard leach test has been applied to a neutral ash (PCA-N, [16]) and the data are
compared with results obtained on another neutral ash (code 13, unpublished results)
subjected to column leaching under slightly different conditions (H=15 cm, D=10 cm), as
well as to data obtained from lysimeters [16]. In figure 6 the molybdate concentrations
are plotted on a log scale as a function of the liquid/solid ratio (log scale). The data on the
neutral ashes indicate that the leaching behaviour of molybdate is very consistent and
virtually independent of the dimensions of the column. Data on large scale lysimeters fit
the leaching profiles from small scale experiments. The alkaline ash is shifted towards a
lower leaching rate, even when the difference in total Mo concentration in the ash is
accounted for. This is in agreement with the observed decrease in Mo leachability in
batch extractions.
At low LS values high Mo concentrations may occur in the presence of high Ca levels.
Based on solubility control by CaMoO4 and taking into account the higher salt content
(activity coefficient= 0.14) a maximum Mo concentration of 18.5 mg/1 would be
expected. Since the Mo concentrations in the ash percolates obtained at low LS exceed
this value more than once, the system is clearly not in equilibrium at this point. In most
cases the ash is wetted only shortly before the leaching experiment is started, which may
leave insufficient time for equilibrium to be established. In the lysimeter experiment with
neutral ash the time for equilibration is longer and the extremely high Mo-levels (100 mg
Mo/1) obtained in the small scale column experiments are not reached.
3.4.Diffusion and migration measurements
3.4.1.Influence of pore structure and water content
The effect of the pore structure and water content on the diffusion rate was assessed with
a few compounds which are assumed not to react with the matrix. In figure 2 data on Na
diffusion have already been presented. The agreement between the measured data points
and the calculated profile based on the diffusion equation for linear, bounded diffusion
[19] is good. From the ratio of the diffusion coefficient (D) of the component in water
[20] and the measured effective diffusion coefficient (De) in the porous matrix a
restriction factor is calculated (T2=D/De [25]). The influence of the water content on the
diffusion rate can also be expressed as a restriction factor, unless the chemical
composition of the pore solution interacts differently with different components under
these circumstances. Table II lists restriction factors for a few matrices, restriction factors
for one material using a few different components and data on the influence of different
water contents.
The restriction values for the acidic ash obtained at constant water content for five
163
different components are in good agreement, although the data obtained for Na appear a
little higher than average. The influence of water content on diffusion is apparent from
the Na and Mo data at a water content of approximately 10 % (weight/dry weight). The
restriction factor of 11 is consistent for this condition, when the larger pores normally
facilitating most of the transport are filled with air. The restriction values for different
materials at constant water content reflect mainly effects of pore structure. The effective
diffusion coefficients (De,x) for elements inter acting with the matrix have to be corrected
for the restriction factor (T2) to arrive at proper retardation factors (R):
where Dx=diffusion coefficient of the component in water at 25C [20].

3.4.2.Diffusion measurements
The effective diffusion coefficients of molybdate in a number of matrices, the contact
times for the diffusion measurement and the retardation factors based on Na mobility data
are given in table III. In most cases carrier-free Mo-99 (Tl/2=66h; Molybdate:<0.001 mg
Mo/1; E=140 keV Tc99m) is used. To verify the validity of the measured diffusion
coefficients, the concentration of the added Mo tracer solution has been increased with 1,
5, 25 and 100 mg Mo per litre. The Mo-concentration in the pore water of the acidic ash
50 is about 20 mg Mo per litre.
For a few materials the exposure time in the diffusion tube has been varied from 50 to
400 hours and in one case a pre-equilibration of 50 hours before starting the diffusion
experiment has been used. In the soil samples the Mo concentration in the porewater is
very low (0.00030.0005 mg/l), which is concluded from groundwater measurements
[26]. To verify the dependence of the diffusion data in soil samples on the Mo
concentration the latter has been increased to 1 mg Mo/1.
The diffusion data for Mo in the acidic ash are consistent under varying conditions of
Mo concentration and contact time. The significance of the second pDe is at present
unclear. This may also be an artifact due to the use of a tracer, since, after previous
equilibration and a long contact time, this second pDe is absent or becoming less
significant (high pDe means a low diffusion coefficient). It is
Table II. Restriction factors of porous matrices
Material
Ash 44
Component
Na-22
Na-22
H-3 (H2O)
1131 (iodide)
Mo-99 (molybdate)
Mo-99
Se-75 (selenate)
Water content* (% w/w) pDe

T
T2
25
9.27 1.57 2.46
11
9.95 3.42 11.7
25
8.90 1.45 2.10
25
9.03 1.41 2.00
25
9.48 1.73 2.99
9 10.05 3.32 11.0
25
9.35 1.45 2.10
164
Ash 50
Na-22
16.6
9.15 1.37 1.88
Na-22
22.2
9.25 1.54 2.37
Ash 9
Na-22
33
9.45 1.93 372
PCA-N
Na-22
37 939 1.80 3.24
VKI
FGD
Na-22
30.6
9.36 1.74 3.03
Na-22
22.4
9.62 2.35 5.52
Clay
Na-22
17.2
9.16 1.38 1.90
Sand
Na-22
90
9.12 1.32 1.74
Peat
* Water content is based on the mass of water per dry mass of solid. For the low
density of peat this leads to a relatively high number in comparison with mineral
samples.
striking to note, however, that in all cases over 50% of the added Mo is rendered
immobile. A retardation factor of 2.53 for the mobile Mo fraction (30% of the total)
appears to be a good estimate. Apparently Mo is present in different forms in the solid
phase.
Both the alkaline ash and the FGD ash feature self-cementation properties, which may
result in a change in pore structure and loss of water by the cementation reaction. If we
assume that the effective diffusion coefficient of molybdate is constant (pDe=9.68), then
the change in the measured effective diffusion coefficient can be translated in a change in
restriction, which covers both effects. For the FGD ash the recalculated restrictivities for
48, 94 and 526 hours are respectively 1.74, 2.24 and 3.55. The question arises, whether
the pDe of 9.68 obtained after 48 hours exposure is already an underestimate of the true
Mo diffusion coefficient in this matrix.
The difference in retardation factors for molybdenum between the acidic, neutral and
alkaline reacting pulverized coal ashes should reflect the differences in leachability
observed in the batch extractions discussed earlier. Based on the Mo contents in the ashes
given in table I and the Mo concentrations in the batch extractions of
Table III. Retardation factors of molybdate in different matrices.
Material
Conditions
Ash 50
T*
3.8 1.37
+1 ppm Mo
+5 ppm Mo
+25 ppm Mo
+100 ppm Mo
50 h equil.
Ash 44
Ash 9
pH
99
99
99
99
99
50
100
400
99
8.9 1.57 74
12.6 1.54 75
pDe SP1 R1 pDe SP2 R2

9.73 24 2.7 10.7 30 53
9.67 25 2.5 10.5 33 17
9.76 32 3.1 10.8 24 34
9.63 22 2.3 10.5 19 17
9.79 35 3.3 10.5
8 17
9.67 24 2.5 10.3 18 11
9.74 26 2.9 10.5 23 17
9.73 34 2.9 11.3 22 106
9.80 31 3.3
9.48 78 1.2
10.0 90 4.2
165
50 9.81 56 2.7 10.5 18

100 9.78 49 2.5 10.4 45
400 10.4 52 11 10.9 20
FGD
12.5 1.74 48 9.68 59 1.6 10.3 38
94 9.90 40 2.6 10.5 40
526 10.3 41 6.6 11.2 45
Sand
3.8 1.38 380 96 0.1 2.1
94 11.6 63 210
+1 ppm Mo
96 11.7 36 230
Clay
8.3 2.35 175 11.5 65 57 9.6 6.5
97 11.2 62 29
+1 ppm Mo
99 11.1 97 23
Peat
4.0 1.32 46 12.0 >50 570 11.0
4
96 11.6 61 230 9
2
+1 ppm Mo
98 11.7 99 290
* T=restriction factor; t=exposure time in hours; pDe=log De with D in m2/s;
SP=fraction of total with given pDe; R= retardation factor.
13
11
33
6.6
10
52
0.7
57
0.47, 3.54 and 0.92 mg Mo/1, distribution coefficients of 10.1, 0.85 and 3.0 are obtained
respectively. If the retardation factors obtained in the diffusion measurements for the
most mobile fraction are divided by this fractional contribution of the mobile species to
the total the average retardation factor is obtained. For the acidic, neutral and alkaline ash
this results in values of 10.6, 1.5 and 4.7 respectively. The agreement between the
distribution coefficients from the batch extractions and the diffusion measurements is
apparently good.
Increasing the Mo concentration in soil pore water almost 1000-fold does not change
the diffusivity of Mo appreciably. Increasing the concentration 100000-fold in sandy soil
resulted in a higher mobility of molybdate indicating that the retention capacity is
exceeded at this level. Under the experimental conditions a full retention of the 100000fold increase would relate to a concentration increase in the solid phase of 25 mg Mo/kg.
The diffusion measurements as described here allow to quantification of the influence
of several parameters on the mobility of a component present in different chemical forms.
As such it may serve as a relatively simple tool for sensitivity analysis of environmental
factors such as changes in pH, redox condition, porewater composition, complexing
agents.
3.4.3.Interactions at the waste/soil interface without flow
The interactions of molybdate at the waste/soil interface has been studied by combining
acidic, neutral and alkaline ash with sand, clay and peat respectively. The Mo tracer was
added to the ash and the diffusion of Mo into the soil was measured. Since the difference
in pore water concentration of Mo between coal ash and soil is large (10), the tracer
reflects the behaviour of the stable Mo, consequently the Mo-radioactivity profiles can be
166
translated directly into concentration distributions. In figure 7 the activity profiles of Mo99 across the ash/soil interface is given for the nine combinations at an exposure time of
about 230 hours.
The qualitative behaviour of molybdate in acidic, neutral and alkaline ash (figure 5) is
reflected in the profiles. From the acidic ash diffusion of Mo into the soileither sand,
clay or peatis limited in spite of the apparent large Mo gradient. The partial mobility of
Mo under acidic conditions is probably responsible for this behaviour. Molybdenum is
depleted rapidly from the neutral ash and fixed into either soil type. The retention is by
far the highest in peat. It is less in sand and the lowest retention is observed in clay.
According to Scheffer and Schachtschnabel [10] the formation of Fe3(MoO4)2 is an
important mechanism in the retention of Mo in natural soils. This is probably true for
Mo-amendment as fertilizer. The question arises, whether the same forms are important
in a system affected by coal ash leachate. The concentration peaks at the interface are
caused by precipitation reactions due to a large difference in mobility in ash and soil. It
should be remembered that in addition to the concentration gradient for Mo other
gradients exist at the ash/soil interface, among which a pH gradient . In spite of this the
agreement between the effective diffusion coefficients calculated from the slopes of the
peaks (peat>12, clay 11.3 and sand 11.8) and those obtained for the homogeneous soils
(table III) is good. Based on the dissolved Mo concentration (10 mg Mo/1 at LS=0.25) in
the neutral ash and the measured activity in the peak at the interface of neutral ash and
soil, assuming all of that activity is in the solid phase, the Mo content at the interface of
peat, sand and clay is increased by 960, 4.5 and 4 mg Mo/kg respectively. In the case of
the neutral ash/peat combination a significant minor fraction (2 %) with an effective
diffusion coefficient of 10.2 is observed (figure 8). This implies that the chemical form of
that minor fraction has to be different from the bulk. Association of Mo with a soluble
organic substance present in peat pore water might be an explanation. In the Mo diffusion
measurements in peat a minor mobile fraction has been observed also.
In the combination of alkaline ash and soils an odd profile is obtained. However, the
behaviour of Mo can be explained on the basis of the pH gradient between the alkaline
ash and the soils. The mobility of Mo is lower under acidic and alkaline conditions
relative to neutral conditions. At or close to the interface between ash and soil a neutral
pH exists. At that position the dissolved Mo concentration is at a maximum.
Consequently Mo concentration gradients are created at the interface causing diffusion
from the interface towards both ends of the tubes. The Mo diffusing back into the alkaline
ash will reprecipitate as soon as a higher pH is encountered. The precipitation in the soil
some distance from the interface is apparent from figure 9, in which the In (Mo-activity)x2 plot is given for the combination of alkaline ash with clay.
The data on the combinations of coal ashes and peat are combined in a 3-d graph to
show the behaviour of Mo at the ash/soil interface as a function of acid-base behaviour of
the ash (figure 10).
By studying the Mo-activity profiles obtained for different contact times in relation to
the associated pH profiles the behaviour of molybdate as a function of changes in the
percolate composition can be assessed in more detail. In these stationary systems the
behaviour of components can be more easily modelled, as diffusion is the only
167
mechanism for mass transfer. The information obtained in this way can be applied in
systems with convective flow.
3.4.4.Interaction of molybdate in the waste/soil system with flow
Using the experimental set-up as shown in figure 1 a number of ash/soil combinations
have been studied. After a certain percolation time the activity in the percolate and the
activity distribution over the ash/soil column was measured. In table IV data are listed on
the waste/soil combination, the flow rate, the concentration in the percolate, the
percentage leached and the concentration in the soil.
In figures 11 to 12 the Mo-activity measured over three waste/soil combinations
neutral ash/sand, neutral ash/peat and acidic ash/sandare shown. In all cases, except the
acidic ash, all Mo added is washed out in the percolation time used. In the acidic ash
some 60% of the originally added Mo-activity is effectively retained in the ash. Evidence
of the nature of the retained chemical phase is not available, although MoO3(s) might be
the solubility controlling phase, since this form is known to dissolve very slowly
Table IV. Data on molybdenum migration experiments
Waste/soil
combination
Percolation LS** Flow rate Percolate data

Increase in
2
time (h)
pH
[Mo]
%*
Mo
content in
(ml/cm
mg/1
soil
(mg/kg)
day)
Ash 50
sand 191 13
1.38 4.0 0.41 19
0.82
sand 192 12
1.86 6.2 2.55 75
0.644.5
Ash PCA-N
sand 120 27
7.60 5.5 1.22 92
0.53
Ash PCA-N
clay 121 14
3.60 8.0 2.61 94
0.55
Ash PCA-N
peat 120 8.7
2.20 3.2 0.0025 0.05
1280; 103
Ash PCA-N
* Percentage of total Mo-activity added collected in the percolate.
** The liquid/solid (LS) ratio is based on the weight of percolate to the dry
weight of ash in the mini-column (kg/kg) .
[11]. From the data presented in section 33 on column and lysimeter experiments it was
shown that Mo is washed out in 23 pore volumes (1 LS=2.5 pore volumes). This is in
agreement with the complete wash out observed here. The concentrations observed in the
percolate are comparable to those observed in field situations, where pulverized coal ash
was applied in road or embankment stabilization [17, 18]. The effective retention of Mo
in peat, as observed in the interface reaction studies, is not seriously affected by the
percolate from the neutral ash. Only a minor fraction migrates through the peat soil. The
acidity of the peat appears to be important in retaining Mo, as the experiments by Jones
and Belling [11] indicate low Mo retention in neutral peat soils. The Mo-peak at the
ash/peat interface is shifted slightly relative to the profile obtained in the stationary
system. This shift is associated with an increase in pH due to the alkalinity of the ash
percolate. As soon as the pH rises over 6 the molybdate is mobilized and reprecipitates at
a pH below 5. In an experiment in which a small peat sample was exposed to a large
168
volume of coal ash leachate, the capacity of peat to retain Mo was estimated to be 1200
mg Mo/kg. The agreement between the measured Mo capacity and the data obtained in
the migration measurements is surprisingly good. As a rough estimate a 12 cm layer of
peat can retain all Mo leached from 1 meter of neutral ash with a Mo content of 20
mg/kg. In the soil system the formation of iron molybdates is regarded as an important
mechanism for Mo adsorption in soil [12], but to what extent that phase is controlling the
retention in the soil system is at present hard to identify. Studies into the movement of
Mo in soil using Mo-99 have been carried out in Australia [11]. With a soil treatment of
100 mg Mo/m2, it was found that acidic laterite soils retained approximately 50% of the
added amount, whereas neutral soils (deep sand) retained only 1020%. Similar to the
coal ash/water system the solubility of anions is minimal at low pH and high at neutral
pH values. In the waste/soil system the solubility controlling phase remains to be
established.
Using different percolation rates and different percolation times the behaviour of
molybdate in the soil system as a result of the changing composition of the soil pore
water by ash leachate can be quantified. The retention capacity of the soil under these
conditions can be calculated. By measuring the behaviour of Na-22 under the same
circumstances the dispersion of the system can be characterized. Finally it allows for
kinetic processes to be modelled. The intention to store waste materials above
groundwater levels and the measures taken to prevent percolate production emphasize the
need for information at extremely low percolation rates, where diffusion becomes more
important.
4.CONCLUSIONS
- The agreement between laboratory leaching experiments and lysimeter experiments
on pulverized coal ash proves to be very good. The leaching behaviour of Mo as a
function of liquid/solid ratio is consistent. Therefore, instead of using a constant
source term, which is applied in many groundwater quality models, the Mo leaching
as a function of liquid/solid ratio should be used as a source release term. A similar
approach is suggested for elements showing a concentration peak at some point in
time after a solubility controlling compound has been leached.
- The sequence of diffusion measurements in homogeneous materials, interactions at
waste/soil interfaces and migration of elements from the waste through the soil leads
to determination of properties describing the behaviour of a component in the
waste/soil system. The changes in the retardation of components caused by changes
in soil properties brought about by the percolate from the waste are most important
in this respect. In the small scale experiments described here these changes can be
followed in great detail and subsequently modelled. The retention capacity of a
given material under a variety of conditions can be measured easily. In the case of
molybdate leached from pulverized coal ash the retention in acidic peat is most
prominent. In both a clay soil and in a sandy soil the retention of molybdate is
limited.
- In the ash matrix the molybdate solubility controlling phases are probably MoO3(s),
169
Fe2(MoO4)3 and CaMoO4. In the soil system the main phases are probably iron
molybdates, although in peat the role of soluble organic substances can not be
disgarded. The retention of Mo in acidic systems (ash or soil) is highest. At neutral
pH a low retention is observed in ash, sand and clay. The chemical forms, in which
the element of interest is present, largely determines the release rate, which is not
necessarily the same for the different phases. For instance, the minor fraction with a
high mobility in peat is transported over much larger distances than the bulk of the
element, which is retained effectively as long as the peat remains acidic. The
variation in soil pH as a function of percolate infiltration is an important variable
controlling retention and mobilization of initially retained elements. Since the
buffering capacity of the soil withstands a change in porewater pH, the release of
either alkalinity or acidity from a waste site as a function of time or liquid/solid ratio
must be adressed.
Acknowledgement
The experimental work presented in this paper has been carried out by Petra Bonouvrie,
Jan Wijkstra and Hans Eggenkamp. The valuable discussions with P.L.Ct, J.McLellan
(Wastewater Technology Center, Burlington, Canada) and Prof H.A.Das are gratefully
acknowledged. This work has been performed within the frame work of a cooperation
between the Water Quality Institute (Copenhagen, Denmark) and the Netherlands Energy
Research Foundation (Petten, The Netherlands) under contract EN3F-0032(NL) and
EN3F-0033(DK). Additional financial support was obtained from the National Coal
Research Programme (NOK) through the Management Office for Energy Research
(PEO), now the Netherlands Agency for Energy and the Environment (NOVEM) and
from the Danish Ministery of Energy under the Energy Research Programme (EFP).
5.REFERENCES
(1)W.R.Roy and R.A.Griffin. 1982. A proposed classification system for coal fly ash in
multidisciplinairy research. J. of Environmental Qual.11(4), 563568.
(2)Chemical characterization of fossil fuel combustion wastes. 1987. EPRI EA-5321.
Electric Power Research Institute. Palo Alto.
(3)G.J.de Groot, H.A.van der Sloot and J.Wijkstra.1987. Leaching characteristics of
hazardous elements from coal fly ash as a function of the acidity of the contact solution
and the liquid/solid ratio. Proc. 4 th Int. Hazardous waste symposium on aspects of
stabilization/solidification of hazardous and radioactive wastes, Atlanta, May 1987.
(4)H.A.van der Sloot, O.Piepers and A.Kok, 1984. A standard leaching test for
combustion residues. Technical report Bureau Energy Research Projects BEOP-31
(5)P.L.Ct and D.Isabel. 1984. Application of a dynamic leaching test to solidified
hazardous wastes. Third ASTM symposium on Hazardous and industriual waste
management and testing . STP 851 , L.P.Jackson, A.R.Rohlik and R.A.Conway, Eds,
American Chemical Society for Testing of Materials, Philadelphia, 4860.
(6)H.A.van der Sloot, G.J de Groot and J.Wijkstra. 1987. Leaching characteristics of
170
construction materials and stabilization products containing waste materials. Proc. 4 th

Int. Hazardous waste symposium on aspects of stabilization/solidification of hazardous
and radioactive wastes, Atlanta, May 1987.
(7)O.Hjelmar. 1982. Marine disposal of fly ash from coal fired power plants. Proceedings
of the International Conference on Coal fired Power Plants and the Aquatic
Environment. Copenhagen, Denmark.
(8)J.J.W.Higgo. 1987. Clay as a barrier to radionuclide migration. Progress in Nuclear
Energy19, 173207.
(9)B.Torstenfelt. 1986. Migration of fission products Strontium, Technetium, Iodine and
Cesium in clay. Radiochim Acta39, 97104.
(10)F.Scheffer and P Schachtschabel. 1982. Lehrbuch der Bodenkunde. F.Enke Verlag,
Stuttgart, 263264.
(11)G.B.Jones and G.B.Belling. 1967 . The movement of copper, molybdenum and
selenium in soils as indicated by radioactive isotopes. Aust. J. agric. Res.18, 733740.
(12)Chemical attenuation rates, coefficients and constants in leachate migration. Vol 1.
1987. EPRI EA-3356. Electric Power Reseach Institute, Palo Alto.
(13)H.A.van der Sloot, E.G.Weijers, D.Hoede and J.Wijkstra. 1985. Physical and
chemical characterization of pulverized coal ash with respect to cement-based
applications. ECN-178. Netherlands Energy Research Foundation, Petten, The
Netherlands.
(14)H.A.van der Sloot and G.J de Groot. 1988. Mobility of trace elements derived from
combustion residues and products containing these residues in soil and groundwater.
ECN-88-29Netherlands Energy Research Foundation, Petten.
(15)H.A.van der Sloot, J.Wijkstra, A.van Dalen, H.A.Das, J. Slanina, J.J.Dekkers and
G.D.Wals. 1982. Leaching of trace elements from coal solid waste. ECN-120,
Netherlands Energy Research Foundation, Petten, The Netherlands.
(16)O.Hjelmar. V.Pohjola, M.Reuss and M.Wahstrm, 1986. Land disposal of solid
residues from combustion of coal and peat. Final report. MIL-1. Environmental
Research Report, 1986:1, Nordic Counsel of Ministers, Gteborg.
(17)P.R.Spee and R.C.Reintjes. 1986. Volker Stevin Wegen en AsfaltB.V. Report AE86-06-902.
(18)N.Bolt. (KEMA, Personal Communication)
(19)F.Schreiner, S.Fried and A.Friedman. 1982. Measurements of radionuclide diffusion
in ocean floor sediments. Nuclear Technol.59, 429.
(20)Y.H.Li and S.Gregory. 1974. Diffusion of ions in seawater and in deep sea
sediments. Geochim. Cosmochim. Acta38, 703714.
(21)Inorganic and organic constituents in fossil fuel combustion residues. Vol 1, 1987.
EPRI EA-5176, Electric Power Research Institute, Palo Alto.
(22)L.G.Sillen and A.E.Martell. 1964. Stability constants of metal-ion complexes.
Special Publication17, The Chemical Society , London.
(23)W.L.Lindsay. 1979. Chemical Equilibria in Soils. John Wiley & Sons, New York.
(24)S.R.Titley. 1963. Some behavioural aspects of molybdenum in the supergene
environment. Min. Soc. Amer. Inst. Min. Metall Pet Eng. Trans.Vol 226, 199204.
(25)J.F.Relyea. 1980. Diffusion coefficients and their use. Nuclear Technology51, 156
171
161.
(26)B.C.Arends, H.A.van der Sloot and W.van Duyvenbooden. 1987. Influence of
acidification on the concentration of less common trace elements in Dutch
groundwater. In: Vulnerability of soil and groundwater to pollutants.Eds. W van
Duijvenbooden and H.G.van Waegeningh. Netherlands Organization for applied
scientific research, Delft, 527534.
Fig. 1. Experimental procedures.
Fig. 2. Diffusion profiles for sodium and selenite (top) and the results of curve
fitting (bottom).
Fig. 3. Variation of molybdenum leaching from coal fly ash as a function of

liquid/solid ratio and contact time.
Fig. 4. Leaching behaviour of molybdenum from coal fly ash as a function of

liquid/solid ratio and pH of the contact solution.
Fig. 5. Leaching behaviour of molybdenum from coal fly ash at LS=5 and
t=24 h. The possible phases controlling leachability are included.
Fig. 6. Comparison of laboratory column leaching data and results from large
scale lysimeter experiments.
Fig. 7. Pulverized coal ashsoil interaction for molybdenum (t=230 hours).
Fig. 8. Mobile molybdate fraction in peat.
Fig. 9. Mobilization of molybdate at the interface.
Fig. 10. A 3-D representation of the coal fly ashpeat interaction of

molybdate as a function of the acid/base properties of the ash.
Fig. 11. Influence of convective flow on the retention of molybdenum from

neutral coal fly ash in sand.
Fig. 12. Retention of molybdenum from neutral coal fly ash in peat, and from
acidic coal fly ash in sand under stationairy conditions (top) and
with convective flow (bottom).
HANDLING AND CONDITIONING OF

FLUIDIZED BED AND PULVERIZED COAL
BOILERS FLY-ASH FOR LANDFILL
DISPOSAL AND REUSE
Author :
Contract number :
Duration :
Total budget :
Head of project :
Contractor :
Address :
J.BLONDIN
EN3F-0071-F (CD)
3 years 1 September 198731 August 1990
ECUS 434 000 CEC contribution : ECUS 190 000
J.BLONDIN
CERCHAR
Tour Albert ler
65, Avenue de Colmar
92507 RUEIL-MALMAISONFrance
SUMMARY
Dry landfill disposal of fly ash and bottom ash from Power Plants has been widely used
for years without problems. The possibilities of using the freshly produced or reclaimed
material have been extensively studied and a significant portion of fly ash is used for road
works, cement manufacture or concrete additives
The emergence of new technologies such as
- Fluidized bed combustion with calcium additives for desulfurization,
- Pulverized coal combustion in small capacity boilers and furnaces,
- Dry limestone injection in the combustion chamber of Pulverized coal or stoker
boilers gives rise to a new kind of fly-ash the characteristics of which may be
different as regards properties, landfill disposal and reuse.
The aims of this research are to provide information about these new types of fly-ash, to
define the best practices for handling and landfill disposal and to promote valorisation.
INTRODUCTION
Fly ash from Power Plants can be handled dry for direct reuse or moistened for storage
without any special problem. As to their utilization, the properties of fly ash are well
known and classifications have been established in terms of silica and alumina or sulfate
and calcium content. Unburned carbon is also a very Important parameter : typically,
over 7 % carbon, fly ash introduction in cement and concrete is not allowed.
182
New fly ash produced by the above mentioned processes is much less well known. Its
behaviour may be quite surprising : moistening before disposal leads to quick setting,
heat and even steam release which does not occur with conventional fly ash.
Our aims are to study the various aspects of these problems.
IFIRST RESULTS
As this project started only a few months ago, few results are available.
Samples produced by a 6 MW pilot fluidized bed boiler and a pulverized coal fired 10
MW firetube boiler have been analyzed. It can be concluded that :
- the carbon content of fly ash is usually fairly high except for very reactive coals
with high fly ash recycling in Fluidized bed boilers;
- Pulverized coal fly ash is finer than that of Fluidized bed boilers;
- Calcium products are obviously present in Fluidized bed fly ash when limestone is
added.
IIRESEARCH PROGRAMME
The research programme will include :
II1Fly ash characterisation
Fly ash from various types of boilers will be characterised in terms of
-
density and morphology,

particle size distribution which may differ according to the sampling point,
carbon content,
major and trace elements composition in relation with that of the parent coal.
II2Eurpgean country regulations survey
Regulations relative to fly ash disposal or reuse may differ from one country to another.
A survey will be carried out in order to get relevant information.
II3Handling systems for fly ash
As previously mentioned, handling dry ash is not a problem but, in many cases fly ash
must be moistened in order to avoid air pollution during discharge at the disposal site.
Different devices for wetting Fluidized bed fly-ash will be studied : rotating screw, pug
mill, drum. The problem of wet ash transport will be studied as well. Concrete rotating
mixer trucks have already been tested : it is a costly solution but it gives encouraging
results.
Handling and conditioning of fluidized bed
183
II4Chemical reactions during hydration

Different reactions which will occur during combustion and hydration are known but not
the relative amount of components involved nor time to reach completion.
In the combustor, added CaCO3 undergoes a decomposition to CaO. In many cases, the
reaction is incomplete and some unreacted CaCO remains in fly ash.
The reaction between SO2 and CaO gives mainly CaSO4. Different forms of anhydrous
CaSO4 may occur, depending on the reaction temperature.
3 forms of CaSO4 exist above 170C :
from 170C to 250C soluble anhydrous CaSO4 III

from 400C to 600C insoluble anhydrous CaSO4 (plaster) II
above 600C
soluble CaSO4 I with very slow setting.
The reactions will be studied in the presence of fly ash. X-ray analysis will help identify
the crystallized forms of the products.
During hydration, pozzolanic reactions occur between free lime CaO and silicoalumina
components.
CaSO4 I and II would be hydrated in setting reactions to give CaSO42H2O.
Additional pozzolanic reactions might occur between these components and take a few
weeks to reach completion.
Hydration reactions will be studied by X-ray diffraction and adiabatic calorimetry.
Tests specific to cement reactions will be carried out in order to understand the hydration
process.
II5Ash utilisation and valorisation
Fly ash from Power Plants has been widely used as a fill material and as an additive in
concrete. Low sulfur and low calcium fly ash develops pozzolanic properties only in
addition or substitution to cement.
Laboratory and small scale experiments have shown that fly ash with high calcium
content has also pozzolanic properties when mixed with water and that it can be used as a
filler or base material for roadworks.
These reactions will be investigated further as well as the conditioning treatment prior
to valorisation. Slaking and subsequent grinding will be studied since the particle size
distribution is an important parameter for the development of pozzolanic reactions and
filler properties.
184
THE UTILISATION OF P.F.A. (PULVERISED

FUEL ASH) AS A FILLER IN RIGID
POLYURETHANE INSULATION FOAMS
Authors:
Contract Number:
Duration:
Total Budget:
Head of Project:
Contractor:
Address:
P.Sheehan, P.OSullivan, T.Hamm

EN'3F-0057-IRL
33 months 1 September 198631 May 1989
IR 336 871 CEC Contribution: IR 168 435.50
L.R.Ball, B.Sc., Chairman, Polycomp Limited
Polycomp Limited
Greenhills Industrial Estate Walkinstown Dublin 12
Summary
The use of Pulverised Fuel Ash (PFA) as a filler for low density polyurethane insulation
foams has been evaluated. The chemical and physical interaction of PFA and
polyurethane were investigated. The mixing characteristics of PFA/polyurethane was
examined. PFA/polyurethane foams were tested to see if their properties were within the
minimum properties specified in BS5608 (1986). Mixing was seen as the key factor in
attaining a good quality foam with high loading levels of PFA. Methods of improving the
mixing of PFA and polyurethane were examined. A longer mixing time was obtained by
removing the catalyst from the polyurethane chemical system and adding it to the
PFA/polyurethane mix at the end of the mixing period. This enabled a 30% PFA loading
in polyurethane chemicals to be obtained with the properties of the resultant foam within
those specified in BS5608 (1986). The study was extended to examine the effect which
silane coupling agents have upon the properties of a polyurethane foam filled with 30%
PFA. It was seen that silane coupling agents decreased the insulation properties of the
foam. Fire tests were completed on PFA filled polyurethane foams. PFA improves the
fire properties of a polyurethane foam by forming a char on the surface of the foam.
Research and development work continues with PFA/polyurethane in a high density
particle board.
1.Introduction
1.1General
The use of rigid polyurethane as an insulation foam is well known. Low density
polyurethane foam is a cellular material with a unigue combin-ation of properties such as
185
very high thermal insulation, good dimensional stability under temperature cycling and
excellent adhesion properties in the wet state. It has wide spread applications as thermal
insulation for buildings and cold storage areas. Its disadvantages are, high raw material
cost and poor fire properties.
Pulverised Fuel Ash (PFA) is a waste inorganic material primarily arising from the
combustion of coal for electricity generation. Though its composition varies depending
upon the type of coal and manner of burning, in general PFA consists of silica and
alumina oxides with various quantities of ferrous oxide, carbon and water. It can be subdivided into positive bouyancy hollow spheres and negative bouyancy solid spheres of
various particle sizes.
There are two incentives to utilise PFA. Firstly it is a material of relatively low cost
and secondly, as it comprises predominantly spherical particles it is theoretically ideal as
a filler.
In combining PFA and polyurethane it is hoped to achieve a conglomerate insulation
material with lower raw material cost and improved fire properties.
Very little work has being completed and published on the use of PFA as a filler in
polyurethanes though one exception was a Polish Patent for a thermally insulating
material particularly for making buildings warmer. (1) The work completed on PFA as a
filler in plastics is on its use with polyolefins. (2)(3)The main body of work published
concerns the use of PFA as a lightweight aggregate for concrete. (4)(5)(6)
1.2Polyurethane Foams
A low density polyurethane foam is formed by the reaction of two chemicals called a
polyol and an isocyanate.
The polyol is a mixture of chemicals of which the main component is called the polyol.
This is a compound containing several alcohol groups. The alcohol is the functional
group on the compound. The polyol contains a blowing agent usually a Chloro Fluorocarbon, a surfactant usually a silicone compound, a catalyst (a tertiary amine), and a
small quantity of water.
The isocyanate known as MDI or more correctly Diphenylmethane-44 Di-isocyanate
has the general formulae:-
The basic reaction to produce polyurethane foams goes as follows:
186
The formation of the polyurethane foam is a little more complex. The small quantity of
water in the polyol reacts with the isocyanate producing Carbon dioxide which acts as a
nucleating agent for the blowing agent vapourised by the exothermic nature of the
polyolisocyanate reaction. The blowing agent expands the mix to a foam-like structure.
The increase in volume is of the order of 2530 times the volume of the original
chemicals used in the reaction. The foam consists of the blowing agent trapped in a
cellular structure. The reaction is quite delicate with a need for the correct level of water
and catalyst particularly important.
2.Experimental
2.1Raw Materials Used
Pulverised Fuel Ash (PFA)For the purpose of the study a PFA sample known as
"Fillite PG" was used. This was supplied by Fillite (Runcorn) Limited, Cheshire,
England. The properties of this sample are given in Table 1.
Table 1. The properties of the PFA sample Fillite PG
Chemical Properties
% Alumina (A12O3)
% Silica (SiO2)
% Iron (Fe2O3)
2735%
5565%
4%
Physical Properties
Density
Packing Factor
Hardness
Particle Size
0.7g/cc
6065%
Mohs Scale 5
5300 microns
PolyurethaneThe polyurethane system used was the Daltolac K133S/35 and

Suprasec DND available from ICI.
2.2The effect of PFA upon the viscosity of the polyurethane chemicals
Good mixing of the polyurethane chemicals is important in order to attain good quality
foam. In order to study the effect PFA will have on the mixing characteristics of the
polyurethane chemicals viscosity measurements were taken of various PFA loadings in
the polyurethane chemicals. chemicals.
187
Table 2. The effect of PFA upon the viscosity of the polyurethane
% PFA by wt. of PU chemicals

0
5
10
20
30
Viscosity (Centipoise)
Polyol
Isocyanate
501
279
549
413
650
752
1253
1504
2130
2757
The increase in viscosity from 0% PFA to 30% PFA is of the order of 400500% for
the polyol while it is nearer 1000% for the isocyanate. This will create problems of
mixing in the PFA given that the chemicals (polyol and isocyanate) commence reaction
20 seconds after mixing.
It must be noted that PFA mixed with the isocyanate must be completely water free
otherwise a reaction will occur between the isocyanate and the water in the PFA giving a
substituted urea and Co2. This will result in a foam with reduced mechanical and
insulation properties.
2.3The effect of PFA on polyurethane reactivity
The reaction to form polyurethane foams goes through a number of clearly defined and
measurable stages. These stages are Cream time, Cup time, Full Cup time, String time,
Tack Free time and End of Rise time. The effect of various loadings of PFA upon the
reactivity of the polyurethane system was measured. These were compared to the reaction
times for the standard polyurethane system. The results are given in table 3 and table 4
for undried PFA and dried PFA respectively.
Table 3. Reactivity times of undried PFA/PLI mixes
%
PFA
10%
20%
30%
40%
Std.
Duration of mix (seconds)

% PFA=% PFA by weight of polyurethane (PU) chemicals
Cream
Cup
Full Cup
String
Tack Free
Time
Time
Time
Time
Time
17.40
56.60
112.80
120.80
167.00
17.00
55.00
113.30
120.75
163.00
16.00
64.25
138.00
182.00
161.25
22.00
85.00
23.20
66.00
121.60
124.80
188.40
End of
Rise
206.00
205.75
246.25
232.00
188
Table 4. Reactivity times of dried PFA/PU mixes
%
PFA
10%
20%
30%
40%
Std.
Duration of mix (seconds)

% PFA=% PFA by weight of PU chemicals
Cream
Cup
Full Cup
String
Time
Time
Time
Time
18.00
51.00
107.66
118.66
20.66
52.33
113.00
126.33
17.66
68.33
151.66
23.20
66.00
121.60
124.80
Tack Free
Time
185.66
181.66
168.33
188.40
End of
Rise
190.00
218.33
241.00
232.00
The following can be taken from the above results

(1) There was an increase in reactivity of polyurethane chemicals upon addition of
PFA. This is because of the water content of the PFA, which was measured at 1.95g per
kg. Water would cause an increase in the reactivity of the polyurethane giving less time
for mixing. The results of mixes with dried PFA show a decrease in reactivity. This result
suggests that in adding PFA to polyurethane chemicals either
(a) A drying stage may be necessary for the PFA.
or
(b) A polyurethane system with a lower level of water may have to be blended.
(2) The results from loadings of PFA for 10% and 20% were very similar. However, at
30% loading of PFA there is a noticeable slowing of the reactivity of the mix. The foam
obtained was friable with a loss in volume of up to 50%. This would suggest that a PFA
loading of between 20% and 30% is the optimum obtainable.
2.4The effect of PFA addition on the properties of a polyurethane foam
To investigate the compatibility of the PU/PFA mix a whole series of tests were
completed. The optimum mixing conditions were defined in terms of mixing speed, time
and temperature. Table 5 summarises the results obtained for various loadings of PFA.
The following conclusions can be drawn from the results in table 5.
(1) There is an increase in closed cell content, tensile strength and compressive
strength up to an addition of 10% PFA by weight of polyurethane chemicals.
(2) A decrease in % friability (a measure of foam structure) and flow/ volume with
addition of PFA to polyurethane chemicals.
(3) On addition of 20% or upward of PFA to polyurethane chemicals there is a decrease
in all desireable properties.
BS5608 (1986) gives the minimum physical property requirements for rigid
polyurethane foams. The most important property given is for closed cell content. It is
this which determines the insulation value and structure of the foam. The minimum value
for closed cell content in BS5608 (1986) is 85%. It can be concluded from the results of
189
table 5 that at a PFA addition between 20% and 30% a foam is obtained with properties
below those specified in BS5608 (1986). This confirms the results obtained with the
reactivity testing.
Table 5. The effect of PFA addition on the properties of a PU foam
% PFA by
wt. PU
chem.
0
5
10
20
30
40
%
Flow/Vol. Tensile
Density Closed Cell
Content Friability
St. Kpa
Kg/m3
41.00
44.04
46.06
52.85
60.23
92.4%
89.6%
96.46%
88.8%
83.46%
78.7%
97.6%
97.0%
95.9%
96.8%
95.5%
100%
98%
97.4%
95.5%
91.5%
81.3%
216.4
no test
202.6
145
91
107
Compressive
St. Kpa
163
no test
172
151
146
112
2.4.2Altering the PU chemical System to improve the mixing of PFA to PU

The most important mixing parameters are temperature, duration of mix, speed of mix
and type of mixer. The temperature of mix is limited by the temperature at which the
blowing agent evaporates (24C). The duration of mix is limited by the time it takes for
the polyurethane chemicals to reach their Cream Time. Beyond this time the viscosity
increases to such an extent as to make further mixing very difficult. The speed of mix is
important but is limited by the time constraint of the chemical system. This is also
governed by the type of mixer used.
We have seen that there is clearly a constraint on the amount of PFA that can be added
to a polyurethane chemical system without a deterioration in desireable properties of the
PU/PFA foam. As the % PFA is increased so is the viscosity of the mix increased (Table
2). It is clear that mixing is the key to successfully marrying PFA and PU.
It was decided to alter the mixing conditions by
(a) Removing the catalyst and adding it in at the end of the PU/PFA mix: The catalyst
in the polyurethane chemical system controls the reaction rate. By removing the
catalyst and adding it at the end of the mixing period a longer mixing duration
could be obtained.
(b) Adding in extra blowing agent: The blowing agent is an unreactive element in the
mix and it was decided to experiment with improvements in volume of the
resultant foam by adding in extra blowing agent.
Note: For the purpose of the experiment foam containing 30% PFA by weight of
polyurethane chemicals was used.
2.4.3The effect of removing the catalyst from the polyurethane system
The catalyst is normally added at a rate of 1.43% per weight of polyol, The mixing
conditions used are given in table 6.
190
Table 7 gives a sample of the results obtained from a number of trials. It was found
difficult to mix the polyurethane chemicals and catalyst thoroughly. It was necessary to
increase the catalyst level in order to obtain improved closed cell content. At a catalyst
level 1.5 times greater than normal (4.3%), a closed cell content was obtained within that
specified in BS5608 (1986). No further significant improvement was obtained at higher
catalyst levels.
Table 6. Mixing Conditions
Mixing Conditions
Duration of mix (secs.)
Speed of mix (R.P.M.)
Polyol+Iso.
12
4400
PFA
60
1500
Catalyst
5
4400
Table 7. The effect of catalyst levels on closed cell content
% Catalyst
4.3%
3.0%
2.0%
1.5%
Closed Cell Content

92.40%
84.30%
30.00%
25.00%
Std Closed Cell

83.46%
83.46%
83.46%
83.46%
% Diff
+8.76%
+1.00%
64.05%
70.00%
2.4.4The effect of altering the amount of blowing agent on the PU/PFA mix
Blowing agent usedArcton 11Trichloro Fluoromethane (CC13F).
% Blowing agent in polyol system is 35 parts blowing agent per 100 parts polyol.
The closed cell content of a foam containing 40% PFA by weight of PU chemicals was
taken with different levels of blowing agent. The results are given in Table 8. It can be
seen that a slight increase in blowing agent can improve the properties of a PU/PFA
foam. However, the results also show that increasing the blowing agent above a certain
level leads to a deterioration in the properties of the foam.
Table 8. The effect of blowing agent on closed cell content
Parts Blowing Agent % PFA Closed Cell Content

52.0 parts
48.0 parts
43.5 parts
39.0 parts
40%
40%
40%
40%
74.42%
78.00%
81.60%
83.00%
% Diff from Standard

40% PFA Closed Cell
5.4%
+3.5%
+5.5%
2.5The use of coupling agents with PFA/PU foams

The effect of coupling agents on the closed cell content of a 30% PFA/ PU foam was
investigated. A coupling agent will chemically bond an organic to an inorganic phase.
Coupling agents are widely used for improving the properties of filled plastics.(7)(8) The
most succussful coupling agents for the purpose are organosilanes. The coupling agents
191
used were
(a) AMEO (3-aminopropyl-triethoxysilane) H2N(CH2)3Si(OC2H)3
(b) DAMO N-aminoethyl-3-aminopropyl-teimethoxysilane H2N(CH2)2NH(CH2)3Si
(OCH3)3
The coupling agent was prepared by dissolving it in Hexane and coating the PFA with the
solvent mixture. The solvent is then evaporated off leaving the coupling agent bonded to
the PFA.
The quantity of coupling agent which gave the best result was 0.1% coupling agent per
weight PFA/PU chemicals. The results are summarised in Table 9.
Table 9. The effect of coupling agents on closed cell content
(1) 30% PFA 0.1% AMEO

(2) 30% PFA 0.1 %
DAMO
Closed Cell
Content
81.20%
81.30%
Standard Closed
Cell
83.46%
83.46%
%
Difference
2.7%
2.6%
The coupling agents have decreased the closed cell content of the foam.
2.6Fire tests on PU/PFA foams
Fire tests were completed according to ASTM D 301486, known as the Butlers
Chimney Test. A foam containing 30% PFA by weight of polyurethane chemicals was
compared to the standard polyurethane foam.
It was concluded that PFA improves the fire properties of a polyurethane foam by
forming a char on the surface of the foam which does not easily break away thus
retarding the rate of burning of the foam.
3.Conclusions
PFA added to polyurethane foam has the following effects
(1) It increases the viscosity of the polyurethane chemicals making mixing more
difficult.
(2) At the mixing conditions used for mixing polyurethane foams PFA decreases all
desireable properties of a polyurethane foam.
(3) The mixing time is the key parameter to be considered in mixing PFA with
polyurethane foams. The mixing time can be increased by mixing the polyurethane
system minus its catalyst and adding in excess catalyst at the end of the mixing
period. This process enables a PFA loading of 30% by weight of PU chemicals to
be manufactured, whose properties are within those specified by BS5608 (1986).
This was the maximum PFA loading obtained.
(4) The coupling agents to bond PFA to PU foam had a negative effect on the foams
192
structure.
(5) PFA improved the fire properties of a polyurethane foam. It affected this by
forming a char on the surface of the foam thus retarding the rate of burning of the
foam.
Note on future work
Work on this project is ongoing. There are a number of alternatives under investigation,
they are
(1) Forming a polyurethane foam with a surface rich layer of PFA.
(2) Using polyurethane to bind PFA in the form of a particle board and using the
particle board with polyurethane foam as a light weight fire resistant insulation
board.
Acknowledgements
The help and advice of personnel in the Materials Engineering and Chemistry
Departments N.I.H.E., Limerick and the Chemistry Department of University College
Dublin towards this project is greatly appreciated.
References
1.Patent No. 200724Office of the Polish Peoples RepublicThermally insulating
material particularly for making buildings warmer.
2.HODD K.A., DAVIES L.C.B. and SOTHERN G.R.Dept. of Materials Technology,
Brunei University, U.K.Pulverised Fuel Ash its use as a filler for polyolefins.
3.PLOWMAN C. and SHAW N.B.CEGB, Harrogate U.K.The use of pulverised fuel
ash as a filler in plastics.
4.The chemistry of PFA in concretePLOWMAN C., CEGB, Harrogate U.K.
5.FABER J.A.Faber Associates Inc., West Virginia, U.S.A. and BABCOCK A.W.
Alleghemg Power Service Corp., U.S.A.Ash marketing and quality control practices
in the United States including the effects of the EPAS guideline for the federal
procurement of ash.
6.BERTHE M.S.A. Surschiste, Charbonnages de France Group25 years of fly ash in
France.
7.MONTE S.J., SUGERMAN G. and BRUINS P.F.Plastic Appliances, Natl. Tech.
Conf.Nov (1975), 197203.
8.HAN C.D., VAN DEN WEGHE T., SHETE P. and HAV J.R.Polym. Eng. Sci.
(1981) 21, 196204.
CONCLUSIONS AND
RECOMMENDATIONS FOR FUTURE
WORK.
Protection of the environment was the main topic of the meeting. This important issue
deserves serious attention since it is unacceptable that the environment should become
more and more endangered because of the expected increase in coal consumption for
power or heat generation. The general trend in strengthening regulations leads to a
continuing effort in developing sound data bases on pollutant emissions and in improving
the efficiencies or decreasing the cost of pollution control equipment.
The Contractors meeting covered a wide range of problems that can be divided into
three categories:
Particulate control
Although particulate control has been widely used for years, there are still possibilities
for improving the efficiencies or cutting the costs for large power plants (pulsed
electrostatic filters), for medium and small capacity boilers (electrostatic filters) and for
small domestic appliances burning high volatile solid fuels. Although one cannot expect a
major breakthrough in the field, marginal improvements may have positive effects on the
economics of coal utilization in an environmentally safe manner.
More innovative are the efforts to develop hot gas cleanup systems. In this case, the
particulate control system is integrated in the process and a failure may have dramatic
effects on the components downstream. It is quite obvious that the future of combined
cycles based on pressurized fluidized bed combustion relies almost entirely on the
emergence of efficient and reliable hot gas cleanup systems. Research on that subject
should be encouraged.
Gaseous pollutants control
Several SO2 and NOx control technologies have been demonstrated on an industrial scale
in large power plants. As for particulate control, no major improvement can be expected
since the subject has been widely investigated but research aiming at reducing the costs
would be beneficial, particularly if the regulations are to be extended towards smaller
capacities.
Conclusions
194
Solid wastes
The management of solid wastes was an important topic of the meeting. Flue gas
treatment or fluidized bed combustion with sorbents give rise to amounts of solid wastes
that have to be disposed of or reused.
In some European countries, landfill disposal may be a problem since there are few
sites available. This justifies research on regenerable sorbents for desulphurization in
fluidized bed combustors. Although the resulting process is likely to be fairly
complicated, it might well be the only answer to the problem in populated areas. It would
be worth continuing investigations on this subject.
Where landfill disposal is possiblein fact it is the common practice of today
concern is frequently expressed about the possible negative impact of trace species
(heavy metals, polycyclic aromatic hydrocarbons) on groundwater. The establishment
of a sound data base on that subject is particularly important because the economics of
using coal may depend greatly on whether the solid wastes are considered harmful or not.
The on-going programme will certainly bring relevant information.
An interesting although problably limited possibility would be to find uses for solid
wastes, especially for fly ash and bed ash of desulphurizing fluidized bed combustors.
The properties of these solid products have to be studied in relation to expected
applications.
Conclusions
Environmental protection is an essential component of any coal utilization development
programme. Continuing efforts in research are necessary to find the most economical
techniques to comply with existing regulations and to make sure that projected future
regulations are based on a scientific background and not on unrealistic fears. Integrated
solutions where pollutant control takes place during the coal conversion process itself
should be promoted as the most cost effective way of reducing pollution.
LIST OF PARTICIPANTS
ANDRIES, J.
LABORATORY FOR THERMAL POWER ENGINEERING
Rotterdamseweg 139 A
NL2628 AL DELFT
BLONDIN, J.
CERCHAR
Tour Albert ler
65, avenue de Colmar
F92507 RUEIL MALMAISON
DINELLI, G.
ENEL (ITALIAN ELECTRICITY BOARD)
via G.B.Martini, 3
I00198 ROMA
DUMONT, J.N.
BERTIN & CIE
Zone Industrielle des Gtines
F78373 PLAISIR CEDEX
FRIGGE, J.
D4300 ESSEN 13
GALLIMBERTI
via G.B.Martini, 3
I00198 ROMA
GAY, A.J.
THE NETHERLANDS ORGANIZATION FOR APPLIED RESEARCH TNO
PO Box 217
NL2600 AE DELFT
HJELMAR, O.
WATER QUALITY INSTITUTE
Agern allee 11
DK2970 HRSHOLM
List of Participants
196
HOY, R.
Commission of the European Communities
Directorate-General Science, Research and Development
200, rue de la Loi
B1049 BRUSSELS
KENNEDY, A.D.
EOLAS
The Irish Science & Technology Agency
Materials Technology Dept
Glasnevin
IRLDUBLIN 9
KLEMM, K.
D4300 ESSEN 13
LENZ, U.
RHEINISCHE BRAUNKOHLENWERKE AG
VF 1 Coal Chemistry
Postfach 41 08 40
D5000 KOELN 1
NOMINE, M.
200, rue de la Loi
B1049 BRUSSELS
OLIVIER
DELFT UNIVERSITY OF TECHNOLOGY
Julianalaan 134
NL2600 AA DELFT
OSULLIVAN, P.
POLYCOMP Ltd.
Greenhills Industrial Estate
Walkinstown
IRLDUBLIN 12
PRINS
UNIVERSITY OF TWENTE
PO Box 217
NL7500 AE ENSCHEDE
197
REA
via G.B.Martini, 3
I00198 ROMA
RENNHACK, R.
INSTITUTE OF CHEMICAL ENGINEERING UNIVERSITY OF PADERBORN
Postfach 16 21
Pohlweg 55
D4790 PADERBORN
RODENBURG, L.J.M.
TNO DIVISION OF TECHNOLOGY FOR SOCIETY
PO Box 217
NL2600 AE DELFT
SENS, P.
200, rue de la Loi
B1049 BRUSSELS
SPITSBERGEN, U.
UNIVERSITY OF TWENTE
PO Box 217
NL7500 AE ENSCHEDE
TAILLET, J.
ECOPOL
26, rue du Chteau des Rentiers
F75013 PARIS
TUENTER, G.
NETHERLANDS ENERGY RESEARCH FOUNDATION
Dept of Chemistry and Materials Science
PO Box 1
NL1755 ZG PETTEN
VAN DEN BERG, P.J.
DELFT UNIVERSITY OF TECHNOLOGY
Julianalaan 134
NL2600 AA DELFT
VAN DER SLOOT, H.A.
NETHERLANDS ENERGY RESEARCH FOUNDATION
PO Box 1
NL1755 ZG PETTEN
WILKINSON, J.K.
Directorate-General Energy
200, rue de la Loi
B1049 BRUSSELS
198
INDEX OF AUTHORS
ANDRIES, J.,71
AULARD, P.,89
BLONDIN, J.,198
CROMWELL, P.,16
DE GROOT, G.J.,171
DINELLI, G.,112
DOYLE, A.,16
DUMONT, J.N.,
FRIGGE, J.,134
GAY, A.J.,134
HAMM, T.,202
HJELMAR, O.,171
KAMPHUIS, B.,55
KENNEDY, A.D.,16
KLEMM, K.,159
LENZ, U.,22
LIPHARD, K.G.,159
MULLER, H.G.P.,3
OROURKE, K.,16
OSULLIVAN, P.,202
PAEFFGEN, H.P.,22
RAMEL, M.,89
RENNHACK, R.,101
RODENBURG, L.J.M.,152
SHEEHAN, P.,202
SNEPVANGERS, L.J.M.,3
SPITSBERGEN, U.,55
Index of authors
TAILLET, J.,101
TUENTER, G.,3
VAN DEN BERG, P.J.,36
VAN DEN BLEEK, C.M.,36
VAN DER SLOOT, H.A.,171
VENDEL, J.,89
WOLFRUM, E.,22
200

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FLUE GAS AND FLY ASH

Proceedings of a contractors meeting organized by the Commission of the European

FLUE GAS AND FLY ASH

ELSEVIER APPLIED SCIENCE

ELSEVIER SCIENCE PUBLISHERS LTD

ISBN 0-203-27257-9 (Adobe eReader Format)

Special regulations for readers in the USA

fluidized bed combustion

This page intentionally left blank.

CATALYTIC NOX REDUCTION

Flue gas and fly ash

Figure 1. Flow-scheme of the conventional and modified SCR

Catalytic nox reduction

Table 1. Properties of TiO2 supported catalysts.

active component (s)

The catalysts were also characterized by Temperature Programmed Reduction (TPR).

Flue gas and fly ash

Figure 2. Schematic diagram of the experimental apparatus

Table 2. Standard conditions.

flow (cm3.s-1 STP)

Catalytic nox reduction

Figure 3. TPR profiles of the catalysts.

The values in this figure corresponds to the relative amount of H2 consumed.

Flue gas and fly ash

Figure 4. Activity of VTT, TT, V/TiO2 and V08 in the NO

From figure 4 it is apparent that the activity of the vanadiumoxide-containing catalysts

Catalytic nox reduction

Table 3. Results of numerical calculation for m, n, ko and E for NO reduction.

Table 4. Results of numerical calculation for m, n, ko and E in NO2 and NO/NO2

Flue gas and fly ash

Figure 5. NO, NO2 and NO/NO2 conversion over V/TiO2.

Catalytic nox reduction

Table 5. Calculation of TN (T=230C).

The TN of the NO reduction is constant within experimental error. This is a very

According to reaction 2, NH3 is consumed, while NO, a reactant in reaction 1, is

Flue gas and fly ash

Figure 6. NH3 oxidation over V08 catalyst.

Catalytic nox reduction

5.EVALUATION OF THE MODIFIED PROCESS

Flue gas and fly ash

Catalytic nox reduction

Flue gas and fly ash

IMPROVED GAS FILTRATION SYSTEMS

Flue gas and fly ash

particulates, e.g. electrostatic precipitators, etc.

provide little or no impedance to the flow of flue gases

Improved gas filtration systems for control of solid fuel

pilot test rigs.

3.DESCRIPTION OF TEST INSTALLATIONS

Flue gas and fly ash

4.GAS FILTER SYSTEMS USED

: Quartz et Silice (Paris)

5.RESULTS OBTAINED TO DATE

Improved gas filtration systems for control of solid fuel

TABLE IPILOT TEST RIGS

Flue gas and fly ash

6.CONCLUSIONS TO DATE/FUTURE WORK

DEVELOPMENT OF A PROCESS FOR

Flue gas and fly ash

1.Introduction, state of the art

2.Characterization of brown coal coke produced in rotary hearthfurnaces

Flue gas and fly ash

Development of a process for removal of so2

Flue gas and fly ash