COMMISSION COMMISSARIAT

OF THE A L'ENERGIE
EUROPEAN COMMUNITIES ATOMIQUE

œa
TREATMENT AND
CONDITIONING OF
RADIOACTIVE
INCINERATOR ASHES
Edited by
L.CECILLE
and
CKEKIESZ
*

ASHES 90
▼

ELSEVIER APPLIED SCIENCE

 TREATMENT AND CONDITIONING
OF RADIOACTIVE INCINERATOR ASHES
Proceedings of a technical seminar jointly organized by the Commission of the
European Communities (CEC), Directorate-General for Science, Research and
Development, and the Commissariat à l'Energie Atomique, Direction du Cycle
du Combustible, Département Stockage Déchets, held in Aix-en-Provence,
France, 12-15 June 1990.

Scientific and organizing committee:

MR L. CECILLE
Commission of the European Communities (CEC)

MR C. KERTESZ
Commissariat à l'Energie Atomique (CEA)

Seminar secretariat:
Ms W.L. TAPPERMANN
Commission of the European Communities (CEC)

MRS J. GIANETTI
Commissariat à l'Energie Atomique (CEA)
TREATMENT AND CONDITIONING
OF RADIOACTIVE
INCINERATOR ASHES

Edited by

L. CECILLE
Commission of the European Communities, Brussels, Belgium
and
C. KERTESZ
Commissariat à l'Energie Atomique, Cadarache, France

ƒmu. EÜR: ι . £.:<:.loth.

N.C./EUR Λ5 W1
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Treatment and conditioning of radioactive incinerator ashes.

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 PREFACE

Taking advantage of the latest developments in the field of treatment and

conditioning of radioactive incinerator ashes - especially within the European
Community - this technical seminar provided an opportunity to review and
analyse all aspects related to the management of these radioactive waste
types while identifying issues and options for further research.

Although limited to a very specific research item, this seminar gathered more
than eighty international experts originating from 10 different countries
demonstrating thereby that management of radioactive incinerator ashes
represents an important concern in the evaluation of merits of incineration
over other candidate techniques for reducing the volumes of radioactive
wastes to be disposed of.

These proceedings include all the papers presented at the seminar together
with the opening addresses, a summary of the main achievements and some
additional data concerning the items debated during panel sessions, or
discussed during the visit of the CEN - Cadarache laboratories. For the sake
of completeness, some complementary papers not having been subject to oral
presentations but in line with the seminar programme are also integrated.
 Vil

CONTENTS

PREFACE ν

ABBREVIATIONS xi

SESSION I
OPENING OF THE SEMINAR /GENER AL OVER VIEW

OPENING ADDRESS
INCINERATION AND TREATMENT OF ASHES
FRENCH APPLICATIONS
G. BAUDIN, Commissariat à l'Energie Atomique,
CEN, Fontenay-aux-Roses, France 3

THE CEC RESEARCH PROG RAMME ON RADIOACTIVE

INCINERATOR ASHES
R. SIMON, Commission of the European Communities,
Brussels, Belgium 6

INCINERATOR ASH CONDITIONING PROG RAMMES AT CEA

C. OTTER, Commissariat à l'Energie Atomique,
CEN, Fontenay-aux-Roses, France 8

INCINERATION: THE OPTIMUM FOR WASTE TREATMENT

R. ODOJ, KFA-ICT/PKS, Jülich, G ermany 13

SPECIFICATIONS FOR ASHES WITH

RESPECT TO CONDITIONING
A. D E GOEYSE AND R. SWENNEN, NIRAS/ONDRAF,
Brussels, Belgium 14

RECENT G NS-EXPERIENCE WITH CONDITIONING OF RESIDUES

FROM INCINERATION OF RADIOACTIVE WASTE
D. RITTSCHER, G . G ESTERMANN AND H. G EISER,
Gesellschaft für Nuklear-Service mbH, Essen, G ermany 22

SESSION II
CHEMICAL BEHAVIOUR OF INCINER ATION ASHES

GAS PRODUCTION BY REACTION OF WATER OR

ALKALINE SOLUTIONS WITH LAW ASHES
M. LASER, KFA, Jülich, G ermany 29
CHARACTERIZATION AND TREATMENT OF
ASHES FROM KFK INC INERATORS
W. PFEIFER, S. DROBNIK AND R. KRAEMER,
KfK GmbH, Hauptabteilung Dekontaminationsbetriebe,
Karlsruhe, Germany 35

OPTIMIZATION AND CHARACTERIZATION OF

CEMENT PRODUC TS INC ORPORATING ASHES
FROM RADWASTE INC INERATION
G. RIC C I AND A. DONATO, ENEA C RE Casaccia, Rome, Italy 45

EXPERIENCE WITH ASHES FROM THE EVENCE C OPPEE

— OVEN OF MOL; PROBLEMS WITH C ONDITIONING
R. GENS AND P. GIELEN, ONDRAF/NIRAS, Brussels,
L. TEUNC KENS, BELGOPROC ESS, Dessel, Belgium 56

PYROLYTIC ASH EMBEDDING USING HYDRAULIC BINDER:

CHEMICAL BEHAVIOUR AND EMBEDDING ASH FORM PROPERTIES
E. REVERTEGAT AND G. MOINE, C ommissariat à
l'Energie Atomique, DRDD/SESD — CEN — SACLAY,
Gif sur Yvette, France 62

CHARACTERISATION OF ASHES C OMING FROM SIMULATED

RADWASTES AND EVALUATION OF CONDITIONING METHODS
L. C AÑADAS AND L. SALVADOR, Departamento de
Ingeniería Química y Ambiental, Escuela Técnica
Superior de Ingenieros Industriales,
Universidad de Sevilla, Spain 72

SESSION ΙΠ
LOW TEMPERATURE IMMOBILISATION PROCESSES

CONDITIONING OF ALPHA INC INERATOR ASH BY

MEANS OF EMBEDDING IN DIFFERENT MATRIC ES
C.J. KERTESZ, P.R. C HENAVAS, L. AUFFRET
AND A. BIAGINI, DRDD, C EA—C EN C adarache,
Saint Paul lez Durance, France 85

MATRIX PROPERTIES OF MODIFIED SULPHUR C EMENT

FOR RADIOAC TIVE INC INERATOR ASHES
A. V A N DALEN AND J.E. RUPKEMA, Netherlands
Energy Research Foundation, EC N Business Unit
Nuclear Energy, Petten, The Netherlands 96
EVALUATION OF THE POSSIBLE EMBEDDING MATRICES
FOR INCINERATOR ASHES: FRENCH EXPERIENCE
J. MISRAKI AND G. KERTESZ, DRDD, CEA—CEN
Cadarache, Saint Paul lez Durance, France 102

HYDROTHERMAL SOLIDIFICATION OF
INCINERATOR ASHES
Y. NAKAMORI, S. KAMADA, K. MORI AND Y. HASHIZAKI,
Nuclear Energy Systems Division, Mitsui Engineering
and Shipbuilding Co. Ltd., Japan 113

CONDITIONING PROCESSES FOR INCINERATOR ASHES

A. JOUAN, N. OUVRIER AND F. TEULON,
Commissariat à l'Energie Atomique,
CEN—Valrhô, Bagnols-sur-Cèze Cedex, France 124

EPOXIDE SYSTEM TO BIND AND EMBED RADIOACTIVE ASH

J. JAHCHAN, J-P. ROGER AND M. ETIEVANT,
Spado Lassailly SA, Gallardon, France 133

SESSION IV
DECONTAMINATION PROCESSES FOR ALPHA ASHES

TREATMENT OF PLUTONIUM CONTAMINATED ASHES BY ELECTRO-

GENERATED Ag(II): A NEW, SIMPLE AND EFFICIENT PROCESS
C. MADIC, J.L. SAULZE, J. BOURGES, M. LECOMTE
AND G. KOEHLY, CEA/DCC/DPR,CEN,
Fontenay-aux-Roses, France 139

PLUTONIUM RECOVERY FROM INCINERATED ALPHA-BEARING

WASTE ASHES AT THE MARCOULE REPROCESSING PLANT
G. CAUQUIL, J. SOMMI AND C. BRESCHET,
COGEMA—Marcoule, Bagnols-sur-Cèze Cedex, France 146

RECOVERY OF PLUTONIUM FROM INCINERATOR

ASHES BY NITRIC/SULFURIC ACID
K. GOMPPER AND H. WIECZOREK, KfK, Institut für
Nukleare Entsorgungstechnik, Karlsruhe, Germany 150

SESSION V
HIGH TEMPERATURE IMMOBILISATION PROCESSES

THE INDUCTION HEAT MELTING/SOLIDIFICATION SYSTEM

FOR LOW-LEVEL RADIOACTIVE INCINERATOR ASH
Y. KARITA, K. YAMAMOTO AND A. KATO,
NGK Insulators Ltd., Nagoya, Japan 161
 χ

CERAMIC ENCAPSULATION OF ASHES

CONTAINING ALPHA EMITTERS
S. CARPENTIER AND B. AUBERT, SG N,
Saint Quentin en Yvelines, France 171

SOLIDIFICATION OF RADIOACTIVE INCINERATOR ASHES BY

INCORPORATION INTO AN ALUMINIUM SILICATE CERAMIC MATRIX
A. LOIDA, KfK, Institut für Nukleare
Entsorgungstechnik, Karlsruhe, G ermany 184

CONDITIONING OF ASHES FROM COMBUSTION

PLANTS IN SPECIAL MELTING FURNACES
B. G ANSER, NUKEM G mbh, Hanau, G ermany 190

CONDITIONING OF PLUTONIUM-CONTAMINATED
ASH BY POWERING MICROWAVE
K. KUDO, M. OHUCHI, H. MIYO, T. NAG ASAKI,
E. INADA AND Y. AsAKURA, Power Reactor and Nuclear
Fuel Development Corporation, Ibaraki-ken, Japan 201

STABILIZATION OPTIONS FOR TREATMENT

OF INCINERATOR ASH WASTES
T. TABUCHI, K. SUZUKI, N. KURUMADA AND
H. KURIBAYASHI, JG C Corporation, Tokyo, Japan 207

INCINERATION OF TECHNOLOGICAL PROCESS

WASTE AND TREATMENT OF THE ASH: THE
POSITION OF ELECTRICITE DE FRANCE
Υ. MAZET, EDF Centre d'Ingénierie
Générale, Marseille, France 216

MAIN ACHIEVEMENTS OF THE SEMINAR AND GENERAL CONCLUSIONS

MAIN ACHIEVEMENTS OF THE SEMINAR 219

GENERAL CONCLUSIONS 223

ANNEX 1 227

ANNEX 2 228

ANNEX 3 229

ANNEX 4 230

LIST OF PARTICIPANTS 235

INDEX OF AUTHORS 239

 ABBREVIATIONS

BELGOPROCESS Belgoprocess, Dessel (B)

CEA Commissariat à l'Energie Atomique
CEA/Cad Commissariat à l'Energie Atomique/
Centre d'Etudes Nucléaires de C adarache (F)
CEA/F Commissariat à l'Energie Atomique/C entre d'Etudes
Nucléaires de Fontenay-aux-Roses (F)
CEA/S Commissariat à l'Energie Atomique/C entre d'Etudes
Nucléaires de Saclay (F)
CEA/V Commissariat à l'Energie Atomique/C entre d'Etudes
Nucléaires de la Vallée du Rhône, Marcoule (F)
CEC Commission of the European C ommunities
COGEMA/M Compagnie Générale pour les Matières Nucléaires,
Marcoule (F)
ECN Stichting Energieonderzoek C entrum Nederland,
Petten (NL)
ENEA Comitato nazionale per la ricerca e per lo sviluppo
dell'Energia Nucleare e delle Energie Alternative,
Casaccia (I)
ENEL Ente Nazionale per l'Energia Elettrica,
Milano (I)
ETS 11 ETSII de Sevilla (E)
GNS Gesellschaft für Nuklear-Service mbH, Essen (D)
JGC JGC C orporation, Tokyo (J)
JRC Joint Research C entre, Ispra (I)
KFA Forschungszentrum Jülich GmbH (D)
KfK Kernforschungszentrum Karlsruhe GmbH (D)
MES Mitsui Engineering and Shipbuilding C o. Ltd.
Tokyo (J)
NGK NGK Insulators Ltd., Nagoya (J)
NUKEM NUKEM GmbH, Alzenau (D)
ONDRAF/NIRAS Organisme National des Déchets Radioactifs et des
Matières Fissiles/Nationale Instelling voor het
Beheer van Radioactief Afval en Splijtstoffen,
Bruxelles (Β)
ONTARIO HYDRO Ontario Hydro, Toronto (C DN)
PNC Power Reactor and Nuclear Fuel Development C orporation,
Tokai-mura (J)
SGN Société Générale pour les Techniques Novelles,
Saint-Quentin-en-Yvelines (F)
UNIV. KOIICIH University of Kohchi (J)
 XU

The rostrum during the final panel session

Group of participants at the visit of the CEN-Cadarache laboratories and facilities

 Session I

OPENING OF THE SEMINAR / GENERAL OVERVIEW

G. B A U D I N (CEA) A N D R. S I M O N (CEC)
 Opening address
INCINERATION AND TREATMENT OF ASHES
French Applications
G. BAUDIN
Département de Recherche et Développement Déchets
C mmissariat à l'Energie Atomique
CEN de Fontenay-aux-Roses
Boite Postale 6
92265 Fontenay-aux-Roses

Abstract
Incineration has a wide variety of applications. Five inci-
nerators are in service in France today, and an equal number
of installations is planned. The ash produced varies considerably,
justifying many different conditioning processes.
Due to the costs of storage, it is important for future
research to aim at a maximum gain in volume.

1. INTRODUCTION
I am happy to welcome you to Aix en Provence, and I wish to thank
the organizers for offering me the possibility to talk about a subject
connected with the reduction in volume of waste to be stored, a matter
just as important for the future as the management of nuclear waste.
The difficulties that we face in public opinion concerning the
opening of waste disposal centres mean that these facilities must
be used with maximum efficiency, namely that the volumes to be stored
must be reduced to the minimum.
Among the volume reduction techniques available, incineration
is worth considering as a top priority, because its applications are
numerous, both for solvents and for miscellaneous solids and biological
substances.

2. THE DEVELOPEMENT OF INCINERATION

In a few moments, Mr. Odoj will deal with the problem of incinera-
tion. But right away, I would like to highlight the gap existing
between the development of incinerators in the research centres, where
they are numerous, and the few industrial applications : power reactors,
reprocessing plants.
There are several reasons for this, one being the relatively
high cost of incineration compared with other techniques, such as
compaction and extrusion. As an example, a recent study on the treat-
ment of technological wastes from EDF reactors showed that the relative
costs were 1 for high-pressure compaction, 1,3 for extrusion, and
1,5 for incineration.
An analysis of the cost breakdown is informative. It shows that
the savings realized over disposal are insufficient to offset the
additional cost of the process. This implies in the future :
an additional gain in volume reduction, hence the reduction
of the secondary wastes other than ash associated with filtration,
research on ash immobilization matrices which preserve this
volume gain, i.e. processes incorporating the maximum of ash per unit
volume,
. lowering the costs of upstream operations such as sorting and
shredding, which account for nearly one-quarter of the total cost :
accordingly, the possibilities of an incinerator without prior sorting,
such as a rotaty furnace, are worth examining.
Note also that the generalization of incineration would be easier
if unchlorinated products (vinyl, acetate) were substituted for chlori-
nated compounds (PVC, neoprene).

3. CEA INCINERATORS AND THE TYPES OF ASH PRODUCED

As we stated earlier, incinerators offer many possibilities,
and therefore produce ash of different compositions. Thus, in France,
we have the following :
. at Grenoble : since 1970, a beta/gamma incinerator for contami-
nated oils and solids (15 hg.h-1),
. at Cadarache : since 1981, a beta/gamma incinerator for solids
(30 kg.h-1)
. at Cadarache : since 198O, an incinerator for beta/gamma liquids
(50 kg.h-1)
. at Marcoule and Valduc : since 1975/1977, an alpha incinerator
for solids (1 kg.h-1)
Currently planned :
. at Marcoule : an alpha incinerator designed to burn chlorinated
wastes (45 % PVC, 17 % neoprene) based on the pyrolysis system, followed
by calcination of 15 kg.h-1,
. at Valduc : the same unit but with capacity limited to 7 kg.h-1
In these types of incinerator, the ash above a certain plutonium
content is treated for recovery. This implies a specific grade of
the ash, containing less than 2 % carbon and 0,5 % chlorine.
at La Hague : a pyrolysis incinerator designed to burn the
distillation residues of spent solvents/extractants from La Hague,
rich in TBP.
EDF and COGEMA are also examining the possibility of the incinera-
tion of the their beta/gamma wastes.

1. ASH CONDITIONING
This programme for a new installation involves the immobilization
of untreated ash, or of ash having undergone wet treatment to recover
the plutonium. The ideal solution would be to use a single process
with a common matrix.
This stuation is far from feasible today, given the variety of
products to be immobilized, ranging from mainly calcium phosphate,
to siliceous compounds or a mixture highly enriched in zinc chloride.
In general, immobilization by hydraulic binders, given their
low cost, is the solution frequently adopted, as shown by the number
of papers devoted to it in this Symposium. However, in view of the
reactivity of the product to be immobilized and the reactivity of
the cement itself, it is indispensable to select a formula for each
type of ash, since the range of variation in concentration remains
narrow.
To extend this range, additives are used to reduce the porosity
of the material and to increase its tensile strength, while reducing
the reactivity and the moisture content. This has given rise to the
use of polymer cement.
The final step is to use these pure polymers or sulphur-based
compounds (modified sulphur cement), with high leaktightness, for
which the absence of a cement/matrix reaction guarantees the possibili-
ty of immobilizing nearly all the ash produced. However, it should be
noted that these products are more expensive than cement.
A comparison of these different types of immobilized waste product
was made at Cadarache, and led us to select a cement if the quality
of the ash is constant (phosphate ash, for example), and a polymer
cement if the ash composition varies or if its alpha content is fairly
high.
The presence of alpha emitters leads to the production of radio-
lysis gas. The importance of the composite matrix lies in its low
moisture content and its high tensile strength. However, if the alpha
content rises too much, it becomes indispensable to use a ceramic
type of matrix.
All these matrices present the drawback of including a maximum
of 40 to 50 % ash, and therefore of causing a loss in the volume gain,
hence the idea of reducing this dilution by using techniques such
as isostatic or conventional compression, with or without encapsulation,
which are still in the research stage.
An examination of the composition of some type of ash leads to
the consideration of a vitrification method with or without additive.
While cementation is the most widespread technique today, I am
convinced that these fusion techniques have a bright future ahead.
At the CEA today, we are focusing on cement and polymer cement
matrices for the short term, for which the techniques are available
and are the subject of full scale tests on the pilot plant that you
will visit at Cadarache. For the long term, we are currently examining
the possibilities of vitrifying the ash.
Vitrification can produce a very effective immobilization matrix,
and this could lead the safety authorities to reconsider recovery
of the plutonium, which is not a simple matter (secondary wastes)
or a cheap one.

CONCLUSION
For incineration to grow, we have to solve this tripe problem :
. limit the secondary wastes from incineration so that the real
gain in volume approaches the theoretical gain higher than a factor
of 100 ; we have set a value of 40 for our alpha incinerator,
persuade the waste generators to replace chlorinated products,
. condition the ash at minimum cost, i.e. simultaneously estimate
the price of conditioning and that of disposal, especially if this
involves a deep geological repository : the additional cost of condi-
tioning could ultimately be a saving if it reduces the volume suffi-
ciently.
I am certain that, on this point, your work will provide convincing
answers.
 6

THE CEC RESEARCH PROGRAMME ON RADIOACTIVE INCINERATOR ASHES

R.SIMON
Commission of the European Communities, Brussels (B)

1. INTRODUCTION
The CEN Cadarache has been a particularly cooperative and active partner in three R&D
programmes on Management and Disposal of Radioactive Waste of the European
Communities. Its participation has covered such a wide scope of our programmes that we
have been able to organize joint meetings on a different topic each year.
This year the specific topic we will address is the treatment and conditioning of
radioactive ashes. During the first two EC research programmes, between 1975 and 1985,
the development of incinerators for alpha-bearing waste was among the most important
issues. Then, in the third programme, the question of durable immobilisation had to be
investigated, as the straightforward cementation approach had, at least in some processing
campaigns, led to an unstable product.

2. OBJECTIVES
During the past five years the objectives of the EC programme concerning radioactive ashes
have been:
— to develop stable products which comply with the acceptance criteria, and
— to reduce the volume of the waste products.
The R&D projects launched to this effect were grouped under the following areas:
— Pretreatment
— Decontamination
— Encapsulation
— Melting/Pressing.

3. R&D PROJECTS
Pretreatment of incinerator ashes
The swelling of cementitious waste forms for ashes can lead to serious damage in the waste
package. The reaction of metals with the cement grout can be avoided by pretreatment, eg,
soaking the ash in diluted NaOH prior to admixing the cement (ENEA—Casaccia).
Ash encapsulation
Ashes containing alpha-emitters require a particularly durable confinement. Three types of
encapsulation matrices are being investigated:
— cementitious grouts and polymer cement matrices (CEA Cadarache);
— modified sulphur cement (ECN Petten);
— ceramics (KfK Karlsruhe).
Melting or pressing of ashes
Conditioning of ashes without addition of matrix material was investigated in two projects:
— the hot isostatic pressing (HIP) of ashes was studied by CEA in Marcoule (France),
and
— the melting of ashes was tested by Nukem in Alzenau (Germany).
Decontamination/removal of actinides
Two projects studied processes for the removal of TRU from incinerator ashes:
— the ashes from the Marcoule incinerator were part of the range of wastes included
in decontamination trials at CEA Fontenay-aux-Roses;
— KfK incinerator ashes (and some samples from Marcoule) were subjected to actinide
leaching at Karlsruhe.
Results of these projects will be presented and discussed more extensively at this
meeting, so it would be premature for me to pronounce conclusions.

4. ACTIVITIES OF THE NEXT EC PROGRAMME

Figure 1 illustrates the spread of activities covered by the 1990/1994 R&D programme. The
emphasis is clearly on research of disposal options, followed by the characterization of
barrier materials. Nevertheless, the development of treatment processes (Task 2) will
continue to be funded on a significant scale.
The main topics of Task 2 for the new term of five years are:
1. Minimisation of radioactive discharges.
2. Reduction of waste volumes.
3. Optimisation of waste management.
4. Conditioning of spent fuel.
5. Transmutation of long-lived radionuclides.
The conditioning of ashes will mainly figure as item 2), reduction of waste volumes.
In view of the progress achieved during the past five years, the main technical problems
will hopefully be solved by the end of 1995.
System Studies
Treatment

Underground laboratories

Characterisation
QA/QC

Safety assessment
TOTAL EC BUDGET: 79.6 MECU

Support to disposal studies

Fig. 1. Breakdown of funds between the different items investigated within the fourth
EC research programme on radioactive waste management (1990—1994)
 INCINERATOR ASH CONDITIONING PROGRAMMES AT CEA
C. OTTER
Département de Recherche et Développement Déchets
Commissariat à l'Energie Atomique
Centre d'Etudes Nucléaires de Fontenay aux Roses
S? n° 6
922 65 FONTENAY aux ROSES
France
SUMMARY
The CEA's Research and Development Programmes on ash
conditioning are described in relation to :
- a project to build an alpha waste incinerator with a capa-
city of 45 t/year, to be commissioned in 1994 in the MELOX
(MOX fuel) fabrication plant at Marcoule,
- pressing needs to condition stocks of bêta/gamma ash exis-
ting at the Cadarache Nuclear Research Center,
- future projects to build alpha and bêta/gamma incinerators
at La Hague or at EDF nuclear power plants.
This Research and Development Programme employs conven-
tional embedding processes, as well as more elaborate pro-
cesses such as isostatic pressing and high-temperature
fusion.
1. INTRODUCTION
Starting in 1985 in addition to a major programme for
developing industrial incineration processes, I was requested
to draw up a programme on ash conditioning.
To accomplish this programme, the first objective was
to draw up a four-year investment plan enabling the CEA to
have the testing facilities necessary to study two projects :
on the one side at the laboratory scale, the formulation and
characterization of embedded ash, and on the other side the
feasibility of the embedding process on an industrial proto-
type.
This programme led to :
- the construction of a glovebox line for the preparation of
samples of alpha embedded ash, wich entered active conditions
in January 1987,
- the construction of an ash conditioning prototype using a
rotary blade mixer of the "Guédu" type, for the preparation
of 100 and 200 litre embedded ash drums.
This prototype enjoys the ability to use several embed-
ding matrices such as cement, thermosetting epoxy resin, and
composite cement/resin matrix. This prototype was commis-
sioned in June 1988.
A second glovebox line entered active conditions in
December 1988, designed to fabricate and characterize samples
of bêta/gamma embedded ash.
2. CEA RESEARCH PROGRAMME ON ASH CONDITIONING
2.1 Conditioning of ash from the MELOX incinerator
For its project concerning a plant for the fabrication
of nuclear fuels of the "light water" type enriched with plu-
tonium (MOX fuel) , COGEMA asked the CEA to develop an alpha
waste incinerator with a capacity of 15 kg/h. The high pluto-
nium content ash resulting from the incinerating operation
has to be treated to recover plutonium. The poor ash and dry
residue from plutonium recovery must be embedded in a matrix.
The average mass composition of the wastes to be inci-
nerated is as follows :
. polyvinychloride 48 %
. polyethylene 8 %
. neoprene 17 %
. latex 17 %
. cellulose 10 %
Annual incinerable waste production is :
. 21.5 tof low Pu waste,
. 25 t of high Pu waste.
After incineration, this waste produces the following :
. 0.5 t of poor ash with activity less than 1.3 TBq.t-1
(36 Ci.t-1),
. 0.3 t of dry residue after Pu recovery from rich ash,
with specific activity between 3.7 and 7.4 TBq.t-1
(100 and 200 Ci.t-1),
. 0.1 to 0.6 t of fly ash rich in zinc chloride, of low
activity.
The production of zinc chloride depends on the zinc
oxide content in the neoprene gloves and in the PVC. The fly
ash is recovered in unclogging operations on the bag filters
used for gas filtration.
The CEA programme on ash conditioning described below
is only concerned with the conditioning of low Pu ash. This
Programm includes the following :
- test to develop a formulation in the laboratory on inactive
ash, using three immobilization matrices :
. a cement matrix,
. a polymer matrix using a thermoset epoxy resin,
. a composite/resin matrix.
- laboratory tests :
. feasibility tests on the formulations and their opti-
mization,
. determination of physical properties, such as the
measurement of density and of swelling under water,
. mechanical strength tests such as the measurement of
hardness and compressive strength,
. leach tests on embedded products containing real ash
and on samples doped with 238Pu02, containing a cumu-
lative integrated dose of 30 MGy (3 Grad) after
internal irradiation of one year,
 10

- tests on the conditioning prototype including :

. the preparation of 100 and 200 litre drums,
. temperature measurement during the setting of the
embedded product,
. testing of the homogeneity of the embedded products
by cutting,
. study of the cleaning of the mixer after pouring the
embedded product, etc.
The tests are designed to select, among the three
matrices investigated, the one most interesting from the
standpoint of disposal safety in a deep repository and the
feasibility of the embedding process. The continuation of the
Programme includes the adjustment of the final formulation to
the conditioning of the residue resulting from the recovery
of Pu from the ash, and the conditioning of fly ash contai-
ning zinc chloride.
In Session 3 of this seminar, Mr KERTESZ will give you
a progress report on this Programme.
2.2 Research on conditioning of the stock of bêta/gamma ash
existing at the Cadarache Nuclear Research Center
A stock of about 5 t of ash exists at the Cadarache
Nuclear Research Center, with a specific bêta/gamma emitter
activity of 3.7 to 370 GBq.t-1 (0.1 to 10 Ci.t-1), and an
alpha emitter activity of less than 3.7 GBq.t-1 (0.1 Ci.t-1).
Due to the variety of chemical composition of this ash,
it was decided to perform conditioning in a composite
cement/resin matrix, which offers the advantage over the
cement matrix of being less sensitive to the chemical compo-
sition of the ash.
The formulation is as follows, expressed in mass :
. epoxy resin and hardener : 30 % (hardener/resin
ratio = 0.6),
. cement and water : 30 % (water/cement ratio = 0.35),
. ash : 40 %.
The embedded product characterization programme
concerns four types of ash :
- Type 1 tributylphosphate incineration ash (phosphate ash),
- Type 2 ash from the incineration of other solvents
(chlorinated solvents, trilaurylamine nitrate, etc)
- Type 3 ash from the incineration of solid technological
wastes (cellulose, wood, latex neoprene, etc),
- Type 4 ash from the incineration of miscellaneous inactive
wastes (cellulose, wood, etc).
A characterization procedure was drawn up to secure
ANDRA approval on the disposal of embedded ash in 100 litre
drums at a shallow-ground disposal site. This procedure
includes measurements on samples of ash packages prepared
with ash of Types 1,2 and 3, such as the determination of the
physical and mechanical properties, leach tests on samples
containing as contaminated with 134Cs, 137Cs, 60Co and 90Sr.
It also includes tests on 100 litre drums prepared with Type
4 ash, allowing tests of strength under load, resistance to
fire and impact, resistance to thermal cyclings, etc.
This characterization programme will be described in
detail by Mrs MISRAKI in Session 3.
 11

2.3 General programme on the conditioning of ash

contaminated with bêta/gamma emitters
The goal is to select the best performing ash embedment
from the standpoint of the retention of bêta/gamma emitters
(Cs, Sr and Co) .
This study should permit the CEA to determine the
embedding process in different matrices to treat ashes. Those
ashes will be produced in the future incineration facilities
to be built to treat the COGEMA's reprocessing wastes and EDF
nuclear reactor wastes.
The ash used for these tests includes active ash produ-
ced by the solid waste incinerator of the Cadarache Nuclear
Research Center.
This R and D Programme is in two phases : in the first,
an optimized ash package formulation is determined using four
immobilization matrices, such as cement, epoxy resin, a
cement/resin mixture and bitumen. The second phase, which
includes leach tests, will serve to compare the retention
properties of the four ash packages on samples of specific
activity of about 0.4 TBq.t-1 (10 Ci.t-1).
2.4 Conditioning of ash produced by pyrolysis of the
tributylphophate/Dodecane mixture
For the destruction of spent solvents, essentially
consisting of a mixture of TBP and 30 % dodecane and oils,
COGEMA has selected the NUKEM pyrolysis process. In this pro-
cess, the solvent mixture and calcium oxide are injected si-
multaneously on silica spheres heated to 400°C. The pyrolysis
reaction leads to the production of calcium pyrophosphate or
of chemical species liable to deviate from the Ca/P stoichio-
metric ratio of 1.
COGEMA asked the CEA to investigate the conditioning of the
pyrolysate in cement.
This programme includes studies of formulations desi-
gned to select the ideal cement for conditioning calcium
pyrophosphate, as well as embedding tests in 100 litre drums
in the conditioning installation developed by the CEA at
Cadarache.
This programme will be described by Mrs REVERTEGAT in
Session 3 of the seminar.
2.5 Other research on ash conditioning
2.5.1 Conditioning by isostatic pressing
Isostatic pressing tests were performed on samples of
inactive ash, and the main fabrication parameters were deter-
mined, such as the choice of the container, the filling tech-
nique, the press operating parameters, the need for ad-
ditives, etc. The main physical and mechanical properties
were determined, and industrial feasibility and preliminary
project tests were conducted.
2.5.2 Ash fusion
Preliminary tests were conducted at Marcoule using
existing vitrification facilities. Ash throughputs of 15 and
20 kg/h were achieved in cold crucibles 35 and 55 cm in dia-
meter, with a glass frit addition of 25 and 50 %.
 Also worth mentioning is an investigation at Marcoule
on the preparation of vitreous and basaltic vitrocrystalline
materials containing inactive ash.
A comparative study was carried out on the ash embed-
ding process by the composite cement/resin matrix, the iso-
static pressing process, and the fusion process. This study
will be described by Mr JOUAN in Session 3.
3. CONCLUSIONS
The CEA's short-term R and D Programme is focused on
ash conditioning processes involving ash embedment. The com-
pletion of this Programme will serve to identify the reten-
tion properties of the different matrices investigated, and
to offer incineration operators an industrial process for ash
immobilization.
To develop the volume reduction technique by incinera-
tion even further, the yield of the incinerators will have to
be improved, with the addition of an ash conditioning faci-
lity characterized by a high volume reduction factor.
In our opinion, the fusion technique is the most inte-
resting, because it allows a gain by a factor of 4 to 5 over
conventional embedding processes, and yields a vitreous
material whose retention properties are well known with res-
pect to most radioisotopes, both in the short and the long
term.
In the next five years, the CEA will try to develop
fusion processes, using the high-frequency cold crucible
fusion technique, or the microwave fusion technique. The dif-
ficulty will be to select an efficient, low-cost process.
I wish to thank the organizers of this seminar for
having included, in Session 5, papers on fusion processes,
which I consider to be a highly promising technique.
 INCINERATION: THE OPTIMUM FOR WASTE TREATMENT

Reinhard Odoj

KFA-ICT/PKS
D-5170 Jülich

For the final disposal of non heat producing waste in the 'Konrad'-mine, FRG, two waste
classes have been identified from safety assessments for acceptance criteria:
Class I: There are no increased criteria at the barrier property of the
packagings other than normal mechanical integrity.
Class II: Packaging with special requirements, eg, leak tightness and thermal
conductivity.
In contrast to Class II, Class I is subdivided into six waste form groups:
1. bitumen and plastic products
2. solid matter
3. metallic solid matter
4. compacted waste
5. cemented/concrete waste
6. concentrates.
From this classification it can be seen that there is no special group or class for
incinerator ashes in the FRG. Conditioned incinerator ashes can meet the acceptance criteria
of nearly all classes or groups, depending on the final conditioning technique.
On the other hand, there are now about 27 quantified characteristic numbers as
relevant properties for the waste packages. Seven of these relevant properties concern only
the packaging. However, the other 19 properties are in relation to the waste itself (seven
properties) and the conditioning process (12 properties). Nearly all the properties
concerning the waste itself are automatically fulfilled if the waste has been burned to
incinerator ashes.
This means that these relevant properties do not have to be examined by the quality
control, which simplifies clearance of the waste packages for final disposal.
 14

SPECIFICATIONS FOR ASHES WITH RESPECT TO CONDITIONING.

A. DE GOEYSE and R. SWENNEN

NIRAS/ONDRAF, Place Madou 1, boites ?.4/25, 1030 Bruxelles

Summary
Conditioning of low level radioactive incinerator ashes is
generally achieved using two different techniques. The first
technique consists in an homogeneous embedding of the ashes in
a solidification matrix such as cement, thermosetting resins
or mixed cement-resin matrix. The second technique consist in
a heterogeneous encapsulation of pellets with supercompacted
ashes in cement.
The quality requirements for incinerator ashes with regard to
such a conditioning have been investigated. A number of
requirements are generally applicable whatever conditioning
mode is applied. They mainly concern the physical form of the
ashes and their chemical composition and should help to avoid
metal corrosion and gas generation so that the integrity of
the package is not compromised. These investigations have lead
to the choice of the second conditioning mode : encapsulation
of supercompacted pellets with cement into the ONDRAF/NIRAS
400 1-standard drum. This choice is justified.
Several test drums are under investigation in order to qualify
the process and to show compliance with the final pruducL
acceptance criteria.
These criteria, which are established with shallow land
disposal as the reference concept, are currently being
finalized.
They refer to the waste form, the matrix and the waste package
itself. The status of the characterization programme is
described together with each of the corresponding acceptance
criteria.

1. INTRODUCTION
Since the beginning of the sixties, ashes have been produced by the
low-temperature incinerator Evence-Coppée located in Mol. These ashes
result from the incineration of various combustible wastes from Belgian
waste producers. Until 1987, these ashes were conditioned taking into
account the criteria for sea dumping.
Since 1988, the year in which the Mol installations were taken over
by ONDRAF and its subsidiary BELGOPROCESS, the ashes are no longer
conditioned but are stored awaiting their conditioning.
At that time, ONDRAF and BELGOPROCESS started to investigate a new
conditioning technique which should guarantee compliance with
acceptance criteria for a shallow land burial, the reference concept.
Several qualification tests ha^e already been performed, specially
with a view of choosing the matrix.
Tests on the final product are currently in progress.

2. QUALITY REQUIREMENTS FOR INCINERVTOR ASHES

The characteristics, i.e. the quality of ashes from incineration,
may vary widely, depending on a number of parameters :
the nature of the waste treated ;
its chemical composition ;
the temperature at which combustion takes place ;
the oxygen available for the combustion process ;
the residence time in the combustion chamber ;
etc.
 15

As a general rule one may state that the more complex the
composition of the waste the more difficult it will be to optimize the
incinerator working conditions. This will result in a deterioration of
the quality of the ashes.
Although quality requirements will differ depending on the way the
ashes are conditioned, a number of requirements are generally
applicable whatever conditioning mode is applied.
First, ashes should be kept dry until the time of conditioning. No
water should be added e.g. for cooling purposes, as was done at Mol
(EVENCE C OPPEE incinerator) for some time. This procedure was proven to
have caused severe corrosion of the drums in which the ashes were
packed during intermediate storage, awaiting their conditioning.
Possible explanations are :
­ In solution ashes from the E.C. generate a pH between 8 and 12,
as a result of the combined effects of carbon and mineral
compounds. Such a solution presents a homogeneous system in which
an equilibrium is reached in a short time. If water is present in
incinerator ashes (the E.C. ­ ashes contained on average 10 wt %)
contact zones will be created, each wich their own pH. The
heterogeneity of the ashes does not allow an equilibrium to be
established and for a number of ashes/metal contact zones the pH
may be slightly acid [carbon compounds, acid pH (PC Z)]. This will
result in local corrosion sites, with attack of the metal and the
generation of hydrogen.
­ Chlorine generated during the incineration of PVC and other
chlorine­containing materials easily combines with elementary
carbon. In the presence of humidity the chlorinated compounds
will hydrolyse with the liberation of hydrochloric acid.

­ C ­ Cl + Η,Ο ­­> ­ C ­ OH + HCl

¿
ι ι

Other compounds may form, such as acid chlorides. Their

hydrolysis will also result in the formation of hydrochloric
acid :

0 0
­ C* + H 0 0 ­­> C"^ + HC l
S 2 V
C1 0H

The acid will attack metals with the liberation of hydrogen :

Fe + 2 HCl ­­> FeCl 2 + H 2

Sulfur too may react with elementary carbon to form sulfur

complexes. The combination of sulfur and oxygen may result in the
formation of mixed complexes_ of carbon, e.g. sulfonic acid, a
strong acid :

­ C ­ SO,
J Η
ι
Chlorine present in the form of soluble salts enhances aerobic
corrosion.
 16

- The creation of slightly acid contact zones will cause an

acceleration of aerobic corrosion. The standard potentials
involved are :

(1) Fe --> Fe 2 + + 2e" - 0,44 V

(2) 0 2 + 2H 2 0 + 4e" --> 40H" + 0,39 V (in neutral and

basic medium)

(3) 0 2 + 4H + + 4e" --> 2H 2 + 1,23 V (acid medium)

Three different reactions, which might occur simultaneously, may

thus contribute to drum corrosion :

(1) Fe + 2H + --> Fe 2 + + H 2

(2) 2Fe + 0 2 + 2H 2 0 -- > 2F e(OH) 2

(3) 2Fe + 0 2 + 4H + --> 2Fe 2 + + 2H 2 0.

A second general requirement is that gas generation in the waste

package containing the conditioned ashes should be such that the
integrity of the package is not compromised, this means that it should
not be pressurized to a level which could lead to its distortion or
premature failure. If gas generation is suspected to occur tests should
be made to estimate the production and release rates.
The permeability of cements for hydrogen essentially depends on 3
parameters :
- The age of the cement : permeability will diminish with time
because hydration of the cement will continue.
- The W/C-ratio : with increasing W/C both porosity and
permeability increase.
- The interstitial water : permeability diminishes with increasing
"free" water content after hydration (a dried cement is 10^
times more permeable than a cement saturated with water).
In the case of supercompacted ashes packed in a 400 1-drum and
surrounded by a 4 cm thick cement layer, the volume of gas diffusing
per unit of time may be estimated using the following equation :

Q = K.S.-n- L · IIS [0_

R1
. τ 2Po
Ax In
R2

Where :
3 1
Q = diffused gas volume (m .s )
K = permeability constant (m )
Ai = hydrogen viscosity (8.76 10"° kgnT^.s)
R 2 = outer radius (35 cm)
Ri - inner radius (31 cm)
P 2 = hydrogen pressure in the cylinder (N mm" )
P^ - pressure of the emerging hydrogen (N mm" )
PQ = ambiant pressure (N mm" )
L = length of the cylinder (mm)
For a slight equilibrium overpressure of hydrogen inside the cement
cylinder (P 2 - Ρ 1)/2Po should be of the order of 20.
 17
For a W/C ratio of 0,33 and a residual water content of 2.5 wt-X
the permeability coefficient should, according to literature data, be
between 1 0 " 1 5 and 1 0 " 1 6 m 2 .
Application of the formula for such permeabilities gives release
rates of respectively 10 and 1 litre per day.
Pressure measurements on drums with conditioned supercompacted dry
ashes have shown that gas release rates are within these limits. Even
wetted ashes gave not rise to inacceptable gas generation rates. In
both cases, however, the ashes contained no or very small amounts of
aluminium fines (the specifications for waste to be incinerated exclude
the presence of metallic aluminium). When substantial amounts of
aluminium are present they may cause inacceptably high gas generation
rates, even in the case of supercompacted ashes where only small
volumes of liquid are available for interaction.
When aluminium is susceptible to be a problem the ashes should,
also in the case of supercompaction. be pretreated with a diluted (1 to
2 molar) solution of sodium hydroxyde.
When ashes are homogeneously incorporated into cement, such a
pretreatment should be applied in all cases, to exclude any possibility
of inacceptably high gas generation after conditioning.

3. C ONDITIONING MODES/C HOIC E OF A PROCESS

For the conditioning of ashes from LLW or HLW a number of matrices
are being investigated in Europe : cement, epoxy thermosetting resin
and mixed cement epoxy resin.
With cement either homogeneous or heterogeneous products may be
obtained. In the latter case pellets of supercompacted drums with ashes
are surrounded by a sufficiently tick layer of cement to give a
mechanically stable waste form.
In Belgium the second option will be adopted because of a number of
advantages of this mode of conditioning :
- Since the ashes will be normally dry there is no electrolytic
medium to support corrosion reactions ;
- Only little solution will be available to interact with the ashes
once the cement has set. Prior to setting interaction
possibilities are limited to infiltration of the water used in
the mixture.
- Acceptance criteria for the non-conditioned wastes may allow the
acceptance of a wide variety of wastes with regard to nature and
composition, except metal which can be oxidized by water
(especially aluminium and zinc) ;
- The weight of ashes per 400-1 standard drum i.e. +/- 300 kg, is
about twice the amount which can be homogeneously incorporated
into cement.
- etc .
Several testdrums have been prepared and are for the moment being
investigated in order to qualify the process and to show compliance
with the final product acceptance criteria.

4. AC C EPTANC E CRITERIA FOR THE FINAL PRODUCT

The acceptance criteria for the final product are imposed by the
different stages of waste package management : transportation, interim
storage and final disposal. Waste packages resulting from ash
conditioning can be of category A or category Β depending on the
radionuclide content.
a) C ategory A waste contains mainly radionuclides with a half-life
below 30 years. The concentratione of radionuclides with a
longer half-life are below the limits imposed by the disposal
concept safety analysis.
 18

This disposal concept is considered when establishing the

acceptance criteria. They are currently being finalized and
refer to the waste package itself, to the waste form and to the
matrix.
b) C ategory Β waste is no heat generating waste; the
concentrations of long-lived radionuclides are above the limits
derived in the shallow land disposal safety analysis. For the
category Β low -and medium- level waste, the disposal reference
concept is an underground disposal in a clay environment.
Sofar acceptance criteria for this waste category have not yet
been determined. For the characterization programme established
for the process qualification of this category of waste, the
same basic acceptance criteria as for category A waste are
considered with special attention to particular problems with
regard to underground disposal such as gas generation.
As already mentioned, the conditioning process considered for
the incinerator ashes consists in the encapsulation into cement
of supercompacted ash pellets in a standard ONDRAF 400 1 drum
with a centering device (see figure 1). Several
characterization tests have been performed on this matrix in
order to show its compliance with the acceptance criteria.
The resulting waste packages are considered "heterogeneous".

4.1. Acceptance criteria for the waste package

Acceptance criteria are imposFd for the physical and mechanical
properties of the waste package. The most important criteria, however,
are related to its radioactive properties and particularly its
radionuclide content.

4.1.1. Physical and mechanical properties

Owing to the existing handling tools of the transport and storage
facilities, the weight of each package is limited to 1.5. ton. All
packages comply with this criterion.
The waste package shall be able to sustain the loads imposed by the
storage and disposal conditions. In addition its confinement properties
shall not be impaired after a drop of 1.2 m or. an unyielding surface.
The corresponding tests intended to show compliance with these
criteria have not yet been perfomed.

4.1.2. Radioactive properties

The radionuclide content for each individual package has to be
reported and must be below the limits resulting from the safety
analysis of the disposal concept. At the moment such limits are being
evaluated but final values are not yet available.
For ash conditioning perhaps the most adequate approch is to
determine the radionuclide inventory of the ashes in the 220 1-drums,
before supercompaction. C onsidering a volume reduction equal to 40 for
incineration and an encapsulation of maximum 4 pellets per 400 1
standard drum (total weight of approximatively 1 T) the commonly used
limit of 3.76 Bq/T (100 mC i/T) for conditioned waste corresponds to
roughly 0,1 GBq/nr (3 m
C i/m ) for the raw waste before
incineration, which is below the detection limit. The corresponding
limit on the ashes before compaction is about 4 GBq/m or 0,8 GBq/220
liter drum. This limit can be detected by existing measuring equipment.
The other radioactive properties of the waste package are related
to dose rate and surface contamination.
 19
4.2. Acceptance criteria for the waste form
The acceptance criteria valid for the waste form are :
- physical and chemical criteria
- confinement properties.

A. 2.1. Physical and chemical criteria

The first criterion concerns the structure of the waste form. The
waste form should be solid, without voids, to provide stability.
Owing to the compaction of the ashes before conditioning, this
criterion is automatically fulfilled for the waste before
incapsulation.
The criterion for the waste form after incapsulation has already
been checked by means of a tomographic analysis of cemented pellets
from various compressible waste types. Figure 2 shows the results of
such an analysis. The same test will be performed with supercompacted
ash pellets.
The second criterion prohibits any interaction after conditioning
between the raw waste and the solidification media (matrix) that could
produce degradation of the mechanical or confinement properties of the
waste package. This criterion is Etili being investigated, especially
with respect to corrosion and gas production problems.
As indicated in chapter 3 the production of gas, mainly hydrogen,
is essentially induced by the presence of metallic particles.

4.2.2. Confinement properties

In the case of heterogeneous waste packages, the confinement
properties are ensured by the inactive matrix layer (cement). This
layer must have a minimura thickness. For the encapsulation of ash
pellets, this thickness is about 3 to 4 cm due to the centering of the
pellets (see figure 1 ) . Maximura values for the diffusion coefficients
for reference nuclides through this layer are imposed and checked.

4.3. Acceptance criteria for the matrix

The acceptance criteria for the inactive matrix essentially concern
its physical and mechanical properties and its behaviour in case of
temperature variations.

4.3.1. Physical properties

Bleeding after 24 hours, to avoid the presence of free standing
water, and shrinkage of the matrix must be minimized.
Tests made according to the corresponding Belgian NBN norms show
the following values for the selected matrix :
- bleeding : 1 X of the initial mass
- shrinkage : 1,2 10 mm/ra after 91 days.
These are acceptable values.

4.3.2. Mechanical properties

The matrix raust have mechanical properties corresponding to an
industrial high-quality product and must remain stable under the loads
inherent to the storage and the disposal conditions.
For cement used as an inactive matrix, the compressive strength
tested following the Belgian NBN norms shall be equal to or higher than
30 MPa after 28 days.
This criterion is largely ful]filled for the selected matrix. The
tests performed on samples show values far above 30 MPa.
Additionaly, bending strengths of about 12 MPa were measured.
 20

4.3.3. Behaviour in case of temperature variations

Representative tests for possible temperature variations must be
performed on the matrix in order to show its behaviour under such
conditions. After the tests the mechanical and confinement properties
of the matrix must be maintained. The selected matrix was submitted to
freeze/thaw cycles in conformity with the NBN norms. Visual examination
of the samples did not show any degradation or alteration. The other
physical properties measured gave good results.

FIGURE 1 : STANDARD ONDRAF 400L-DRUM WITH CEMENTED PELLETS

 21

CT 37Θ7Α

FIGURE 2 : TOMOGRAPHIC EXAMINATION OF CEMENTED PELLETS

(PERFORMED AT BAM-BERLIN)
 ΊΊ

RECENT GNS-EXPER IENCE WITH CONDITIONING

OF R ESIDUES FR OM INCINER ATION OF
RADIOACTIVE WASTE

DIETER RITTSCHER, G ERT G ESTERMANN and HEINZ G EISER

Gesellschaft für Nuklear-Service mbH

D-4300 Essen

SUMMARY

During 1988/89 about 320 tons of combustible waste from G erman power
plants were incinerated. The incineration residues were filled into special
180 1 drums and compacted in a 1200 ton compactor. The compacted pellets
were packed without any further treatment into a standardized 10 m3
container which is acceptable for interim storage and final disposal. The new
conditioning technique was applied because former cementation of ashes
showed a significant gas-generation (hydrogen) after cementation which has
to be avoided due to German waste acceptance criteria for final disposal.

1. INTRODUCTION
Incineration of solid combustible waste originating from nuclear power plant operation is,
beside high-force-compaction, preferably used as a conditioning method in the Federal
Republic of G ermany. In a recent campaign during 1988/89 about 320 tons of solid
combustible waste were incinerated. The incineration residues (ash, slag and filter dust)
were filled into special 180 1 drums and compacted with a high-force compactor. The
compacted pellets were packed without further treatment into a standardized 10 m3
container. A simplified flow diagram of this conditioning process is shown in Figure 1.
During recent years compaction instead of cementation has been preferred as the
treatment method of ash because after cementation a significant gas generation (hydrogen)
in the waste packages is observed. Furthermore compaction leads to higher volume
reduction compared to cementation.

2. COMPACTION METHOD
For the compaction of drums filled with ash the GNS mobile high-force compactor FAKIR
is used. This compactor can be installed at the incinerator facility or at any other suitable
location. The mobile compactor is shipped in a 20 ft container and can be installed within
three days. In the recent campaign the compactor was installed at the incineration facility
and during a period of two weeks 35 tons of incineration residues were compacted. The
incineration residues are filled into compactable drums and the drums are charged into the
compactor. Each drum contains 120 kg/150 kg of ash. The volume reduction factor during
compaction of the drums is about 2.5. The compacted drums are filled into four
standardized 10 m3 containers.
 23

180 l-drum
filled with ash

high-force compaction

compacted drum
70 - 90 liter

standar ized
10 m3 container

70-90 pellets/container

Fig. 1. Flow diagram for ash compaction and packaging

Figure 2 shows the outer dimensions of the 180 1 drums used for ash-compaction
whilst in Figure 3 the main components of the high-force compactor FAKIR are shown.

3. PRODUCT CONTROL
Radioactive waste arising from operation of nuclear power plants is currently treated under
very stringent controls and QA measures. Prior to a waste conditioning campaign, a
document is prepared giving each step in production of a waste package for interim storage
or final disposal. This document is submitted to the licensing authorities and checked by
 24

an independent organization. After approval, the waste treatment can take place. The related
control steps are indicated in the specific 'Production and Quality Control Specification'
for each waste treatment campaign and for all package types containing the waste product.
These documents include the hold and witness points in which individual production and
control steps are specified.
~^V-
Lid

1801-drum

0 535

Fig. 2. Dimensions of a compactable drum

1) Exit 6) Tipping device

2) Sliding door 7) Charger

3) Jib crane 8) Working platform

4) Grab 9) Hydraulic system

5) Compaction chamber 10) Hydraulic zylinder

Fig. 3. Main components of high-force compactor FAKIR

 25

For Q A purposes the following (mandatory) characteristics of ash (prior to compaction) are
measured:
— nuclide composition
— spec, activity (Gamma/Beta + Alpha)
— weight/density
Additional (non-mandatory) characteristics such as particle size distribution and
chemical composition are measured for information.
In Figure 4 through Figure 6 typical results of ash characteristics are presented. The
age of the corresponding raw waste is about two years.
A comparison of the specific activity of ash resulting from incineration of six
different PWR and six different BWR is shown in Figure 4. There is no significant
difference (with one exception) between spec, activities of ashes from PWR and BWR.
Figure 5 shows the main radionuclides present in incinerator residues. Nearly 80% of the
total activity inventory results from Co-60.
Figure 6 gives a distribution of the grain sizes of ash. This is for additional
information only and not necessary for quality control.

4. VOLUME REDUCTION
Compacting of ash is applied for two reasons:
— to avoid hydrogen generation in the waste product
— to achieve additional volume reduction compared to cementation.
In the recent incineration campaign 320 tons of solid combustible waste have been
incinerated resulting in about 35 tons of incineration residues. The corresponding raw waste
volume delivered to the incinerator was about 1200 m3. After compaction and packing into
waste containers a waste volume (incl. package) of 40 m3 is generated. This leads to a total
volume reduction factor of about 30.

Ash Activity (Bq/g)

5000

4000

3000

2000

1000

1 2 3 4 5 6

Fig. 4. Spec, activity of ash resulting from different PWR and BWR
 26

Cs-137
2.3

Mn-54
12.2

Remaining
0,6

Fig. 5. Nuclide composition of ash

wt %

< 0.0063 0.06..0.25 0.25..1 1..4 4..8 ) 8

Size, mm

Fig. 6. Particle size distribution of ash

 Session II

CHEMICAL BEHAVIOUR OF INCINERATION ASHES

R. K O S T E R ( K F K ) A N D R. V E R B E K E ( O N D R A F / N I R A S )
 29

GAS PRODUCTION BY REACTION OF WATER

OR ALKALINE SOLUTIONS WITH LAW ASHES
M. LASER
Forschungszentrum Juelich GmbH (KFA)
Decontamination Department
D 5170 Juelich
Summary
The ash of low level radioactive waste contains me-
tallic aluminum and aluminum carbide. In contact with
water and alkaline solutions a gas containing hydrogen
and methane is evolved. The gas influences the quality
of the waste product and may cause explosions during
conditioning, storage and final disposal. It is
recommended to pretreat the ash with sodium hydroxide
solution before cementation or to enclose the ash in a
gas tight drum.

1. INTRODUCTION
Combustible low level radioactive waste is a mixture of
many different materials and objects like paper, wood,
plastics, rubber, HEPA filters, etc. It contains also noncom-
bustible components like tools, metal fittings and spray
cans. Presorting can reduce the content of incombustibles,
but this procedure is expensive, dangerous, less effective
and causes unnecessary radiation exposure.
Therefore the Juelich Incineration Process has been de-
veloped to process unsorted waste with a content of incom-
bustible material up to about 15 to 20 %. The resulting ash
contains metallic iron, steel, copper and aluminum. Sur-
prisingly, the metallic aluminum is not oxidized completely,
but forms small droplets. Partially also aluminum carbide is
formed.
In contact with water, alkaline solutions or cement
grout a gas consisting of hydrogen and methane is evolved.
This gas influences the quality of the waste product and may
cause explosions during conditioning, storage and final dis-
posal .
2. CHEMISTRY OF THE GAS PRODUCTION
Metallic aluminum reacts with water producing hydrogen
2 Al + 6 H 2 0 ► 2 Al (0H) 3 + 3 H 2 (1)
The reaction rate decreases gradually because of the
formation of a hydroxide layer on the surface.
With strong alkaline solutions like NaOH, KOH or C a(OH) 2
aluminum forms soluble aluminates, e.g.
2 Al + 6 H 2 0 + 2 NaOH ► 2 Na[Al(0H)4] + 3 H 2 (2)
The reaction is not delayed by a surface layer.
The formation of methane results from the reaction of
aluminum carbide with water or alkaline solutions
 30

A1 4 C 3 + 12 H 2 0 ♦ 4 Al(OH) 3 + 3 CH 4 (3)
Aluminum carbide is formed by reaction of the elements
at temperatures above 650°C
4 Al + 3 C f A1 4 C 3 (4)
or by reduction of C O or C C >2 at temperatures above 900°C ,
e.g.
6 Al + 3 CO ^^4^3 + A1 2 0 3 (5)
At temperatures below 550°C aluminum carbide is unstable
and can decompose into the elements.
3. GAS COMPOSITION
The gas produced by the reaction of the LAW ash with wa­
ter or alkaline solutions consists of hydrogen and methane.
The methane content was varying between 1 and 12 %. It de­
pends strongly on the reaction conditions during the com­
bustion of the waste and the thermal history of the ash.
4. GAS PRODUCTION OF DIFFERENT ASH FRACTIONS
The gas producing components aluminum carbide and metal­
lic aluminum are distributed inhomogeneously in different
fractions of the ash. Detailled examination of a normal run
of the incinerator with unsorted waste have shown that the
highest specific gas production is found in sieve fractions
between 1.5 and 10 mm and in specific weight fractions be­
tween 2.2 and 2.8 g/cm3 (tables 1, 2 and 3 ) . The over all
specific gas production of this ash sample was about 63 ml/g.

Sieve Fraction Weight­% Speci fie Gas Production

mm ml/g

< 0.063 1.1 0

0.063 ­ 0.1 4.6 0
0.1 ­ 0.2 14.6 2.9
0.2 ­ 1.5 30.1 59.5
1.5 ­ 5.0 24.2 109.5
5.0 ­ 10.0 11.3 110.2
> 10.0 14.1 41.8

Table 1: Specific gas production of different sieve fractions

(gross specific gas production 63.2 ml/g)
 31

Sieve Fraction Specific Weight Specific Gas Production

mm g/cmJ ml/g

0.2 ­ 1.5 2.0 ­ 2.2 39

2.2 ­ 2.6 238
2.6 ­ 2.8 small amounts
1.5 ­ 5.0 2.0 ­ 2.2 12
2.2 ­ 2.6 262
2.6 ­ 2.8 179
5.0 ­ 10.0 2.0 ­ 2.2 166
2.2 ­ 2.6 423
2.6 ­ 2.8 small amounts

Table 2: Specific gas production of different specific

weight fractions
In the same sample the total aluminum content comprising
of metallic aluminum, aluminum carbid and oxidized aluminum
compounds was determined analytically. This value was com­
pared with the value calculated from the gas production
assuming that all the gas consists of hydrogen. The results
given in table 3 show that the highest metal + carbide
content is found in the specific weight fraction between 2.6
and 2.8 g/cm . This agrees well with the specific weight of
metallic aluminum of 2.7 g/cm­3.

Specific Weight Metallic Aluminum

%
ι
J
g/cm Total Aluminum
2.0 ­ 2.2 10.9
2.2 ­ 2.6 64.7
2.6 ­ 2.8 91.9

Table 3: Metallic aluminum related to total aluminum content

It may be concluded from these results that aluminum in
low specific weight fractions and in small grain fractions is
oxidized to a high extent.
The examination of the ash of another run with well sor­
ted waste "without visible amount of aluminum" has shown that
this ash produces gas with a specific gas production of about
14 ml/g. This relatively high value compared to the value of
63 ml/g ash from unsorted waste proves that aluminum cannot
be excluded from combustible waste by presorting.
 32

The total aluminum content and the content of metallic

aluminum + aluminum carbide depend on the composition of the
raw waste and processing conditions. Table 4 shows data from
different runs. Whereas the total aluminum content differs by
a factor of 3, the metallic aluminum fraction is between
about 9 and 92 %.

Run Al Content (mg/g ash)

Total Metallic

33.9 2.9 8.6

95.9 55.4 57.8
67.3 10.6 15.8
76.7 70.2 91.5

Table 4 : Aluminum content of ash samples

5. GAS PRODUCTION AT DIFFERENT pH VALUES
The gas production rate and the total amount of gas de-
pend strongly on the pH value of the ash slurry. A treatment
with sodium hydroxide solution results in a complete dissolu-
tion of metallic aluminum in less than 24 hours. With de-
creasing pH value also the gas production rate decreases (ta-
ble 5 ) . The reason may be the surface layer of aluminum hy-
droxide formed at lower pH values. In this case the reaction
rate is diffusion controlled and may last over a long time,
possibly over some years.

pH Gas Production
during 24 h
ml/g

14.8 47.0
14.1 19.3
13.9 5.7
12.9 5.0

Table 5: Gas production rate at different pH values (pH 12.9

corresponds to a mixture of ash, cement and water).
The pH value of an ash slurry depends strongly on the
chemical composition of the ash. For example, the ash of ion
exchange resins is an acidic ash with a pH value between 4.5
and 5.5. Contrary the combustion of calcium carbonate con-
taining sludges results in an alkaline ash with a pH value
between 10.0 and 11.7.
Conditioning of the ash with cement produces an alkaline
slurry with a pH value between 12.0 and 12.9 (table 6) nearly
 33

independently on the chemical composition of the ash.

Therefore a mixture of LAW ash, cement and water produces
remarkable amounts of gas. The gas production continues after
solidification of the mixture, possibly for several years.
Measurements of the gas evolution of pieces of aluminum
covered with concrete show that the reaction is not finished
after three years.

ph of the Ash pH of a Slurry of

Ash, Cement and Water

5.0 12.0
7.2 12.9
9.8 12.8
11.1 12.8

Table 6: pH values of ash-cement-water slurries from ashes of

different chemical composition.
To prevent such a long lasting gas production after con-
ditioning with cement a pretreatment of the ash with sodium
hydroxide solution is advised.
A pretreatment of the ash with humid air, water or steam
is not sufficient to "inactivate" the ash. The alkaline reac-
tion of the components of the ash produce a surface layer of
aluminum hydroxide which reduces the reaction rate.
Some observations may illustrate the behaviour of the
ash:
• In contact with humid air an ash sample produced about 0.3
ml gas/g during 10 days. After addition of water no further
gas was evolved. Addition of sodium hydroxide solution re-
sulted in about 14 ml gas/g during 4 days. However the gas
production was not finished after this time. This behaviour
can be explained by the formation of a relatively dense
surface layer, which is slowly dissolved by a strong alka-
line solution.
• In contact with water (ash-water-ration 2:1) the ash pro-
duced about 1.4 ml gas/g during 7 days. The pH value of the
slurry was 10.7.
• The treatment of ash with steam at room temperature or at
elevated temperatures resulted in a slow gas production for
an undefined period.
• An ash sample pretreated with humid air and sodium hy-
droxide solution was filled in a small steel can and
compacted with a laboratory press. During the following 12
days about 10 ml gas/g were evolved.
• Untreated samples of ash were filled in small steel cans,
compacted and embedded into cement grout. In spite of the
"steel barrier" the gas production started after about 2
hours. During 16 days about 1.8 ml gas/g ash were formed.
After some days the cement matrix was cracked by the
swelling pellets.
 34

• Untreated ash samples filled in small steel cans, com-

pacted, covered with a bitumen coating and embedded into a
cement grout produced only small amounts of gas (about 0.14
ml gas/g ash). The reaction rate decreased to nearly zero
after 18 hours. Accordingly the bitumen can reduce but can-
not prevent the gas production.

6. CONDITIONING OF ASHES
The low level radioactive ashes must be conditioned for
final disposal. Several procedures are employed.
• The ash is mixed with cement and water by tumbling. Ac-
cording to the alkalinity of the mixture gas is evolved and
the grout is swelling. The gas production continues after
solidification. The total amount of gas may be up to 5 m J
per 200 liter drum.
• To prevent the "uncontrolled" gas production the ash is
mixed with sodium hydroxide solution (about 20 liter 20 %
NaOH/100 kg ash). After about 10 hours cement is added and
the mixture is tumbled.
• To achieve a maximum volume reduction factor the ash is
filled in special 180 liter drums, which are supercom-
pacted. The pellets are packed into KONRAD containers for
final disposal. The gaps between the pellets are filled
with cement or concrete grout. Because the metal hull of
the pellet is perforated before and damaged during
supercompacting, water diffuses into the pellet and
produces gas.
• To prevent the gas production the pellets can be packed
into Type A 200 liter drums. The drums are packed in KONRAD
containers and the gaps are filled with cement grout. Addi-
tionally the gap between the pellets and the 200 liter drum
can be filled with bitumen.
7. CONCLUSION
To prevent any risk from the evolution of hydrogen and
methane from conditioned ash the ash must be
• pretreated with sodium hydroxide solution before condi-
tioning with cement or
• packed in gas tight packages.
8. ACKNOWLEDGEMENT
I am please to acknowledge the experimental work done by
Mr. K. Truemper and the fruitful discussions with Dr. E.
Zange and Mr. W. Schlenter.
 35

CHARACTERIZATION AND TREATMENT OF ASHES FROM KFK INCINERATORS

W PFEIFER, S DROB NIK, R KRAEMER

Kernforschungszentrum Karlsruhe GmbH

Hauptabteilung Dekontaminationsbetriebe
Weberstr. 5, D­7500 Karlsruhe
Federal Republic of Germany

Summary
The compositions of ashes and filter dusts are described for the
example of an incineration plant. Experience accumulated in homoge­
neous cementation of ashes is described. The technique of conditioning
ashes by high pressure compaction, which is currently employed, is deri­
ved on the basis of the repository storage criteria for waste generating
no heat.

1. INTROD UCTION
The Central Decontamination Plants Department (HDB ) processes all
low and medium level radioactive residues and wastes arising on the site of
KfK. Various techniques are employed for this purpose IM. In processing bur­
nable materials into waste forms fit for repository, incineration has been
found the optimum way to achieve major volume reductions. KfK/HDB
operates three incineration plants:
One plant for incinerating beta­contaminated wastes with a t h r o u g h p u t
of approx 50 kg/h. This plant has been in operation since 1974.
One plant f o r t h e incineration of more highly alpha­contaminated materi­
als with a throughput of 60 70 kg/h. This plant was commissioned in 1989
and differs from the first plant mentioned above mainly in its alphatight
containment design
One Plant for solvent combustion with a throughput of approx. 30 kg/h.

All plants are equipped with wet flue gas scrubbers to meet the concen­
tration dependent emission limits for chlorine, fluorine, SO2, CO, and dust as
specified in the Technical Clean Air Regulations of the FRG. In plans providing
for efficient processing of saline liquid scrubbing solutions, these solutions
are to be recycled to a point in the incineration plant at which temperatures
are higher, the salt produced in this way is to be processed together w i t h as­
hes into a waste form fit for repository 121 This paper contains a description
of the alpha incineration plant, a characterization of the ashes, and an outli­
ne of the methods of conditioning ash residues, which have been applied sin­
ce 1983.

2. PRINCIPLES OF OPERATION
Figure 1 is a schematic diagram of the al ρ ha­meine ratio η plant. 200 I
drums containing burnable waste in 30 I plastic bags are connected to the
alphatight feed system by means of a double­lid system. The bags are
transferred into the shaft furnace through a transit lock.
A cylindrical shaft furnace with a refractory lining is used for waste
incineration. The furnace is 6 m high and has an inside diameter of 1 m. A
propane burner heats the furnace to about 900°C. Then the furnace is char­
 36

ged. The mass flow in the furnace varies between 50 and 70 kg/h. Incinera-
tion takes place at about 1000°C and may be regarded to be almost complete.
To obtain a uniform temperature in the ash bed, steam is added to the com-
bustion air. The temperature in the downstream afterburning chamber is
kept between 1000 ans 1200°C by means of a propane afterburner. Before
the flue gas is passed through the first ceramic filter, its temperature is re-
duced to 900°C by adding cooling air. Further reduction of the temperature
takes place before the flue gas enters the second ceramic filter.
A two-stage srubbing system is located downstream of the t w o ceramics fil-
ters. Here, noxious gases (chlorine, SO2 and fluorine) are removed from the
flue gas by means of scrubbing. A controlled supply of sodium hydroxide so-
lution holds the pH of the srubbing water between 3.5 and 5 in the first
scrubber and at 7 in the second scrubber. The saturated flue gas is heated by
adding hot air to prevent the temperature in the downstream system compo-
nents from falling below the dew point. Then the flue gas is passed through
HEPA filters. Afterwards it is released into the atmosphere through a stack of
70 m height. An exhaust fan that keeps the pressure in the systems below at-
mospheric is used for this purpose.
After release into the environment, the chemical and radiological pollu-
tants of the flue gas are measured continuously. The ash and the filter dust
are transported into the ash discharge box by a vibrationg chute and
collected in 200 liter drums. The ash drums are compacted for further volume
reduction and charged in steel sheet containers.
Samples are taken from approx. 28 ash drums, which form one waste
package; they are mixed, homogenized, and analysed with respect to activi-
ty, specific nuclides and, if necessary, chemical composition.

3. ASH COMPOSITION
Table 1 lists the mean chemical compositions of the ash and filter dusts,
where as Table 2 summarizes some physical properties. Depending on the ori-
gins of burnable wastes, the metal compositions may vary by up to a factor
of 10. If, e. g., parts of wooden frames of air filters are incinerated, which are
covered w i t h an aluminium foil, the fraction of aluminium in the ash may rise
up to 50 g/kg.
The carbon content is a function of burnout in the furnace. Rising car-
bon contents have been observed to reduce metal oxide compounds to ele-
mental metal. Over the past few years, some modifications to the process
technology of the furnace have improved the burnout, thus allowing the car-
bon fraction in the ash and the filter dust content to be decreased. Ash and
filter dust are produced in a quantitative ratio of 3:1. The mean activity com-
position of the ash is listed in Table 3
Some first measurements of polychlorinated dibenzo dioxins (PCDDs)
andfurans (PCDFs) are presented in Table 4. The measurements show very
low PCDD/PCDF contents which, in addition, are largely independent of the
PVC content of the feed. The process temperatures in the furnace and on the
ceramic candle filters, from which ash was sampled, were >600°C.

4. CONDITIONING INCINERATION RESIDUES BY CEMENTATION

In 1983, homogeneous embedding in a cement matrix was planned as a
conditioning technique to be used on incineration residues. An outline is gi-
ven below of the cement formula, the design of the continuous cementation
plant, and the experience accumulated with the technical waste form pro-
duced.
 37

4.1 D EFINING THE FORMULA

To define the boundary conditions of cementation, cementation trial
runs were made with shredded non­radioactive ash from a refuse incinerati­
on plant and with radioactive ash, of a composition as shown in Tables 1 ­ 3 ,
which came from the beta­incineration plant. A waste form was to be gene­
rated which was solid and minimized in volume, ι. e., had minimal water and
cement contents Instead of the Portland cement used in conditioning evapo­
rator concentrates, fluid mortar under the trade name of " M a x i t " was used,
which had better fluidity properties. The waste forms made in the laboratory
with a weight of 40 % ash, 40 % fluid mortar and 20 % water had these pro­
perties:
The ash was distributed homogeneously; no cracking was detected.
Setting took approx. 58 days.
The compressive strength attained levels of up to 4 N/mm2.
The density was between 1900 and 2000 kg/m3.
The entrained air volume (DIN 18, 555 II) amounted to 10 vol. %.

Rising ash fraction of the product caused the entrained volume to increa
se and the compressive strength to decrease at the same time.

4.2 CONTINUOUS CEMENTATION PLANT FOR INCINERATION RESID UES

Figure 2 shows the process scheme of the cementation plant designed
as a box ­ type facility Ash, also in the form of broken filter candles, was
crushed in a shredder of 800 kg/h throughput to a maximum grain size of 15
mm and then passed by a screw type conveyor to an ash bin of 2 m3 interim
storage volume.
Fluid mortar and ash were mixed in a dry mixing section to a weight ratio of
1:1 at a throughput of 640 kg/h. In another mixing section, water was added
at approx. 160 l/h. The waste form produced in this way was directly fed to a
200 I drum attached to a double­lid system.
No problems were encountered in generating waste forms of non ­
radioactive ash. The waste forms made of radioactive ash showed gas evolu­
tion during the setting process, and there was pressure buildup in the closed
200 I drums.

4.3 GAS EVOLUTION FROM THE CONDITIONED ASH PRODUCTS

Some of the drums filled with cemented ash were fitted with special lids
which allowed both gas samples to be taken and temperatures to be measu­
red. The gas volumes measured were 0.2 to 25.8 I (STP)/kg of ash. Gas chro­
matographic examination indicated the following composition:
Hydrogen 7 4 ­ 7 8 vol. %
Nitrogen 12 ­ 19 "
Oxygen 0 5­ 3"
Methane 0.1 ­ 7 "
Ethane, acetylene, propane traces
The gas evolution is due to reactions of elemental zinc, t i n , copper, and
aluminium with calcium hydroxide. Hydrocarbons, such as methane, origina­
te from reactions between carbides and alkaline components of the cement
matrix. The following observations were made:
gas evolution began approx 2 hours after the waste form had been pre­
pared
The maximum rate of gas evolution occurred after 18 ­ 20 hours. At the
time of maximim gas evolution also the highest temperatures of approx.
45"C, which are caused by hydratation of the fluid mortar, were measu­
red in the center of the drum.
 38

No major gas evolution occurred after 8 ­ 1 0 days.

Further studies, especially on ways and means of controlling the gas evo­
lution and also on determining leaching rates, were stopped as the reposito­
ry storage criteria for waste generating no heat seemed to make homoge­
neous embedding of ashes in cement unnecessary. In addition, it stands to be
expected that improved burnout of the ash, i. e., low C­content and, hence,
metals present in their oxide forms, will cause the gas evolution in homoge­
neously cemented ash to play a secondary role.

5. WASTE ACCEPTANCE REQUIREMENTS FOR CONDITIONED INCINERATION

RESIDUES
The specifications to be met by a technique of conditioning incineration
residues are based on the preliminary waste acceptance requirements for the
Konrad mine, which are shown as systematic diagram in Figure 3.
The permitted maximum activity inventories for waste form categories
1 and 2 as a rule exceed the activity levels measured in ash residues from
technical plants. The maximum permissible levels for waste form category 2,
e. g., are 2 x 4 E12 B q/waste package for beta­activities and 3 χ 3 E l l
Bq/package for Pu­239.

Figure 4 shows the criteria to be met by a waste form. The waste forms
with conditioned ash generated at KfK meet the criteria applying to com­
pacted waste in waste form group 02.
Detailed inspection of the criteria for this case indicates that it is not
necessary at present to know the details of the chemical composition of ash
residues. The very incineration process ensures that ash residues react under
normal conditions, do not enter into chemical reactions and, because of the
compaction technique selected, will not interact with the surrounding ma­
trix.

6. COMPACTING ASHES AT KFK/HDB

Ash compaction has been used since 1984. The process is shown in Fig. 5.
Ash filter dusts and broken candle filters from the incineration plant are
collected in 180 I steel sheet drums. These drums are taken to the high pres­
sure compaction caisson. The press operates at a compaction force of 2000
kN. All installations can be operated remotely. The compacts are put into a
200 I drums attached to the caisson and subsequently filled into a container.
The steel sheet container of 7.2 m3 volume can accommodate 14 χ 200 I
drums. The remaining voids are mixed with cement mortar prior to delivery
to the repository. Compared to cementation, compaction of the ash achieves
a much higher volume reduction factor. The density of the ash after com­
pactions is 1600 kg/m3. One container accommodates the incineration residu­
es of approx 300 m3 of burnable material, which result in an effective volu­
me reduction factor of about 45.
Before compaction, a sample is taken from each ash drum, ground, and
homogenized. A composite sample is prepared, which is representative of
the content of one container. A nuclide spectrum is established and a Pu­
isotope analysis carried out for each composite sample.
As, most probably, also the behavior of toxic chemical substances in the
intermediate storage and in the repository will have to be considered
alongside with the behavior of radioisotopes, an analytical program now
started is devoted to determining
heavy metals,
polychlorinated dibenzo dioxins and furans.
 39

REFERENCES
IM Pfeifer, W : T r e a t m e n t o f l o w a n d m e d i u m level residues a n d wastes
f r o m processing, K e r n t e c h n i k 54/4, 1989

121 B r e n n e c k e , Ρ , W a r n e c k e , Ε. R e q u i r e m e n t s o f Radioactive Wastes f o r

Disposal
PTB SE 17(1987)

Ash Filter dust

g/kg g/kg
Sodium 43 50
Potassium 11 70
Calcium 83 40
Magnesium 35 10
Zinc 72 70
Iron 212 120
Silicon 137 25
Aluminium 22 20
Lead 15 15
Tin 0.9 4
Copper 63 ­
Nickel 1.9 8
Fluorine 10.1 1
Chlorine 32 8
Nitrates 01 7
Sulfates 112 65
Phosphates 22.1 16
Carbonates 31 8
Carbon 8 21

T a b l e 1. Chemical c o m p o s i t i o n

Ash Filter dust

Annealing lossat (wt.%) 15
900ÜC
Melting point (C) 1200­ 1500°C
Bulk weight (kg/m3) 560­1050 580­700
Paticle size (pm) coarse 20­250

Table 2. Physical ρ roperties of unt reated ash and filter dust.

 40

Total activity Bq/kg

α­ 1.5 E7
ß­ 1.5 E8
Nuclide activity
Co ­60 1.7 E4
Ru ­ 106 3.6 E6
Sb 125 1.1 E6
Cs­ 134 3.7 E5
Cs­ 137 2.2 E6
Cd ­ 109 7.4 E5
Ce ­ 144 1.5 E6
Eu ­ 154 3.7 E5
Eu ­155 3.0 E5
U­ 235 1.2 E3
U­ 238 2.5 E4
Pu ­238 9.0 E6
Pu ­239 1.4 E6
Pu ­240 2.0 E6
Pu ­241 1.2 E8
Am ­241 3.0 E6

Table 3: M ean a

Type of sample D
DPC PCD F

ng/g ng/g
Ash, afterburner/Furnace <0.1 <0.1
Fly ash, 1st filter stage 0.34 8.12
Fly ash, 2nd filter stage 2.59 1.22

Table 4: PCCD/F concentrations in ashes

 41

AFTER- HEPA-
FURNACE BURNER FILTER JET SCRUBBERS FILTER STACK
•dOOO'C 1200«C <1000«C <500»C <150*C 75"C 100· C 70m

FEEDING SYSTEM PROPANE AIR COMPRESSED AIR

»RAO
WASTE WATER
MAIN STREAM
COMPACTION
BY-PASS STREAM
AUXILIARIES

Fig. 1. Incineration of solid radioactive waste

Fig. 2. Homogeneous cementation of ashes

 42

high

100%
A

Inventory
of Nuclides
per Package

2 0,3%
7?-
I high
5 4 3 2
Quality / *
high of Waste
, Packagings
— Quality of Waste Products —
tow
Fig. 3. Preliminary KONRAD repository criteria
 43

Waste form groups

01 Q2 03 04 05
Product criteria

Random moet ure of substances

Metal with less than 0 1 act% of non-metaJ

Metal with 0.1 to 1 act% of non-metal

Uqutø or buik material, respectively, in cement stone

Scrap in cement stone

Solids (Compressée strength > 10 N/mm2 )

No materials sed - igniting below 70 °C

Ftssite content up to 50 g per 1001 of product

Content of explosible substances up to 3 g per 2001
of product
Content of free liquids limited to 1 voL%

Gases In emty vessels with max 1.5 bar at 20 C

Content of burnable substances limited to 1 %

Content of burnable substances more than 1 %

Nuclide inventory limit

Product solid or solidified

Gas evolution up to permissible operating pressure

Compressive strength of product > 10 N/mm2

A/npoutes,flasks, gas cylinders open

Voids in waste container filled up

Waste/immobtlization agent ratio < 1.5

Cartridge compacted at > 30 M Pa

Cartridge (wall thickness > π 75 mm) compacted
at > 30MPa

Metallic product prepared at > 30 MPa

Radioactrve substances evenly distributed

throughout product
In case of Rrv220 release, product enclosed all round χ χ

χ - required o - permitted

Fig. 4. Product criteria for various waste form groups in Class I

with containers without specified leaktightness
 44

15.000 kN-Press Lifting gear

for compacts
Double
Caisson Lid lock

Sludge (water)

Removing ash-box
Cement

LQ
Riling in Pressing Measuring Grading Packaging Filling the
1 BO l-sheet-drums Removing in Container Container with
Storing through locks Cement grout

Fig. 5. Conditioning of ashes by compaction

 45

OPTIMIZATION AND CHARACTERIZATION OF CEMENT PRODUCTS

INCORPORATING ASHES FROM RADWASTE INCINERATION

G. Ricci, A. Donato

ENEA CRE-Casaccia, Rome (Italy)

Summary
In this work the phisico-chemical characteristics of two
ash tipes coming from the incineration of exausted ion
exchange resins used in the Caorso Italian power plant have
been investigated. The ash immobilization in the cement has
been performed and the cemented products have been
characterized by mechanical strength, setting time, exothermic
peak temperature and long term leach test . The swelling
phenomenon that occurs when the ashes are immobilized in the
cement has been studied and a suitable ash pretreatment has
been proposed to avoid it.

1 . INTRODUCTION
The incineration is presently considered a very good way to
obtain strong volume reductions of intermediate and low
activity solid radwastes obtaining at the same time a product
apparently easy to be conditioned. In the case of the ash
solidification nevertheless some problems often arise: this
was ascertained, for example, during the cementation of the
ashes coming from the incineration of the Italian Caorso power
plant radwastes at Studsvik (Sweden). It was observed there in
fact a mortar swelling during the cement setting phase and
moreover an ammonia evolution was noticed. Because of this
strong swelling the mortar went out of the drums and the
solidified product was very porous. Similar problems are
reported to have been met in other nuclear plants / l / .
So the research work reported in this paper aimed to
investigate about the reasons of these phenomena by means of a
physico-chemical characterization of the mentioned ashes with
the objective to define the best waste/cement mixtures with
respect to the mechanical and leaching resistance properties.

2. PHYSICAL AND CHEMICAL ASH CHARACTERIZATION.

The investigation was focused on the ashes coming from the
incineration carried out at the Studsvik Incinerator in Sweden
on 1985 of real radioactive exhausted ion exchange resins
already conditioned in urea-formaldehyde, coming from the
Caorso power plant, and carried out on 1986 on the same
wastes with the addition of other solid radwastes 12/. About 1
Kg of real ash from the 1985 1st campaign (called here NUST 1
ash) and 10 Kg of real ash from the 1986 2th campaign (called
here NUST 2 ash) where obtained from the Italian Company
NUCLECO. The incinerator burning temperature was about 800°C.
The two above-mentioned ashes have been characterized by
means of the following analysis:
- Density
- Particle size distribution
- Gamma radiometric analysis
 46
Nitric, ammoniacal and organic nitrogent content
determination
Atomic Absorption metal analysis
Thermogravimetric analysis
Differential Thermal Analisys

Density
The ash density has been determined both as "fill density"
(density obtained filling a 500 cc gratuated cylinder without
any settlement and weighing the obtained ash volume) and as
"tap density" (obtained taping the ash with the special
apparatus required by the ASTM Β 527-81 standard method / 3 / ) .
The density results are reported in the Table I: the Nust 1
and Nust 2 ashes show quite different density values due to
the different composition of the initial wastes.
FILL DENSITY TAP DENSITY
ASH TYPES g/cm3 g/cm3

NUST 1 0.57 ± 0.02 0.80 ± 0.03

NUST 2 0.86 ± 0.02 1.10 ± 0.02

TABLE 1. The density of the Nust 1 and Nust 2 ashes

Partie]e size distribution.

The ash particle size distribution, as determined by
sieving according to the ASTM C 136-82 standard method / 4 / , is
shown in the Fig. 1.

FIG.l Grain size distribution of the ashes Nustl and Nust2.

By visual examination the Nust 1 ash appears to be quite

homogeneous, although conglomerates of various sizes are
visible.
 47

On the contrary the Nust 2 ash is quite heterogeneous, as

it contains, in the bigger fractions, metal and glass pieces.

Gamma spectrornetric analysis.

The gamma spectrometric analysis results of Nust 1 and
Nust 2 ashes are shown in the Table 2. The radioactivity
concentration in both ashes is very low and is 35-40 times
higher than in the original waste. 90% of the radioactivity
is due to the C o60 produced mostly by neutron activation in
the reactor.
Nuclides Nust 1 Nust 2
μΟί/Κς Error % μΟϊ/Κς Error %
Th 234 8.5 3.8 Ν.D.
U 235 0.7 1.6 Ν.D.
Sb 125 0.7 2.3 0.4 9.8
Cs 134 0.2 10.1 Ν.D.
Cs 137 1.2 2.5 Ν.D.
Zn 65 6.1 32.9 Ν.D.
Mn 54 0.8 4.7 0.3 6.4
Co 60 40.0 0.2 20.8 0.3

TABLE 2. Gamma-ray emitters in Nust 1 and Nust 2 ashes

Nitrogen content determination.

All the Nitrogen analysis have been carried out according
to the sludges analysis methods issued by the Italian
Institute for Research on the Waters (I.R.S.A.) / 5 / , on
grounded to powder samples (particle size > 120 mesh).
The total nitrogen was measured performing the chemical
reduction of nitrites and nitrates to ammonia by chromium
powder in acidic media. The organic nitrogen was converted to
ammonia by digestion in sulphuric acid on a suitable catalyst.
All the ammonia was then distilled in alkaline media,
collected in boric acid and determined by Potentiometrie
titration
The ammoniacal nitrogen was measured dissolving in acid
media the ammonium salts contained in the ash, converting
the ammonium salt to ammonia by magnesium oxide and distilling
then the ammonia as said before.
The nitrites and nitrates have been determined extracting
them from the ashes by water; then the nitrites were oxidized
to nitrates by hydrogen peroxide. The colour developed by the
reaction between nitrates and phenolsulphuric acid was used
for the spectrophotometric determination at 480nM.
 48

Nitrogen I Nust 1 Nust 2

Total 0.71 ± 0.05 0.11 ± 0.008

Ammoniacal 0.12 ± 0.008 0.017 ± 0.001

Nitrous-Nitric <0.001 (D.L.) 0.003 ± 0.0002

Organic 0.59 + 0.04 0.093 ± 0.006

TABLE 3 Nitrogen analysis results on the Nust 1 and

Nust 2 ashes

The organic nitrogen was measured as difference between the

total nitrogen and the nitric and ammoniacal nitrogen.
The analysis results are listed in the Table 3.The total
and ammoniacal nitrogen content in the Nust 1 ash is about 7
times higher than in the Nust 2 ash. As in the case of the
density, the difference can be explained observing that the
Nust 1 ash comes from the ion exchange resins incineration
alone, while the Nust 2 ash was obtained from the incineration
of ion exchange resins mixed with ordinary solid wastes.

Atomic absorption metal analysis.

The AA analysis has been carried out after fusion of ash
samples with lithium metaborate followed by dissolution of the
melt in nitric acid / 6 / . The concentration of the following
chemical elements has been determined: Si, Al, Fe, Ca, Na, Cu,
Zn, Mg, Cr, Pb, Ni, Mo, Co. The analysis results are reported
in the Table 4. Si, Al and Fe concentrations are the highest.
The different concentrations of these elements found in the
two ash types can be explained by the different ash origin, as
said before.

Element % Nust 1 Nust 2 Element % Nust 1 Nust 2

Si 4.9 13.0 Cu 0.6 0.8

Al 2.4 6.2 Cr 0.2 0.2
Fe 13.5 7.0 Ni 0.06 0.08
Ca 1.8 2.3 Pb 0.06 0.05
Na 4.7 1.8 Co 0.02 <D.L.
Zn 1.0 1.6 Mo <D.L. <D.L.
Mg 1.3 1.4

TABLE 4 AA metal analysis results on the Nust 1 and Nust 2 ashes.

(D.L. : Detection Limit)
 49

Thermogravimetric analysis (TGA).

The t h e r m o g r a v i m e t r i e analysis has been p e r f o r m e d in t h e
t e m p e r a t u r e range 1 0 0 - 9 0 0 °C, b o t h in n i t r o g e n a n d in a i r
a t m o s p h e r e , on ash samples p r e v i o u s l y g r o u n d up t o p a r t i c l e
size £ 1 2 0 m e s h . The instrument used for the a n a l y s i s w a s a
Perkin-Elmer thermogravimetrie balance mod. TGS-2 connected to
a P e r k i n - E l m e r m o d . 3 6 0 0 Data S t a t i o n C o m p u t e r . F o r e a c h
determination about 3-5 mg of ash were used.
The TGA results in air are shown in the F i g . 2 . The thermal
b e h a v i o u r of b o t h a s h e s is s i m i l a r in n i t r o g e n a n d a i r
a t m o s p h e r e , with only small d i f f e r e n c e s of the o r d e r of the
a n a l y t i c a l e r r o r in the t o t a l weight l o s s . T h e Nust 1 a s h
shows a t o t a l weight loss of about 19 %, w h i l e the Nust 2
weight loss is about 8.5%. M o r e o v e r t h e Nust 1 w e i g h t loss
appears in the temperature range 300-600°C about, while in the
case of Nust 2 it seems to be continuous up to about 800°C.
The differences in the thermal behaviour could be explained
on the basis of the chemical composition of the two a s h e s .

100.0

ι
g
ui
90.0

80.0
220.0 300.0 380.0 460.0 540.0 620.0 700.0 780.0 860.0
TEMPERATURE ( " O TG

FIG.2 TGA of NUST 1 and NUST 2 ashes in air

In fact in the case of Nust 1, talcing into account the

origin of the ash, the main salt anion is the sulfate, coming
from both the powdex resins and the catalyst used for the
urea-formadehyde polimerization, while in the Nust 2 the
sulfate concentration is strongly reduced by the presence of
ash coming from the ordinary power plant solid wastes. As
shown in the Table 5 ΠΙ, the most part of the sulfate salts
contained in the ashes decomposes in the temperature range
from 460°C (sodium pirosulfate) to 770°C (aluminium sulfate).
 50

As the Aluminum concentration in the Nust 2 is much higher

than in the Nust 1, (see the Table 4) this can explain why the
Nust 2 weight loss is continous up to about 800°C . Moreover
the Nust 1 total weight loss is higher than the Nust 2 because
of its bigger sulfate content.

Sodium Pyrosulfate 4 60°C

Iron Sulfate 480°C
Zinc Sulfate ZnSO,) 600°C
Copper Sulfate CuS0 4 650°C
Aluminium Sulfate A12(S04)3 770°C
Magnesium Pvrosulfate MnS04 1174°C

TABLE 5. Decomposition temperature of some sulfate salts.

Differential thermal analysis (PTA) .

The differential thermal analysis of ashes has been
performed in the temperature range 100­1000 °C , both in
Nitrogen and in air atmosphere, on samples previousy ground up
to particle size >120 mesh, using a Perkin­Elmer mod. DTA
1700 apparatus connected to a Perkin­Elmer mod. 3600 Data
Station C omputer.
The phenomena occurring in the air atmosphere appear to be
very different than in the case of Nitrogen atmosphere. The
Nust 1 and Nust 2 analysis carried out in air atmosphere show
in fact an exothermic peak in the temperature range 400­600°C ,
as shown in the fig.3, while this peak is missing in the case
of nitrogen. This means that part of the weight loss during
the sample heating is due to the oxidation of some ash
component, which probably has been not completely burned
during the incineration.
8.0
SCAN RATE: 40.0 deg/min

« ­ NUST 1

0.0 ■ 1 1 1 1 1 1 1 1 Κ­
110.0 190.0 2700 350.0 480.0 510.0 590.0 670.0 750.0 830.0 910.0

FIG.3 DTA of NUST 1 and NUST 2 ashes in air.

 51

3. PRELIMINARY STUDY OF C EMENT PRODUC TS INC ORPORATING NUST 1

AND NUST 2 ASHES.
The cement type used to immobilize the Nust 1 and Nust 2
ashes is the Pozzolan C ement 325, which is more resistant to
leaching than the Portland C ement, due to the best C a/Si ratio
/ 8 / . In the immobilization experiments the ashes have been
incorporated in cement at 1/4, 1/3, 1/2 ash/cement ratios,
using the minimum water amount required to obtain a workable
mixture, the ratio water/ash+cement being in this way nearly
constant. In any case the water/cement ratio used was in the
range 0.4+0.5.

Cemented ash characterization.

The cemented ashes have been characterized determining the
setting time according to the Vicat method, the thermal
evolution at the sample center in adiabatic conditions and the
mechanical strength after 28 days of normal curing.
For the setting time determination the % penetration
depths in cement of a Vicat apparatus needle versus time is
measured. The results concerning the Nust 2 ash are reported
in the Fig. 4. The setting time for the ash/cement ratio 1/4,
1/3 and 1/2 are of 7, 7 and 9 hours respectively versus 6
hours of the plain Pozzolan 325 Cement.
As far as the Exothermic peak temperature is concerned,
the maximum temperature value reached by the cement mixtures
during the hardening phenomena has been experimentally
measured and recorded placing, immediately after the
preparation, 1 kg of ash/cement mixture in a Dewar adiabatic
system with a termocouple in the mortar centre. A maximum
temperature of 60 °C has been reached in the case of the
ash/cement ratio 1/4.
The compressive strength has been determined for
cylindrical samples according to the ASTM C 39­79 Method
/9/, and for cubic samples according to the UNI, Italian
Standard Methods, 6132­72 Test /10/.
In the Table 6 the compressive strength results are
summarized together with the setting time and the exothermic
peak results.

100 c
% penetration
· ♦ ­ cpz325
00­
•o­ nu3!2/cem 1/2
βο­
■­ nusl2/cem 1/3
70­ •D­ nust2/cem 1/4

βο­

50­

40­

30­

20­

10­

FIG.4 Vicat needle % penetration vs time for various

ash/cement ratios (Nust 2 ash) .
 52

CPZ 325 Nust 1 Nust 2

Ash/cement w/w — 1/4 1/3 1/2 1/4 1/3 1/2

Water/cement w/w 0.33 0.47 0.50 0.62 0.41 0.45 0.50

Size (mm) 100x100x100 100x100x100 0 e h =60
Mechanical strength
at 28 days (KN/m2 E03) 31 14 13.5 13.5 16 13 14
Exothermic peak (°C) 63 N.D N.D N.D, 58 55 35

Setting time (h) 6 N.D. N.D. N.D. 7 7 9

TABLE 6. Some characteristics of Nust 1 and Nust 2 cemented

ashes in comparison of plain pozzolanic cement.

4. INVESTIGATION ABOUT THE SWELLING PHENOMENON

The cementation of the Nust 1 and Nust 2 ash types has
shown that the swelling concerns both ashes in a similar
extent. The volume increase due to the swelling amounts to
about 6% and occurs in the first hours after the mortar
preparation. In order to understand the origin of the swelling
phenomenon a chromatographic analysis has been carried out on
the gases collected during the cemented ashes setting. The
analysis has shown the presence in them of remarkable H2
amounts at a concentration of about 10"5 moles H2/gr.ash.
Moreover the microscopic analysis of the ash has shown the
presence of small metallic pieces in both ash types (see fig.
5 and 6).
In order to understand the origin of the H2 evolution from
the mortar, some experiments have been carried out by
cementation of metallic powders composed of Aluminum, Iron and
Zinc. An important H2 gas evolution was detected during the
cementation only in the case of Aluminum metal powder: at an
Aluminum concentration of 50 ppm nearly the same swelling
effect as in the case of the Nust 1 and Nust 2 cementation was
observed.
Some experiments have been therefore carried out in order
to prevent the mortar from swelling by a suitable
pretreatment. In this way it was possible to establish that
the swelling effects could be avoided if the ashes are
contacted for more than 24 hours, before the cementation, with
a 0.01 M NaOH solution at the same ratio as the water-cement.
This solution will therefore replace the water needed by the
cementation process. The samples obtained by cementation of
Nust 2 ash after the above-mentioned pretreatment have shown
that, apart the setting time, which is slightly longer, the
other product characteristics remain nearly the same.
Looking at the characterization results, very few
differences have been noticed between the different ash/cement
mixtures. All the compositions either pretreated or not
pretreated, are therefore acceptable from the point of view of
the Italian rules as concern the compressive strength 711/.
 53

5. LONG TERM LEAC H TEST.

The long term leach test procedure applied for the
leachability determination is the ISO 6961/82 Standard Method,
performed at 40°C in distilled water / 1 2 / with real
radioactive cemented ashes.
The shape of the cemented ash samples was cylindrical, 5
cm both in diameter and height.
The leaching rate measurements concerned the C sl37 and C o60
nuclides, the only ones detectable.
The leach test has been performed on the following
ash-cement mixtures:
Nustl ash: ash/cement = 1/2 w/w
ash/cement = 1/2 w/w after ash pretreatment by
NaOH 0.01 Ν
Nust2 ash: ash/cement = 1/4 w/w
ash/cement = 1/3 w/w
ash/cement = 1/2 w/w
ash/cement = 1/2 w/w after ash pretreatment by
NaOH 0.01 N.
Some leach rate results are reported in Fig.7 in terms of
leach rates and in Fig.8 in terms of cumulative leached
fractions.
The obtained results are similar to those reported in the
literature for C s and C o from cemented radwastes /13/, /14/,
/15/, /16/. The C s leached fraction increases remarkably when
the ash-cement ratio exceed 1/3 w/w (see fig. 8) .

FIG.5 Metal pieces in Nust 1 ash FIG.6 Metal pieces in Nust2 ash
(microscopic analysis) (microscopic analysis)
 54

" - ' 1 — l _ L _ l _ l _ l _ I_ l_ I I =d
Q = 2 0 = 4 0 = 6 = 8 0 — 100Z12CZ1ÍOZ160ÍI80Z200

0,01 -fm

m Nusï2 1/2 Ca

0 Nust2 1/2 Ca pretr

Rn (qr/cra -d)
■ Nua 12 1/2 Ca

α Nust2 1/2 Co pretr

0,000001

FIG.7 C sl37 a n d C o60 leaching rates Rn for

N u s t 2 / C e m e n t = l / 2 w/w w i t h and w i t h o u t p r e t r e a t m e n t .

20

t
18
I ·"
16
0
1 3 • Cs. Nust2 1/2
14 ■
• ■
■ 0 Cs. Nust2 1/3
12 0 ■
• 1
• .■,° )
■ Cs. Nust2 1/4
lAn/Aot 10
• D Co. Nust2 1/2
8 0
A Co. Nust2 1/3

6
tf
"""■ Δ co. Nust2 1/4
Λ
4

■
2

0 MBH. SÜ.H ! g It ÍJ S η

0 20 40 60 80 100 120 140 160 180 200

days

FIG.8 C sl37 and C06O % leached fraction from Nust2 ash

in cement at various ash­cement ratios.

6. C ONC LUSIONS.
On the basis of the work performed , it is possible to make
the following conclusions:
­ the amount of the ashes could be strongly reduced by
increasing the waste residence time in the incinerator and/or
by incinerating the wastes at higher temperatures;
 - the immobilization in cement of the Nust 1 and Nust 2
ashes gives products with acceptable compressive strength
characteristics for all the examined ash/cement ratios,
according to the Italian rules;
- the investigations about the swelling phenomenon seem to
show that this phenomenon arise because of the H 2 produced by
easely oxidable metal like Al in alkaline media;
- the swelling can be avoided pretreating the ashes by NaOH
0.01 Ν solution. The pretreatment in the case of the Nust 2
ash gives more homogeneous cemented products having greater
resistance to leaching, the best ash to cement ratio being 1/3
weight by weight;
- in the case of the Nustl ash although the pretreatment is
effective to avoid the swelling phenomena, nevertheless it
does not influence at all the leaching resistance of the
cemented product.

7. REFERENCES.
Ill C EN-SGK, MOL. Private communication.
/ 2 / S. C ao, C . Hernborg, P. Mantovani. "Experience in
burning ion-exchange resins solidified in polymers".
Energia Nucleare. (3), 2, Sett. 1986.
/3/ ASTM Β 527-81 "Standard test method for tap density
measurement"
/ 4 / ASTM C 136-82 "Standard method for sieve analysis of
fine and coarse aggregate".
/5/ I.R.S.A. "Metodi analitici per i fanghi", C.N.R. 1985
Quaderno η. 64 Vol. 3.

/6/ Β. WELZ. "Spettroscopia di assorbimento atomico".

Pag.261-62. ETAS LIBRI. 1976. MILANO
11/ Handbook of Chemistry and physics.
The C hemical Rubber C o. Cleveland, Ohio
/8/ E. Mariani "C himica applicata ed industriale". Vol. II.
UTET. 1974.
/9/ ASTM C 39-79 "Standard test method for compressive
strength of cylindrical concrete specimens"
/IO/ UNI 6132-72 "Prove distruttive sui calcestruzzi. Prova
di compressione".
/Il/ ENEA-DISP. "Guida Tecnica N. 2 6 " . Sicurezza e
Protezione. 14, 1987.
/12/ ISO 6961-1982 (E) . "Long-term leach testing of
solidified radioactive waste forms"
/13/CEC. "C haracterization of low and medium level
radioactive waste forms". EUR 8663 EN. 1983
/14/CEC. "Etudes des mécanismes de piegeage du C esium par
des melanges additif-cement pour le conditionnement des
déchets nitres". EUR 8663 EN. 1983
/15/CEC. "Evaluation of conditioned waste and qualification
of engineered barriers". EUR 12141 EN. 1989
/16/ IAEA "C onditioning of low and intermediate level
radioactive wastes". Techn. Report Series N. 222. Wien,
1983
 56

EXPERIENCE WITH ASHES FROM THE EVENCE COPPEE - OVEN OF MOL;

PROBLEMS WITH CONDITIONING
Robert GENS - Paul GIELEN (ONDRAF/NIRAS)
L. TEUNCKENS (BELGOPROCESS)
ONDRAF/NIRAS, Place Madou 1 btes 24/-^ " 1030 Bruxelles
BELGOPROCESS, Gravenstraat - 2480 Dessel

Summary
The Evence Coppée incinerator is in service since the early 60's.
The incineration facility is located on site 2 of Belgoprocess in
Mol (Belgium), its nominal capacity being 100 kg/hour. The
combustible waste is originating mainly from nuclear power plants,
research centers, and at a lesser extent from industrial and
medical radioisotopes applications.
About one thousand 200 1 ash drums have been produced till now.
Several investigations have already been carried out in order to
characterize these ashes. The results dispersion is indicative of
their inhomogenity, especially with regard to their unburnt
material content.
The poor quality of the ash entails a great reactivity potential.
Attempts to immobilize these ashes without pretreatment in a
concrete matrix have failed, due partly to, gas releases during
setting. Another consequence of this reactivity, is the heavy
corrosion of some drums (C-steel). A study programme on this
problem has recently started. To this purpose, the behaviour of
four selected metals in contact with ashes in specific conditions
is investigated on a laboratory scale
The hydrogen production is also investigated. First results are
expected soon.
For the conditioning, the feasibility of ash compaction and
encapsulation of the pellets in a cement mortar which has been
qualified for the immobilization of supercompacted pellets, is now
being examined. Experiments on full scale drums are in progress.
Selected ash drums have been compacted during a mobile
supercompaction campaign to carry out the encapsulation tests.
Preliminary results already available are reported.
According to the first observations, a pretreatment before any
conditioning can not be ruled out (basic neutralization or thermal
treatment, since the heat value of the ash burnable fraction
compares roughly with that of graphite carbon).
Recently, the CILVA project has been launched in order to meet our
futur requirements in the frame of the treatment and conditioning
of low level solid waste.
Two techniques shall be provided for : supercompaction and
incineration. Our goal is to elaborate a conditioning process
which applies as well to the E.C. ashes as to the ones expected
from the CILVA incinerator.

1. Introduction

This paper deals with the investigations which have been carried
out about the Evence Coppee ashes characterization and conditioning.
 57

The incinerated wastes are mainly composed of clothes, papers, rags,

plastics, rubbers, carcasses, ion exchange resins, filters, aqueous or
organic liquids, oils ...
The poor quality of the collected ashes brings up two problems :
drum corrosion some drums are heavily corroded due to the
wetting of the ashes during their removal out of the oven. This
practice has now been abandoned.
qualification of a simple, suitable conditioning process which
shall apply as well to the E.C. ashes as to the ones expected with
the future CILVA incinerator.

2. Ash characterization
Four characterization campaigns have been scheduled between
September 85 and December 88. The sampling operations and analyses
were performed by CEN/SCK in Mol (1-4).
For the various characterization studies, the following statistics
have been computed or listed :
- μ : arithmetic mean value
- <ƒ : standard deviation
- C-I 95 X : confidence interval at 95 % level. The limits have been
estimated by the short-cut method u +/- 1.96 χ » , which
holds for a normal distribution
­ Min, Max : minimal and maximal measured values.
The coherence between these figures and the C.I. ­ 95 % limits
roughly indicates the normality degree of the results distribution.
The results are given in tables 1 and 2.

II σ C.I . 95 % Min Max

W. X > 20 mm 26.74 22.31 0­ 70.47 0.31 92.00

10 ­ 20 " 12.16 6.55 0­ 25.0 0.60 34.60
2.5 ­ 10 " 2/.83 13.69 1.0 ­ 54.66 2.88 69.34
1 ­ 2.5 " 14.54 8.87 0­ 31.93 0.87 41.87
< 1 18.77 13.15 0 ­ 44.54 1.78 53.38
0.31 ­ 1.41
bulk density 0.86 0.28 0.31 1.30
W X humidity 9.73 10.60 0 ­ 30.51 0.27 33.08
W X burn, fraction 33.86 18.14 0 ­ 69.41 0.54 74.36
U.H.V. (kJ/kg) 9193 3596 2145 ­ 16241 3715 17800
W X soluble 3.56 2.95 0 ­ 9.34 0.50 13.30
pH leachate 9.99 0.98 8.07 ­ 11.91 7.80 11.60

Table 1 : Physico­Chemical Properties

(Excluding the humidity and the particule size analysis, all
weight percentages are given on dry basis)

C13H H20 Fe304 SiO_, Al203 C aO

X 29.46 9.73 10.58 26.45 15.87 7.9

(IN WEICHT)

Table 2 : Ash Mean C omposition

 58

These data call for the following comments :

the results dispersion clearl/ shows the inhomogeneity of the

recovered ashes. The burnable fraction content is indicative of
the incineration inefficiency ;
from a thermodynamic point of view, taking into account the ash
heat value, a thermal posttreatment is seemingly possible ;
a statistic examination of the element analysis results seems to
indicate a correlation between the chloride and calcium contents.
The incineration of wastes with higher calcium content apparently
enhances the chloride retention in the ashes.
The unburnt material content mean value falls down to 17 %
(instead of 33 %) when the feedrate is limited to 75 kg/h.
Nevertheless, the results dispersion remains important.

3. Drum corrosion

3.1. Theoritical_conş.ideraţionş.
The ash moisture provides a suitable medium for sustaining
corrosion processes. Among the different possible mechanisms, we point
out :
aerobic corrosion possibly enhanced by dissolved chloride ions
(pitting corrosion) ;
hydrolysis of chlorinated compounds with HCl release.
Most important and best known among the surface compounds of
carbon are those with oxygen and sulfur, although other elements
such as chlorine can also combine with elementary carbon. This may
occur with the incineration of PVC, PVDC, neoprene ... (5,6)
some carbon surfaces are characterized by a pH (PZC ) slightly acid
(7). This could lead to ash-drum contact points with significant
corrosion rate. However, it is expected that this phenomenon has
little if any effect upon the drum degradation.

3.2. Experimentation
We have decided, for a first step, to investigate on a laboratory
scale the behaviour of 4 possible drum metals, in contact with ashes
in specific conditions (see table 3.)
The tested metals are : C-steel, stainless-steel (type AISI-430), 13
fiia chromised-steel and galvanized-steel.

Experiment C hloride content Water content

(% in weight) (% in weight)

A 0.5 5
Β 0.5 20
C 2 5
D 2 20
Table 3 : Corrosion Experiment C onditions

The experiments are carried out in air-tight vessels, at room

temperature and initiated under normal atmospheric pressure. We are
looking for any pressure build up (gas sampling and analysis are
foreseen).
 59

The corrosion rate shall be assessed by weight sample losses

determination. The experiments have to be considered as orientating
ones, from which further investigatiDn will be decided.

4. C onditioning

4.1. ûsh cementation

Preliminary experiments have been carried out with regard to
homogeneous encapsulation. This method has been swiftly discarded
because of :
important bleeding in most cases (water in excess to avoid
workability problem) ;
hydrogen release during the matrix setting.
Hence, we have decided to investigate the feasibility of ash
compaction and immobilization of the pellets in a cement mortar.

4.2. lmrapb.i;l.iz.a.ì.Ì2n_iri b_i£umeQ

Attempts of ash pellets immobilization in bitumen have failed. The
drums have swollen.

4.3. Ç_om.pac£.io.n_te_s.Es
Beginning 1990, a supercompaction campaign took place in Mol on
site 2 of Belgoprocess, by means of a mobile unit.
During Lhis campaign, scvetdl trials were carried out, of which the
compaction of eighteen 200 1 ash drums. Water was added in few cases
to simulate the most stringent conditions.
The pellets did not show any visible tearing. The inhomogenity is
once again appearing in the density values dispersion. One should note
that the ashes with the highest carbon content (+/­ 70 %) have a
density which is close to the one of compacted active charcoal (­ 1 ­
1,1 Kg/dm ). The achieved height reduction factor allows up to 4
compacted pellets per 400 1 drum i.e. about 350 kg ashes.

4.4. £ell£t_im.m2bÍ.liza.tÍPD. Iríais

4.4.1. Immpb.ili£a.£,io.n_gr.out
The cement grout used for these trials has already been qualified
for the immobilization of supercompacted pellets.

4.4.2. Ash Eel.le.ts immpb_il.iz.aţion

Six 400 1 drums have been produced, each one containing three
pellets. Four drums have been sealed up with a special lid in order to
detect any pressure build up and to allow gas sampling. Twelve days
after immobilization, the highest pressure values were recorded and a
gas sample was taken out of drum A.(the drum tightness has been
checked for a over­pressure of 0.3 bar)
 60

400 1 drum reference A Β C D

(1) (2) (1) (3)

pellets number 1-2-3 10-11-12 13-14-15 16-17-18
over-pressure (bar) 0.24 0.13 0.08 0.075
Table 4 : Ash Pellets Immobilization Trials
(1) + 15% water
(2) + 7.5% water
(3) dry ashes

The gas sample analysis gave the following results

Element H2 N2 02 C 02 C H^ Ar

% (in volume) 35.4 62.7 0.9 0.02 0.35 0.7

Table 5 : Gas Analysis

The hydrogen release is attributed to the oxydation of metal

fines. According to literature, aluminium is generally reported as the
possible cause. One should remind that the non-conditioned waste
specification precludes aluminium metal in the combustible rsaterials.
One should also point out that the most significant gas production
relates to the case with 15% water addition. Moreover, neither during
the pellets immobilization nor later, any evidence of gas release was
noticed (no bubble, no cracking of the mortar surface). Until
otherwise proved, the hydrogen production does not seem to be
harmful1. To this purpose, mortar samples from drum A shall be
examined.
Furthermore, laboratory experiments are now carried out to
evaluate the hydrogen released volume vs. ash weight.

5. Conclusion and perspective

We have definitely discarded the homogeneous encapsulation, one of
the utmost disadvantage being the restricted ash quantities allowed in
the matrix composition (15 - 20% in weight).
We have therefore decided to investigate the feasibility of ash
compaction and immobilization of the pellets with a cement grout.
Preliminary results appear promising despite a small hydrogen
production.
Investigations shall be undertaken to account for the hydrogen
release consequences on the package integrity. Should a hydrogen
production be avoided and should simple drying be insufficient,
experiments based on ash neutralization might be performed as usually
applied in such cases.
Presently, no ash thermal treatment is envisaged, since the high
carbon content does not seem to be a problem for the concerned
process. On the other hand, a thermal treatment does not necessary
yield an ash free of non-oxydized metal fine.
 61

6. Bibliography
[1] L. Froment
"Characterization of Evence-Coppee incinerator ashes-Summary" 0/N
89650 (1989)
(2] L. Froment en P. Geuzens
"Thermische nabehandeling van de verbrandingassen van Evence-Coppee
incinerator", Eindverslag, SCK/CEN, 88/44/PG/MV/342 (1988)
[3] R. ADRIAENSENS
"Meten van de pH van Evence-Coppee as in funktie van de tijd" ;
Belgoprocess 07397 (1990).
[4] "Karakterisatie van Evence-Coppee as" , SCK/CEN, 85769/RAd/DT
(1985)
[5] R.W. COUGHLIN. F.S. EZRA and R. N. TAN. J. Colloid Interface Sci.,
28(3/.4), 386 (1968)
[6] P. EHRBURCER, O.P. MAHAJAN and L. WALTER, JR. J. Colloid.
Interface Sci, 57(2), 2 (1976)
[/] G. MuLLER, C.J. RADKE and J.M. PRAUSNITZ
J. Colloid Interface Sci, 103 (2), 466 (1985)
[8] J.P. ELINCK
Université Libre de Bruxelles, Faculte des Sciences Appliquées -
Laboratoire d'Essais des Matériaux
"Essais divers sur mortiers d'enrobage"
Proces-verbaux 30556, 30557, 30558, 30662 (1989)
 62

PYROLYTIC ASH EMBEDDING USING HYDRAULIC BINDER: CHEMICAL BEHAVIOUR AND

EMBEDDING ASH FORM PROPERTIES

Eliane REVERTEGAT - Gervaise MOINE

Commissariat à l'Energie Atomique, DRDD/SESD - CEN - SACLAY,
GIF sur YVETTE, 91191 (FRANCE)

1 - INTRODUCTION

It is clear that, to avoid any incompatibility between a waste and its

immobilization matrix, and to select the ideal cement, it is necessary to
identify the physicochemical properties of the waste.
To provide aid in controlling the cementation process, 13 types of ash
were characterized, produced by the pyrolysis of the tributylphos-
phate/dodecane mixture in the presence of milk of lime. The influence of
their physicochemical composition on the sensitivity of an immobilization
formula was then analyzed.

2 - ASH CHARACTERIZATION

2.1 - Chemical characterization

Characterization and cementation tests were performed on ash for which

different pyrolysis parameters were modified (Table 1 ) :
• 5 batches were obtained by varying the Ca/P mole ratio from 0.8 to 1.2,
by introducing variable amounts of milk of lime,
• 8 batches were obtained by keeping a Ca/P ratio of 1, and of these
8 batches:
. 2 were prepared by varying the TBP/dodecane ratio,
. 4 by varying the addition of oil from <j% to 20%,
. 1 batch was prepared at low temperature (LT),
. 1 batch was prepared at high temperature (HT).

mol
Batch TBP Dodecane Oil Ca/P( ) Bed Temp.
Nr. % v %V % v mol 'c
theoretical

1 60 40 _ 0.8 400
2 60 40 - 0.9 400
3 60 40 - 1.0 400
4 60 40 - 1.1 400
5 60 40 - 1.2 400

6 90 10 _ 1.0 400
7 30 70 - 1.0 400

8 57 38 5 1.0 400
9 54 36 10 1.0 400
10 51 34 15 1.0 400
11 48 32 20 1.0 400
12 60 40 _ 1.0 360
13 60 40 - 1.0 500

Table 1 - Theoretical values of Ca/P ratio.

 63

These Ca/P values correspond to the Ca/P ratio of the products

entering into the pyrolyser. We shall refer to them as theoretical values.
To check the values of the theoretical Ca/P ratios, ranging from 0.8
to 1.2, four different laboratories performed chemical analyses of calcium
and phosphorus, using different methods:
• for Ca:
. complexometry, atomic absorption, plasma emission spectrometry,
• for P:
. gravimetry, plasma emission spectrometry, colorimetry.
Some determinations were duplicated. Only one analysis was made for
the other types of ash.
The results obtained show very wide differences from one laboratory to
another and, for most of them, higher than the stated theoretical value
(Table 2 ) .

Theoretical Ca/P Analyzed Ca/P

min. max.
0.8 0.82 1.31
0.9 0.61 1.21
1.0 0.99 1.55
1.1 1.07 1.50 (+ 362)
1.2 l.ll 1.55

Table 2 : Experimental stoechiometric Ca/P ratio.

Under these conditions, the ranges of values that could be considered

the most probable, were estimated. To estimate these ranges of values, each
type of ash was heated at 1000°C, and after this thermal treatment. X-ray
diffraction spectrum was performed. At the average pyrolysis temperature
(400 C ) , the chemical reactions between CaO and P2O5 are incomplete, giving
rise to many and complex crystallographic phases. Eight different phases
were found for each type of ash. After treatment at 1000°C, only one or two
phases still exist, corresponding on the P20c-Ca0 binary diagram, to a
precise concentration range.
For example, considering the ash with a theoretical Ca/P ratio of 0.8,
we found that the experimental Ca/P ratios ranged from 0.82 to I.31.
corresponding to analyzed calcium oxide weight % values ranging between
39·3 and 5O.8. After passage at 1000 C, however, only one phase appears by
X-ray diffraction, calcium pyrophosphate, which only exists on the diagram
for a CaO value ranging between 4l.3 and 44.1% (Figure 1 ) . The only ana-
lyses corresponding to this range are 43.1 and 43.42. All the values lying
outside this range were discarded (Table 3) ·

CaO 39-3 40.1 43.I 43.4 44.8 50.O 50.8

p2o5 6O.7 59-9 56.9 56.6 55-2 50.O 49.2
Ca/P O.82 O.85 O.96 0.97 I.03 1.27 I.31

Table 3: Weight % obtained by analysis (CaO + P2O5 = 100) for the type of
ash with theoretical Ca/P ratio of 0.8.

Consequently, for this type of ash, the most probable value of the Ca/P
ratio is about O.96 to 0.97.
 64

1400
I I 1 1 I The same argument was
applied to each type of ash,
enabling us to establish a
/ 1 classification by increasing
1300 ­
order of the estimated
Liquid
values of C a/P. To help us
/«­2CaOPiOs· j
/ liquid ι
in this classification when
1200
two cristallographie phases
/ a^CaOPjOs J were present, the ratio of
/ « a n d n­2CaOP;Ü5.SS —r$
the intensities of their
main X­ray lines was consi­
1100 dered. It was assumed, as a
/ n­2CaOP;05.SS­Liquid|
ï­CaOPjOs j first approximation, that
*Tromelite / the ratio of the line inten­
*­CaO P Î 0 5 , SS \ / sities is proportional to
Tnimelite ƒ
1000
I­CaOPîOiSS­^ss
♦ Liquid 1 the ratio of the mass
♦ Liquid j¿— ■ ^\ß­2CaOP;Os,SS / 3 concentrations.
' « a n d n N/Nromeliti» v .Tromelite / o
s
From the values of the
CaO P¡Os,SS S^ T ^i
O
/ Ca/P ratio obtained by ana­
900 flCaOPjO^
• Tromelite
! ­ lysis and through line
/n­CaOP^.SS
¿r.n­Cao p¡o s ss. o intensities, the different
' «Liquid ¿j* dr*
eC rKaO^Q,SS
o n­iCaOPA.ss
σ
o batches investigated can be
1 " 1 7i , classed into two families
25 30 35 40 Ί ¡45 (figure 2 ) :
■P205 ! CaO­ . a family for which the Ca/P
! ! ratio is less than or close
41,3% 44,1% to 1, hence low in calcium,
Figure 1: P20c_CaO binary diagram.
. a family lying bet­
ween the Ca/P ratios of
1.2 and 1.31 hence with
a higher molecular
concentration of cal­
cium than of phospho­
rus.

Oil 015 022 095 126 1.62 163 197 3 67

Ca^O, Cä 2 P 2 07 Ca2 P2 O7 3 CaO P 2 0 5 3CaOP205

dominant dominant dominant strong dominant

CaP2 0 6 3CaO P 2 0 5 Ca2P207 Ca2P207

limit limit limit

value ^ ­ =0B 9 value ^ ­ = 10 value
Ca/P = 13
Cristallographie phases after heating at 1000°C

Figure 2: Classification of the types of ash by increasing order of

experimental Ca/P ratios.
 65
The ash batch containing 20* oil lies between these two families. All the
properties of the corresponding immobilized waste packages confirm this
subdivision, essentially into two families.

2.2 ­ Crystallographic characterization

For the crystallographic analysis, a characteristic peak was selected

corresponding to each of the phases present in the pyrolysed ash. The abso­
lute value of the peak intensities (plotted on the ordinate) was used to
determine the overall phase changes occurring in the 13 samples, classed by
increasing order of C a/P ratio, as determined by chemical analysis
(Figure 3)·
­­ C a / P _ . ♦
Eight different 0 66 1 30
crystallographic phases
were found, their chan­
ges closely related to γ ΜΕΤΑ­PHOSPHATE
the Ca/P ratios.
These changes clearly
confirmed the presence . C aO.P2Os C a/P=05
of two families:
. a family with C a/P Ρ ΜΕΤΑ­PHOSPHATE
less than or close to
1, in which the low
calcium phases predomi­
nate, particularly the
metaphosphate, and for TROMEUTE Ca/P=0.7
which the lime content
is very low, ¿►Ca0.3P205
. a family with C a/P
over 1.1, of which the
two main properties are
the absence of meta­ a PYROPHOSPHATE Ca/P=1
phosphate and the pre­ 2CaO.P205
♦
sence of a high lime
P=cst (excepted HT/1
content,
. ash with 20X oil,
lying at the transition HYDROXYLAPATITE
between these two fami­ Ca/P=1.7
lies. 1/2[Ca(OH)2.3Ca3(POv)2|
Two types of ash
are distinguished:
. HT ash without lime
(lime decomposes at CalOHIj
500*C),
. LT ash with a maximum CaCOj
of lime (lime does not
begin to decompose at
360'C).

Figure 3: Crystallographic characterization of the

different types of ash.

A break for the theoretical C a/P = 1 ash, which had a high carbonate
content, was also obtained. C arbonation probably occurs in the milk of
lime, before pyrolysis. In these conditions, the calcium partially blocked
in the carbonate does not react during pyrolysis, because it does not
decompose below 750°C. Given the low solubility of the phosphates, the most
important parameter is undeniably the lime content of the ash. It is well
 66

known that lime plays an important role in the reactivity of slags present
in cement.

2.3 " Laser grain size di stri buti on

The grain size distribution for t ach type of ash is between 0 and
200 pm. The median size of the ash is comparable to filler particule size.
. ash - 8 pm
. silica fumes 0.2 pm
. filler 2 pm (0 to 100 pm)
. cement 30 pm.
Unlike the silica fumes, however they do not fill the porosity of the
capillaries (1 to 0,1 pm) . All the types of ash are identical except the
ash with the theoretical C a/P ratio of 1 (10% oil) which is coarser grained
(median size: 13.2 pm).

2 Λ - Conclusi on on ash characteri zati on

Only an overall change was observable as a function of the Ca/P ratio,

with the presence of two main families:
Ca/P < 1 with low lime content,
Ca/P > 1,2 with lime content varying with carbonation.
The ash batch containing 20% oil lies between these two families. No
discrimination of the type of ash as a function of oil content or of
TBP/dodecane ratios was possible. Only the estimated C a/P mole ratios of
the ash varying from 0.86 to I.30 and the free lime content were considered
to explain the physico-mechanical properties of the waste packages. The
free lime content, which is an important parameter with regard to the
blended cement reactivity, depends on the pyrolysis temperature and the
content of milk of lime introduced into the pyrolyser.

3 - ASH CEMENTATION

3.I - Cementation formula

A nominal formula was selected following pre-characterization tests

(Table 4 ) .

% by liter (average)
ash 30 586 g
water 24.7 483 g
water-reducing admixture 1.1 21.5 g
cement (C LK) 44.2 862 g
56)
(E/W = 0.56

Table 4: Nominal formula.

The slag cement was chosen for its inherent properties:

. low heat of hydration,
. development of very fine porosity, important for leaching,
. good durability.
30# by weight of each type of ash was introduced with respect to the waste
product, and the fluidifier was added in the batching water for industrial
operation issues. Twenty liters of waste product was prepared with each
type of ash.
 67

3.2 - Rheology (Figure 4)

For each waste

form, we only consi-
dered the shear forces
developed at the speed
TORSION TORQUE
of a viscometer closest
to that of the mixer
mN.m at 277 r/mn
(310 r/min) , and the
corresponding torsion
torque is plotted on
the Y axis. The waste
forms are classed on
the X axis as a func-
tion of the increase in
the Ca/P ratio analysed
in the ash.
The same two fami- DYNAMIC VISCOSITY
lies are always found:
. for ash with a low Pa.s at 50 r/mn
Ca/P ratio, the forces
necessary for shear are 5% 15% 20% LT
weak, with a minimum
for HT ash without free
lime: these waste pro-
ducts are nearly as
fluid as water,
. for ash with a high
Ca/P ratio, the pastes RETENTION IN THE
are''stiff with a maxi-
mum for LP ash con- MIXER %(on the T.W.)
taining the most free
lime: these pastes can
block the blades of the
mixer,
. ash samples giving
the best fluidity are Figure 4
those with 20% oil, ly- Rheology of the cement pastes embedding
ing midway between the the different types of ashes.
two families.
The curve of dynamic viscosities of the pastes, subjected to the
lowest mixer speed (50r/min) at the time of their flow, exhibits the same
profile. The same applies to the retention of waste products in the mixer
after drainage. However, very thick waste products can be removed in
"packets" and producing less holdup.
In these conditions, it is essentially the early activation of the
slag by the free lime present in the ash that seems to be the most
effective parameter. Since the ash has the same grain size distribution,
the Theological properties of the pastes could be identical, except for the
type of ash with 10% oil, which has a coarser grain size distribution.

3.3 - Bleeding

Bleeding after 3 hours is below 1% for all the pastes. It is a maximum

after 21» hours and ranges between 0.6 and "i.1%.
- For ash with low Ca/P ratio, bleeding is above 2% and is not totally
reabsorbed.
- For ash with high Ca/P ratio, it is less than 1.5% and is reabsorbed
 6S

after two days. These waste forms display the best behaviour
with regard to bleeding.

3.4 ­ Setting time

Setting time is very long (Table 5) and cannot be correlated with the
Ca/P ratio. It very probably depends on two superimposed mechanisms more or
less predominant.
. the rapid reactivity of the slag with the lime, giving rise to aluminate
and silicate gel. This gel forms a screen around the cement grains and
delays ionic diffusion, which is necessary for the formation of hydrates,
. the well­known screen effect of phosphate ions.
This setting time is not penalizing if the waste package is correctly pro­
tected against desiccation.

Initial Final

air storage 22 h 30 h
(HT: 46 h
LT: 42 h)

water storage 40 h 54 h

Table 5: Setting time of the different waste products.

3.5 " Shrinkage and weight loss

The shrinkage measurements on 4x4x16 cm specimens result from the

superimposition of two processes:
. the first due to the evaporation of part of the water: plastic shrinkage,
. the second due to the contraction of the material caused by the hydration
reactions: hydraulic shrinkage.
It may be observed that the entire high C a/P ratio family exhibits the
highest shrinkage, but with the lowest moisture loss (Figures 5 and 6 ) .
This accordingly indicates preponderant hydraulic shrinkage associated
with the high and early reactivity of the slag.

SHRINKAGE (μ m / m ) 28 — 365 D (Average)

30/70
4^80/10
- 3000· ~*\BT 1

Ν,Ι.2
- 1600 ■ ^ ^ 1 . 1
EÜ5I
^•^^103 0,9 HT
- 1600·
B 0.Θ
Z__i_?£i^30/70
55:
- 1400 ■
\ 1.2

- 1200 ■ \^53 1.1

~*^\0.8 10s HT 0,9
is·:
- 1000 ■
■*■ 28 days ■+■ 365 days Ν5Γ!

- 600-

Figure 5
 69

DELTA Ρ (Kg/ m 3) 28 — 365 D (Αν erage)

ο.β
I
250· \ " HT
0.9 s · ιοί:
—-- SOT!

200- 51 —- / X ™ BT
gcg\ ^^1.1
90 10
^ ^ \ 1.2
30 70~j*J\
150-
BT
\„ \^1
1.2~"­~\
90 10.
100- \
-*■ 28 dayi ­*­ 365 dayi

SO­

Figure 6

The shrinkage values measured are high because, added to the con­
traction of the material are the severe storage conditions, including 502
relative humidity. These conditions are in fact quite different from the
actual confined storage environment.

3-6 ­ Compressive strength

As for shrinkage, the compressive strength of specimens stored on

water is always higher for the family containing ash with a high Ca/P
ratio, around\h0% higher, and the type of ash with 20% oil always displays
median properties (Figure 7)·
However, it appears that the development of the properties of the
hardened material is less related to the free lime content than the Theolo­
gical properties of the fresh material. In fact, it is possible that the
appearance of carbo­aluminates or phospho­aluminates modifies the structure
and the texture of the waste product in time, but it was not possible to
identify these components by X­ray diffraction.
MP» STRENGTH C - 2 8 - 9 0 - 1 8 0 - 3 6 5 D (Average)

°- a 5·: 0.9

» 1Θ0 e 365 day»

CUSS

Figure 7
 70

3­7 " Porosity

The cement reactivity can be observed in studying the variation in its

porosity.
The pore volume, which was originally occupied by water, decreases
with the formation of hydrates. At 90 days, for example, the residual
capillary porosity, estimated between 0.9 and 0.03 V™. is practically nil
for samples with a high C a/P ratio. Conversely, the porosity of the C ­S­H,
ranging between 0.03 μω and 30 A, is the highest, but the break in the
slope shows that, in its turn, it decreases as a function of the reactivity
of the slag or the formation of new crystallographic compounds (Figures 8
and 9 ) .
The properties of the hardened waste products are closely connected
with this porosity closure.
MP« STRENGTH EVOLUTION VERSUS C APILLARY PORO.

65- 80/10

1 PO Dsvsl
60-
!* 30/70

55- *« 1.2 1.1

50· 1 "··­.. BT

45-

40-

SO- ---... 1 0 " HT 15ΓΪ

"""■-..* o.a
SO-

5
25-
0.9 ."" "
20-

0.9 TO 0.03 μιη

Figure 8
STRENGTH EVOLUTION VERSUS C­S­H PORO.

65- » 80/10

60-
"·« 30/70
55· \ '·1.12
/

50· ..«' BT

45-

40-
À |ŞŞ|
35-
,<5Ô b a y s ! ■^.
m
»'Ίο*
30.
"/isx
»'Ό.8
25-
57. . '» ° · 8
20-
15 20
0.03 TO 0.003 (im

Figure 9
 71

CONCLUSION

Cementation tests were performed on an optimized formula with a slag

cement (CLK) and 30X ash.
Most of the structural and physico-mechanical parameters studied with
these embedded packages - Theological behaviour, shrinkage, weight loss,
mechanical strength, porosity - reveal uniform behaviour, but this is
perfectly distinguished according to the two main families investigated.
But more than the Ca/P ratio, in fact, it is very probably the free lime
content of the ash that induces the activity of the cement and the
properties of the waste products, more or less accelerating the hydration
of slag in CLK cement.
This lime content depends on a number of parameters, including the
milk of lime feed, temperature and probably reaction time and carbonation.
The ash family with a Ca/P ratio ¿ 1.2 displays the best mechanical
strength, the lowest weight loss and the finest porosity, an important
parameter for leaching. On the other hand, it develops high shrinkage and
displays "stiff" behaviour during mixing, requiring vibration during place-
ment.
This is why, in this study, we selected an intermediate type of ash
with an analyzed Ca/P ratio close to 1.1 (ash with 20J! oil) whose proper-
ties all lie between those of the two families.
 72

CHARACTERISATION OF ASHES C OMING FROM SIMULATED RADWASTES

AND EVALUATION OF CONDITIONING METHODS

L. CANADAS and L. SALVADOR

Departamento de Ingenieiía Química y Ambiental

Escuela Técnica Superior de Ingenieros Industriales
Universidad de Sevilla

Summary.
The physical and chemical properries of six incinerator ashes
and their behaviour with respect to two conditioning processes aie
evaluated. The ashes were obtained by incineration of simulated mixed
radwastes, from textile rich to plastic rich wastes.
Ash characterization has included the determination of the
physical and chemical parameters which influence volume reduction or
ash cementation. C ementation has been evaluated by testing the
setting and mechanical stahility of specimens obtained from different
ash/cement/water pastes. High pressure compaction was also studied by
measuring ash volume ι eduction as a function of compacting pressuie.
The main results show important differences in the physical and
chemical properties of ashes, related to the variation of primary
wastes. C emented pieces of high compressive strength have been
obtained from mixtures having up to 50% wt . ash on a dry basis, thus
even achieving small volume reductions during cementation. C ompacted
pellets reach volume reductions in the range of 2.2 to almost Ί,
depending on ash type and compacting pressure.

1. INTRODUCTION.
This paper presents the early results of a research programme funded
by the Empresa Nacional de Resíduos Radiactivos. S.A. (ENRESA) which is
currently being developed in the Department of Chemical and Environmental
Engineering of the University of Seville.
The programme is based on the physical and chemical characterisation
of several incinerator ashes and in the technical evaluation of two
conditioning methods: cementation and high pressure compaction. The ashes
are obtained from 10 previously specified simulated radwastes, classified
in 5 generic groups: 1. Heterogeneous waste without PVC ; 2. Heterogeneous
waste with PVC ; 3. C harcoal; Ί. Scintillation liquids and vials; and S.
Medical and research organic wastes. Wastes are incinerated in a two
chamber pyrolysis incinerator with a design rate of 100 kg/h.
The main programme objetives are to determine the expected ash
variability with the original waste composition. to evaluate the ash
behaviour with respect to the conditioning methods, and to define the
influence of the most important operating variables on the final
conditioned products.
Results in this paper only cover the first phase of the programme,
which include the analysis of ashes f ioni waste groups numbers 1 and 2,
both corresponding to mixed wastes composed of different proportions of
plastics, clothes, wood, paper, and rubber.

2. PRIMARY WASTE C OMPOSITION.

The mean compositior. of original wastes included in this study are
presented in Table 1. Basically, three substantially different waste types
have been incinerated, specified according to ENRESA experience in
 73

radiictive waste production in Spain: Type A. General waste; Type B.

Textile rich waste; and T\ pe C. Plastic rich waste. These three types are
similar in groups 1 and 2, but replace a part of PE with PVC in group 2.

GROtP 1 GROTP 2

TYPE A TYPE Β TYPE C TYPE A TYPE Β TYPE C

Waste corat-ositi °l) (X *ζ·)

Plastic: PE 37 20 75 32 15 70
PVC — -- — 5 5 5
Clothes 33 80 20 33 80 20
Wood 16 — -- 16 — --
Paper 9 — — 9 — —
Rubbeι 5 — j 5 — 5

Ash production (% w-ζ..) 1.80 0.37 1.48 1.82 0.44 1.57

TABLE 1. SPECIFICATION OF PRIMARY WASTES AND

ASH PRODUCTION AF TER INCINERATION

Table 1 also shows the ash percentages obtained after incineration.

Although all the wastes have presented a high degree of combustibility,
textile rich wastes (type B) have an ash production substantially lower
than the othei wastes, wheteas the highest ash production is obtained by
type A wastes. In all cases PYC tends to increase ash production.

3. EXPERIMENTAL PROCEDURES.
3.1. Physical and Chemical Analysis.
The physical properties and chemical composition of ash samples have
been determined in compliance with the standard methods originally issued
for coal fly ashes. Only parameters directly related to volume reduction
factors during conditioning or to ash behaviour as a cement admixture have
been measured:
1.- Physical properties: specific gravity, according to ASTM C 188;
bulk density; and fineness, according to UNE 83.450.
2.- Chemical composition: moisture content, according to UNE 83.431;
elemental analysis by atomic absortion spectrophotometry,
according to XNSI/ASTM D 3682-78; loss on ignition, adapted from
UNE 83.433; sulphates content, according to UNE 83.432; carbon
content by I.R. spectrophotometry (LECO carbon test); clorides
content by gravimetry; and pH-value.

3.2. Cementation Tests.

In order to study the conditioning by cementation, 16 ash/cement
pastes have been prepared with each ash sample. These pastes included 4
different ash contents, mixed with 2 cement types and with 2 water
dosages. Ash/cement mixtures with 10, 30, 40, and 50% ash have been used.
Cement types were a fast-setting, high-resistent Portland cement (type I)
and a standard Portland cement with pozzolanic admixtures (type II). Water-
dosages have been directly related to paste rheology, using low water
contents to produce pastes with a minimum workability le\el (L dosages),
and higher water contents to obtain fluid pastes (H dosages).
 74

All the pastes were tested by measuring the setting time, expansion,
and strength development, according to adapted procedures from cement and
fly-ashes-in-concrete standards :
a) Starting and finishing setting times have been determined in
compliance with UNE 83.454, by directiv- measuring fresh pastes,
immersed in water, hardening.
b) The expansive character of pastes has been measured in two ways,
according to UNE 83.453: after a 7 days curing period in water
at 20°C, and after an accelerated curing test in boiling watei.
c) Pastes strength development has been evaluated by measuring the
bending and compressive strength of test pieces after curing
periods of 2 . 7 , and 28 days. UNE 83.451 and UNE 80.101 were
used as reference standards.
In addition to the above mentioned parameters, the ash volume
reduction factors in the cemented pieces were also determined.

3.3. High Pressure Compaction Tests.

The compaction tests were performed in a laboratory device where the
volume reduction factors achieved with pressures in the range of 200 to
450 kg/cm2 have been measured.

ASH SAMPLE

1-A 2-A 1-B 2-B 1-C 2-C

Physical properties
Bulk density (g/cm 3 ) 0.33 0.32 0.73 0.60 0.53 0.42
Specific gravity 2.3 2.4 3.3 3.1 2.9 2.4
Fineness (% w t . ) :
> 90 um 49.8 53.6 49.1 39.0 54.0 60.0
45 - 90 vim 10.0 10.fa 9.3 9.1 7.7 7.7

Chemical composition
(% w t , as received)
Moisture 1.1 1.8 2.4 0.4 1.1 1.5
Loss on Ignition 33.0 32.4 8.2 18.7 36.6 42.1
Si02 15.4 17.7 11.7 11.6 6.1 4.3
A1203 8.3 9.1 2.9 3.0 2.5 2.3
Fe203 2.3 2.6 13.3 4.4 3.2 2.9
CaO 0.8 10.3 12.2 10.5 7.2 6.2
MgO 2.2 2.5 7.3 ." . 5 1.1 1.0
Na20 1.4 1.9 3.7 1.8 0.4 0.5
K20 4.0 2.5 1C.3 11.7 2.0 1.2
Ti02 9.S 9.S 21.3 21.3 2'. .9 26.0
P205 0.8 0.9 3.4 2.8 0.6 0.8
SO3 4.4 2.6 1.1 0.7 2.7 2.2

Chemical properties
Carbon (% w t , d.b.) 30.4 27.2 2.7 2.7 38.4 41.3
C l ~ (% w t , as received) 1.2 3.3 2.1 9.5 2.1 1.9
PH 10.5 9.7 11.3 10.9 10.1 9.2

TABLE 2. PHYSICAL AND CHEMICAL ASH PROPERTIES

 75

U. PHYSIC AL AND C HEMIC AL ASH PROPERTIES.

The results of C he ash haia teiisation are shown in Table 2. As
expected, ash properties depend greatly ­>n waste typt and, within the same
ash type, only m i n o nliffeiences ate found between the tuo ash gioups.
Bulk density values range from 0.3 to 0.7 g/cm3. A relationship
between ash bulk densit\ and ash productioN of the wastes has become
appâtent, showing that the lowei densities correspond to the higher ash
pioducti3ns. thus negativei) affecting rhe \oluwe reduction factors
achie\ed ilui ing incinerati m.
All the incinerator ashes tend ro have a aigh content of alkaline and
alkaline­earth elements, but titanium is the predominant element in most
of them. This unusual titinium content may be due t) the waste pigments.
Substantial diffeiences in loss on ignition (LOI) and carbon content
values are also found. C arbon in the ash seemed to be primarily related to
the rubber content of the waste and, secondarli), to the plastic content.
For ash types A and C unburned carbon is lesponsible for the greater pait
of the LOI, but for a^h type B. with a considerably lowei carbon content,
clorides and alkaline elements may constitute an important amount of the
LOI. In geneial, a high caibon content, as encountered in ash types A and
C. has a \ery negative influence on the behaviour of cemented ashes.
The PVC content of the waste tenis to inciease the amount of ash and
also the ash doride content. This fact is more evident in low­ash­
producing wastes such as type B. where considerable differences in the
cloiide content have been found. In this case. clorides have a clear
influence on the LOI.
A remark must be made about the spurious iron oxide content measured
in sample 1­B. This sample was the fiist obtained in the incineration
programme and it was slightly contaminated by remains of the used cast­
iion grate. Kith the following samples this grate was replaced by a
refractoiy steel grate and no contamination was apparent.

".. RESULTS OF THE CEMENTATION TESTS.

During the cement ition tests five parameteis ha\e been determined as
a function of ash type and paste dosane: water requirement, setting time,
expansion, stiength development and volume reduction.
The watei lequiienient of cement/ash mixtuies tends to inciease with
the ash content, but foi all the samples and dosages most water/mixture
weigth ratios are in the range of 0.3 to 0.5. To obtain a similar
workability, the water content when using cement type I (UNE denomination
I/^A/SR­MK) should be slightly lowei than when using cement type II (I'NE
denomination II­F/35A). In Table 3 the water content limits used in the
different cement pastes aie presented. These limits include both cement
t>pes and both water d isages.
The setting of ci­ment pastes is influenced by all the operating
\ariables: ash type, ash content, water dosage and cement type. Table Ί
shows the measured setting times corresponding to cement type I. For­
cement type II the setting times were highei, but a similar structure of
data was obtained.
As a general trend, cement setting was slowed down by an increase in
ash and watei contents but, although all ashes tend to increase the cement
setting times, different beha\iours were obseived with low­carbon­content
ashes (type B) and with the high­carbon­c mtent ones (types A and C ) . The
admixture of type B ashes slows down the setting process but keeps up a
natural piste haidenrng process, with a continuous consistancy increasing
with time. Howe\er. a leversrble setting process is observed when ash of
 76

types A or C is used, with an initial hardening of the paste and a later

softening which leads to typical setting times over 24 hours. As a result
of this reversible phenomenon, there is some weakness in the starting time
data presented in Table 4. Furthermore, an uneven cement setting occurs
with all ash types, but in a greater degree with high-carbon-content
ashes. So. in the same test piece zones with diffeient consistency levels
are found, as a consequence of different local hardening rates.
In addition to the mentioned characteristics, ashes of group 2 (PVC
containing wastes) present greater setting times than ashes of group 1.

ASH SAMPLE

1-A 2-A 1-B 2-B 1-C 2-C

% Ash
10 25-30 30-35 27.5-35 30-3 5 28-33.5 27.5-34
30 35-40 35-40 27.5-40 35-45 32.5-45 32.5-39
40 39-39.5 38-43 32.5-40 35-45 40-45 39-46
50 45-55 42-49 33.5-42 37.5-44.5 39-44.5 44-50

Expressed as % wt. of dry ash/cement mixture.

TABLE 3. WATER REQUIREMENT RANGE OF CEMENT PASTES

ASH SAMPLE

1--A 2--A 1--B 2--E 1--C 2-•C

S F S F S F S F S F S F

% Ash
10 (L) >8 >8 <1 >8 <1 1:15 1:30 7:00 <1 <1 <1 2:30
30 (L) 1:30 >24 >8 >24 <1 1:00 5:30 >8 8:00 >8 3:30 >24
40 (L) >8 >24 >S >24 <1 3:15 >8 >8 1:00 >8 4:30 >24
50 (L) >8 >24 >8 >24 2:00 4:30 >8 >8 1:00 8:00 4:45 >24

10 (H) >8 >8 >8 >24 1:00 >8 6:15 7:30 >8 >8 3:30 >8
30 (H) 1:15 >24 >8 >24 <1 7:15 8:00 >8 >8 >24 3:00 >24
40 (H) >8 >24 >8 >24 <1 5:00 >8 >8 1:30 >8 >8 >24
50 (H) >8 >24 >8 >24 2:45 6:30 >8 >8 1:00 >24 >8 >24

Nomenclature: S = starting time; E = finishing time. (h:min)

L = low water content; H = high water content.

TABLE 4. SETTING TIME OF CEMENT PASTES (CEMENT TYPE I)

The expansion test results show a non expansive character of the

ashes in the strict sense. However, in setting tests swelling of specimens
was observed. Pastes presented a spongy appearance with elastic behaviour
 77

during setting, but when they hardened the swelled specimens acquired
dimensional stabilit;. . The swelling extent was greater for high-carbon-
content ashes, and it was directly related to ash content.
Taking into account that, according to expansion test procedures,
fresh pastes were imnieised in water just after mixing, loss of weight
during curing was detected in some specimens, particularly those with
setting time greater than 24 hours.
Strength development of cemented ashes was tested by measuring the
bending and compressive strength of prismatic test pieces (40x40x160 mm)
at 2, 7, and 28 days. In compliance with UNE standards, specimens should
be cured immersed in water but, due to the slow setting process and the
negative influence of water on the fresh pastes, specimens of ash types A
and C were not exposed to water.
From a global survey of results, a perfect correspondance between
bending and compressive strength values of specimens can be stated,
therefore in the following, references to mechanical resistance will be
made using compressive strength values.
As a general trend. the lower the water and ash contents used the
greater the compressive strengths obtained. However, a low water content
implies poor workability of pastes, and a low ash content, a low volume
reduction factor of cemented pieces. So, these three parameters should be
accurately balanced to give the best result in each specific application.
Pastes composed of type I cement have better behaviour at early
stages (2 and 7 days) and also in most cases at mid-term stages (28 days),
with the exception of those of type C ashes, which reach equal or greater
compressive strengths with type II cement.
The specimens tend to have a rise in compressive strength with time,
but the greatest absolute values are always obtained by type Β ashes,
probably as a consequence of their lower carbon content (Figures 1 and 2 ) .
However, no direct relationship between the ash carbon content and the
compressive strength of specimens can be stated, as is shown by results
for ash types A and C.
The ENRESA requirements for radwaste package code numbers applicable
to immobilized ashes (1.2) impose a minimum compressive strength, after a
decay period of 23 days, of 100 kg/cm2 or of 300 kg/cm2, according to
theii total activity levels. Other less restrictive package requirements
impose a minimum compressive strength of about 50 kg/cm2 (3). Table 5
presents the values obtained at 28 days using cement type I and their
compliance with the mentioned requirements, assuming that the compressive
load must be exclusively resisted by the cemented ashes. Host pastes are
able to meet the lowest requirement (50 kg/cm 2 ), even those with 40% and
50% ash content, with the only exception of sample 1-A. The ENRESA
requirements for low activity packages (100 kg/cm 2 ) can be completel> met
by type Β ashes and by samples 2-A and 1-C . but water content must be
carefully controlled. On the contrary, only a few 10% ash pastes can meet
the ENRESA requirements for high activity packages.
Obviously, ash t\pe and ash content have a capital influence on
volume reduction during cementation. Obtained volume reduction factors,
defined as volume of raw ash to volume of cemented piece ratio, are
plotted in Figure 3. According to data from Table 5, with all the ashes
studied, excluding sample 1-A, it is possible to obtain cemented pieces of
high compressive strength (more than 100 kg/cm 2 ) not only without
increasing waste volume but even with a small volume reduction.
 78

(CEMENT TYPE I. LOW WATER DOSAGE)

ASH CONTENT (% wt)

40 % I I 30 % Ü Ü 10 5

1-A 2-A 1-B 2-B I-C 2-C

FIGURE 1. COMPRESSIVE STRENGTH OF

CEMENTED ASHES AT 7 DAYS

(CEMENT TYPE I. LOW WATER DOSAGE)

ASH CONTENT (% wt)

I 40 % I I 30 %

1-A 2-A 1-B 2-B 1-C 2-C

FIGURE 2. COMPRESSIVE STRENGTH OF

CEMENTED ASHES AT 28 DAYS
 79

AiH C ONTENT (% u t )

10 30 40 50

Wat e ι dosaie Ash sample

1-A 237 40 23 25

2-A 290 136 122 104

1-B * 542 * 282 270 151

L *
2-B * 4 95 * 283 144 122
t
1-C * 393 * 156 128 176

2-C * 338 * 152 86 36

1-A 247 21 25 12

2-A 86 68

1-B * 505 321 239 130

2-B * 445 * 113 130 90

1-C 200 133 94 98

2-C 293 88 66 44

****************
* > 300 kg/cm2 * > 100 k g / c m 2 > 50 k g / c m 2
****************

TABLE 5. COMPRESSIVE STRENGTH OF PASTES A T 28 DAYS (C EMENT TYPE I )

6. RESULTS OF HIGH PRESSURE C OMPAC TION TESTS.

A useful pressure range of 200 to 450 k g / c m 2 w a s selected to perform
ash compaction tests, although compacting pressures in the range of 3 0 0 to
800 k g / c m 2 have b e e n reported ( 2 ) .
Evolution of volume reduction factors with compacting pressure is
presented in Figure 4. Volume reductions of u p to almost 4 times a r e
obtained with some samples, b u t a great dependency of reduction factors o n
ash type is observed. Type A ashes present far and away the best behaviour
of all the samples.
As can be observed in Figure 4, volume reduction factois have a
slrght, but constant, increase when the compacting piessure moves from 200
to 450 k g / c m 2 . However most of the volume reduction is achieved at the
initial compacting stages when very low pressures have b e e n applied.
The volume reduction factors presented correspond to the a s h pellets
b u t , w h e n considering the last conditioning step (encapsulation with
VOLUME REDUCTION FACTOR VOLUME REDUCTION FACTOR

3.5

=?
2.5

L.5 1-A 1-B 1-C

2-A 2-B 2-C

10 20 30 40 50 60 150 200 250 300 350 400 450 500

ASH CONTENT (% wt) PRESSURE (kg/cm2)
FIGURE 3 . VOLUME REDUCTION IN FIGURE 4. VOLUME REDUCTION IN
CEMENTATION TESTS HIGH PRESSURE COMPACTION TESTS
 81

cement), volume reduction will be considerably lowei than previously

mentioned. Typical final volume reduction factors for the tested ashes
could i ange between 1.5 and 2.5.

7. C ONC LUDING COMMENTS.

The primary waste composition has a strong influence on some physical
and chemical propeities of the ash obtained by incineration of mixed
wastes. Ash bulk density is the most influenced physical parameter. Wood
and paper containing wastes produce an exceptionally low density ash (0.3
g/cm 3 ), while ashes from textile rich wastes reach density values in a
more usual range (0.6 - 0.7 g/cm 3 ). Ash chemical properties depend on
global waste composition. However, the ash carbon content seems to be
mainls produced by the rubbei existing in the waste, so the presence of a
small lubbei amount in the primary waste alwajs leads to high-carbon-
content ashes. No substantial difference in characteristics are found
between ashes from PVC and non PVC containing wastes, with the exception
of the cloiides content of certain samples.
The global results obtained show that cementation is a suitable
conditioning method for all the tested samples, leading to cemented pieces
of high complessive strength which can be prepared even with a small
volume reduction.
In addition to the intrinsic ash properties, there are three other
operating variables which influence ash behaviour during conditioning by
cementation: ash content, water dosage and cement type. All ashes present
a faster setting process when they are conditioned using a high quality
cement (a fast-setting, high-resistant Portland type) than when a standard
cement (a Portland type with pozzolanic admixtures) is used. However, not
all of them reach higher mechanical resistence with the best cement.
The minimum water dosages are imposed by the workability of the
pastes but, as a general trend, a higher water content implies a slower
cement setting, and a lower strength development of the cemented pieces.
The ash type and the ash content are the most important parameters in
cementation. Taking into account their global behaviour, two main ash
classes could be considered: high-carbon-content and low-carbon-content
ashes, although some important differences can be found between samples of
the same category. Cemented high-carbon-content ashes typically present a
slow and uneven setting process and acquire lower mechanical resistance
with time. They also tend to swell during the setting process, and their
fresh pastes are negatively influenced by immersion in water. On the other
hand, the increase in the ash content degrades the mechanical stability of
specimens, but increases the volume reduction reached.
The ash conditioning by compaction produces higher volume reductions.
However, volume reduction factors depend greatly on ash type and, to a
lesser extent, on the compacting pressure. Ashes coming from the most
heterogeneous wastes (type A) achieve the gieatest volume reduction, of up
to 3.5 - Ί times, while maximum volume reduction factors of ashes from
wastes predominantly composed of clothes and plastic have a value of 2.8.

REFERENCES.
1.- ENRESA. C lasificación > C riterios de Aceptación de los Resíduos
Radiactivos de Operación, Rev. 2. Madrid. Enero 1987.
2.- M. Ruhbaum, et al. Study C oncerning Incorporation of Radiactive Kaste
Ashes in a Solid Matrix. SIEMENS Report. Offenbach, May 1988.
3.- M. Ruhbaum. Qualification of Immobilized Ashes. KWV Report.
Kailstein. October 1986.
 Session III

LOW TEMPERATURE IMMOBILISATION PROCESSES

C. C O U R T O I S ( C E A / C A D ) A N D G. S A N D R E L L I ( E N E L )
 85

CONDITIONING OF ALPHA INCINERATOR ASH BY MEANS OF EMBEDDING

IN DIFFERENT MATRICES

C.J KERTESZ - P.R. CHENAVAS - L AUFFRET - A. BIAGINI

Département de Recherche et Développement Déchets

Centre d'Etudes Nucléaires de Cadarache - C E A FRANCE

ABSTRACT
The programme of conditioning alpha incinerator ash coming from a MOX fuel
fabrication plant - MELOX project - has several steps. The first one is the fabrication of
embedding formulation representative ash. The following step is an embedding
formulation study at laboratory scale, with a comparison between three embedding
matrices is. cement, thermosetting epoxide resin, and an epoxide cement compound
To establish the confinment behavior, a study was done including leaching test
and radiolysis of Pu doped samples.
At the industrial scale a polyvalent pilot plant called "PICC" was put in service.
The qualification of the polymer cement process is shown.

INTRODUCTION
In the framework of a mixed fuel fabrication plant project, studied for COGEMA -
MELOX project, the CEA Department of Wastes launched in Cadarache a programme of
incinerator ash conditioning. In this programme the basic process was the solidification by
embedding in a matrix : however, R-D studies on ash melting or isostatic pressing were
performed in other laboratories located in Marcoule.
In the MELOX project, the burnable technological alpha wastes are treated by
incineration. Two kinds of incinerator ash are planned to be produced :
- ash, with a low plutonium content : their calculated Q activity is about 36 Ci.t These
wastes are directly sent to the conditioning process,
- ash, with a high content of plutonium, having to be treated by chemical aqueous
process : after drying, the residue will be solidified by embedding (the alpha activity of the
residue is between 100 and 200 Ci.t"1).
In the conditioning programme, the first step was the fabrication of representative ash :
this was obtained making two incineration campaigns, one active and another inactive.
The following step was a laboratory study for the determination of embedding
formulations, using several embedding matrices, to then determine the main properties of each
embedded ash form, such as leaching resistance and radiolysis behavior, in order to evaluate
the damages due to their high plutonium content.
In the same time, the pilot plant, called PICC for radioactive incinerator ash embedding,
was designed and put into service : it allows to make the transposition, at full scale -100 I or
200 I drum - of the laboratory scale formulations [1].

1 MELOX a ASH CONDITIONING PROGRAMME

1 1. Ash fabrication
In order to carry out the conditioning studies two ash qualities were fabricated :
- inactive ash, coming from inactive products, the chemical composition of which being
that of reprocessing plant or nuclear laboratory wastes, i.e. PVC, polyethylene, latex, neoprene,
cellulose,
- active a ash, with uranium and plutonium content, assigned to active tests to be
performed such as leaching or a radiolysis behavior
Two incineration campaigns, using two different incineration plants, were carried out :
the first one on inactive products was done in 1984, using an incineration plant
prototype , 650 kg of inactive products gave a 21 kg ash production
 86

A second incineration campaign was performed in 1985 using the alpha incinerator of
the UP1 Marcoule reprocessing plant. The treatment was done on real a wastes coming from
Cadarache and from Marcoule. The results of there two campaigns are shown in the table n° 1 :
in the active campaign, two types of α ashes were produced. The quality, called A, coming
from Cadarache waste, was only used to the conditioning tests. Also in the table n° 2 data are
given on the ash alpha activity and isotopie analysis for alpha emitters.

Characteristics Inactive ash Q bearing ash

Origin Inactive products A) a wastes from

CAD/DPFER/SFER

B) a wastes from
MAR/UP1

Initial waste
composition PVC 50 % Cellulose, PVC, latex
Neoprene 27%
Latex 15%
Cotton 4%
Kleenex 4%

Ash weight 21 kg Quality : A 2,556 kg

Quality : B 2,445 kg

Pu mass 0 Quality : A 33 g
Quality : B 34 g

U/Pu 0 Quality: A 11,2

Quality : B 7,6

Table n° 1 - MELOX programme - Incinerator ash supply

Ash Cad. type MELOX Ash - UP1 wastes

Quality A Quality B

Mbq.g"1 mg.g"1 MBq.g"1 mg.g"1

238 p u 6.9 0.011 5.6 0.009
239 p u 22.6 9.9 19 8.2
240 p u 15
17.8 2.12 1.8
241 p u 880
82.0 0.196 0.210
241
Am 10.6 0.089 6.1 0.051

Table n° 2 - Incinerator ash from technological wastes - UP1 Mar. campaign

(Activity and isotopie analysis)

1.2. E mbedding formulation study

Three embedding matrices were studied :
- the cement matrix, with the comparison of three cements :
. the CPJ 45 -french appellation- which is a blend of OPC and secondary constituents,
 87

the CLC 45, containing OPC, BFS and flying ashes,

an aluminous cement,
­ the thermosetting epoxide matrix.
Two systems were compared
a CIBA GEIGY product, using XF431 epoxide resin and XF388 hardener,
. a CDF chimie product, with MN201 epoxide and D2000 hardener,
­ an epoxide cement compound, using the CLC cement ­1 part­ and the epoxide CDF
chimie system, ­part 1­.

1 2 1 Feasibility tests
Feasibility tests were made at laboratory scale on 100 ml samples For each embedded
ash form, the maximum embedding ratio and physico mechanical properties were determined
The main results of this feasibility study are shown on table n° 3 The embedding ratio,
using each matrix is found (40 % with epoxide resin and epoxide cement compound and 20 °o
with cement). The mechanical strength for epoxide and epoxide cement forms are very above
the value for the cemented form. Among the three cemented ash forms, the only CLC
formulation will be utilized due to the ageing ability and durability of this material
During this feasibility step, the embedding process was established, including the
reagent feeding order (liquids first, and then powders). It was found that the use of vacuum
could avoid bubbles in the paste. These data will be applied to design the full scale conditioning
pilot plant [2],

Matrix Formulation Speette Water Hardness Compression Setting

weight % weight absorption shore strength time
28 d MPa hours
kg m"3 to 3
weight %

CEMENT ■ Cement water

weight 8 0 % 1 73 32 4 to 6
CPJ
CLC ■ Ash weight 20 % 1 73 23 5 to 7
Aluminous (w/c ■ 0 68)
1 73 54 3

EPOXIDE RESIN Epoxide weight 60 %

CIBA GEIGY ■ Ash weight 40 % 16 009 B2 125 48

EPOXIDE CEMENT • Epoxide weight 30 %

compound Cement ♦ water 1 8 0 1 85 65 24 10 36
weight 30 %
■ Ash weight 40 %

Table 3 MELOX ash ­ Formulation and properties of embedded ash lorms

Finally, three formulations, using three different matrices will be utilized in the following
tests
cemented ash form ash weight 20 % ­ CLC cement + water 80 w °o
(W/C 0 68)
­ epoxide ash form ■ ash weight 40 % ­ CIBA GEIGY epoxide 60 w °o
(h/e 0 6)
• epoxide cement ash form ash weight 40 % ­ epoxide CDF chimie 30 w %
CLC cement + water 30 w %
(W C 0 35)
 88

1.3. Leaching test - Ash a activity 50 Ci.t"-1

A one year leaching test was performed at the laboratory scale, on samples of 100 ml
volume.
The ash Q activity was 50 Ci.t ; the activity of the embedded ash form was depending
on the embedding ratio :
for the cemented ash form, the a activity is 10 Ci.t
- for the two other matrices, the α activity is 20 Ci.t" .
Three samples, for each matrix have been made (total number of nine samples) [3].
According to the chemical behavior of the plutonium which is insoluble at the
experimental pH of the water, the plutonium release has to be measured in the leachant, and
also on the walls and the bottom of the leaching vessel (this is obtained using a removable
coating of the tank, which can be dissolved in strong acid : the a activity is then measured on
the solution) :
- i.e. AQ = Ac + A,g (As soluble activity - A|g insoluble activity)

The figure n° 1 give the cumulated activity fraction of release

A
o
The following table give the main results of this test :

Results Epoxide Cement Epoxide-Cement

Initial activity A
Bq 108 6.107 1.3.108
mCi 2.7 1.6 3.5
1.2.10"5 5.10"5 6.6.10"6
pR 270 2.-1
E M L g c m .d 5.2.10"8 2.7.107 3.5 10~8

It can be noticed that, the activity of the cemented ash forms is divided by a factor of
two.

1.4. Embedded ash forms, containing Pu - Radiolysis study

Embedded ash forms in the three matrices were prepared containing alpha ashes,
used previously, and a calculated amount of 238 Plutonium dioxide. The 238 Plutonium weight
and activity are calculated to give, in each embedded ash form, the integrated a dose, which is
absorbed after a time of 10 years at the nominal plutonium content [4]. (This corresponds to
1.7Ci of Pu for cemented ash forms and about 3Ci for the two other forms : the weight of
each sample is equal to 150 -170 g).
For each matrix, the samples, were utilized to :
- a 1 year leaching test (1 sample),
- a radiolysis study, carried out in tight containers under Argon atmosphere
(2 samples),
- after the radiolysis study, 2 types of test were performed on a irradiated samples :
. a 180 d leaching test (1 sample),
. a compression strength measurement (1 sample).

1.4.1. Leaching test on a irradiated samples

The figure n° 2 show the variation of Lp during this 1 year leaching test on 100 ml
samples, doped with Pu.
The main results are given in table n° 4.
Moreover, a first fracture of the cemented ash form appeared between 180 and
270 days.
 89

Results Epoxide Cement Epoxide cement

Initial activity Ci 3 1.7 3.3

Specific activity Ci.t 2.1.10 4 10 4 2.10 4

Σ3|
L
R360 " τ~ 1.2.10"3 Broken 2.10" 4
A
o (180 d)

EMLgcm"2.d"1 4.10" 6 1 10" 6

Table n° 4 - Leaching test on samples doped with Pu

1.4.2. Radiolysis gas (low

Measurements of the radiolytic gas flow was carried out on the same 238 Plutonium
doped samples than used for the leaching test : two samples for each matrix were used. The
samples are kept under argon in stainless steel containers and the radiolytic gas flow measured
by sampling of the atmosphere once a month during 1 year. The table n° 5 give the results of
this experiment for each sample :

G a s How m ml per year

sample Matrix H
2 N2 CH 4 CO Integrated G(H2)
°2 <· d o s e ( r a d )

1 Epoxide 284 SO 2 10s 0 05

2 345 12 41 11

4 Epoxide/ 530 17 10 50 2 109 01

5 Cement 236 5 10 10 50

7 Cement 658 213 12 1 IO S 02

θ 539 203 10

poo
Table n° 5 · Radiolytic gas flow on (100 ml samples) doped with Pu (time 1 year)
The hydrogen is the main component of the radiolytic gas flow for cemented ash
forms, an oxygen gas flow is present The value of G(Hp) is given for each matrix [4].

1 4 3 Leaching test on a irradiated samples

After the 1 year radiolysis study, one sample of each embedded ash form was utilised
to carry out a leaching test, in order to measure the leaching property evolution
Figure n° 3 show the leaching curves for LR 1 f i n , on samples having been a irradiated
direct leaching test on 238,Pu doped samples and those of the second leaching test after 1 year
of radiolysis
 90

Direct leaching Epoxide Cement Epoxide/cement

Integrated a dose
(rad) 3.4.10 9 1.5.10 9 2.5.10 9

L 4.10- 4 Broken 0.7.10" 4

R 180

E 3.10" 6 - 0.9 10" 6

ML180Gcm"2-d"1

Leaching after
1 year radiolysis test

Integrated a dose
(rad) 4.9.10 9 2.3.10 9 3.7.10 9

L 1.2.10"3 0.7.10" 4 2.10" 4

R 180

E 1.10"5 10" 6 3.10" 6

ML180

Table n° 6 - Evolution of leaching properties on Pu doped samples

1.4.4. Evolution of mechanical properties

The second sample of each embedded ash form coming back from the radiolysis
experiment, was utilized fora compression strength measurement [5].
The results are given in table n° 7 : it can be noticed that a radiolysis has only a light
effect on the compression resistance.

Matrix
Epoxide Cement Epoxide cement
Compression
strength (MPa)

On inactive sample 125 22 64

On a irradiated sample > 200 30 60

9 9
Integrated α dose (rad) 3.10 1.5.10 2.5.10 9

Table n" 7 - Evolution of the compression strength on a irradiated samples

2. TH
E ASH CONDITIONING PILOT PLANT "PICC"
In the mid 88, the "PICC", a pilot plant for the incinerator ash embedding was put into
service. The facility was designed to perform the transposition, at the industrial scale -100 I or
200 I drum-, of the laboratory scale formulations. The PICC embedding polyvalent process
possesses the unique property to work with three different embedding matrices and to
therefore produce three different embedded ash forms. The three binders, studied in the
laboratory work, are possibly used in the process [6].
 91

2 1. The PICC process and apparatus

The PICC process is operated discontinuously. The major component of the apparatus
is a high performance mixer, in which ash and reagents are fed by the means of gravity
In order to improve the quality of the embedded product, several possibilities can be
utilized :
- premixing of the pulverulent compounds in a special tank,
- use of vacuum for degassing either in the premixing tank or in the mixer,
- temperature regulation using a coolant circulation in the double wall vessel of the
mixer.
After mixing, the collecting of the paste is done in a 100 I or 200 I metallic drum, placed
in a collecting chamber designed to work under vacuum. Figure n° 4 shows an embedded ash
form at 100 I scale.

22 Improvements to the polymer cement process

The comparison of different embedding matrices having shown the interest of the
epoxide cement compound, a transposition work was done on the pilot plant "PICC" : at the
industrial scale this work needed ashes to be available and also large amounts of polymer
products. The ash supply was obtained from an incineration plant from the CEN Cadarache,
devoted to the inactive burnable waste treatment For the polymer supply, different products
were tested from CIBA GEIGY, DOW CHEMICAL and SPADO LASSAILLY due to the end of
CDF chimie epoxide fabrication. Several embedding campaigns were done, using different
epoxide resin or hardeners, to recover a good embedding formulation [6].

2 2.1. Polymerisation exotherm study

Working at 100 I or 200 I scale, needs to check the maximum temperature, during the
hardening period : the temperature peak, mainly due to the exothermic polymerization reaction
of the epoxide system, has to the maintained below that of boiling water -at 100°C, the water
vapourizes occuring the inflation of the epoxide cement product-.
Figure n° 5 shows the polymerization temperature curves, using different epoxide
systems from SPADO LASSAILLY Co The two last curves, obtained with SL MN206 epoxide
and SL D2005 or SL D2010 hardeners give low polymerization temperature, with maxima at 65
or 69°C. lower than that the initial reference system CDF LOPOX MN201 - D2000.

2 2 2. Cleaning of the mixer

Due to the adhesive properties of the polymer cement ash form against the stainless
steel mixer, an important work was done on the cleaning process.
Two ways were studied :
- The choice of an appropriate solvent :
Different organic chemicals were tested, such as epoxide diluents or solvents : heavy
ketones like Methyl Ethyl Ketone (MEK) give good results. The best were obtained with
tributylphosphate, diluted in dodecane (30/70 solution).
- The use of high pressure :
The cleaning operation can be achieved successfully using mechanical action.
Different apparatus having been tested, the mixer lid was equipped with a high pressure
cleaning device - Barthod trade mark - This device can operate using water, or TBP/dodecane,
at a 200 bar pressure.

CONCLUSION

The conditioning programme of MELOX a ashes by using embedding matrices, started

in Cadarache, in 1985.
At the laboratory scale, embedding formulations were established. The embedding
ratio is 20 w % in cement while it reaches 40 w % in epoxide or epoxide cement matrix
- Leaching tests were done using active samples at nominal activity or doped with
238
Pu.
 92

- At nominal activity of plutonium the alpha release data are in the same range , on
doped samples the cemented form is broken, due to a radiolysis and water immersion.
- Dry radiolysis study give the nature and composition of gas, where the main
component is hydrogen.
Also data on leaching and mechanical properties were obtained on a irradiated
samples.
At the industrial scale a pilot plant was put into service : it operates with a polyvalent
embedding process, allowing to change the matrix.
- Due to the interesting properties of the polymer cement ash form, the embedding
process was optimized : the choice of the right epoxide system was done and the cleaning
process of apparatus was realized.
These points allow the epoxide cement process to be qualified at the industrial scale,
and to work on real active incinerator ash.

REFERENCES

[1 ] C. KERTESZ, C. COURTOIS
Conditionnement des cendres des incinérateurs de Cadarache -
International symposium on management of low and intermediate level radioactive
wastes
Stockholm 16 - 20 Mai 1988 - IAEA SM 303/81.

[2] C. MARCELLIN
Etude de conditionnement des cendres alpha et beta gamma produites par incinération
de déchets
radioactifs dans différentes matrices - CEC research contact FI1-W0005F progress
report n° 1.

[3] C. MARCELLIN
Etude de conditionnement des cendres alpha et beta gamma produites par incinération
de déchets
radioactifs dans différentes matrices - CEC research contact FI1-W0005F progress
report n° 2.

[4] C. KERTESZ et al.

Etude du conditionnement des cendres alpha et beta gamma produites par incinération
de déchets
radioactifs dans différentes matrices - CEC research contract FI1-W0005F progress
report n° 3 - 4.

[5] C. KERTESZ et al.

Etude du conditionnement des cendres alpha et beta gamma produites par incinération
de déchets
radioactifs dans différentes matrices - CEC research contract FU -W0005F progress
report η" 5 - 6.

[6] C. KERTESZ, P. CHENAVAS, G. NAUD

The starting up of a pilot plant for radioactive incinerator ash - Results of two embedding
campaigns.
International symposium Waste Management 90 - TUCSON AZ (USA) 25 February -
7 March 90.
 93

¿AL
AO "13
S
,η­5 . 1 , 2 , 3 Τ ι « π η ο ««tung r»«tn
« : 2 0 CLt­1

EMBEDDED WASTE FORMS .10,11,12 Polym« c « i « l

« : 20 cLt­1
.13,14,15 C«m«nt
tK :10 cLt­1
­V­.

­· MS
^
3.10­5 '/"
\
. 1
,~* —
l'
•3
­' 'is -ζ
11
­· M
1 r 1 1 1 1 1 1

40 80 120 160 200 240 280 320 360 ( days )

Fig. 1. MELOX a incinerator ashes — leaching test

Cumulated leached activity fraction

κ T S . IAI/A0) 10-4

10­­

B­­

6­
Θ EPOXID E

­I­ EPOXIDE/CEUENT

* CEMENT
«­­

2­

Fig. 2. Embedded ash samples, doped with 238PU—leaching test

Cumulated activity Traction of release
 94

i2o- r S.(AI/A0)*10-5

+ EPOMDE/ŒUENT

\ DAYS

Fig. 3. Embedded ash samples, doped with 238PU—back from radiolysis test
Cumulated activity fraction of release

Fig. 4. Epoxide/cement process

Embedded ash form — 100 1 drum
 95

DEGREES
­ MN201 + D2000
110 ■
+ MN201L+D2005
100­ * MN201L+D2005
Ö MN201L + D2005
90­
X MN206L+D2005
­ MN206L+D2010
80­

70­ _

/ '
βο­
y χ ""^Sfc^<^­ ^ ^ »
50­

(TEMPERATURE!
■«0-

30­
ι -'Zs^
HOUR1
20 — I 1 h 1 : \
10 IS 25

Fig. 5. Exotherm peak for different epoxide systems

 96

MATRIX PROPERTIES OF MODIFIED SULPHUR CEMENT

FOR RADIOACTIVE INCINERATOR ASHES

A. VAN DALEN and J.E. RIJPKEMA

Netherlands Energy Research Foundation, ECN

Business Unit Nuclear Energy
Westerduinweg 3. 1755 ZG Petten
The Netherlands

Summary
Modified Sulphur Cement is a fairly new product; about ten
years ago this material has been suggested for use in nuclear waste
management as backfill and waste matrix for non-heat producing
wastes. Thanks to a CEC-contract the properties of modified sulphur
cement could be studied on laboratory scale. During the two year
contract research, much was learned about the properties of the
material, and also the preferred waste types to be encapsulated:
incinerator ashes and precipitates. This presentation is intended
to give an overview of the results obtained regarding leachabi-
lity, porosity-permeability, compressive strength and radiation
resistance.

1. INTRODUCTION
The words cement and concrete, in combination with modified sulphur
are used in the original meaning of a material with binding properties
and a solid mass formed by coalition of particles. Usually the words are
reserved for materials reacting with water to form hydraulic products,
e.g. Portland Cement. Modified Sulphur Cement, however, is a thermoplas-
tic material produced from elemental sulphur and (di)cyclopentadiene. In
history sulphur has been used as a filling material in joints because of
the physical properties of easy to melt and at ambient temperatures a
solid and inert material. The disadvantage of the crystal phase transi-
tion at 96 °C prevented the use of sulphur as a construction material.
In view of the surplus production of sulphur by desulphurisation of na-
tural gas, oils and, in the future, coal, a product was developed by the
US Bureau of Mines with favourable properties. After the reaction of
sulphur with (di)cyclopentadiene the modified sulphur does not show
the phase transition in the solid state. The product has the same yellow
colour and the same melting point as elemental sulphur has. The product,
named Chement 2000, is delivered in the form of small chips at a price
about equal to that of bitumen.

2. PREPARATION AND PROPERTIES OF MODIFIED SULPHUR

Waste products mixing with Modified Sulphur Cement (MSC) has to be
done at temperatures above the melting point of MSC. Waste materials are
heated to temperatures around I30 'C before molten MSC is added. The
addition of MSC is ended when a good workable mix is obtained. The mix
is poured into a suitable mold or container for solidification. The pre-
paration technique resembles that of bituminisation. Due to the heat
treatment step in fabrication of the wastes, some problems are in common
with bitumen. Both matrices are sensitive to the effect of swelling
wastes by uptake of water. Bitumen reacts by dilatation, as a plastic
 97

material, the MSC waste product loses strength. The worst case is formed
by ionexchange resins: in a few hours the MSC waste form désintégrâtes
once immersed in water. Best fitting in the MSC matrix are ashes and
precipitates; a product with a compressive strength comparable with
Portland cement products is obtained. Sulphur and modified sulphur is
attacked only by strong oxidants, strong alkalies and organic solvents.

3. POROSITY, PERMEABILITY AND LEACHING

The main function of the MSC matrix as a barrier against disper-
sion of the radioactive components in the waste is due to the low per-
meability. The permeability depends on the porosity of the matrix and
proved to be complex. It can be explained by following the steps of the
production of the waste form.
During the investigations with several types of wastes, it was dis-
covered that more or less air is entrained in the molten mass. Maximal
with silicates as asbestos, and minimal with aluminium oxide. This fi-
nely divided air in the matrix is the origen of one part of the poro-
sity. The other type of porosity seems to originate from the shrinkage
of the MSC during the solidification. Both types of porosity are visible
in the electron microscope images (see Fig. 1 ) . The longer pores are due
to the shrinkage of the MSC matrix. The pore diameters are small, so the
permeability is low. The total shrinkage of the waste form can be mini-
mized by maximal loading with waste. In case of the incinerator ashes or
precipitates, both consist of fine particles, about 25~30 weight percent
can be taken up in MSC to form a workable paste.
The porosity has been measured by following the diffusion of HTO
through a disk of 3 m m thickness. The resulting plots of the amount of
HTO diffused from the spiked side of the disk to the barren side, devi-
ates from the well known graphs, due to the two types of porosity. The
shrinkage porosity seems to act as microscopic pinholes. The final po-
rosity is found when all the pores are engaged in the diffusion process.
The effects of the material incorporated on the diffusion is reflected
in the graphs of Fig. 2. The porosities calculated from the effective
diffusion of HTO are in the range of ^0% when asbestos is present, 2~5%
for chalk as aggregate and 0.1-0.2JÍ for aluminium oxide. Due to the
small pore sizes, the permeabilities are low to very low. The time nee-
ded to attain the steady state for HTO diffusion through the disks, is a
few weeks for the asbestos containing, to about two years for the alumi-
nium oxide containing.
The process of leaching is diffusion of water into the pores of the
matrix, the formation of a saturated solution in the matrix, and diffu-
sion out of the waste form of the dissolved components. This means that
the relation between the diffusivity and solubility of the component is
a simple one. Fig. 3 shows the result: the square root of the diffusi-
vity is proportional to the solubility of the components. Due to the use
of simulated wastes for laboratory experiments, the composition of the
wastes is known. Also the diffusivity of pure water fits in the plot;
for Co leaching the solubility of CoS has to be taken, due to the pre-
sence of minute amounts of H 2 S during the preparation of the MSC waste
specimen. The results of leaching in terms of diffusivities and leach
rates are given in Table 1. It has to be remarked that the values are
those obtained after a leaching period of nearly two years. According to
 98

the experience obtained, the initial leach rates are about one third of
the final ones, due to the two types of porosity. For the low permeabi-
lity materials, such as modified sulphur and bitumen, the standard leach
period of three months is too short for reliable results.

4. COMPRESSIVE STRENGTH
A few days after preparation of the specimen with ash type mate-
rials, silicates and metal oxide, the compressive strength is in the
range of 60 MPa; increase to 80-100 MPa is observed after two years of
dry storage. Saturation with water of the samples results in a conside-
rable lowering of the compressive strength, values around 20 MPa are
found. Water inside the pores may act as a lubricant. After drying the
samples in a stove at 80 'C the initial compressive strength is re-
stored.

5. RADIATION RESISTANCE
Gamma irradiations with spent fuel of the HFR at Petten have been
carried out on several simulated waste types in the dry state. Up to a
total gamma ray dose of 20 MGy no effect was noted regarding change in
dimensions of the specimen or evolution of gaseous products. Only a
small increase in compressive strength was recorded, which may be due to
accelerated ageing by release of the internal stresses from the solidi-
fication process. The gamma dose absorbed by the samples is about the
same as for the intermediate waste from reprocessing spent fuel contai-
ning 1 kCi of beta, gamma emitters per m' .
The effect of alpha emitters has been simulated for the equivalent
of 0.5 Ci/m3 by neutron irradiation of boron containing samples. Also in
this case no effects were recorded.
Irradiation experiments with water saturated specimen have not been
carried out during the two year research period because of the long time
needed for saturation of the samples. Unknown is thus the effect of the
radiolysis products of water: are they diffusing fast enough out of the
matrix or will they introduce internal pressures?

6. FIRE RESISTANCE
A controversial point for the use of modified sulphur as a waste
matrix is the flammability of sulphur. The temperature of self ignition
in air of sulphur and modified sulphur is about 220 'C. In practice
the effect of a fire is small because the heat conduction in sulphur is
poor, comparable to wood. There is only one experiment cited in litera-
ture concerning the exposure of a modified sulphur concrete with fly-ash
to a gasoline fire for 16 minutes. Only minor surface roughing was
observed.
Our experience is that remelting of waste specimen takes a consi-
derable time, even at the low melting temperature of 120 'C, the heat
conductivity is too small.

The results of the two year investigation under contract with the
CEC have been published in the Report EUR 12303 by A. van Dalen and J.E.
Rijpkema: Modified sulphur cement; a low porosity encapsulation material
for low, medium and alpha waste (1989).
 99

Figure 1.

Electron microscope images of modified sulphur cement, MSC, with Pbl ,

(top) and A1,0, (bottom), show the porosity of the material present in
the MSC fraction. The total porosity depends on the material incorpora-
ted in the MSC matrix. Due to the much smaller porosity with A1 2 0, in
the matrix, the small cracks from shrinking at solidification are good
visible. The origin of the degree of porosity depending on the material
incorporated, is unknown, although the catalitic effect of asbestos on
the reaction of sulphur with hydrocarbons to produce hydrogensulphide,
is known for almost a century.
 100

Diffusion
200

c 1βΟ
y
J­í 120
•i-I
>
βο
(D

40

0, y. 1 · . t

time (days)

(2)

time (days)

4­)
•Η
> (3)

100 300 4βΟ βΟΟ

time (days)
Figure 2 .

The effects of the total porosity and the two forms of porosity is re­
flected in the diffusion measurements of HTO through a disk of 3 m m
thickness of MSC with chalk (1), A1 2 0 3 containing incinerator ash (2)
and asbestos (3). The transport of HTO in the initial stage is not zero
as is normally measured when a homogeneous porosity is present. The de­
viation from the ideal situation is caused by the "crack" porosity. In a
later stage all the pores are engaged in the diffusion proces. Porosi­
ties calculated for the situation that the steady state has been reached
are asbestos containing MSC 0.5. chalk containing 0.02­0.05 and Al 2 0,
containing 0.02.
 lul
io­ r
DIFFUSIVITY HT O/asbestos

10 10"· 10~* 10"* 10° 102 10"

3
solubility [kg/m ]
Figure 3-

The simple relationship between the diffusivity and the solubility of

waste components is due to the fact that modified sulphur is an inert
material, only porosity (permeability) determines the leaching beha­
viour. The band­width is related to variations in porosities of the
waste forms.

Sr Co Eu HTO
Cs (H 2 0)

borate 5E­14 3E­14 9E­19

waste ΘΕ­4 4E­4 2E­6

KEMA 7E­14 3E­15 8E­20 1E­17 3E­15

ash 1E­3 9E­5 6E­7 1E­5

3E­13
asbestos

3E­14
CaCO,

ECN total 1E­15

sludge θ 5E­5

1E­15 D ( =) m'.s­
2
Pbl 2 I 7E­5 f \ <= ) g.cm .cT'

Table 1.

Overview of leachrates (g/cm2/d) and diffusivities (m 2 / s ) measured for

modified sulphur containing several types of simulated nuclear waste
materials. Note that the solubility is primarily determining the
leachability, not the waste type.
 EVALUATION OF THE POSSIBLE EMBEDDING MATRIC ES
FOR INC INERATOR ASHES : FRENCH EXPERIENC E

J. MISRAKI - C. KERTESZ

Département de Recherche et Je développement sur les Déchets

CEA-CEN C ADARAC HE
BP N°l - 13108 ST PAUL LEZ DURANCE

ABSTRACT
Depending upon the origin of the incinerated radioactive
wastes :
- technological wastes from Research Centers,
- technological wastes from reprocessing plants,
- solvents including T.B.P.,
- solvents including oils, chlorinated compounds,
the ashes provided by the incinerators can present some different
characteristics :
- physical characteristics : density, particles size,
- chemical characteristics : Ca/P ratio, presence of metals,
- radioactive characteristics : amounts of β', γ emitters and/or a
emitters.
The conditionning method which is studied is the embedding of
the incinerator ash in a solidification matrix.
Different matrices have been tested : cements, thermosetting
epoxide resins, and a cement-epoxide matrix.
The use of these matrices permits to obtain an embedding ratio
lying between 20 and 40 %.
Several tests, concerning the physical and mechanical
properties, the confinement power and its maintenance, have been
performed or forecasted, on samples or packages "scale 1" in order :
- either to check the transposition at the industrial scale of a
formulation resulting of a laboratory work
- ot to have the possibility to choose a matrix
- or to characterize a finished product.

We have a very wide experience in dealing with ash conditioning

in the Waste Storage Department at Cadarache. it is closely related to
the type of ash consideration and the current status of the studies.
At present, our experience can be devided into tree categories :

1. First category : in this category we find studies conducted to

enable a matrix to be chosen. This is the case of the test carried out
as part of the study of α ash conditioning. These studies are part of
the MOX fuel production project.

2. Second category : the embedding matrix has been chosen but the
embedded waste must be defined. This is the case of ashes from the
incinerators that treat organic liquids, and solid technological waste
with low activity from the Research Center.
 103

Table 1. Composition of the Ashes (W%)

ORIGIN Ashes without Ashes with

rubber rubber

NA 0.2 1
CA 7.2 9.1
Ρ 1.3 1
S 3.9 2.1
C 0.1 0.1
AL 7.4 12
FE 11 0.6
SI 13 14
MG 0.1 1.5
Κ 4 3.1
TI — 0.02
ZN 4 5.5
CL 0.4 0.02
d 0.41 0.26

Table 2. Composition of" the Ashes (W%)

INCINERATOR OF CAD (INACTIVE)

CA Ρ S C AL FE SI CL d
6.5 0.1 — 7 11 0.7 25 0.8 0.46

TOWN INCINERATOR

SIO: 44.7 ZNO 0.3

ALA 12.9 PBO 0.4

FEO, 4.2 CDO 0.2

TIO, 1.0 Co 0.3
CAO 22.2 CL 1.3
BAO 0.2 PA 1.6
MGO 2.8 SO, 2.4
NA,0 + K: 4.8
 104

3. Third category : the formulation of the embedding matrix has

been defined in the laboratory and must be converted to the industrial
scale. This is the case of phosphate ashes.

I) a ASHES

These ashes come from the incineration of technological waste

from the MOX fuel production project installations. Alpha emitters
cause such a degree of activity that surface storage of the embedded
waste is impossible.

The test program should make it possible to choose between three

possible embedding matrices :
- cement
- epoxy resin
- cement-epoxy resin compound
For this program, we have worked with two different types of
ash :

a) inactive ashes from an incinerator in Valduc. These were

obtained after a compaign on technological waste with a P.C.V.,
rubber, neoprene, latex, cotton and kleenex base.

b) active ashes from an incinerator in Marcoule. These were

obtained after a compaign on technological waste with a cellulose,
P.C.V. and latex base. The chemical composition of these ashes is
given in Table 1. In order to study the interaction between cement and
ashes, we have also studed, along with these two types of ash :

a) inactive ashes from an incinerator in Cadarache,

b) inactive ashes from a city incinerator.

The composition of these ashes is given in Table 2.

The first part of this research consisted in determining the optimal

formulation for each matrix.

1. Cement

The cements tested were :

- CLC 45 cement (slag and ash cement)
- CPA 45 cement (artificial Portland cement with secondary
constituents)
- high-alumina cement

Our goal was to obtain a high embedding coefficient and a good

compression strength.
The results of the tests carried out on the test samples are
given in Table 3.
It can be seen that the embedding coefficients are approximately
20 % and that the compression strength values are between 17 and 59
MPa.
 105

Tuble 3. Results of the F ormulation Tests — Cement

CLC CLC CPA ALUMIN.

TEST 1 TEST 2
WATER/CEMENT 0.63 0.68 0.62 0.55
EMBED. RATIO 19.7 19.2 19.9 20.5
TEST UNDER H,0 7 days 28 days 7 days 7 days
COMPRESSIVE STRENGTH 17.5 22.6 32.5 54.3
MPa
RESISTANCE TO 4 4 7 7
TRACTION MPa
SWELLING μτη/m + 480 + 400 + 420 + 400
MASS VARIATION kg/m3 + 32 + 36 + 48 + 79
TEST IN AIR 28 days
COMPRESSIVE 2.33
STRENGTH MPa
RESISTANCE TO 4.8
TRACTION MPa
SHRINKAGE μτη/m - 1600
MASS VARIATION kg/ m3 - 32

Table 4. Some Results of Tests Inactive Ash/C ement

COMPRESSIVE 18.5
STRENGTH MPa
RESISTANCE TO 3.2
TRACTION MPa
SWELLING μm/m 656
SHRINKAGE 427
(AIR) ¿im/m

Table 5. Ash/Epoxide Resin

CDF CIBA
TIME SETTING h 24 48
DENSITY 1.61 1.65
HARDNESS 80 82
COMPRESSIVE STRENGTH 105 125
MPa
MASS VARIATION UNDER 0.11 0.15
WATER % 56 d
 106

Despite the fact that CPA and high-alumina cements have a better
compression strength, CLC cement was chosen for its more progressive
setting time (lower risk of cracking).
The interaction between ashes and cement was studied using raw
ashes from a city incinerator, without sorting. These ashes contained
unoxidized metallic elements. During embedding, a large gaseous
discharge occurred while the cement was setting, causing swelling of
the embedding.
Heat treatment of the ashes at 700°C, then at 1100°C, for 20-30
hours reduced this phenomenon, while soda treatment of the ashes
nearly eliminated it completely.
A test embedding at scale 1 (100 liters) was carried out with
inactive ashes from an incinerator in Cadarache. Gaseous discharge was
observed during setting. The results of the tests carried out on test
samples with a 100-liter drum casting are given in Table 4.

Conclusions : the formulation chosen was of CLC 45 cement with a ratio

of E/C = 0 . 6 5
The embedding coefficient is 20 % of the mass. The density of
the embedded waste is approximately 1.75. Using cement as an embedding
matrix is inexpensive ; the alkaline medium is a retention medium for
plutonium, but the interaction between ashes and cement largely
depends on the composition of the ashes.

2. Epoxy resin

The systems tested were the following :

- CIBA-GEIGY XF 431 epoxy
- CIBA-GEIGY XF 348 hardening agent
- CDF Chemicals MN 201 epoxy
- CDF Chemicals D 2000 hardening agent
- CDF Chemicals with D/E : 0.6
The goal was to obtain a high embedding coefficient and good
mechanical resistance of the embedded waste.
The results obtained are given in Table 5. The embedding
coefficients are 40 % of mass. Scale 1 (100-liter) feasibility tests
were carried out with the two systems ; the two formulations behaved
differently : the CIBA system's polymerization time took 48 hours,
while the CDF system only took 24 hours. Moreover, the temperatures
reached at in the core of the 100-liter embedding were 165°C (CDF) and
150°C (CIBA). Dried ashes must therefore be used.

Conclusions : the formulation chosen is the XF 431 epoxy resin,

hardening agent XF 348, with D/E = 0 . 6 (Ciba - Geigy).
The embedding coefficient is 40 % of mass. The density of the
embedded waste approximately 1.4. It is therefore mandatory to work
with degassed, dried ashes. Moreover, depending on the mixer used, the
ashes may have to be sifted.
 107

Table 6. Ash/Cement Epoxide

NORMAL VACUUM
MIXING MIXING
TIME SETTING h 24 24
DENSITY 1.81 1.91
HARDNESS 85 85
COMPRESSIVE STRENGTH 64 65
MPa
MASS VARIATION UNDER 0.47 0.17
WATER % 56 d

Table 7. Resistance to Leaching

CEMENT EPOXIDE CEMENT +

EPOXIDE
ACTIVITY BQ 6 10' 108 1,3 10"
5 5 6
CUMULATED RELEASED 5 10 1.2 10 6.6 10
FRACTION 270 d
: 7 8
LEACHING RATE gem d ' 2.7 10 5 10 3.5 10 "

Table 8. Resistance to Leaching Doped Samples

CEMENT EPOXIDE CEMENT +

EPOXIDE
ACTIVITY GBq 63 110 120
MASS ACTIVITY GBq/kg 370 780 740
4
CUMULATED RELEASED broken 1.2 10 ' 2 10
FRACTION 360 d
; 6 6
LEACHING RATE gem d ' 4 10 10
 108

II 3) Cement-epoxy resin compound

To combine the properties of the two matrices (cement and epoxy

resin), it was suggested that ashes be embedded in a composite matrix.
The purpose is to obtain a high embedding coefficient and an
embedded waste with good physical and mechanical characteristics.
Different feasibility tests led to the choice of the following
formulation (inactive ashes from Valduc) :
- CLC cement + water 50 % of mass
with E/C = 0 . 3 5
- CDF epoxy system 50 % of mass
MN 201 resin
D 2000 hardening agent
with D/E = 0 . 6
The results obtained are given in table 6, for two types of
mixing, normal mixing and vacuum mixing.
An embedding coefficient of 40 % of mass was obtained, along
with good physical and mechanical characteristics for the embedding.
A scale 1 (100-liter) feasibility test was performed with
inactive ashes from the incinerator in Cadarache. The temperature
obtained at the core of the embedding was under 100°C.

Conclusions : the formulation chosen is the one mentioned above,

i.e. :
- 30 % cement + water
- 30 % epoxy system
- 40 % ashes
An enbedded waste with a density of = 1.72 was obtained.
Exothèrmicity was under 100°C.

The second part of the study considered in determining the confinement

power and how to maintain this confinement power. This was done using
100 ml test samples of the embedded waste with the matrix formulation
defined above.

1) Resistance to leaching with embedded active α ashes.

Leaching was carried out for 270 days.
The results are given in Table 7.

2) Maintaining confinement power

In order to test resistance to irradiation, tests were carried
out on embeddings doped with 238 Pu0 2 .
- Resistance to leaching :
Activity of the different embeddings :
Cement : 6.3 10 10 Bq (3.7 10 11 Bq kg"1)
Epoxy : 1.1 IO11 Bq (7.8 IO11 Bq kg"1)
Composite : 1.2 1 0 u Bq (7.4 10 11 Bq kg"1)
The results are given in Table 8.
It should be pointed out that the cement embedding broke up
after 180 days under water (5 106 Gy).
- Gaseous releases :
Gaseous discharges were measured for one year on test samples which
were also doped with 238PuO and kept in containers under inert gas.
 109

Table 9. Released G as Doped Samples

CEMENT EPOXIDE CEMENT +

EPOXIDE
DOSE Gy 107 2 107 2 107
GAS:
VOLUME cm5 820 410 458
COMPOSITION %
H2 73 77 84
02 25.5 19.5 —
N2 1.5 1.0 3.5
CH4 — — 2
CO, — 2.5 10.5
GH2 0.2 0.05 0.1

Table 10. Compressive Strength Doped Samples

CEMENT EPOXIDE CEMENT +

EPOXIDE
DOSE Gy 1.7 107 3 107 2.5 107
BEFORE 22 125 64
EXPOSURE
AFTER 30 > 200 60

Table 11. Composition of the Ashes (W%)

ORIGIN TBP OIL TECH. WASTES INACTIVE

CA 30 10 5-27 6.5
Ρ 23 10 0.1-4.5 <0.1
S 7.3 1.5-6
c 7.3 2-10 7
AL 11-47 11
FE 2.5-10 0.7
SI 11-22 25
CL 4-15 0.8
d 0.27-0.42 033-0.59 0.46-0.51 0.46

PARTICLE SIZE: TBP 20-80 μπι; OIL 0.33-0.59 μα; TECH. WASTES 0.1-3 mm
 110
The results are given in Table 9.
- Variations in mechanical properties under irradiation.
A compression test was carried out on embedded samples of the
same type before and after irradiation.
The results are given in Table 10.
- Behavior under water.
The various long-term leaching tests made it possible to observe
the behavior of the différents samples when submerged under water.
No dimensional changes appeared in any of the three types of
embeddings with active ashes.
With doped embeddings, no changes were found for epoxy and
composite embeddings ; the cement embedding broke up (after 1.5 years,
40 % of the total mass was in pieces of approximately 1 cm 3 ).

Conclusions
For a given type of ash, three matrices were tested : cement,
epoxy resin and a cement-epoxy compound. After searching for the best
formulation, the mechanical and physical properties of the different
embeddings obtained were satisfactory.
With the cement matrix, the resistance of the embedded waste is
closely related to the chemical make up of the ashes, if there is
metallic content, the ashes must be pre-treated. The embedding also
showed poor resistance under very high irradiation. Cement is very
easy to use, however, and is inexpensive.
The epoxy matrix provides a higher embedding coefficient, but
requires dried, degassed ashes.
The compound matrix provides certain advantages, it is
compatible with the different types of ash tested and gives embeddings
with good mechanical characteristics.

B. Ashes from the incinerator at the Cadarache center

These ashes are produced by the incineration of organic

liquids : oil and various solvents, T.B.P. dissolved in dodecane ; and
technological waste (cellulose, gloves, wood, cardboard, paper). Ashes
from an inactive incinerator were also added to the study.

The activity of the ashes was as follows : MBq"1

Origin α activity β a activity
Organic liquids 0.37 from 3.7 to 37
with a max. of 3.7 with a max. of 370
Technological waste from 0.074 to 3.7 from 0.37 to 19

Chemical compositions are given in table 10, along with densities and
particle size analyses.
A fairly large diversity in compositions and particle sizes can
be noted.

Depending on the tt activity of these ashes and on French law

concerning surface storage of solid waste, these ashes must be
embedded.
 Ill

Table 12. Conditioning of Ashes — Cadarache Incinerator Characterization Programme

NUMBER OF TUBES TESTS ON

TESTS ON TUBES PACKAGE NUMBER
'SCALE Γ
TBP OIL T.W. Paper
1. Physical 1.
properties
— porosity 1 1 1 1
— permeability filling rate 1
(water gaz) 1 1 1 1
— density 1 1 1 1
— shrinkage 3 3 3 3 homogeneity 1
2. Mechanical 2.
properties
— compressive resistance to
strength 2 2 2 2 load 1

shock
resistance 1
3. Confinement 3.
power
— resistance to
water
leaching 3 3 3 3 degasing 1

4. Maintenance 4.
of the
confinement
— resistance to resistance to
thermal thermal cycles 1
cycles 2 2 2 2
— sensitivity to
contact with fire
water 1 1 1 1 resistance 1

Table 13. Phosphated Ashes Cement

WITHOUT WITH
PREMIXING PREMIXING
WATER SWEATING % - 2.3 2-3
SETTING % 0.4 1.7
COMPRESSIVE 29 30
STRENGTH MPa
HARDENING T° °C 65 65
 112
The embedding matrix chosen for the reasons presented above was
the compound matrix.
- CLC 45 cement + water 50 X of mass
with 0.3 < E/C < 0.36
- epoxy resin 50 X of mass
with D/E - 0.6

IV. The embedded waste has the following composition :

- epoxy resin + hardening agent 30 X of mass

- cement + water 30 X of mass
- ashes 40 % of mass
A density of approximately 1.9 is obtained.
Weight increase when submerged under water for 56 days :
- 0.47 X with normal mixing
- 0.17 X with vacuum mixing

V. The planned characterization tests are listed in Table 11.

C. Phosphate ashes

The purpose of this study was to convert a formulation developed

in a laboratory to an industrial scale.
The ashes were mainly made up of Ca Ρ 0 , with a mass composition of
Ca : 30 X
Ρ : 25 Χ
and a molar ratio of Ca/P = 0.94.
Their density vary between 0.8 and 1, and, for 90 X of the
compound, the particle size ranged from 1.3 to 60 /im.
The matrix used was a CLK slag cement with a ratio of E/C - 0.56
The embedding obtained had an embedding coefficient of 30 X.
Determinations for sweating, settling, compression strength and
embedding core temperatures were conducted in two cases : without
premixing of the different components, and with pre-mixing. The
results are given in Table 13.
With embeddings produced at a slow mixing speed, an ogive-shaped
crack occured when the embedding was cut open.

D. C onclusions
Tests on low-activity ash and phosphate ash did not change the
previous conclusions in any way.
For a ashes, a matrix has not been chosen. Thes will depend on
the specifications concerning the interim storage and underground
storage of the packages. Other factors should also be taken into
account, such as : the type of container, biodegradation of the
matrices, gas discharges caused by biochemical phenomena.
An economic point of view shoul also be given along with the
technical aspects : the cost and the ease with which the procedure can
be used should also be taken into consideration.
 113

Hydrothermal Solidification of
Incinerator ashes

Y.Nakamori,S.Kamada,Κ.Mori and Y.Hashizaki

Nuclear Energy Systems Division

Mitsui Engineering ft Shipbuilding C o.,Ltd
5­6­4 Tsukiji C huo­ku Tokyo 104 Japan

M.Yamasaki
Kohchi University

Summary
Hydrothermal Solidification System has advantages of
higher volume reduction ratio, better characteristics of
the solidified product, and simplified solidification
plant concept. It seems to be most suitable for ash
solidification. This paper shows the summary of Mitsui
Engineering and Shipbuilding C o.,Ltd(MES)'s activities in
developing and establishing the technology.

1. INTRODUC TION
Basic principle of Hydrothermal Solidification is derived
from the production mechanism of natural aqueous rock such as
sandstone or mudstone. When inorganic powder­like waste such
as incinerator ash mixed with alkaline aquae is kept under
hydro­ thermal condition, synthetic rock is produced in a
short time.
In our Hydrothermal Solidification System, radioactive
waste such as incinerator ash, pyrolysis product of spent
solvent etc., mixed with alkaline aquae, is fed into the
cylindrical reactor, compressed by hydraulic press, and heated
up with external electric heater. Solidification conditions
are ;
Temperature ; ab.SOOT)
Compression pressure; ab.30MPa
Reaction period ; ab.30minutes
Major advantages of the system are;
a) Higher volume reduction with minimum required additives.
b) Homogeneous solidified product.
c) Lower reaction temperature.
d) Better characteristics of the product.
e) Simple plant configuration.
We started our development work in 1983, and since then
bench scale test and pilot scale test have been carried out.
Full scale mock­up test plant is now under construction and
overall plant feasibility test will be carried out from this
April.
During these tests , we have clarified basic character­
istics of solidified product especially in such as leaching
rate of radio nuclides, and based on the test results, we are
convinced that our Hydrothermal Solidification Product will be
compatible with the comming Japanese deposition criteria for
LLW which is now under preperation. We have finished the study
of basic plant design, and are ready to supply actual
solidification plant according to the requests.
In the following chapters, detailed explanation of our
study and activities are shown.
 114
2.HYDROTHERMAL SOLIDIFICATION
Basic Principle
Generally, condition where water exists at above 100°C is
called as "Hydrothermal Condition", and chemical reactions
which proceed under hydrothermal condition are called as
"Hydrothermal Reactions".
When inorganic powder-like waste such as incinerator ash
is mixed with alkaline aquae,after thousands of years,it is
converted into rocklike product by dissolution and deposition.
In the nature,aqueous rock such as sandstone or mudstone is
made through above mentioned reactions after extremely long
time under the layer. If such mixture is kept under hydro-
thermal condition these phenomena is much accelerated and
synthetic rock is produced in a short period.
Hydrothermal Solidification is to change the inorganic
particles such as ash into rocklike solidified product by the
hydrothermal reaction under high temperature and high pressure
condition. (See Fig.1)
In our Hydrothermal Solidification, incinerator ash which
is mainly composed of S1O2, AI2O3, Fe2 0i, is mixed with small
amount of alkaline aqueous solution fed into the cylindrical
reactor, compressed by hydraulic press,and heated up with
external electric heater. Solidification conditions are;
Temperature ; ab.BOOT)
Compression pressure; ab.30MPa
Reaction period ; ab.30minutes
Under these condition, dissolution reaction of the
components such as SiO2 and AI2O3 is accelerated by hydrolysis
and neutralization with alkali, then these materials form a
deposit matrix,the basis of which is homogenious crystaline
silicate. (See Fig.2)

Outines of the process;

Fig.3 shows the schematic process flow diagram of the
Hydrothermal Solidification.
a) If the ash condition is not so good,that is content of
coarse materials or metal parts is rather high, addition
of silica powder is necessary.
After addition with an appropriate amount of additives
the waste is blended by being stirred in the mixer while
being sprayed with a prescribed amount of alkaline aqueous
solution as solidificiation activating agents.
b) Mixed waste is then fed into the reactor cylinder where
it is compressed at about 30 MPa with press while being
heated up to about 300Ï by use of the heater. It is held
in this hydrothermal condition for about 30 minutes, then
the material is turned into a solidified form.
c) After cooling, the solidified product is taken out off
the cylinder, charged into a drum and is conditioned
finally for disposal.
Hydrothermal Solidification can be applied to wide
variety of the radioactive waste, as long as the waste is
mainly consist of inorganic powder such as SÌO2, AliOietc..
Therefore, following waste can easily be solidified without
the silicate additive.
a) Incinerator Ash
b) Spent ceramic fiber
c) Spent asbestos
 115

Hydrothermal]
.Conditions^

Incinerator High Pressure

Ash High T e m p e r a t u r e

Solidified

| Water |
+ | N aO H| Acceleration
Product

of Reaction

Fig.l Principle of Hydrothermal Solidification

Incinerator ash

_L
Mixing w i t h alkaline solution
Piston rod

Λπ
J c
Gland packing
Filling to cylinder

Piston _L
• .* ' Pressing
Material for solidification

';·!■ Cylinder
Heating

_L
] c
Cooling
]
Removing from cylinder

Solidified body

Fig.2 Basic S o l i d i f i c a t i o n Co ncept

Ash Additive NaOH

m Press

Heater
π
Solidified
Product

/
Cylinder
Π 0I
L J C
Feeding Hot-pressing Removing Canning

F i g . 3 S o l i d i f i c a t i o n Process
 116
d) Spent silicagel
e) Spent solvent pyrolysis product
In addition, dried residue of concentrated waste can
also be solidified with certain amount of silica powder
additive.
Major advantages of the process;
Based on the above mentioned basic principle, the Hydro-
thermal Solidification has many outstanding advantages
compared to cement solidification system or melting system.
a) Higher volume reduction;
Hydrothermal solidification utilizes ash itself as a
solidification matrix, therefore basically no additive
except alkaline solution is necessary. Volume reduction
ratio from ash to solidified produt is expected to be more
than 6.
b) Homogeneous solidified product;
In the system,homogeneously mixed waste is solidified,
therfore, solidified prodcut is also homogeneous and it
will be applicable for the expected disposal criteria.
c) Lower reaction temperature;
Hydrothermal reactions is completed under the temperature
of up to 3 5 0 ^ which is far below to the melting process.
Therefore, usual steel material can be applied to the
reactor cylinder, no significant consideration for
disintegrity of structure is required and no emission of
volatile nuclide from the waste solidified product is
expected. This characteristics will reduce the plant
construction cost, especially in avoiding the off gas
purification devices.
d) Better characteristics of the product;
During our development, it is confirmed that hydro-
thermally solidified product has higher mechanical
strength, higher resistance characterisics toward weather,
radio active circumstances, and lower leaching
characteristics of radio nuclides. So, it will easilly be
applied for the disposal.
e) Simple plant configuration;
This system is not necessary to have the complexed ash
pretreatment such as shredding and grinding, and off gas
treatment from the reactor. Stable batch-wise operation
can be achieved without any complexed ash feeding or other
system.
 117
3.CURRENT STATUS OF DEVELOPMENT
Technical development programs;
Our development programs for Hydrothermal solidification
are summarized in the listing of Fig.4, and the following is a
total lineup of testing facilities on hydrothermal
solidification which are used in the development,
a)Bench scale testing device;
Cylinder sizes; I.D. 20 mm and 30 mm χ H 50 mm
Press rating; 10 ton
Number of units; 2
b)Engineering scale testing device;
Cylinder size; I.D. 50 mm χ H 100 mm
Press rating; 50 ton
Number of units; 2
c)Prototype testing device;(See Fig.5,6)
Cylinder size; I.D. 180 mm χ H 360 mm
Press rating; 100 ton
Number of units; 1
d)Full­scale testing device;
Cylinder size; I.D. 250 mm χ H 400 mm
Press rating; 200 ton
Number of units; 1
Characteristics tests of incinerator ashes;
Using the above devices, various kind of tests were per­
formed, by using various types of simulated waste and hot
active ashes in order to determine their characteristics in
hydrothermally solidified form.
a) Simulated incinerator ashes
b) Mitsui Juelich incinerator ashes
c) Radioactive incinerator ashes(hot) from laboratory
These tests consist of the following items;
a)External appearance and internal inspections
b)Specific gravity and mechanical strength tests
c)Leach resistance test
d)Weathering test (heat cycle test), Radiation resistance
test, water resistance test and Thermal resistance test.
During the development, we expanded the target waste from
the ash from the incinerator in the power station, to the
various kind of waste from the reprocessing plant.

Fiscal Year
Items
'83 '84 '85 86 '87 88 89 '90 91
• Basic Reserch
• Engineering Scale Test (Cold)
• Engineering Scale Test (Hot)
• Prototype Test (tf>180mm)
• Prototype Test («250mm)

• Application to The Waste

Irom Reprocessing Plant
• PNC TRP
• JNFS Shimokita JRP

• Full Scale Mock­Up

Test Plant

Fig.4 Development Schedule

Fig.5 Prototype Test Device(I.D.180mm)

-!<**'"■ „■'/■**■

Fig.6 Solidified Product(O.D.180mm)

 119

4.CHARACTERISTICS OF HYDROTHERMALLY SOLIDIFIED PRODUC T

Overall characteristics of the solidfied product is
summarized in the Table 1.
Specific gravity and mechanical strength;
As hydrothermally solidified, the incinerator ashes range
in specific gravity from about 1.8 to 2.0. Their compressive
strength is more than 300 kg/cm­. These characteristics does
not significantly vary, and remained about the same, between
the specimens solidified in the bench scale test, engineering
scale test and those from the full scale(I.D.180 mm) test.
Resistance to the circumstance;
The solidified product showed favorable resistance to
weather,radiation and water. Changes in their specific gravity
and mechanical strength before and after the 300 cycles of
heat test were small enough to ignore, as well as the C o­60
irradiation at 10'Gy(10"Rad) and the waterproof test of 100
days.
Leach resistance;
To evaluate the characteristics of the product to with­
stand tentative and/or long­term storage, leaching test were
conducted. The nuclides used in these tests are cesium,
cobalt, strontium,ruthenium and cerium. The test methods used
are duly consistent with the IAEA,MC C and ANSI methods,
a)Radioactive incinerator ashes,­
Leaching tests were conducted according to the IAEA
method. Leach rates of bUCo and157C s were measured with
leachant of hydrothermally solidified radioactive incine­
rator ashes, with borosilicate glass as additives used in
varying amounts.
In the case of ''"Co, most of the leachates were below the
analytical limits. Leach rates are, therefore below
5 χ 10 ''g/cnr' day .
In the case of 1,7 C s, as shown, leach rate of the solidi­
fied product containing 15 wt% of borosilicate glass is
about 1 χ 10 "g/cnr day. (See Fig.7)

Table 1 Major C haracteristics of the Product

Item Test method Results

External/internal
Visual and SEM microscopy Homogeneous rocks
inspections
Sp. gravity mechanical Dimensions, weight and
ab.1.9/gt.300kg cm 2
strength compressibility meas'ed

Weathering test Heat cycles of—10 to 30'C

No adverse effect
per 8hrs.x300times

Radiation resistance test " C o irradiation at 10° Gy

No adverse effect
(10e Rad)

Leach resistance test (IAEA, MCC & ANSI) 10"5g cm 2 day

 120
b) Simulated ashes,­
Leaching tests were made in accordance with ANSI/ANS­16.1
specifications ­the method recommended by the U.S. Atomic
Energy Society. The size of specimen us ed in these tests
are 20 mm in I.D. and about 20 mm in he ight. The tests
comprised of a cold leaching test using ruthenium and
cesium as tracer and a hot leaching tes t using 10, Ru, ,,7 C s
and' i9Ce as RI tracer.
Fig.8 and Table 2 shows the test resul ts. From the
results, superior characteristics of leach resistance is also
confirmed.Followings are the determination of Leachability
Index in the ANSI method.

_ 1 10
Σ log(/5/D)
L=
10 1 η
L:The leachability index of nuclide
β : constantd.OcmVs)
D : effective diff usivity [cmVs]
a
D=TT
n/Ap
(At)n
an:activity released from the specimen
during leaching interval n.
A 0 : total activity of the specimen at the beginning

10" 10"
Radioactive Ash 60­Co Radioactive Ash 137­Cs
Addtive Content
O Owt% Addtive Content
Δ 15wt O 0wt%
η 30wt 7 10" Δ 15wt%
ν 50wt I I 30wl%
V 50wt%
ίο­
E
o
Ξ lo­

ier
ia i o ­

10" 3 5 7 9 11 13 15 17 19 21
TO" 8 t Leaching time (weeks)
3 5 7 9 11 13 15 17 19 21
Leaching time (weeks)

Fig.7 IAEA Results

 121

Ru-103

O 10 20 30 40 50 60 70 BO 90 XX)
Leaching time (days)

Cs-137

0 10 20 30 40 50 60 70 80 90 TOO

Leaching time (days)

Fig.8 ANSI Results

Table 2 Summary of ANSI Test

Amount of
Nuclide Leachate Leachability
per Specimen index

Ru 0.1 gRu as Ru oxide 12.9

Cs 0.18gCsas Cs salt 12.7

103 0.19MBq
Ru 15.3
1
37„ 0.19MBq 13.4
Cs
139^ 0.26MBq 16.2
Ce
 122

5. OVERVIEW OF THE SOLIDIFICATION PLANT

Based on the results of bench scale and pilot scale test,
we started the basic design work of the actual ash solidifi-
cation plant. In the study, we applied following design
conditions.
a) Solidification plant is connected to single radioactive
incineration plant.
b) Capacity of the incineration plant is 100-200 kg/h.
c) Ash from the incinerator is solidified every next day.
d) Solidification operation shall be finished during day
time.
e) To avoid radiation exposure, fully remoted operation
except maintenance work shall be applied.
f) Complexed ash pre-treatment shall be avoided.
According to the design conditions, we clarified the
concept of the plant. Selected solidified product size is
200mm and 250mm in diameter, and 15 to 35kg ash can be
solidified every day. Required capacity of the hydraulic press
is 100 ton and 200 ton respectively. In the plant no special
ash pretreatment such as shredding and grinding or milling is
required, but separation of coarse material is only
neceessary. Followings are the necessary requirements toward
the ash;
a) Size of coarse material; L.T. 50mm in diameter
b) Contents of coarse material; L.T. 30%
c) Contents of unburnt carbon ; L.T. 10%
and metal parts can be accepted without any significant effect
on the characteristics of the products. The plant consists of
ash drum tilting device, ash receiving tank, mixer,
solidification unit including hydraulic press, product
receiving drum and its transportation unit, and other
auxiliary equipments such as filters and blowers, and overall
plant can be installed in the single process room which is
about 8mx8m in space and 10m in height.
Overall plant can be operated by single operator who is
sitting in the control room. All the necessary operation can
be done on the control panel observing the indicators,
recorders and ITV monitor. If required, fully automated plant
operation is also available.
In the course of test operation of our pilot scale test
rig, we have accumulated the necessary operational
informations, and these data are well applied to the
operational criteria of the plant. In addition, we have
constructed the full size, full scope mock-up test plant with
the support of Japan Nuclear Fuel Service Company Ltd. and
MITI. Using this test plant, we are planning to perform
operability test, reliability test and maintenability test of
the overall plant system this year.
 123

6.CONCLUSION
We have performed a series of development work on
Hydrothermal solidification process for the radio-active
incinerator ash.
Because of its out standing advantages of
a) Better characteristics of the product
b) Applicable for the expected disposal criteria
c) Simple plant concept
We are convinced that Hydrothermal solidification is the
most suitable for the radio-active ash treatment.
We have also performed the basic design work of the plant
and clarified the plant concept. We are ready to supply the
actual solidification plant according to the requests.
 124

CONDITIONING PROCESSES FOR INCINERATOR ASHES

A. JOUAN*, N. OUVRIER and F. TEULON

Commissariat à l'Energie Atomique

CEN-Valrhô,BP171
30205 Bagnols-sur-Cèze Cedex, France

SUMMARY
Three conditioning processes for alpha-bearing solid waste incineration
ashes were investigated and compared according to technical and economic
criteria: isostatic pressing, cold-crucible direct-induction melting and cement-resin
matrix embedding.

1 INTRODUCTION
Applied research in the area of conditioning solid alpha-bearing waste incineration ashes
has been conducted in recent years by the Commissariat à l'Energie Atomique under the
auspices of the General Directorate for Science, Research and Development of the
Commission of the European Communities. The objectives of this program have been to
enhance the quality of the finished product for long-term storage, and to ensure maximum
volume reduction.
Incinerable wastes taken into account for this study consisted of the following standard
composition: 50% polyvinyl chloride (glove box sleeves), 5% polyethylene (bags), 35% rubber
(equal amounts of latex and neoprene), 10% cellulose (equal amounts of cotton and cleansing
tissues). This mix corresponds to projected wastes from a future mixed oxide fuel fabrication
plant with an annual production of 100 metric tons. The conditioning unit will be required to
process 1700 kg (i.e. 5.7 m3) of ashes produced by the incineration facility each year.
Three ash containment processes were investigated and compared: isostatic pressing,
melting and cement-resin matrix embedding. An engineering study was also carried out by a
specialized department to determine the operating flow diagram and chronology, the resulting
plant layout and process control principles under nuclearized operating conditions. The
investment costs and annual operating costs were assessed.

2 ISOSTATIC PRESSING

Technical Overview
Compaction by high-temperature isostatic pressing involves applying multidirectional
pressure on a vacuum-sealed container filled with waste ashes. The feasibility of this process
was demonstrated with cylindrical stainless steel canisters of increasing diameters: 36 mm to
define the pressing parameters, 140 mm to assess the physicochemical properties of the
compacted ashes, and 300 mm to demonstrate industrial feasibility. Each cylinder was first
packed successively using a 100 MPa unidirectional press to an ash density of about 1.6 to
1.8 gem" 3 . The canister was then fitted with a lid and vacuum-sealed before proceeding with
the actual isostatic compaction process under a pressure of 150 MPa at 800°C, with a 2-hour
residence time for the 36 and 140 mm dia canisters, and 4 hours for the 300 mm dia canisters.
Examination of a cross section through the canisters showed that the ashes were
uniformly compacted. The physicochemical properties of the resulting material were
investigated. The compression strength and leaching resistance were highly satisfactory (see
comparative table in § 5 below).
A modified formula with a glass frit additive was investigated and found to be very
effective in increasing the density of the resulting product, but the greater complexity of the
process and severely deformed canisters outweighed this advantage.
 125

Process Schematic
The t\vo-part schematic (Figures 1 and la) indicates the major process equipment
requirements and the chronology of operations up to the constitution of the waste package.
The process was designed for 180 mm diameter canisters to allow the pressed products to be
placed inside the larger R7 canisters used for vitrified fission product solutions. Each R7
canister can accommodate two layers of three pressed ash containers. Fifteen working days
(i.e. 3 weeks) would be required on a 2-shift basis to process 1700 kg of ashes annually,
producing 86 compressed canisters occupying 15 R7 waste canisters.

shuttle container
dump station
to reusable filter candles

•«1% ­»­to reusable filter candles

storage
hopper

feed vacuum
hopper automatic |¡ne
filling —' welding
machine machine

ÜJ3¿ lAJrJEU
■"■■ ■" " '" .it lefrfihTf decontamination
canister entry P Kfilling
" ^ , ' ]lid welding] Lsealing / monitoring
+ seal weld cutoff
stainless!
steel
powder
filling

Figure 1 - ISOSTATIC PRESSING SC HEMATIC DIAGRAM

cell ventilation silica feed

system hopper

lid canister

Î
examination basket with " removal welding entry ­

isostatic & removal loading silica and removal

pressing installation

Figure la - ISOSTATIC PRESSING SC HEMATIC DIAGRAM

 126

Proposed Layout
The isostatic pressing process layout based on the preceding flowsheet is shown in
Figure 2.

section B B

section CC

0.0m

/.canister ¿filling Lsealing ¿.decontamination final

entry monitoring conditioning
isostatic _ 1
section AA pressing

Γ^3~"Ξ~ί^_"^Γ®"_1(5ΐίΡ)] t
. ·ι ι nrnross > ® ί welding control Β
control console,"I P [ ° ? e _ Ş , s . „ η — π & monitoring /
3
controllers]
welding

¥-
press control
& monitoring
T­H
+
pressinq control
GLOVE B OX
PERSPECTIVE VIEW
^ & monitoring

Figure 2 - ISOSTATIC PRESSING PROC ESS LAYOUT

3 COLD­CRUCIB LE DIRECT INDUCTION MELTING

The ashes can be melted without additives at 1300 or 1400°C , but greater process
flexibility is achieved by adding a primary glass.
Technical Overview
The objective is to form a new glass material from the primary glass and the waste ashes.
The two technical aspects of the problems are the primary glass composition and the
technological process.
Glass Composition
Two series of laboratory tests using ashes with silica (network former) and fluxing agent
additives demonstrated that ash vitrification was feasible, and that a primary glass additive is
preferable to allow easier melting and conditioning of ashes with different compositions,
ensuring at least minimal network formation while allowing the process to be implemented at
lower temperatures. Further testing will be required to specify the glass formula best suited to
the induction heating process, requiring a glass resistivity between 1 and 10 Ω cm at the
process temperature.
Technological Process
The direct induction melting facility comprises the following specific equipment items:
• the current generator (approx 10 000 V at 100-200 kHz);
• the furnace, comprising a cold crucible, an inductor and a casting system.
 127

The copper crucible is an assembly of independent water-cooled quadrants and is

transparent to the electromagnetic field. The resulting induced currents dissipate their energy
by Joule effect in the glass and ash melt batch.
Process feasibility was demonstrated by the SDHA at Marcoule using existing equipment
with a glass composition routinely used to vitrify fission product solutions. The operation
includes three major steps:
• First, the primary glass is melted to form the process heel, a routine step in glass melting.
• The ash and primary glass mixture is then added to the heel (the ashes melt readily and are
perfectly incorporated into the glass)
• The molten mass is cast when a suitable level is reached in the crucible.
Throughput rates of 15 or even 20 kgh" 1 were obtained in cold crucibles 35 and 55 cm in
diameter by melting airborne ashes from a domestic garbage incinerator together with 25-50%
previously formed glass.

Process Schematic
Figure 3 shows the chronological order of the operations and indicates the required
process equipment. A conditioning unit of this type would be operated two weeks a year in
three 8-hour shifts 5 days a week to process 1700 kg of ashes. It would produce a total of six
R7 glass canisters each year.

to reusable filter candles storage and

[eed hopper, off gas exhaust
shuttle η
container
dump , Δ )££> metering superheater
station ♦ ( Γ Η QQp \ 1) ? unit cold trap
hepa filter
to reusable demister
filter candles

cell
ventilation ·
system
melting
furnace

canister
°^ S 8^2

<$=*> ^=g ■<i—n' ,1 , ^ ^ Γ ■5=?

r ο: -> ­i.o ■
entry casting lid lid decontamination
Installation welding monitoring
Figure 3 - DIREC T-INDUC TION MELTING SC HEMATIC DIAGRAM

Proposed Layout
The direct induction ash conditioning process schematic implies the layout shown in
Figure 4.
 128

section CC
¡oooooo.

Λ
1

O.OOm
CL IJ] LíLiOEü
canister filling welding \ ,
entrv r^ .· . . Vdecontamlnation o.5m
12.75rn y ° section AA monitoring

furnace power,
supply
(HF generator) B ¡ |

BTC ■{ÆffeHEEM
process _ L , |—rJ7] r~~l GLOVE B OX

f
controllers ^""^ PERSPECTIVE VIEW
^ welding control
casting nozzle & monitoring
generator microwave
control j generator
console

Figure 4 - DIREC T-INDUC TION MELTING PROC ESS LAYOUT

4 C EMENT-RESIN MATRIX EMBEDDING

Technical Overview
This process ensures uniform embedding of ashes in a cement and thermosetting resin
matrix. Weighed quantities of ashes, cement, water, resin and hardener are mixed together,
and the resulting material is poured into 100- or 200-liter waste drums.
The results of compression strength and leaching resistance measurements on the
embedded material are indicated in the comparative table in § 5 below.
Process Schematic
The process chronology is indicated in the diagram (Figure 5) together with the
equipment requirements. Seven working days by two shifts would be necessary to condition
1700 kg of ashes in fourteen 200-liter drums.
 129

to reusable filter candles ­ cement storage hopper

shuttle container
dump station

hardener
storage
w^f^ft. to reusable filt?
­*­ candles and
vacuum line

water/hardener solvent tank

emulsion tank
storage hopper,
. metering mixing and
cell ventilation system. degassing tank

ini­IHhTTHGi Ι­Π­
•q n' ι 'u ty ι 'π π' 'a ' n' 'n ti'
entry casting lid installation ~ ° decontamination
and crimping monitoring

Figure 5 - C EMENT-RESIN EMBEDDING SC HEMATIC DIAGRAM

Proposed Layout
T h e proposed resin-cement matrix embedding facility is shown in Figure 6.

6.80m

drum 3.50m
entry­removal
decontamination
monitoring
ΓΙ"!
l
/ ,­'J ­­,M i g "¿4
J P l|af"18|| 0.00m

mixing^' filling J L_lid installation

installa
& crimping

control
console
IrnJJm
1m

GLOVE B OX
PERSPECTIVE VIE'
Figure 6 - C EMENT-RESIN EMBEDDING PROC ESS LAYOUT
 130

5 TECHNICAL AND ECONOMIC COMPARISON OF THE THREE PROCESSES

Technical Assessment
Two major parameters are compared in the following table:
• the final product quality, indicated by compression strength and leaching resistance
measurements;
• the volume reduction factor, (the ratio of the final product volume to the initial ash volume).

Technical Direct . ... Resin-

C ement
, , .. Isostatic .. . .
Parameters Induction n Matrix
Pressing
Melting Embedding
Mechanical C ompression
Properties Strength 100 MPa 100-200 MPa 65 MPa

Dynamic Mass loss

Leaching (g-cm^d-1) 2.16 χ IO"4 7.40 χ IO"4 12.72 χ 10 4
Resistance after 14 days

Final Product Volume* 1.1m3 2.8 m 3 3.1m 3

• corresponding to the annual ash volume of 1700 kg (i.e. 5.7 m3) of ashes

Table 1 - TEC HNIC AL ASSESSMENT

Except for the higher compression strength of the isostatically pressed material, the most
favorable results were obtained for cold-crucible direct induction melting; this product gave
better results for all three criteria than resin-cement embedding.
The comparative volume reduction is illustrated in Figure 7.
m3 „
5.7 m 3
6i / =

4
3.1 m 3

3 2.8 η ν

2
1.1 m 3
H

o
INITIAL ISOSTATIC MELTING RESIN­CEMÈNT
VOLUME PRESSING B EM EDDING
Figure 7 ­ COMPARISON B ETWEEN I N I T I A L * A N D CONDITIONED A S H V O L U M E S
(*ANNUAL INC INERATION FAC ILITY PRODUCTION VOLUME)

Economic Assessment
In addition to the final waste volume, the three processes were compared according to
the following criteria:
 131

layout volume (i.e. α containment volume): Figure 8 shows that the isostatic pressing facility
would require the largest floorspace and volume, while the other two processes have similar
layout requirements.
investment cost: Figure 9 clearly indicates the cost-ineffectiveness of isostatic pressing (due
to the prohibitive cost of the unidirectional and isostatic presses); the investment costs for
melting would be about 1.5 times higher than for embedding.
annual costs (including depreciation): Figure 10 again shows the cost handicap of the
isostatic pressing process; annual operating costs for the melting process would again be
about 1.5 times higher than for embedding.

ISOSTATIC PRESSING V ­ 144 m^

MELTING RESIN­CEMENT
V ­ 52 m3 EMBEDDING
V ­ 52 m3
Figure 8 COMPARATIVE LAYOUT VOLUMES
(a C ONTAINMENT)

MF
25­ 23.6 D equipment 1 process controllers
D equipment 2 support frame
alpha containment
20
D
D
equipment 3
container tilling
m
Eä others
E2 electricity Ξ overhead
M ventilation
15-
isostatic press

pipes/
10- valves/
effluents

mixer
mixer feeding
ISOSTATIC MELTING RESIN­CEMENT
PRESSING EMBED.
Figure 9 COMPARATIVE C APITAL C OST
 132

capital cost
direct labour
packaging
process materials
energy

1.23
0.76
v////////////////.'Şi*.

0-H
ISOSTATIC MELTING RESIN-CEMENT
PRESSING EMBEDDING

Figure 10 - COMPARATIVE TOTAL ANNUAL COST (MILLIONS O F FRANCS)

PRODUCT
PROCESS COST FEASIBILITY J^ TOTAL
QUALITY

HIP 1 1 2 2 6
Melting 2 2 3 3 10
Embedding 3 3 1 1 8

1: poor
2: satisfactory
3: very good

Table 2 - OVERALL COMPARISON

6 CONCLUSIONS
Despite the good quality of the finished product, the isostatic pressing process for ash
conditioning is heavily penalized by a containment volume 3 times larger and investment and
operating costs 3 to 4 times higher than for the other two processes.
Compared with the resin-cement matrix embedding process, cold-crucible direct
induction melting requires a similar layout volume and incurs investment and operating costs
about 1.5 times higher. Conversely, the final product quality is significantly better with
induction melting, and the final volume reduction is nearly 3 times greater (this parameter is
very significant in the case of a geological repository, and thus from an overall cost-
effectiveness standpoint).
In the final analysis (Table 2), on the basis of the four major criteria considered (cost,
feasibility, final product volume and quality) induction melting is the most favorable process.
 133

EPOXIDE SYSTEM TO BIND AND EMBED

RADIOACTIVE ASH

J.JAHCHAN, J-P.ROGER, M.ETIE\A\T

General Manager, Research Director, Technical Sales Director

Spado Lassailly SA
Gallardon, Erance

Summary
Radioactive ash, resulting from incineration of paper, rags and
other burnables that may have been exposed to radioactivity, need to
be bound and embedded for disposal. A mortar combining cement and
epoxy glue is used as a binding and embedding element for the ash.
The system combines the ability to drench and bind organic and
mineral particles, to control reactivity to limit exothermic heat
and to obtain adeguate fluidity for manipulation and casting in
drums. Spado tassailly has elaborated a resinhardener combination
which meets the required objectives, using for the resin a mixture
of three resins and for the hardener a controlled combination of
specific products of low reactivity.

Subject
Ashes resulting from incineration of wastes such as paper, clothes
and other material which may be contaminated from exposure to radioactive
products, must be treated in order to avoid any environmental contamina-
tion. The conventional process for such treatment of ashes is embedding
in an appropriate material.
In this process, the embedding material is a combined mortar of
cement and epoxy system. Ashes are homogeneously agglomerated by the
mixture of hydraulic cement with water and the expoxy system, which also
acts as a binding agent.
The binding epoxy plays an essential role in the hardening of the
concrete. The combined action of concrete and epoxy improve the mechani-
cal and chemical properties, as well as the stability of the whole system.

Object i ve
The embedding of ashes is considered accomplished when all the compo-
nents, that is : ashes, cement, water and epoxy system, give, after mixing
in the reactor, a perfectly homogeneous mass.
The required homogeneity implies that :
first: the epoxy system has an intrinsic binding capacity.
Second: the exothermic heat generated in the reactor during the
mixing process, by cross linking of the epoxy system, should be low enough
to avoid a thermal run away of the mass under treatment. If not, it will
produce a strong increase of water vapor tension which would perturb the
mass, affecting its homogeneity, leading to blisters and fissures on the
surface. The mechanical action of stirring, because of shearing, also
produces an increase of heat which will be added to the heat generated by
the exothermic reaction.
- The agglomerate must also be fluid enough to flow out of the
reactor for casting in drums.

The required qualities of the epoxy system

The epoxv system formed bv the resin and the hardeners must perfectly
fulfill a set of criteria resulting from the goals defined beforehand :
 134

- The system must be a drenching system, that is to say it must be able to

coat the whole of particles forming the mortar : ashes plus cement. Some
particles have an organic origin and others a mineral origin.
- The system must have a controlled reactivity in order to limit the exo-
thermic heat produced simultaneously by the epoxy system cross linking
reaction, the hydratation of the cement and mechanical stirring.
- The initial viscosity of the system must lead, at the end of the mixing
process, to an adequate fluidity of the agglomerate suitable for its
casting in drums.

Nature of the epoxy system

In view of the set of conditions defined, Spado Lassailly has elabo-
rated a resin-hardener pair defined by the following parameters :
1 ) Viscosity
The viscosity is directly related to the binding power and the agglomera
ting faculty. Our proposed system has a low viscosity : at 20 degrees
celsius, 15 poises for the resin and 20 poises for the hardener.
To obtain this low viscosity, we have selected the following process :
- For the resin part, we use a mixture of three resins, one of them acts
as adjuster of the final fluidity since this resin is very fluid.
- For the hardener part, we use a controlled combination which involves
specific products of low reactivity.
2) Wetting
Wetting is the fundamental factor of coating. It simultaneously requires
from the system, hydrophilic power in regard to the mortar, and a wetting
power in accordance with the superficial tension corresponding to the
average granulation of the ashes plus cement mixture.
In order to control the wetting during laboratory and industrial
runs, it was necessary to carry out various sgnificant tests, such as
checking of homogeneity by observation under binocular at a 20 times
magnifying power.
Specific observations were also made on :
. evolution of tint : a homogeneous tint is necessary for the whole mass.
. The occurence of sweating
. The optimum wetting was obtained by balancing the density : 1.1 for the
resin as well as for the hardener, incorporating appropriate surfactants,
specific to the epoxy system.
. Also contributing to appropriate wetting was the selection of hydrophi-
lic plasticizer.
3) Reactivity
Reactivity must be controlled at its peak (exothermic peak) and its
spreading.
The exothermic peak must be sufficiently below 100 degrees celsius
to prevent, in the reactor, any excessive vapor tension of water, and run
away of the reaction. A controlled slow reaction, and the subsequent
spreading of the exothermic curve, permits to avoid warm points in the
case of preferential streams and bad thermal conductivity, which is
essential to ensure regularity of the mixture.
During laboratory studies, thermic controls were done with a langa-
vant calorimeter (AFNOR standard) on 640 g mass of mixture. In this case
exothermic peak must not exceed 58 degrees celsius; in the tests the peak
was obtained in 12 hours. Industrial tests were carried out on 80 kilo-
grams of mixture, in this later case, the exothermic peak must not exceed
85 to 90 degrees celsius in k to 5 hours.
 135

We are in the case of an expoxy system of very low reactivity. This

low reactivity was obtained by :
­ the use of a low reactivity resins, one of them being very resilient
epoxy number of the resin is 180 to 190 g mol
­ the use of very slow imires an ine number Γ ^8 t 3 0 m g K H g
­ the introduction of adduct also permits lowering significantly the exo¬
­­ermic peak, and t o control it.
4 C asting
By casting we refer to the ability of the final agglomerate to easily
flow out the reactor and be handled. This property is related to use si­
ty,
obtained by adding a specific plasticizer.
b Mechanical strength
The mechanical strength is in fact the resultant of homogeneity and harde­
ning capacity of the obtained epoxy concrete.
The control of mechanical strength was realized with the following
laboratory hardness tests :
Hardness SHORE D of the agglomerate : 65
In a general manner, controls of the parameters explained above were
realized in close cooperation with the C EA Laboratory at C adarache.

fhe experience of Spado Lassailly in the formulation of epoxy systems and

unking of hardeners allows us to find solutions for a number of such
applications, adapted to specific technical requirements, including this
case of a very low reactivity system for application to a casting system
mass.
for example, we have been asked to resolve other similar problems
concerning the treatment and conditionning of wastes such as ionic
exchange resins or others.
System:; put in place have required the elaboration of a precise
definition of objectives and requirements between the manufacturer, Spado
lassailly, and our customer. Moreover, we have also elaborated and put
to work a charged epoxidic system which is mixed and distributed by an
automatic chain in a confined zone.
We also formulate other mixed systems like epoxy tars that may
eventually contain various mineral charges or metals such as lead or
others.

Quality control
Of course, Spado Lassailly controls all the elements involved in
fabrication, from the reception of raw materials to the final product,
including all intermediairy steps of the production process.
Standard controls used are the AENOR standards. Each batch of
fabricated product receives an identification card conformed with
standards.
 Session IV
DECONTAMINATION PROCESSES FOR ALPHA ASHES
B. HUNT (JRC) AND G. NAUD ( C E A / C A D )
 139

TREATMENT OF PLUTONIUM CONTAMINATED ASHES

BY ELECTROGENERATED Ag(ll) :
A NEW, SIMPLE AND EFFICIENT PROCESS

C. MADIC, J.L. SAULZE, J. BOURGES, M. LECOMTE

and G. KOEHLY

CEA/DCC/DPR
Centre d'Etudes Nucléaires de Fontenay-aux-Roses
BP n ° 6 92265 FONTENAY-AUX-ROSES, FRANCE

Summary
Incineration is a very attractive technique for managing
plutonium contaminated solid wastes, allowing for large volume and
mass reduction factors. After waste incineration, the plutonium is
concentrated in the ashes and an efficient method must be designed
for its recovery. To achieve this goal, a process based on the
dissolution of plutonium in nitric solution under the agressive action of
electrogenerated Ag(ll) was developed.
This process is very simple, requiring very few steps. Plutonium
recovery yields up to 98 % can be obtained and, in addition, the
plutonium bearing solutions generated by the treatment can be
processed by the PUREX technique for plutonium recovery. This
process constitutes the basis for the development of industrial
facilities : 1) a pilot facility is being built in MARCOULE (COGEMA,
UP1 plant), to treat active ash in 1990 ; 2) an industrial facility will be
built in the MELOX plant under construction at MARCOULE (COGEMA
plant).

1. INTRODUCTION
The incineration of solid plutonium contaminated waste generates ash
with various compositions containing almost all the plutonium. Plutonium is
present in the ash in chemical form(s) particularly difficult to dissolve with
conventional processes. Nitric acid dissolution, for example, is inefficient.
Using mixtures of HNO3 and HF at boiling temperature, (10 M HNO3, 0,2 to
0,6 M HF) plutonium dissolution can be achieved (1,2). Ash treatment by
concentrated H2SO4 at elevated temperature is also feasible (3). The major
drawback of these processes is the generation of effluents containing
agressive agents, such as F" and SO4 2 " ions, which are difficult to manage.
An alternative to these techniques can be found by the use of a non
permanent agressive reagent. To this respect, electrogenerated Ag(ll) is
ideal ; it was already found suitable for the dissolution in nitric acid solution
of impure batches of PUO2 (4,5).
The application of this technique to the treatment of plutonium contaminated
ash was developed in collaboration with COGEMA, MARCOULE (6). The
aims of the research were to optimize the different steps of the process in
order to design simple and compact facilities. The main achievements of this
work are presented briefly in this paper.

2. RESULTS AND DISCUSSION

Plutonium containing ashes
Three different batches of plutonium containing ash, amounting to a
total of more than 6 Kg and placed in 8 different boxes, were obtained from
 140

UP1 MARCOULE, COGEMA as part of cooperation for the development of

this process. The main properties of these ashes are listed in the Table I.
COMPOSITION
mass of PLUTONIUM cr SÌO2 C
Sample ash in
No. individual mass (g) % % % %
box (g) (gamma) (neutron) (mass) (mass) (mass) (mass)
764.2 24.9 26.8 3.4 6.7 13 1.5
1 868.9 26.8 28.3 3.2 6.7 13 1.5
508 7.08 1.4
2 834.2 33.9 20.1 2.4 to 4.0 6.7 40 0.4
804 26.4 22.2 3.0
859.2 21.7 21.3 2.5
3 916.1 20.4 31.1 2.2 to 3.4 18 29 1.1
604.3 13.0 16.2 2.4

Table I Plutonium containing ash used in the study

(informations provided by UP1 COGEMA,
Marcoule, producer of the ash)

The plutonium content found is close to 3 % by mass. Moreover, the

compositions in major constituents can change significantly : for example,
the S1O2 ash content is 13 % in sample 1, 40 % in sample 2 and 29 % in
sample 3.
The chloride ion content of the ash must be stressed : this is a very
important parameter when developing a process based on the use of silver
nitrate solution. The presence of high chloride content in the ash is may be
due to te incineration technique used in the UP1 incinerator in which the
solid plutonium wastes are burnt directly in air.
The ash has the appearance of a grey powder containing large particles (up
to several millimeters).
Mechanical pre-treatment
The ash must be ground to extend the area of the ash to be leached
by aqueous solution, thus increasing the rate of the chemical operations. It
was demonstrated that it is not necessary to obtain very fine particules : the
maximum particle size compatible with efficient use of the process is 1 mm.
Chemical pre-treatment = chloride ion removal
Prior to treatment by electrogenerated Ag(ll), the chloride ion must be
removed from the ash. Two methods were investigated : 1) leaching of the
ash with water or nitric acid solution, 2) leaching of the ash by HNO3 and
elimination of chloride ion by electrooxidation to CI2 and removal by air (or
N2) flow.
Table II shows the results obtained after ash leaching tests. The mixture
(ash + solution) must be stirred at least one hour to obtain a constant
chloride concentration in the leachate. The CI" leaching efficiency, calculated
using the initial CI" ion content determined by COGEMA (6.7 % by mass),
was moderate in all the tests. The best result corresponds to test No 5 with
a CI" ion removal efficiency close to 72 % for a one hour stirring. It may be
observed that this efficiency rises with increasing HNO3 concentration.
This technique is not suitable for process development due to the poor CI'
removal efficiency and need to separate the leachate from the pulp before
treating the solid by electrogenerated Ag(ll). Its development was
accordingly discontinued.
Chloride ion removal can be achieved efficiently by a new process based on
nitric acid leaching of the ash and elimination of CI" from the mixture by
 141

electrolytic conversion to CI2 and dilution in an air (or N2) flow. The
oxidation of CI" can be written as follows :
CI" ­ 1/2 Cl 2 + e (Eo = 1,36 V/ENH).

Test No. 1 1
3 4 5 6 7
Ash, mass (g) 10 10 10 10 10 10 20
Leachant Type H2O H20 H20 HNO3 HNO3 HNO3 HNO3
0.2 M 0.5 M 4M.
4 M
Volume
(ml) 100
0.113*" 0.121*"
Leachate CI" 0.107" 0.107* 0.08* 0.132* 0.224*
content (M) 0.116* 0.136*
Ci' leaching 60** 64.3**
efficiency 56.9* 56.6" 42.4* 69.9* 59.3*
(¡η %) 61.3* 71.9'

Agitation time : *= 1 h
·* = 30 mn
Table II : C hloride ion removal by ash leaching.

It can be performed directly by electrolysis on an anode, or by using an

electrochemical mediator possessing higher formal potential than 1.36
V/ENH.
A study was conducted to opti­
mize several parameters presumed
to have an influence on CI" ion
removal by electrolysis, such as
the IM2 flow rate, the temperature
of the mixture, and the type and
concentration of electrochemical
mediator.
The N2 flow rate is not a critical
parameter for the efficiency of the
process, and one can be develo­
ped with a moderate value for this J I I L
0 10 20 30 40 50 60 70 80 90 100
parameter. On the contrary, tem­
perature is an important factor. At Time of electrolysis (minutes)
elevated temperature, the solubi­ Conditions: Anolyte = 100ml ΗΝ03 = 4Μ
lity of CI2 in nitric acid solution is HCl = 0.1M
low and the faraday efficiency Catholyte = 5ml HN03 = 11.3M
rises due to the increase of the CI" Anode: Pt screen = 10cm2
ion diffusion constant. Figure 1 il­ I = 0.5A
lustrates this behaviour ; it shows Fig. 1 REMOVAL OF CI" BY ELECTROLYSIS = EFFECT
the kinetics of CI" ion removal by OF TEMPERATURE
electrolysis and N2 sparging at
two different temperatures, 50 and 8 0 ° C . At the beginning of the
electrolysis the faraday yield is close to 0.9 and decreases with time.
Tests were performed of the potential efficiency of the following
electrochemical mediators
Mn(VII)/Mn(ll) Eo = 1,507 V/ENH
Ce(IV)/Ce(lll) Eo = 1,61 V/ENH
Co(lll)/Co(ll) Eo = 1,82 V/ENH
 142
?r
Only the presence of cobalt ion " *A ' ^
was found to be beneficial. The
presence of Mn(ll) and Ce(lll),
by contrast, induces a drop in
the efficiency of CI" removal by Ζ 10"'­
electrolysis. Figure 2 shows the
effect of the presence of cobalt
ion on the kinetics of CI" ion
removal by electrolysis.
It may be observed that the ef­ J I I I I I I I L
ficiency of the electrochemical 0 10 20 30 40 50 60 70 BO 90 100
mediator depends on its Time of electrolysis (minutes)
concentration. To secure an
Conditions: Anolyte = 100ml HN03 = i.M HCl = 0.1M
important advantage in time, Co = 0 à 0.5M
the concentration of the media­ Catholyte = 5ml HN03 = 11.3M
tor needed is fairly high. This is Anode: Pt screen=10cm2
a major drawback because of I = 05A 0 = 50°C
the increase in metallic salts to Fig. 2 REMOVAL OF CI" BY ELECTROLYSIS INFLUENCE
be conditioned. Thus the addi­ OF THE PRESENCE OF Co IONS
tion of Co ¡on to decrease the
time needed for CI" ion removal
by electrolysis is not recom­
mended. To obtain a similar
effect it is preferable to raise
the temperature of the mixture
during electrolysis.
This technique was applied
successfully to treat large
samples of plutonium
containing ash. Figure 3 shows
the kinetics of CI" ion removal
0 30 60 90 120 150 180
during this treatment. After
Time of electrolysis (minutes!
three hours of electrolysis with
a current of 80 A, CI" ion Conditions: Anolyte = 61 HN03 = 4M
HjPO ; = 0.1M (courbe 11
removal efficiencies higher than
Catholyte = 100ml HN03 = 11.3M
99.5 % were obtained. Anode: Pt screen=1000cm2
Electrogenerated Ag(ll) I = BOA θ = 45 à 60°C
treatment : plutonium
dissolution Fig. 3 ■ REMOVAL OF CI" BY ELECTROLYSIS = RESULTS
OBTAINED WITH TWO BATCHES OF PLUTONIUM
The study of the solubili­ BEARING ASHES
zation of the plutonium contai­
ned in the different ash batches, in nitric acid solution under the agressive
action of electrogenerated Ag(ll), was conducted at different scales,
between 25 g and 916 g of ash per experiment. Electrochemical treatment
was carried out using three different electrolyzers. The largest, with a total
capacity of about 7 litres, was previously designed for the dissolution of
large PuC>2 batches. Figure 4 shows the solubilization kinetics of Pu and Am
contained in a batch of 150 g of ash.
Plutonium is solubilized in three steps : 1) before electrolysis about 13 % of
the plutoniun is dissolved by simple HNO3 attack, ­ 2) the beginning of elec­
trolysis causes a sharp increase on Pu in solution, ­ 3) the rate of Pu solubili­
zation gradually decreases with time. For 2 4 1 A m it may be observed that its
dissolution curve is homothetic to that of plutonium, after nitric acid
 143

attack causing preferential solubilization of 2 4 1 A m , the dissolution behaviour

of Am is conditioned by that of the plutonium compound(s).
The essential part of the study
was devoted to reducing the time
required to complete achievement
of the second phase of Pu dissolu­
tion. It was found that to increase
the Pu dissolution rate, it is
necessary to define the best
conditions of Ag(ll) electrogenera­
tion. This is understandable since
a large share of the ash must be
oxidized by Ag(ll).
After optimization of all the para­
meters of the process, experi­ 2 i. 6 β 10
ments were performed using large Time of electrolysis Ihours)
batches of ash. For example, Conditions: Mass of active ashes = 150g
figure 5 shows the treatment of a Granulometry £ 1mm
batch of 809 g of ash in optimal Anolyfe: HN0 3 =i.M
conditions. The ash was dispersed AgN0 3 =0.036M
in 6 litres of 6 M nitric acid Anode: Pt screen=100cm2
containing 0.11 M AgNOß. The I = 5A θ = 25°C
electrolysis current was 80 A and t: start of the electrolysis
the temperature was maintained at Fig. I ­ KINETICS OF THE SOLUBILIZATION OF Pu AND Am
30°C during the experiment. The FROM 150g OF ACTIVE ASHES UND ER THE ACTION
OF ELECTROGENERATED Agili)
plutonium was dissolved in three
steps: 1) before starting electroly­
sis, about 20 % of the plutonium
dissolves under the simple action I 1 L ­ t . L k

of HNO3, ­ 2) after starting elec­ •

trolysis, the Pu dissolution yield
rises rapidly to nearly 80 % after
two hours, 3) the last step corres­
ponds to slow Pu solubilization ;
nevertheless, after 5 hours more,
75

50
-f
1
­

­
the Pu solubilization yield was •
98 %. 25 7 ­
After ash treatment by electroge­ 1
nerated Ag(ll), most of the solid is 0 2 K 6 8 10 12 14
dissolved, leaving only 35 to Time of electrolysis Ihours)
40 % of the ash mass in the solid Conditions: Mass of active ashes = 809g
part of the pulp. This solid residue Anolyte = 61 HN0 3 =i.M
contains silica which must be AgN03 = 0.11M
separated from the plutonium dis­ Temperature= 30°C
solution liquor by filtration. This Current = 80A Voltage = 9V
step is one of the most critical. Stirring = 750RPM
After separation, the solid must be Fig. 5 ■ KINETIC OF Pu D ISSOLUTION FROM B09g OF ASHES
washed by dilute nitric acid to REALIZED IN A PILOT SCALE ELECTR0LYSER
remove residual plutonium solu­ (optimized conditions)
tion.
Plutonium exists in the dissolution liquor in the form of Pu(VI) and must
therefore be reduced to Pu(IV) before its recovery by the PUREX process.
This can be achieved by NO x or H2O2 treatment.
Optimized parameters and conceptual flowsheet
 144

Table III lists the

STEP OPTIMIZED PARAMETER
optimized parameters
corresponding to the dif- Grinding Particle Size ^ 1 mm
ferent steps of a process Electrolyzer
for the treatment of Pu Volume : used (1) 4.5*
containing ash by elec- total (1) 7.5*
Electrodes: anode type Pt screen
trogenerated Ag(ll). It surface(cm ) 1000*
includes information cathode type Ta hollow tube
surface(cm ) 180
concerning the electroly- Separated compartment aluminum silicate
zer to be used for CI" ion
removal by electrolysis CI" removal by electrolysis
anolyte : type 6 M HNO3
and Pu solubilization volume (1) 4*
under the action of catholyte : type II.3MHNO3
Ag(ll). Current (A) 80*
Temperature (CC) 50 to 60
Figure 6 shows concep- Time (h) S 3
tual flowsheet for the Pu Solubilisation by Ag(II)
treatment of plutonium Anolyte : type 6 M HNO3 ; 0.1 M AgNOj
bearing ash by electroge- volume (1) 4*
catholyte : Type II.3MHNO3
nerated Ag(ll). It com- flow rate (ml/h) 150*
prises eight different Current (A) 80
steps : 1) grinding of the 0 (A/cm2/MAg) 0.8
Temperature (°C) (30 + 10)
ash ; 2) CI" ion removal Time (h) 6 to 7
by electrolysis and dis-
Filtration maximum retention of
solver off gas treatment ; liquid = 10%
3) Pu solubilization by
Pulp washing
electrogenerated Ag(ll) ; solution : type 0.1 M HNO3
4) separation of the Pu volume (1) 4*
bearing solution by filtra- Filtration maximum retention of
tion ; 5) pulp washing by liquid - 10%
dilute HNO3 ; 6) filtration
Pu valence adjustment NOjt or H2O2
to separate the solution addition
from the pulp ;
7) concentration of the ' Parameters normalized for treatment of 1 kg of ash
plutonium solutions ; and
Table III Optimized parameters for treatment of Pu bearing ash by
8) Pu valence adjustment electrogenerated Ag(ll)
to Pu(IV).

3. CONCLUSION
The treatment of plutonium bearing ash by electrogenerated Ag(ll) is
an efficient process in the laboratory for experiments performed with ash
batches up to 916 g.
Plutonium solubilization yield closes to 98 % can be routinely obtained with
reasonable treatment time : ranging from 6 to 7 hours. About 60 % of the
ash mass dissolved in the nitric acid solution with the plutonium. The remai-
ning solids, essentially S1O2, must be removed and washed. One of the main
advantages of the process is the nitric acid nature of the plutonium bearing
solutions, compatible with the PUREX process for Pu recovery.
For ash with high CI" ion content thorough pre-treatment is necessary to
remove CI" ion. This can be done by electrooxidation of CI" to CI2 followed
by N2 sparging.
This process will be applied shortly in the facility built in the UP1 plant and
in the MELOX plant under construction at MARCOULE.
 145
(ASHES) DOC
treatment

\
Cl lon Pu solubilization
Grinding removal by by Filtration Pulp Filtration Pulp
electrolysis clectrogencrated washing to be
Ag(II) conditioned
1
" 'solutioη 'solution

A
/
1 concentration!

Pu
valence to Pu recovery
adjustment by PUREX

Figure n°6 : C onceptual flowsheet for the treatment of Pu bearing ashes by electrogenerated Ag(II)

REFERENCES
(1) RYAN,J.L, B RAY,LA. (1980). Dissolution of plutonium dioxide. A
critical review ­ in Actinide Separations, ACS Symposium Series 117,
NAVRATIL.J.D. and SCHULZ.W.W. (Eds) American Chemical Society,
Washington D.C. ρ 499.
(2) LEC0MTE,M., B OURGESJ. and MADIC,C. (1987). Applications du
procédé de dissolution oxydante du bioxyde de plutonium ­ in
Proceedings of the RECOD 87 Conference, vol.1 ρ 441 ­ SFEN Editor,
Paris.
(3) G0MPPER,K. and WIECZOREK.H. (1990). Recovery of plutonium from
incinerator ashes by nitric/sulfuric acid ­ in this conference ASHES 90.
(4) B OURGES,J., M A D I C C , KOEHLY.G. and LECOMTE,M. (1986).
Dissolution du bioxyde de plutonium en milieu nitrique par l'argent II
électrogénéré. J of the Less Com. Met ­ 122, 303, 1986.
(5) B RAY,L.Α., RYAN,J.L. and WHEELWRIGHTS.J. (1987). Electro­
chemical process for dissolving plutonium dioxide and leaching
plutonium from scrap or wastes. Aiche Symposium Series 254, vol.83
ρ 120 (1987) American Institute of Chemical Engineers New­York,
NewYork 10017.
(6) CAUQUIL,G., SOMMI,J. and B RESCHET,C. (1990). Plutonium
recovery from ashes of the alpha incinerated wastes of the Marcoule
reprocessing plant, (1990) ­ in this Conference ASHES 90.

ACKNOWLEDGMENTS
The work described in this paper was partially funded by the Commission of
the European Communities under the Third E.C. Programme On Management
and Disposal of Radioactive Wastes, 1985­89, Group Task No. 2, contract
FIW/0013.
 PLUTONIUM RECOVERY FROM INCINERATED ALPHA-BEARING WASTE ASHES
AT THE MARCOULE REPROCESSING PLANT

G. CAUQUIL, J. SOMMI and C. BRESCHET

COGEMA -Marcoule, BP 170

30205 Bagnols-sur-Cèze Cedex, France

SUMMARY
Alpha-bearing waste at the Marcoule reprocessing plant has been
incinerated since 1971 to reduce the total waste volume. Some 800 kg of' ashes
containing various amounts of plutonium have been produced and stored. Using a
process developed by the CEA, plutonium is recovered from the ashes by
dissolution of Pu0 2 in nitric acid with a strong oxidizing agent Ag 2+ generated in
the anode compartment of an electrochemical cell by passing a current through the
solution. After filtering out any residues, the nitric acid solutions containing Pu
are purified and the residue is mixed with fission products and vitrified.
The Marcoule laboratory had to solve a number of problems concerning
chlorine elimination, Pu recovery efficiency, and the final separation of residue by
filtering the Pu-containing nitric acid solutions. The industrial facility was
designed by the Marcoule chemical engineering department, and contains three
glove boxes: one for ash entry, weighing and feeding, one containing the
electrochemical cell and plate filter, and a third for liquid storage, pumping
equipment and utilities. The unit is scheduled to begin operation during the
second quarter of 1990.

1 INTRODUCTION
The ash treatment unit operated by COGEMA at Marcoule is part of an existing
intermediate-level facility at the ÛP1 reprocessing plant used for miscellaneous process wastes
contaminated by alpha-emitters with a significant plutonium content.
The new ash treatment unit scheduled to begin radioactive operation during the first half
of 1990 will replace the old nitric-hydrofluoric acid dissolution process and its excessive
operating constraints. The new unit will handle all the ash production from the UP1 alpha-
bearing waste incinerator, as well as eliminate the existing backlog of plutonium-rich ashes.

2 WASTE ASH PROPERTIES

The ash composition produced by the UP1 alpha incinerator varies according to the
incinerated waste mix. The principal component fractions are silica (20-60%); alumina
(15-40%); chlorides (3-20%); calcium, sodium and barium (1-8%); and plutonium (3% on
average).

3 RECOVERY PROCESS RESEARCH AND DEVELOPMENT

The basic process, consisting in dissolution of plutonium with an electrolytically
generated oxidizing agent (silver), was developed by the Transuranium Nuclide Service of the
Commissariat à l'Energie Atomique (CEA). It was applied to ash treatment jointly by the CEA
and the DCI Group in the COGEMA laboratories at Marcoule.The process involves the
following steps.
 147

3.1 Preparing Ash Solutions

In order to increase the reaction surface area and enhance solid-liquid exchanges, the
raw ashes are ground before they are mixed with nitric acid at concentrations of 100 gl" 1 and
stirred to obtain a homogeneous suspension.

3.2 Dechlorination
It is important at this stage of the process to eliminate the chloride ions from the ashes
to prevent subsequent precipitation of silver chloride. After testing chloride ion entrainment
by aqueous rinsing, the method adopted eliminates the chlorine by electrochemical oxidation.
The chloride ions in the ashes are dissolved, oxidized electrolytically and released as off-gases.
The process operating conditions were optimized to improve the dechlorination rate and
efficiency: better than 99% dechlorination is now obtained under industrial conditions.

3.3 Electrolytic Plutonium Dissolution

After eliminating the chloride ions, silver nitrate (0.1 molel" 1 ) is added to the ash
solution. Ag 2+ formed by passing a direct current through the solution oxidizes impurities in
the ashes, notably converting plutonium oxide (PuO->) into soluble plutonyl (Pu0 9 + and
P u 0 2 2 t ) ions.
In order to minimize spurious Ag(II) reducing reactions, the medium is cooled to a
maximum temperature of 35°C. The plutonium oxide solubilization times were determined by
prior testing under industrial conditions, making continuous monitoring of the Pu
concentration unnecessary in normal operation.

3.4 Solid-Liquid Separation

Following oxidation, the solution containing the solubilized plutonium must be separated
from the matter in suspension. This is achieved by vacuum filtration. The residue,
representing about 40% of the initial ash weight, still contains some 20% of the solubilized
plutonium which is recovered by repeated acid rinsing.
This process step required considerable development work to specify the optimum filter
medium in order to obtain a final solution with very low suspended matter content while
permitting extended use without irreversible clogging.
Plutonium solubilized to valence VI is reduced to valence IV by the action of nitrous
fumes. This is essential for subsequent reprocessing. The plutonium recovered in the filtrate
and acid rinsing solutions represents 98-'99% of the initial Pu mass in the ashes.

3.5 Process Waste Treatment

Process wastes basically include ash residue and off-gases (chlorine, nitrous fumes,
electrolysis gases). The gaseous wastes are entrained by the ventilation system and neutralized
with sodium hydroxide and sodium sulfite solutions. Sodium sulfite prevents hypochlorous
ions from forming and raising corrosion problems. The ashes are returned to suspension in
acid and transferred to the fission product solution concentration evaporator for vitrification
at the Marcoule Vitrification Facility.

4 DESCRIPTION OF THE Pu RECOVERY FACILITY

The throughput capacity of the semi-industrial facility is about 10 kg of dry ashes per
week in 1 kg batches. About 20 hours are necessary for the complete process. Except for
manually filling the ash feed hopper, operation of the unit is fully automatic. The process
equipment is installed in three glove boxes (Figure 1).
 148

Figure 1 - Process Schematic

4.1 Glove Box 1: Ash Feeding

The ashes are stored in a feed hopper with a dry ash capacity of 6 kg. The glove box
contains a metering unit supplying the grinding mill at a rate of 5 kg dry weight per hour. The
ground ashes are transferred to the mixer in the second glove box by a vibrating conveyor
driven by a pneumatic vibrator.

4.2 Glove Box 2: Mixing, Dissolution, Filtration

The mixer is supplied with nitric acid and with ashes from the vibrating conveyor via a
bellows connection. The mixture is stirred continuously to obtain a homogeneous suspension,
which is transferred to the dissolver by a two-step procedure: first via a vacuum line to an
intermediate tank from which it flows by gravity into the dissolver.
The dissolver is a borated water-cooled double-wall zirconium vessel. It includes a
platinum anode, a cathode compartment, a stirrer, an air scavenging inlet, an outlet to the
neutralization column, and an AgN0 3 supply line. The sintered alumina cathode compartment
contains a hollow tantalum cathode cooled by borated water circulation. It includes an air
scavenging inlet and an outlet to the neutralization column, and is supplied with 11 Ν HNO;,
by a pump maintaining a constant fluid level. The reaction current is supplied by a generator
with a 150-amp rating at 10 volts. The contents of the dissolver are transferred to the filter by
gravity flow.
 149

The filter has a useful volume of 12 liters. The filter medium is a fine stainless steel
mesh between two flanges supported by two perforated plates. The lower portion of the filter
is removable, and includes a compressed air inlet, a pressurized declogging fluid inlet, and an
outlet for transferring the filtered solutions to the storage tanks. The filter also includes a
variable-speed stirrer to return the residue to suspension, an acid inlet, a sampling port, an
immersed pipe for recycling residue back to the dissolver, and an immersed drain pipe leading
to the residue storage tank.
Off-gases released in the dissolver and in the cathode compartment are entrained by the
ventilation system to the absorption column, which is supplied from the top with a
neutralization solution of sodium hydroxide and sodium sulfite. The solution is recycled by an
airlift system. The saturated solution is transferred via an overflow line to the liquid waste
storage tank.

4.3 Liquid Storage

Plutonium-rich solutions are stored in two flat subcriticai tanks equipped with sampling
devices. The plutonium solutions are treated in a reducing column outside the glove box,
where Pu VI is reduced to Pu IV by nitrous fumes.
Liquid wastes from the absorption column are collected in a 35-liter cylindrical tank with
sampling provisions, connected to the process ventilation system and by means of a valve to
the chemical waste treatment system. Solid wastes are returned to suspension and transferred
to a 35-liter storage tank.
 150

RECOVERY OF PLUTONIUM FROM INCINERATOR ASHES BY

NITRIC/SULFURIC ACID
K. Gompper, H. Wieczorek
Kernforschungszentrum Karlsruhe GmbH (KfK)
Institut für Nukleare Entsorgungstechnik
Postfach 3640, D-7500 Karlsruhe, Germany F.R.
Summary
The nitric/sulfuric acid system has proved to be
generally useful in the treatment of plutonium bearing
incinerator ashes in the ALONA facility. It has been
possible to convert into plutonium sulfate more than 95%
of the insoluble plutonium oxide. However, the con-
centrated sulfuric acid used in plutonium oxide di-
gestion became saturated with dissolved residues after
about 0.6 kg ash per liter throughput. Adding a pre-
treatment step to the process avoided this drawback. In
this step, the incinerator ashes are treated with 1
molar nitric acid at 100°C to dissolve inactive com-
ponents of the ashes soluble in acid.

1. INTRODUCTION
The incineration of plutonium bearing wastes is one of
the most promising treatment options because of its high vol-
ume reduction factor. The arisings of plutonium bearing in-
cinerator ashes are expected to increase in the near future.
As the plutonium-content in these ashes may reach high levels
(up to 10 wt.%) their disposal could become a problem in the
light of disposal criteria set up by safety authorities.
Likewise, it may be valuable to recover plutonium from these
ashes for recycling purposes. Therefore, the development of
effective plutonium recovery processes appears to be
worthwhile.
Most of the plutonium oxide in the ashes is insoluble in
nitric acid. Therefore, only very few dissolution systems are
compatible with usual methods of plutonium purification (e.g.
TBP extraction etc.) and which work without requiring exotic
chemicals. Besides the two main methods of plutonium oxide
dissolution, i.e. the nitric acid/hydrofluoric acid system
and the electrochemical process with Ag(II) or Ce(IV), the
use of sulfuric acid as dissolving agent is of interest.

2. PLUTONIUM DISSOLUTION BY DIGESTION IN CONCENTRATED

SULFURIC ACID
In this process, the plutonium dioxide is converted to
plutonium sulfate by digestion in concentrated sulfuric acid
at 2 50°C for several hours. Because of the high sulfate con-
centration in the sulfuric acid the plutonium sulfate, which
in itself is easily soluble, precipitates almost quanti-
tatively to a concentration as low as 0.2-0.3 g/1. The plu-
tonium sulfate can be dissolved in a diluted acid, such as
0.1 molar sulfuric acid. After a purification step, the
plutonium can be recycled in fuel fabrication.
 151

This method, together with the

plutonium purification step (1,2), was Element mg/g
tested on a technical scale in the
ALONA facility at EUROCHEMIC in Mol,
Si 167
Belgium (3,4). Some 7 kg of plutonium
Al 97
were recovered from 800 kg of burnable
Ca 95
alpha bearing waste. The process was
Fe 59
insensitive to such disturbing factors
as chlorine or carbon and the rate of Na 35
plutonium recovery was as high as in Zn 30
other processes. Mg 14
Ba 10
Ni 6
3. TREATMENT OF INCINERATOR ASHES IN Cr 3
THE ALONA FACILITY
Mo 1
In the treatment of waste from
Mn 1
EUROCHEMIC, approx. 10 kg of in-
Cu 1
cinerator ashes were treated in the
ALONA facility in September/October
Pu 94
1985. The ashes had originated from
Am 2,3
burnable alpha waste incinerated in
Marcoule, France. The plutonium con- U 2,2
tent was in the range of 30 to
140 g/kg. One batch of these ashes was C 244
anlayzed at KfK. Table 1 shows its Cl 48
composition. Depending on the specific
incineration process run in Marcoule, Tab. l: Chemical
carbon and chlorine concentrations are composition of the
relatively high, with levels of ashes D EUR 1/1
approx. 240 g/kg and 50 g/kg, (EUROCHEMIC)
respectively. The
inorganic components
were mainly Si
followed by Al, Ca
and Fe. These ele- digestion ashes Pu content Pu in digestion Pu in
ments represent more tire [h] [kg] [g/kg] residue [X] solution [X]
than 40 wt.% of the
bulk ashes. 12 0.9 93.6 5.0 95.0
12 0.98 51.6 1.4 98.6
Treatment was
15 0.94 71.4 0.9 99.1
conducted in 11
batches with a dos- 15 1.12 105.5 0.9 99.1
age rate of 0.5 to 20 0.98 41.9 0.7 99.3
2.2 kg of ashes per 20 1.06 30.1 6.0 94.0
hour. The average 20 0.87 97.9 1.3 98.7
consumption of sul- 20 0.97 42.0 13.0 87.0
furic acid was 30 0.48 151.0 0.4 99.6
around 3.2 liter per
kg of residue.
Approximately 1 li-
ter of nitric acid Tab. 2: Treatment of incinerator
was necessary to ashes in the ALONA facility
oxidize the carbon.
With the exception of one batch, the plutonium dissolution
rate was between 94 and 99% (Table 2 ) . No influence of the
digestion time was observed within the range of 12-30 hours.
The installations, such as the ring reactor and the filter
 152

equipment, proved to work satisfactorily in principle. The

drawback associated with the process was the relatively high
consumption of the digestion agent sulfuric acid. After a
throughput of around 0.6 kg of ash per liter it had to be
completely replaced on account of its being saturated with
dissolved residues. To avoid this drawback, the constituents
of the ashes soluble in acid must be separated before the
digestion step with concentrated sulfuric acid is carried
out. To this end, studies were conducted to pretreat the
ashes with nitric acid. This acid was chosen because it is
already used in the process and chemically compatible with
the usual reprocessing and fuel fabrication processes.

4. SOLUBILITY OF ASHES IN NITRIC AND SULFURIC ACID

Three non­radioactive types of ashes were investigated
with regard to their dissolution behavior. One ash had origi­
nated from the incineration of a synthetic mixture of burn­
able waste, while the two other types had been produced
during non­radioactive trial operation of the new incinerator
for alpha bearing burnable waste installed at KfK. Their com­
positions are indicated in Table 3. The main components are
Si, Al and Ca. Calcite and anorthite and, to a lesser extent,
mullite crystalline phases were detected.
In the experiments on
the solubility of synthetic
ash, solubility was found Element 71­88 1­7­88 1­8­88
to increase with rising [mg/g] [mg/g] [mg/g]
temperature. Parameters
such as the nitric acid
concentration, grain size, Na 8,1 4,4 13,4
time needed for dis­ Mg 7,2 31,1 19,1
solution, and ash/nitric Al 157,7 127,5 132,6
acid ratio, had no notice­ Si 189,3 195,1 218,9
able influence within the Ρ 12,0 <0,4 1,7
experimental conditions Κ 22,3 9,0 10,5
selected (Table 4) . The Ca 63,5 112,5 77,2
solubility of ashes Cr 2,6 <0,7 3,0
produced during incinera­ Fe 19,9 19,0 24,5
tion at 950°C was poorer by Zn 36,6 7,4 3,1
about 5­9% than that of Sr η . m. 2,2 η . in.
ashes from incineration at Ba 22,9 55,4 7,8
750° C whose solubility at
boiling temperature of
nitric acid were in the 36­ Tab. 3: Chemical composition of
46% range. The solubility the ashes 77­88 (synth.), 1­7­
of the two ashes from the 88 (KfK) and 1­8­88 (KfK)
KfK incinerator was lower,
amounting to 20­30%.
Dissolution experiments with water and nitric acid at
various concentrations were performed with the KfK ashes. As
expected, the lowest solubility is encountered in water. Only
Ca, Al, Κ and Na can be detected at concentrations between
0.02 and 0.1 g/1. When 2 molar nitric acid is used, the con­
centration of the dissolved oxides already rises consider­
ably. The maximum concentration of more than 10 g/1 is at­
 153

tained by calcium, followed by 4­5 and 1­1.4 g/1, respec­

tively, for aluminum and magnesium. Sodium, potassium,
barium, iron and zinc occur at concentrations of about 0. Ι­
Ο. 4 g/1, while the strontium and cerium concentrations are
less than 0.1 and 0.01 g/1, respectively. The solubility of
compounds increases slightly with rising nitric acid
concentration. It attains a peak at 10 molar nitric acid and
decreases again slightly at 14.5 molar nitric acid (except
for cerium).

Depending Parameter Exper. Influence

on the concen­ Conditions
trations of
elements or
compounds in Temperature 20­110"C increase
the ash, only Acid cone. 1­14.5 mole/1 no
3­5% of sodium Grain size 30­500μιη no
and potassium Leaching time l­7h no
and around 1% Ash/acid ratio 10­100g/l no
of C a are dis­
solved in Tab. 4: Dissolution of ashes with nitric
water. The low­ Acid. Influence of Parameters on the
est solubili­ solubility.
ties of 1 to 8% are found for the oxides of cerium and barium
in nitric acid. The best solubilities of about 90% in 2­ to
10­molar nitric acid are obtainend for C a. Zinc is likewise
highly soluble, the respective levels are around 45%. The
other elements investigated, Na, Mg, Al, Κ, Fe and Sr,
exhibit solubilities of about 10% in case of strontium and up
to more than 40% in case of sodium and magnesium.
Consequently it was of interest to study the behavior of
the ash constituents in concentrated sulfuric acid and
compare it with the solubilities in nitric acid. The ashes
therefore were subjected to the conditions of plutonium oxide
digestion in sulfuric acid. The ash­to­sulfuric acid ratio
was varied between 100 and 500 g/1. The solubility of most of
the ash constituents did not depend on the ash­to­acid ratio.
The highest
concentration in the
acid was found for Ca.
Fig­ure 1 shows a <"" dissolved
comparison between the
concentration of dis­
solved ash components
after 8 hour of
digestion in sulfuric
acid at 250'C and
after treatment in 2­
molar nitric acid over
a period of 2 hours. B|- m P — Ρ "Η *ι 1 F — « F 1 1—
Ne Mg Al Fa Zn ΘΙ Ba
The solubility of
the most important 3Ü oono. reso IZmHN03
elements is higher
in nitric acid than Fig. 1: Treatment of ashes 1­7­88
in sulfuric acid. with H 2 S0 4 (250'C , 8h) and with HNO 3
(100­C, Ih).
 154
Only Na and Κ showed
lower concentrat­ions.
With respect to the g/1 dissolved
discharge of the
sulfuric acid this is
of little impor­tance
because of their low
concentration in the
ashes. The result of
the experiments is
important. It indi­
cates a possibility to
separate the soluble
ash components and, in
Ìζ m HN03 12m HN03 <· oono H2S04
this way, prolong the
useful life of the
sulfuric acid diges­ Fig. Treatment of the ashes 1­7­88
tion agent. Experi­ with H 2 S0 4 after pretreatment with
ments, in which resi­ HNO, '3­
dues from pretreatment with nitric acid were digested in
sulfuric acid at 250°C confirmed these results. Except for Na
and K, no other solubility was observed (Fig. 2 ) .
As a result, pretreatment of incinerator ashes with
nitric acid serves its purpose satisfactorily. In the light
of secondary waste arising, the use of diluted nitric acid is
to be preferred, as no significant influence of acid strength
on solubility was observed.
5. PLUTONIUM RECOVERY FROM ALPHA BEARING ASHES
Based on the results obtained in the non­radioactive
experiments, plutonium recovery was tested on a laboratory
scale with two alpha bearing incinerator residues. Like the
residues treated in the ALONA facility, the first ashes
originated from waste produced at EUROCHEMIC and incinerated
in Marcoule. Their plutonium content was 94 g/kg. 3­5% of the
plutonium in the ashes was dissolved during pretreatment in
boiling 1­molar nitric acid. 3­7% was found in the con­
centrated sulfuric acid after a digestion period of 8 h.
After the last step, i.e. the dissolution of plutonium sul­
fate, between 77 and 90% of
the plutonium was found in the Treatment step Pu (%)
diluted sulfuric acid (Tab.
5) . Treatment with 4­molar
nitric acid raised the Step 1: 1 M HNO3 3­5
plutonium losses in the first Step 2: cone. H 2 S0 4 3­7
step to 10­18% because of the Step 3: 0.1 M H 2 S0 4 77­92
higher solubility. C onse­ undissolved 1­13
guentely, only some 65% of the
plutonium was found after Tab. 5: Pu recovery from the
dissolution in diluted sul­ ashes D EUR 1/1.
furic acid. Distribution of Pu.
The other ashes investi­
gated originated from the non­radioactive trial operation of
the new KfK incinerator. They served as model substances for
residues from this type of incinerators. KfK does not intend
 155

to recover plutonium from alpha bearing ashes. To test the

behavior of plutonium, the ashes were mixed with plutonium
oxalate and heated to approx. 800'C for the oxide to form. In
this way it was guaranteed that ashes and plutonium oxide
were subjected to the same temperature. The plutonium
concentration was only 1.3 g per kg ash, which is about 70
times lower than in the ashes from EUROC HEMIC . In order to
allow a comparison to be made, the experimental conditions
corresponded to those ashes.

After the pretreatment step, only 1­2% of the plutonium

originally present in the ashes was found in the 1­molar
nitric acid. The concentrated sulfuric acid used for diges­
tion contained between 44 and 64%, because the plutonium
sulfate generated due to the low plutonium concentration
remained in solution. Only 6­10% was found in the 0.1­molar
sulfuric acid.
Between 27 and
47% of 100­ «
plutonium *­­«M cone H2SO*
0 . 1 m H2SO+ ^s^
S ^ ^ ^ ­ ^ ^
^*^^^ '
remained Pu(total) ^S^ ^
80­
undissolved in > / ^^­A*.^
the residue.
60­
This means tC ~ "·*.^
that the di­
gestion peri­ 40­

od, which had

been long 70­
enough for the w"*"
EUROCHEMIC
ashes, was too ° n
short. After h e a t i n g t i m e in s u l f u r i c a c i d (h)
it had been
extended to 15 Fig. 3: Treatment of l­8­88Pu
and 2 0 hours, Influence of the digestion time on the
respectively, distribution of Pu
more than 95%
of the plu­
tonium was
dissolved. 240^ o O. m H 2 S O *
220­1 ·­ A cone. H 2 S 0 4
However, 200­
α ) + b>
around 60­70% i βο­
A
remained dis­ ιβο­ V*v
solved in the 140­
concentrated 120­
sulfuric acid 1 DO­
ΕΤ"~
(Fig. 3 ) . SO­
.··
In order
60­
..­''
to saturate
40­
*·'
20­
the sulfuric 0­
acid with plu­
tonium sulfate ash in s u l f u r i c a c i d ( g / l )
the acid was
used repeated­ Fig. 4: Reuse of H,S04 in the treatment of
ly in several 1­8­88PU .Distribution of Pu
 156

digestion batches. In this way the solubility product of

plutonium sulfate should be exceeded. Figure 4 shows the
results. Between 0.1 and 0.2 g per liter of sulfuric acid
remained in solution. These findings are in good agreement
with those reported by Stojanek and Lieser (5) . The results
indicate that concentrated sulfuric acid saturated with
plutonium sulfate can be used repeatedly without adding to
the plutonium losses.

6. PLUTONIUM RECOVERY PROCESS

Based on the experiments carried out with non­
radioactive and alpha bearing incinerator ashes and on the
experience with the ALONA facility, the plutonium recovery
process now comprises these three steps:
Step 1: Pretretament of the ashes in boiling nitric acid to
dissolve as much as possible of ash components.
Step 2 : Treatment of the undissolved residue in concentrated
sulfuric acid at 250°C to convert plutoni­um oxide
into plutonium sulfate. The sulfate precipitates al­
most quantitatively in the concentrated sulfuric
acid.
Step 3: Dissolution of precipitated plutonium sulfate in 0.1­
molar sulfu­ric acid. The dissolved plutonium can be
re­cycled for further processing.
The process allows plutonium to be recovered from ashes.
The pretreatment step serves its purpose satisfactorily. The
plutonium dissolution rate is high and amounts to more than
95%. The process is insensitive to chlorine and carbon. The
product of the process is plutonium sulfate dissolved in
diluted sulfuric acid. It can be recycled for further
processing. As always 0.1­0.2 g plutonium sulfate per liter
remain in the digestion agent, the process should be applied
to ashes with a plutonium content above 1 wt.%.

REFERENCES
(1) SWENNEN, R., CUYVERS and van GEEL, H.J. (1983). The
Treatment of Alpha Waste at Eurochemic by Acid Digestion
­ Feed Treatment and Plutonium Recovery ­
in: The Acid Digestion Process for Radioactive Waste
EUR 8609
(2) STOJANEK, B., GREILING, H.D. and LIESER, Κ. H. (1985).
Auflösung von Plutoniumdioxid bei der Naßveraschung von
Plutonium­haltigen Abfällen mit Schwefelsäure und Ver­
fahren zur Abtrennung von Plutonium aus schwefelsauren
Lösungen
BMFT­FB­K 85­001
(3) WIECZOREK, H., OSER, B. and DECKWER, W.D. (1987).
Entwicklung und aktive Demonstration des Verfahrens der
Naßveraschung brennbarer plutoniumhaltiger Festabfälle
EUR 11057 DE (1987)
(4) SWENNEN, R., CUYVERS, van GEEL, H.J and WIECZOREK,H.
(1984) The Treatment of Combustible Alpha­Waste at
EUROCHEMIC using Acid Digestion and a Plutonium Recovery
 157

Process.
First Results of the Active Operation of a Demonstration
Plant
presented at: Fuel Reprocessing and Waste Management,
Jackson (USA), August 26-29, 1984
(5) STOJANEK, B. and LIESER, K.H. (1981). Über die Auflösung
von Plutoniumoxid bei der Naßveraschung von MAW
in: Nukleare Entsorgung, Band 1, Verlag Chemie, Weinheim,
Deerfield Beach, Basel
 Session V

HIGH TEMPERATURE IMMOBILISATION PROCESSES

R. KOHOUT (ONTARIO HYDRO) AND B. VIGREUX (SGN)
 THE INDUCTION HEAT MELTING/SOLIDIFICATION SYSTEM
FOR LOW-LEVEL RADIOACTIVE INC INERATOR ASH
YOICHI KARITA, KOJURO YAMAMOTO AND AKIRA KATO
NGK INSULATORS, LTD.
2-56 Suda-cho, Mizuho-ku, Nagoya 467, Japan
SUMMARY
Combustible solid wastes generated at nuclear power plants have been
largely reduced in volume by the incineration process in Japan. The ash,
however, is stored without solidification in drums.
The authors have conducted research into the properties of the ash,
developed an ash solidification unit and tested it to evaluate the
possibility of its practical use. The results proved that the system can
solidify the ash into solid glass of approximately a true density without
any special preconditioning and that it is effective in volume reduction
by approximately one third. For the radionuclides in the ash, more than
99 1 of the 6DCo and more than 80 X of the 134<137> C s could be confined in
the solid body; the volatilized nuclides were well trapped by the ceramic
filters. The solidification process was advantageous in its strength and
confinement of the radionuclides, and so could be applied when burial
disposal is to be carried out.
Thus, this system has been proved to be practical enough for
incinerator ash treatment.
1. INTRODUC TION
Low-level radioactive wastes are classified into the following
groups, combustible solid waste including spent resin, non-combustible
solid waste and evaporator concentrate. C urrent management practice for
low-level radioactive wastes which originate in nuclear power stations in
Japan is shown in Fig. 1.

Combustible Incineration Ash

solid waste drum

Polymerization
Spent resin Bitumenization Storage
Cementation

Evaporator
concentrate Storage in
Drying box or silo
"
Non-combustibie Storage in
solid waste i * box or drum
'' Baling

Fig. 1 Flow chart of low level radioactive waste treatment

at nuclear power plant in Japan
Combustibl e solid waste has b een incinerated to get a large volume
reduction effec t. However, the as h has been stored in drums with no
volume reductio η nor solidificatio Spent resin has been solidified by
polymerization or pelletization
An inciner ation system for sp ent resin has been developed, and its
practical appli cation is under con sideration. Non-combustible solid waste
has not been hi therto treated, but directly stored. Evaporator
concentrate has been treated by ce mentation, polymerization,
bitumiηizat ion, or pelletization.
Except for non-combustible so lid waste and incinerated ash, treatment
methods for was tes are already dev eloped and now running. Though great
efforts have be en made in the deve lopment of non-combustible solid waste
and incinerated ash treatment, the se wastes are still stored in drums with
no volume reduc tion nor solidifica tion.
Recently, since land disposal is definitely planned, the volume
reduction and s olidification of as h has become very important, based on a
cost and safety analysis of dispos al and transportation.
 162

The authors have developed a new solidification system for

non­combustible solid wastes, including ash, adopting the high­frequency
induction heat melting method. This system is able to solidify these
wastes into stable products with further volume reduction.
This report describes the characteristics of the ash generated at
nuclear power plants and the result« of solidification tests of the ash
with the induction heat melting/solidification method. (1) ­ (3)
2. CHARACTERISTICS OF THE ASHES
Fig. 2 shows the typical process flow of an incineration unit for
combustible solid waste and spent resin.
The combustible solid waste is fed into this unit intermittently from
the top of the incinerator. The spent resin is fed into the incinerator
continuously by a feeder. The off­gas is discharged after removing the
dust by ceramic filters and HEPA filters. The incinerated ash is
discharged through the bottom of the incinerator or a ceramic filter. The
former is called furnace ash and the latter is called filter ash.

Back b i n . .
Pruarr «nil fondar,
cerane HEPA
fi Iter Miar

Η Χ Τ Eihausl (as
aun harr bioser

> Q Γ1ΠΠ
Drus tappine *»¡«>tn
alorase
srilen

Fig. 2 Typical process flow of an incineration unit

The authors examined th e physical and chemical properties of both
furnace and filter ash. (4)
The typical properties of incinerated ash are shown in Table 1. The
major constituents of ash ge nerated by the incineration of combustible
solid wastes are Si02, A1203, CaO and MgO, which make stable glass when
melted, and the melting poin ts are around 1,200 to 1,300 °C.
Furnace ash contains cl inker­type masses and misplaced materials,
such as wire, bolts and nuts These need to be preconditioned before
solidifying the ash by the s olidification method which requires
pulverization for the mixing They causes no problems, however, in the
induction heat melting metho d, and can be processed without
preconditioning.
 163

Itera F urnace ash F ilter ash

Chemical S i as Si0 2 25 ■• 41 14 - 33
compos i t ion Al as A1 2 0, 7 ·■ 14 2 ■• 11
(WtX) Ca as CaO 7 ■■ 23 2 ■• 26
Mg as MgO 4 ■■ 10 0 ■ 8
Fe as Fe 2 0 3 9 ·■ 34 0 - 8
Zn as ZnO 2 ■■ 6 0 ■■ 32
Ti as T i 0 2 5 ·■ 6 0 ■ 8
Na as Na 2 0 0 ·■ 3 1 ■ 9
S as S0 3 0 ■ 2 5 - 26
Ignition loss (Wt%) 1 ■ 8 0 - 4
Melting point ( C) 1,200 ■• 1,300
Size <5 mm 50 ■■ 70 100
distributionι 5 - 30 mm 20 ■■ 30 0
(WtZ) 0 - 100 mm 10 ·■ 20 0
>100 mm 0 - 5 0
True density (g/cm 3 ) 2.8 - 3.2
Bulk density (g/cm 3 ) 0.7 - 1.1 0.4 - 0.6
Specific activity (Bq/g) 1 χ 10 3 -■ 1 χ 10 s
Misplaced Content (Ut%) 0 - 10
materials Details Wire, bolt,
nut, glass,
alumi-foil,
asbestine-
packing,
silicatine -
board, etc.

Table 1 Typical properties of incinerated ash

3. OUTLINE OF THE INDUCTION HEAT MELTING METHOD
To generate heat of high temperatures, induction heating utilizes the
Joule heat generated in the conductive material in the coil when
alternating electricity of several hundred hertz to several thousand hertz
flows along the coils located around a conductive material (such as metal
and carbon). Therefore, a stable melting operation irrespective of the
character of the waste is possible when a conductive pot is
induction-heated to melt the waste with the heat transmitted from the pot.
When compared with other heating methods, it has the characteristics shown
below:
(1) High efficiency due to direct application of electric energy to the
objects to be heated (melting pot).
(2) Heat generation of high temperatures in a short time due to the high
density of power application to the object to be heated.
(3) Less off-gas due to a lack of combustion air and purge gas.
(4) Easy temperature control.
(5) Simple and compact construction of the furnace.
For the above reasons, the authors have adopted high frequency
induction heating as the method for melting non-combustible solid waste.
Fig. 3 shows melting methods by induction heating. The two melting
methods are the in-can melting method and the pot melting method.
In-can melting: A canister which is changed for every batch of
solidification serves as both a melting pot and solidification canister.
It is suitable for conditioning wastes which require high temperatures for
melting and causes aggressive corrosion to the melting pot.
Pot melting: Molten waste is taken out from the nozzle of the melting
pot into a canister and solidified. This method has a high flexibility of
solidified shape, and the operation cost is cheaper than with in-can
melting method.
The composition and melting point of the ash are rather stable.
Since the melted material can be poured easily from the melting pot and
since the smaller melting furnace has more cost merit due to the small
amount of ash generation, the pot melting method is more desirable.
 164

From the composition of the ash, however, the pot has to be replaced
frequently due to quick corrosions, therefore, in this case, the in-can
melting method is more effective.
Process flow of the melting solidification system for ash
Fig. 4 shows a process flow chart of a typical induction heat
melting/solidification system for incinerated ash with the pot melting
method. In this system, incinerated ash stored in drums is discharged by
the discharger. The ash is automatically and intermittently fed into the
melting furnace with a vibration feeder and weighing device.

Waste Waste

High r II
1
II N.rrh
f requency
coi I
: IP
LU
frequency
v . c o 11

Can ι ster T ^ Mel 11ng pot

Β Loil [rol 1
:ί||||!Γ\ \ cHigh
oi 1
frequenc y
a UU a
(.Freeze valve;

^ \ Can i ster

I η-can me 11 i ng method Pot me 111ng method

Fig. 3 Melting methods utilizing induction heat

Ash drum
storaee ar

Canister Drum

nnnnhjigş β

Fig. 4 Typical induction heat melting system for incinerated ash

 165

The melting furnace consists of a high-frequency generator (1,000 to

3,000 Hz) and conductive ceramic pot with a nozzle that produces heat to
melt the ash. After each melting cycle, the nozzle at the bottom of the
furnace is heated so that the solid glass in the nozzle is melted and
molten waste in the pot flows into a canister. In the canister, the
molten waste is cooled by air and made into a solidified product.
The solidified product in the canister is placed into a drum, mortared to
fill any space and capped after cementation.
The off-gas that arises from the melting furnace is usually treated
in the off-gas treatment system of the solid waste incinerator and
therefore an additional off-gas treatment system is not required.
4. SOLIDIFICATION TEST OF A PILOT PLANT
A pilot plant test was made with a ceramic melting pot to examine the
melting rate, volume reduction ratio and properties of melting solidified
products.
Test apparatus
Table 2 shows the major specifications of the pilot plant. The
induction melting furnace is capable of performing both the pot melting
process and the ln-can process. The pilot plant has recorded about 4,000
hours of operation.

Induction heat Method Pot melting, In-canmelting

melting furnace Induction capacity 100 kW
Frequency 3,000 Hz
Melting pot size Max. 450 mm00 χ 600 mm"
Melting pot capacity 20 - 50 liters/batch*
Melting rate 25 - 60 kg/h*
Operating temperature 1,000 - 1,600 °C
Handling system Discharger 200-liter drum size
Vibration feeder 0.4 m/h*
Backet conveyor 15 liter/backet
*: Depends on melting pot size
Table 2 Outline of the pilot plant

Operating conditions
In the pilot plant test, melting pots of two different sizes were
used to check the melting rates. Table 3 shows the operating conditions
of the pilot plant test.

Method Pot melting

Melting pot size 310 mm10 χ 600 mm" 370 mjnID χ 600 mm"
Melting pot capacity 30 liters 45 liters
Operating temperature 1,400 °C

Table 3 Operating conditions of pilot plant test

The test method for finding the melting rate was as follows:
after heating the melting pot to 1,400 °C , a prescribed amount (4 to 6 kg)
of simulated ash was fed at a constant intervals. After each melting
cycle, the nozzle at the bottom of the melting pot was heated and molten
waste in the melting pot flowed down into a canister. Fig. 5 shows
photographs of this test.
 166

Fig. 5 Photographs of an incinerated ash melting test

Results of the pilot plant test
Melting rate: Fig. 6 shows the relation between the pilot plant
melting rate and the melting pot size. The figure additionally shows the
melting rate with hot test equipment (melting pot size: 180 mmID χ 250
rnmH, capacity: 5 liters). The melting rate was in direct proportion to
the inner diameter of the melting pot: the rate was 30 kg/h with a pot of
310 m m I D (capacity: 30 liters) and 50 kg/h by the pot of 370 mm ID
(capacity: 45 liters).
^ · S i n c e , t h e incinerated ash at each site is 10 to 20 tons per year and
this can be sufficiently treated by an melting furnace at 20 to 30 kg per
hour a unit of a size similar to the pilot plant is considered adequate
M
Properties of the
solidified product:
Table k shows the properties
of the solidified product. £
The melted solid product from 'M
the incinerated ash is an ^
aluminosilicate glass.
Its density is 2.7 to 2.9 ­=
g/cm3 and the true specific <=
gravity was close to that of ~
the incinerated ash. °
The volume reduction factor ■"
at this point by the package
(200­liter drum) basis was ^
about one third. —
Its compressive strength is "MΠ
800 to 1,200 kg/cm2 and its
high strength well endures 100 200 300 400
rough handling and land
disposal. melting pot Diameter (mm)
»Hot test plant data

Fig. 6 Melting rate for the pilot plant

Type of glass Aluminosilicate glass

Density 2.7 to 2.9 g/cm3
Compressive strength 800 to 1,200 kg/cm2
Table 4 Properties of the solidified product
 167

5. HOT TEST
The pilot plant test has proved that incinerated ash could be melted
into a highly volume­ reductive inorganic solid product.
Since the operating t emperature for melting is 1,200 to 1,600°C ,
semi­volatile nuclide s, such as C s , may be volatilized while melting; it
is necessary to monit or the process. To evaluate the safety of storing
the solidified produc ts for a long time, it is important to verify the
exudation of the nucl ides from the solid body.
For all these pu rposes, a hot test using the incinerated ash was
conducted to check th e behavior of the radionuclides during melting
operation (the decont amination factor of each line) and the exudation of
radionuclides from a solidified product. (5)
Test apparatus
Fig. 7 is a flow chart for the test apparatus used which includes a
high frequency genera tor (frequency: 3,000 H z , induction capacity: 30 kw) ,
an induction neat mel ting furnace, a ceramic melting pot (5 liters) and
off­gas treatment sys tem.

(250°C)

HEPA
BI ower
filter

ÍSP) ­ Sampling point of off­gas

High frequency
generator
(250°C)
me 11 m g
P o t C eramic filter
Induction heat melting furnace

Fig. Flow chart for the hot test apparatus used

The capacity of the apparatus is about 6 kg/h. Off­gas from the

induction heat melting furnace is cleaned by a ceramic filter chamber
which has three SiC elements, and a HEPA filter.
Operating conditions
The metling pot was heated to 1,100 °C , 1,400 °C or 1,600 °C and 200g
lots of ash were fed into it over a period 10 minutes until a total of 1.0
to 2.8 kg of ash had been fed in. When the process temperature was 1,100
°C 12C , an additive (sodium tetra borate) was supplied to the ash to lower
the melting point.
During the above operations, the radioactivity of the 60 C o and
U4(U7)£S a n ^ the a m o u n t 0 f dust in off­gas were measured at the outlet of
the melting furnace and at the outlet of the ceramic filter chamber.
Leachinp. test method
Test specimens of solidified products were prepared by the following
procedures: approximately 300 g of ash was placed in a melting pot (45
mm 1 0 χ 300 m m " ) , the melting pot was heated to 1, 100 °C, 1,400 *C , or 1,600
°C, and held at these temperatues for one hour. After melting, the
solidified products were removed from the pot and cut to the appropriate
s ize .
The above leaching tests were carried out in accordance with the
method recommended by IAEA.
Results of the hot test
Volatilization rate: Fig. 8 shows the volatilization rate of the
radionuclides and dust from the melting furnace. The volatilization rates
of the 60C o and dust were less than 1 X.
 168

10°
F u r n a c e I F il t e
5

10 '

2
- 10

1.000 1.200 1.400 1.600

Temperature ( Ό

Fig. 8 Volatilization rate from the melting furnace

This indicates the released 60Co may be entrained with dust. The
volatilization rate of the 134Cs was about 20 % at 1,600 °C . This data
suggests that the retention rates of the 60Co and 134C s in the products
were above 99 % and 80 % respectively for the temperatures to 1,600 °C.
Decontamination factor: Table 5 shows the measured decontamination
factor of radionuclides in the ceramic filters (off-gas temperatue:
250°C). Radioactivity in the off-gas proved to be less than a detectable
lower limit at the ceramic filter outlet. The decontamination factors of
the ceramic filters calculated from the detectable lower limit were about
103 or more for 60Co and 106 or more for 134C s. The over-all
decontamination factor from the melting furnace to the ceramic filter was
more than 105 for the 60Co and more than 106 for the 134C s. This data shows
the released radionuclides and dust were trapped efficiently by the
ceramic filter.
Leachiability of the product: Figs. 9 and 10 show the cumulative
leaching rate of the 6UCo and 1J"C s respectively, as a function of the
square root of leaching time. The fraction of the 60Co leached from the
speciment was 10"" to 10~3 after 100 days. The fraction of 134Cs leached
from the specimen was 10"3 to 10~2 after 100 days. Diffusion coefficients
were calculated from the gradients of the latter linear part of the
leaching curve of Figs. 9 and 10. The diffuction coefficient of the 60Co
and 134C s was found to be 10" n to 10"9 (cm2/day) and 10"9 to 10"7 (cm2/day)
respectively.
 169

Heating temperature 1,400 1,400 1,600 1,600

CO
Incinerator ash Furnace Filter Furnace Filter
ash ash ash ash
Off­gas volume 19.1 19.9 20.0 20.6
(Nm3/h)
Off­gas temperature 251 245 247 250
CO
Activity in "Co 4 . 1 χ 10 6 1.3 χ 10 6 2 . 2 χ 10 5 3.7 χ 10 6
ash(Bq)
4
Cs 5.2 χ 106 7.0 χ 106 1.9 χ 10 7 2 . 6 χ 10 7
Activity LO 1.0 χ 10* 5.6 χ 1 0 ' . 1 χ 10 2 1.1 χ 10*
a t o u t l e t of
134 s s
f u r n a c e (Bq) C s 8.9 χ 10 4 . 1 χ 10 5
4 . 1 χ 10 1.7 χ 10 6
Activity*l at "Co < / . 8 χ 10"' <5.9 χ 1 0 ' < 2 . 9 χ 10" < 2 . 6 χ 10-
ceramic f i l t e r
134 1 1
o u t l e t (Bq) C s < 7 . 4 χ IO" < 3 . 6 χ IO" < 2 . 3 χ 10" < 2 . 4 χ 10-
3 3
DF of c e r a m i c °Co >1.3 χ 10' > 9 . 4 χ ΙΟ > 2 . 8 χ 10 > 4 . 2 χ 10"
filter
134 6 s 7
Cs > 1 . 2 χ 10 > 1 . 1 χ 10 > 1 . 8 χ 10 > 7 . 1 χ IO 6
60
O v e r - a l l DF*2 C o > 5 . 4 χ IO6 >2 . 1 χ IO 6 >7 . 5 χ IO 5 > 1 . 4 χ IO 7
134
Cs > 7 . 2 χ IO 6 > 2 . 1 χ IO 6 > 7 . 5 χ IO7 > 1 . 1 χ 10 e
*1 Below detectable limit of activity
*2 Activity in ash/Activity passed through outlet of ceramic filter

Table 5 Over­all decontamination fact in the off­gas cleaning system

X10

2 10
Furnace ash Filter ash
ΐ 9
•^ 8
°Co: U ■ .°'
1, 100°C
! ^
u 6
~ 5
"S 4
- 3
Ï 2
1,600°C
™ 1

9 10

Fig. 9 Leaching of 60Co from solidified products

(Leachant: Deionized water, temp.: 25 °C)
 170
ΧΙΟ

·< 10 1,100°C „­­­O

Furnace ash Filter ash
^ D 4
Cs: O ·
W
Ν­^
8
ο
ι
._
υ fi
^
j =
5
4
ra
ω
3
> 2

4 5 6

V~Time (days)

Fig. 10 Leaching of 134Cs from solidified products

(Leachant: Deionized water, temp.: 25 °C)
6. C ONC LUSION
The results of this test and experience in the test plant operation
have proved that an induction melting solidification system is excellent
in the following points:
(1) Incinerated ash contains misplaced materials, such as masses of 100
mm, nuts and bolts, but this system can solidify the ash without removing
them.
(2) The melting speed depends on the size of the melting pot, but a
melting pot of a 30­liter class capacity can melt 30 kg/h: a compact
furnace design is practical.
(3) The volatilization rates of the radionuclides are 1 % or less for 60Co
and 20 % or less for 134Cs : Most of the radionuclides can be confined
inside the solidified product.
(4) The volatilized radionuclides can be trapped by a ceramic filter and a
high DF can be expected.
(5) Since the volume of the solidified product is reduced almost to the
true density, it has a high volume reduction effect. It also has a high
confiment of the radionuclides and high strength.
To promote safe burial disposal of radioactive wastes, long­term
containment of the existing radioactivity is essential. This system
offers the highest volume reduction ratio and best formed solids for
incinerated ash.
REFERENCE
(1) Takahashi.et al., Autumn Seminar Reports K16, K17, 1983, the Atomic
Energy Society of Japan
(2) Kato, et al., Autumn Seminar Reports G44, G45, 1984, the Atomic Energy
Society of Japan
(3) Inoue, et al., Autumn Seminar Report K5, K6, 1985, the Atomic Energy
Society of Japan
(4) Kato, et al., Journal of the Atomic Energy Society of Japan Vol. 31,
No. 8, P930­935, 1989
(5) Kato, et al., Journal of the Atomic Energy Society of Japan Vol. 31,
No. 9, P1053­1061, 1989
 CERAMIC ENCAPSULATION OF ASHES
CONTAINING ALPHA EMITTERS

Serge Carpentier , Bruno Aubert

SGN, Saint Quentin en Yvelines, France

INTRODUCTION
Low-and intermediate-level radioactive wastes containing alpha
emitters are generated in the nuclear power fuel cycle by spent fuel
reprocessing and plutonium-bearing fuel fabrication, and in nuclear
weapons manufacturing.
Combustible alpha wastes can be burnt in incinerators with the same
basic design as for other radioactive wastes, but providing special
features for:
- plutonium recovery ashes;
- safe geometry of equipment (e.g., in ash storage area);
- leaktightness ;
- confinement in general and static or dynamic containment barriers
in particular;
- enhanced radiation shielding;
- liquid poisoning to absorb neutrons (e.g., when water is used to
cool equipment walls);
- nuclear materials accounting.
When ashes are not processed, they must be immobilized in waste
packages with excellent long-term reliability and stored in safe
facilities. The concept of ceramic waste encapsulation has existed for
many years, but no simple method was available until now. This paper
describes a method of ash confinement in ceramic material.
The ceramic material formed by simple pressing has no open pores and
effectively prevents through-wall migration of radionuclides. It also
traps and immobilizes all radionuclides within the first few millimeters
of penetration from the ash ceramic interface.
The process is applicable to a wide range of substances other than
ashes. These substances include mineral solids, filtration fibers, metal
containers, and chemical compounds such as lead iodine.

1 CERAMIC CONTAINERS
Production techniques
The process developed mainly involves preforming the container
Jacket at a slight pressure (less than 5 x 106 Pa), inserting the wastes
and then covering them with green ceramic material, and pressing to form
a monolithic container with the contents. A natural cold weld is thus
formed by compressing the various container components.
 172

Precompacting

'/,
5

Canister
Ejection
Incorporation Final
of green compacting
ceramic,
material

Incorporation
of wastes

Ζ
10

Figure 1 - Ceramics containers

Materials employed
The green ceramic material used to encapsulate the waste is in the
form of a powder obtained from sandstone or porcelain slip which has been
finely pulverized in a hot vessel. This powder has a relatively small
grain size (200 to 500 um) and a moisture content of about 5% by weight.
Silico­aluminous compositions of sandstone and porcelain prepared
from sand, feldspar, clay and kaolin are preferred. Typical compositions
(in % by weight) are given in the following table:

METALLIC OXIDES Si02 A1 2 0 3 Na20 K2O MgO CaO Fe2Û3

SANDSTONE 69.0 22.0 3.0 2.0 1.5 1.5 1.0
PORCELAIN 66.9 27.9 0.9 3.0 0. 1 1.2 ­
Table 1 : typical compositions of sandstone and porcelain
(% by weight)

The final temperature for firing the ceramic materials ranges

between 1150°C and 1250°C.
 173

Containers structure and texture

Prior to firing, the ceramic container has a large proportion of
open pores (about 30%). It should be handled with some precaution and
dried slowly.
Container porosity decreases as the temperature rises and becomes
practically nil (< 0.1%) at the end of firing. A degree of waste gas
release (CO2, SO2, NO2, etc.) through the ceramic material is thus
tolerable at low and medium temperature without deterioration of the
container (a loss of 10% by weight during firing poses no gas release
problems).
As a result of ceramic material densification (elimination of
porosity), the container volume decreases by about 25î.

2 SIMULATED WASTE ENCAPSULATION

Incinerator ashes
Encapsulation tests were performed on several types of ashes:
- beta-gamma ashes;
- alpha ashes;
- animal ashes.
The following table shows a typical composition of inactive beta-
gamma ashes:

METALLIC METALLIC
J by weight % by weight
OXIDES OXIDES
S1O2 17.52 BaO 0.83
A1 2 0 3 21.71 Cr203 0.70
T1O2 4.98 Sn02 0.75
Fe203 10.63 MnO 0. 12
CaO 12.81 PbO 3.69
MgO 2.08 ZnO 11.43
K2O 1.30 Sb203 0.67
Na20 1.08 CdO 0.05
P2O5 5.75 CuO 3.90

Table 2 : Typical composition of inactive beta-gamma ashes

A firing loss of 11.5% by weight can be simulated using carbonates

and sulfates to represent unfavorable conditions with waste ashes
containing unburnt materials. Production of the containers with these
ashes posed no problem and, as a result of compacting, the stored waste
volume did not increase due to encapsulation.
The firing cycle determined as a function of ash gas release was
successfully applied. The containers obtained are monolithic in shape and
free of any cracks. The ashes are protected by a uniform, continuous
layer of virtually non-porous ceramic material.
Silicon carbide
Silicon carbide grains used in the post-combustion chambers of
CEA SGN radwaste incinerators were encapsulated in the same way as the
ashes. Results were excellent and the volume increase factor was 1.5.
 174

Asbestos
Asbestos fibers used in hot gas high-temperature filters were
successfully encapsulated in a sandstone container.
Due to the elasticity of the compacted fibers, the asbestos had to
be mixed with green sandstone, which affords a degree of plasticity.
Encapsulation was then feasible witn a volume increase factor of 2.
Monolithic containers containing glass
Stainless steel glass-containing containers of the type used at the
Marcoule vitrification facility (AVM) were produced on a small scale. The
containers were 30 mm in diameter and 30 mm high.
These mini-containers were coated with a refractory fiber felt or a
thermodegradable film (paraffin) to compensate for expansion differences
between the ceramic material and the metal. This assembly was then
encapsulated in sandstone by pressing as described above.
After firing and cutting for inspection, the metal container was
found to be surrounded by a uniform layer of ceramic material.
Lead iodide
Lead iodide (Pbl2) is a compound that decomposes and evaporates at a
relatively low temperature (350°C ). Its incorporation in this state into
a monolithic ceramic container would cause an abrupt uncontrolled gas
release and subsequent rupture of the ceramic container. Radioactive
iodine would then be released.
The lead iodine must therefore be combined with a matrix so that the
matrix will trap the released iodine by sorption or chemical reaction.
For this purpose, the zirconium-based matrixes gave the best results of
all the matrixes tested. C ontainers obtained after firing with this
matrix are free of cracks and demonstrate that gas release was
controlled.

3 C ONTAINER C HARAC TERISTIC S

Mechanical strength
Compressive strength tests were performed on sandstone containers
containing simulated low-level radioactive waste ashes. The machine used
for these tests was a PERRIER hydraulic press.
The fired containers withstood a compression load of up to 75 χ 1θ6
Pa in the case of sandstone. In the case of porcelain, pressures far in
excess of 150 X 10& Pa were achieved, which is excellent.
Leach resistance
Leaching tests were performed on sandstone containers containing
ashes with added cesium and cobalt.
The containers are immersed in a specified volume of distilled
water. The water is changed and analyzed daily for the first five days,
then once a week for five weeks, and once a month thereafter.
The curves in the following figure plots the total percent of cesium
(or cobalt) collected in the leaching water (relative to the initial
content in the ashes) versus time.
 175

,
' % Total

io­ 4

105.

<■<;

10 6 _

Y
~//^

1(1­7
f 1 1
1
Time in days
ι
1
a
·
1 day 25 days 60 days

Figure 2 - Radioelement loss versus time

These curves can be used to calculate the instantaneous leaching

rates after 60 cays.
ν 1
Ä = ( >totalat time t) X ­ X ­
s t
where :
t : time
v = volume of the container
s = surface area of the container
Results for cobalt are R = 6.3 x 10­7 cm/day.
Results for cesium are R = 1.7 X 10­8 cm/day.
For the sake of comparison, under the same testing conditions but
over a longer period (180 days), results R for cesium and other materials
are:
­ polyester/cement Res = 5 x 10­5 cm/day;
­ epoxy Res = 5 X 10­7 cm/day;
­ polyurethane/cement Res = 5 X 10­6 cm/day;
­ concrete Res - 10_1* cm/day.
Furthermore, the leachabilities of cesium and cobalt are:
Lc s = 3.8 x 10­10 g cm2 day
Lc 0 = 3.8 x 10­9 g/cm2/day
where:
1 1
Lc 3 = i.% total at time t) X {mass of cesium) X - X -
i s
1 1
Lc = {% total at timet) X (mass of cobalt) X - X -
o t s
Porosity
Open porosity of the fired containers was measured by inserting the
containers into a vessel kept at a slight negative pressure. The
containers were then covered with water and porosity was determined by
weighing before and afterwards.
The porosity results were less than 0.1%, which is low.
 176

Figure 3 - Sandstone container fired at 1150°C

Inside: 400 g of simulated ashes

Figure 4 - Sandstone container fired at 1150°C

Inside: 80 ml of ashes
 177

Figure 5 - Sandstone container fired at 1150°C

Inside: Pb I2

Figure 6 - Sandstone containers fired at 1150°C

(before cutting)
 178

-,-: .ij/MljMIM;lll|¡lli|i!ll|illTjfflt|||Htmijflitjir
ΙΑ Λ*

Figure 7 ­ Sandstone container with glass­filled

stainless steel jacket

!
í///);/ií//|/MI)'llrl/iM!|¡ll'Mi1ll:|lllljlli'l¡1i::p

Figure 8 ­ Sandstone container

Inside: silicon carbide
 179

1Λ V4
ι »... .. ' m

Figure 9 ­ Sandstone container

inside: silicon carbide

tTrWImPvnft ι ·
udWuH­H­uT­ *^

Figure 10 ­ Red sandstone container fired at 1150°C

inside: ashes
 180

Figure 11 - The Perrier press

Tracer concentration orofile in the containers

Electron microanalysis (Castaing microprobe)
The basic operating principle of the Castaing probe is electron
excitation. The probe electrons are accelerated by a potential of 5 to 40
kV and produce different signals as a result of their interaction with
the sample. Primary electron backscattering occurs with emission of
secondary electrons, together with X rays and light in the ultraviolet,
infrared and visible regions.
Electron probe microanalysis mainly exploits the emission of X rays.
The other signals are however often used for complementary analysis.
- Analysis and results
Concentration profiles were plotted for the ceramic containers
containing ashes with cesium, cobalt and iodine.
• Preparation of samples
Each sample was impregnated and then cut up, encapsulated in resin
and polished. The polishing plane intersects the central gray area
corresponding to the wastes and the outer white area corresponding to the
ceramic wall (see Figure 13).
 ÏSI

Primary
Electrons

Backscattered
\ ι' Electrons
X rays

UV/IR light ' / Secondary

/ f Electrons

// // /
Heat
release

Figure 12 - Electron microanalysis (Castaing microprobe)

• Light microscope examination of samples

In this examination, the white and gray areas are mainly
distinguished by two features:
­ their porosity, which is moderate and open in the central gray
area (pores of 0.5 to 1.3 mm) and extremely low and closed in the outer
white area (pores of 0.01 to 0.1 m m ) ;
­ their crystalline structure with overlapping of many crystals
having varied shapes in the central gray area and more globular, far less
visible crystal formations in the outer white area.
• Camebax analyses (C astaing probe)
These analyses were performed in six passes. Examination of the
resulting profiles reconstituted in Figure 4 led to the following
conclusions :
­ Iodine
a. This element is present in the central area (passes 1, 2
and 3 ) .
b. It diffuses into the ceramic material within a radius of about
0.5 mm, at the waste ceramic material interface.
c. Iodine concentration in ;he outermost part of the outer white
area is below the microprobe detection limit (pass 4) under the
analytical conditions employed.
­ C esium
a. This element is concentrated within a zone about 700 microns
wide located near the waste ceramic material interface (pass 5 ) .
b. C esium concentration in the outermost part of the outer white
area is below the microprobe detection limit (pass 4) under the
analytical conditions employed.
­ Cobalt
a. This element is concentrated into a zone at the waste 'ceramic
material interface boundary on each side of the interface.
b. The cobalt appears to have migrated within the outer zone at a
distance of 600 um from the interface.
 182

w h i t e area (ceramic wall)

Sa,mpling
GRAY area (ashes)

Sampling

spectrometer Intensity
background
Passes 1,2, 3 noise

Pass 5
Co

Pass 6
Cs

„500 prr
Pass 4
700 μ η
■* *■

Figure 13 ­ Castaing microprobe analysis :

concentration profile measured by the microprobe

CONCLUSION
Results of the study undertaken demonstrate that sandstone and
porcelainite ceramics are excellent for immobilizing and encapsulating a
wide range of environmentally hazardous radioactive and non­radioactive
materials. The porosity of such ceramics is very low and through­wall
migration of radioactive elements is negligible.
The chemical elements iodine, cesium and cobalt apparently do not
penetrate more than 1 mm into the ceramic material.
 183

In addition, as a result of its composition and crystalline

structure, the ceramic material traps and fixes the radionuclides after
tne first millimeters of penetration from the waste ceramic interface. It
thus forms a reliable containment carrier.
Sandstone ceramics are well known for their excellent chemical
inertia. Their total leach resistance is proven by the absence of
significant radionuclide leakage during one year of laboratory testing.
The long-term stability of ceramic materials under severe conditions
(on the ocean floor or in underground repositories) is acknowledged.
Archaeological excavations in China have uncovered Ming pottery appearing
completely new after burial for over seven centuries.
Ceramic materials also have the following physical properties:
- outstanding mechanical qualities in the case of sandstone ceramics
(compressive strength of about 15 x 106 Pa for porcelain);
- excellent fire resistance;
- substantial reduction of final storage volume due to pressing and
heating effects on the ashes and ceramic material.
The total container volume for incinerator ashes, for example, is
less than the initial processed ash volume (about a 15% reduction).
In conclusion, it should be mentioned that raw materials required to
make ceramics are inexpensive. The production method employs only simple
equipment, which also ensures low cost.

REFERENCES
[1j Pascal, Paul. Nouveau traité de chimie minérale. Masson et Cie.
[2] Jouenne, C. A. Traité de céramique et matériaux minéraux. Seventh
Edition.
[3] Bernard, A. and Nomine, J.C. Saclay Nuclear Research Center, France.
Long-term Leaching Tests on Full-scale Blocks of Radioactive Wastes.
Nuclear and Chemical Waste Management. Vol. 3, pp. 161-168, 1982.
 1S4

SOLIDIFICATION OF RADIOACTIVE INCINERATOR ASHES BY

INCORPORATION
INTO AN ALUMINUM SILICATE CERAMIC MATRIX.
A.LOIDA
Kernforschungszentrum Karlsruhe GmbH
Institut für Nukleare Entsorgungstechnik
Postfach 3 640
D-7500 Karlsruhe 1

Summary
Aluminum silicate ceramics loaded with the
incinerator ashes containing TRU-elements(EUR1/1 and EUR
3/1) have been studied with a view to phase formations,
physical properties(density, compressive strength,
porosity), and TRU leaching in brine as a function of ash
load. The stability of this waste form decreases if
sodium bearing phases, such as nepheline and plagioclase,
arise and increases significantly in the presence of
corundum and spinel. Using low-sodium ash(EURl/l) allowed
a waste load of 60 wt.% to be achieved without any
deterioration in the final product.

1. INTRODUCTION
Ashes from the dry incineration of burnable radioactive
wastes may contain up to 15 wt.% of TRU oxides, depending on
the radioactive inventory of the original waste. If
plutonium is not recovered from the ashes, they must be
converted into a waste form able to incorporate considerable
amounts of TRU elements and unaffected by high alpha doses.
These requirements are met by ceramic matrix materials.
Moreover, ceramic waste forms

- cause no radiolytic hydrogen,

- are very resistant against the attacks of aequous solutions
and heat,
- cause only minor problems of compatibility between the
waste and matrix compounds if, e.g.aluminum silicate cera-
mic matrix materials are used.
This permits waste loads of > 2 0 wt.% to be attained.
This study is to demonstrate the feasibility of
conditioning TRU ashes by incorporating them into an aluminum
silicate ceramic matrix and to characterize the resultant
ceramics as a function of ash load.
2. ORIGIN OF THE ASHES(EURI/1 AND EUR 3/1)
Two different batches of real TRU ashes(EUR 1/1 and EUR
3/1) were used for the ceramization experiments. They had
arisen in an incineration campaign of solid burnable TRU
wastes of EUROCHEMIC Mol, Belgium, performed at the CEA
incinerator in Marcoule, France. The ashes were brownish to
 185

yellowish in color, and their mean particle size was

estimated to be around 50 μπι, after milling in a ball mill.
More detailed information on the ashes and their origins is
provided by Swennen(l).
As the chemical composition of the ashes is not
constant, two different TRU ashes were selected for
ceramization. Sample EUR1/1 is high in A1203, Si02, and
carbon and low in alkali oxides, whereas sample EUR 3/1 is
high in alkaline oxides and low in A1203, Si02 and carbon.
The Pu02 contents of the two samples are 8.28 and 14.80 wt.%,
respectively. Their specific alpha activities are 7.75 E 8
Bq/g and 1.48 E 9 Bq/g as estimated from the following Pu-
isotopic composition according to Swennen(l):

Pu -- 238, 0.3 wt.%

Pu -- 239, 76.1 wt.%
Pu -- 240, 17.2 wt.%
Pu -- 241, 5.1 wt.%
Pu -- 242, 1.2 wt.%

The chemical compositions of both ashes as determined by X-

ray fluorescence analysis and ICP, respectively are shown in
Table 1.

Table 1: Chemical composition of two different TRU—ashes and the

corresponding ceramic products(waste load 20 wt.^) in wt.^.

TRU-ASH CE RAMICS TRU-ASH CE RAMICS

component TRU -ASH E UR 1/1 TRU--ASH E UR 3/1 EUR 1/1 EUR 3/1
AI203 14.23 1.00 67.82 57.60
S!02 27.77 1.00 23.40 18.00
CaO 10.32 23.00 2.16 6.90
Fo203 6.55 tr 1.62 0.30
Na20 3.66 43.00 0.87 B.70
K20 - 14.00 0.84 3.80
ZnO 2.32 tr 0.48 tr
MgO 1.B3 tr 0.39 tr
BaO,NIO.Cr203,
2.00 3.00 0.42 0.60
Mo03.Mn02

Pu02 8.28 14.80 1.74 3.00

Am203.U02 0.38 tr 0.08 0.02
C.CI- 22.66 tr - -
s p e c . a - octlv'ty 7.75 E 8 Bq g 1.48 E 9 Bq/g 1.24 E 8 Bq/g 2.96 E 8 B q / g

3. PREPARATION AND CHARACTERIZATION OF THE ASH BEARING

CERAMICS.
For use as a matrix for immobilizing dry radioactive
incinerator ashes, the aluminum silicate ceramic raw material
 186

should have an A1203/(A1203+SÌ02)­ratio of 0.78. This can be

achieved in a raw materials mix consisting of reactive
corundum, ¡caolinite and bentonite in the appropriate
amounts(2). The ashes are added to that mixture in the ratio
required to reach the desired waste load. Wetting the mixture
with 18­23 wt.% of water allows green pellets to be produced
by extrusion and cutting. Heat treatment at Tmax=12 50°C and
1350°C transforms these pellets into stable ceramic
products. A simplified flowsheet of the process is shown in
Fig. 1.

Fig. 1: Simplified Flow­Sheet of the Process to Produce

Radioactive Waste B earing Ceramics.

CERAMIC
/RAW MATERIALS
ι * Clay minerals j­
\ * reakt.Corundurr /
\ Additives /

PRETREATMENT FORMING HEAT TREATMENT FINAL TREATMENT

­ Evaporation — Hornogeniz. ­ Drying ­ Embedding in

­ Denitration — Extrusion ­ Sintering containment
­ Neutralization — Cord cutting Tmax. 1300°C
­ Precip.Separ.

' TRU­WASTES
* Dissol. residues >
* TRU ­ Ashes j
* Sludges from /
v
(medium)active
Solutions.

The chemical compositions of the aluminum silicate

ceramics containing either 20 wt.% of high alkali ash(EUR3/l)
or low alkali ash(EURl/l) are shown in Table 1. Depending on
the presence of alkali and alkaline earth oxides, crystalline
phases such as alkali and alkaline earth aluminum silicates
will occur in the matrix. The following phases have been
detected by X­ray powder diffractometry:

­ Corundum(Al203) is one of the main phases, when the

waste load is below 30 wt.%; otherwise,
the alkali and alkaline earth oxides
react with it by forming appropriate
aluminates and/or aluminum silicates.
 187

Nepheline
([Na,K]AlSi04) occurs when the alkali oxide content is
above 5 wt.%.
Anorthite
(CaAlSi208) is present when CaO exceeds 5 wt.%;
plagioclase mixed crystals are also
common phases produced by the additional
incorporation of Na20.
Spinel(AB204) occurs in those types of samples, whose
A=Mg,Mn,Ni,Zn ash content exceeds 30 wt.%.
B=Al,Fe3+,Cr3+
Hematite(Fe203) can be recognized in ceramics with
high ash loads(>50 wt.%).
Actinide oxide
(Pu02) has also been found to be present as a
main phase.
Their microstructure consists of a fine grained matrix
(grain size < 2μπ>) and inclusions of TRU­particles up to 250
μπι in size, randomly distributed over the matrix. The
principal features of the microstructure are shown in Fig. 2.

Fig.2: B asic Feature of the Microstructure of an Aluminumsilicate

Ceramic Including Radioactive Waste Compounds.

l.e.Ceramlcs, containing
TRU ­ ashes

Arfinideoxides((Pu,U,Arn)02),
Spinells(AB204),
A=Mg,Mn,NI,Zn,...
B=AI,Fe»+,Cr»+...
Hematite(Fe203)

CorundumiAkOO,
Nephe)ine((Na,KjAISi04),
Feldspars(Ca,Na—AlSilicates),
Glassphase

The resultant ceramic products yield densities of

approx. 2.75 g/cm3, compressive strengths in the range
between 170 and 365 N/mm2, and open porosities between 3.7
and 1.5 vol.%.
 188

Leaching tests corresponding to the ISO test were

performed over a period of one year in Q-brine at room
temperature. The leach rate relative to the total alpha-
activity was determined to be 7E-3 g/m2d on the high-Na
ceramics loaded with EUR 3/1 ash, and about 1E-3 g/m2d for
the low-alkali ceramics immobilizing the EUR 1/1 ash.

Since 20 wt.% of waste load had been selected

arbitrarily, several series of experiments were carried out
with increasing loads of ashes in order to study the
compatibility between compounds of the matrix and the ashes.
Using a EUR1/1 sample, aluminum silicate ceramics were
synthesized with ash loads up to 60 wt.%. The chemical
compositions of the resulting aluminumsilicate ceramics are
given in Table 2.
Table 2: Chemical composition of aluminumsilicate ceramics loaded
with TRU-ash EUR1/I as a function of waste load in wt.°o.

Ash l o c d 3 0 wt.% Ash load 4 0 wt.°¡ Ash load 50 w t ° ; Ash o a d 60 wt.";.

component

AI203 63.06 57.62 51.37 45.88

S!02 24.85 26.20 27.62 29.11
CaO 3.34 4.57 5.84 7.19
Fe203 2.34 3.07 3.86 4.69
Na20 1.31 1.71 2.16 2.34
K20 0.12 0.10 0.09 0.08
ZnO 0.76 1.03 1.31 1.62
MgO 0.59 0.81 1.04 1.28
Ba0,Ni0,Cr203,
C.65 0.90 1.15 1.38
Mo03,Mn02
Pu02 2.68 3.66 4.68 6.06
Am203 0.07 0.09 0.11 0.14
U02 0.07 0.09 0.11 0.14

spec.ex- activity 1.86 E 8 B q / g 2.96 E 8 B q / g 3.10 E 8 B q / g 3.77 E 8 B q / g

In this case, the densities of the final products decreased

from 2.62 to 2.03 g/cm3, their compressive strengths dropped
from 365 to 69 N/mm2, and their open porosities increased
from 2 to 11 vol.%. In contrast, their leach rates were
lower, for high ash loads,i.e. 1 E-4 g/m2d after one year in
Q-brine at room temperature according to the ISO test, as can
be seen in Fig. 3.
This might be explained by the low content of sodium, which
entails the formation of nepheline and a glass phase.
Moreover, the increasing content of a spinel phase in the
ceramic as a function of the ash load may be related to these
results from the leach tests.
 189

Fig. 3: Leach ra+es for TRU from ceramics loaded wim the ash
EUP1., 'l(ash load 20 ­ 60 w1.""") at room temperature in Q­brine.
• 20" 40" ^ 60~
!
TRU­!each rate(g, m d) 30^ ■ 50~

E­3

E­4 :

E­5 =

E­6
50 100 150 200 250 300 350 400
Total leaching time(days)
4. C ONC LUSION
Based on the results of the present experimental work
the suitability of aluminum silicate ceramics as a matrix to
immobilize radioactive incinerator ashes was demonstrated.
Aluminum silicate ceramics incorporating real TRU ashes were
prepared on a lab scale and characterized by ceramographic
methods and leach tests.
R&D work on the development of a technical ceramization
process is under way, but still at an early stage.
Applying the process of ceramization of dry radioactive
incinerator ashes allows a significant volume reduction of
the final waste products to be achieved, especially by
increasing the waste load up to about 60 wt.%. In this case,
however, the ashes should be low in alkali oxides and rich in
A1203 and SÏ02, as in the EUR1/1 sample.

REFERENCES :

(1) Swennen,R.,(1976), IAEA Report No.ETR 291.

(2) Loida,A., Schubert, G.,(1988), EUR 11030 DE, C EC ­
Brussels.
 190

CONDITIONING OF ASHES FROM

COMBUSTION PLANTS IN
SPECIAL MELTING FURNACES

Dr. B. Ganser
NUKEM GmbH
P.O. Box 11 00 80
D-6450 Hanau-11
Fed. Rep. Germany

Summary:
To define the state of the art, a literature survey was
performed for melting techniques and ash compositions. Based on the
literature data inactive ash simulates were composed. Laboratory
experiments for melting point reduction and leaching of the pro-
ducts were systematically performed. An addition of 50 % Na-Borate
was sufficient for lowering the melting point of all simulates to
< 1000 °C, the leaching behavior was comparable to vitrified HAW.
Full scale melting experiments showed the necessity of an alkaline
off gas treatment. The products showed more or less the same
properties like the lab products, the compressive strength was up
to 160 N/mm , porosities down to 0.2 Vol. %, leach rates (B) E-17
up to E-19 m / s .

1. Introduction
Ashes from nuclear combustion plants are actually treated by
cementation or they are shipped directly to intermediate storage without
conditioning. For melting or slaging of these ashes R+D-programmes were
performed, but nevertheless up to now doesn't exist an unexpensive
simple process.
Scope of our work was the qualification of a simple and unexpensive
melting furnace in order to get products of high quality for final
disposal.

2. Acquisition of basis data

The work started with a literature survey and contacts to furnace
manufacturers in order to get a basis data. We used the literature data
systems DATA-STAR, STN and INKA to get information about the raw wastes
and the composition of the resulting ashes, also about the types of
furnaces used in conventional and radioactive waste combustion.

2.1 Types of raw waste

In nuclear facilities solid and liquid wastes are given to com-
bustion. The solid wastes are wood, paper and polymer materials (PVC,
rubber, resins etc.) the liquids in general organic solvents (TBP) and
contaminated oils. The not burnable content with < 5 % is comparable low
because of waste selection.

2.2 Composition of ashes

In the literature we detected totally the analytical data of 6
different ashes (see tab. 1 and 2 ) . Depending on the different raw
wastes, especially the content of TiO- and MgO (filler materials of
paper or filters) is higher compared with domestic ashes, the FejO,
content is lower. The composition of TBP-ash is naturally different, and
 191

consists mainly of Phosphate salts. The chemcial character of the ashes

is acid, therefore the careful selection of oven materials is important.

2.3 Types of processes and furnaces

In the conventional industrie similar processes are used in the
glass and ceramic production and in the domestic waste combustion. The
furnaces used are e.g. tank furnaces or tunnel kilns, the processes are
continuous. The heating at glass/ceramic production is done in general
by direct current resistance, sometimes like at domestic waste com-
bustion by support flames. The throughputs are some tons per day, which
is not comparable to nuclear waste generation. For the nuclear use two
parameters are important:
- off gas treatment
- volume reduction
Therefore the selection of furnaces resp. melting processes has to
be performed in order to avoid large off gas volumes (connection with
combustion off gas line) and secondary wastes like melting containers or
furnace wall materials. Two types are common in nuclear use:
- In-can-melting
- Melting/Filling.
The In-can-melting takes place directly in a possible storage
container. To avoid off gas problems, the electrical heating is effec-
tive (inductive or direct resistance). Because of the metal containers
the maximum temp, is limited to 1050 °C. The Melting/Filling is inde-
pendent from the storage container and can work at higher temperatures,
but with the same type of heating the melting containment has to consist
of graphite ceramic. This creates a significant corrosion.

3. Laboratory experiments

3.1 Melting experiments

For the melting experiments we composed ash simulates according to
the literature data by mixing the grinded oxydes resp. salts. The
compositions are given in tab. 3. The total mass of ash simulate used
for one experiment was 50 g. Melting device was a muffle furnace.
Additives used for melting point reduction were Na.B.O^, B-O,, Na~ CO,,
Na-jPO. and glass frit (glass formers, network transformers). Temperature
range was 1000 "-1300 °C.
All ash simulates had melting points < 1500 °C.
Na-Tetraborate was the most successful additive, followed by Boron
Trioxyde and glass frit. At 1000 °C the addition of 50 % Na-Tetraborate
was enough to melt all simualtes (1300 °C: only 30 % ) . The average
volume reduction factor achieved at 1000 °C was 2.9 (1300 °C: 3.6) at
densities between 1.9 - 2.9 g/cm 3.

3.2 Leach tests

At all samples produced with 1000 °C/Na-Tetraborate we performed
leach tets according to ISO 6961. Analysis was done for the structure
element Boron and the doting elements Cs, Eu, Mn and Co. The release is
determined by diffusion. The diffusion coefficient (D = 1 E-17 m / s )
and the leach rates (R„ = 5 E-5 g/cm d for Cs) are significantly better
than from cemented ashes (E-3 g cm d for Cs) and are correlated to the
SiO- content (high SiOj-content - low leach rate).
 192

4. Construction of a pilot plant

Based on the literature data and the results of the laboratory
experiments we contacted furnace manufacturers. The random criteria for
the pilot plant:
­ 50 kg ash per day
­ 50 %/30 % addition of Na­tetraborate (1000 "C /1300 °C )
­ In can melting
­ Heating by current resistance
­ Melting can accessible for e.g. manipulators
­ Off gas treatment by incinerator mainly
For the performance of full scale tests we selected two different
furnace types, from the companies Linn and Naber.

4.1 Naber furnace

The Naber­furnace (fig. 1) is rectangular with a special fixation
for the crucibles. The heated inner volume can be closed by a Bwing
cover. In the cover we attached two openings for exhaust air ((5 400 mm,
center) and for the material feed (ţa 72 mm, half radius). The furnace
has a programmable control. For the off gas cleaning we constructed a
special filter device (particle deep bed filter), because of acid
pH­values in the off gas line (see below).
The function tests of the Naber­furnace gave following results
­ Heating time with filled crucible: 3 h/1050 °C ,
5 h/1300 °C
­ Cooling time with filled crucible: 1050 °C to 750 °C
within 12 h
­ Accuracy of temperature control; + 50° C
­ Temperature gradient above crucible height: < 50 °C
­ Temperature at off­gas opening: 550 °C
­ pH­value of condensed off­gas humidity: 2.5 (due to SO­)
­ Off­gas flowrate: 5.3 m /h
­ Loss of pressure by off­gas filter: < 10 mbar

4.2 Linn­furnace
The LINN­furnace was delivered at October 1988. C onstructive
defects concerning the bottom (light material, not suitable for weight
of > 100 kg), the heating space (no inner protection) and the electrical
equipment (Ampère­meter, fuses) were responsible for the fact, that we
could not perform systematic melting tests.

5. Performance of full scale tests

5.1 Experimental (Naber furnace)

The ash simulates (AS) used for the fullscale tests were the same
like used for the laboratory experiments. As melting temperature for the
can­melting process we selected 1050 °C , which is the maximum tempe­
rature for stainless steel containers. One experiment (AS8) was per­
formed also at 1300 °C for comparison. The procedure was a batch pro­
cess, i.e. the ash simulate was after homogenizing filled into the
crucible and then heated to the final temperature. Because of the higher
bulk volume of the ash simulate powder than of the crucible (50 1 vs.
30 1 ) , the residual amount was added to the melt within the first 2
hours of the melt experiment. Each product was kept at the maximum
temperature for 10 h.
 193

The leach rates were measured according ISO 6961, the porosities
according to DIN 52102, the compressive strength according to DIN 1164.

5.2 Results
The melted products showed depending on the composition of the
simulates different homogeneity. The products with rather low melting
points were optical homogenious, the other products partially rough and
unhomogenious surfaces. In the most products the upper part had a
signifcant optical detectable porosity, as could be seen after core
drilling. The product melted at 1300 °C was mostly vitrified. The
average densities were slightly below the densities of the labsamples
and were between 1.9 ­ 2.7 g/cm . The corrosion tests, showed Β and Al
Diffusion coefficients, which were comparable to the lab samples (1.0
E­12 up to 8.3 E­18 m 2 /s after 28 days).
The porosities were like expected: vitrified products had poro­
sities between < 0,03 ­ 0,13 % by volume (AS 2/8). Homogenious crys­
talline products (AS 4,7,8,9) had values between 4,7 ­ 16,5 % by volume,
and products with visible inhomogeneities had porosities of 19 ­ 30 % by
volume (AS 1,3,6)
The mechanical strengths were clearly correlated to the structure.
Porous samples had compressive strengths between 12 ­ 34 N / I M , vitri­
fied samples from 68 ­ 160 N/mm .
The results concerning volume reduction, corrosion and compressive
strengths are summarized in tab. 4 ­ 7 .

6. Planning of a "hot" facility

6.1 Enqeneerinq
Based on the experience of the full scale tests, NUKEM performed
the basic engeneering for melting facility, based on an average ash
production of ­ 100 kg/d (e.g. incinerator of Kernforschungszentrum
Karlsruhe) . The flowsheet and process description are available by the
author of this presentation. The plant consists mainly of the following
components:
­ ash feeding box
­ Mixing container
­ Melting furnace
­ Handling box for melting containers
­ off gas filter facility

6.2 C ost aspects

The construction of the unit and the experimental experience
allowed an estimation of the investment and operating costs of a melting
facility, and a comparison with the costs for cementation and high force
compaction, which are actually performed as routine service. The cost
estimation included:
­ investment
­ operation
­ personal costs
3
­ final disposal (5000 DM/m in the German KONRAD mine)
We got the following data:
­ Melting 19 DM/kg ash
­ Cementation 15 DM/kg ash
­ High Force Compaction 15 DM/kg ash
 194

Conclusions
The objectives of our work could be mainly reached. The basic
process and the necessary product recipes could be developed. From the
viewpoint of leach resistance the products showed properties like
vitrified HAW, much better than cemented ashes.
The technical realization was also principally successful. The
process could be tested in full scale, and the properties of the techni-
cal products were nearly as good as the lab products.
The cost comparison showed, that one has to deal with costs of
about 20 DM/kg ash, which is about 20-30 % higher than for conventional
conditioning techniques. From the economic viewpoint our objective
"unexpensive" could not be reached totally.
But depending of quality requirements (leach rate, corrosion
resistance) the melting of ashes could be a serious alternative.
 195

TABLE 1

Selected ash simulates (literature)

Battelle PNL Glove box wastes

2. CEA Marcoule PVC, rubber; low Si0 2 content
3. Rocky Flats average waste; high TiO-, content
4. Rocky Flats combustion of average waste simulate
low SiOj content
5. Rocky Flats HEPA-filter ash, high MgO content
6. Rocky Flats average waste
7. Battelle Pacific average waste
Northwest Laboratories
8. KfA Jülich average waste
9. KfA Jülich average waste

TABLE 2

Composition of ashes of solid burnable

radioactive waste

COMPONENT CONTENT REMARK

Si0 2 12 - 40

A1 2 0 3 12 - 35

CaO 0-30 also as

Caci-, CaSO.

Fe 2 0 3 0 - 8

Ti0 2 0-25

MgO 0-34

Na 2 0 1-16 also as
NaCl, Na 2 C0 3 , Na 2 S0 4

0 - 1

0-12

0 - 5 also as

CI 0-12

S0 3 0-1.5
others Zn0 2 , BaO, B 2 0 3 , C r 2 0 3 u.a.
Ash s i m j l a t e SiO, CaO Ρβ2θ 3 ï&pfcp M9O TiO, Others
No. (% b.w. <%b.w. ) (%b.w0 (%b.w.) (*b.w.) (%b.w.) (*b.w.) (%b.w.)

34,2 17,0 5,5 16,6 CaCl2 . 2H20 =8,2/CaS0 4 = 1,6/NaCl = 1,8

KCl = 1,3/C = 13,8

23,9 4,0 ρ η CaCl2 . 2 ^ 0 = 18,8/CaS04 = 6,9/Pb02 = 3 , 4 / C = 7

15,0 13,0 ­

25,5 18,6 4,0 1,4 3,1/­ 5,3 24,3 C = 9 , 7 / P 2 0 5 = 4,8/Zr0 2 = 1,7/BaD = 1,6

10,0/­ NaCl = 15/Na2S0 4 = 5/C = 1 2 / C r ^ = 1 1 /

12,0 35,0

(5 10,4 17,2/­ ­ Na 3 P0 4 = 68,9/C = 0,5/Cr 2 O 3 = 3,0

39,6 11,9 2,2 2,6 ­ 33,9 Na 3 P0 4 = 3 , 6 / ^ 5 0 , , = 1,2/C = 3,8/Cr 2 0 3 = 1,2

3­

35,0 20,0 8,0 8,0 3,0/­ 4,0 10,0 Cr 2 o 3 = 2,0/NiO = 1,0/ZrO = 2,0/C = 7,0

39,7 19,2 6,4 9,5 6,5/0,9 1,5 Al = 5,0/ZrO = 2,6/CuO = 1,9/Ci-pi = 0,7
PbO = 0,7/NiO = 0,2/MrD = 0,1/P.2 θ 5 =
2,1/C = 3,0

44,3 7,0 11,1 3,9/0,9 1,9 Al = 3,0/CaCO3 = 14,6/ZnO = 2,0/CuO = 1,9/

C r ^ = 0,1/Ptn ',2/NiO = 0,1/MrO = 0 , 1 /
p ^ = 2,8/1­ = i,4/CaCl 2 . 2H,0 = 3,5

Composition of ash simulates Tab. 3

NUKEM
 Aeh Simulate C ontent of Na­Tetra­ Weight Temperature Density (g/cm1) Volume reduc­
No H ·­»►» concerning Full scale Lab tion factor
..u weight tests tests
(JJ (käi íl£l
ASI 50 63 1050 1.88 2.11 2.0

AS2 50 75.6 1050 2.31 2.52 2.5

AS3 50 58.5 1050 2.03 1 .95 2.0

AS4 50 58.0 1050 1.81 1 .92 1 .9

AS6 50 60.0 1050 1.84 2.40 1 .9

AS7 50 72.3 1050 2.20 2.41 2.4

­J
AS8 50 74.7 1050 2.43 2.49 2.7

AS8 50 74.7 1050 2.41 2.49 2.7

AS8 30 74.7 1300 2.30 2.60 3.0

AS9 50 78.0 1050 2.44 2.60 2.7

Tab. 4 Results of volume reduction and density of the melted products

NUKEM
 Diffueloncoeffizient (π'/s) after 28 d
Ash si-. Temp. Full scale tests Sample- Lab tests
mulate position
( * C) Al Β Β
ASI 1050 4.7 E-16 2.2 E-13 above 2.1 E-16
i .9 E-16 2.4 E-15 below
AS2 1050 4.0 E-18 5.3 E-15 above 5.0 E-15
4.3 E-18 _2.1 E-14 below
AS3 1050 5.7 E-17 7.0 E-16 above 1.2 E-15
2.9 E-17 2.6 E-16 below
AS4 1050 1..4 E-14
1.4 E-14 8.3 E-13
8 .3 E-13 above
above 4.4 E-13
1 .6 E-14 1 .0 E-12 below
AS6 1050 4,.5 E-16 2,.0 E-14 above
3.,0 E-17 2..6 E-16 below
AS7 1050 3.2 E-17 1.9 E-15 above 7.2 E-17
1.2 E-19 1.2 E-15 below
AS8 1050 1.4 E-17 4.8 E-17 above 7.0 E-17
1.4 E-17 5.9 E-17 below
AS8* 1050 7.2 E-18 3.5 E-17 above
1.7 E-17 2.8 E-16 below
A sa 1300 3.2 E-18 7.6 E-17 above
3.1 E-18 7.4 E-17 below
AS9 1050 1.4 E-17 3.9 E-17 above 5.8 E-17
8.8 E-18 8.3 E-18 below
* Ash simulate was filled continuously within 10 h

Tab. 5 Results of the corrosion tests of the melted products

Comparison of lab and fullscale samples

NUKEM
 Full scale tests Rema rks
Ash Contents of Na­Tetra­ Tempera­
Simulate borate concerning ture bending and compressive
No ash weight strength (N/mm J )
(%) CO (Naber­furnace)
1050 3.5 9.0 porous
ASI 50
9.6 110 vi tri f ied
AS2 50 1050
2.9 12. . 0 porous

12.2 3 1 .. 0 porous
AS3 50 1050

1050 5.θ 12. .4 porous

AS4 50

1050 6.7 14. ,3 porous

AS6 50

1050 5.0 1 8 . .4 porous

AS7 50

1050 10.0 6 8 . .1 vi tri f ied,

Asa 50 sâmple broken
7.5 121 vitrified

5.1 1 7 . .4 porous
ASS* 50 1050

1300 33.6 »•140 viti i f i ed

A sa 30
1050 46.4 »160 vitri f ied
AS9 50 porous __
7.5 33. 5

* Ash simulate was filled continuously within 10 h

Results of mechanical teats of the melted products

Tab.

NUKEM
 fc¿

Fig. 1 Naber furnace (Tiegelofen T5 05) Fig. 2 Linn-fumace (Sonder-Rohrofen FRVT-3-350/750/1600)

 201

CONDITIONING OF PLUTONIUM C ONTAMINATED ASH BV POUERING MIC ROWAVE

K. KUDO, M. OHI JHI, H. MIYO, Γ. NAGASAKI E. INADA and Y. A3AKURA

Power Reactor and Nuclear Fjel Development C orporation (PNC)

y 33, Muramatsj, Tokai mura, Naka gun, Ibaraki ken 319­II, Japan

Summary
PNC has been processed the r a d i o a c t i v e wastes from the MOX fuel
fabrication f a c i l i t i e s for the volume reduction and conditioning in the PUTF.
The combustible wastes are burned by an i n c i n e r a t o r , and the ash i s
converted into ceramic like block by powering microwave. 31 tons of wastes
have been treated untili the end of May 1990.

1. INTRODUC TION
The p l u t o n i u m c o n t a m i n a t e d various wastes generated from t h e MOX fuel
fabrication facilities h a v e been t r e a t e d for t h e volume r e d u c t i o n and
c o n d i t i o n i n g in the Plutonium contaminated Uaste Treatment F a c i l i t y (PUTF) s i n c e
l a t e 1987 i n PNC Tokai-works. The c o m b u s t i b l e w a s t e s have been burned in t h e
i n c i n e r a t i o n process, and t h e ash has been melted and d u r a b l e t o be c e r a m i c - l i k e
block i n t h e microwave m e l t i n g p r o c e s s . The p r o d u c t s a r e packed i n t h e 200 £
drums and s t o r e d t e m p o r a r i l y in the Plutonium contaminated Uaste Storage
F a c i l i t y (PWSF). Figure 1 shows the plutonium contaminated waste p r o c e s s i n g flow
a t PUTF.
In t h i s paper, t h e o p e r a t i o n a l e x p e r i e n c e s of the microwave m e l t i n g p r o c e s s
and the r e s u l t s of c h a r a c t e r i z a t i o n of t h e produ -to a r e ¡escribed in connection
with the ash t r e a t m e n t .

2. PROC ESS DESC RIPTION

2. 1 Incineration Proce.ss
The combustible wasW 3 rwh 1 ; piper, "l th, rag, wood, p l a s t i c and HEPA
f i l t e r have been burned in the conventional incingi'it jr. The conventional
incineration unit consists of feeder, incinerate r, asli transfer unit and off
gas treatment u n i t . The i n c i n e r a t o r i.· compose i cf primary and secondary
combustion chamber, and coverd with s t a i n l e s s s t e e l casing to keep alpha-
tightness and prevent the leakage of radionuclides. The temperatire and pressure
in the incinerator are regulated automatically at 800~900 "C in the primary
 202

C Plutonium-contaminated H a s t e t
IEI
NDA

3oru ng/Shredding

(^ Metal Haste ) ( Combustible »aste) (^Spent HEPA Filter) f C hloro'prene )

Incineration Æ1
Cyclone Acid
I Incineration Digestion
Metal Melting

Oxide Slag) J Microwave Melting

('Metal Ingot ) C^ eramic )

Plutonium­contaminated Haste Storage Facility(PHSF)

Fig. 1 Plutonium­contaminated waste processing flow at PUTF

combustion chamber, 900~1000'C in the secondary one and ­40 mmH2 0 in the
incinerator by controlling the flow rates of exhaust gas and kerosene. 2 kg
paper bagged combustible wastes and cut pieces of HEPA filters fed into the
primary combustion chamber from the top of the incinerator.

2.2 Microwave Melting Process

As shown in Figure 2, the microwave melting unit consists of mei ter, ash
feeding system, microwave generator and wave guide. The melter and ash feeding
system are installed in a glove box and the microwave is introduced to the
melter through wave guide from the microwave generator installed outside of the
glove box. The melter is equipped with tuner, power monitor, isolator,
discharge detector and ITV monitor. The microwave melting process is based on
the dielectric heating principle to melt the ash by oscillating the molecules of
the ash. The microwave generator has the output of 10 kW with the 2,450 MHz
frequency. The cavity type melter focuses the microwave energy on the ash by
vertically adjusting the tuner. The incinerated ash is melted without any
additives to be a 20 ~ 3 0 kg ceramic­like block in the canister made of
stainless steel (129 mm φ diameter, 770 mm height).
 203
Giove box
Ι ρH Microwave
I Generator
Tuner

200 Í Drum | Mejter_

Fig.2 Microwave melting process

3. OPERATION EXPERIENC ES AND RESULTS

3.1 Incineration Performance
Approximately 31 tons of combustible wastes have been incinerated to be 2. k
tons of ash untili the end of May 1990. Main compounds of the analyzed ash are
SiO 2 , MgO, A l 2 0 3 and CaO. The size­distribution of crushed ash is averaged to
be 1.7 (i m φ · Results of measurement of differential thermal analyzer, the
incinerated ash contain approximately 10 wt% combustible residue.

3.2 Microwave Melting Performance

The ash is fed continuously at the rate of 3. 0 ~ 1 . 0 kg/h and melted in the
canister at 1200~1400"C and converted into the ceramic like block.
Approximately 2. 4 tons of ash have been melted by powering microwave to be
105 canisters of ceramic like block (13 drums). Volume reduction ratio is
approximately 1/130 by incineration and melting comparing the volume of the
containers between untreated wastes and products.
During the operai ion of microwave melting, electric discharge has been
occurred because of the pyrolysis and ionization of generated carbon monoxide.
It is to avoid generation of electric discharge by decreasing the feeding rate
of the incinerated ash, controlling the utput microwave and tuner, and an
improvement of melting is btaitit­d.
 204
Table 1 shows the Operating data of the incineration and melting.
Table 2 shows the weight and volume reduction ratio of the incineration and
melting.

Table 1 Operating data of the incineration and melting

conventional incineration microwave melting

\ ^

waste combustible, HEPA filter incinerated ash

feed rates 2.0 kg/2 min. (paper bag) 3. 0~¿J. 0 kg/h

5.0 kg/7 min. (HEPA filter)

operating primary chamber : 800~900 "C 1200~l400t

temperature secondary chamber : 900~1000TC
high-temperature filter: 500~600 "C

operating -¿10—50 mmH20 - 4 5 — 5 5 mmH2 0

pressure

exhaust gas 7000~9000 Nm3/h 3~4 NmVh

density 0. 5~0. 6 g/cm3 2. 2~3- 0 g/cm3

Table 2 Height and volume reduction ratio of the incineration and melting

^ ~ ^ \ ^ treatment method incineration melting

items~" —_____^

weight of treated waste combustible 31 tons 2. 2 tons ash

product 2.2 tons ash ceramic-like block

105 blocks

weight reduction ratio 1/13 1

volume reduction ratio 1/130

 205

3.3 C haracterization of C eramic-like Block

Small canisters made of s t a i n l e s s s t e e l (129 mm¿ diameter, 200 mm height)
have been used for e v a l u a t i o n . Scanning e l e c t r o n microscope, X-ray micro
analyzer, I n d u c t i v e l y c o u p l e d plasma e m i s s i o n s p e c t r o m e t e r , X-ray
diffractometer, α-ray spectrometer and leaching apparatus have been used for
characterization of the ceramic-like block. The evaluation include observation
of surface, measurement of density and leaching rate.
As r e s u l t s , the density of the ceramic-like block i s 2 . 2 ~ 3 . 0 g/cm3. The
major mineral phase i s feldspar included f o r s t e r i t e . The 28 days leaching rate
of these ceramic-like block i s ~10~ 5 g/cm z · d.
Figure 3 shows the leach rate as a function of time in 28 days leaching test.

1 H 21
■ Leaching Time (d)
Fig.3 Leach rate in 28 days leaching test of ceramic-like block

4. CONCLUSIONS
(1) Microwave melting process was demonstrated to be available as a
conditioning technique for plutonium­contaminated waste.
(2) The volume reduction ratio of 1/130 for the combustible wastes has been
attained by the combined process of conventional incineration and microwave
melting.
(3) The incinerated ashes has been conditioned to be the durable waste form
without any additives by powering microwave.
(U) Leaching rate of ceramic­like block is obtained ~10~5g/cmz· d.
 206

REFERENCES
(1) F. KOMATSU, Y. SAMADA, Κ. OHTSUKA and J. OHUCHI, "Development of a new
solidification method for wastes contaminated by plutonium oxides", Radioactive
waste management (IAEA-SM-246/4, PP, 325-337, 1981)
(2) Y.OG ATA, J. OHUCHI, E. INADA and N. TSUNODA, "Processing of plutonium-
contaminated wastes a t PWTF" (Proc. Symp. IAEA Stockholm, May 16-20, 1988,
Vol. 1 1989 PP. 325-339)
(3) K. MIYATA, J. OHUCHI, E. INADA and N. TSUNODA, "Incineration and Ash Melting
for Plutonium-contamir.ated Conbustible Waste" (The 1989 Incineration conference,
Knoxville, May 1-5, 1989)
(4) M. OHUCHI, K. MIYATA, J. OHUCHI, E. INADA and N. TSUNODA, "Melting pf Pu-
contaminated Residues by Powering Microwave" (4th International Symposium on
Ceramics in Nuclear Waste Management, Indianapolis, April 23-27, 1989)
 207

STABILIZATION OPTIONS FOR TREATMENT OF INCINERATOR ASH WASTES

T. Tabuchi, K. Suzuki, N. Kurumada and H. Kuribayashi

JGC CORPORATION, (Tokyo, Japan)

Summary

This report concerns the stabilization of incinerator ashes:

advanced cement solidification, high-frequency induction melting, and
high temperature incineration.

(1) Advanced Cement (AC) Solidification

The most important points in this process are the pretreatment of
ashes by the addition of Ca(0H)2 and the use of a high shearing
mixer for homogeneity. The products contain 35 wt% ashes, and
have high compressive strength (200 kg/cm^) and low
leachability.

(2) High-Frequency Induction Melting (HFIM)

Ashes are melted at between 1,200 and 1,600°C by induced heating
using a 25 kHz high-frequency in a melter made of carbon
material. The vitrified products have good physicochemical
properties. Furthermore, the process is capable of treating
concrete, thermal insulation materials and other noncombustible
dry active waste (DAW).

(3) High Temperature Incinerator (HTI)

A mixture of combustible and noncombustible wastes is burned and
melted at between 1,000 and 1,400<>C; vitrified granular products
are obtained without the generation of ashes. Ashes from
conventional incinerators may also be easily treated by the HTI
since their chemical constituents produce good quality granules.

INTRODUCTION

The stabilization of incinerator ash wastes is classified into two

main processes; one is embedding in a binder matrix"''2', and the
other is melting into hard blockst-*' or granules. Cement-, bitumen-,
and plastic-solidification belong to the former process. These are
easily operated by simple equipment; however, both the volume and the
weight of the solidified products are increased. The latter is the
melting treatment by fossil-fuel burning or electrical methods such as
Joule-heat, high-frequency induction or microwave. These processes have
higher volume-reduction but involve considerably more complicated
systems.
The application of these techniques to actual wastes should be
selected with consideration given to several parameters; waste-volume,
-weight, -form, contamination levels by radioactive and/or hazardous
materials, required capacity and foreign materials in the ashes.
This paper reports on AC solidification and HFIM, which were
developed by JGC, and on the HTI, originally developed by Belgonucléaire
and CEN/SCK Research Center of Belgium and commercialized by JGC, for
the stabilization of radioactive ash wastes.
 208
ADVANCED CEMENT SOLIDIFICATION

I. Concept of AC solidification
The AC solidification process for incinerator ashes consists of two
main procedures: pretreatment and homogeneous mixing by a high shearing
mixer. Figure 1 shows the basic flow diagram of the AC solidification
process. Pretreatment is required to effectively prevent a
cement-hydration reaction due to the presence of Zn-, Pb- metal
compounds. Furthermore, such pretreatment can avoid compressive
strength deterioration of the products due to H2 gas generation by a
reaction of aluminum metal and cement. The abovementioned metal
compounds are generally contained in incinerator ashes.
The process proceeds with the direct addition of Ca(0H)2 and NaOH
into ash-wastes in the presence of an appropriate amount of water.

II. Properties of cement product

To obtain a satisfactorily homogeneous mixture of cement and the
pretreated ash waste, a high shearing mixer as shown in Figure 2 has
been used under the mixing condition of 35 wt% ash-waste content and a
1:1 water-to-cement weight ratio. The pretreatment requires about one
day.
The physicochemical properties of the products are summarized in
Table 1. The density and compressive strength range from 1.7 to 1.9 and
200 to 400 kg/cm^, respectively. Thus, incinerator ashes are
effectively embedded in the cement matrix by the AC process.
Leaching index (LI) values, defined by ANS 16.1, are measured for
radioactive Co and Cs, based on the leaching tests results over 90
days. These LI values satisfy the requirement of LI being greater than
six (6).

III. Features of the process system

Pretreatment of incinerator ashes by the addition of Ca(0H>2
enables stabilized products to be obtained. The required equipment is
very simple and the operation is easy to perform. However, the weight
and volume of wastes inevitably increase, though minimally.
A homogeneous mixture of cement and ash-waste (35 vt% content) is
achieved by the special high shearing mixer.

HIGH FREQUENCY INDUCTION MELTING

I. Concept of HFIM
Figure 3 illustrates the main system-components in the HFIM pilot
plant. Noncombustible wastes, which are shredded or crushed, if
necessary, are fed to a melting pot made of carbon material. The pot is
surrounded by high-frequency induction coils. The wastes are directly
melted in the pot without any additives and then blown down into a
canister in which the vitrified products are stored. The off-gas is
cleaned through a combination system of cyclone, electrostatic
precipitator and HEPA filter. The main wastes to be treated are as
follows:

- Incinerator ash
- Thermal-insulation material
- HEPA filter material
- Concrete debris
 209

The melting temperatures of these wastes range from 1200 to 1600°C, with
the result that the wastes can be melted by the HFIM in either their
individual or mixed forms.

II. Features of the pilot plant

The main features of the pilot plant are shown below:

Throughput 15 kg/h (based on incinerator ash)

Melting pot 5 liter
Electric power: 42 KWH
Cooling water 3m3/h (12.5 GPM)
Off-gas 12 - 13 Nm 3 /h
Canister 50 liter

Figures 4 to 6 show the induction heating melter, canister holder,

and off-gas treatment system, respectively. The melted wastes are blown
down from the bottom of the pot by controlling the carbon rod stopper
set on its bottom. Figure 7 shows a sample of the vitrified product.

III. Characteristics of the process

(1) Melting pot material
Tests were conducted on the applicability of carbon and
silicon-ceramic materials to a melting pot in the HFIM process. The
results showed that the ceramic material suffered severe damage due to a
complicated reaction with a small amount of iron metal in the melted
wastes. On the other hand, although the carbon material readily reacted
with oxygen and decreased in weight under high temperatures, a long
operation time of between 60 and 100 hours could be achieved under the
nitrogen atmosphere. Therefore, carbon was selected.

(2) Off-gas treatment

In order to confirm the performance of the off-gas treatment
system, wastes containing °"Co and ^ 3 ^Cs were melted in the melter.
Table 2 shows the decontamination factor (DF) in the off-gas system.
More than IO* is obtained as the total DF value.

(3) Physicochemical properties of vitrified products

Table 3 shows the volume-reduction factors of noncombustible wastes
treated by the pilot plant. High volume-reduction was achieved. Table
4 summarizes the product properties of density, compressive strength and
leaching ratio measured for typical vitrified products. The
leachability measured for Fe and Na by the MCC-5S method (100°C, 7 days)
ranges from 1 0 - 3 to 10° g/cm^ day, being almost the same range as
that reported for conventionally vitrified products.

IV. Features of the process system

Various noncombustible wastes can be treated simultaneously and
continuously.
Final products are obtained in hard block form with excellent
physicochemical properties. A high volume-reduction ( 5 - 9 for
incinerator ashes) is obtained.
The melter is heated gradually using high-freguency induction coils
and ash carry-over is minimized.
The inventory volume of melted wastes in the melter is designed and
maintained at a low level, thus allowing the dose rate to be low and the
maintenance of the melter to be easily performed.
 210

HIGH TEMPERATURE INCINERATOR

I. Concept of HTI
The HTI directly converts solid mixtures of combustible and
noncombustibie radioactive wastes, as well as ash and sludge wastes,
into volume-reduced stable granules suitable for final disposal. The
HTI was developed jointly by Belgonucléaire and CEN/SCK Research Center
of Belgium. The first commercial plant in Japan was constructed for the
Tokyo Electric Power Company in 1990 by JGC Corporation. The simplified
process flow sheet is shown in Figure 8. Wastes consisting of a mixture
of wood, paper, cloth, rubber, metal pieces, concrete block, ash and
thermal-insulation material are crushed or shredded, then fed to a
mixing bin. The waste mixture is then fed to the incinerator where it
is heated up to about 1,500°C by an oil burner and burned or melted.
The melted material falls from the bottom of the furnace in the form of
droplets into a water bath and is quenched into granules. JGC ' s
demonstration unit is shown in Figure 9.

II. Features of HTI

Because of the high operation temperatures of the HTI, waste
residue can be converted into glass-like granules as shown in Figure 10,
which have a high volume-reduction ratio and very low leachability
(Table 5 ) . Since almost of all the organic wastes are decomposed and
burned, while heavy metals are encapsulated and fixed in granules, the
HTI is considered to be one of the candidate systems for the treatment
of hazardous waste.
Ashes usually contain Si-, Ca-, and Fe- compounds which make a good
binding matrix for the formation of stable granules. Ashes are
therefore a desirable feedstock for the HTI and, if there are large
amounts of combustible and noncombustible radioactive/hazardous wastes
to be treated, and/or a low-level radioactive ash inventory requiring
treatment, construction of the HTI will be justified.

CONCLUSION

As a result of the experiments, it was confirmed that all three

options, the AC solidification, HFIM and HTI processes, can be applied
for the treatment of incinerator ash wastes. The AC solidification
process is suitable for treating large amounts of ash wastes less
contaminated by radioactive and/or hazardous materials, while the HFIM
process can be applied for the treatment of small amounts of highly
contaminated ash wastes. The HTI, on the other hand, is suitable where
large volume of combustible and noncombustible wastes need to be treated
and where low-level ash wastes have accumulated at the same site.

REFERENCES

(1) D. L. Charlesworth et al.. The International Conference on

Incineration of Hazardous Radioactive & Mixed Wastes, May 3 - 6 , 1988,
pB*-2
(2) N. Kurumada et al., Waste Management 85, Vol. 2, 1985, p211
(3) K. Kato et al., J. At. Energy Soc. Japan, Vol. 31, No. 9, pl053
(1989)
 211

Basic Flow Diagram

llncinerator
Bag Filter Bottom Ash
Dust
Coarse
Ca(OH) 2 ­
NaOH­ Crushing
Water­

Pretreatment

Cement

τ
Products

Figure ^ R « ¡ , Flow Diagram m * r Snliriifi,ation for Ashes Figure 2 Hiqh Shearinq Mixer

Table 1 Characteristics of Cement Products for Ash Wastes

Compressive Leaching Index

Waste Content Density Value
Strength

Incinerator 35wt% 1.8 420 kg/cm* 60Co : 14

bottom ash
Filtered ash 35wt% 1.6 620 kg/cm* i34Cs : 8

Compressive Strength ; at the curing time = 30 days

Leaching Index ; the required LI value > 6, at 90 days, in ANS 16.1
 212

Discharge ^>

vLp- Canister
^ handling
systCM

Figure 3 Basic Flow of HFIM Pilot Plant Figure 4 HF Induction Heating Melter

ad-:Xi*.
Figure 5 Canister Holder

Figure 6 Off-gas Treatment System Figure 7 Vitrified Product Block

 213

Table 2 DF in Off-gas Treatment

Nuclide Cyclone Electric Pricipitator

60Co 8x102 10

134CS 2x102 6x102

Table 3 V o l u m e Reductivity of Wastes

Waste VR Factor

Ash 5-9
Thermal-insulation 9-53
HEPA-filter 13-54
Concrete debris 1 -3

Table 4 Characteristics of V i t r i f i e d Wastes

Compressive Leaching Ratio*

Waste Density Weight Loss
Strength Fe Na

Ash 2.7 >4000kg/cm2 0.02 - 2 w t % 10-4-10-6 10-2-10-5

Ash/Heat-insulator 2.6 >2000 0.2 - 2 w t % 10-4-10-5 10-3-10-4
(50/50)
Ash/HEPA-Filter 2.5 >1Q4 0.2 - 2 w t % 10-3-10-6 10-3-10-4
(50/50)

*g/cm2· day
MCC-5S(100C,7days)
 214

HEPA Riter

Bag Filter

Mam Combustion
Chamber

Water Chamber

Figure 8 Simplified Flow Sheet of HTI

W
Sr.- ,

Hf

Figure 9 HTI Demonstration Plant

Figure 10 Granules
 215

Table 5 Leaching Rates

Duration Leaching rate*

Element
(day) ( g/cm2-day )

Weight 3 1.6 χ 10-7

Fe 3 8.4 χ 10-8

Na, Κ 3 1.5 χ 10-6

Co 28 8.4 χ 10-9

Cs 28 **8.9 χ 10-8

* * Calculated f r o m t h e detection limit

Non-combustibles/combustibles = 70/30 ( w t / w t )
* Measured by t h e MCC-5S m e t h o d
 216

INCINERATION OF TECHNOLOGICAL PROCESS WASTE AND

TREATMENT OF THE ASH:
THE POSITION OF ELECTRICITE DE FRANCE

Y. MAZET

EDF Centre d'Ingénierie Générale

Marseille, France

EDF has carried out a feasibility study into the capacity of an incineration facility to treat
the technological waste produced by French nuclear power plants. This waste amounts to
some 2 200 tonnes per year and comprises:
— 100 tonnes of waste oil with a net calorific value of 40 000 kilojoules per kilogram;
— 2 100 tonnes of solid waste comprising:
200 tonnes of incombustibles (mainly metal elements such as steel or,
occasionally, aluminium);
1 900 tonnes of burnable products with a net calorific value of 20 000
kilojoules per kilogram and including approximately:
40% of cellulose products such as paper and textiles, glass wool and fibres;
60% of plastics or similar products such as PVC, polyethylene, rubber, etc.
One of the design hypotheses was that the pure PVC content would be restricted to
10% by weight of the total waste.
The mean radioactivity of this waste has been estimated at 20 mCi per tonne. This
activity is only of the beta and gamma types. Two units of EDF Construction and
Engineering Division, SEPTEN in Lyon and CIG in Marseille, have worked on this project.
If we assume that the incinerator will be shut down for maintenance three months
per year, and at other times will operate continuously, its capacity will be around
350 kg/hr. The unit would consist of a rotary oven fed by an automatic system for grinding
and loading the waste. This waste would reach the plant in pre-compacted form, packed in
disposable plastic bags. The installation also includes smoke filtration and neutralisation
equipment which has been studied to withstand the chlorine content of the incinerated
waste. The sensitivity of this equipment to an increase in chlorine content should be
studied.
The incinerator produces 35 to 40 kg/hr of ash and dust with high steel content. This
has led to the proposal for and the consideration of a high temperature fusion process to
eliminate this waste. As part of EDF's policy to promote the plasma torch, this was the
solution studied. The development of such a fusion plant would need further studies and,
above all, tests. A first series of tests into the characteristics of the combustion residues,
feasibility of their fusion, required temperatures and powers, etc., should in the short term,
form part of a wider test programme into the possible applications of the plasma torch
process, undertaken jointly by EDF and Aerospatiale.
At present, EDF has not made a final decision as to whether such a project might
be undertaken or the studies continued.
MAIN ACHIEVEMENTS OF THE SEMINAR
&
GENERAL CONCLUSIONS
L. CECILLE (CEC) AND C. KERTESZ (CEA)
 219

MAIN ACHIEVEMENTS OF THE SEMINAR

The review of the different management options for the treatment and conditioning of
radioactive incinerator ashes was given in the 23 presentations which covered the following
topics : disposal criteria, chemical behaviour, low temperature immobilisation processes,
decontamination of alpha incinerator ashes, high temperature conditioning options. In addition,
in order to discuss in more detail some important management aspects (e.g. prevention of the
chemical reactivity of incinerator ashes, quality of the waste products resulting from low
temperature conditioning processes and secondary wastes resulting from high temperature
solidification processes) three panel sessions were organised.

The main achievements of the seminar can be summarised as follows:

1. Waste acceptance criteria

Waste acceptance criteria for disposal of low and medium level beta-gamma incinerator ashes
were addressed extensively by the French and German regulations (near surface sites in France
and the Konrad mine in the Federal Republic of Germany).

In the first case the ANDRA acceptance criteria impose, up to now, an homogeneous
embedding of radioactive ashes in an immobilisation matrix. However, although cementation is
generally used for a number of other radioactive wastes, its application to incinerator ashes
proved to be problematic on account of their chemical reactivity which can affect the
mechanical properties of the resulting waste product and give rise to evolution of inflammable
gases during the cement setting.

In the second case, although the waste acceptance criteria linked to the "Konrad mine" do not
require any immobilisation of radioactive incinerator ashes in a matrix, they are quite
restrictive where gas release is possible. As waste containers cannot be guaranteed to be free
from wet wastes susceptible to chemically reacting with incinerator ashes, there might be
therefore some uncertainties about the safety of such kind of disposal option.

Concerning alpha incinerator ashes with high plutonium content, no waste acceptance criteria
related to disposal in deep geological formations are in existence.

2. Chemical reactivity

The chemical reactivity of some types of low level beta-gamma ashes was shown to result, on
the one hand, from the presence of reducing metals such as aluminium and zinc (actually, in
most of the nuclear facilities, combustible solid wastes are only coarsely separated out prior to
incineration) and on the other hand from poor combustion performance of incinerators which
leads to the presence of carbon coming from unburnt materials in the ashes up to 30wt-% as
well as to some chloride compounds resulting from the incineration of PVC.
Action of water and especially alkaline solutions on such ashes gives rise to hydrogen and
methane evolution according to the well known relationships:

Al + OH' + H 2 0 --> A10 2 " + 3/2 H 2

A1 2 C 3 + 12H 2 0 - > 3CH 4 + 4Al(OH) 3

(Similar reactions may occur with zinc).

 220

When ashes are mixed with a cement grout, some detrimental phenomena affecting the quality
of the final products were shown to happen such as swelling, acceleration or inhibition of the
hardening kinetics. It must be stressed that these conditioning problems are enhanced when
ashes contain noticeable amounts of products like zinc chloride.

To prevent or to decrease the extent of this chemical reactivity, three main specific approaches
can be followed:
- realisation of a thorough separating out of the metallic components of the wastes prior to
incineration;
- improvement of the incinerator combustion efficiency;
- implementation of a chemical pretreatment of the ashes.

In the opinion of most participants in the seminar, it appeared very unlikely that one would rely
on the waste producers to make sure that the wastes to be incinerated are free of metallic
components. A manual sorting of the waste prior to the incineration step would be unavoidable
in all cases. However, in the countries where an important fraction of the combustible solid
wastes come from hospitals and pharmaceutical faculties, since the waste might contain toxic or
bacteriological substances the sorting operation is excluded.

The improvement of the combustion efficiency of incinerators is, no doubt, a more attractive
alternative solution. Nevertheless, this needs the development or application of more powerful
incineration techniques. It is worth noting that EDF in France would be about to launch an
experimental programme on incineration trials for low level waste based on the use of a plasma
torch.

Concerning the chemical pretreatment of ashes, significant developments were made KFA-
Jiilich. The process set-up consists in macerating ashes in a solution of sodium hydroxide for
approximately 24 hours in order to speed up the evolution of hydrogen and methane. Actually,
for various reasons, the kinetics of this reaction was shown to decrease rapidly as a function of
time so that processed ashes may remain somewhat chemically reactive after this treatment.

3. Decontamination of alpha incinerator ashes

Two decontamination processes for alpha ashes were reported to recover as much fissile
materials as possible. The first one, set up at the CEN-Fontenay-aux-Roses, is based on the
oxidizing properties of the A g ^ + / HNO3 mixture which enables a quantitative solubilisa tion of
plutonium dioxide containing ashes. In this connection, an industrial prototype has been
constructed and commissioned on the CEN-Valrhô site for the decontamination of a backlog of
800 Kg of alpha ashes as a first step. This plant should be operational by the end of 1990.

In the Federal Republic of Germany, a decontamination process for alpha ashes relying on the
past exploitation of the Alona acid digestion plant was developed. This process, based on the
leaching behaviour of H2SO4 / HNO3 mixtures, also proved to be capable of recovering more
than 95% of plutonium dioxide from Marcoule ashes. Unfortunately, due to successive
operating delays which occurred in the new alpha incinerator installed at KfK-Karlsruhe, this
process has not yet been validated on genuine German alpha ashes.

4. Ash embedding or compacting

To cope with the chemical reactivity of incinerator ashes, two main treatment/conditioning
alternatives are currently envisaged or practised.
The first one deals with ash super-compaction which enables a volume reduction by a factor 2.5.
The compacts thus obtained are then simply placed into appropriate waste containers for
subsequent transport and disposal. This management route which is currently practised in the
 221

Federal Republic of Germany is also being studied in Belgium. However, as this latter country
is considering near surface disposal sites for this kind of waste, the approval of the waste
packages by the safety authorities is still under discussion (need for an homogeneous
embedding into an immobilisation matrix) by analogy with the ANDRA regulations .

With respect to immobilisation matrices, three options were subject to investigation and
experimentally compared: pure epoxy resin, epoxide/cement matrix and modified sulphur
cement. On account of the price, little consideration was given to ash immobilisation in
polymers. On the other hand, because of their capability to embed a wide range of ashes,
including alpha incinerator ashes, the epoxide/cement matrix (containing up to 30 wt-%
polymers) might appear as an interesting conditioning alternative, as it gives rise to very little
gas evolution.

As far as modified-sulphur-cement is concerned, this matrix might find a useful application for
ash immobilisation on condition that it can be demonstrated, on a significant scale, that it
provides a distinct superiority over more conventional matrices like epoxide/cement matrix. In
this respect, it must be pointed out that some promising results have just been achieved at the
CEN-Cadarache for the immobilisation of alpha ashes within the framework of an
intercomparison exercise launched by the Commission of the European Communities.

Half way between compaction and thermal treatment, a Japanese treatment process for ashes
developed by Mitsui deserves to be mentioned. Consisting of pressing ashes (previously mixed
with sodium hydroxide) at temperatures not higher than 300°C, this process was claimed to lead
to waste products with high mechanical properties provided that the alumina content in the
original ashes is at least equal to 15 wt-%. This process should be applied in the near future to
the immobilisation of ashes generated in the PNC, TRP and JNFS incinerators in Japan.

A comparison between the main characteristics of the waste products generated through a
selection of immobilisation processes is described in annex 1.

5. High temperature processes

Three principal process categories were reviewed at the seminar:

- ceramisation
- melting
- isostatic pressing
Ceramisation only seems justified for high active alpha ashes for which a long term stable
immobilisation matrix might appear necessary. In this respect, two processes, both based on the
production of silico-aluminous ceramics were reported, one focused on the packaging integrity
of the ashes (SGN process) while the other improves the quality of the immobilization matrix
(KfK process).

Ash melting was extensively studied in Japan where the latest technological developments led to
the construction and operation of three types of furnaces: induction furnace (NGK), microwave
((PNC) and ash recycling into a high temperature incinerator (JGC). In the Federal Republic
of Germany too, a research programme aimed at developing a melting process for a wide range
of incinerator ashes was launched in 1986. This led to the construction and the inactive
commissioning of a pilot plant by NUKEM. The important R&D programme conducted in
France on the vitrification process might also have some spin-off on the immobilisation of
incinerator ashes by melting.

The range of melting processes for incinerator ashes which are currently available on the
market or about to be, is therefore wide. However, it must be pointed out that on account of
 222

their rather high throughputs, most of these processes are oriented towards the melting of
incinerator ashes usually generated in large amounts (i.e. low level beta-gamma ashes).
Actually, for alpha ashes the production of which should not exceed 2 t/a (case of the Melox
plant in France for the fabrication of UO2-PUO2 fuels), the microwave technique seemed to be
better adapted.

Even if the operating costs associated to melting processes are unavoidably significantly higher
than those related to conventional embedding, the former have the advantage of achieving the
best volume reduction factors.
Another advantage relies on the fact that melted ashes can comply with the acceptance criteria
defined for a near surface disposal site irrespective of the ash chemical composition.

As a new alternative for ash conditioning, the CEN-Valrhô also looked into the potential and
the industrial feasibility of the high isostatic pressing technique. From the investigations it
would seem that despite the high quality of the ash blocks thus produced, the capital and the
operating costs would be quite prohibitive in comparison with the other competiting processes
like melting or embedding.

Finally, during the panel session, it was stated that high temperature solidification processes do
not appear to create new or additional problems by subjecting radionuclides to the process
temperatures used. It was recognized that incineration process temperatures are very close to
the high temperature solidification processes, and therefore the radionuclides that are volatile
at these temperature should be already absent in ashes due to the preceding incineration
process. The panel members also considered that the generation of an off-gas during ash
melting process is very insignificant in volume and that actinides have very low volatility at their
melting temperature.
 223

GENERAL CONCLUSIONS

1. Low level beta-gamma ashes

In the event of homogeneous immobilisation of radioactive incinerator ashes being required by

the disposal criteria, embedding in a cement-based matrix can only be recommended for the
ash types containing low amounts of reducing metals and/or unburnt materials (e.g. the epoxy -
cement matrix for the low level beta-gamma ashes generated at Cadarache). Otherwise a
chemical pre-treatment has to be carried out on the ashes.

Implementation of melting processes can also provide good ash conditioning alternatives for
complying with disposal criteria in a near surface site. In comparison to ash embedding, these
conditioning processes have the important advantage of covering a wider range of ash chemical
composition. Unfortunately, these might reveal to be quite penalising from an economic
viewpoint.

Super-compaction appears as an efficient ash treatment/conditioning technique especially

when volume reaction is aimed at. Despite the fact that, up until now the resulting waste
products are only suitable for a deep repository (e.g. the Konrad mine), this technique would
provide the most attractive ash conditioning option, both in terms of range of application,
easiness of implementation, cost and volume reduction. Therefore, it might be appropriate to
investigate about the type of overpacking which could comply with disposal criteria associated
with a near surface site.

The current developement of more efficient incinerators (e.g. plasma torch) which are bound to
make ashes chemically unreactive would enlarge the range of treatment/conditioning options.
However, their capabilities of treating combustible radioactive waste are not yet demonstrated.

2. Alpha bearing Incinerator ashes

Quantitative plutonium and americium removal from alpha ashes by leaching with Ag(II) was
experimentally proven.

In addition to simple embedding,the melting of alpha ashes in microwave furnaces is likely to

be the most appropriate treatment/conditioning option from an economic viewpoint as far as
low process throughputs are aimed at (less than 10 m/a).

3. Possible areas for further research

Amongst the many items which were debated throughout the seminar, the following areas
might deserve a more thorough investigation.

- setting up of a more efficient chemical pretreatment than leaching with sodium hydroxide
for the deactivation of incinerator ashes
- demonstration of the merits of the plasma torch to improve the combustion of radioactive
waste and thereby to ease the management of the resulting ashes.
- development of the microwave technique for melting alpha ashes.
- study of new packagings which could enable disposal of compacted ashes in a near surface
disposal site.
 ADDITIONAL INFORMATION

During the panel discussion, attempts were made to evaluate the performance of alternative
immobilisation processes for incinerator ashes. In this respect, a questionnaire containing a list
of basic criteria has been established (see annex 1). As an illustration of this comparison
exercise, data related to two different processes are quoted hereafter in annexes 2 and 3.

Following the visit of the CEN - Cadarache laboratories, a description of the incineration plant
for the low level organic liquids is reported in annex 4.
 227

ANNEX 1

CRITERIA FOR EVALUATING SOLIDIFIED ASH FORM

1. Physical properties
Density
Water absorption

2. Mechanical properties
Compression strength
Hardness

3. 1 v. leaching test
release of: alpha emitter
60 Co
137 Cs

4. Effect of alpha irradiation : on mechanical properties

on radiolytte gas

5. Gas release
. during conditioning process
. long term

6. Chemical stability (temperature, relative humidity, pressure)

7. Need for pretreatment or accurate ash characterization for the process

8. Expected plant capacity at industrial scale

 228

ANNEX 2
1. PROPERTIES OF EMBEDDED INC INERATOR ASHES
IN A POLYMER/CEMENT MATRIX
(CEN - Cadarache)

1. Physical properties
* Density : 1.8 to 1.9
* Water absorption (28 days curing): 0.1 to 0.3% according to the fabrication recipe

2. Mechanical properties
* C ompressive strength : 60 to 65 MPa
* Shore D hardness : 85

3. Leaching behaviour
Iso tests performed with the Cadarache mains water at room temperature:
(270 days curing) (360 days curing)
8 1 1
Leaching rate E ^ 3.5 χ 10" g . cm" , d" 2 χ lO^g . cm"1 . d"1
Released fraction L R 4.6 χ IO"6 1 χ IO"6
Ash alpha specific 50 Ci alpha/t 50,000 Ci alpha/t
activity (doped samples)

4. Irradiation effect
* on the mechanical properties: no modification of the compressive strength after an alpha
irradiation up to 10^ rads.
* on the radiolytic gas: hydrogen is the major component of the gas generated (2ml I ^ / g
embedded waste form produced during accelerated test simulating a storage of 10** years
at the nominal value).

5. Gas released
* during conditioning: hydrogen formation in presence of reducing metals in ash. The
limiting value in A1(0) or ¿n(0) is < 0.5 wt-%. A higher content requires ash chemical
pretreatment.

6. C hemical Stability
* No degradation identified under normal temperature and pressure.
* In case of fire, the embedded epoxy-cement form is a little degraded.

7. Need for a pretreatment or an accurate characterisation for the process

The process is flexible enough to embed several types of ashes (ash from industrial wastes,
organic liquids, phosphates containing ashes) provided that the carbon content is < 10 wt-%

8. C apacity of an industrial installation

The PIC C pilot plant exploited at the C EN-C adarache in a normal working day has a
treatment capacity of 250 to 350 Ke/d ash, hence 4 χ 100 1-drums/d or 3 χ 200 1-drums/d
embedded ashes. This capacity might be increased when the installation is operated in 3
shifts.
 229

ANNEX 3

PROPERTIES OF VITRIFIED INC INERATOR ASHES

(CEN - Valrhô)

The properties given hereafter correspond to the R7T7 glass or to borosilicate glasses used for
the vitrification of fission products solution; they represent a realistic first approach of what
would be those achieved with ashes.

1. Physical properties
* Density : 2.75
* Water absorption : 0
2. Mechanical properties
* C ompressive strength : 80 to 110 MPa
* Vickers hardness : 930 + /- 50 Kg/mm 2
measurement made with microhardness Reichert)
3. Leaching behaviour
This is very dependent on the media (water composition and pH) and the temperature.
- C s-137 about 10"'g.cm"2.d"l at room temperature
about 2 χ 10- 4 g.cnr 2 .d-l in soxhlet at 100°c
- Alpha emitters about 10"8g.cm"2.d"l at pH 8 to 10 and room temperature
4. Irradiation effect
* on the mechanical properties: no significant effect after cumulative impact of 3 χ 10^
alpha disintegration per gramme of glass
* on the radiolytic gas: The generated helium diffuses into the glass at room temperature
(diffusion coefficient: 2x10"^' cm 2 /s)
5. Gas released
* during conditioning:
all the CC>2 generated from unburnt carbon;
possibly SC»2 and C I2 according to the fabrication temperature.
6. C hemical stability
* No degradation identified under normal temperature. The relative humidity and the
pressure have no visible impact.
* At high temperature (from 500°c), crystallisation phenomena may appear depending on
the glass formulation selected.
7. Need for a pretreatment or an accurate characterisation for the process
A priori, neither pretreatment nor ash characterisation are necessary. Only addition of
primary glass or calcinate might be needed.
8. C apacity of an Industrial Installation
Using an induction heating furnace (cold crucible type) a treatment capacity of 30 Kg/h ash
might be reached. For smaller throughputs (e.g. those to be achieved for the alpha ashes to
be produced in the Melox plant, i.e. 500 g/h), ash melting in a microwave furnace would be
preferable.
 230

ANNEX 4

INCINERATION PLANT FOR THERMAL DESTRUCTION

OF RADIOACTIVE LIQUID WASTES

B. BARTOLI - P. LISBONNE

1. INTRODUCTION

In order to destroy organic liquids contaminated by radionuclides we have selected

incineration.
This treatment offers the advantage of reducing the volume of wastes considerably. Therefore
an incineration plant has been built within the nuclear research centre of Cadarache.
Starting operations, made with inactive organic liquids, were conducted from June 1980 to
March 1981.
After this experimental work, the incineration plant was approved by safety authorities for the
incineration of organic liquids contaminated by radionuclides.
About 250 m-' of organic liquids, differing widely in their origins and nature have been
incinerated since the month of April 1981.

2. CHARACTERISTICS AND ORIGIN OF ORGANIC LIQUIDS

2.1. The organic liquids we are allowed to incinerate have to meet the following specifications:

2.1.1 Radiochemical standards

radionuclides alpha < 37.10^ Becquerels/m 3

radionuclides beta-gamma < 37.10° Becquerels/m·^
(Cobalt 60 < 15.108 Becquerels/m 3 )
tritium < 37.108 Becquerels/m 3

2.1.2 Chemical and Physical standards

chlorine < 20 wt-%

phosphorous < 1 wt-%
fluorine < 50 ppm
solid suspended matters < 5 wt-%

Before incineration, we prepared a 5 m batch of organic liquids that are homogenised and we
check the specifications.
If chemical and physical standards are not reached, we can try to get them through additional
treatments.

2.2. Origin of contaminated organic liquids

Most of the organic liquids we usually incinerate come from four origins and in nature are very
varied.
 231

2.2.1 French nuclear research centres

Inside every centre there is a radioprotection department (SPR) that collects organic Liquids
used for the chemical treatment of nuclear materials or for cleaning contaminated materials.
These liquids are mainly :
- solvents such as tributylphosphate or trilaurylamine, used for refining uranium or plutonium.
- chlorinated hydrocarbons such as trichlorethylene.

2.2.2 The specialised agency ANDRA ( National Agency for Radioactive Wastes)
belonging to the Health Protection, must gather all contaminated organic Liquids generated by
small manufacturers in FRANCE, such as hospitals, universities, and industrial research
centres.
These organic wastes are mainly composed of scintillation liquids.

2.2.3 Nuclear power reactors worked by EDF

They mainly generate mechanical oils.

2.2.4 Industrial plants of COGEMA company

They generate also :
- tributylphosphate
- chlorinated solvents
- various oils coming from mechanical equipments used for uranium or plutonium production.

3. DESCRIPTION OF THE INCINERATION PLANT

The standard characteristics of the incineration plant are the following :

- thermal power : 200,000 kcal per hour
- liquid flow : 20 to 50 litres per hour depending on heat of combustion
- combustion temperature : about 900°c.
The main steps of the incineration process are the following :
- reception and preparation of organic liquids to be burnt.
- incineration
- Filtration and purification of combustion gases.
- removal and embedding of the incineration ashes.

3.1. Reception and preparation of organic liquids

This unit has equipment designed to transfer liquids from their various packing containers into
a tank, having a mesh screen of 1 mm in size.
The liquid then passes through a 100 microns cartridge filter and is poured into a 5 nv* tank
equipped with an impeller for continuous homogenisation.
In this way, we obtain a homogeneous batch ready for incineration. Beforehand we take this
batch from a sample in order to check chemical and radiochemical specifications.
 232

3.2. Incineration

The incinerator plant is composed of burners, horizontal combustion chamber, followed by a

vertical chamber for cooling gases.
The pilot chamber is fed with propane fuel gas and ignites the main burner. During starting
time the main burner is first fed with fuel oil until the kiln temperature reaches 900°c.
At this moment, contaminated organic liquids are injected through the burner in place of fuel
oil.
Combustion is controlled by regulating the flows of organic liquids and combustion air.
The shape of the horizontal combustion chamber is cylindrical (900 mm diameter, 3000 mm
length). It is made from special refractory bricks, a sheet of diatomite bricks, then insulating
lining with mineral fibres and an external shell made from steel (6 mm in thickness). With this
structure, external temperature of the shell stays lower than 50°c.
The vertical chamber for cooling gas is also cylindrical in shape (600 mm in diameter, 4000 mm
in height).
At the top of this chamber, demineralised water is injected couterflowing in order to lower the
gas temperature to 650°c.

3.3. Filtration and purification of combustion gas

The combustion gases, successively flow through a prefiltration unit, a filtration unit and a
water sprayed tower.
- The prefiltration unit is equipped with filtering bags made of PTFE, the maximum
temperature allowed is 200°. For this purpose, air at room temperature is sprayed into the
gaseous flux just before the prefiltration unit. Solid particles are caught on the external side
of the filtering bags which are cleaned by counterflow blowing air. The solid particles then
fall down to the bottom of the prefiltration unit.

Unit filtration has five absolute filtres, made of fiber glass. Retention efficiency of each
absolute filter is 99.9% according to the standard AFNOR X 44.011. The working temperature
must be lower than 200°c. Coming out of the filtration unit the gases are cleaned from the dust
particles, the average size being higher than 0.3 microns, but still contain acid compounds
formed during the incineration. They are neutralised by a sodium hydroxide solution. The gas
liquid contact is obtained by spraying solution with a hydro-ejector. Two fans for extracting the
gases are placed after the washing device and maintain the pressure inside the incinerator
lower than the 10 mm water column.

3.4. Removal and embedding οΓ the incineration ashes

An initial device for the removal of the ashes is placed at the bottom of the vertical chamber.

Most of the ashes accumulate at the bottom of the prefiltration unit. An extraction device has
been designed in order to transfer them into 100 litre containers where the ashes are kept
before conditioning. The embedding of the ashes is processed into a well-fitting matrix,
(epoxide cement compound)
 233

4. THE RESULTS OF EXPERIMENTS

4.1. The incineration plant works continuously five days a week. The resulting interruption,
every week end, very often causes thermal stresses to the refractory materials of the kün. In
spite of this, the refractory bricks appear to be in satisfactory condition and do not present
abnormal corrosion.
For maintenance, the front lining, surrounding the burner is changed every year. The
incinerator has been in operation for 7000 hours. During this accumulated time, about 275 m^
of contaminated organic liquids have been burnt, and their distribution is represented as
follows :

36 m-* of solvents composed with 30% TBP

25 m* of chlorinated solvents
- 130 m-'of scintillation liquids
84 m·* of mechanical oils

At the beginning, this experimental incinerator had been used as a research and development
plant. We have therefore defined operating conditions to incinerate contaminated liquids of
widely various conditions.

4.2. The incineration of solvents containing TBP was the most difficult problem to solve. The
chemical compounds, resulting from combustion and derived from phosphorous acid, very
quickly clogged PTFE bag filters. To avoid this trouble, we have selected a calcium salt which is
injected directly into the combustion chamber and neutralises phosphoric acid which is
converted into calcium phosphate. The ashes formed this way are not sticky and are easily
removed from the bags filters. Their apparent density varies from 0.3 to 0.4 g/cm^. About 70 kg
of ashes are formed for every 1 mP TBP solvent incinerated.

4.3. The incineration of the other organic liquids does not present the same difficulties except if
both chlorine and phosphorous are present. For every 1 m of organic liquids incinerated, about
7 kg of ashes are generated and this represents a very interesting concentration factor.
Moreover, ash density varies from 0.1 to 0.3 g/crn^.

4.4. More than 99% of the radioactivity content, contained in the organic liquids, is
concentrated into the ashes which will be embedded in thermosetting resins.
Chemical and physical characterisations of the ashes have been determined relative to their
origin and have been used to define the embedding process.

4.5. The other wastes resulting from the incineration are the alkaline solutions used for the
neutralisation of acid vapours present in the combustion gas.
The alkaline solutions have practically no radionuclides and the alpha content is lower than
37.10-' Bq/m·'. Therefore these liquid effluents are considered to be inactive chemical effluents.
The gases are released into the atmosphere but their content of radionuclides alpha, beta-
gamma are continuously monitored. The average alpha activity remains lower than 3700 Bq/m^
of gases. On the gas flux there is an one line analyser with an alarm value set at 10^ Bq. If we go
beyond this limit the incineration is stopped and the origin of this irregularity must be found.
 234

5. CONCLUSION

On the basis of eight years of operation the incineration plant has shown reliable operating
conditions in the destruction of various organic liquids contaminated with radionuclides alpha
and beta-gamma.
The capacity of incineration ranges from 20 1/h to 50 1/h depending on the heat of combustion
of organic liquids, but at the same time we are continuing research and development
programmes in order to improve unit operation of the process (for example gas filtration) or to
obtain better knowledge concerning the lifetime of materials planned in the construction of
future incinerator plants.

DCC / DSD CEA / CADARACHE t

SER / STUE

Air Compressed air

Air
Quenching water
Regulating

Captions : 1. Furnace
2. Cold oir diluter
3. Sleeve type prefilter To radioactive effluent
4. Absolute filtration treatment station
5. Gas scrubber
Active solvents
·—©- 6. Effluent tank

INCINERATION OF RADIOACTIVE ORGANIC LIQUIDS

 235

LIST OF PARTICIPANTS

AUFFRET L CARPENTIER S.
CEA SGN
DRDD/SDFMA/SETED 1, Rue des Hérons
Bat 326 Montigny le Bretonneux
CEN/CADARACHE F-78182 St Quentin en Yvelines
B.P. 1
F-13108 St Paul-lez-Durance CAUQUIL G.
COGEMA MARCOULE
BATAILLES LANNES J.C. B.P. 170
COGEMA MARCOULE F-30200 Bagnols sur Ceze
B.P. 170
F-30205 Bagnols sur Ceze CECILLE L.
CEC
BAUDIN G. DG XII/D/2-ARTS 2/16
CEA 200, Rue de la Loi
DCC-Coordination Retraitement Déchets B-1049 Bruxelles
Bat 467
CEN/SACLAY CHEVANAS P.
B.P. 2 CEA
F-91191 Gif sur Yvette D RDD/SDFMA/SETED
Bat 326
BERGAMASCHI O. CEN/CADARACHE
SINCOS SRL B.P. 1
Via Zuretti 47 F-13108 St Paul-lez-Durance
1-20125 Milano
CHRISTEN D.
BOSSY R. CEA
CEA Bat 355
DCC/DRDD/BECC CEN/CADARACHE
Bat 352 B.P. 1
CEN/CADARCHE F-13108 St Paul-lez-Durance
B.P. 1
F-13108 St Paul-lez-Durance CODEE H.
COVRA N.V.
BOYER D. P.O. Box 20
EDF CIG Dir Equipement NL-1755ZG Petten
140 Avenue Vitön
B.P. 560 CORYN P.
F-13401 Marseille COGEMA/S2M
116, Avenue Aristide Briand
BRAMY W. F-92223 Bagneux
USSI
116 Avenue Aristide Briand COURTOIS C.
F-92223 Bagneux CEA
DRDD/SDFMA/SETED
BRESCHET C. Bat 352
COGEMA MARCOULE CEN/CADARACHE
B.P. 170 B.P. i
F-30205 Bagnols sur Ceze F-13108 St Paul-lez-Durance
CAÑADAS L. DOUTRELUINGNE P.
ETSII COMEGA MARCOULE
Dep. IQA B.P. 170
Avd Reina Mercedes, S/N F-30200 Bagnols sur Ceze
E-41012 Sevilla
 236

DUREC J.P. JOUAN A.

USSI CEA
116, Avenue Aristide Briand CEN/VAL RHO
F-92223 Bagneux B.P. 171
F-30205 Bagnols sur C eze
ETIEVANT M.
SPADO LASSAILLY KAMADAS.
64, Faubourg de Ia Bretonnière MES
F-28320 Gaiïardon 6-4 Tsukiji 5-C home
Chuo-Ku
GANSER Β. J-Tokyo 104
NUKEM GmbH
P.O. Box 1313 KASTELEIN J.
D-8755 Algenau COVRA N.V.
P.O. Box 20
GAUTHEY J.C . NL-1755 ZG Petten
TECHNICATOME
B.P. 34 KATOA.
F-13762 Les Milles NGK INSULATORS LTD
2-56 Suda-Cho, Mizuko-Ku
GEISER H. J-467 Nagoya
GNS mbH
Zweigerstraße 28-30 KERTESZ C .
D-4300 Essen 1 CEA
DRDD/SDFMA/SETED
GENS R. Bat 326
ONDRAF-NIRAS CEN/CADARACHE
Place Madou 1 B.P. 1
B.P. 24-25 F-13108 St Paul-lez-Durance
B-1030 Bruxelles
KOBAYASHI J.
GESTERMANN G. JGÇ C ORPORATION
GNS mbH Paris Office
Zweigertstraße 28-30 Centre d'affaire. Le Louvre
D-4300 Essen 1 2, Place du Palais Royal
F-75044 Paris Cedex 01
GHYSELS J.P.
EDF - SEPTEM KOHOUT R.
12-14 Avenue Dutrievoz ONTARIO-HYDRO
F-69628 Villeurbanne 700 University Avenue
CANADA - Toronto Ontario M5G 1X6
GIELEN P.
ONDRAF-NIRAS KOSTER R.
Place Madou 1 KFK (INE)
B.P. 24-25 Postfach 3640
B-1030 Bruxelles D-7500 Karlsruhe 1
GOMPPER K. KRÄMER R.
KFK (INE) KFK
Postfach 3640 P.O. Box 3640
D-7500 Karlsruhe 1 D-7500 Karlsruhe
GUIROY J.J. KURIBAYASHI H.
FRAMATOME JGC CORPO RATION
Tour Fiat New Ohtemachi Bldg.
F-92084 Paris La Défense C edex 16 2-1 Ohtemachi 2-chome
Chiyoda-Ku
HUNT Β. J- Tokyo 100
JRC EURATOM, TP800
1-21020 Ispra LASER M.
KFA
JAHCHAN J. P.O.Box 1913
SPADO LASSAILY D-5170Juelich
64, Faubourg de la Bretonnière
F-28320 Gaflardon
 237

LE BLA YE G . MISRAKI J.
SGN CEA
1, Rue des Hérons DCC/DRDD/BECC
Montigny le Bretonneux Bat 352
F-78182 St Quentin en Yvelines CEN/CADARACHE
B.P. 1
LEE D. F-13108 St Paul-lez-Durance
AEA TECHNOLOG Y
Building B73 MORALES LEON A.
Winfritn Technology Centre ENRESA
UK- Dorchester,Dorset,DT2 8DH Emilio Vargas 7
E-28043 Madrid
LINS W.
KAH NAUD G .
Im Breitspiel 7 CEA
D-6900 Heidelberg D RDD/SDFMA/SETED
Bat 326
LISBONNE P. CEN/CADARACHE
CEA B.P. 1
DRDD/SDFMA/SEAPI F-13108 St Paul-lez-Durance
Bat 160
CEN/CADARACHE NIETVELTJ.
B.P. 1 TRACTEBEL
F-13108 St Paul-lez-Durance Ariane Laan 7
Β-1200 Brussels
LOIDA A.
KFK (INE) ODOJ R.
Postfach 3640 KFA
D-7500 Karlsruhe 1 P.O. Box 1913
D-5170 Jülich
LUYCX P.
BELGOPROCESS OTTER C.
Gravenstraat 73 CEA
B-2480 Dessel DCC-Coordination Retraitement Déchets
Bat 467
MADIC C. CEN/SACLAY
CEA pp Τ
CEN/FAR F-91191 Gif sur Yvette
F-92265 Fontenay aux Roses
PALMER J.
MALHER P. BNFL
CEA Sellafield Seascale
DRDD/SCECA/CIDN UK- Cumbria CAOO IPG
Bat 352
CEN/CADARACHE PECH R.
B.P. 1 SGN
F-13108 St Paul-lez-Durance 1, Rue des Hérons
Montigny le Bretonneux
MAZET Y. F-78182 St Quentin en Yvelines
EDF CIG Dir Equipement
140 Avenue Viton PORTAL R.
B.P. 560 EDF/DPT
F-13401 Marseille Cedex 09 Service des Combustibles
23 bis Avenue de Messine
MELLOUET F. F-75384 Paris
CEA
SPR REMY D.
CEN/G RENOBLE CEA
BP. 85X SASICC/SAED
F-38041 Grenoble Bat 08
CEN/FAR
MERGAN L. F-92260 Fontenay aux Roses
ONDRAF-NIRAS
Place Madou 1
B.P. 24-25
B-1030 Bruxelles
 238

REVETEGAT E. VAN AVERBEKE J.

CEA BELGONUCLEAIRE
DRDD/SESD/SECBO Rue du Champs de Mars, 25
CEN/SACLAY B-1050 Bruxelles
B.P. 2
F-91191 Gif sur Yvette VAN DALEN A.
NERF-ECN
RICCI G. Westerduinweg 3
ENEA NL-1755 LE Petten
CRE CASACCIA
Via Anguillarese 301 VERBEKE R.
1-00100 Roma A.D. ONDRAF-NIRAS
Place Madou 1
R I T S C H E R D. B.P. 24-25
GNS mbH B-1030 Bruxelles
Zweigertstraße 28-30
D-4300 Essen 1 VIGREUX B.
SGN
SANDRELLI G. 1, Rue des Hérons
ENEL Montigny le Bretonneux
Via Rubattino 54 F-78182 St Quentin en Yvelines
1-20134 Milano
WOIGNIER S.
SIMON R. COGEMA MARCOULE
CEC B.P. 170
DG X n / D / 2 - Arts 2/14 F-30200 Bagnols sur Ceze
200, Rue de la Loi
B-1049 Bruxelles YONG CHIL SEO
KAERI
SOMMI J. P.O. Box 7
COGEMA MARCOULE DAE DUK DANJI
B.P. 170 KOREA - Taejon Korea 305-353
F-30200 Bagnols sur Ceze
ZAKINEC.
TAINE B. SGN Laboratoire
TECHNICATOME 4, Avenue des Fresnes
B.P. 34 Montieny le Bretonneux
F-13762 Les Milles F-78182 St Quentin en Yvelines
TEULON F.
CEA
CEN/VALRHô
B.P. 171
F-30205 Bagnols sur Ceze
 239

INDEX OF AUTHORS

ASAKURA, Y., 201 LASER, M., 29

AUFFRET. L., 85 LECOMTE, M., 139
AUBERT. B., 171 LOIDA. Α., 184

BAUDIN, G., 3 MADIC, G, 139

BIAGINI, Α., 85 MAZET, Y., 216
BOURGES, J., 139 MISRAKI, J., 102
BRESCHET, C , 146 MIYO, H., 201
MOINE, G., 62
CANADAS, L.. 72 MORI, Κ., 113
CARPENTIER, S., 171
CAUQUIL, G., 146 NAGASAKI, T., 201
CHENAVAS, P.R., 85 NAKAMORI, Y., 113

DE GOEYSE, Α., 14 ODOJ, R., 13

DONATO, Α., 45 OHUCHI, M., 201
DROBNIK, S., 35 OTTER, G, 8
OUVRIER, N., 124
ETIEVANT, M., 133
PFEIFER, W., 35
GANSER, Β., 190
GEISER, Η., 22 REVERTEGAT, E., 62
GENS, R.. 56 RICO, G ., 45
GERSTERMANN, G., 22 RIJPKEMA, J.E., 96
GIELEN, P., 56 RITTSCHER, D., 22
GOMPPER, K., 150 ROGER, J-P,. 133

HASHIZAKI, Y., 113

SALVADOR, L., 72
INADA, E., 201 SAULZE, J.L., 139
SIMON, R., 6
JAHCHAN, J., 133 SOMMI, J., 146
JOUAN, Α., 124 SUZUKI, K., 207
SWENNEN, R., 14
KAMADA, S., 113
KARITA, Y., 161 TABUCHI, T., 207
KATO, Α., 161 TEULON, F., 124
KERTESZ, C.J., 85 TEUNCKENS, L., 56
KERTESZ, G., 102
KOEHLY, G.. 139 VAN DALEN, Α., 96
KRAEMER, R., 35
KUDO, Κ., 201 WIECZOREK, H., 150
KURIBAYASHI, H., 207
KURUMADA, N., 207 YAMAMOTO, K., 161
 Related Titles
ELSEVIER A P P L IE D S C IE N CE

Flue Gas and Fly Ash

Proceedings of a contractors' meeting organized by the Commission of
the European Communities, Directorate-General XII for Science,
Research and Development, held in Brussels, Belgium, 16 June 1988.
P.F. Sens and J.K. Wilkinson, Editors,
Commission of the European Communities, Brussels, Belgium.
1989 24 χ 16.5 cm viii + 176 pages 93 illus. 1-85166-324-X

X-Ray Analysers in Process Control

K. Carr-Brion
Process Measurement Consultant, Sandy, Bedfordshire, UK.
1989 22 χ 14 cm x + 162 pages 40 illus. 1-85166-334-7

Modern Chlor-Alkali Technology

Volume 4
Published on behalf of SCI
N.M. Prout, and J.S. Moorhouse, Editors,
Staveley Chemicals Limited, Chesterfield, Derbyshire
1989 24 χ 16.5 cm xii +380 pages 268 illus. 1-85166-392-4

ISBN 185166 655 9