Calcination Process

.. I'll.
*>
f «-- 44, 4
1 DO - 14622
April 1964
\./ 8
4,c3O
V
COMPARISON OF VARIOUS CALCINATION PROCESSES

31 FOR PROCESSING HIGH LEVEL RADIOACTIVE WASTES
-
MISTEit
B. R. Wheeler, J. A. Buckham, and J. A. McBride

DISCLAIMER
This report was prepared as an account of work sponsored by an

agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.
DISCLAIMER
Portions of this document may be illegible in

electronic image products. Images are produced
from the best available original document.
PRICE $1.75
AVAILABLE FROM THE

OFFICE OF TECHNICAL SERVICES
U. S. DEPARTMENT OF COMMERCE
WASHINGTON 25, D. C.
LEGAL NOTICE
This report was prepared as an account of Government sponsored work. Neither the United
States, nor the Commission, nor any person acting on behalf of the Commission:
A. Makes any warranty or representation, express or implied, with respect to the accuracy,
completeness, or usefulness of the information contained in this report, or that the use of any
information, apparatus, method, or process disclosed in this report may not infringe privately
owned rights; or
B. Assumes any liabilities with respect to the use of, or for damages resulting from the use
of any information, apparatus, method, or process disclosed in this report.
As used in the above, -person acting on behalf of the Commission" includes any employee or
contractor of the Commission, or employee of such contractor, to the extent that such employee
or contractor of the Commission, or employee of such contractor prepares, disseminates, or
provides access to, any information pursuant to his employment or contract with the Commission, i
or his employment with such contractor.
PRINTED IN USA
IDO-14622
AEC Research & Development Report
Waste Disposal and Processing
TID-4500 (27th Ed.)
Issued: April 1964
...
I ... 0
A COMPARISON OF VARIOUS CALCINATION PROCESSES
FOR PROCESSING HIGH-LEVEL RADIOACTIVE WASTES
by
B. R. Wheeler
J. A. Buckham
J. A. McBride
PHILLIPS
PETROLEUM
COMPANY
' EFflE
W -
Atomic Energy Division
1
. ./ -1.-*.., Contrbct AT(10-1)-205

Idaho Operations Office
U. S. ATOMIC ENERGY COMMISSION
1..
-THIS PAGE
WAS INTENTIONALLY
LEFT BLANK
PREFACE
The Atomic Energy Division of PhillipsPetroleumCo. has been working for approximately eight years
at the National Reactor Testing Station on the development of the fluidized bed calcination process for reducing
liquid nuclear wastes to solids. Experimental work has been performed with cold, simulated waste solutions,
employing 6-inch and 12-inch diameter pilot-scale calciners, a 24-inch square calciner, and a 4-foot diameter
process demonstration and production unit which began operation at the Idaho Chemical Processing Plant
on high-level radioactive aluminum nitrate wastes early in December 1963. During the early part of the
Phillips program, a brief parallel development was carried on in the Chemistry and Chemical Engineering
Division of Argonne National Laboratory, using a 6-inch diameter pilot-scale calciner, and operating on
nonradioactive, simulated wastes and high level ICPP aluminum wastes, diluted at least 1 to 8 with non-
radioactive simulated waste.
During approximately this same period of time, three other major process development programs, as
well as two or three minor efforts,. on the reduction of liquid nuclear wastes to solids have been supported
by the Atomic Energy Commission at other sites. In the summary session of the Second Working Meeting
on Fixation of Radioactivity in Stable, Solid Media (Idaho Falls, Idaho, September 27, 1960) we suggested
that an objective comparison of the various calcination processes be made, based on experimental results.
It was suggested that this comparison be a technical evaluation of the processes with respect to plant investment
costs per unit of capacity, product characteristics, process versatility, and economics of operation (TID-7613
pp 736-737). The evaluation presented herein meets the major part of the requirements.
A significant function of research and development management is the continuing evaluation of projects
against possible competitors. In addition to providingforone's own project an indication of where development
effort need be concentrated and where further effort is unnecessary, such evaluation provides the yardstick
against which to measure one's own project and, in certain cases, to identify the time when it is profitable
to abandon a project in favor of devoting more concentrated effort elsewhere. This provides a further reason
for our continuing close attention to the work of others in the field of waste calcination in recent years. Through
a joint program with the Oak Ridge National Laboratory in 1961-62, we became intimately familar with the
ORNL pot calcination project, developing a design for a process demonstration pilot plant and evolving a
process demonstration program. This work was published in December 1962 in ID0-14596, "Design of a Pilot
Plant Facility for Radioactive Demonstration of the Pot Calcination Process." It was intended to use the same
basic hot pilot plant equipment in a subsequent demonstration of the radiant-heat spray calcining and rotary-
.,. ball kiln calcining processes, which have been under development at the Hanford Laboratories and Brookhaven
National Laboratory, respectively. Because of this aspect of the overall program, we also became well
acquainted with these processes.
It soon became apparent in our studies that superficial comparison of published data on these pro-
cesses was inadequate to compare realistically the advantages, disadvantages, and potential utility of the
various processes. Yet, such a comparison seemed vitally necessary both for the purpose of establishing
a sound and logical process development program for the processes and to permit a valid assessment of
fluidi:r.ed bed calcination, theprocessofourprimaryinterest. We, therefore, undertook the task of assimilating,
evaluating, and correlating all the published information available on these calcination processes. We feel
that the results of the evaluation we have made will be of value to others who are concerned with the growing
inventory of nuclear wastes and with the problem of what to do about it.
Our evaluation is based on published data and information on the processes considered, except that
in the case of the fluidized bed calcination· process we have been able to draw on a considerable amount of
unpublished data. In the many cases where specific data have not been available in terms which would.permit
a direct comparison of process features, we have calculated values for comparison based on such data as
were available. In the several cases where no specific data have been published on a particular process
characteristic, as for example, on the limiting capacity of the radiant-heat spray calciner, extrapolations
have been made using any available data. We have tried in all such cases to use the most recent data available,
and where a point was in doubt, to give the benefit of the doubt to the process in question.
Although every effort has been made to keep all bias out of this comparison, our far more intimate
acquaintance with details of the development work on the fluidized bed calcination process may have in-
advertently introduced some bias in favor of this process. We acknowledge this possibility, but state again
that our primary objective in the preparation of this report was not to present an ironclad case for fluidized
bed calcination, but rather to provide a rational basis for comparison of the four principal waste calcination
processes.
J. A. McBride
iii
FOR PROCESSING HIGH~LEVEL RADIOACTIVE WASTES
B. R. Wheeler
J. A. Buckham
J. A. McBride
.
ABSTRACT
Published information and data relative to the four principal radioactive waste ·calcination techniques,
the fluidized bed, the pot, the radiant-heat spray, and the rotary-ball kiln are summarized on a comparative
basis. An ultimate combined capacity of about 1000 gph is expected to be necessary to process generated and
accumulated wastes between the years 1965 and 2000. The effects on product properties and on economics
of ultimate waste disposal of the type of calciner selected are considered from many standpoints, including
the composition, concentration, and activity level of the waste solution and the calcination conditions. Also
discussed are creation of glass-like compounds from calciner products, personnel and equipment requirements,
and the present status of development of each of the calciners. One or more calciners may be suitable to
process any particular waste, depending on the desired type of product and other circumstances.
iv
. 'coNTENTS · ~ .
ABSTRACT 0 • 0 • 0 0 0 •• 0 0 0 0 •••••• - • .0 ... 0 0 •• ! • 0 • 0 0 •• 0 o. 0 0 < •••••• 0 ••• 0 • o. 0 0 0 •••••••• iv
.
I. SUMMARY .AND CONCLUSIONS .
•••••••••.••• , ·• • • •. • • • • • • • • • • • • • • . • • • . • • • • • • • 1
II. INTRODUCTION .•.. , .•••••••••.•••••.•.•••••• , • • • • • • • • • • . • . • . • . • . • . • . . • 3
A. Safety Considerations in Waste Disposal •••••••••• ••••••••••••••••. ••••••••• 3
B. The Magnitude of the Waste Problem 4
ill, COMPARISON OF CALCI,NATION PROCESSES • , ••••••••••• , • • • • . • • • • • • • • • . • . . . • 6
1. Calciner Description and Operation , . . . . . . . . . , , ••• , ••• , . • . • . . . . . . . . . • • • . • • . 6
2. Heat Introduction and Temperature of Operation • 0 • 0 0 •••• 0 ••• 0 0 " • 0 •. 0 ••• 0 ••• 0 0 0 10
3. Waste Throughput Capacity .•••••••.•••••••••••••••.•••.•••••.•.•••••• , • 14
4. Feed Introduction ••.•••.•.•••.•. , .•••.•.•••••••• ,.••••••••.•.• , •••. , . 20
5. Off-Gas Processing System •••.••.••. , ••.•••••.••.••••••••••....••. ; .•.• ~ 22
IV. PRODUCT PROPERTIES •.•••.••••••.••••••••••••••••••••.• ·, • . • . • . • . • • • • • 26
1. Size and Shape of Calciner Product .•• , ••.•••••..•...•..•.•. , • • • • • • • • • • • • • • • • 26
2. Leachability ••••.•••.•..• , .•.••..•••••••.•.•••••• , . • . • . . . • • , , • • • • • . 30
3. Nitrate Content ••• , .• • , , • , , .•••.•. , • ~ ••• , •••••. ~ • . • . . . • • . . • • •••• , • • • • • 32

" 4. Thermal Conductivity •••••••••••••. , •••••••••••••.•...•....••••... • . . • • 34
5. Bulk Density, Porosity, and Volume Reduction Factor •••• , ••.•••. , • , .•• , . • • • • • . • 36
6. Effect of Gross Porosity on Storage of Calciner Products •.•••• , • , ...••• ·••• , , , •• , • 40
V, PRODUCTION OF GLASS-LIKE MATERIALS •••• , ••.•. , , •••• , , ••..•••••. , ••••• , 42
VI. APPLICABILITY OF CALCINERS FOR PROCESSING VARIOUS WASTES • . • • • • • . • • • . • • • . • 44
1. Waste Activity Level •. , •.•••• , •••• , , ••• , . , . , •••• · ••••••••.....•.•.•••• _. 44
2. Waste Composi~ion 46
3. Waste Concentration , , , .•• , , , . , , , , , .•••••••••••••••.•••••••••.••••••• , 50
VII, WASTE DISPOSAL PLANT CONSIDERATIONS 52
1. Equipment •.•• , • , . , •••• , • • • . , •••• ; , . • . . . • • • • • • • • • • • • • . • . • . • . . . • • • • 52
2. Safety Considerations o o • • • • • • • o o n • n a a o • • • o 1 e o • ' o • o o • o o • • o o • • o • o o o o o o o 56
VIII. DEVELOPMENT STATUS 58
1. Current Status ••••••.•• , • , , , ••• , .••••.••..••.•••. , • • • • • • . . . • . • . • • • • • 58
2. Potential Problems ••••••• . •• ••••••••••• ••. •. •. ••••• •••••••••••• ••••• 58
,. 3. Facility and Personnel Requirements ••••••••••.•••••••••••••••.•••••••.••• 60
IX. REFERENCES , ••••• , •• , •••• , • , • , , , .•• , ••••• , , •••••••••••••••••• , • • • • • 62
APPENDICES . •• . •. . •. . •. . ••. . . . . • . . . . •. . . . . . •. . . . . . . . . . . . . . . . . . . . . . . . . . . 68
v
FIGURES
1. A conception of the relative safety resulting from storage of liquids, calciner products, or
vitreous materials . . . . . . . . . • . . . . . . . . . . · . . . . . . . . . . . . . . . . . . . . . . . • . . . . . • . . . • . 4
2. Relative amounts of highly radioactive wastes that may be generated by the year 2000 · · · · · · · · · · 4
3. Forecast of high-activity waste accumulation and conversion to solids for the United States . . . . . . .
. .
5
.
4. Fluidized bed calciner . . . . . . . . . . . . . . . • . • . . . . . . . . . . . . . . . . . . . • . • . . . • • . . • • . . . . 6
5. Pot calciner . . . . . . . • . . . • . . : • . . . . . . . . . . . . • . . . . . • • . . . . . . . . . . . . . • • . • • • • . . . • ~
6. Radiant-heat spray calciner . . • • . . . . • . . . • . . . ; . • • • . . . . . • . . . . . . . . . . • . • . . ; ....•• \· 7
7. Rotary-ball kiln calciner . . . . . . .' . . . . . . . . . . . . . . . . . . . • . . . . . . . . . • . . . . . . . . . • . . . • 7
8. Capacity of fluidized bed calciner . ·. . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . ; . . . . . . . 16
9. Capacity of single pot calciners 16
10. Capacity of radiant-heat spray calciners of! f f f! f f t I I I I I I I Ill I I I I • • • • o • • • • • • • • • • • 17

11. Capacity of rotary-ball kiln calciners 17
12~ Off-gas processing systems · . . . . . . . . . . . . . . . 23
13. Relative storage costs of radioactive waste solids 41
14. Relative volume of wastes compared for calciner products and glass-like materials . . . . . . . . . . . . . 43
15. Relative storage costs for cellular and granular materials produr.erl h·om aci.dic Pttrex-type wastes . 43
16. Alternative process requirements "for disposal of lObO gph of Purex-type waste 53
f
TABLES
1. Comparison of Fluidized Bed, Pot, Radiant-Heat Spray, and Rotary-Ball Kiln Calcination Processes . 2
2. Required Size of a Fluidized Bed Calciner to Process Waste Resulting

From Various Nuclear Power Requirements ·, , , , • ; .•••..•• , , , ••••••••.• , ••••..•.•. .18
3. Required Number of Pot.Calciners in Simultaneous Operation to Process

Waste from Various Nuclear Power Requirements • ~ • , . . . • . , •••...•••• , •. , .•• , • , , •. , , 18
4. Required Number of Radiant-Heat Spray Calciners in Simultaneous Operation

to Process Waste Resulting from Various Nuclear Power Requirements . . . . , •••••••••••••• 19
5. Required Size of a Rotary-Ball Kiln Calciner to Process Waste Resulting

from Various Nuclear Power Requirements ••••••. , .•••••• , •• , • , , • , ••• , • • • . . . . . . . . 19
6. Size and Shape of Fluidized Bed Calciner Product 28
7. Size and.Shape of Pot Calciner Product 28
8. Size and Shape of Radiant-Heat Spray Calciner Product • • o • • o o , o • • • o • o • • • .o • o ·o o o o o • • • o

29
9. Size and Shape of Rotary-Ball Kiln Calciner Product 010001010111110101101000000011.0

29
10. Nitrate Content of Fluidized Bed Calciner Product •• , .•••••••••••••.•.•••• , ••••• , .•. .32
~
11. Nitrate Content of Pot Calciner Product ••...•••• , ••••••.•.••••••••••••••• , •.•.•• 32
12. Thermal Conductivity of Fluidized Bed Calciner Product 34
vi
13. Thermal Conductivity of Pot Calciner Product 34
14. Thermal Conductivity of Radiant-Heat Spray Calciner Product • • • • • • • • • • . • . • • • • • • • • • • • • • 35
15. Thermal Conductivity of Rotary-Ball Kiln Calciner Product . ~ ••• •••••••• •. •••••. ••• •••• 35
16. Bulk Density, Porosity, and Volume Reduction Factor of Fluidized Bed Calciner Product • • • . • • • • 38
17. Bulk Density, Porosity, and Volume Reduction Factor of Pot Calciner Product ••.•••••••••••• 38
18. Bulk D~nsity, Porosity, and Volume Reduction Factor of Radiant-Heat Spray Calciner Product ••. • 39
19. Bulk Density, Porosity, and Volume Reduction Factor of Rotary-Ball Kiln Calciner Product 39
20. A Comparison of the Volumes of Solids That May Result From Use of
Various Processing and Solids Storage Techniques • ·• • • • • • • • • • • . • • • • • • • • • . • • • • • . • • • • • 47
,.
.vii
B, R. Wheeler
J. A, Buckham
J. A. McBride
1. SUMMARY AND CONCLUSIONS
The urgency of developing suitable methods for safe ultimate disposal of highly radioactive wastes will
intensify as the nuclear power industry matures. In the United States, major development effort has been
concentrated on four calcination processes, the fluidized bed, the pot, the radiant-heat spray, and the rotary-
ball kiln, for disposition of this waste, the accumulation of which may exceed 500 million gallons by the year
2000. To process this amount of waste the combined capacity of all disposal plants using one or more of these
calcination processes, assuming 1965 start-up and 300-day per year operation, must be on the order of 1000
gallons per hour.
Considerable information has been published on waste disposal and calcination; unfortunately, it cannot
readily be compa,red due tQ differences in reporting bases and in state pf development of the various processes.
This report attempts to rectify, partially, the former situation by reducing much of the published data to
common bases.
Detailed study and comparison of the calcination processes show that the mechanics of waste decomposition
are similar for all calciners. The fluidized bed, the radiant-heat spray, and rotary-ball kiln calciners are all
capable of continuous operation, while the pot calciner is inherently a batch unit in· which the process vessel
also serves as the final storage container. Off-gas from any of the calciners can be decontaminated in either
a condensing or noncondensing off-gas system, depending on the requirements of a particular waste disposal
plant...By employing appropriate proved techniques, the final volume of off-gas released per unit of waste for
all calcination processes can be reduced to the same minimum amount, containing only instrument purge gases
and certain noncondensible reaction products. Various other aspects of calcination are listed in Table I.
A number of generalized conclusions pertaining to end products of calcination may be drawn from this
comparison. The ideal end product for ultimate storage should be noilleachable in water, thermally and radio-
lytically stable, and should have the minimum attainable volume and other properties to permit storage
in economical facilities with a minimum of continuing surveillance. Because all these features are not currently
attainable in any single product, any process selected for waste disposal should offer the best practical
compromise based on economics and safety. The three general types of end products now possible are (a)
gro.nulo.r materials as proc:ln~P.d in the fluidized bed, radiant-heat spray, and rotary-ball kiln calciners,
(b) cellular materials as produced in pot calciners, and (c) glass-like materials which can be made from the
primary product of all calciners through the use of suitable fluxing agents.
The technical merits of a glass-like material over a primary product of a calciner are questionable.
Utlless totally nonleo.ohable , glaRRAR rP.flUire containment; benefits of low leachability are realized only
with breached storage vessels. Except with some high-porosity products, fluxing agents reqmred to produce
a glass-like material increase the final material volume over that otherwise possible. To be attractive
economically, the increased expense of producing glass-like materials must be offset by savings achieved
either· due ·to a decrease in volume or through the use of larger, cheaper storage facilities because of a
highe·r thermal conductivity of the glass-like material.
Batchwise production of cellular calciner products, or glasses in individual pots, has several unique
economic disadvantages. Requirements of remote manipulation, handling, and transportation may limit
maximum pot size and increase labor costs. ThP.se considerations, rather than maximum permissible
temperature during storage,' govern pot size for medium activity wastes resulting from chemical decladding
and for high-level wastes older than three to ten years. Inability to remove cellular materials from the initial
container makes this economic penalty permanent for all wastes.
· . Granular products, nearly free from these limitations, can be retrieved pneumatically at any time for
further process.ing; if desired, or transferred to less expensive vessels, taking full advantage of activity
decay. Also, since granular products c.an always be stored in large inexpensive vessels limited in size only
by considerations of ultimate product temperature, advantage can be taken of variation in activity level of a
waste at time of processing. These materials then have characteristics which meet, in part, the suggestion of
those of the oo~ontific commnnit.y that believe no present or near-future treatment should irrevocably remove
radioactive W'clStei:l frum al;cessibility by futuro generations. IntArim ::;torage of these materials l:l.i:l uall.:iut::u
granular solids offers a greatly reduced hazard over liquid storage, but retains much of the accessibility.
1
TABLE 1
COMPARISON OF FLUIDIZED BED, POT, RADIANT-HEAT SPRAY, AND ROTARY-BALL KILN CALCINATION PROCESSES
CAICmATION PROCESS
Fluidized Bed Pot Radiant-Heat Spray Rotary-Ball Kiln .
Single Unit Througjlput, gph < 1 to 1500 < 1 to 10 < 1 to 65 <1to300
Calciner Product Properties

Average Size, mm 0.25-1.20 Not. Applicable 0.002-0.013 0.13-0.16
Product Type Granular 1 Spherical Cellular Granular, Fra.e.nented Granular, Fragmented
Bullt Density, g/cc 0.5-3-0 0.4-1.6 0.18 to 1.1 0.65 to 0.95
Porosity, 'f, 44-76 51-86 67-94 69-79
Volume Reduction
Typical 7-20 5-9 2-4 7-10
Maximum 23 20 l~ lJ
Thermal Conductivity Up to 0.27 at 800°C llp t.o 0.6 at 900°C Up to 0.13 at P.00°C 0.1 at unspeo.i 1'1 e.rl.
BTO/(hr )(f't )("F) tliillm):"'Q-r.QtiJ:-;tf"
~ - 0
- Nit·rate Content, '/> 5-12 at 300-500 C Not reported Not reported
Volume of Glass-Like
Material With Respect to Greater About same Smaller
Primacy Pl"odl.lot
Calclua.tlou Temperature
Product, °C 300-550 900 300-800 300-700
Heating Surface, °C Up to 730 900 800-825 Up to 8oo
Applicabil!:.J;Y. Aluminum nitrate, and AJ.uminum n1trate, and eto.in- Aluminum nitrate, I:Wd t:Jta.in- Aluminum nitrate, and stain-
stainless steel nitrate· less steel nitrate-type less steel nitrate-type less steel nitrate-type
type wastes. Purex wastes wastes. Purex wastes may wastes. Purex wastes may wastes. Purex wastes may
may require add.it 1ve . require additive. Organic require additive. Fluoride require additive. Fluoride
Fluoride bearing wastes at bearing and fluoride bearing bearing wastes probably can- bearing wastes at tempera-
temperatures less than wastes probably cannot be not be calcined. tures less than 500°C' bv
'}009r: ~Y ug;S.na 11 eti:loium l!.u.l...:.ined. using a calcium oxide
oxide additive. Rr1rHtil.rl:ll,
Effect of Waste Activity Ultimate disposal costs Ultimate disposal costs Ultimate disposal costs Ultimate disposal costs
Level on Processing Costs should decrease w1 tb de- independent of activity independent Qf CM:tivity Rhnnlrt ri~I'Jr9P.t'O \11th de ..
cn~a~l.~...~g l;lC l.l v1 Cy lwei. except f6i' extremely high- P.YrP:rt f'm• extremely high- · . crcaoing ...::LlvHy level.
level wastes. 1 PVP.l t.rUi!lt~;.
Relative Unit Waste Disposal Low because: High because: High because: Intermediate because:
Costs (l) A single calciner suit· (1) Low throughput capacity (1) Multiple ~alciners in (1) Single calciner may be
able for most plants, re- requires multiple calciners simultaneous operation used in most plants, operating
sulting in small facility "in simultaneous operation needed in plants having costs nearly independent of
and P.CJ.u1.pment requirements; for moat applications, througl:lput capacity greater throughput •
CCttl1tal. a.nr1 ~rat1na nt:'-:!t'1 n~ratina ?Q!:'i;!J nof\W.:,o III'G tLu.u uuuu ~ G' gv!J.
essentially independent of portional to 1;hro\lR!Il1ut,
t.hi:'Otigbput •
\2) IHtb pneumatic trans- {2) Pot size limited and (2) Product collection for {2) Higjl maintenance costs
port of granular product, labor requirements increased melting 1n pots rP.Rn.l:t:.B in are indicated by consider•
h1gjl labor and remote by remote manipulation, · conaiderable remote handling able number of mechanical
handling costs can be handling, and transport con- and all associated costs· parts of calciner.
avoided. ditiona. Pot size and labor require
ment5 higb.ly U~pendei:it · on
remote handling and .transport
AR[I""'rt.R.
( 3) H1gjlly instrumented .• ( 3) Mechanical e'luJ.!"""'nt. may ( 3) Mechanical equipment may

has virtually no· mechani- require frequent ma.inte- require frequent mainte-
cal equipment; minimum size nance. nance.
maintenancP. anti o:rerating
labor force required.
Most problems identified; Sane problems related to 'DOt Same prnh 1 PmR l"P 1At.t:ot:l. to Devvlopmont effort hats Ue~n
!1\llllerowi operating and handling, product over- pot handling, product re- llar;;"'lYI on rotating seals;
process correlations es- heating, pot corrosion at moval, and deposits of pro- • henc:e,\manylpOtential. probiems
tablished. Plant-scale higb temperature, and ot'f'- duct on vessel walls during \ reilated to feed introduction,
. Waste Calcining Facility 'gas line plugging remain. operation still remain. product bai:tdling 1 rotating
processing' wastes since . Actual waste processed Actual waste processed: seals 1 instrumentation of
.D.ec. 1963. · 1n laboratory scale calciner 1n laboratory-scale calciner rotating kiln, etc., remain.
at Hanford since late 1962. since late 1962. · Demon- No further development work
Demonstrational pilot plant strational pilot plant bas been announced.
facility scheduled for facility scheduled for
operation with radioactive operation with radioactive
wo.atee in 1965. wastes in 1965.
2
II. INTRODUCTION
An intensive world-:-wide effort isunderwaytodevelopsuitable processes for fixing waste activity in stable
solid media. From the United States' effort, four different calcination processes, the fluidized bed [1],
the pot [ 2], the radiant-heat spray [ 3], and the rotary-ball kiln [ 4] are emerging. Product from any of these
processes can be converted to glass-like material in a step subsequent to calcination, or be dispersed in
insoluble matrices to reduce the leachability of the activity by water and increase its thermal conductivity.
Other techniques under development, but not as advanced as these calcination processes, include direct con-
version of waste solutions to glass-like compounds [5-8], decomposition of waste and fixation of the metallic
salts therein in molten sulfur t9], and adsorption of radioactivity in solutions on clay-type minerals followed
by high temperature calcination [ 10]. ·
It is likely that one or more waste disposal plants using some form of calcination will be constructed in
the near future for converting radioactive solutions to the solid form for added safety. For optimum design
of these plants, special cognizanceofthefollowingfactors is desirable: (a) the size and suitability of a process
with respect to the amount and types of waste in question, (b) product properties with respect to safe ultimate
storage and the potentiality for further product processing, (c) process economics with respect to the quantity
of waste activity placed in storage, and (d) ·the long term suitability of a process with respect to future
developments in nuclear fuels and processing technology. This last item is particularly important since
considerable data and operating techniques will be evolved from the operation of initial waste disposal plants
that will be of incalculable value in the design of subsequent facilities; hence, a process of rapid obsolescence
should not be adopted, even in the face of favorable short term economics.
Unfortunately, selection of a calcination process for an optimum waste disposal plant would be difficult
now because (1) there is uncertainty as to the best final resting place for solidified wastes, (2) the major
processes are in different stages of development, and (3) existing reports do not, in general, present data in a
form to permit ready comparison of process characteristics, or, indeed in some cases, to permit evaluation
with respect to previously reported information on the same process. The authors attempt in this report to
compare on a common basis the four most highly developed calcinatio-n unit~ using published data and infor-
mation wherever possible and using best estimates where data have. not been published.
The character of the waste disposal problem is discussed in this section. The main body of the report is
·devoted to detailed, point-by-point comparison of the fluidized bed, the pot, the radiant-heat spray, and the .-·.•.
rotary-ball kiln calcination processes with respect to the most important process and product characteristics.
A. Safety Considerations in Waste Disposal
Early workers correctly concluded that haphazard disposition of radioactive wastes could harmfully
affect all succeeding generations of life, and therefore established the policy, yet in effect, that waste activity
would be contained or sufficiently dispersed to prevent accumulation in unsafe quantities in populated areas.
Since this early definition of the problem, many· scheme~ have been proposed for ultimate waste disposal;
however, because natural decay of waste activity is the only truly final means of disposition, all processes for
concentration, fixation, removal of fission products, etc, are only partial measures to reduce the hazards or
to improve the economics of storing radioactive wastes.
The billions of gallons of low activity waste solutions produced yearly in various segments of the nuclear
fuel cycle have been decontaminated and dispersed safely to the environment by employing a variety of proved·
techniques; the high activity waste solutions, however, some of which contain thousands of curies of activity
per gallon, have been stored in large underground tanks. It has been recognized generally that this type of
containment is only a stopgap measure. Tank integrity to date has been generally satisfactory; however, the life
expectancy of storage tanks is uncertain. Although only indirectly applicable, oil industry experience has been
about one tank failure per 3400 tank years of service, indicating that even vessels as simple as tanks are
subject to failure. At the remote Hanford location and at the Savannah River Plant, tanks containing high
activity wastes have leaked [ 11], fortunately without adverse effects on the population. Vessel leaks due to
corrosion, or vessel rupture due to a catastrophe, must be guarded against even more in highly populated
regions.
Ultimate safety in the dispositi.on of waste activity would result only with solids completely nonleachable.
in water and placed in a totally remote location. A method to prepare such a material is not yet available;
therefore, even glass-like materials must be placed inside containers for long term storage. In Figure 1,
an attempt is made to show qualitatively the relative degree of safety associated with storage of the various
forms of radioactive wastes. A minimum level of safety results from simple disposal of activity to the ground
OF to waters accessible to mankind. On the other end of the scale, maximum safety would occur from fixing
activity in a totally nonleachable material and storing this material in a completely isolated location. Between
these two extremes are varying degrees of safety which depend on the type of storage container, its location,
and the leachabilityoftheradioactivematerial;thethreshold of minimum acceptable safety must be established
for any given situation. For conditions above this threshold, economics should play a significant part in the
selection of a waste disposal method.
3
B. The Magnitude of the Waste Problem
Approximately 80 million gallons of high-level

waste solutions have already been accumulated at
various locations in the United States [ 12]. As the
nuclear power industry matures, this volume of
waste may mushroom, as shown in Figure 2, to
levels as high as 500 million gallons by the year >-
1-
2000, depending on various factors such as continued w
LL.
need for· production fuels, rate of development of
~
the nuclear power industry, the types of reactors (.!)
and fuel elements employed, the burnup levels of z
the fuels, and the technology of fuel reprocessing. Vi
<(
w
a::
More detailed information on expected future u
z
volumes of power fuel wastes is given in Figure 3.
1n this figure are given the results .of various
predictions [13-16, 130-132], including Curve (a)
showing the 1959 Bruce [13] estimate of future
volumes of power reactor fuel wastes which assumed
chemical decladding, and Curve (c) based. on the
1962 Seaborg prediction [16] of the rate of growth UNSAFE
Pf/\Z/\~oous
of nuclear energy for electric power and a waste ro LIFE
generation of 50 gallons per ton of uranium, probably
an irreducible minimum; also shown is the cumulative
volume of waste, Curve (b), that would result
assuming the Seaborg prediction and a waste gener-
ation of 400 gallons per ton of uranium as expected Fig. 1 A conception of the relative safety resulting from storage
with the Nuclear Fuels Services Processing .Plant of liquids, calciuer· vrulluc.:ts, ur vitreous materials. There are
at least two degrees of freedom for obtaining any level of safety:
[130, 131]. Arbitrarily, it was assumed that wastes separation from humanity and degree of leachability. Even a
from other AEC activities would be created at the totally nonleachable material--not yet attainable--must be
rate of five million gallons yearly through 1985, removed from the habitat of man; however, a modest separation
after which only an insignificant volume of this results in a considerable improvement in safety as compared to
that possible with solutions or highly leachable solid materials.
type waste would accumulate. The zirconium-type Ultimate safety is represented by a totally nonleachable material
waste shown in Figure 3 will originate from process- stored in a completely isolated location, perhaps deep in the
ing enriched zirconium alloyed fuels being used to earth. Storage of solutions in this same location could result in
an increasing extent in compact locomotion equip- a tolerable degree ot satety. Between the extremes ot solutions
and t.otally nonlf.'ar.habl.;o. mat~t'.ial.s are various 0Rlr.\nP.t'prorft~r..ts
ment. The cumulative volume of this type waste is and vitreous materials with overlapping degrees of leachability.
based on a prediction of the number of sea-going The assignment of values to the scales on this diagram is a
reactors to be constructed in the next 9 to 21 challenge now facing the scientific co nun unity.
years [1321.
The magnitude of the waste problem is related
in Figure 3 to the cumulative amount of wa:ste that
can be processed between 1965 and any future year
with plants having a combined capacity of 10 gph,
PRODUCTION FUEL 100 gph, or 1000 gphfor 300-day per year operation.
WASTES
190 )( 100 GALLONS It. appear~> that. the combined capa.cit.y of waste
~ ..--.......-......- ....- ....-.. disposal plan to in the United States will have to exceed
..... "'""'''" '.' ~ 100 gph and probably exceed 1000 gph, to convert to
I 190x 106
.c~;,~~!.~i~?:~.
solids by the year 2000, all the wastes presently in
storage together with those generated in the interim.
The number of plants built will be, no doubt, depend-
cul uu lhc uu!Huer' .:,f l.:,cati-:,1~.3 at which waoto io
165 )( 106 ~enerated, although it seems highly desirable to min-
'""""'""' '"' """'"'"'' '"''"""""'"'
imize this number because all radioactive materials
030 x IQ6; 2000 will require some type of perpetual surveillance.
Therefore, typical future plants for converting waste
80 )( 106 (35.J<J0!/ 1990 solutions to solids should have individual capacities
exceeding 100 gph of waste solutions.
1980
1963 Waste disposal plants should be developed
rapidly since funds used for the construction--
and later for perpetual surveillance--of liquid tank-
Fig. 2 Cans depict the relative amounts of highly radioactive
wastes now in existence together with those that may be generated age could be better spent for ultimate solids storage
by the year 2000. Arbitrarily, it was assumed that five million facilities. Calcination is the only technology suf-
gallons of production fuel wastes would continue to accumulate ficiently developed today to meet the needs of the
annually through 1985, after which essentially all new wastes waste disposal problem; hence, only the fluidized
would be those from power reactor fuels; the volume of power
fuel wastes shown Is based on the Bruce estimate [13].
bed, the pot, the radiant-heat spray, and the rotary-
ball kiln processes are considered in this report.
4
109
.!!!
0 5
"'
r.ti
w
f-
~
2
>- 10 8
f-
5
i=
u
<f 5
I
(.!)
I
lJ._
0
2
w
:::;:
:::::>
_J
10 7
5!
w 5
>
~
_J
:::::>
:::;: 2
:::::>
u
10 6
1960 2000 2010 2020 2030 2040
YEAR CPP -S -2972
Fig. 3 Forecast of high activity waste accumulation and conversion to solids for the United States. Values of the cumulative volumes of
waste solutions converted to solids at processing rates varying between 10 and 1000 gph are superimposed on estimated volumes of cumulative
quantities of waste based on several predictions [13-16, 130-132]. The initial combined capacity of several solids conversion plants beginning
operation in 1965 on a 300-day-per-year schedule probably must be over 1000 gph to process present wastes along with all new wastes by
the year 2000.
5
III. COMPARISON OF CALCINATION PROCESSES
The chemical process of converting radioactive waste solutions to solids is similar in all calcination
techniques. Waste--an aqueous solution of metal salts--introduced to a heated vessel is converted to oxides
or other solid compounds, depending on the nature of the waste and the calcination temperature. With the
fluidized bed, the radiant-heat spray, and rotary- ball kiln calciners, potentially all continuous operating
units, product is removed from the calcination vessel and collected or transported to a storage container.
With the pot calciner, a batch unit, product remains in the process vessel which serves also as the final
storage container. Descriptions of each calcination process and its operation are discussed in this section.
(Continued on page 7)
1. Calciner Description and Operation
Fluidized Bed Pot
Present Situation Present Situation
Waste solution sprayed into a well-fluidized, Waste solution introduced to an electically-

heated bed of granular solids--shown in Figure 4-- heated cylindrieal pot--shown in Figure 5--is evap-
coats the particles in the bed; water vapor and
volatile gases flash from the spray droplets leaving
the oxides of metallic salts in the waste uniformly
deposited on bed particles. At equilibrium con-
ditions, the effect of particle growth is balanced CALCINER OFF - GAS TO
by the formation of new seed particles and by -sCRUBBER OR
CONDENSER
removal of product; particle size distribution is
stabilized at a value characteristic of the operating
conditions employed. The bed temperature is main-
tained at a predetermined value in the range
300-500°C by internal heat exchange surfaces. The
spheroidal granular particles , ranging in diameter
from 0.1 to 1.5 mm, are continuously removed
from the calciner and are pneumatically trans-
ported to storage facilities. The transport gas,
ZONED
after separation from the calciner product. is INDUCTION POT HEIGHT N 10'
merged with the fluidizing gas and the gaseous FURNACE POT DIJI.METER- 6-24
reaction products in the calcination vessel. Solids
removed in the off-gas system from the fluidizing
gas may be returned directly to the bed or combined
outside the calcinatiOn vessel with the bed product;
~COOLING
the latter represents current practice. WATER
- - - - - CALCINER OFF -GAS TO

SCRUBBER OR CONDENSER
MECHANICAL
r.JACKS
OVERFLOW
Fig. 5 Pot calciner.
orated to dryness and calcined at temperatures in

'---FEED SOLUTION
the range 700-900°C. Metallic salts deposit in
radial layers along the vessel walls and gradually
CIRCULATING fill the pot as a massive porous solid. Water vapor
-~I----BED-SUPPORT, GAS
and volatile docompooition producto po.oo continu-
DISTRIBUTOR PLATE
ously at an ever-diminishing rate around an over-
head baffle in the pot and are introduced to an
off-gas processing system. The pot calciner serving
as a final storage container is transported by
conventional remote manipulation practices to a
Fig. 4 Fluidized bed calciner. repository.
III. COMPARISON OF CALCINATION PROCESSES (Continued)
These descriptions are based on the processes used during development work but include in some cases
certain innovations believed by some investigators desirable for plant operation.
Organization of information: In this and following sections, information generally applicable to all of
the processes, usually is presented as an introduction followed by a detailed comparison of the calcination
processes. The comparisons are subdivided into a Present Situation section for presentation of reported
data and known facts and a Discussion section where this information is interpreted with respect to a waste
disposal plant.
1. Calciner Description and Operation
Radiant-Heat Spray Rotary- Ball Kiln
Waste solution atomized near the top of the With the rotary-ball kiln calciner--shown in
radiant-heat spray calciner--shown in Figure 6-- Figure 7--waste solution is dripped or sprayed onto
falls freely through the cylindrical yessel, which is
electrically-heated to a temperature between 700 and
825°C. Tile suspension of atomized feed dropl ets KILN BEARING SUPPORTS
passes through zones of evaporation, drying, and cal-

cination resulting in a finely divided powder varying in ELECTRIC FURNACE
average size from 1 to 12 microns (22]. Removal of
the powdery produut from the calcination vessel may
require a vibrating-screw feeder [23]. Water vapor,
volatile decomposition products, and the gas used to
atomize feed are separated from the product by blow-
back filters outside the calcination vessel. Product
usually has been collected in pots below the cal-
ciner [3, 22], which in a plant facility would be
transferred by remote manipulation to a repository.
ELECTRIC HEATERS
_...----INSERTED INTO
HOLLOW CENTER WALL
CALCINER OFF-GAS Fig. 7 Rotary ball-kiln calc iner .

~TO SCRUBBER OR
I CONDENSER
a bed of moving m etal balls in a slowly rotating
cylinder, electrically-heated to a temperature be-
tween 600 and 800°C. Product formed from deposition
of the oxides of m etallic salts on the balls is
pnlvRrized during kiln rotation into particles varying
in size from 0.05 to 0. 8 mm [48, 49]. The product
VIBRATOR ' " overflows from tile calciner concurrent with the
off-gas and enters a cyclone or metallic filters for
product-gas separation. Product usually has been
VALVE collected in pots below the calciner.
FURNACE
COLLECTION
POT
Fig. 6 Radiant-heat spray calciner.
7
1. Calciner Description and Operation (Continued)
Fluidized Bed Pot
Present Situation (Continued) Present Situation (Continued)
Various fluidized bed calciners, diameters in the Pot calciners varying from two inches in
range 6 to 48 inches at the Idaho Chemical Processing diameter and 18 inches long to eight inches in
Plant (lCPP) [24-28], six inches at the Argonne Na- diameter and 90 inches long have been employed
tional Laboratory [29], and eight inches at Han- in various studies at Oak Ridge National Laboratory
ford [ 30, 31], have been successfully operated to cal- (ORNL) to calcine simulated waste solutions
cine simulated waste solutions. High activity solution, [2, 34, 35]. At Hanford, similar studies have been
diluted at least eight to one with nonactive synthetic made with pots varying from three inches in diameter
solution, was calcined in a six-inch calciner at and seven inches long to eight inches in diameter
Argonne in 1958 [29]. The 48-inch diameter Waste and 66 inches long [36-41); Hanford studies also
Calcining Facility (WCF) at ICPP, which began hot were made with annular pots, the largest of which
operation in December 1963, is the first large were constructed from four- and eight-inch standard
scale unit to process significant quantities of radio- pipe, 5-1/2 feet long[ 42], At Hanford, small quantities
active waste solutions. In nonnuclear industries. of high activity wastes are being 0al0inArl in R
fluidized bed calciners are commonly used for lahoratory-scale pot calciner (36, 43, 44); an
a variety of purposes (32], in sizes as large as 20 engineering s0alA pot calciner is scheduled for
feet in diameter [::!::!J. Thus, considerable scale-up operation with radioactive wastes posRibly by
data are available for this type calciner. 19115 [45].
Discussion Discussion
The fluidizing medium introduced at the bottom Pot calcination is inherently a batch process
of this calciner can be any suitable gas (air, in which an individual pot is connected to a feed
superheated steam, reducing or oxidizing gases, line, filled with solids, and then replaced with
or recycled decomposition gases from the calcination another pot requiring considerable remote handling
reaction), final selection of which will depend upon equipment and operator time. Some important details
the chemistry and the economics of an integrated visualized as necessary to operation of this calciner
waste dl:::;po:::;al plant. are shown in Figure 5 and are discussed in Section
VII of this report.
The upper size limit of a fluidized bed calciner
for processing radioactive solutions has not been The maximum size of a pot calcination vessel
established; however, it appears that 60- to 90-inch is limited either by the specific activity of the
diameter vessels are entirely feasible without waste or by rAqlli rements of remote handling and
necessitating the use of excessively large cell transporting filled pots; the latter aspect overrides
facilities. A well-designed fluidized bed calciner the former. Hancher [34] and Perona et al [17]
should have a heated height about equal to the assume that future waste disposal facilities may
diameter of the heated section of the vessel. Use use pots 8-15 feAt long and 6-24 inches in diameter.
of tapered beds or enlarged overhead sections is A pot calciner must be baffled and have a de-
desirable for high feed capacities to limit the entrainment section 1- J /2 to 2 feet long; thus
superficial velocity of gases above the bed and the usable volume of this calciner is 75 to 87
thereby prevent excessive product elutriation. percent of its total volume.
8
1. Calciner Description and Operation (Continued)
Two radiant-heat spray calciners, both ten feet Three rotary-ball kiln calciners have been
high, one eight inches in diameter [22], and the other operated at Brookhaven National Laboratory
18. inches in diameter [36, 41], have been used at (BNL): a six-inch diameter, 36-inch heated-length
Hanford to calcine simulated waste solutions. A ten- unit; an eight-inch diameter, 84-inch heated-length
inch diameter, five-foot high laboratory-scale cal- unit [4, 4ff, 49]; and a staged calciner with two
ciner [3, 36, 43, 44] has been used since late 1962 to four-inch, diameter, 12-inch long kilns [50]. (Al-
process small quantities of high activity solutions. A though a calciner employing a rotary-ball kiln
process similar to radiant-heat spray calcination, principle has not been designed to process actual
referred to as the Atomized Suspension Technique, is wastes in the United States, the French are devel-
being used in Canada to process sewage sludges and oping such a small-scale calciner for this pur-
industrial waste liquors [ 46]. Gauvin [ 4 7], who pose [8].) In nonnuclear industries, 12-foot diameter,
poineered the Atomized Suspension Technique, esti- 475-foot long kilns have been used for various pur-
mates that calciners as large as three feet in diameter poses [51]; ball mills up to nine feet in diameter
and 65 feet high would be practical for processing usually have an L/D ratio of about one.
sulfite liquors.
During development work, deposits of powder Mechanical seals needed with this calciner to
along the' vessel wall of this calciner limited heat couple the rotating kiln to stationary equipment
input [36, 54, 55] and led to excessive vessel components of the process have required con-
corrosion [39]. The annular channel shown in Fig1!re siderable development [ 4, 48, 49]. Recent results [ 49]
6 is an outgrowth of early development work [22] indicate the necP.ssity of further work.
which indicated that such a device could prevent
powder deposits; however, subsequent work has not A product collection pot, as ·used in development
borne this out [36]. Wall deposits have been con- studies and shown in Figure 7, will require remote
trolled by. means of a vibrator during many runs handling equipment.
[22, 36, 44].
A practical upper limit for the size of a
Use of a productcollectionpotwiththiscalciner, rotary-ball kiln calciner has not been established.
shown. in Figure 6, will impose the need for remote A feasibility study [53] by Blaw-Knox suggested use
handling equipl;Iient as discussed in Section VII of this of a rotary-ball kiln calciner 2-1/2 feet in diameter
report. by 20 feet long for a proposed waste disposal
plant. Rotary kilns (Without moving balls) in non-
The upper practical size of a radiant-heat spray nuclear industries vary widely in size; however,
calciner for processing high activity solutions has not the common denominator [5lj appears to be a
been established. Johnson [52] calculated that the value varying between 1.5 and 5.0 ft-1 for the ratio
diameter of a radiant-heat spray calciner may be as
large as three feet without prohibitively maskingthe kiln length
heat transfer to the center of the calciner. An upper diameter2
value of height may be around 20 feet if it is assumed
that a practical depth for a cell to house a calciner This ratio for the eight-inch diameter pilot plant
is about 30 feet; necessary appurtenant equipment calciner employed at BNL in 15. 7; however, it is
below the calcination vessel would require the re- generally recognized that future calciners should
maining ten feet of cell depth. The L/D ratio, 6. 7, have smaller values of this ratio [49J. Assuming
of a three-foot diameter 20-foot high calciner is that the size of a rotary-ball kiln calciner will be
considerably less than the 13 to 20 value recom- limited by the size ofthehousingfacilities, the upper
mended by Gauvin [47, 56] but is approximately that practical length may be about 20 feet with a diameter
of the laboratory scale calciner used at Hanford. of about 2-1/2 feet.
9
2. Heat Introduction and Temperature of Operation
The rate at which heat can be supplied to a calciner limits the capacity of each of the calcination processes.
Of the variables affecting heat input, heat transfer area and temperature differential in the calciner offer the
greatest latitude for the design of a single calciner of any given capacity.
All calciners may employ heated vessel walls; some also may use heated internal s·urfaces, eg, ·tube
bundles or heated annular sections. Use of tube bundles greatly enhances the throughput capacity of a calciner
because the area of its surfaces can increase with the square of vessel diameter for any given array, while
wall surfaceincreasesonlylinearlywithvesseldiameter. Under some conditions, heat introduction to calciners
may be increased further by injecting a fuel into the calciner along with the feed solution [22, 29].
Temperatures ranging from 300 to 900°C have been employed with the various calcination processes to
calcine synthetic waste solutions. High temperature operation has been studied to insure that the product
in storage can always be at a lower temperature than calcination to prevent evolution of volatile gases,
primarily nitrogen oxides at temperatures up to 800-900°C, Some nitrogen oxides will be evolved in any
Fluidized Bed Pot

<H •••-M ••
Various heat introduction methods have been At ORNL [ 18] heat has been furnished for pot
used with the fluidized bed calciner, including_ heat r.R.lr.im1tinn th:r.ougb the walls of the oaloino.tion
transfer from vessel walls and from high temperature vessel J::iy a six-zone electrical resistance furnace
fluidizing gases; the preferred method employs and at Hanford [3, 40] by induction furnaces.
internal heated surfaces which may be a tube
bundle with circulating NaK heated in an oil-fired The pot calciner has usually been operated at
furnace, sheathed electric heaters, or direct-fired about a 900°C temperature level at ORNL [ 2, 18], the
tubes. Heat fluxes have been found tobe similar in highest practical temperature for existingmaterials
all cases, overall coefficients of heat transfer of construction and furnace designs. During some
ranging from 40 to 100 Btu/ (hr)(ft2WF) [ 25J. studies at Hanford [41, 42] pot calciners have been
operated at a temperature level between 400 and
. Fluidized bed calcination has, during most 500°C on the early part of a run when feed was intro-
development studies, been carried out at temper- duced to the calcination vessel. The nitrate content
atures between 300 and 5tiU"C. Bed temperatures (and probably mercury content) of product created at
were found uniform within the 5°C accuracy of 900°C is in the range of a few parts per million.
measurement [60], except in the narrow feed zone.
T~mp~ratures below 300°C are not recommended
because of an inherent possibility of caking in the
bed. At bed temperatures of 300°C, amorphous
alumina product is usuallyproducedfromaluminum-
type wastes: the nitrate contP.nts vary between
8 and 13 percent. The product retains between
70 and 90 percent of the mercury fed to the unit,
and the product has 50 £ercent less pore space
than that created at 500 c, At oed temperatures
of 550°C, alpha alumina is usually produced (if
boric acid is absent from feed solutions) with
nitrate contents varying between four and six percent.
Less. than 30 percent of the mercury in waste
solutions remains with product created at a temper-
ature of 550°C, Other properties of product for
various wastes are discussed. in Section IV.
10
2. Heat Introduction and Temperature of Operation (Continued)
case due to radiolytic decay of residual nitrates which could pressurize a sealed storage container. With
a vented container, evolution of volatile gases can be permitted; the rate of evolution will be dependent on
product temperature and rate of radiolytic decay._
Considerable incentive .exists to calcine wastes at low temperatures with the heating surface at ahigh
temperature because fn all processes, the net throughput capacity is greatly increased and, at least in the
case of the fluidized bed calciner, the porosity of the product is related directly to calcination tempera-
ture [ 64]. Calcination of some wastes must be performed at relatively low temperatures to prevent excessive
evolution of mercury and sulfur compounds. Withfluoride-bearingwastes, as discussed in Section VI, additives
may have to be employed to retain fluoride in calciner product even under low temperature calcina:tion. With
Purex Wastes, low' temperature in calcination and .the use of additives may be necessary to prevent product
fluxing. At Hanford [30], product of a high sulfate, Purex-type, simulated waste processed in a fluidized bed
calciner, sintered around ele.ctrical heaters at sheath temperatures between 600-650°C; at sheath temperatures
between · 700 and 800°C a solid cake formed. Product fluxing on heated surfaces for similar wastes without
additives could be equally troublesome with the radiant-heat spray and rotary-ball kiln calciners during
operation at temperatures exceeding 600-650°C. ·
Radiant-Heat Spray Rotary-Ball Kiln
. Heat has been generated during development In development units, heat has been furnished
wo;rk with the radiant-heat spray calciner both to the zone of calcination through the walls of
from a circumferential band of electrical heaters the rotating kiln by a circumferential electrical
on the upper section of the calcination vessel resistance furnace [4, 48],
and also by passing a low voltage, high am-
perage current through the walls of the vessel On most runs, the kiln walls have been at
itself [3, 22]. a temperature level of about 700°C; interior temper-
atures have varied between 590 and 680°C [48].
A gas-fired radiant-heat spray calciner referred The first stage of a laboratory two-stage kiln
to as a flame denitrator [42], a f.rototype of the calciner was operated at 325°C during calcination
Mallinckrodt Flame Denitrator [62 , also has been of a zirconium-type simulated waste [50]. .
used in studies at Hanford. The atomizing nozzle in
the Hanford unit was surrounded by an annular A depression in kiln temperature, as much as
propane burner which provided heat for evaporation several hundred degrees, usually exists near the
and calcination of feed droplets. The product from point of feed introduction.
the flame denitrator was essentially the same as
that from the electrically heated radiant-heat spray
ca~ciner.
The normal operating temperature of the vessel

walls of this calciner has been about 825°C during
development studies [22]. The temperature of pro-
ducts in the vessel varies with the distance from the
atomizing nozzle; product temperatures 15 inches
below the nozzle have been as low as 325°C [22],
while product near the bottom of the vesselis usually
at a le!I1perature very near that of the wnll [23J.
Excessive temperatures have resulted in particle
agglomeration and product caking in the calciner [ 42].
Maximum product density results when the tempera-
ture in the top of the vessel is maintained at a level
of about 325°C [22].
11
2. · H~at Introduction and Temperature of Operation (Continued)
F'luidized Bed Pot
Heat introduction to the fluidized bect calciner Heat introduction "to a pot calciner is probably
through internal heated, surfaces results in a .very limited to the means p'resently employed. Alternate ·
large capacity for any. given vessel diameter. methods, heated internal surfaces, use of organics,
Electrical resistance heaters are not recommended etc., have one or more serious drawbacks.
for. plant usage because excessive heater burnout
has been experienced when small sections of a bed It has been recommended [ 45] that the Hanford
were poorly fll.lidized; even momentarily. demonstration pot calciner use an induction furnace
with water-cooled coils to permit almost instan-
Heat input. may be further increased by injecting taneous heating or cooling of the calciner because
a fuel into a fluidized bed as.. done in pilot plant of a possible heat removal requirement [61]. During
studies at Argonne [ 29]. Priestly reports a similar the feeding and calcining portion of a run, heat must
technique for a fluidized bed used for calcination be introduced to a pot calciner; however,_overheating
of limestone [33], . of the product may occur near the eng of a :rYJl
whAn hARt. rPI}nirAmAnt~ fnr r.::~lr.in::~tinn nf thA ]11~t
l''or low temperature operation of this calciner material are less than the heat available from
the throughput will be greater than for high temper- decaying isotopes. Overheating may cause volatiliza-
atur.e operation; fl1.1orides, sulfates, and mercury tion of fission products and decomposition of
can be retained with product and the product will corrosive compounds or may endanger the structural
have a low porosity. However, by operating at high strength of a pot. On the other hand, product not
bed temperatures the volatilization of ruthenium cooked at a sufficiently high temperature may retain
from waste solutions will be very low, even.without an excessive amount of volatile materials, potentially
the use of add1t1v~s [?9]. troublesome if pots are sealed during storage.
The feasibility of calcining fluoride-bearing

wastes in this calciner is dubious since there is
no known additive that can be used to retain
fluorides at 900°C. Calcium has been used in feed
solutions at ORNL to minimize the evolution of
corrosive sulfur compounds. At the high operating
temperature of this calciner, addition of phosphites
and nitric oxide effectively suppressed ruthenium
vola tlli:.~.a lion.
'12
2. Heat Introduction and: ~emperature of Operation (Continued)
· Radiant-Heat Spray
...
Discussion· .Discussion.,_-;·,·:.•.
Heat· for the calcining reaction in this . unit No atte'mpts, :have been reported for employing
originates primari_ly as radiant energy from the ... alternate !Jr)>upplemental m~ans ofheatintrqductio~:
vessel walls. Therefore, it is desirable to use the. to this calciner. Neither external nor internal
highest calcination temperature commensurate with flame heating appears attractive. Use of an internal
corrosion and life of construction materials to obtain flame could result in a urut similar to the direct-
maximum rate of heat input [22]. High wall tempera- . fired spray calciner (flame denitrator) · studied at
tures, however, may cause the ever-present deposits · Hanford but with the.added .complication .or' rotation
of.' calciner product on vessel walls [36] to fuse and · and its attendant desigij'_.ppoblems. . · .. · ·
cake or to decompose and evolve. corrosive
compounds [39]. The upper region of the cal- Development studies have not progressed suf-
cination vessel constitutes an evaporation zone ficie:ntly to determine the effect of temperature on
and requires a greater rate of heat input than calcination variables, nor have pilot scale calciners
doe~ the bott,om region (_22]. been sufficiently instrumented to obtain adequate
temperature profiles during operation. It is probable
·Use of heating elements hung in an annular that this calciner can be operated at suitable
configuration from the top of this calciner was temperatures, with various additives employed
suggested by Allemann [ 22]; the resulting channel in the feed to suppress volatilization of ruthenium
(Figure 6) could nearly double the heating surface and corrosive compounds.
area in the calciner and perhaps would limit
deposition of powder on the vessel walls. However,
because · the outer wall of such an annulus wo)l].d
be facing away from the zone of calcination,· the
effectiveness of a heating annulu:s Io1• increasing
capacity needs to be established.
The capacity of the radiant-heat spray calciner

may be increased through use of combustion heating
or per)laps by using an organic additive in feed
solution [22]. Among the disadvantages cited [42] for
combustion heating are an increased volume of
off-gas, a narrow temperature zone in. which satis-
factory· operation can be. achieved, and attendant
complioations in instrttmenting the calciner.
Various additives in the feed solutions may

be required to suppress volatilization of sulfates
a,nd ruthenium .from the material deposited on the
wall.
13
3. Waste Througllput Capacity
The presence of several indeterminate factors makes it impossible to set a capacity now for future waste
disposal plants. The immediate need for several large capacity plants has been clearly shown in Figure 3;
still there may be circumstances justifying one or more low capacity plants only for the next few years. Such
circumstances need not impede planning for the future because no calciner must be operated at its design
capacity; all can· be operated at rates ranging from design down to 1/10 of design, in some cases with no loss
in efficiency and only a small increase in operating cost. Operation at very low percentages of design capacity
may require dilution of the waste feed with a large recycle water stream, requiring additional furnce heat;
however, this is not a significant factor in the overall economics of waste disposal.
If the investment cost of a continuous operating calcination facility increases with capacity to a power of
orily 0.1-0.2, as is the case for most nuclear fuel processing plants, spare capacity can be provided with only
a small increase iil investment cost. A waste processing plant designed on this basis could thus adapt to
increasing demand without incurring additional capital costs; in effect a large capacity calcination unit would
be operated at less than design capacity duringearly years, with a gradual shift to higher throughput levels as
the demand increased. An attractive alternative if the waste processing unit is built in connection with a fuel
reprocessing plant, is to operate the calciner part time in its early years, alternating the operating crew with
chemical processing assignments, which require similar ·talents. If the ultimate capacity requirement of
a waste calcination plant is uncertain, it would appear advisable to err on the side of providing excess initial
capaCity.
The capacity of a calciner is limited by those variables which govern the amount of heat that can be
transferred into the zone of waste decomposition and calcination. As illustrations of individual calciner
capacities, capacity correlations (Figures 8 through 11) follow, along with Tables 2 through 5, which show the .
number :and size of calciners require to process waste from an expanding nuclear economy.
Fluidized Bed Pot
The capacity of a fluidized bed calciner at any The average feed rate to a potcalcinerhas been
given feed composition is dependent upon the heat found to vary between 20 and 25 liters per hour for
transfer area, the bed temperature, thetemperature Purex-type synthetic waste, and between 25 and 30
of the heating mediu1n, the particle size, and the liters per hoUr for aluminum nitrate-type synthetic
fluidized bed density, the latter two tP.rmR l)f;'i.ng wn.oto v.1th o. 7-1/ll-foot long, eigi•L-lnl!htllarn~terpot
those that influence the controlling heat transfer calciner [ 34]. As the salt concentration of a waste has
coefficient .. Figure 8 shows the capacity per unit a significant effect on throughput capacity of the pot
heat transfer area as a function of the mean temper- c:alr.inP.r r122]' these rates are neooooo.rily dependent
ature of the heating surface for several values of UDQn waste compoRition. Tt r.nn l:to :!!hown m~tha
IJtlll temperature, assuming a heat transfer co- matically that the average feed rate to a cylindrical
efficient of 50 Btu/ (hr) (ft2) (6 F) selected from the pot calciner for any particular waste, excluding turn-
range of experimentally observed values of 40-100 around time, is directly proportional to the length
Btu/(hr)(ft2)rF> [25). When themassmedianparticle of the calcination vessel and independent of its
diameter of product in the bed becomes significantly diameter· this also. has been established experi-
greater than 0.8 to 1.0 nun, the resulting decrease i
mentally 17]. The average rates cited were calculated
in the overall heat transfer coefficient reduces the on the basis of the actual timeoffeed introduction to
throughput capacity shown in the curves of Figure 8. a pot and do not include the times required to calcine
Values of the heat transfer coefficient as low as the solids after the feed is stopped, or to change pots
40 Btu/(hr)(ft2)rF) have been observed only when at the end of each run. The average throughput
the mass median particle diameter of the bed capacity for a pot calciner, as shown in Figure 9, is
exceeded 1.0 mm. During normal operation, the based on a complete cycle; ie, itincludesthe time of
heat transfer coefficient has easily been maintained feed introduction at an average rate of 36. 7litcrs per
above 75 Btu/(hr)(ft2)rF) by keepin_g the average hour, and an 11 hour turn around time for a pot, as-
size of bed particles below 0.6 mm [2oJ. sumptions consistent with those of Perona etal£17].
3. Waste Throughput Capacity (Continued)
. The figures are based on the best available data assuming calcination of a typical 1. 7M aluminum nitrate
type waste. Tables 2 through 5 show that plant capacity can be increased for some calclners by employing
larger calcination vessels; in other cases, additional capacity can be obtained only by employing multiple
calciners in simultaneous operation.
The tables are based on assumptions similar to those employed for an extended ORNL cost study [ 17 • 65 • 66]
by.pot calcination. The assumptions are as follows:
(1) A uranium converter fuel, burnup level 10,000 MWd per metric ton of fuel
(2) Power plant thermal efficiency, 27 percent
(3) Acidic Purex-type waste, 50 gallons per ton of fuel (Waste compositions are tabulated in the Appendix.)
(4) Negligible volume of fission products (This assumption made to simplify calculations is not s.trictly
true; fission products will constitute a significant part of the metallic salts in some Purex wastes.)
(5) Waste disposal plant on a 7200 -hour-per-year basis
. (6) For the fluidized bed and rotary-ball kiln calciners, mean temperature of heating surface limited to
650°C to avoid possible fluxing of the product. For the radiant-heat spray calciner, wall temperature
is 800°C even though freedom from product fluxing cannot yet be guaranteed under such conditions.
At lower wall temperatures, throughput rates would be considerably less because heat introduction·
is accomplished primarily by radiation. With the pot ca~ciner, fluxing of product may result in higher
thermal conductivities and greater feed rates.
Feed rates up to four gph have been achieved with The feed rate to a pilot plant scale, eight-
the eight-inch diameter, ten-foot long radiant-heat inch diameter, seven-foot heated length rotary-ball
spray calciner [22, 57], and up to 25 gph with the 18- kiln calciner has varied between 3 and 5 gallons
inch diameter, ten-foot long calciner for a short per hour. Regan [4] reports the capacity to be limited
time [ 19] during calcination of simulated waste solu- by the effective rate of heat input to the kiln. A
tions. The ten-inch diameter, five-foot longcalciner correlation showing the estimated capacity per
being used with radioactive wastes was designed for a square foot of heating surface is shown in Figure
nominal capacity of one gph [3]. 11; this figure is based on anoverallheating surface
coefficient of 30 Btu/ (hr) (°F) (ft2), a value which
The capacity of this calciner is difficult to pre- was calculated from meager data for runs in which
dict, but according"toAllemann etal[57], capacity is the operating conditions were not varied significantly.
reached when incompletely dried particles deposit
excessively on the calciner wall. Figure 10 relates
capacity to nominal residence time of particles and to
vessel· diameter, with limitations imposed by the heat
flux input. The limitations were established duringa
development study [36] using water feed before any
deposition of solids on the calciner wall and aite1· a
run in which deposits were maintained at some equi-
librium value by rapping. The necessary residence
time to insure desired drying and calcination in a
reactor is uncertain. Gauvin reports satisfactory re-
sidence time varying between 16 and 126 seconds [47];
Allemann et al [57] cite satisfactory residence times
varying between. 5 and 15 seconds. However, for the
_latter work, it was reported that incompletely calcined
powders decomposed further to oxides of iron and
aluminum when heated to 900°C. The three-foot-
diameter limitation shown in Figure 10 indicates the
upper size at which Alleman et al [57], and Johnson
[52], believe heat transfer into the center of the vessel
will not be masked and result in uneven temperature
distributions.
15
Fluidized Bed Pot

w
(f)
0
:I:
I-
3.0
~ rJ)
I 0 a::
a:: w
w
~I LL.
z
~
u a:: (.)
~ w ...J
>-a: '"'
:I:
LL.
LL.
<t
(.)
I-
0
~::::>
c:;cn 0 a:: a..
it
<~:z
(!) 2.0
Ai "
...J
(310
(f)
I- :I:
w LL.
0
~~
I=
~
(.)
~:I:
T
.,.~I >
I-
u
::.J
f
LL.
1"1
·(.!)
~
(!)U.
::::>0 ~ u w
...J
<t 8
0...:
O::u.
:I: . 1.0
(.) ct
<t 0
~c' I- (.) w
:::> I-
0~ 0.. I <t
w
5~ :I:
o:r (.!) :I:
:rs:..
0
:::> a::
(!) 0 0
a:: LL.
:I:
I- ......
0 ~
:::> :i
0 ...J
Fig. 8 Capacity of fluidized bed calciner based on a surface- ...J <t
to-bed heat transfer coefiicient of 50 Btu/ (hr)(ft2)("F). The (.)
experimentally observed range of heat transfer coefficients is
40-100 Btu/ (hr)(ft2)("F), dependent inversely on bed particle I-
(.)
size. Thus,· operation With a small bed particle size could result <t
in even hi~er capacities. The limiting temperature of the heating a::
surface allows for a so•c differentia1 between it and the boiling ll.
point of a 22 percent sodium, 78 percent potassium heating
fluid. . . . 7 8 9 10
HEATED LENGTH OF POT, FEET
Fig. 9 Capacity of single pot calciners based on a pot wall
tempP.raturP. of 900•r., aluminum nitrRt.P. WRRtP. RolutionR, feecl
rRtP. inciP.pfmciP.nt of pnt cliameter, feecl rAteR ohsP.rvecl <luring
development studies, and a pQt t\1!'!1 !!!'Q\!!ld time qf 11 I!Q\!r$.
The salt concentration ()f the waste being calcined will have a
marked effect on capacity with this calciner.
Heat transfer alone has limited throughput Although the average feed rate to a pot calciner
rates to development calciners: no test unit has is independent of diameter, the average cyclic
empl9yed as large a heat transfer area as its throughput capacity depends on this parameter be-
volume would perrhit. The extrapolated maximum cause of the pot turn around time. The average cyclic
throughput capacity of a single 60- inch diameter throughput capacity approaches the average feed rate
calciner is about 1500 gph of aluminum nitrate as the pot diameter increases. The net capacity of a
waste. (With Purex-type wastes, a 100°C lower cylindrical pot calciner per square foot of heating
heating surface temperature would result in a :w surface decreases from a value of 0.34 to a value of
percent lower capacity.) These capacities are based 0.15 gph/ft2 as pot diameter increases from 6 inches
on the use of NaK circulated through a tube bundle to 24 inches, which would be misleading if shown in
in the fluidized bed having 3/4-inch tubes on a two- a figure since capacity of a pot does increase with
inch triangular pitch, a configuration similar to pot diameter. Figure 9, therefore, shows the capacity
those of pilot plant calciners. The height of the of a pot and not capacity per unit heat transfer area as
tube bundle was assumed equal to vessel diameter with the other calciners.
(Continued on page 18) (Continued on page 18)
16
3.0
w
u
~
>-. ~
s(/)
~(!)
<{ z
u!i
1- w
::::> J:
a..
J: La..
(!) 0
::::>
Fig. 10 Capacity of radiant-heat spray calciners based on soo•c o..:
a: La..
furnace temperature and outlet gas at 400°C and 12 psia. Heat
flux limits wwe experimentally established with water feed before ~ c'
and after ·formation of normal wall deposits in a calciner. 0 ~
Capacity of a single calciner may be limited by residence time, 3 ...:
vessel din meter, vessel length, or heat flux. Requi rerl rP.sidence o,J;
:::1.:1--
time (nominally based on outlet conditions), dependent on the 0
(!)
degree of calcination sought, may vary over wide range.
MEAN TEMPERATURE
Fig. 11 Capacity of rotary-ball kiln calciners based on a

surface to bed heat transfer coefficient of 30 Btu/ (hr) (ft2) (°F)
calculated from meager data. Further development work is
desirable to substantiate the calculated heat transfer rate, and
to establish that feed can be dispersed effectively .~ver long_
portions of ~ heated kiln.
The extrapolated maximum capacity for a single The maximum capacity of a single rotary-
radiant~heat spray calciner is about 65 gph of ball kiln calciner is difficult to estimate, but
aluminum nitrate wn.ste, :u;suminguse of a three-foot it may be as high as 200-300 gph, provided the
diameter by 20-foot long vessel and the lower heat feed, and, hence, the demand for heat can be
flux limitation shown in Figure 10. This would give an effectively dispersed throughout the length of the
apparently satisfactory residence time of about calciner. Such dispersion of the feed has been
15 seconds. assumed in preparing Figure 11. Simply increasing
the kiln diameter to obtain greater surface without
. Assuming the size of a radiant-heat spray increasing the kiln length may result in unforeseen
calciner cannot .be varied sufficiently (diameter problems. A Blaw-Knox engineering feasibility
fixed hy heat transfer and vessel length by cell study [53] ( assumptions unstated) indicated a
depth considerations) to increase significantly .the rotary-ball kiln calciner 2-1/2 feet in diameter
throughput capacity of a· waste disposal plant, it by 20 feet long would have a capacity of 100
follows tha.t some pla.nts may reqmre m.ultiple 2Ph.
(Continued on page 19) (Continued on page 19)
17
Fluidized Bed. Pot

Discussion (Continued) Discussion (Continued)
in accordance with the current conception of a The maximum capacity of a single pot calciner,
well designed calciner. 24 inches in diameter and 12 feet long (10 feet of
heated length), is about 10 gph for calcination of
Other factors which affect the capacity of a aluminum nitrate-type wastes and 8 gphfor Purex-
calciner need not be extrapolated beyond proved type wastes, based on results reported from pilot
pilot plant performance to ·achieve the capacities plant scale studies [ 17].
implicit in Figure 8. More spray nozzles will be
needed than employed in any unit to date; however, The · size of a single pot calciner canno.t be
tests have shown that nozzles can be installed both varied sufficiently to significantly alter its capacity;
above and below the heating bundle, requiring no therefore, many waste disposal plants would require
increase in spray density per unit volume. Table 2 multiple pot calciners in simultaneous operation,
shows the necessary diameter of a fluidized bed as· shown in Table 3 for various waste disposal
calciner for various waste disposal requirements. requirements.
J'A1lLE ~ TABLE 3
REQUIRED SIZE OF A FLUIDIZED BED CALCINER TO REQUIRED NUMBER OF POT CALCINERS IN

PROCESS WASTE RESULTING FROM VARIOUS · SIMULTANEOUS OPERATION TO PROCESS WASTE
NUCLE:AR POWER REQUIREMENTS FROM VARIOUS NUCLEAR POWER REQUIREMENTS
Number Diw:neter Equivalent· Number Required

Amount of' of' Amount of' of' Calciners Equivalent Number
of' Calciners Plant Plant
Nuclear Power in Calcination Capacity Nuclear Power in of' Pots
'(MWe) Simultaneous Vessel (Mwe) Simultaneous Capacity Per
Operation (inches) (gal/hr) Operat.~.nn
{gal/hr) YP.A.r [A.]
10,000 1 12 10,000 1 9.4 14-19

100,000 1 27 100,000 11 94 140-190
.t,ooo,ouo .L 6u 1,000,000 110 940 1400-1900
[a] Based on a calculated volume reduction factor·

of 1) -20 ( t~ee ::Je:.:: l.lun IV 5) •
Table 2 is based on:
(1) Throughput capacity relationship in Figure 8. Table 3 is based on:
(2) Bed temperature 400°C, heating surface (1) Capacity relationship in Figure 9.
temperature 6o0°C.
(2) Acidic Purex waste solutions storP.d for ahont
(3) Heating tube bundles designed in accordance seven years before calcination for activity
with pilot plant experience--3/4 inch tubes decay, thus permitting use of 24-inch di-
on a two-inch triangular pitch. ameter pots, 12 feet long overall. (See Perona
et al [17].) If the age of waste is 2-1/2
years, maximum pot rliameter will hP. ahout
12 inches. Fourteen percent more calciners
·wouh.l llH::u be ueeLleLl lu ~::;lmullaueuw; op-
eration because of the pot turn around time;
and about four times as many pots would be
needed to contain calciner product.)
The low capacity of a cylindrical pot calciner

cannot be increased appreciably. Heat input is
severely limited by thermal conductivity of calciner
product. Operation at higher temperatures to induce
product melting may accelerate pot corrosion,
or seriously impair the structural strength of a
vessel. Annular configuration may, with a properly
designed furnace, increase the effective heating area;
however, this would have to be established by
further development.
111
Discussion (Continued) Discussion (Continued)
radiant-heat spray calciners in simultaneous oper- Additional development work is desirable to

ation. This is shoWn in Table 4 for various waste substantia:te the estimated heat transfer rates and to
disposal requirements. relate operating conditions to the heat transfer
coefficient.
Table 5 shows the estimated capacity of a single

rotary-ball kiln calciner as a function of kiln size.
TABLE 4 TABLE 5
REQUIRED NUMBER OF RADIANT-HEAT SPRAY CALCINERS IN REQUIRED SIZE OF A ROTARY-BALL KILN CALCINER TO
SIMULTANEOUS OPERATION TO PROCESS WASTE RESULTING PROCESS WASTE RESULTING FROM VARIOUS
FROM VARIOUS NUCLEAR POWER ·REQUIREMENTS NUCLEAR POWER REQUIREMENTS
Number Diameter Number DiB.Lleter

of Calciners of EquivalenL Eql.l,i valent
Amount of Plant Amount of of Calciners of
Nuclear Power in Calcinatio!l Capacity Plant
Nuclear Power in Calcination Capacity
(Mwe) Simultaneous Vessel (gal/hr) (Mwe) Simultaneous Vessel
Operation (inches) (gal/hr)
Operation (inches)
10,000 1 13 9.4 10,000 1 12 . 9.4
100,000 2 36, 24. 94 100,000 1 24 94
. '
1,000,000 14 36 940 1,000,000 6• 30 940
· Table 4 is based on: Table 5 is based on:

(1) The capacity relationship in Figure 10. (1) Mean temperature on kiln. luledor about
400°C, heating surface temperature about
(2) A 20-foot calciner length. 650°C.
(3) Vessel wall temperature 800°C, gas and (2) Throughput capacity relationship in Figure
product outlet temperature 300°C. 11.
(4) Conservatively, the time required to switch (3) Effective use of the entire heated surface of
product collection pots will not significantly the kiln.
reduce overall throughput rate.
Supplemental heat from the use of organic

materials in the feed or the use of a direct flame
in the calciner may increase the capacity of this
process. However, further development work is
required to substantiate this.
19
4. Feed Introduction
Fluidized Bed Pot
Aqueous feed usually has been introduced Aqueous feed generally has been int.roduced to the
to fluidized bed calciners at the ICPP through pot calciner through a small diameter pipe at such a
one or more two-fluid spray nozzles mounted rate (variable) as to maintain a constant liquid level'
in the vessel wall below the surface of the bed. in tl).e calcination vessel. The feed rate is controlled
Single-fluid pressure nozzles also have been by a differential temperature device which employs
used below the bed with .an. auxiliary air jet a thermocouple embedded in a rod on the pot
to control the growth rate of particles. With centerline extending 9 to 12 inches below the
two-fluid nozzles, particle growth rate is ef- normal liquid level in the pot [ 18]. The thermo-
fectively controlled by regulating the rate of flow couple senses a temperature that is a function
atomizing air [60]. of the submerged depth of rod. After a pot calciner
is filled with solids, or when feed can no longer
Vapor-space feed nozzles have been used to be introduced, the solids are cooked eight to ten
disperse feed on the top of a bed at Battelle Memorial hours to. reduce the nitrate content to a low
Institute [58]. value [ 341. .
Most oi the atomized feed .introduced to the Open pipe feed introduction has been entirely
fluidized bed is deposited and dried in layers on satisfactory; however, a means to cool the feed
the granular particles; however, some spray dried pipe (perhaps water jacketing) may be desirable
particles escape to the calciner off-gas requiring to prevent caking.
subsequent removal. Tests employing chemical
tracers in calciner feed solution show that the rate Several different time cycles possibly may be
of spray drying is relatively constant for a· nozzle employed to improve characteristics of the pro,-
oper~ting at any· given conditions and that 20 to 70 duct [45]: (a) Following the usual feed introduction-
percent of the fines elutriated from a fluidized bed product cooking procedure, feed could be reintroduced
calciner originate from spray drying-,type mecha- to the pot and the product cooked at 900°C a second
nisms, depending on the operating conditions [59J. time. During the second period of feeding, cold
Position of an atomizing spray nozzle is not critical feed may thermally shock and shatter bridged porous
if the nozzle face is below the bed and the spray product and make available considerably more
does not impinge· on internal structures such as volume for additional IJlB.terial, (b) A steep temper-
heaters. An atomizing nozzle, ·located above the bed, ature gradient could be employed across 11. pot
produces mostly spray dried micron-size product. during the feed introduction period to melt solids
The use of more than one feed nozzle for blanketing in the lower portion of a pot, while calcination
the entire cross section of the ca1Cil1e:r is believed a.nrl eva.po:ra.tion. occur in the upper portion of
desirable to incorporate fines generated by be(} the pot. (c) A run cmtld he ~tarter.!. with a fliied
attrition into larger particles and thus reduce their concentrating-evaporating period (the period in which
elutriation. Elutriation rates have been found by many the highest feed rate is obtained before solids
investigators to be directly related to particle deposition reduces the heat input to. the calciner),
size [32]. employing high feed rates while operating the
calciner at relatively luw temperatures, 400-500°C;
The atomizing medium for two-fluid nozzles can this could be followed by a period of calcining
be any suitable gas, ie, air, steam or decomposition and melting the solids at about 900°C; this two-
gases recycled from the off-gas processing system. step cycle could be repeated as often as desired.
20
'4. ·Feed Introduction (Continued)
Two-fluid nozzles have been used during Various solution feeders, pipes with large
development studies for atomizing and introducing orifices, and nozzles have been employed to
aqueous feed to this calciner. When steam was used introduce feed to the rotary-ball kiln calciners
to atomize the feed, no significant effects on calci- at BNL. Solution feeders extending into the rotating
nation could be !lttributed to varying the steam kiln have been coupled to necessary piping
pressure from 40 to 75 psig; however, the steam- through either ·a rotary union "or a rotating seal.
to-feed ratio probably has a practical lower limit [ 22]. When . using a rotary union the solution feeder
Atomization must be controlled to prevent formation has been insulated rather than water-cooled to
of large feed droplets which may not dry properly simplify the coupling of stationary piping to · a
.during their fall through the calciner vessel. Satis- rotating vessel." Various combinations of nozzles
factory atomizing steam-to-liquid rates are de- and feed pressures have been tested to "hump"
pendent on the nozzle design and on such properties the feed solution over the entire heated length
of the feed solution as viscosity, density, and of the kiln [ 49].
surface tension [22]. ·
. Any · suitable gas would be satisfactory as Pipes with large orifices have not been entirely
the atomizing fluid for feed nozzles in this calciner; satisfactory for feed introduction because the feed
however, a condensible gas is preferred at Hanford solution is not well dispersed and thus imposes a
to minimize the net rate of release of off-gas [22]. large heat duty on a small section of the vessel and
limits the capacity. The feed humping technique
Allemann et al report [22] that centrifugal employed during recent work may be the most
nozzles may be feasible with a large diameter effective way to utilize the heat transfer area of
vessel but cannot be used in small diameter calciners this calciner, although decreasing the kiln length-to-
since the resulting spray droplets would strike diameter ratio also may be effective.
the walls of the calcination vessel and form a
deposit. Some feed caking has occurred in the noncooled
solution feeders; therefore, the use of insulated
feeders in a plant unit may not be practical.
21
5. Off-Gas Processing System
Operational requirements and overail economics of any waste disposal plant will determine the type of
off-gas system employed. If there are local requirements for nitric acid or if local air-pollution control
regulations prohibit release of nitrogen oxides, then a condensing off-gas system together with a conventional
nitric acid decontamination system may be ·desirable. On the other hand, if there is no requirement for
slightly contaminated nitric acid (thus presenting a pos!)ible disposal problem), a noncondensing off-gas
system may be desirable. Off-gas from any calciner can be decontaminated in a condensl.ng or noncondensing
system equally satisfactorily, and by employing proved techniques, the net volume of off-gas released per .unit
.of waste can be similar for all calcination processes. Deconta~ination factors from feed to off-gas· for actual
wastes have been reported at Hanford [134] for a condensing system in the range 10~ to 109 and 106 to 109 at
the outlet of the condenser and. the outlet of the downstream high efficiency filte:r:s, respectively. Argonne [29J
reports decontamination factors at the outlet of a condenser in the range.105' to :1,07 for a condensing off gas
system. At the ICPP decontamination factors for the noncondensing system of the WCF during calcination 'of
actual Wc\-Stes for particulate matter have been in the range 104 to 105 and 106 to 107 at the inlet and outlet of
the . high efficiency filters,· respectively. The various decontamination faCtors reportEd for the different
processes, especially for ruthenium, . are difficult to compare because different techniq1;1es are bei~g used to
measure activity level and particulate matter concentration in the off-gas from tJ:le calciners. If the release of
off-gas from a plant must ever be reduced to a theoretical minimum. CQIJ,densible or absorbable ga.ses or
perhaps recycled ~ses can be_ used for pneumatic inst:rumentation, for feed a.tomi:r.ation wh~rP. 11ppl.ic~.!:lle,
and for tluidization m the case of fluidized bed calciners.
The composition of off-gas from a calcination vessel is dependent on the waste. feed rate, temperature,
and mode of operation. This gas may contain various quantities of water vapor, nitric acid, oxides of nitrogen,
oxides of sulfur, ruthenium tetroxide, mercury, other volatile compoui).~S, and entrained solids, as well as
air from inleakage and other sources; prior to its release, virtuaily all particulate matter and fission products
mw;;t 'be· removed. Furthermore, off-gas .scrubbing streams and condens!J.tes m~st. be decontaminated, re.-
cycling at least a portion of them to the calcfner, or, less desirably, placed into separate storage. Typical
condensing and noncondensing off-gas systems are shown in Figure 12.
In a noncondensing system,. the final off-gas will contain esse'(ltially all gases (except those removed
in scrubbers and adsorbers) resulting from the calcl.nation reaction together. with any air employed or leaking
into the process. In a condensing system, the final off-gas will contain only those noncondensible, non-
absorbable gases that pass through all equipment in the off-gas train. The products of a condensing system
will i.nclude in.addition to a gas stream, two or more liquid streams containing nitric acid, water, and perhaps
various compounds of low volatility that cannot be retained by calciner product. The liquid streams would be
produced from decontaminating the acidic condensates, possibly by continuous equilibrium vaporization [45J.
22
NONCONDENSING
CALCINER OFF-GAS PROCESSING SYSTEM
RECYCLE
TO FEED
REHEATER
AEC TYPE
FILTERS
GAS FROM
.VENTURI
SCRUBBER
REGENERATING
SOLUTION
CONDENSING
CALCINER OFF-GAS PROCESSING SY§TEM
RECYCLE TO CALCINER FOR FEED ATOMIZATION

OR FLUIDIZATl.ON fF APPLICABLE
CONDENSER
~--~---.------------~ ~--.-TO STACK
GAS FROM
CALCINE~R;...._ _ _-( AEC TYPE
FILTERS
OR SCRUBBER
RECTIFIER
EVAPORATOR
RECYCLE
TO FEED NITRIC ACID
Fig. 12 Off-gas procc:;l3ing oystem&. Off-g'"' from the calciner (not shown) may be decontaminated in either a condensing or a non-
condensing system. In addition to that equipment shown, a calciner may employ cyclones, filters, etc. By recyc.:llug uouoondensiblc
Jgases to a calciner for feed atomization or fluidization where applicable, the net off-gas per unit volume of waste processed is
identical for all calciners.
23
5. Off-Gas Processing System (Continued)
Fluidized Bed Pot
The basic elements of both the condensing Condensing off- gas systems have been employed
and noncondensing off-gas systems have been in all tests to date with the pot calcination process. At
employed with fluidized bed calciners at ICPP. ORNL, ·off-gas downstream of a condenser is re-
For both, a primary cyclone has been followed leased; the condensate is evaporated to simulate,
by a venturi scrubber. In the noncondensing partially, a proposed integrated radioactive plant [ 18],
system of the Waste Calcining Facility (WCF), Evaporator overheads after being condensed were
off-gas leaving the scrubber is passed through discharged to a drain.
silica gel adsol'l.Jtm:> then to AEC-type high-
efficiency filters before release [ 121]. In the Off-gases from a pot calciner [45] scheduled for
condensing systems employed with pilot plant radioactive demonstration at Hanford will be intro-
calciners, off-gases from the venturi scrubbers duced first to a condenser then in turn to an evap-
were introduced to a condenser; · noncondensibles 'orator. a rectifier. a condenser. and finally to an
were recycled or released [24, 25], At Argonne AEC-type filter. The condensate will be decontam-
during the calcination of high activity waste inated in the evaporator and the rectifier.
solutions in a pilot plant · calciner, a condensing
~y~tF.i!m Wll~ \li'id [29],
Discussion l)i 8oussion
Blow-back filters were used in lieuofaprimary Because a relatively small amount of product
cyclone on a pilot plant scale calciner in initial tests fines is entrained in the off-gas from the pot
at ICPP [24] and at Argonne [291. However, their use calciner under normal operating conditions, it is
on large scale calciners is not recommended because believed no significant benefit could be gained from
of unresolved corrosion problems and because the use of primary cyclones or blow-back filters.
required number of such filters becomes excessive
at production-scale capacities.
24
5. Off-Gas-Processing System (Continued)
Pre~ent SitUa.tion Present Situation
Radiant-heat spray calciners used in develop- In studies at BNL with pilot plant scale calciners,
ment studies have employed a condensing off-gas a condensing off-gas system has been employed,
system. Calciner off-gas separated from nonactive The product and decomposition gases have been
product by blow-back filters has been passed through discharged· from the same end of the kiln (a four-
a c.ondenser and a caustic scrubber [22). Off-gas inch diameter discharge tube) and separated satis-
separated from active product" by blow-back filters factorily on some runs without baffles, cyclones
has been passed through !1. condenser, a packed caustic or dust-arresting devices [4, 48]. The off-gas
scrubber, an electrostatic bubble . scrubber [63], has then been passed through two cyclone separators,
a silica gel adso.rber, and two AEC-type filters in a condenser, a scrubber, a mist trap, and a filter.
series· [3, 44]. Condensate· apparently has not been Condensate has not been decontaminated to simulate
decontaminated for discharge as would be done in expected operation of an integrated waste disposal
an integrll;ted waste disp?sal plant .. plant.
Large volumes of decomposition gases from. a Although nurumum entrainment of product has
plant scale calciner may. require the use of a large been experienced to date with this calcfner [ 4],
number of blow-back filters requiring excessive cell extrapolation for greater feed rates is risky. At
space. Use of a cyclone instead of blow-back filters low feed rates and consequent low off-gas rates,
for the initial product-gas separation (product and gas satisfactory operation without dust arresting units
are discharged from the same outlet in this cal- may be comparatively simple to that which may
ciner) was not entirely satisfactory because of the be experienced with high feed rates. Blow-back
small particle size. of the product [22, 57]. filters or a primary cyclone may be a necessity
to product-gas separation in a waste disposal
plant. As with other calciners, the practicability
of filters will depend to a large measure on the
feed processing rate of the calciner.
25
IV. PRODUCT PROPERTIES
Properties of calciner products significantly affect considerations of long term storage and, at times, the
calcination process itself. Both the physical and chemical properties of calciner products can vary over wide
ranges depending on the waste, calcination process, mode of operation, processing subsequent to calcination,
etc. With respect tophysicalproperties,asharpdemarcation exists in appearance; viz, products may be either
granular or cellular.
Granular products are produced in the fluidized bed, the radiant-heat spray, and the rotary-ball kiln calci-
nation processes; a cellular product, but not necessarily vitreous, is produced in the pot calcination process.
Through use of proper fluxing agents, the final products of all the calcinati<!ln processes can be made into
vitreous or glass-like materials at practical temperature levels, 800-1000°C, having a relatively low water
leachability and high thermal conductivity. Because the properties of a glass-like material are essentially
independent of the calcination process employed to generate the initial product and because the use of fluxing
agents in all cases will result in a product of greater volume than that minimum volume theoretically obtainable
otherwise, the subject of glass-like materials is considered separately from calciner products in Section V
of this report.
Granular materials may be pneumatically conveyed from a calciner to 'a storage facility in pipe lines,
transported in pots, or perhaps conveyed with the aid of vibratory equipment, Cellular materials. on the other
hand, will be ~nerated in .(>Ots which must be transported to a repository u!?ing remote handling equipment.
Transportable pots may be limited by considerations of remote manipulation, handling, and transport to move
them from the processing cell to the storage area as well as by considerations of maximum storage tempera-
ture. Attendant labor and equipment costs as well as the storage facilities themselves can be many times
those of pneumatically transporting granular material to storage bins limited in size only by utilmate product
temperature. Relative storage costs for granular and cellular materials also are affected by the specific
activity of. the material involved; this aspect is discussed in Section VI of this report.
On the other hand, the water leachability of a granular product will be higher while the thermal conductivity
(and in a few cases the liquid-to-solid volume reduction factor, as discussed later) will be somewhat tower
than those of the corresponding cellular product. Thermal conductivity and specific activity of product, together
1. Size and Shape of Cal_ciner Product
Fluidized Bed Pot
P .L'eseut 3Huatluu .Present :Situation

The spheriodal granular product of the fluidized The product of the pot calcination process is
bed calcination process is free-flowing and is readily usually a porous cake; that from -aluminum and
conveyed pneumatically through long pipe lines. A stainless steel nitrate-type simulated wastes is
typical cumulative size distribution is 2% < 60 Tyler crumbly, whereas cake from Purex-type simulated
mesh, 20% < 35, 65% < 28, and 98% < 20 mesh. wastes is generally relatively hard. Although the
product has a cellular appearanoe, Godbee [::In] states
The average particle size of product during that it has a thermal conductivity similar to that
formation is influenced by a complex mechanism of a granular material.
of growth and attrition but is controllable within a
desired range of 0.25 to 0.60 mm by adjusting the
rate of product attrition through changes in nozzle
atomizing gas and/or fluidizing gas, by adding seed
size material to the bed, or by jet-grinding the bed [ 1].
Photomicrographs of sectioned product particles
show that linear rate of growth increases with
particle size [ 1]. Some attrition of bed materials is
desirable to form needed seed-size material, but it
must be controlled to prevent an off-gas cleanup
problem.
Workers at Argonne [29] andHanford[30] report
that Purex-type simulated waste formed an agglom-
erated granule during fluidized bed calcination; how-
ever, Loeding [67] reported that product size and
agglomeration were effectively controlled by using an
air jet grinder, and by adding sugar to the feed.
. IV. PRODUCT PROPERTIES (Continued)
with the diameter of the storage vessel and rate of heat dissipation therefrom, govern the temperature of
product in storage. This temperature must be limited to avoid volatilization of radioactive isotopes or
corrosive compounds. Economically,·· it is highly desirable to use the largest containers possible--that
diameter that will result in maximum allowable temperature at the time of product interment--for permanent
storage of radioactive materials because :vessel costs increase approximately linearly with vessel diameter
while the useful storage volume increases with the square of vessel diameter.
Even though a cellular matei,'ial may have a higher thermal conductivity than does a granular material,
the granular material offers other important economic advantages independent of transportability. A granular
material may be stored in annular bins of greater length than a transportable pot (the cost of an annular bin
per unit volume is about 70 percent E>f that of a corresponding cylinder) and secondly, a principle of interim
st~rage _can be employed with a granular product not possible with the cellular material.
Some investigators [18] have suggested that a period of interim storage of liquid wastes should precede
calcination for the decay of activity to allow the use of large, economical storage containers. An alternative
procedure·, which does not involve storage of the liquid waste during its period of greatest hazard,is possible
with granular calciner products which can be placed in interim storage and later ·be moved pneumatically
after the decay of activity either to less expensivej)ermanent storage or to a final processing step for
vitrification or inyestment in a heat conducting.matrix [123, 124]. With interim solids storage, the difference
in thermal conductivity between the granular and cellular materials loses its economic importance.
While these advantages of easily transportable product are obvious, there is another less obvious but
perhaps significant point. A retrievable product meets in part the suggestion of those in the scientific com-
munity who believe that no present or near-future treatment should irrevocably remove radioactive wastes
from accessibility by future generations (20, 21, 136]. Interim storage of these wastes as granular solids
offers a greatly reduced hazard over liquid storage, but retains much of the accessibility. Thus preparation of
a granular waste product today represents a reasonable compromise between the extremes of permanent tank
storage as liquid and immediate production of small-volume pots of vitreous material, both with ·respect
to present day safety aspects and with respect to flexibility for future utilization of any economic values in
the waste.
Descriptions of specific product properties with respect to process operation as well as to long term stor-
age are discussed in the remainder of this section.
1. Size and Shape of Calciner Product
The granular product from the radiant-heat Granular product of this calcination process is
spray calcination process is in the size range shaped by the grinding action of balls in the rotating
1.6 to 12.6 microns (surface-area-average particle kiln; it has a mass median particle diameter in
size) ao measured by an air-permeability method r22], thfl range 0.13 to 0.16 mm. A typical size distribution
and consists of the fragments of hollow or porous is 6% < 270 Tyler mesh, 18% < 150 mesh, 64% < 60
spheres. Allemann et al (22] explained that feed mesh, 91% < 35 mesh, and 99% < 20 mesh. Neither
droplets while drying form hollow spheres which the flow characteristics nor any attempt to control
shatter as they fall through the calciner. Product, product size have been reported. Information relative
particularly that created from low-sulfate Purex to the size and shape of this product is summarized
waste, is rather dusty and exhibits a tendency for in Table 9.
sluggish flow [22]. This resistance to flow has been
attributed to the small size of the product and to
its irregular shape. The average purtiule size has
varied depending on feed composition and column
tP.mperature; attempts to control product size are
not reported. Despite the fact that the air-per-
meability method indicates the surface area-average
particle size is as low as 1. 6 microns, there are
some indications that the minimum thickness of
most particle fragments. exceeds two microns [221.
27
1. Size and Shape of Calciner Product (Continued)
Fluidized Bed Pot
Typical values of size and description of products See Table 7.

are given in Table 6.
TABLE 6 TABLE 7
SIZE AND SHAPE OF FLUIDIZED BED CALCINER PRODUCT SIZE AND SHAPE OF CALCINER POT PRODUCT
Size Range* Waste Type Shape

Mass Median Shape
Waste Type Particle Diameter Aluminum nitrate Cake that crumbles easily
(=)
Purex cake
~~~
Aluminum 0.25-1.35 granular, Stalnless Steel
~:Ji t.-r.\l.t"fil o.2n-o.53 sph~rioal ulLr~oJ.Le CWI.e that crumbles easily.
Purex 0.47-0.56 (c) agglomerated
granules
Pur ex 0.33-0.53 (d) granular
Purex 0.14-0.37 (b) agglomerated
granules
* by sc1·eeulug
(a) ICPP values from runs averaging 240 hours [64]
(b) Hanford values from runs varying from four to
six hour~ [30,31].
(c) Argonne values from runs averaging six-eight
hours [29];
(d) Argonne values from runs averSRinR si~-e1ght
hours on which attrition air and sugar additives
were employed to control particle growth rates[29]
Discussion
Values of product particle size shown in Table

6 for runs lasting under eight hours are only
indications of the equilibrium size of calciner
product. During calcination of aluminum nitrate
and stainless steel nitrate simulated wastes at
the lCPP, a change in operating variables was
seldom accompanied by a rapid change in product
size; at times product particle size approached
steady state only after several hundred hours
of operation. The range of sizes of all Purex-
type products produced at Argonne and Hanford as
shown in the table are in a size range normally
considered desirable at the ICPP. Agglomerates
of these sizes would not create any problem to a
fluidized bed calciner employing a fluid heat transfer
system.
1. Size and Shape of Calciner Product (Continued)
Radiant-Heat Spray.· .· Rotary- Ball. Kiln
See Table 8. See Table 9.
TABLE 8 TABLE 9
SIZE 'AND SHAPE OF RADIANT~HEAT SIZE AND SHAPE· OF ROTARY-BALL·

SPRAY CALCINER PRODUCT KILN CALCINER PROmiCT
Average Mass Median

Particle Shape Particle
Waste Type Waste Type Shape
Diameter* Diameter*
(mm) (mm)
Aluminum nitrate Dusty powder; Aluminum nitrate 0.13-0.16 Finely

fine particles divided
Purex 0.0016-0.0126
agglomerate to granular
Stainless steel form fluffy powder
nitrate material Pur ex
No data reported
* air-permeability method Stainless Steel nitrate
* by screening
The powdery product from this process will It is believed that the size of product from this
be difficult to handle as evidenced by the need for process would be primarily affected by the speed of
vibratory equipment to make rroduct flow satis- kiln rotation. The flow characteristics may be similar
factorily into collection potR [23 , to those of product of the radiant-heat spray calciner.
29
2. Leachability
Granular calciner products have a higher leachability in water than corresponding cellular products
because of the higher surface areas per unit volume. Leachability may be considered a liability that may
cause ·problems if a storage vessel were to rupture. It is an advantage if, however, reclamation of isotopes
becomes desirable.
Fluidized Bed Pot
Isotopes in the readily retrievable productfrom Cellular product from this process would be
this process are highly leachable in 0.5M nitric less leachable than corresponding products of other
acid as shown by exploratory studies [ 68], - calciners because of a much smaller area-to-.
volume ratio. An estimate of a leachability factor
Grimmett and Brown report that more than is difficult since there is no direct wayto determine
99.99 percent of the cesium [69], up to 99.9 percent the size of voids, their shape, or number in situ
of the strontium [133], and up to 90 percent of the in a pot calciner. ---
cerium [ 133] in calciner product generated from
aluminum-type wastes can be removed by leaching The caked or melted form of product in a pot
with 0.5M nitric acid in a counter-current leaching probably precludes reclamation of isotopes,
process. A counter-current liquid-solids contactor
suitable for this purpose has been developed [ 70].
The leachability of this spherical-type product

would be a function of the area-to-volume ratio
which is estimated to vary from 4 to 24 mm-1.
30
2. Leachability (Continued)

Isotopes in the granular ·powder from this · ISotopes in, .the . granular product from this
process should be highly leachable although ·their process should be highly leachable. Product leach-
reclamation could require a highly specialized ma- ability would be a function of the area-to-volume
terial handling system because of flow characteristics ratio which is estimated to be about (38-46mm-l)S
of the product. Product leachability would be a where S is a shape factor greater than unity
function of the area-to-volume ratio estimated .to necessary because of the fragmented shape of the
be (375-4760mm-l)S where s is a shape, factor particles.
greater than unity necessary because the particles
are fragments of spheres.
31
3. Nitrate Content
The nitrate content of a calciner product will be a function of calcination temperature; it is of minor
significance unless product is stored in sealed containers, Radiolytic decay of nitrate compounds in a sealed
container could result in bursting pressures. With vented containers, gradually evolving gases can be safely
released through a storage breather system.
Fluidized Bed Pot
The nitrate contents of products ccreated in this The nitrate contents of products created in this
process at various bed temperatures are listed in process are listed in Table .11.
·Table 10,
TABLE 10
TABLE 11·
NITRATE CONTENT OF FLUIDIZED
BED CALCINER PRODUCT .NI'l'RA'l'l!! CONTENT OF' :PRODUCT FROM THE POT CALCINER
Residual
Calcination
Residual Calcination
Nitrate Nitrate (
Waste Te{era.ture Waste T~mp~n~.tur~
Content a c) CouLenL . ( oc)
(wt percent) (wt percent)
Aluminum 1-8 [29] 600-400 AJ.u.mlnum [2,35,87]

0.06-6 1000- 400
Nitrate Nitrate
4-12 [64] 550-300 Purex· 0.00.6.-4. 1· [2,35,881 1000- 400
Purex 0.05-6.7 [30] 600-400 Stainless
Steel 0.008-2.78 [2,35,87] 1000- 400
·Nitrate
Discussion
Considerable emphasis· has been placed on using

permanently sealed containers to store products,
oi p6t 61i.l6inati6li;. therefore;.: the nitrate content ..
must be minimized .. ·
32
·3. ·Nitrate Content· (Continued)
Radiant:..Heat Spray Rotary-Ball Kiln
Present Situaiion Present Situation
No values are reported. No values are reported.
..•
.
,
;~~
.;.J.;
·q
·-·: ''{~
·,~;- ~... ~ii·
-~~,~?~·._ ; ~:
i[i,7:, '"'"''
33
~. Thermal Conductivity
Thermal conductivity of any given material is an inverse function of its porosity; however, cellular ma-
terial generally has a higher thermal conductivity than granular material of the same porosity [76]. Factors
affecting thermal conductivity of porous solids are reported by various investigators [76-84]. When any
calciner product is heated to temperature above 650-850°C, sintering and perhaps melting may occur, resulting
in various proportions of cellular and granular product with correspondingly higher thermal conductivities.
Fluidized Bed Pot
TABLE.l2 TABLE 13
THERMAL CONDUCTIVITY· OF FLUIDIZED THERMAL CONDUCTIVITY OF POT C.AU:INER PRODUCT
·BED CJ\LCINER PRODTJI:''l'
Thermal
Waste Thermal Conductivity Temperature Conductivity Temperature
Btu/(hr)(rt)( °F) ( •c) Waste ( •c) Remarks
Btu/(hr)
( f't)(. !i')
Aluminum · 0.08-0.27 55-1100
Nitrate (86] (amorphouo alumina)
~uminum o.o65-0.395[35] 110-840 Calciner
N~tra.te
0.28-0.30 1000-1550 Product
(alpha alumina)
1.05-1.60[17) 150-575 Glass-Like
PureX' [07] U.l2-0.14 425-600 Material
Purex 0.2[38] Not Calciner
Reported Product
0.4-0.45[)8,39] Not Glass~Like
Reported Material
Stainless
St.P.P.l O.OCJ5-0.14[35] 40-820 Cn\~l:led
Nitrate Product
Thermal conductivity of a granular fluidized Thermal conductivities of calciner ·products

bed product from Purex-type simulated wastes produced from Purex.:.type simulated wastes with
was increased from a value of 0.12 to 0.3 Btu/ calcium magnesium or sodium additivesvariedfrom
(lir)(ft)(°F) by sintering [87], A thermal conductivity 0.2 to 0.67 Btu/(hr)(ft)(°F) in the temperature range
of 2. 5 Btu/ (hr)(ftWF) was obtained by adding sodium 180 to 875°C [35]. Godbee [35] reports that thermal
sulfate to granular rroduct and heating it to form conductivity behavior of calciner product from this
a iolidified melt [87 . unit .is similar to that of granular material. although
thP. product has a cellular appearance.
4. Thermal Conductivity (Continued)
ORNL investigators report [74, 85) that a thermal conductivity of 0.1 Btu/(hr)(ft)(°F) is probably high enough
for storage of product created from calcining most wastes, assuming use of cylinders less than two feet in
diameter stored in a constant-temperature air sink.
Typical values of thermal conductivities for calciner products and solidified melted products, where
available, follow (Tables 12, 13, 14, and 15):
TABLE 14 TABLE 15
THERMAL CONDUCTIVITY VALUES OF THERMAL CONDUCTIVITY VALUE Of ROTARY-
RADIANT- HEAT SPRAY PRODUCT [ 22 ] BALL KILN PRODUCT
.
48 J .
Thermal Waste Thermal Conductivity Temperature

Conductivity Temperature Btu/(hr)(ft)(•F) (•c)
·Waste Remarks
Btu/(hr} (•c)
. ( ft}( °F) Aluminum 0.098 Not Reported.
Nitrate
Aluminum 0.05-0.135 40-200 Powder
Nitrate 0.32~0.5 200-500 Glass-Like
Material
Purex 0.05-0.135 40-200 Powder
0.84-0.44 220-800 Glass-Like
Material
Thermal conductivities of product from this

process are more a function of product density
(porosity) than of composition [22). Conductivities
vary linearly with temperature at least up to 600°C.
35
5. Bulk Density, Po.rosity, and Volume. Reduction Factor
A liquid-to-solid volume reduction factor. is a figure of merit used as orie gauge ·of the overall.performa:nc.e
of a calcined process; for the purpose of this report, it is defined .as the. ratio of the initial volume of waste
stored in underground tankage to the final volume of the end product\ ·Values of this factor reported herein
may differ from those in other publications due to differences in definition. For example, if it is assumed
that a waste must be neutralized· for interim storage prior to calcination, a calculated volume .reduction
factor of the end product may have either a low or high value, depending on whether it is based on the liquid
volume of original waste or on the volume after neutralization.
The product properties bulk density and porosity are closely associated with the volume reduction
in that they are related to the specific volume of end product. Bulk density, the weight of a unit volume of
product as stored, is a function of product composition and the fraction of voids in and arounct·product. High
porosity in a product results in uneconomical storage because expensive volume is occupied only by a gas
and because porosity lowers the heat dissipation capability of a product. Since some product may have a high
density and low porosity but still occupy a large volume because of the space occupied by additives employed
during processing, it is believed that volume reduction is a superior factor to porosity or·density of the product
by which to rate the.performance of a waste disposal process.
Values of voiume reduction, bulk density, and porosity of calciner products are listed for eaCh of the
calcination processes in Tables 16 through 19. Unfortunately, similar wastes have not been processed in each
of the calciners, thus preventing a direct comparison. Development work at Hanford with a fluidized bed,
a radiant-heat spray, and a pot calciner employed different Purex-type simulated wastes [22, 30, 37-41}, The
pot calcination work at ORNL employed different wastes from those employed at Hanford; even .the composition
of hypothetical Purex-type wastes assumed for an ORNL study [ 17} differs from that waste employed in any
of the experimental studies. A direct comparison is further complicated because· different experimental
techniques have been employed by various investigators to measure bulk density of product; both tapped and
untapped bulk densities have been reported. Product in storage will not be compacted; therefore, untapped
bulk density values are most representative of stored product and were employed for the tables.
Fluidized Bed Pot
A thorough study offactors affecting the porosity The porosity of product from the pot calciner
of an amorphous alumina product showed that only is at least partial!fJ dependent on operating con-
calcination temperature and feed concentration had ditions. At ORNL [ 1} a dense layer of product in
any significant effect [64}. Product inter-particle the bottom of the pot and a porous sinter layer in
porosity is essentially constant at 41 percent, while the upper portion of the pot have been observed.
the intra-particle porosity varies between 5 and 60 Feed rate [72} and heat flux [73} to a pot also may
percent depending on the operating conditions. It affect product porosity. Product of synthetic waste
thus appears that, by careful selection oi operating s~turated with organic materials had bulk densities
conditions, the porosity of product from this calciner 50 pe;rc.:ent luwer than pr·oduct of similar waste free
can be minimized, with the resulting final waste of organic material [74}. Hanford reports [39, 41}
volume approaching the theoretical minimum. that foaming of feed solutions in a pot (which leads
to low porosity of "t"eRulting product) is dependent
on pot goomotry, V.'O.oto oompooition, boil-up o:r-
Pi'ocessing rate, a11d the feed additives employed.
Various modes of operation, including the use of
antifoaming agents, o.ir spo.rging, and varying heat
input rates to a pot calciner, have been employed
to reduce foaming with varied results, none of which
appears to be entirely satisfactory .
.. 36
5. Bulk Density;· P.orosity, :and Volume Reduction Factor (Con~inued)
Because of the general lack of common bases for comparing calciner products, the following two ap-
proaches were employed:
(1) Values of bulk density are listed for experimentally obtained product wherever possible; corresponding
to these values are calculated porosities and volume reduction factors.
(2) A volume reduction factor was calculated for each calciner for a variety of hypothetical waste solutions.
(Four of these solutions were calcined at Hanford but not in all calciners. Acidic, neutralized, and
reacidified Purex-type wastes of hypothetical compositions are listed among the wastes to tie in-
formation in this report to that of an ORNL study [ 17]). For this approach, a best estimate of bulk
density or porosity was employed, based on experimentally obtained values.
It was assumed that the composition of calciner product is solely a function of. waste composition and
independent of the process generating the material even though this may have resulted in smaller volume
reduction factors than those. attainable in some cases. For example, calcium nitrate included as a waste
additive for some Purex-type solutions, necessary with the pot calciner to prevent excessive volatilization
of corrosive sulfate compounds, may be omitted at low calcination temperatures with other calciners.
Neutralized Purex wastes, and those with a high sodium nitrate concentration, probably can be processed
in all these processes, except pot calcination, by employing an organic reducing agent as demonstrated at
Hanford with the radiant-heat spray calciner [22]. Since use of organic additives in a pot calciner may result
in an explosive hazard, neutralized Purex wastes probably must be reacidified to avoid during pot calcination
the formation of solid sodium nitrate, believed to be insufficiently stable in the presence of high temperatures
and radiation for ultimate storage [ 17] in sealed containers. Reacidification of neutralized wastes is un-
de::;iralJle; it results in up to a 1/:J increase in the volume of solidified waste.
Compositions of the wastes used for the tables are tabulated in the Appendix.
Radiant-Heat Spray Rotary-Ball Kiln .
The bulk density of the powdery product from the The development program of the rotary- ball kiln
radiant-heat spray calciner is dependent on the initial calciner has not progressed sufficiently to identify
composition of the feed and the temperature in the top operating variables. that may affect product porosity
of the column [22]. For most Purex-type wastes, a or bulk density. Factors such as waste composition,
high sulfate content and a low temperature near the operating temperature, feed rate, method of feed
top of the column has resulted in the most dense introduction, speed of kiln rotation, and product hold-
product. up may have some effect on product porosity.
In gerieral, effort at Hanford has been directed

towa1·d the use of additives and subsequent fusing of
th~ product after calcination rather than toward
Optfmi z:ing OpAriJ.ting COnditionS to minimize porosity
of the gr:1nula:r product.
37
5. Bulk Density, Porosity, and Volume Reduction Factor (Continued)
Fluidized Bed Pot

TABLE 16 TABLE 17
Btn.K DENS.rl'Y, POROSITY, AHD VOLtiME REDli:'TION FACTOR BULK DENSITY, POROSITY, AND VOLl.ME REDtrl'ION FAC'roR
OF FlUIDIZED BED CALCINER PROD!CT OF Par CALCI!ml PRODU::T
Cal.cul.ated Calculated
Porosity
Dens~~[b]
Bulk Porosity Volume Volume
Wastt: Type [a] Density [b] Waote Type (al
(Percent Reduet.ton
(Percent Reduction
(s/cc) Voids) Factor (s/cc) Voids) Factor.
Aluminum Nitrate Aluminum Nitrate

Calcined at Argonne o.8-o.9 [29] 70-75 Calcined at ORNL 0.4-0.8 ! 18 1 73-86 5-9
0.6-0.7 [31] 7-23 [d)
Calcined at Hanford
Calcined at ICPP 0.5-1.6 [24,25, rti~ [641
~~cined e.t ORNL [c) 1.4-1.6 [18] 51-64 6-9
27,751
Bypotbetical, Assuming
Calcined e.t Hanford [d) 1.1-1.9 [371 36-64 3-7
44-761> Porosity 0.7-1.6 8-18 Low Acid
Not Calcined
PW'eA
Aoouming $1-641> l'orooity Ll-1.5 .4-~
L6\l A~1d
1.4 [29] High Sul.fa.te
~2 5
~:!~~ 4tf~o~~s1ty- 0.7-1."1 --~-f)-- Nnt:, 0"'1rfnnoi
Assumins 51·64~ Porosity 1.2-1.6 3-5
IT1AA Oulfate
~l~~~l
Current Firct Cyole
r.alr:tned at ~onl 63 4
nuL Oc.luiuod
/\oouming '•'•-7Porosity ~-5
Assuming 51·64~ l'orosity Ll·L5 10-13
Cw·.t~ut.Fll"e.t Cycle
Calcined at Hanford 1.2 [30) 61 10 Acidic (Hypothetical)
Assuming 44-76'1> Porosity U."{-1."( 6-15 AsGumiD8 51-64'1.> P.:.ro~;~!'t:.;y 1 .2-.1 .n 15-20
Acidic (Hypothetical) Neutralized
Assuming 44-76i Porosity o.8-L8 10-23 Cannot be Calcined in Pot
Calciner
N~utn~:11 '1.1!!1'1 ( RypnT.heT.te.a.1) [c)
Assuming 44-7(51, Porosity 0.6-1.5 1.2·3.1 Reaciditied ( lfYPOtbetie:al)
Assuming 51-6lf1, rorosi ty 1·0-1.) 1-5-2-1
Reacidified; does not apply,
Neutralized vastes can Stainless Steel Ni tro.te
be calcined v1 thout Calcined at ORNL 0.9-1.4 [18] 72-83 6.10 [e)
reacidification (Hypothetical)
Stainless Steel Nitrate > 1.6 {e 1 Assumins 72-BJ/, Poros1 ty 0.9-1.5 5-8
Cal.dned at ICI'I'
(aj Waste compositions given in Appendices A e.nd c.
(Hypothetical)
· Aoouming 44-761> Porooi ty l. 3-3.0 7-15 [b) Weight of product per unit volume of storage container utilized is
basis for bulk density values reported by ORNL.
[a] Waste compositions given in Appendices A and B. [c) Engineericg-scale calciner.
(b) ICPP values of bulk densi.ty for untapped product. [d) Laboratory-scale calciner. 8
Hanford values for untapped material cBl.cul.ated from experimental values
for tapped product. Argonne vorkers did not identif'y procedures for [e] Volume reduction factor fo:r synthetic vaste calcined. Actual vastes in
4Gtermlft1ftg aw..a. aena1 tY. gtnna.aA p'N\hah1J 1!11'\:J"CC r.nn~entrat.en; see vn11nne rerlur.t1on far.tar for
hypothetical w.aw.
[c) Assumes sodium carbonate in calciner product.
[d) Volume reduction factor for synthetic waste calcined.
Actual wastes in storage more concentrated; see volume reduction factor
fot' h¥PQthgtli1d \l'llste.
re 1 Bulk density value tor product of a synthetic waste priol' to
equilibrium conditions. Wastes in stora.ge have different CCIJIPOSition.
See val.\&851 for hypotheticfl.l YB.sT...e.
To date, detailed studies of porosity have been The majority of development work on this
confined to aluminum nitrate-type wastes; however, process with full scale pots has been performed at
it is believed that the observed mechanisms affecting ORNL; therefore, ORNL values of bulk density and
intra-particle porosity are essentially independent of volume reduction are believed most representative
of waste composition. Values of porosity attainable of product that may be generated in a waste disposal
with alumina product were used, therefore, to calcu- plant.
late values of bulk density and volume reduction for
other wastes.
38
5. Bulk Density, Porosity, and Volume Reduction Factor (Continued)
Radiant-Heat Spray~ Rotary-Ball Kilri
Present Situation (Continued) Present· Situation (Continued)
Tw.E 18 TW£19
:BULK DENSITY, POROSITY, AND VOLUME REDUCTION FACTOR BULK DENSITY, POROSITY, AND VOLUME REDUCTION FACT01l:
OF RADIANT-BEAT SPRAY CALCINER PRODu::T OF ROTARY-BALL KILN CALCINER PRODu::T
Ca.l.culBted Calculated
Bulk . Porosity Porosity Volume
Den!~
Waste Type (a) Volume Waste Type [a]
Density [b] (Percent Reduction [b] (Percent Reduction
(g/cc) Voids) Factor (gg/cc) Voids) Factor
Aluminum Nitrate Aluminum Nitrate 8-12[c)

Calcined at Hanford 0.18 (22 ] 94 Calcined at BNL 0.65-0.95 [48, 49] 69-79 °
Hypothetical
Purex Assuming 69- 79'/J Porosity 0.7 -1.0 7-10
·calcined at Hal:itord 0.4-0.85 [ 22 ]
Purex
• Low Acid
Not Calcined Lov Acid
Assuming 67-Sf71, Porosity 0.4-1.0 ·2-4 Not Calcined
Assuming 69-7% Porosity 0.6-0.9 2-3
Higb Sulfate
Not Calcined , _High Sulfate
· AssUmins: 67-&)1, Porostiy 0.5-1.0 L4-2.9 Not Calcined
Assuming 69-79/JPorosity 0.7-1.0 2-3.
Current First Cycle
Not Calcined Current First Cycle
Assuming 67-Bfll, Porosfty ·o.4-L'o· 4-9 Not Calcined
Assuming 69-7% Porosity 0.6-0.9 6-8
Acidic (Bypoth.etica.l.)
Assuming 67-S&fo Porosity 0.5-1.1 6-14 Acidic (Hypothetical)
Assum1og 69-791> Porosity 0.7-1.0 9-13
Neutralized (Hypothetical) [c l
Aasum1n8 67-a&j,"Porosity 0.4-0.9 0.9-1.9 Neutralh.ed (Hypothetical) [d]
Assum1og 69-791> Porosity 0.6-0.8 1.3-1.7
Reacidified; doe's not apply,
Neutralized wastes can be Reacidified; does not apply,
calcined without reac1d1f1cation NeutraliZed wstes can be .........
calcined vitbout reacidification
Stainless Steel Nitrate
Calcined at Hanford 0.8 84 ll [d] Stainless Steel Nitrate
Not Calcined
(Hypothetical)
Assuming 641t Porosity '0.9 4.0 (Hypothetical)
Assuming 69- 79'/J Porosity 1.1-1.6 6-8
[a] Waste compositions given in Appendices A arid B.
[a] Waste compositions given in Appendices A and E.
[b] R~ported bulk de.nsities assumed to be for ~tapped prOduct.
[b) Only two values of bulk density reported for product created from
[c) Assumes sodium carbonate in calciner product.' aluminum-type wste, assumed values were for untapped product.
[d) VOlume'- reduction factor for synthetic wste calcined. Actual wstes in [c] Volume reduction factor for synthetic vaste calcined. Actual wstes
storage probably more concentrated; see volume reduction factor for in storage probably more concentated; see volume reduction factor for
hypothetical waste. hypothetical waste
[d) Assumes sodium carbonate in calciner product.
39
6. Effect of Gross Porosity on· Storage of Calcine'r Products
It is generally recognized that the porosity of a product should be miniiJ.lized (if pqs~ible without the use
of additives) to optimize storage costs. A reduction in product porosity results in a corresponding increase in
the specific activity of the calciner product (in the absence of additives) and in lhe thermal conductivity, all
affecting unit storage costs to some degree. An attempt to relate these factors has been made ·in Fig\J.re 13,
whichshowsrelativecostfactorsofradioactivesolidsfor two temperatures of storage. A number of simplifying
assumptions were necessary to generalize this correlation, and therefore, it is not a rigorous relationship.
Figure 13 then is useful primarily to indicate the direction and approximate magnitude of the effect of gross
porosity on storage costs for calciner ·products. .
For this correlation, it was assumed:'

·, , .
(1r Capital costs of storage containers are directly proportional to diameter, while useful capacities are
proportional to the square of the di:ameter, · ·
(2) The temperature of stored product must be limited to prevent the volatilization of fission.products and
corrosive compounds; it will be a function of vessel diameter, thermal conductivity and specific
activity of the product, and the rate of heat dissipation from the vessel walls.
(3) All calciner product, regardless of its origin, will be stored in cylindrical vessels identiCal in con-
figuration and suitable £or pot calcination, This assumption is convenient, but it penalizes storage
economics. ,associated with calciners other than the pot ca.lciner since the cost per unit volume of
annular vessels can be · shown to be 70 percent o£ this cost for cylindrical vessels. Furthermore,
vessels used for pot calcination ~ust have a greater corrosion allowance than do storage vessels not
also used for calcining.: $to rage vessels, except those for material from the pot calciner, would be
vented so that the ·storage temperature of product could exceed the calcination temperature.
(4) Heat generation and heat dissipation will be uniform.
(5) Thermal properties of product will be independent of temperature but a function of porosity. The
thermal conductivity of calciner product would vary inversely with porosity in accordance with the
empirical Russel ·equation [77] ··and would be nearly independent of product composition. The Russel
equation was derived for granUlar material, but it is applied also to material from the pot calciner
since that material exhibits a thermal conductivity behavior similar to that of a granular material.
For simplification,· apparent conductivity due to radiation was neglected,
40
6. Effect of Gross Porosity on Storage of Calciner Products (Continued)
1.2 ~~
~~C(.: 0 oC
.....J. <?>~ '-'";)0
<l :\,~\... s~\...
I-I- ~~~ '-l~s
z<t ~~~ ~~~
-W X.\)'\ :\ 0~
J:
I-
-u.. ~~~\)io~ s
~0 0.8 ~\' C(.: ~\)'t\
z ~<(,.; ~~~
0::0
w- ~\)~ ce(.:
o...t- ~i-\ ~~\)
<t ~ ~\...
t-O:
(I)W ~~
oz. BASIS=
uw(!) (I) CYLINDRICAL STORAGE VESSELS
w· (2)THERMAL CONDUCTIVITY IS FUNCTION
>u.. 0.4
-0 -
OF PRODUCT POROSITY AS GIVEN BY
..... RUSSEL EQUATIONl77J
<tw r"t,
.....Jt-
w<t :':.! -... ~ .
a:: a: .0.2 .... i •
... ~·
40 50 60 70 ·.\ . fil•.
POROSITY, PERCENT VOIDS ·:...; :" ..
Fig. 13 Relative storage costs of radioactive waste solids assuming use of cylindrical storage vessels and an empirical variation [77]
of thermal conductivity With porosity. A reduction in product porosity has the net effect of lowering unit costs for all storage temperatures.
41
V. PRODUCTION OF ,GLAS8-LIKE MATERIALS ....
Means to incorporate radioactive wastes into glass-like materials are being studied widely as evidenced
by work being done intheUnitedStatesat BNL [5], Hanford [22, 38-40, 42, 90], MIT [91], and ORNL [6, 18, 96];
in Canada at Chalk River [92, 93]; in the United Kingdom at Harwell [7, 94]; in France at Saclay and Fontenay-
Aux-Roses [8]; and in Czechoslovakia at the Nuclear Research Institute [95]. Glass-like materials can be
created by adding various fluxing agents to waste solutions prior to calcination, or by adding the agents to
calciner product [99] and then fusing the mixture at high temperatures. '
In some "glass" processes, waste solutions would be continuously converted to molten mixtures and dis-
charged into cylinders [5]. In other processes, an intermediate calcin~r product would be made from waste
solutions for later conversion to a molten mixture in auxiliary facilities [ 5, 8, 22,]. Properties of a glass-
like material and the amount and type of additives required for production of such material will be governed
by waste composition rather than by the process employed to generate the end product. ·
Glass-like materials have been created from aluminum nitrate, Purex, and stainless steel nitrate-type
simulated wastes by using one or more fluxing agents. including phosphites, borax, silica, sodium hydroxide,
aluminum phosphate, oxides of lead (18], borosilicates [7], and molybdenum oxide [8]. Volume reduction factors
of .waste solution-to-·"glass" vary from two to nine. depending on the waste composition R.nd Rmount Rnrl type of
fluxing agent used [ 18]. Thermal conductivities of typical aluminum "glasses" vary from 1.0 to 1.6 Btu/ (hr)(ft)
(°F) in the temperature range 200 to 600°C (18). However, the conrluctivities of other glass-like materials are
in a range 0.4 to 0.8 Btu/(hr)(ft)(°F) at temperatures varying from 200 to 800°C [22, 38, 39]. ·
The British report that irradiation of up to 1010 rads did not significantly affect leach resistance·of a
glass, and that leach resistance is at least partly dependent on its waste oxide content [7). ORNL [18] reports
a declining leach rate from 2 x 10-6 to 2 x 10-::-7 g/(cm2) (day) during a five-week interval for a typical glass
created. from aluminum-type waste. At Hanford [41, 42], phosphate-type "glasses" with about 50 percent cesium
or strontium incorporated in them were found quite soluble in boiling water.
High equipment corrosion rates have been encountered with some of the fluxing agents, necessitating use
of specialized equipment or different fluxing agents. Because of the corrosion aspect, use of a calciner to
generate· an intermediate product for conversion to a "glass" may be superior to generating a glass directly
from waste solutions.
Akin to "glass" studies is the work at HaDiord [39] in which the ~odium sulfate content of.Pttrex-type
:3imulated wastes ha·s been adjusted so that calcinerproduct would fuse, at temperatures around 900°C, reduce
void spa.ce, and increase thermal conductivity. At the proper composition, calcmer products from the fluidized
bed [99], the pot [38-40], and the radiant-heat spray calciner (22] have been fused.
Fluidizod Bod Pol
Additives put into waste so that fluidized bed With the exception of stainless steel nitrate
calciner product can be fused into a glass-like waste, volume reductions possible with glass-like
material will increase ultimate volume over that materials are about the same as those of calciner
otherwise possible. Some granular products can product for this process. Any increased processing
be mixed with a fluxing agent in the future to form costs due to vitrification of pot calcination product
a glass-like compound as shown by Hanford work must be justified then by the higher thermal con-
in which fluidized bed product from a Purex-type ductivity and lower leachability of the glass.
simulated waste was mixed with sodium sulfate
and fused at a temperature between 800 and
900°C [39, 991. The volumes of the end products
were 16 to 58 percent greater than that of the
calciner products. It appears, therefore, that the
expense of creating glass-like materials need not
be borne until it becomes necessary for other
reasons to create such materials.
42
: V. PRODUCTION OF GLASS-LIKE MATERIALS (Continued)
(J)
Merits of glass-like materials over corre.sponding cal- IJJ PRIMARY PRODUCTS (J)
ciner products are dependent to a large degree on the relative t; ....1
....1 ct
final volumes per unit of waste and whether interim storage
of the calciner product is feasible. Glasses, unless totally
ct
3=
0
w ~
1-a..
<t
co
'
..J
(!)
N
nonleachable;. require containment; benefits of low leachability 0 ~(f) li
materialize only· with breached storage vessels. Except with
-o
=>w 1-
0
o!;:t
<tW
f!!Z
o:::!
some high-porosity products, required fluxing agents generally it co a.. a: :I: a:~
increase final material volume as shown in Figure 14. This

figure. is based on the amount of waste oxides from various
wastes incorporated into glass-like. materials and the resulting
densities as reported by investigators at ORNL [ 181. Relative
volumes of calciner products are those calculated from best
estimates as shown in Section IV. Properties of experimental
glass·-like materials produced at ORNL are shown in Appendix F.
To be attracti v~ ~conomically, the increased expense
(combined chemical, operating, and capital costs) of producing
a glass must. be. offset by savings achieved either due to a
further decrease in volume or through the use of larger,
cheaper storage vessels, because of a higher thermal con-
ductivity of the final product.
. Most glasses, because of their relatively high conductivity,

probably can··be· contained in vessels limited in size only by
the considerations of remote manipulation; however, ultimate
stora:ge in a vessel that small imposes. an economic penalty
on overall costs, since storage costs are optimized by· employing
containment vessels limited in size only by temperature con- Fig. 14 Relative volume of wastes compared for
siderations. With respect to temperature only, radioactive calclner products and glass-like materials. that may
materials,· could be stored in vessels with ever increasing result with the use of the various calcination
diameters as activity decays. For those materials which can processes. The dotted lines Indicate the range of
volumes possible based, In the case of the calclner
be. easily retrieved and transported to less expensive vessels, products, on the estimates In Section IV and In the
full advantage can be taken of ::tctivity decay. In this case, the case of the glasses on properties of slmlllar
benefit of the higher conductivity of a glass largely disappears. materials as shown In Appendix F.
The volume of glass-like materials produced Use of additives to produce glass-like materials
from aluminum nitrate and Purex-type wastes is from products of this calciner has mixed results on
significfl.ritly lnwf:'r than corrat:ponding product fhu1.l vohtmtl, Lkl.Jtlnlllng on the waste. The expense
generated in the radiant-heat spraycalciner. Studies of creating glass-like materials from this product
at Hanford [22, 57] show that the volume of most need not be borne until justified, however.
products from this calciner can be reduced 50 to
75 percent by using additives and subsequently
fusing the product in collection pots at temperatures
exceeding 800°C.
43
VI. APPLICABILITY OF CALCINERS FOR PROCESSING VARIOUS WASTES
Waste activity, composition, and concentration may affect ultimate ·cos~s differently, depending on the
calcination process employed. These factors are considered in this section .
. 1. Waste Activity Level

EFFECT OF WASTE ACTIVITY ON STORAGE COSTS
Activity level could have a considerable effect FOR ACIDIC PUREX AND THOREX WASTES
3.0,.------.-...:__...:_____.:.--.-----,----,.-----,
on waste disposal costs. Perona [ 110] reports that
disposal costs probably will not be affected sig-
nificantly by removal of fission products prior
to processing; however, his conclusions are based
on a. specialized case--pot calciners ten feet long
with a maximum diameteroftwofeet--andtherefore, ·
are not generally applicable to larger storage vessels.
BASED ON ORNL 3192
Since lowest storage costs· are achieved by storing ORNL TM 559
IDO -14595
calciner products in the largest possible containers--
limited in size only by the maximum allowable
storage temperature, a function of acti vity--1t follows
that a iimitaUon to vessel size lmpu~;~::u uy 1•em.ote
handling req.uirements can prevent realizatiOn ot "o!:=----;1.6..-.--··.-·- 1k' 18 2
lowest ,possible costs tor many waste::; a~; sltuwn MAKIMUM POT D!ftUOT~9nR FniiiVAl F.NT BIN THIC!<_Nt;:!;S,
(LIMITED BY ACTIVITY)
in Figu:r:e 15. The figure shows that costs continue
DECREASING ACTIVITY OF WASTE
to diminish for granular materials With decreasing
activity level, but for materials in pots, costs be-
come constant in spite of decreasing activity when Fig. 15 Relative storage costs for cellular and granular
materials produced from acidic Purex-type wastes. Costs shown
the remote handling limitation overrides the maxi- exclude 'all expenses associated with processing per se; only the
mum temperature limitation to storage vessel r;.iie. costs of storage containers, cooling facilities, vaults in which
The maximum size of a vessel as limited by handling the storage containers are placed, and necessary transportation
requirements is not clear, and therefore, neither and surveillance_ costs: are: included. , The br~ad r!lnge for
granular products covers products having the range of gross
is the minimum activity of wastes that could be porosities observed with the fluidized bed, rotary-ball kiln,and
placed in transportable pots without an excessive radiant-heat spray calciners. By employing a principle ofinterim
economic penalty. An ORNL study [66] assumes storage, overall s~orage costs for granular products will be still
that the maximum size of a cask to transport lower. For wastes less · active than Indicated on the figure,
significantly lower costs· for granular products are indicated,
cylinders containing radioactive materials would bUt no appreciable reduction in the cost of storage of cellular
be that corresponding to a weight of about 100 tons; materials is possible because of. the size limitation on pots
the inside dimensions of a hollow cylinder in such imposed by remote handling requirements.
(Continued un page 45)
Fluidirsod Bed Pot

Ultimate disposal costs should decrease with de- This unit may be best suited for calcining high
creasing activity for waste processed in fluidized bed activity wastes. Calcination of low activity wastes
units if product is pneumatically transported tofinal or wastes of various activity levels interchangeably
storage. would result in waste disposal costs nearly as high
for the low activity wastes as for high acttvl.ty wastes.
44
VI. APPLICABILITY OF CALCINERS FOR PROCESSING VARIOUS WASTES (Continued)
a ··ca·sk would be- five feet in· diameter by ten feet long with 12-inch thick lead shielding. It seems, however,
that. specialized handling techniques would have to be developed to move and transport vessels that large.
Solids having a heat generating capacity lower than about 100 to 300 Btu/(hr)(ft3), depending on thermal
coriductivity .. and temperature considerations,.·shbuld be traJ?.sported via pipe lines to the proper size storage
vessel to achieve minimum disposal costs.
If a-waste·disposal plant must process several wastes of widely different activity levels, those processes
employing transportable pots may require two or more furnaces, a corresponding increase in cell area, and
perhaps additional remote handling equipment. Pots heated by a circumferential induction furnace, preferable
for several reasons to a resistance furnace, could not use a common set of furnace coils for widely different
diameter pots because furnace efficiency is a function of the gap between furnace coils and heated surface.
Radiant- Heat Spray Rotary-Ball Kiln
This calciner is best suited for the high A rotary-ball kiln probably can be used to
activity wastes because product probably will be process in an economical manner wastes of all
collected. and melted in an auxiliary pot below the activity levels, interchangeably.
calciner. Because· the maximum size- of a melt pot
will be limited by convenience of remote handling,
calcination .of low activity wastes or wastes of
various activity levels interchangeably may need-
lessly equalize waste disposal costs for high and
low activity wastes.
45
2. Waste Composition
The composition of a waste affects product properties as indicated in Section IV and also may affect the
selection of operating conditions, feed additives, and perhaps certain processing equipment. For example,
calcination of mercury-bearing wastes, at temperatures above 400-500°C, may require use of a trap to
separate mercury from calciner off-gas for separate storage as a contaminated liquid. Calcination of the
sulfate-bearing wastes, at temperatures about 600-800°C, may necessitate use of an additive in the feed to
prevent evolution of sulfur compounds and the consequent increasing concentration of sulfuric acid in re-
cycled process streams, excessive corrosion of equipment, and an additional disposal problem [2]. Additives
used in Purex-type simulated wastes at ORNL for this purpose include various compounds of sodium, calcium,
and magnesium [2). At Hanford, alkaline earth compounds have been added at Purex-type wastes to prevent
evolution of sulfur compounds reported to be corrosive to off-gas equipment [55).
The fluoride-bearing wastes from processing zirconium fuel elements appear to present the greatest
problem in calcination, as well as in storage. Of the two possible approaches to calcining this waste, it
appears that the most practical is addition of calcium oxide to the waste, followed by calcination at a suitably
low temperature, less than 500°C. Such a procedure has been demonstrated satisfactorily in laboratory-scale
equipment with no detectable amounts of fluoride being volatilized[75,111, 135]; however, further development
work in pilot plant scale equipment is necessary. In theory at least, a second approach for calcining these
WliRtP.s would emolov l?tJE;l<;:ial corrosion-resistant equipment. Work at BNL [GO, 114] shows that Illiwu-C,
InconP-1-X, Haynes-25, and Nionel would be satisfactory cunsh·uction materials tor a. caiciner pruul::lt:H:!lug
fluoride- bearing waste at 700°C; however, the problem of finding suitable materials for off-gas processing
equipment remains unsolved. Fluorides and nitrates volatilizing from calciner product will condense from the
off-gas and result in a highly corrosive mixture of contaminated nitric and hydrofluoric acids. Economically
p:r,-actical materials for equipment in which to decontaminate such liquid by evaporation or distillation techniques
are unknown.
Ruthenium. if volatilized from waste dw·ing calcination, must be separated from off-gas and recycled to
the calciner or stor~d as a separate waste stream. Ruthenium can be recycled to the calciner and much of it
retained with product [24] at a 400°C calcination temperature level. The use of phosphites in feed solutions
and calcination in nitric oxide atmospheres have significantly reduced ruthenium volatilization at high
calcination temperatures [2, 6, 94].
The use of additives in a waste solution, although necessary with some wastes or with some calcination
processes to minimize corrosion or to reduce the melting point of the waste solids to a practical level,
will have a net effect of increasing the final material volume over that theoretically possible otherwise.
As an illustration of this, volume reduction factors have been calculated for four cases as shown in Table 20.
(Continued on page 4 7)
Fluidized Bed
Aluminum . nitrate-type simulated wastes of Aluminum nitrate, stainless steel nitrate, and
various compositions have been processed in a Purex-type simulated wastes have been processed
fluidized bed calciner at the ICPP [24, 25], in a pot calciner at ORNL [2, 17], and Purex-type
Argonne [29], and Hanford [31], with no sl.gliltl- Wctstes hav~ IJ~~u cah.:iuel.l .o.t IIArlford [!3~ft4?.] v.1th
cant problems. Stainless steel nitrate-type simulated no insltl'mountable prolJl~Iw:s. Wa::ste solution when
wastes have been processed in this calciner at saturated with organic material has foamed
the ICPP [24] with no problems, and Purex-type exc~::s::sively and caused excessive entrainment in
simulated wastes have been calcined at Argonne[:f9] the off-gas [2, 17, 88].
and Hanford [30]. Workers at both Argonne and
Hanford report some agglomerate formation for Excessive solution foaming in a pot calcitler
Purex-type wastes (possibly a result of the low also has occurred [ 40-42] at Hanford under certain
melting point, 308°C, of sodium nitrate in these modes of operation with Purex wastes, indicating
wastes), but at Argonne, growth of these agglomerates that operating techniques will have to be adapted to
was successfully controlled by adding sucrose or the waste being processed. ORNL reports that
by using a jet grinder in the bed. Laboratory studies neutralized Purex wastes must be reacidified prior
of fluidized bed calcination of zirconium fluoride to calcination in this process to avoid the formation
wastes have shown promise for quantitative re- of solid sodium nitrate which is not sufficiently
tention of fluoride as CaF2 by addition of lime to stable for storage in sealed containers in the
the feed solution [ 135]. However, pilot plant tests of presence of radiation at high temperatures [17J.
this process have not yet been undertaken. An
early scoping study [24] with these wastes at ICPP
in a six-inch diameter pilot plant calciner indicated
satisfactory calciner operation but did not attempt to
demonstrate retention of the fluoride.
2. Waste Composition (Continued)
TABLE 20
A COMPARISON OF THE VOLUMES OF SOLIDS THAT MAY RESULT FROM USE OF
VARIOUS PROCESSING AND SOLIDSSTORAGE TECHNIQUES.[a)
Volume of Liquid Assumed Volume Reduction Volume of
Circumstances of Processing and Waste at Time Porosity of Factor (Initial Solids
St~ring Radioactive Wastes
of Calcination Calciner Volume of Liquid Stored {gal
(gal per ton of Product to Final Volume per ton of
Uranium)" (Percent) of Solids) Uranium)
(Case l) High activity Purex waste, calcined
when created. Resulting solids can be
stored for a number of years in small 50 50 20 2.5
·containers and then transferred.to
large containers.
(Case 2) Same high activity Purex waste; neu-
tralized for interim storage as a
.liquid. After.same number of years
in interim storage as in Case 1, 8o 50 1.8 28
waste is reacidified, calcined, and
stored in large containers identical
to those-of Case 1.
(Case 3) Same as Case 2 but product is fusedj
storage containers may ,be larger than
in Case l because thermal conductivity
80 0 3.6 14
of the solids will be greater.
(Case 4) High activity neutralized Purex wastes
. p1·e;;eu~l.Y ln storage. Wastes have de-
cayed suffictently to use storage con-
tainers equal to those of Case 3. Sugar 60 0 4.5 ·n
is used in waste and product is fused.
Thermal conductivity similiar to the
product in Case 3·
[a] The waste compositions and v9l~es used in calculations for the table were similar to those of hypothetical
wastes assumed in another study Ll7J; for convenience, the volume of fission products in the wastes was neglected ..
The initial volume of the waste for all cases was 50 gallons per ton of uranium.
The m1rumum volume of solids and, therefore, m1rumum disposal costs would result in Case 1, which
assumes interim solids storage to permit ultimate use of large low cost storage facilities. The comparison
in Table 20 indicates that the volume of stored solids resulting for any given waste can vary widely depending
on the combined treatments a waste is subjected to between the chemical processing plant and ultimate storage.
Aluminum nitrate, stainless steel nitrate, and Satisfactory product has been generated from
Purex-type shnulated wastes have been successfully aluminum nitrate-type simulated wastes in a rotary-
calcined in a radiant-heat spray calciner at Han- ball kiln calciner at Brookhaven. Scoping studies
ford [22, 57]. Neutralized Purex-type simulated also have been made to determine the feasibility
wastes containing high concentrations of sodium of calcining fluoride-bearing wastes in this
nitrate have been processed using sugar to reduce unit [4, 48, 50, 114].
the nitrate. Organic materials such as tributyl
phosphate, kerosene, and sugar in waste solutions
created no problems during calcination.
Catastrophic corrosion of a radiant-heat spray

calciner occurred when a fluoride-bearing waste
neutralized with oaue:tio was on.lcincd [22].
47
Fluidized Bed Pot
Waste composition will not significantly affect Except for wastes containing fluorides or or·ganic
operation of the fluidized bed calciner. By employing compounds, it is expected that most wastes can be
proper additives or suitable operating techniques, it processed in a pot calciner by employing suitable
is expected that nearly all types of waste can be operating techniques and proper additives. Calcium,
processed. A significant advantage to this calciner magnesium, and sodium compounds are necessary
is its satisfactory. operation at relatively low-temper- with some sulfate-bearing wastes to prevent the
atures; therefore, it may be uniquely suited for evolution of sulfur compounds at 900°C. At the high
processing the fluoride-bearing wastes·. Organic ma- operating temperature of this calciner, calcium
terials probably must be used with neutralized oxide will not retain fluorides with product during
Purex wastes to prevent melting of the product calcination of fluoride-bearing wastes.
during calcination, a procedure similar to that
employed for these wastes during calcination in It is expected that ~ssentially all mercury
the radiant-heat spray calciner at Hanford [22]. present will be vohttHized from the calciner, and
therefore, a mercury trap will be required in the
MoRt of the merc\.lrv volatilizing from the off-gas stream [18] when processing mercury-
calciner can be separated from off-gases and re- bearing wastes. Altetna.nvely, rnert:ury t:uuh.l Le
8yr.lP.rl for eventual retention in the product at removed "from the feed solution by a special process-
normal operating temperatures. Mercury volatilizing ing stt:p. prior to calcination. Strl.ngent. precaulious
from calciner product in the center of a storage must be ·taken to keep .even small concentrations of
container during storage may be trapped by the organic compounds out of wastes processed in a pot
relatively cold outer zone of product. calciner; as some organic.: materials could react
v.iolently with nitrate Sf!lts in this calciner [2].
48
Radiant-Heat Spray· Rotary-Ball Kiln
With, the exception of fluoride-bearing wastes, It i$ expected that waste composition will not .
it is expected that ,.inost waste solutions can be significantly affect the operation of this calciner.
proces.sed in this calciner by employing suitable By employing proper additives or suitable operating
· !l.dditives or operating techniques. Adequate retention techniques, satisfactory product and operation can
of fluorides in calciner product through use of be achieved for all wastes .
..calcium oxide and low calcination temperatures
probably cannot be accomplished because of the high Though not tested experimentally, Purex-type
temperature reached in deposits of calciner product wastes probably can be processed at low calcination
on vessel . walls. Such wall deposits also result temperatures or by using an organic reducing agent
in vessel corrosion [39] as discussed in Section VII. in the feed.
Use of a mercury trap or prior removal of Most of the mercury volatilizing from calciner
mercury with the mercury-bearing wastes may be product can be recycled for retention in the product
necessary. at low operating temperatures.
49
3. Waste Concentration
Waste concentratio!). :Will affect calciner throughput capacity; since wastes in storage··are inherently less
than saturated because· of jet dilution, addition of decontaminating solutions, etc; it may be desirable to pre-
concentrate wastes in an evaporator. · ·
Waste concentration also" may affect product porosity. A thorough study of factors,affecting the porosity
of fluidized bed product from calcination of aluminum-type waste showed that only feed concentration and
calcination temperature had any significant affect [64]. There is a need to determine the optimum concentration
for each waste to be calcined. Increased operating costs due to processing wastes less concentrated than
saturation would have to be balanced for the specific case against any savings resulting from· a low porosity
product, with its decreased storage volume, and from elimination of the separate feed concentration step.
· Fluidized Bed- Pot
. Wheeler et al [64] report that productporosity The pot calciner inherently has a low throughput
Oil.!,hP. minimized QY selecting suitable feed con- capacity, and therefore, a feed evaporator has
centrations and calcination temperatures for iluidized alway~ I.Jt:eti employed in pilot work to prP.r.nn-
bod oo.loinlirli. ccntrate simulater.l waRte solutions nearly to sat-
uration. Ail. evapu1·alu1' ltai5 bce11 propoood for.
stmila:r reasonf! for a demonstration of a pot
caloiner with radioactive wastes [45],
Discu8sion Discussion
The fluidized bed calciner inherently has an Wastes almost certainly must be preconcen-
extremely high throughput capacity; therefor·~. no trated for processing in a pot calciner. Howeve·r,
economic necessity exists to preconcentrate wastes during some studies, the bulk density of _pot product
before calcination. Incremental internal heating appeared to be related to feed rate [ 72J. It is con-
surface probably can be added to this calciner at ceivable that product porosity is a function of feed
less cost than by providing a supplemental evaporator concentration with this unit also. Additional studies
with comparable heating duty. Overall waste disposal are desirable to provide quantitative data and permit·
costs are probably minimized with this calciner by an economic evaluation.
use of a somewhat dilute feed because of the porosity
effect.
no·
3. Waste Concentration (Continued)
The effect of waste concentration on the op- The effect of waste concentration on the op-
eration of a radiant-heat spray calciner has not eration of a rotary-ball kiln calciner has not been
been reported. reported.
It is doubtful that the porosity of product gen- Development studies appear desirable to de-
erated in this calciner can be reduced sufficiently, termine any effect waste concentration may have on
by varying waste concentration, to preclude the porosity of product generated in this calciner.
desirability of converting the product to a glass .
. 51
VII. WASTE DISPOSAL PLANT CONSIDERATIONS
Significant requirements of equipment, safety, personnel, and housing facilities are considered in this
section to the extent that it is possible to do so at the present stage of development of the four calcination
processes.
1. Equipment
The amount and type of equipment in waste disposal plants will be highly dependent on throughput capacity,
variety of wastes handled, and the product handling system of the calcination process employed. Minimum
equipment requirements are likely to result when a single calciner can be used to process the entire throughput
·of a plant; use of multiple calciners for this will certainly multiply at least part of the required equipment,
as shown in Figure 16. This figure shows the approximate number of calciners required for each process to
handle 1000 gph of waste solutions. Not shown in Figure 16 is the equipment required for feed preparation,
off-gas decontamination, and product handling.
Equipment used in the feed preparation and off-gas systems of a plant will be least affected, and equipment
in the product handling system will be most affected by the calcination process selected.
DP.sign of a feed preparation system will be affected by factors such as waste composition and concen-
tration. addit~ve .:reQuirements, and. plant capacity. Equipment in the off-.~s system will. be d~pendent 0rt t~e
type of system selected--condensmg or noncondensing, gas compo::nl:ion, and quantity of gas. J:o'or most
applications, a single feed preparation system and a single off-gas system should suffice for any number of
calcine:rs in the same plant used to process a given waste stream.
The amount of equipment in a product handling system can vary over a wide range, depending on the
type of product and on the number of calciners in simultaneous operation. Granular product can be pneu-
matically transported from the calcination vessels to storage facilities where it can be separated from the
transporting medium by one or more high efficiency cyclones. Use of a steam or air jet instead of a blower to
supply motivating force would virtually eliminate the need for any mechanical equipment with its attendant
high maintenance costs or for viewing windows in the housing facility.
On the other hand, the amount of remote handling equipment and attendant labor involved with any process
whose final product is contained in transportable pots is indicated by a procedure that has been outlined for
the pot calcination process [18, 45].
(1) An empty pot is placed inside a water-cooled induction furnace mounted on a movable mechanical dolly.
(2) The dolly is moved to a second station and is centered below a stationary head.
(3) The pot and furnace are mechanically jack~d upward until the cylinder mates with the head.
(4) The head and pot are connected by means of a special connector and a ulamp.
(5) · The furnace is connected to electrical and water-cooling leads. Movement of the furnace along with the
dolly between two or more stations may result in excessively long electrical leads and low furnace
efficiencies, hence, the need for remote furnace connections.
(6) After the pot is filled with solids (for some cases in which a granular product is generated in a separate
vessel, a vibrator may be required to cause solids to flow from the calc1ner to the colleetlon put) lhe
furnace and pot are disconnected from their respective leads and the dolly is moved tu a capping
station.
(7) At the capping station, some type of cap may be mechanically attached or welded to the pot dependLug
on various intangible factors.
(8) The pot is lifted from the furnace and is replaced by an empty cylinder.
(9) The capped pot is moved to a different location for external decontamination.
(10) ·The pot is then pulled i!lto a shielded cask and transported to a repository.
(11) At the repository, the pot is removed from the cask and set into the final storage position.
Viewing windows and several sets of manipulators and hoists will be required to perform the many steps
necessary for remote manipulation of transportable containers in a radioactive cell. The number of mechanical
dollies, furnaces, and manipulators near the calciner would probably have to equal the number of calciners in
simultaneous operation; however, through judicious design of programming, perhaps the capping and de-
contaminating stations could be common to several calciners.
52
VII. WASTE DISP OSAL P L ANT CONSIDERATIONS
1. Equipment (Conti nued )
1FLUIDIZED BED
42000-96000
FT3/YR.
GRANULAR
CALCINER
PRODUCT
OR
4 ROTARY- BALL 74000 -107000

FT3/YR.
KILN CALCINERS GRANULAR PRODUCT
OR
68000-160000 FT3/YR.
15 RADIANT- HEAT GRANULAR PRODUCT
SPRAY CALCINERS
1900-2900 POTS/YR.
GLASS
OR
1500-2100
100 POT LINES POTS /YR.
CELLULAR PRODUCT
Fig. 16 Alternative process r equirements for disposal of 1000 gph of P urex type waste. CA lr.iner vesse ls and s torage volumes
are shown approximately to scale with r espect to e ach other. The r equired volume for stor age of e nd pr oducts Is based on
the range of porosity exhibited by experime ntally obtained m aterial from each process.
53
1. Equipment (Continued)
Fluidized Bed Pot
Inherent characteristics of a fluidized bed Although the pot calciner itself may be con-
calciner which will result in a minimum amount of sidered the utmost in simplicity for converting
equipment, essentially none with moving parts, are: solution to solids (3, 34, 44, 113], the overall
a large range of capacities in a single processing process appears highly complex. This inherently
vessel, a fully continuous process readily adaptable batch process will require multiple calciners,
to nearly all wastes; productionofagranularproduct furnaces, dollies, and much auxiliary product
that can be pneumatically conveyed to storage and handling equipment for plant throughputs greater
later retrieved if desirable or transferred to larger than about 10 gph.
containers.
f)4
1. Equipment. (Continued)
Product of the radiant-heat spray calciner will The calciner in this process has a rotating kiln
probably be collected and melted in individual pots connected to stationary components through moving
to decrease product porosity; hence, the previously seals. At least one of the seals must contain a
described product handling system involving multiple thermally-hot, radioactive, dusty gas in the kiln.
remote handling steps is applicable to a plant The seals, balls in the kiln, kiln bearings, and motor
employing this process. A single calciner probably driven gears will all be subject to varying amounts
can be used to process waste at rates up to about of wear and will require periodic replacement.
65 gph; higher plant capacities will require additional Adequate viewing facilities, remote handling equip-
calciners tt.nd equipment. ment, and cell space must be provided for this
maintenance.
Waste disposal plants with capacities up to

200-300 gph could probably employ a single rotary-
ball kiln calciner. ·
55
2. Safety Considerations
An intensive hazards ~valuation of the many facets of calcination has been. made in the case of the fluidized
bed process [68] but not for the other processes. Although such an analysis is desirable for all processes,
it is beyond the scope of this report. However, some of the more obvious factors are considered in thi.s section.
Organic materials of sufficient· quantity in waste solutions may form explosive mixtures with .nitric acid
at temperatures· exceeding· 300°F, as evidenced by experimental work [ 116, 11 7]. Wastes may contain small
but significant quantities of organic materials due to mal-operation of the solvent extraction equipment or.
inadvertent discharge of certain decontaminating solutions to waste storage tanks. ~.
Equipment corrosion can be very hazardous with ve§lsels ·containing ra9.ioactive materials; however, it
usually can be minimized by employing a combination of suitable construction materials for process vessels,
relatively ·low operating temperatures, and suitable complexing agents. ,.
Fluidized Bed Pot
Organic Materials in waste solutions present no Waste solutions containing organic materials
problem to fluidized bed calcination because there probably should not be processed in a pot calciner
is virtually no liquid holdup in the calciner. At the because the organic mate:rial may accumulate and
temperatures normally employed, both kerosene explode [2, 113]; however, wastes saturated with
and sucrose readily burned in pilot plant fluidized dibutyl and monobuty:l phosphate have been calcined
bed calciners [29], in a pilot plant unit [ 72]. With a demonstrational pot
calciner (45], the original intent was to calcine only
Corrosion should be relatively low at the 300- waste removed from the midportion of storage tanks.
5000C bed temperature level normally used. The desirability of using a pot:.calciner to process
waste directly from a chemical processing plant is
Overheating of products due to thermocouple dependent on finding an alternate positive method of
or instrument failure is not likely to create hazards keeping organic materials . out of waste solutions.
(except for wastes containing fluorides) because the
differential between normal operating temperature C~ of pot calcination vessels may be high
and the temperature of product decomposition is at the 900°C wall temperature employed. However, pot
extremely wide. Fission product overheating of calcination vessels are in contact with corrosive
calciner product retained in a bed during shutdown liquids only for a short time on most runs; neverthe-
can be prevented either by circulating unheated fluid less, undetected localized hot spots and attendant
through the heat exchange tubes, by fluidizing the serious corrosion may develop because the number of
bed, or by introducing water through the feed nozzle. thermocouples--which are used but a single time in a
pot calciner--should be minimized for economy. On
sev~;~r!ll. tlilot Plant r1.ms [89, 126). t~ots have failed
f.L'UIU L:U.L'.L'U81Ull, 1Jt:!dlalJ8 UUt:! (.u lht:!.L'IllUL:UU!Jlt:! fallU!'t:!
and resultant product overheating [ 71]. .
Overheating [2, 45, 61, 1J.5) neartheendofa run
when residual heat requirements are exceeded by heat
release from activity decay must be prevented to
avoid volatili~ation of fission p:rQQ,~Jcts or corrosive
compounds. TnvP.sti gatnrs havP. ca.lculatP.cl tP.mpP.r-
ature profiles of product [61], proposed the use of
a program [115] to remove heat from a pot and
proposed use of an induction furnace [45], Instrument
or thermocouple failure may cause almost immediate
overheating since the normal operating temperature
of a pot calciner is high.
Miscellaneous. Pressurization ofpotcalciners

has been observed at Hanford [39, 40, 42]; at ORNL
an eight-inch diameter, four-foot pot ruptured when
a half-inch off-gas line plugged during an early
run [ 118]. On later runs a second vent line has been
used on pot calcination vessels, but some line pluggittg
and pot pressurization has continued to occuiT88,
119]. The molten contents of a pot on one run erupted
into the off-gas system [ 88). Pressurization of pots
is possible even without human error; therefore, this
weakness must be guarded continuously to prevent a
possible catastrophe.
2. Safety ·considerations (Continued)
Overheating radioactive solids during-calcination may evolve highly corrosive or radioactive compounds
and . also maS impair the structural strength of vessels. For example, oxides of sulfur from some Purex
wastes [ 2 ,- 5 1· or fluorides from fluoride-bearing wastes would be highly corrosive to an off-gas system.
For processes involving fusing or melting calciner products, a pressure surgE) may blow product into a
vent line, pressurize the system, and burst a container. Hanford workers report [39, 40, 42] runs in which
partial melting of product in the lower portion of a pot WaS accomranied by gas release, pressure surges, or
calciner product erupting from the pot, ORNL workers [88, 119 report similar situations in which off-gas
lines plugged and pressurized pots.
Safety considerations peculiar to each calciner follow:
Organic Materials in waste solutioii!s present no Organic Materials in waste solutions present
problem to radiant-heat spray calcination, Sugar no problem to rotary-ball kiln calcination because
has been used without mishap many times as a feed there is virtually no liquid holdup in the calciner.
additive in pilot plant scaleruns[22, 57].
Corrosion and erosion of the rotating kiln may
High Corrosion rates of the calcination vessel be relatively high because of high wall temperatures
may be experienced· _at the 800°C temperature level coupled with moving balls, The balls may tend to
normally employed. Allemann et al [22], report grind or wear a way any corrosion resistant metal
Inconel and AISI 446 SS appear to be satisfactory oxides formed on kiln walls.
calcine!' vessel materials for most wastes. During
calcination of a fluoride-bearing waste, an lnconel Product overheating resulting . from thermo-
column failed; perhaps corrosion was accelerated couple failure may be a difficult problem with this
by an excessive vessel temperature, 1000°C, attri- calciner. The thermocouples inside the rotating kiln
buted to a faulty thermocouple [22]. must be supported and connected to a stationary " .. '·j:'
lead, and, hence, their number will probably be
Overheating . of vessel walls and perhaps de- minimized to simplify design. With stationary cal-
... '/.
composition of product deposits, especially in case cination vessels, several control thermocouples
of thermocouple failure, can be serious, Deposits are used as insurance against thermocouple failure
of product on vessel walls, routinely observed during and excessive temperatures; such a procedure is
pilot plant studies [22, 57], insulate the walls and more costly with this calciner.
may cause a temperature rise and resultant product
decomposition, product melting, or higher rates Miscellaneous. Fission product heat may have
of vessel corrosion. Walker [39] studied corrosion to be removed from retained product in the kiln
of a radiant-heat spray calciner and reported, at shutdown, possibly with water bled into the kiln
"lt _ would appear that the most significant factor through the feed nozzle.
contributing to the failure of the spray calciner was
the accumulation of calcined waste products on the The rotating seals of this calciner may be the
calciner Wa.ll. These products appear to be severely weakest link, thus requiring frequent preventative
corrosive at the normal operating temperature of maintenance; mal-operation or an event causing
the calciner and their accumulation would result in a stoppage of steam purge to these seals could result
decreased heat transfer at the point of accumulation. in dispersion of powdery product to the cell.
This woUld cause an increase in the wall temperature
at that point and a corresponding increase in the
corrosion rate." Allemann et al [22] suggest use
of an annular wall in the calcination vessel to
circumvent backmixing and wall deposits; however,
in subsequent work, vibrating or hammering the
calciner has continued to be employed to dislodge
wall deposits [::!].
57
VIII. DEVELOPMENT STATUS
The current status and potential problems for each of the calciners are summarized in this section. Based
on the length of time each has been under development and the scale and intensity of the development effort, it
is believed that the four calcination processes stand in the following decreasing order of advancement:
fluidized bed, pot, radiant-heat spray, and rotary-ball kiln calcination.
1. Current status
Fluidized Bed Pot

Radioactive waste solution was first successfully Calcination of high-activity wastes in a
calcined in a pilot plant fluidized bed calciner at laboratory-scale pot calciner was started at Han-
Argonne in 1958 [29]; although diluted 8:1 with a ford [44, 36, 134] in late 1962. The first full-scale
nonactive synthetic solution, the problems of activity pot calciner is scheduled for operation with radio-
containment, off-gas decontamination, andpersonnel active waste at Hanford -- possibly by 1965 [45].
protection were not appreciably different from those
encountered. with any radioactive waste. Plant scale
calcination of high activity wastes was accomplished At ORNL [ 18], an evaporator needed for pot
for the first time in the world when the WCF began calcination haS been developed, and val'luu~ syuthetic
prnr.eRRing stored alumin\Lrn nitrate waste solutions wastes have been calcined in pots. A suitable method
at 60 gph in December 1963. to handie mercury in wastes 1s still lfi rievelopmt:mL
Mochanioo.l cquipm9nt r~qn.i.rP.d fo.r l.he r•nt turn-
Development studies [24, 25, 26, 64, 127, 128] around cycle- has been tested [ 125], Laboratory
with several ·calciners have produced considerable studies show various additives can be used in
process data and have shown the adaptability of this waste solutions to create gla~s-like compounds,
calciner to essentially ·all wastes regardless of and to minimize the volatilization of ruthenium
wastes composition; concentration or activity level. and the decomposition of corrosive sulfates. At
The process as developed employs a m1mmum Hanford [ 38-42], the sulfate composition of synthetic.
of mechanical equipment, a desirable attribute for Purex wastes has been adjusted so that calciner
any radioactive process. product would fuse at temperatures between 850-
9000C.
The pilot plant "glass" process being developed

in the United Kingdom [7, 94] is similar to the
pot calcination process.
2. Potential Problema
Fluidized Bed Fot
Potential problems exist with the few pieces The cunsldet·able remote handling equipment
of necessary mechanical equipment of the WCF, necessary to this process may require frequent
namely the off-gas blowers and scrubbing-solution maintenance. Other possible problems involve solu-
pumps. These units are installed in duplicate in the tion foaming during calcination, fouled or plugged
WCF; however. erosion and wear may necessitate off-gas lines during processing, pot failure, due
theil" ooo!il.~ionll.l r!i!pl~0~;>rnPnt. to hot soots occuring from thermocouple failure,
product bridging in a pot. and satisfactory pro.:
In development work, eros"ion of all other gramm.ing of heat input and removal for high
equipment, except for that with a product transfer activity wastes [ 45].
jet, has been insignificant. Jet erosion has been
prevented in the WCF by using liners of boron
carbide, a highly erosion-resistant material.
58
Vlll, DEVELOPMENT STATUS (Continued)
1. Current Status
High activity wastes have been processed in a High activity wastes have not been processed in
~aboratory scale radiant-heat spray calciner at Han- the rotary-ball kiln calciner in the United States.
ford since late in 1962 [3, 44, 36]. Reported feed Most of the development effort has been devoted to
rates thus far have been in the range 0.5-0. 7 gph. rotary seal and feed introduction problems [4, 49];
hence, there are few process data available for
All~mann et al [22, 57] have reported the detailed evaluation of rotary-ball kiln calcination.
results of calcining a wide variety of wastes during No plans for additional development work have been
a series of short duration runs in pilot plant scale announced.
radiant-heat spray calciners. , Feed composition,
product characteristics, effect of additives in the
simulated waste solutions, thermal conductivity of
the product, effect. of various operating variables
on product, and solids off-gas separation were among
the items studied.
2. Potential Problems· (Continued)
Considerable remote handling equipment--all The many moving parts of the rotary-ball kiln
subject to wear--will be required to manipulate may require frequent replacement. Entirely satis-
pots for collecting and melting product of this factory rotary seals are yet to be demonstrated in
process. Product deposition on vessel walls may lead long-term tests. At best, these seals and the balls in
to corrosion problems, Remote use of vibrators the kiln must be periodically replaced. Perhaps even
or automatic hammers for removing such deposits, the kiln itself will have to be replaced occasionally,
as in development work [3, 22, 36, 57], is far from A satisfactory means of dispersing feed over the
ideal and may be troublesome in plant scale operation. entire heated length of the kiln remains to be
demonstrated.
Other potential problems involve a remotely
operated product valve to seal the outlet of the The feed nozzle inside the 500-700°C kiln may
calciner while product pots are changed. Inherently require cooling to prevent product caking and plug-
poor flow characteristics of the product, the pos- ging. The design of a satisfactory two -fluid nozzle, to-
sibility of loosening scale from vessel walls thro~gh gether with its connection through a rqtary seal to the
vibration, and valve wearmayallprovetroublesome. sources of the solution, could present many problems.
59
'· 3. Facility.- and .Personnel.Requirements
Facility and personnel requirements of a waste disposal plant will be affected to a greater extent by the
number of calciners in simultaneous operation and by the type of product than by the size of calcination equip-
ment involved. No attempt was made to estimate detailed facility and personnel requirements for each of the
processes, but published information is summarized,
Fluidized Bed Pot
Present Situation Present Situation : · ·
In a preliminary study based qn actual costs for Perona [ 17] estimates between 41 and 84 people
the WCF, stevens [121) estimates that 25 people would be required for operating 2 to 16 pot calciners
would be required to process waste from a hypo- simultaneously in a hypothetical disposal plant,
thetical fuel reprocessing plant in a single fluidized depending on ·composition and activity of wastes
bed .calciner; the operating costs. would be inde- from a 15,000 MWe nuclear economy using 1500
pendent. of the processing rate. This hypothetical metric tons of uranium converter fuel and 2 70 metric
plant, described by Perona et al [17] would be tons of thorium converter· fuel annually. The plant
capable of processing all fuel from a 15,000 MWe area may vary between 1200 and 3200 square feet.
llUClt!Ul' !:lUUIIUIUY. Bet·w·eei"l 2G7 to.u.d C170 cnldllll.tion vc.!.!c.ls ycnl'ly
would be filled with prod\lOt from Thorlix•typil vn.st<a
and fl'om 58 to 3490 vessels yearly ·with product
from Purex..:type waste, depending on the size of
the pots employed,
Discussion DJscuss.ion
The cell area and· labor requirements for a The pot calcination process requires a large
fluidized· bed process will be almost independent facility and labor force because of the necessary
of throughput capacity because a single unit can be remote handling which requires specialized equip-
employed for most applications. Also conducive to ment and cells and highly-trained personnel,
a small facility and labor force is the absence of
significant amounts of remote handling equipment, Extrapolation of the cost figures given by
absence of equipment with moving parts, and lack Perona [ 17] to other situations is difficult. More
of a clear need to melt the calciner product. broadly-based cost figures are expected to be
generated by the operation of the full-scale de-
monstrational pot calciner at Hanford in 1965, et seq.
l'
60
3. Facility and Personnel Requirements (Continued)
. There are no reported estimates of facility and There are no reported estimates of facility and
personnel requirements for this process. personnel requirements for this process.
It is believed that facility and personnel re- Maintenance to replace rotary seals, add balls ... ,..,
quirements will be directly related to the solids to the kiln, or replace a kiln may require costly
output capacity if products are collected and melted equipment and a large staff. .-....r
in pots which require an elaborate remote product
handling system. Depending on plant throughput,
multiple calciners may be required which could
multiply facility and personnel requirements.
61
IX•. REFERENCES
1. J. A. Buckham and J. A. McBride, Pilot Plant Studies of the Fluidized Bed Waste Calcination Process,
pp 234-254 of "Treatment and Storage of High-Level Radioactive Wastes", Vienna, International Atomic
Energy Agency, 1962.
2. J. M. Holmes et al, Pot-Calcination Process for Converting Highly Radioactive Wastes to Solids, Ibid.,
pp 255-286.
3. R. T. Allemann et al, Radiant-Heat Spray Calcination Studies, Ibid., pp 217-232.
4, w. H. Regan et al, Continuous Calcination of .!Qgh-Level Radioactive Wastes by a Rotary Ball Kiln,
Ibid., pp 179-194.
5. L. P. Hatch et al, Ultimate Disposal of High-Level Radioactive Wastes; Fixation in Phosphate Glass with
Emphasis on the Continuous Mode of Plant Operation, Ibid., pp 531-542.
6. w. E. Clark and H. w. Godbee, Fixation of Simulated HighlY Radioactive Wastes in Glassy Solids, Ibid.,
pp 411-439.
7. M. N. Elliot et al, Fix-ation of Radioactive· wa.ste in Glas~. Parl'I. Pilut·Plaiit ]]xpcrionoo at Hal'well.-
Part II. The Experimental Evaluation of Phosphate and Borosilicate Glasses, Part III. The Removal of
Ruthenium and Dust from Nitric Acid Vapours. Ibid., pp 465-506. ·
8. R. C. Bonniaud et al, Vitrification of Concentrated Solutions of Fission Products: Study of Glasses and
Their Characteristics, Ibid., pp 355-380.
9. w. E. Winsche et al, Calcination of Radioactive Waste in Molten Sulphur, Ibid., pp 19G-21G.
10. W. G. Belter, Present and Future Programs in the Treatment and Ultimate Disposal of High-Level
Radioactive Wastes in the United States of America, Ibid., pp 3-22.
11. B. F. Campbell et al, Current Practices in the Management of High-Level Wastes in the United States
of America, Ibid., pp 23-42.
12. W. G. Belter, Radioactive Wastes, Intern, Sci. Tech., No. 12 (December 1962) pp 42-43; 46-51.
13. F. R. Bruce, Waste Treatment and Disposal Problems of the Future Nuclear Power Industry, Hearings
before the Special Subcommittee on Radiation of the Joint Committee .on Atomic Energy, Congress of the
United States, Eighty-sixth Congress, First Session on Industrial Radioactive Waste Disposal, January 28,
29, 30; February 2 and 3, 1959. Vol. 3. Washington D.C., Joint Committee on Atomic Energy 1959,
p 2345.
14. Edison Electric Institute, Radioactive Waste Handling in the Nuclear Power Industry, New York: Edison
Electric Institute, March 1960. (EEl Publication Number 60-46).
15. James A. Lane, "Nuclear Fuel Requirements for Large-Scale Industrial Power", Nucleonics, 12, No. 10
(October 1954), p 6!5+•
16. United States Atomic Energy Commission, Civilian Nuclear Power -- A Report to the President -- 1962,
Washington, D. C., U. S. Printing Office, 1962. ·
17. J. J. Perona et al, Evaluation of Ultirnate Disposal Methods for Liquid and Solid RHdioac:tive Wastes.
Part II. Conversion to Solid by Pot Calcination, ORNL-3192 (October 1961).
18. Chemical Technology Division Annual Progress Report for Period Ending June 30, 1962, ORNL-3314
(September 1962).
19. w. H. Reas, HW-77709C, May 1963 (Secret).
20. D. W. Clelland, Closing Discussion, "Treatment and Storage of High-Level Hadioactive Wa~te~::;", Vienna,
International Atomic Energy Agency, 1962, p 650.
21. B. Manowitz, Fission Product utilization and its Effect on Waste Disposal, Hearings betore the Special
Subcommittee on Atomic Energy, Congress of the United states, Eighty-Sixth Congress, First Session on
Industrial Radioactive Waste Disposal, January 28, 29, 30; February 2 and 3, 1959. Vol. 3, Washington D.C.,
Joint Committee on Atomic Energy, 1959, pp 2324. ' ·
62
22, R; T, Allemann and B, M, ·Johnson, Jr., Radiant-Heat Spray Calcination Process for the Solid Fixation of
Radioactive Waste. Part I, Nonradioactive Pilot Unit, HW-65806 (Pt. I) (February 1961).
23. B. M. Johnson, Jr., Radiant-Heat Spray Calcination, TID-7613 (February 1961) pp 27-45.
24 ... D, R; Evans, Pilot Plant Studies with a Six-Inch Diameter Fluidized Bed Calciner, ID0-14539 (April 1961),
25. B. P. Brown et al, Development of a Fluidized Bed Calcination Process for Aluminum Nitrate Wastes in
a Two-Foot-Square Pilot Plant qalciner. Part I, Equipment Development and Initial Process Studies,
ID0-145~6 (June 1962).
26. W. P, Palica and L, T, Lakey,Developmentof Fluidized Bed Calcination of Aluminum Nitrate in the Waste
Calcining Facility, ID0-14608 (to be published).
27. J, R. Bower (ed,), Chemical Processing Technology Quarterly Progress Report, October-December, 1961,
ID0-14583 (March 1962).
28. J, R. Bower (ed,), Chemical Processing Technology Quarterly Progress Report, January-March, 1962,
ID0-14589 (June 1962).
29.•. J. W, Loeding et al, The Fluid-Bed Calcination of Radioactive Waste, ANL-6322 (May 1961).
30, M, D. Alford, Fluidized Bed· Calcination of Simulated Purex High Activity Level Wastes, HW-66384RD
(September 1960),
31. K. J, Schneider, Fluidized Bed Calcination Studies with Simulated ICPP Waste Solutions, HW-65838
(June 1960),
32. F, A. Zenz and D. F. Othmer, Fluidization and Fluid-Particle Systems, New York: Reinhold Publishing
Corp, 1960.
. -·
33. R. J. ·Priestley, "Where Fluidized Solids Stand Today", Chern. Eng., 69, No. 14 (July 1962) pp 125-132.
34, C. W. Hancher and J, C, Suddath, Pot Calcination of Simulated Radioactive Waste with Continuous Evapo-
ration, Paper presented at the National Meeting of the American Institute of Chemical Engineers, Los
Angeles, California, February 4-7, 1962.
35. H. W. Godbee, Characterization of Solid Products of Pot Calcination, TID-7613 (February 1961) pp
485,;.513.
36. E, R, Irish, Research and Development Activities - FixationofRadioactive Residues. Quarterly Progress
Report, October - December 1962, HW-76262 (January 1963).
37. A. M. Platt and J. J. Shefcik, Laboratory-Scale Batch Calcination Studies; Interim Report, TID-7613
(February 1961) pp 111-132.
38, D. w. Pearce (ed.), Research and Development Activities, Fixation of Radioactive Residues Quarterly
Progress Report for July - September 1960, HW-67334 (October 1960).
39. D. W. Pearce (ed.), Research and Development Activities Fixation of Radioactive Residues Quarterly
Progress Report October - December 1960, HW-68193 (January 1961).
40. D, W. Pearce (ed.), Fixation of Radioactive Residues, Quarterly Progress Report January - March 1961,
HW-69176 (April 1961).
41~ E. R, Irish (ed.), Research and Development Activities Fixation of Radioactive Residues Quarterly
Progress Report, July - September 1961, HW-71374 (October 1961).
42, E. R, Irish (ed.), Quarterly Progress Report Research and Development Activities Fixation of Radioactive
Residues, April - June 1961, HW-70517 (July 1961).
43. E, R. Irish (ed.), Research and Develo ment Activities, Fixation of Radioactive Residues.
Progress Report, July - September 1962, HW-7529 (October 1962),
11, R, T, Allemann et al, Hot-Cell studies on the Solidification of Hanford High-Level Wastes by Radiant-Heat
. Spray and Pot Calcination, HW-SA-2877 (January 1963).
45. B, R, Wheeler and J. A. Buckham, Design of a Pilot Plant Facility for Radioactive Demonstration of the
Pot Calcination Process, ID0-14596 (December 1962).
63
46. Present Status of Atomized Suspension Technique, The Paper Industry (January 1960) pp 703, 748.
47. W. H. Gauvin and J. J. 0. Gravel, "Chemical Recovery from Sulfite Spent Liquors by the Atomized
Suspension Technique", Tappi, 43, No. 8 (August 1960) pp 678-683.
48. R. F. Domish et al, Rotary Kiln Calcination of High-Level Wastes as a First Step in Ultimate Disposal,
TID-7613 (February 1961), pp 180-201.
49. R. F, Domish, Operating Data on a Rotary Calciner Pilot Plant for the Treatment of High-Level Wastes,
Paper presented at the 50th National Meeting of the American Institute of Chemical Engineers, Buffalo,
New York May 5-8, 1963.
50. R. F. Domish et al, Calcination of High-Level Atomic Wastes as a Step in Ultimate Diswsal, BNL-535
(December 1958).
51. J. H. Perry, Chemical Engineers' Handbook, Third Edition, New York: McGraw-Hill Book Company, Inc.,
1950.
52. B. M. Johnson, Jr., Heat Transfer in Radiant-Heat Spray Calcination, HW-58641 (Fe1J1·uary 1959).
53, W, H, Regan, "Ball ·Kiln Calcination of Alloy Fuel Element Wastes", Report of Working Meeting on
Fixation of Radioactivity in ~table, ~olid lVledia a.ttne J-ohn HuJ..!k.lw; Uulv~::a~ily J<mc 10-!31; 1067, TID-7550
(March 195H) pp 48-57.
54. w. H. Reas, HW-76315C, February 1963 (Secret).
55. W. R. Reas, HW-75925C, January 196::! (~ecret).
56. W. H, Gauvin, "Application of the Atomized Suspension Technique", Tappi, 40, No. 11 (Nuvernber 1957)
pp 866-872.
57. R. T. Allemann and B. M. Johnson, "Radiant-Heat, Spray Calcination Process for Solidification of
Radioactive Waste", Industrial and Engineering Chemistry Process Design and Development, ~. No. 3
(July 1963) pp 232-238.
58. G. E. Lohse (ed.), Tests of a Vapor-Space Feed Nozzle for Calcining Aluminum Nitrate Solutions in a
Fluidized Ded, 100-14568 (March 1962).
59. J. R. Bower (ed.), Chemical ProcessingTechnologyQuarterlyProgress Repul't, 2nd Qtr, 1963, 100-Hti~l.
60. J. A. Buckham et al, Development of the Fluidized Bed Waste Calcination Process, Paper presented at
50tJ:!.·Nationlil Meeting of the American InstituteofChemical Engineers, Buffalo, New York, May 5-8, 1963.
61. J. J. Perona, The Effects of Internal Heat Generation ou Pot Calcination Hates for Radioactive Wast.~R,
ORNL-3163 (October 1961).
62. Patricia Fain, J. A. Nelson, Process Development Quarterly Progress Report for April-:-June 19GO,
lVlC W-H~l (Augu!>l 1900).
63. R. T. Allemann and U. L. Upson, The Electrostatic Bubble Scrubber, IIW-74210 (July 1962).
64. B. R. Wheeler et al, Development of a Fluidized Bed Calcination Process for Aluminum Nitrate Wastes in
a Two-Foot- uare Pilot Plant Calciner. Part II. Factors Affectin the Intra-Particle Porosit of Alumina,
IDO-i4587 (July 19 2 .
65. R. L. Bradshaw et al, Evaluation of Ultimate Disposal Methods for Liquid and Solid Radioactive wastes.
Part I. Interim Liquid Storage, ORNL-3128 (August 1961).
66. J. J. Perona et al, Evaluation of Intimate Disposal Methods for Liuquid and Solid Radioactive Waste.
Part IV, Shipment of Calcined Solids, ORNL-3356 (October 1962). ·
67. J. w. Loeding, "Discussion Morning, Session A, September 27", Report of the ~econd Working Meeting
on Fixation of Radi£activity in St~ble Solid Media at Idaho Falls, Idaho, September 27-29, 1960, TID-7613,
Book 1 (February 1961) p 83.
68. J. R. Bower and L. T. Lakey (eds.), ICPP Waste Calcining Facility Safety Analysis Report, 100-14620
(January 1964).
69. J. I. Stevens (ed.), Idaho Chemical Processing Plant, Radioactive Waste Disposal Projects Technical
Progress Report (for) January - March 1960, 100-14530 (September 1960).
70. E. S. Grimmett and B', P, Brown, Physical and Operational Features of a Pulsed ·continuous Countercurrent
Liquid-Solids Contactor, 100-14541 (Apri11961).
7L Chemical Technology Division Annual Progress Report for Period Ending May 31, 1961;· ORNL-3153
(September 1961).
72. R, E. Blanco and E. G, Struxness, Waste Treatment and Disposal Progress Report for October and
November 1961, 0RNL-TM..;133 (March 1962).
73.·: M, E. Whatley et al, Chemical Technology Division Unit Operations Section Monthly Progress Report
for June 1960, CF-60-6-11 (October 1960).
74 . .-R. E, Blanco and E, G, "Struxness, Waste Treatment and Disposal Progress Report for December 1961 and
January 1962, ORNL-TM-169.
75~ J, ·R, Bower (ed.), Chemical Processing Technology Quarterly Progress Report, 3rd Qtr 1960, 100-14540
(February 1961).
76. H. W. Godbee and J, T. Roberts, Survey on the Measurement of Thermal Conductivity of Solids Produced
by Evaporation and Calcination of Synthetic Fuel Reprocessing Solutions, ORNL-2769 (August 1959).
77. H. W, Russell, "Principles of Heat Flow in Porous Insulators", J. Am. Ceram. Soc., 18 (1935), pp 1-5.
78. F. R, Charvat and W. D, Kingery, "Thermal Conductivity: XIII, Effect of Microstructure on Conductivity
of Single-Phase Ceramics", J, Am. Ceram. Soc., 1Q_, (1957) pp 306-315 ..
79. J, Franc! and W, D, Kingery, "Thermal Conductivity: IX. Experimental Investigation of Effect of Porosity
on Thermal Conductivity", J, Am. Ceram. Soc., 37 (1954), pp 99-107 . .
80. J. B. Austin, "Factors Influencing the Thermal Conductivity of Non-1\:letallic Materials", ASTM Symposium
··:on Thermal Insulating Materials, (March 1939) pp 3-67. ·
81. W. D. Kingery, "ThermalConductivity:XIV,ConductivityofMulticomponent Systems", J. Am. Ceram. Soc.,

42 (1959) pp 617-627.
82. W. D, Kingery, "Thermal Conductivity: XII, Temperature Dependence of Conductivity for Single Phase
Ceramics", J, Am. Ceram. Soc., 38 (1955) pp 251-255.
83. W, D. Kingery and M. C, McQuarrie, "Thermal Conductivity: I, Concepts of Measurement and.Factors

Affecting Thermal Conductivity of Ceramic Materials", J, Am. Ceram. Soc., 37 (1954) pp 67-72.
84. Arthur L. Loeb, "Thermal Conductivity: VIII, A Theory of Thermal Conductivity of Porous Materials".
··.). Am. Ceram. Soc., ::!7 (11!54) pp 96-99.
85. J; J, Perona and M, E. Whatley, Calculationof Temperature Rise in Deeply Buried Radioactive Cylinders,
ORNL-2812 (February 1960).
l:!ti. JJ..N. Kelly, Thermal Conductivity of Alumina Produced by the Fluidized Bed Process, 100-14592
(September 1962).
87. A. M: Platt, "Discussion, Morning, Session A, September 27", Report of the Second Working Meeting
On Fixation of Radioactivity in Stable, Solid Media at Idaho Falls, Idaho, September 27-29, 1960, TID-7613,
Book 2 (February 1961) p 79.
88. M, E, Whatley et al, Chemical Technology Division Unit Operations Section Monthly Progress Report,
December 1961, ORNL-TM-136 (April 1962).
89. R, E, Blanco and E, G. Struxness, Waste Treatment and Disposal Progress Report for April and May 1961,
CF-G1-7-3 (Augu~l 1961).
90. D, W. Pearce (ed.), Research and Development Activities;. Fixation of Radioactive Residues. Quarterly
Progress Report, April - June 1960, HW-66571 (July 1960).
91. S, Lawroski, Reactor Fuel Reprocessing 1_, No. 4 (October 1961) p 62.
92. A:, R, Bancroft et al, The Volatilization and Collection of Ruthenium and Cesium in a System for In-
corporatmg_l"ission .Products iqto Qla§g, AECL-1233 (Januar·y 1961). ·· ·
65
93. L.C. Watson etal, Equipment and Method of Operation for Incorporation of Fission Products into Glass,
AECL-756 (1958). .
94. M. N. Elliot et al, The Disposal of Fission Product Wastes by Incorporation into Glass, AERE-R-3610
(January 1961).
95. J. Ralkova and J. Said!, Incorporation of _Radioisotopes into Melted Silicates, "Treatment and Storage
of High-Level Radioactive Wastes", Vienna, International Atomic Energy Agency, 1962, pp 341-354.
96. H. w. Godbee and W. E. Clark, The Use of Phosphite and Hypophosphite to Fix Ruthenium from High-
Activity Wastes in Solid Media, ORNL-TM-263 (June 1962).
9 7. J. ~.Bower (eo.), Chemical Technology Quarterly Progress Report, 3rd Qtr 19 62, I00-14599 (December
1~62).
98. C. M. Slansky and F. M. Warzel, Radioactive Waste Disposal Projects. Idaho Chemical Processing
Plant Technical Progress Report (for) July - September 1959, J.I. Stevens (ed.), I00-14514 (July 1960).
99. D. w.. Pearce (ed.), Fixation of Radioactive Residues. Research and Development ActiVities Quarledy
Progress Report (for) January - March 1960, HW-65209 (Apr·ll 19GO).
100. Nucleonics News of the Month, Radiation News;-Nucleonics Hl lUCtooer 19M) 1J .31.
101. s. Lawroski, Reactor Fuel Processing.§., No. 1 (January 1~ti<l) pp 50-tiS.
102. s. Lawroski, Reactor Fuel Processing ,1, No. 1 (January 1961) pp 46-52.
103. s. Lawroski, Reactor Fuel Processing .1_, No.2 (April 1961) pp 62-74.
104. R. L. Moore and R. E. Burns, Fission Product Recovery from Radioactive Effluents, Hearings before the
Special Subcommittee on Radiation of the Joint Committee on Atomic Energy, Congress of the United
States, Eighty-Sixth Congress, First Session on Industrial Radioactive Waste Disposal, January 28, 29 0
30; February 2 and 3, 1959. Vol. 3, Washington D,C., Joint Committe€'! on Atomic Energy, 1959, p 2313.
105. A. F. Rupp, The Oak Ridge National Laboratory Fissiori Product Pilot Plant, Ibid., p 2335.
106. R. E. Blanco and J. T. Roberts, Removal of Fission Prorlue1ts from High-Level Radioactive Waste
Elolutiono, Ibid., p 2264..
107. Possible Large-Scale Uses of Separated Fission Products, TID-8521, Presented at the November 1959
Meetine- of the AtQmic Industrial Forum (April 1960).
108. Aeroprojects Incorporated, Ultrasonic Leaching of Simulated Calcined Wastes, NY0-2el77 (Augul::lL 1900).
109 .. A. Abriss et al, Separation of Cesium and Strontium from Calcined Metal Oxides as a Process in Disposul
of High-Level Wastes, BNL-453 (April 1957). ·
llO. R. E. Blanco and E. G. Struxness, Wa!:lte Treatment and Disposal Progress Report for June and July
1962, OHNL-'l'Nl-::Hi6 (December 1962).
lll. J. R. Bower (ed.), Chemical Processing Technology Quarterly Progress Report, 3rd Qtr 1960, I00-14553
(May 1961).
ll2. J. R. Bower (ed.), Chemical Processing TechnologyQuarterlyProgress Report, 2nd Qtr 1961, I00-14567
(Novem hP.r 19nl).
ll3. H. W. Godbee and J. T. Roberts, Laboratory Development of a Pot Calcination Prouess for Converting
Liquid Wastes to Solids, ORNL-2986 (September 1961).
ll4. R F. Domish et al, "Calcination of High-Level Wastes for Ultimate Disposal", Nucleonics 17, No. 12
(DecemhP.r 19!19) pp 7fi-79.
ll5. J. M. Holmes, The Control of Pot Calciner Temperatures to Ensure Calcination at 900°C, ORNL-TM-259
(May 1962).
116. T. J. Colven,Jr., et al, TNX Evaporator Incident,· January 12, 1953. Interim Technical Report, DP-25
(1953).
66
117. G. S. Nichols, Decomposition of the Tribiifyl 'Piio~phate-Nitrate Complexes, DP-526 (November 1960).
\
118. J. C. Bresee et al, Chemical Technology Division, Unit Operations Section Monthly Progress Report
(for) September 1959, CF-59-9-69 (January 1960).
119. R. E. Blanco and F, L. Parker, Waste Treatment/and Disposal Quarterly Progress Report, 3rd Qtr 1962,
ORNL-TM-482 (March 1963).
120. J. R, Bower (ed.), Chemical Pl'ocessing Technology QuarterlyProgress Report, 4thQtr 1962, ID0-14611
····(June 1963). ·
121... J •."I. Stevens, An Economic Evaluation ofUltimateDisposal of Liquid Radioactive Wastes by the Fluidized
Bed Calcination Process, ID0-14595 (October 1962). ·
122. F. L, Parker andR, E. Blanco, Waste Treatmez{(and Disposal Progress Report for November - December
i962, and January 1963, ORNL-TM-516 (June 1963).
123. D. W. Rhodes, "Fixation of Fission Products in Stable Media and Storage of Calcined Wastes at ICPP",
Report of the Second Working Meeting on Fixation of Radioactivity in Stable, Solid Media at Idaho
Falls, Idaho, September 27-29, 1960, TID-7613, Book 2 (February 1961) pp 514-530.
124. T. Tamur'a, "Summary ·and Conclusions, Session F, September 29, Morning", Report of Second Working
Meeting on Fixation of Radioactivity in Stable, Solid Media at Idaho Falls, Idaho, september 27-29, 1960,
TID-'.'613, Book 2 (February 1961) pp 764-769. ·
125. E~ W. Miller, Mechanical Development and Evaluation of the ORNL Pot Calciner, ER-6297 (July 1963).
126. M. E. Whatley et al, Unit Operations Section Monthly Progress Report, January 1963·, ORNL-TM-54i
(August 1963).
127. E. J. Bailey, Testing of Pumps for Use in Nitric Acid - Alumina Slurry ~er~ce, IP0-.14612 (r.!Jay 1963).
'128: ·B. P, Brown··et·al, Development of a· Fluidized B·ed Calcination Process for .. Alillnint.un Nitrate Wastes
in a Two-Foot-Square Pilot Plant Calciner: Part III. Intermediate Process Studies, ID0-14618 (January
1964).
129. J. 0, Blomeke eta!, Estimated Costs for Management of High-Activity Power Reactor Processing Wastes,
ORNL-TM -559 (May 1963).
130. T. C. Runion, "NFS Chemical Processing Plant - Capability and Cost Bases", paper presented at 1962
Nuclear Congress·.:.. June 4-7~ }962, New York New· York.
131. a
\v. A. Rodger, ''Selection.of Waste Man:igement Methods for ·Privately Op~rated Chemical Reprocessing
·Plant", paper presented a_t 50th National ~eetingAmerican Institute of Chemical Engineers, May 5-8, 1963,
Buffalo, ·New York.
132. J.' R. Bower (ed.) Chemical Processing Technology Quarterly Progress Report, 2nd ~tr 1960, ID0-14535
(December .1960).
134. E. · R. Irish,· Quarterly Progress Report Research and Development Activities Fixation of Radioactive
Residues, April-June, .1963, HW-78188 (July 1963).
135. R. L. Hickok and J. S.'Madachy, Interim Report on the Calcination of Zirconium Fluoride Waste Solutions,
ID0-14537 (March 1961).
136. L. · J. Haworth, Presentation to Joint Committee on Atomic Energy February 20, 19fi::l, Hearings on
. · Development; Growth, and State of the Atomic Energy Industry Part 1. p .51.
,:.·
. 67
APPENDICES
APPENDIX A
COMPOSITION OF HYPOTHETICAL WASTES
Purex (b.l Stainless

Aluminum Purex· Purex [b) Purex [c) Purex [c) Purex [c)
Component Current First Steel
Nitrate [a) Lov Acid [b) High Sulfate Acidic Neutralized Reacidified
Cycle Nitrate [d)
.+++
Al !:! 1.72 0.3 0.1 0.1
+++ '
0.6 0.3
' !:!
Fe 0.003 1.1 0.25 0.36 0.23 l. 75
Cr+++, !:! 0.03 0.01 0.01 0.53
++
Ni M 0.018 o.oo6 o.oo6 0.25
+
Na, !:! 0.10 3.0 1.0 1.0 0.7 8.4 6.3
++
IIg M O.'Xl
I
H' M 1.26 U.J ~.u 6.0 '(•] ~~. ~ 1 .0
N03-, M 6.60 3.21 'i'.l b.y 8.4 r.o ~·C 6.)11
S04:, ~ 1.')0 L8 0.73 n 3~ 0.~ ].15

P04:, !:! o.o6 0.02 0.02
0
Cl pp"l 200
[a] Composition of waste in WM-182 at ICPP.

[b) Waste calcined in pilot plant scale fluidized bed calciner at Hanford [30),
[c) Hypothetical composition of waste assumed in an ORNL study [171.
[d) Probable concentration of future Stainless Steel Nitrate wastes.
ArPEN.DIX B
CONI'OGI'l'ION OF SXl\TTHETH~ WAH'I'~:H CALC:Il'IED IN FLUIDIZED BED Cl\LCINERS
Alwuluum Nitrate Purcx [29] .l'urex [29] Purex [30]

Purex [30J Purex 130]
Hl!!)l Current Stainless
Component ICPP [24,25,64, 751 Argonne [29] Hanford [ 31] Low Acid High Acid Low Acid
Sulfate First Cycle Rt.eel
Argonne Argonne Hanford
Hanford Hanford Nitrate
Al+++,.!:! 1.29-2.2 2.1 2.0 0-37 0.17 0.3 0.1 0.1 0.19-0.71
+++ 0.6 0.6 1.1 U.<!,
Pe •!! 0.25
+++ 0.01 0.03 o.oo6 0.03 0.01 0.01 O.Q9-0.10
Cr !1
Ni++
!1 0.018 o.oo6 0.018 o.oo6 0.006 0.)1-0.)6
+ 0.28-0.o89 (a] 0.40 3.0 1-0 1.0
Na !:! 0.15 0.15 3.0
Hg++ o.oo6-0.0l5 0.008
!1
H
+
' !1 1-25-2.84 1-25 1-0 0.5 6.2 u.~ 6.0 c.o ''·5"5 -3
N03-, !:! 5.16-9 ·56 1·1 7.18 3.21 7.10 3.21 7-1 6.9 6.5-7-1
so,,:, !1 1-50 0.15 1.~0 1.0 0-53
O.o6 0.015 o.o6 0.02 0.02

1'04=· !1
[a] Occasionally, concentration of Na bas varied betveen 0.03 and 0.2~ !:!· .ll61'0n, 0.03 Lu 0.2::; !:! added to feed on lo.tsr r\.UlS t.n
suppress formation of crystallinity in the product.
68
APPENDIX C
COMPOSITION OF SYNTHETIC· WAS;l'E CALCINED IN POT CALCINERS
Alum.inlll!l Nit:t:ate .. -. l'urex .. Pur ex Stainless

Component
Hanford ('a]·
~
N~~~~~e [18,113]
"
ORNL ,[],~,34!.113] ORNL [18, 34, 113]

Al+++ 1.6-1. 72' 0.1 0.123
' !:!
0.09-3:25
+++
Fe 0.002-0.003 0.5 0.35-1.08 0.68-1.2
+++
' !:!
Cr 0.01 0.01 0.01-0.04 0.16~0.4
++
' !:!
Ni , !:! 0.01 0.007-0.02 0.075-0.2
+
Na , !:! 0.1 0.3-0.6 0.3-10.6
++
Hg, !:! 0.02
H+, !:! 0.5-1.26 0.06'(-3.72 2.10-2.95
NH4+, !:! 0.05-0.07
Mn++ 0.04
' !:!
No 3; !:! 5·35-6.6 (5.1-7.0 0.64-6.22 6.10-7.2
S04:, M 0.026-0.03 0. 75-1.0 '0.75-3.66
Cl - M 0.0008-0.001
'
0.06
[a] Exploratory studies in laboratory scale pot calciner [37]
APPENDIX D
COMPOSITION OF SYNrHETIC WASTES ·:ALCINED IN RADIANr-HEAT .SPRAY CALCINERS [22)
Purex· purex. Purex . Purex Purex Purex

Aluminum Acid-Killed Acid-Killed High-Acid High-Acid Mixed Coating Stainless
Component Neutralized
Nitrate High-Sodium Low-Sodium Plus Neutralized Steel
Coating and Organic Nitrate
Al+++ 1.6 0.25 0.20 Q.l [c] 1.23 [d) 1.44 0.123
!:!
F +++ ' 0.002 0.50 0.60 0.2 [c) 0.061 [c) 0.75 [c) 0.68
e +++ ' !:!
Cr !:! 0.025 0.02 0.010 [c) 0.002 [c) 0.04 [c) 0.16
N'++ ' 0.015 0.01 0.006
[c)
0.02
[c) 0.075.
]. ' !:!
Na+, !:! 2.50 1.00 7.65 2.7 8.00 3·43
+
K' !:! 0.15
Hg++, !:! 0.01
+
H '+ !:! 0.5 0.50 2.22 2.94
NH4, !:! 0.05
N03-, !:! 5·5 2.86 0.52 7.15 0.84 2.3 0.31 6.1
N02 -, M 0.83
S04:, !:! 0.02 1.25 2.60 0.50 0.20 1.00
co :, !:! 1.5
3
Mn ++ !:! 0.15 [c)
Si04, !:! 0.017
Na2B404,
1.22 (R)
!:!
H P04 !:! 1.62 (a] 1.16 0.01
3
Sugar g/1 259 [b) 150-250 [b) 200 [b) 150 [b) 100 [b) 150 [b)
H3 D03 g/1 75 (aJ 75 [a)
[a) Used as additive to create glass-like compound.

[b) Used as additive.
lr.J In waste ac oolid3.
[d) 0.55 !:! in solution; 0.68 !:! present as solids.
69
APPENDIX E
COMPOSITION OF SYNTHETIC.WASTE CALCINED

IN ROTARY-BALL KILN CALCINER [48]
Component Aluminum"Nitrate
+++
Al M 1.6
Fe+++·
' M o:on
+
Na , M- 0.036
+
H' M 1.0
N03-, M 5.86
Cl-, M 0.001
APPENDIX F
- ----
COMPOSITION OF GLASS-LI!ill MAT.i!:RIALS P.HOJJUl:f:JJ .l\.'l' t:J:8NI • f1 Ol
Pur!=::! X Stainless Aluminum Nitrate

Compound Steel
wt% Niti:ate •wt% wt%
Fe2 o 8.6-11.9 9.2-20.0 o.o6-0.09
3
Al203 . l.l-1.6 0-23.5 25.0-33.8
NiO ""0.2 1.2-3.0
Cr2o "'0.2 2.7-6.4

3 ,
Na o 15.5-34.4 17.2-21.7 .18.6-25.5
2
. I>2o; ~5.9-32., C1.1o45o9 JR.SJ.Wl.l
803 1'( .)-23.9
PhO O-jj.1 0 15.9
Mn02 0.3-0.8
MgO. 0-1].3 0-0.2
B203 0-15.6 0-20.8 0-11.6
l:liO:> 0-9·5
c..o 0-12.0
Ru~2 "'0.1 0.003-0.01 "'0.01

Waste Oxides· 31.4-44.5 13-32 27.1-35.2
Density, g/cc 2.67-2.78 2-7-3.8 2.41-2.84
70
Sd1111Hd
'
i
i
1
, -"
i

Calcination Process

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Calcination Process

Uploaded by

Copyright:

Available Formats

.. I'll.

COMPARISON OF VARIOUS CALCINATION PROCESSES

B. R. Wheeler, J. A. Buckham, and J. A. McBride

This report was prepared as an account of work sponsored by an

Portions of this document may be illegible in

AVAILABLE FROM THE

A COMPARISON OF VARIOUS CALCINATION PROCESSES

FOR PROCESSING HIGH-LEVEL RADIOACTIVE WASTES

. ./ -1.-*.., Contrbct AT(10-1)-205

ABSTRACT 0 • 0 • 0 0 0 •• 0 0 0 0 •••••• - • .0 ... 0 0 •• ! • 0 • 0 0 •• 0 o. 0 0 < •••••• 0 ••• 0 • o. 0 0 0 •••••••• iv

II. INTRODUCTION .•.. , .•••••••••.•••••.•.•••••• , • • • • • • • • • • . • . • . • . • . • . • . . • 3

A. Safety Considerations in Waste Disposal •••••••••• ••••••••••••••••. ••••••••• 3

B. The Magnitude of the Waste Problem 4

ill, COMPARISON OF CALCI,NATION PROCESSES • , ••••••••••• , • • • • . • • • • • • • • • . • . . . • 6

1. Calciner Description and Operation , . . . . . . . . . , , ••• , ••• , . • . • . . . . . . . . . • • • . • • . 6

3. Waste Throughput Capacity .•••••••.•••••••••••••••.•••.•••••.•.•••••• , • 14

4. Feed Introduction ••.•••.•.•••.•. , .•••.•.•••••••• ,.••••••••.•.• , •••. , . 20

5. Off-Gas Processing System •••.••.••. , ••.•••••.••.••••••••••....••. ; .•.• ~ 22

IV. PRODUCT PROPERTIES •.•••.••••••.••••••••••••••••••••.• ·, • . • . • . • . • • • • • 26

1. Size and Shape of Calciner Product .•• , ••.•••••..•...•..•.•. , • • • • • • • • • • • • • • • • 26

2. Leachability ••••.•••.•..• , .•.••..•••••••.•.•••••• , . • . • . . . • • , , • • • • • . 30

3. Nitrate Content ••• , .• • , , • , , .•••.•. , • ~ ••• , •••••. ~ • . • . . . • • . . • • •••• , • • • • • 32

6. Effect of Gross Porosity on Storage of Calciner Products •.•••• , • , ...••• ·••• , , , •• , • 40

V, PRODUCTION OF GLASS-LIKE MATERIALS •••• , ••.•. , , •••• , , ••..•••••. , ••••• , 42

VI. APPLICABILITY OF CALCINERS FOR PROCESSING VARIOUS WASTES • . • • • • • . • • • . • • • . • 44

1. Waste Activity Level •. , •.•••• , •••• , , ••• , . , . , •••• · ••••••••.....•.•.•••• _. 44

3. Waste Concentration , , , .•• , , , . , , , , , .•••••••••••••••.•••••••••.••••••• , 50

VII, WASTE DISPOSAL PLANT CONSIDERATIONS 52

1. Equipment •.•• , • , . , •••• , • • • . , •••• ; , . • . . . • • • • • • • • • • • • • . • . • . • . . . • • • • 52

2. Safety Considerations o o • • • • • • • o o n • n a a o • • • o 1 e o • ' o • o o • o o • • o o • • o • o o o o o o o 56

VIII. DEVELOPMENT STATUS 58

1. Current Status ••••••.•• , • , , , ••• , .••••.••..••.•••. , • • • • • • . . . • . • . • • • • • 58

2. Potential Problems ••••••• . •• ••••••••••• ••. •. •. ••••• •••••••••••• ••••• 58

,. 3. Facility and Personnel Requirements ••••••••••.•••••••••••••••.•••••••.••• 60

IX. REFERENCES , ••••• , •• , •••• , • , • , , , .•• , ••••• , , •••••••••••••••••• , • • • • • 62

6. Radiant-heat spray calciner . . • • . . . . • . . . • . . . ; . • • • . . . . . • . . . . . . . . . . • . • . . ; ....•• \· 7

7. Rotary-ball kiln calciner . . . . . . .' . . . . . . . . . . . . . . . . . . . • . . . . . . . . . • . . . . . . . . . • . . . • 7

8. Capacity of fluidized bed calciner . ·. . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . ; . . . . . . . 16

9. Capacity of single pot calciners 16

10. Capacity of radiant-heat spray calciners of! f f f! f f t I I I I I I I Ill I I I I • • • • o • • • • • • • • • • • 17

12~ Off-gas processing systems · . . . . . . . . . . . . . . . 23

13. Relative storage costs of radioactive waste solids 41

2. Required Size of a Fluidized Bed Calciner to Process Waste Resulting

3. Required Number of Pot.Calciners in Simultaneous Operation to Process

4. Required Number of Radiant-Heat Spray Calciners in Simultaneous Operation

5. Required Size of a Rotary-Ball Kiln Calciner to Process Waste Resulting

6. Size and Shape of Fluidized Bed Calciner Product 28

7. Size and.Shape of Pot Calciner Product 28

8. Size and Shape of Radiant-Heat Spray Calciner Product • • o • • o o , o • • • o • o • • • .o • o ·o o o o o • • • o

9. Size and Shape of Rotary-Ball Kiln Calciner Product 010001010111110101101000000011.0

11. Nitrate Content of Pot Calciner Product ••...•••• , ••••••.•.••••••••••••••• , •.•.•• 32

12. Thermal Conductivity of Fluidized Bed Calciner Product 34

14. Thermal Conductivity of Radiant-Heat Spray Calciner Product • • • • • • • • • • . • . • • • • • • • • • • • • • 35

1. SUMMARY AND CONCLUSIONS

Fluidized Bed Pot Radiant-Heat Spray Rotary-Ball Kiln .

Single Unit Througjlput, gph < 1 to 1500 < 1 to 10 < 1 to 65 <1to300

Calciner Product Properties

( 3) H1gjlly instrumented .• ( 3) Mechanical e'luJ.!"""'nt. may ( 3) Mechanical equipment may

A. Safety Considerations in Waste Disposal

Approximately 80 million gallons of high-level

1. Calciner Description and Operation

Fluidized Bed Pot

Present Situation Present Situation

Waste solution sprayed into a well-fluidized, Waste solution introduced to an electically-