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ORNL-TM-3563.txt
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3‘, o
TN T O AR T P ST TR TR TR ey s T WS Y > B T o .y T S e g A » R TR e RN T e R
- T, - % o ! T . . . ! ' . . ' : ; . ! . | P k : - Lk Aoy o ol e L
?..;*n
"‘"OAK RIDGE NATIONAL LABORATORY
| operafed by | N
UNlON CARBIDE CORPORATION | R
. NUCLEAR DIVISION S
S for the
U, S ATOMIC ENERGY COMMISSION
ORNL TM 3563
CARBIDE‘
| THIS DOCUMENT CONFIRMED As'
- B UNCLASSIFIED _
DIVISION OF CLASSIFICATION
| AVAILABILITY OF NATURAL RESOURCES FOR MOLTEN<SALT BREEDER REACTORS
MSJ. Bell
. ABSTRACT =
B An investigatlon has been made of the availability of, and
' f_the anticipated demand for, materials of importance to the MSER
- program. Materials considered ‘included the constituents of
~__ Hastelloy-N, coolant salt, fuel salt, and materials required for
"~ construction and Operation of the processing plant.: It was fouhd
. that the world reserves of beryllium, fluorine, and bismuth are
being rapidly depleted by non-MSBR uses, and that these reserves
can be expected to be exhausted by the turn of thé century. Ample
"~ resources of beryllium and fluorine are available to sustain a
- large MSBR 1ndustry, but development of an improved mining tech-
. nology will be required to make their recovery economical. Ore
from which thoria is recoverable for $10/1b will be available into
~ the. middle of the twenty-first century. MSBR demands for all
-~ materials, with the possible exception of hafnium used in modified
'Hastelloy-N, comprise only a small fraction of the predicted world
© -~ primary demand for these minerals. The fuel cycle cost was. found
- to be relatively ingensitive to the price of raw materials; an
~~ increase in the cost of carrier salt to ten times its present
. level, or an increase in the price of thoria or Hastelloy-N to
- - three times their present levels, would 1ncrease the fuel cycle .
- cost by 0.1 mill/kWhr._'jT‘ :
, _Kez' Words: -"Availability, Materials, Natural Resources, beryl-
lium, bismuth, fluorine, thorium, MSBR. T e ,
'NBTIGETh.s document contains mformohon of a prelimmory nature
and ‘was prepared primarily for internal yse at the Oak Ridge National
Laboratory. It is-subject to revision or correction ond therefore does
" not represent a fmal report -
msmaflmu OF Ims BOSUMENT IS uuuxm‘m)
Rnsoo
DATE - November 11, 1971
£ o i b o e <
This report .was p}ebared as an Zéccdunt of work ksbonso’red by the United -
States Government, Neither the United States nor the United States Atomic
Energy Commission, nor any of their employees, nor any of their :contractors,
subcontractors, or their employees, makes. any warranty, express o'r.impiied, 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. ' o
W
s CONTENTS
Page
ABSTRACT « + v v v ¢ v o v 6 o v e o o v e o o o o o o o o 0 o v 1
L. INTRODUCTION « ¢ ¢ v v o o v ¢ o o o o o o o o « o o o o o o b
2. MATERIAL INVENTORIES IN AN MSBR POWER PLANT . . . « . . . . . 5
5. WORLD PRIMARY DEMAND FOR MSBR MATERIALS . « + « ¢« ¢ o o « . . T
4. PREDICTED GROWTH IN DEMAND FOR MSBR MATERIALS . . . . . . . . 9
D+ DISCUSSION OF RESULTS . ¢ & v v o ¢ v 4 o o o o o o o o o o 12
561 Beryllium ¢ v v v 4t h e v v e e e e e e e e e e e 14
5.2 FI.UOrine - . . . - . . . . - . . . . ® - ® . - - . - ® ° 15
5.3 Bismuth « v ¢ v b vt e e e e e e e e e e e e e e e 16
5.4 Thorium « ¢ v v v b i e e e e e e e e e e e e e e e 17
6. CONCLUSIONS AND RECOMMENDATIONS « . + & ¢ « v & o & o o « o . 18
T . REFERENCES - . * . * 2 ® . - * . . . - . & ® . . . & ® o * ® ® 25
NOTICE— —— i
This report was prepared as an account of work
sponsored by the United States Government, Neither
the United States nor the United States Atomic Energy
Commission, nor any of their employees, nor any of
their .contractors, subcontractors, or their employees,
makes any warranty, express or implied, or assymes any
legal liability or responsibility for the accuracy, com-
pleteness or usefulness of any information, apparatus,
product or process disclosed, or represents that its use
would not infringe privately owned rights.
1.0 INTRODUCTION
The Molten-Salt Breeder Reactor is being developed by the 0ak Ridge
National Laboratory as a thermal breeder reactor that will produce low-
cost electrical power, while conserviag the nation's fuel resources.
f 255UF dissolved in a carrier
salt which has the composition 72-16-12 mole % LiF-BeFeuThF The
Fuel for this type of reactor consists o
L
reactor vessel, heat exchangers, drain tank, piping, pumps, and most
equipment which contact either the fuel salt or the coolant salt are
fabricated of a modification of the nickel-base alloy Hastelloy-N. Fuel
salt is withdrawn from the primary reactor system on a 10-day cycle for
chemical processing by fluorination-reductive extraction tc remove ura-
nium and to isolate protactinium. The resulting salt is treated by the
metal transfer process, a sequence of reductive extraction steps devel-
oped at ORNL, to remove Sx, Y, Ba, and the rare-earth fission products.
The reductive extraction steps consist of contacting the fuel salt or
the metal transfer acceptor salt (TL101) with lithium-bismuth solutions.
The current development program anticipates that the vessels for the
salt-metal contactors will be constructed of, or lined with, molybdenum.
The purpose of this report is to examine the availability of materials
which are required to sustain an expanding MSBR power economy, to indi-
cate materials for which natural resources are in short supply, and to
anticipate the possiblé impact of such shortages on the MSBR concept.
Data for the world reserves and world primary demands of various minerals
1,2
havwe been obtained from U.S. Bureau of Mines and U.S8. Geclogical Survey
R.eports.2 The author would like to acknowledge the generous cooperation
of W. 0. Fulkerson, H. E. Goeller, P. R. Kasten, and R. C. Robertson, of
ORNL, in compiling the information presented in this report.
2.0 MATERIAL INVENTORIES IN AN MSBR POWER PLANT
The inventories of fuel salt and Hastelloy-N in an MSBR power plant
5 The fuel for
an MSBR is 255UFM dissolved in a mixture of molten fluoride salts of
have been considered previously by Kasten and Robertson.
nominal composition T2-16-12 mole % TLiF-Bng-ThFh. Hastelloy=-N is a
nickel-base alloy, designed specifically for use in molten fluoride sys-
tems, with the composition given in Table 1.
Table 1. Chemical Composition of Modified Hastelloy-N
for Use in MSBRs®
Element Composition
(vt %)
Nickel Balance
Molybdenum 12
Chromium ' T
Iron 0=k
Manganese 0.2-0.5
Silicon 0.1 max
Boron 0.001 max
Titanium 0.5~1.0
Hafnium or Niobium 0=2
Cu, Co, P, S, C, W, Al (Total) 0.35
aMSR Program Semiann. Progr. Rept. Feb. 28, 1970, ORNL-
hShS, p. 45.
The amount of molybdenum required to comnstruct the salt-metal contactors
in the processing plant, in addition to the amount of molybdenum already
present in the Hastelloy-N, is estimated to be 16 tons. The present pro=-
cessing flowsheet also requires a bismuth inventory of 17.L tons ahd a
salt discard rate of 0.3 .:‘E"f:i/day.,)'L Table 2 summarizes the inventories
of various materials in an MSBR power plant, and compares the MSBR in-
ventories with the estimated world reserves and world resources for these
Table 2. Material Inventories for a 1000-MW(e) MSER, and
World Reserves and Resources of MSBR Materials
Element MSER Inventory World Reservesb Reserve to World ResourcesC
(tons) {tons) Inventory {tons)
Ratic
. 5 b 6
Fuel Salt Li 17.9 7.5 % thd L2 x 105 6 x 106d
(225 tons) Be 5.1 1.2 x 105e 2.3 x 105 1.6 x 105&
Th 99u1 509 X IOTf 509 X 105 9-5 X }.OTf
F 102.9 2.2 % 10 2.1 x 10 L.Lh x 10
Hastelloy~N Ni SThh T4 x 1og 8.5 x 10i g
(1.%2 X Mo 150 5.4 x 105 3.6 x 107, g
10” tons) Cr T8 8.0 x 10,4 1.0 x 109 large 4,
rooom, pexw lyam Sy
! el To *x 8 J'5 X ,r -5 x
Ti; 5.6 1.5 x 10T 2.7 x 10, large
Nbi 1.1 1.0 x lO5 9.1 x 105 g
HE 1.1 3.1 x 10 2.8 x 10 g
Other ©Bi 17.4 1.0 x 107 5.7 x 102 8.2 x 10
B 50 T2 x 10 1.h x 10 g
au.s. Geological Survey, Geological Survey Professional Paper 600, "Mineral-Resource Appraisals”
(1968).7
b .
Reserves are known materials that may or may not be completely explored, but that may be quan-
titatively estimated; considered to be economically exploitable at the time of the estimate.
“Resources are materials other than reserves that may be ultimately exploitable; they include
undiscovered but geologically predictable deposits of materials similar to present reserves
as well as known deposits whose exploitation awaits more favorable economic or technologic
conditions.
dtnciudes deposits containing at least 1% equivalemt beryl (C.1% BeC).
“ores from which‘ThOE is recoverable for $10/1b.
fOres which contain at least 35% CaF2 or equivalent value in combined fluorspar and metallic
sulfides.
gData not available.
h .
Molybdenum inventory includes 16.0 tons required for salt-metal contactors in processing
plant.
'Niobium and hafnium are being considered as alternate additives for modified Hastelloy-N.
JF. H. Persse, Bismuth in the United States, USBM Irformation Cirecular 8439 (1970).
G materials. Throughout this report, the definitions of "reserves" and
"resources” given by the U.S. Geological Survey are employed.2 Reserves
are known materials that may or may not be completely explored, but that
may be quantitatively estimated, and that are considered to be economi-
cally exploitable at the time of the estimate. Resources are materials
other than reserves that may be ultimately exploitable. Resources in-
clude undiscovered but geologically predictable deposits of material
similar to present reserves as well as known deposits whose exploitation
awaits more favorable economic or technologic conditions. The ratio of
the world reserves of a material to the MSBR inventory of that element
can be interpreted as the number of 1000-MW(e) MSBRs that could be built
if the entire world reserves of the various elements were committed to
MSBR construction, and if no materials were recycled. The world reserves
of beryllium, bismuth, and thorium are adequate to construct only a few
thousand MSBRs, while the world reserves of lithium, nickel, and molyb-
denum are sufficient to construct a few tens of thousands of MSBR power
plants.
The world resources of the elements lithium and beryllium are quite
large, and these elements will be available for use in MSBRs, although
at an increased price. World resources of $lO/1b thoria are estimated
to be equally as large as the world reserves, and higher priced thorium
ores are very plentiful. Bismuth resources are not reported to be large,
but the foreign potential bismuth resources are not well known. World
resources of MSBR materials are sufficient to construct many hundreds of
thousands of reactors 1if the processing flowsheet is modified to reduce
the bismuth inventory.
3.0 WORLD PRIMARY DEMAND FOR MSBR MATERIALS
In addition to the consumption of natural resources by the MSR pro-
gram, the present and future non-MSBR uses of these materials must also
be considered. Table 3 compares the world primary demand for MSBR mate-
rials in the year 1968 with the known world reserves of these materials.
The data show that the world reserves of fluorine, beryllium, and bismuth
i are being rapidly depleted. In the case of fluorine, the world reserves
will be depleted in about twelve years based on the 1968 primary demand, s
and the estimated world resources of ores containing %5% fluorspar will
be consumed in 25 years. The Bureau of Mines anticipates, however, that
as fluorspar reserves are depleted, technological advances will be made
in exploring for fluorspar. and in recovering fluorine from phosphate
rock, so that U.S. production will be maintained to the year 2000 at
approximately the current ratio of production to demand. The USBM antici-
pates approximately a 33%% increase in the cost of fluorine, however.
Table 3. Year 1968 World Primary Demand for MSBR Materials and World
Reserves of MSBR Materials '
1968 World 5 USGS Estimated Reserve to
Element Primary Demand World Reserves Demand
(tons/year) (tons) Ratio
Fuel Salt Li 4400 7.5 x 102 170
Be LT78 1.2 x 10 25
Th 200 5.9 x 10$ 3000
F 1.8 x 10 2.2 x 10 12
Hastelloy-N Ni hoT x 102 T4 x 102 158
Mo 6.9 x 10¢ 5.4 x 104 78
Cr 2 x 10g 8.0 x 1044 %00
Fe h.3 % 10¢ 1 x 10g 230
Mn 8.2 x 10, T-3 x 10g 89
Ti 1.4 x th 1.5 x 10 105
Nb L. x 10 1 % 10! 2300
1f 43 5.1 x 107 7200
Other Bi 3800 5 1.0 x 103 27
B 2.k x 10 2 x 10 300
aU.,S° Bureau of Mines, Mineral Facts and Problems, Bulletin 650, 1970
ed.
bU.S. Geological Survey, Geological Survey Professional Paper 600,
"Mineral~Resource Appraisals® (1968}.
The cumulative world demand for beryllium and bismuth also cannot
be met by known world reserves. Heindl1 concludes that mechanical tech-
niques must be developed to replace the present hand-cobbing of pegmatite
i ores to recover beryl, if the cumulative world demand for beryllium to
the year 2000 is to be met. Such improved mining techniques would make
available 100,000 tons of beryllium at ore prices 50% greater than the
present cost.
Current world reserves of bismuth are inadequate to meet the cumu-=
lative world demand to the year 2000. Bismuth does not occur in high
concentration in the earth's crust. and is recovered as a byproduct in
refining other metals, principally lead and copper. In order to meet
the demand, it is necessary that new base metal ores, from which by-
product bismuth can be obtained, be developed, and that more effective
recovery and recycle techniques be employed. Current ore reserves are
inadequate to meet the high range of the cumulative 1968-2000 primary
demand for lead, so that development of new base metal ores may be ex-
pected to occur. It should be noted, however, that the development of
these additional lead resources will require a continued expansion of
the use of tetraethyl lead in gasoline, which is in contradiction to
current trends.
L .0 PREDICTED GROWTH IN DEMAND FOR MSBR MATERIALS
Table 4 summarizes the estimated growth in MSBR installed electri-
cal capacity, and the requirements. for Hastelloy-N and carrier salt,
through the year 2000. The MSBR installed electrical capacity is assumed
to grow according to the relation:
1.5
P = 5180 (T - 1985) s
where P is the megawatts (electrical) generated by molten-salt breeder
reactors at time T, in years, after 1985. This function is an attempt
to represent growth in MSR generating capacity predicted by the Systems
Analysis Task Force for a power economy in which gas-cooled fast breeder
reactors and plutonium-fueled molten-salt converter reactors constitute a
large fraction of the generating capacity.5 The MSBR demand for natural
resources in the year 2000 as a result of this growth function is com-
pared with the estimated world demand for these materials in Table 5.
b Except for the two elements thorium and hafnium, the MSBR demand for
Table 4. Estimated Growth of MSBR Installed Electrical Capacity and Demand for
Hastelloy-N and Carrier Salt to the Year 2000
Hastglloy--Na _ Fue Saltb
Year New Capacity Installed Capacity (10 tons) (10° tons)
(103 Mw(e)] [103 MW(e)] Per year Cumulative Per year Cumulative
1986 5 5 5.6 5.6 1.2 1.2
1990 16 58 18.1 63.2 .0 1h.1
1995 2L 164 26.7 176.3 6.6 43,6
2000 30 301 33 .6 303 .7 9.1 91.6
% tncludes 1.12 x lO5 tons of Hastelloy-N per 1000 MW(e) installed capacity plus re-
placement of reactor vessel head every four years.
bIncludes 225 tons of salt inventory of nominal composition 72-16-12 mole % LiF-BeF -
ThF“ plus replacement of 8.8 tons/yr of fuel salt per 1000 MW(e) installed capacity
operating at a 0.8 load factor.
Ol
11
i Table 5. Range of Year 2000 Estimated World Primary Demand for
- MSBR Materials
a USBM Estimatedb
Element MSBR Demand World Primary Demand MSBER Demand
(tons/year) (tons/year) World Demand
Fuel Salt Li 725 1.5-2.1 x 10” 3.4-4.8%
Be 207 1.6-3.0 x 107 T-13%
Th 4000 (1.2-8.1 x 10°)° hog
F 4160 7.0-9.3 x 106 0.04-0.06%
Hastelloy-N Ni 2600 1.1-1.6 x 106 0.16-0.26%
Mo 4500 2.2-3.0 x 105 1.5-2.0%
Cr 2500 2.7-5.6 x 106 C.0u%
Fe 720 6.7-9.4 x 10° ~1o'u%
Mn 72 3.3-h. x 106 0.002%
Ti 180 L.2-4.5 x 106 0.C05%
Nb 36 1.4-3.0 x 101‘L 0.12-0.26%
HE 36 0.8-1.7 x 10° 21-45%
Other Bi 520 4.8-7.6 x 107 6.9-10.58%
B 1500 0.7-1.1 x 106 0.1-0.2%
aRoy C. Robertson, ORNL Reactor Division, personal communication, esti-
mates 30 new MSBRs installed in the year 2000.
bU.S. Bureau of Mines, Mineral Facts and Problems, 1970 ed.
“low forecast assumes the absence of nuclear reactors operating on the
thorium fuel cycle. High forecast anticipates an expanding nuclear
economy based on the thorium cycle.
dRatio is based on high range of forecast world primary demand.
12
materials constitutes only a small fraction of the estimated world de-
mand. The fact that MSBRs would account for 49% of the worid consump-
tion of thorium is simply the result of the assumption that MSBRs would
represent a large fraction of the electrical generating capacity in the
year 2000. The relatively large fraction of the world demand for haf-
nium that would result from the assumed MSR economy reflects the fact
that the world demand for hafnium is very small at present and is not
expected to grow rapidly. Hafnium is obtained in quantities far ex-
ceeding world demand from ores from which zirconium is recovered. It is
anticipated that MSBR requirements would not, of themselves, place a
severe strain on the world capacity to produce any of the raw materials
shown in Table 5.
The cumulative world demand for certain MSBR materials during the
rest of this century is predicted to be quite large. Table 6 compares
the cumulative requirements for natural resources necessary to sustain
the assumed MSBR economy, and to satisfy the anticipated range of the
world primary demand. Again, except for thorium and hafnium, the MSBR
cumulative demand is expected to represent only a small fraction of the
world demand. However, the world demand for fluorine, beryllium, and
bismuth is expected to exceed the known world reserves of these materi-
als, and the world demand for several other materials (notably Mo, Mn,
Ni, and Li) is expected to severely deplete world reserves. In the
cases of fluorine and bismuth, the cumulative demand may even exceed the
anticipated world resources.
5.0 DISCUSSION OF RESULTS
A survey has been made of the reserves of, and future demand for,
natural resources of particular importance to the MSBR program. These
data have been compared with material requirements necessary to sustain
a growing MSBR power economy. It was found that sufficient reserves of
beryllium, bismuth, and thorium are available to build only a few thou-
sand MSBRs, even if all the reserves of these materials are committed to
MSBR construction. Also, reserves of fluorspar ore, the principal raw
o,
P
Table 6. Period 1968-2000 Estimated World Primary Demand for MSBR Materials
Cumulative
Cumulative World Demand
Element MSBR 1985 -2000 World 1968-2000 MSBR Demand World Demand World Resources +
Cumulative Demand Cumulative Demand World Demand World Reserves World Reserves
(tons) (tons) (%) (%) (%)
Fuel Salt Li T3 x 10? 2.T=3.3 x lOi 2<% 36-LL -
Be 2.1 x 107 3.0-4.2 x 10y, 5-T 4 250-360 1.9-2.7
Th 4.0 x 10, 2.3-8.4 x 10g 49 h.5-16 1.7-6.3
F h,2 x 10 1.2-1.4 x 10 0.03-0.04 500 =600 180-210
Hastelloy-N Ni 2.5 x 102 2.4-2.9 x 102 0.8-1.0 32-39 -
, Mo 3.9 x 10 h.2-5.0 x 10g 0.8-0.9 78-93 -
Cr 2.3 x 105 C.9~1.1 x IO10 0182 11-14 -
Fe 6.5 x 102 1.7-2.1 x 108 <10 7 17-21 24
Mn 6.5 x 10; 3.9-h.6 x 10, <1077 5% -63 .3
Ti 1.6 x 107 1.9=4.4 x 105 G.0L-0.08 1.2-2.9 -
Nb 3.2 x 103 2.7-4.0 x 103 0.08-0.12 2.7-4.0 -
Hf 3.2 x 10 1.9-2.9 x 10 11-17 0.6-0.9 -
Other Bi 5.2 x loi 1.4-1.8 x 10% 2.9=3.7 140-180 78-100
B 1.5 x 10 1.4-1.8 x 10 0.08-0.1 20-25 -
aU.S° Bureau of Mines, Mineral Facts and Problems, 1970
b
Ratio based on high range of forecast world cumulative
ed.
demand .
¢1
1k
material for recovery of fluorine, are being rapidly depleted by non-
MSBR applications. The following sections summarize United States
Bureau of Mines information on reserves, mining technology, applications,
and potential resources of these four materials.
5.1 Beryllium
Beryllium occurs at an average concentration of about 6 parts per
million in the earth's crust, and is an essential constituent in some
fiO minerals. Beryl, bertrandite, phenacite, barylite, and chrysoberyl
are the most common beryllium minerals, but beryl (§BEO°A1205-68102) is
the sole commercial source of beryllium. When pure, beryl contains
about 1L% beryllium oxide or about 5% beryllium metal. Commercial beryl
is hand sorted to obtain crystals and lumps of beryl containing about
11% BeO, or 4% beryllium.
The world's principal commercial sources of beryl are heterogenecus
granite pegmatites, where the mineral occurs in rich zones, usually con-
taining only a few thousand tons of pegmatite rock. Occasionally peg-
matites are mined for beryl alone, but more often beryl is recovered as
a byproduct of feldspar, mica, and other minerals. Pegmatite deposits
are mined by drilling or blasting, then hand-cobbing the blasted rock,
a procedure by which barren rock is broken off with hand hammers and
discarded, and the valuable minerals, including beryl, recovered.
Beryl, feldspar, and some other pegmatite minerals have densities so
nearly the same that it is difficult to separate beryl by mechanical
means. Thus, all commercial beryl is hand~cobbed, and crystals less
than one inch in size are not usually recovered. It is estimated that
only one~third of the beryl in an average deposit is recovered by the
hand methods now in use.
The United States primary demand for beryllium in 1968 was 328
tons, and the rest-of-the-world demand was 150 tons. The range of the
United States demand for beryllium in the year 2000 is expected to be 1250
to 1740 tons, and the range of rest-of-the-world primary demand in the year
2000 is predicted to be 400 to 1300 tons. Beryllium is used, primcipally
15
T in the form of beryllium-copper alloys, in switchgear, welding appara-
tus, computer equipment, and radio and television equipment. Few data
are available on world beryllium reserves, which are roughly estimated
to be 12,000 tons. Domestic reserves of pegmatite ores containing: at
least 1% beryl are only about 400 tons. However, there are some 50,000
tons of beryllium contained in lower-grade pegmatite ores found in North
Carolina, and 27,000 tons of contained beryllium in bertrandite deposits
in Utah. 1In this country, attention is being given to recovering beryl-
lium from these latter deposits. It is estimated that 15,000 tons of
the beryllium in bertrandite at Spor Mountain, Utah, could be recovered
at no change in ore price, and that an additional 25,000 tons could be
recovered at a 50% increase in ore price. The cost of the ore is a
small part of the cost of the metal, so that the price of the metal is
actually expected to decrease about 20% by the year 2000 as the result
of improved extractive technology and from economies of scale. The cost
of the fluoride, which is intermediate between the cost of the contained
beryllium in the ore and the cost of the refined metal, should show no
large price increase during this period.
5.2 Fluorine
The principal fluorine-containing minerals are fluorspar,(CaFg),
cryolite (NaBAlF6L and phosphate rock. Fluorspar, the principal fluo-
rine mineral, is mined in this country and abroad, with domestic re-
sources of about 5.4 million tons of contained fluorine and rest-of-the-
world resources of 33.4 million tons. The only known natural eryolite
deposit at Ivigtut, Greenland, was exhausted in 1963, but stockpiled ore
is available to supply needs for 15 to 20 years. Fluorine compounds may
be recovered from phosphate rock, but, because of the high cost of recov-
ering the fluorine, most of this material is neutralized and discarded.
Thirty-five percent of the fluorine consumed in 1968 was used in the
form of HF to manufacture fluorocarbon compounds. Thirty-three percent
of the fluorine consumed was in the form of fluorspar for use as a flux
in the steel industry, where from 3 to 12 1b of fluorspar is required
per ton of steel produced, depending on the process. Fluorine, in the
16
form of cryolite, is used by the aluminum industry to dissolve alumina s
for electrolysis. This use accounted for 18 percent of the 1968 flug-
rine demand. The domestic demand for fluorine was 646,000 tons in 1968
and is expected to rise to 2.1 to 2.7 million tons by the year 2000.
Rest-of ~the-world demand for fluorine in 1968 was 1.2 million tons and
is expected to rise to 5.0 to 6.6 million tons. Domestic resources of
fluorine are expected to be depleted in 25 years, and rest-of-the-world
resources are expected to be exhausted in less than 20 years. However,
it is believed that technological advances in exploring for fluorspar
deposits will be made so that a sufficient supply of fluorspar will be
available to meet the demand through the year 2000 at an increase in ore
cost of about 33%.
5.3 Bismuth
Bismuth is a relatively rare element, occurring in the earth's
crust at a concentration of about 0.1 part per million. It is found in
the minerals bismite (BiEOB) and bismuthinite (31255), which occur in
low concentration in ores throughout the world. As a result of the low
concentration of bismuth in most ores, deposits are not mined for the
bismuth content alone. Most bismuth is recovered as a byproduct of the
mining and processing of other minerals containing small amounts of bis-
muth. The technology of bismuth extraction and refining is well estab-
lished in connection with lead-refining plants. The bismuth in lead
ores, concentrates, and flue dust is collected in the lead bullion, from
which it is recovered. About 50% of the bismuth consumed is used as an
alloying material in fusible alloys, specialty aluminum, and malleable
iron and steel. Another 40% of the bismuth consumption is for use in
pharmaceuticals and cosmetics. The United States and rest-of-the-world
primary demands for bismuth in the year 1968 were 1100 and 2700 tons,
respectively. The range of the U.S. primary demand for bismuth in the
year 2000 is expected to be 1400 to 2300 tons. The rest-of-the~-world
reguirements for the year 2000 are expected to grow to 340C to 5300 tons.
World reserves of bismuth are estimated to be 100,000 tons, a quantity
which is insufficient to satisfy the cumulative world demand for bismuth s
17
g to the year 2000. Potential bismuth resources in the U.S. and fifteen
foreign countries surveyed by the Bureau of Mines total 82,000 tons.
In order to meet the cumulative world demand for bismuth through the
year 2000, it is necessary that new base metal ore reserves (from which
bismuth is obtained as a byproduct) be developed. Domestic reserves of
bismuth from lead ores total 14,000 tons. Potential domestic bismuth
resources of 5000 tons are associated with marginal lead cres, and addi-
tional resocurces totaling lfi,OOO tons are associated with other base
metal ores. The production of bismuth is closely related to the demand
for lead, so that it is necessary for the demand for lead tc increase
in order that additional lead and associated bismuth rescurces be devel=-
oped. Since 20% of the lead demand in the year 1968 was for use as
tetraethyl lead in gasoline, the trend toward low-lead gascline may re-
tard the development of bismuth resources. 1In this case, bismuth demand
would have to be met by developing resources associated with copper and
zinc ores.
5.4 Thorium
Thorium is a widely distributed element, having an abundance of 10
to 20 parts per million in the earth's crust. It is found in the form
of the minerals thorianite, Thog, and thorite, ThSiOh, and may be asso-
ciated with varying amounts of UO2 and U05. Monazite, an important
thorium-bearing mineral, is a rare-earth phosphate which may also con-
tain up to 18%'Th02- Monazite deposits are found in India, Brazil,
Australia, Ceylon, Indonesia, Malagasy Republic, Malaysia, the Republic
of South Africa, Canada, and the United States. Monazite is generally
recovered from river and beach sands by placer mining methods. The mon-
azite is concentrated, chemically processed to separate the rare earths,
and purified by solvent extraction. The principal uses of thorium are
in the manufacture of incandescent gas mantles, the production of magne-
sium~thorium alloys, other metallurgical applications, and as a catalyst
in the petroleum and chemical industries. World primary demand for
thorium in 1968 totaled 200 tons. Should nuclear reactors operating on
the “9°Th-"27
U fuel cycle prove successful, the high range of the world
18
thorium demand for the year 2000 is predicted to be 8100 tons, and the i
cumulative demand for the period 1968-2000 is expected to be 84,000 tons.
World reserves of thorium at $10 per pound of Thog are 590,000 tons, and
world resources at this price are predicted to be almost_one million
tons. Although it is apparent that inexpensive thorium ores will be avail-
able well into the next century, even larger quantities of thorium will be
available at higher prices. Table T summarizes the magnitudes of the
thorium resources in the United States as a function of the cost of Thog.
While data on the amount of ore available in foreign countries at higher
prices arenot available, it is believed that analogous quantities would
be recoverable at increased prices.
Table 7. Domestic Thorium Resources as a Function of Price of Th02a
Price Range per Pound Reasonably Assured Estimated Total
of ThO Resources Resources
() 2 (tons) (tons)
under 10 100, 000 400, 000
10-30 100, 000 200, 000
20-100 7,000, 000 35,000,000
100-500 1,000,000, 000 3,000, 000, 000
aAEC, Civilian Nuclear Power, a Report to the President, 1967, as
presented to the Joint Committee on Atomic Energy, 88th Cong.,
Feb. 20 and 21, 1963.
6.0 CONCLUSIONS AND RECOMMENDATIONS
The elements beryllium, bismuth, and fluorine have been identified
as materials whose mineral reserves are insufficient to satisfy the pre-
dicted world demand for these elements by the year 2000, thus creating
an economic situation which might not favor the growth of an MSBR power
economy. Of these three elements, the outlook for beryllium is most
promising. The domestic demand for beryllium is met, at present, almost
19
4 entirely by imports of beryl, which is mined from pegmatite ores by
primitive, hand sorting methods. While this country does not have large
resources of hand-cobbable beryl, the mineral bertrandite is found in
large quantities in the western part of the United States. Unlike beryl,
bertraniize occurs indeposits associated with minerals whose densities
differ sufficiently from bertrandite that mineral beneficiation techni-
ques are feasible. If the western U. S. bertrandite deposits are devel-
oped successfully, the demand for beryllium through the year 2000 can
be met with no increase in the cost of beryllium metal or beryllium
fluoride.
The element fluorine, in the form of fluorspar and cryolite, is
used extensively in the steel and aluminum industries. Fluorine is
mined in the form of fluorspar, a mineral whose mining technology is
already well developed and highly mechanized, so that greater produc-
tion via improved mining technology is unlikely. The U. S. Bureau of
Mines believes that technological advances in exploring for fluorspar
deposits and recovery of fluorine from phosphate rock will result in an
adequate supply of fluorspar to the year 2000 at about a 33% increase
in price. The resources of fluorine contained in phosphate rock de-
posits in this country alone are estimated at 2.8 x 10 tons, a quan-
tity which far exceeds the resources of fluorspar. As the price of
fluorspar increases, ‘it is-likely that more efficient use of the miner-
al will be made in the steel industry, where the quantity of fluorspar
consumed per ton of steel varies from 3 to 12 1b. Within the MSR Pro-
gram, it will be necessary to make efficient use of fluorine. The
complete recycle of fluorine in the uranium removal system of the pres-
ent flowsheet is an example of the type of improvements required.
Consideration should also be given to discarding a chloride waste salt
rather than a fluoride salt. 1In the year 2000, replacement of discarded
salt will account for 25% of the fluorine consumed by the MSR economny,
based on the present flowsheet. Also, at the end of the thirty-vear
life of a réactor, the carrier salt as well as the fissile material
should be recovered and recycled to other reactors. Recovery is possible
by means of low-pressure distillation, a process whose technology has
g 6
been demonstrated by Hightower et al.
20
Bismuth reserves are also insufficient to meet the world cumula-
tive demand for this metal through the year 2000. Bismuth supply is
closely linked to and limited by resources and production of lead and
copper. The supply varies, therefore, according to the demand for
these metals, rather than according to the independent requirements for
bismuth. The relatively limited and inelastic supply has prevented use
of bismuth for applications requiring substantial quantities. 1In order
to meet the demand for bismuth, more effective recovery techniques, in-
creased secondary bismuth recovery, and development of new base metal
ores are required. Substitution of alternate materials for bismuth in
pharmaceuticals and cosmetics may reduce demand somewhat. A large frac-
tion of the bismuth inventory in the MSBR processing plant is employed
to dissipate the radioactive decay heat from the rare-earth fission
products in the metal transfer system. The bismuth inventory necessary
to operate the metal transfer process could be significantly reduced if
another means is used for dissipating the fission product decay heat.
Bismuth and fluorine appear to be the two elements in the MSBR
fuel cycle which are most vulnerable to depletion of low-cost natural
resources. Present estimates by the U. S. Bureau of Mines are that re-
serves will be expanded to meet the demand for these materials through
the year 2000. The availability of these materials beyond this point
at prices near present costs appears quite uncertain. Although beryl-
1ium reserves which can be recovered by today's hand mining techniques
are small, large resources are known to exist, and it is expected that
mechanical mining techniques can be developed to recover beryllium from
these ores at no increase in the cost of beryllium fluoride or berylli-
um metal. Reserves of $10/1b thoria are adequate to supply an MSBR
economy well beyond the year 2000, and large resources of higher priced
thoria are available, so that fertile material will not be in short
supply in the foreseeable future.
A large fraction of the world reserves of elements Li, Mo, Ni, and
Mn will also be consumed by the year 2000. 1In all cases, the MSBR de-
mand for these materials will be a small fraction of the world demand.
Increases in the costs of nickel and molybdenum that result when these
21
reserves are depleted will have a greater adverse effect on the MSBR
program than on competing reactor types, because of the relatively high
content of these materials in Hastelloy-N and the use of molybdenum as
a material of construction in the processing plant. (A typical 1000-
MW(e ) LMFBR power plant would require about 15% of the Ni and less than
1% of the Mo in an MSBR.) It is possible, however, that reserves of
these materials will be expanded sufficiently rapidly that large in-
creases in price will not occur until well beyond the year 2000.
Consideration has been given to the effect of large increases in
the price of raw materials on the fuel cycle cost of power produced by
an MSBR. The inventory and replacement charges for a number of materi-
als are given in Table 8 for a 1000-MW(e) MSBR as presently envisioned.
Table 8. Inventory and Replacement Charges for
Materials in a 1000-MW(e) MSBR
Inventory and
Material Price Inventory Replacement Replacement CoSta
{3/1b) (tons) (tons/yr) (mill/kWhr )
TLi 55 17.9 1.0 C0.055
Be 3g.2° 5.1 0.2 0.010
Th 8.6° 99.1 6.3 0.050
F 0.5 102.9 2.9 0.0025
Hastelloy-N 10.80% 1120 10 0.51k
Bi 6 17.4 0 0 .00k
2 Assume inventory charge of 1L4% per annum and 0.8 plant factor.
bCost of contained beryllium based on a cost of BeF2 of $T.5Q/lb.
“Cost of contained thorium based on a cost of ThFzP of $6.50/1b.
dAverage cast of Hastelloy-N based on finished shapes costing $8 to
$20/1b. .
These data show that an increase in the price of beryllium, fluorine, or
bismuth by an order of magnitude would increase the fuel cycle cost by
22
at most 0.1 mill/kWhr. If the price of ThO. rises to $30/1b, the in- i
crease in fuel cycle cost would also be aboit 0.1 mill/kWhr. The cost
of natural lithium is about $1/1b which, compared to the price of
isotopic separation, is quite small. An increase of an order of magni-
tude in the cost of natural lithium would result in an increase in fuel
cycle cost of only O.1 mill/kWhr. The case is similar with the compo-
nents of Hastelloy=-N, which has a value of about $1/IB, but which is
estimated to cost $8 to $20/1b when fabricated into finished shapes.
An increase of 100% in the cost of nickel, the major constituent of
Hastelloy-N, would result in an increase in fuel cycle cost of only
0.05 mill/kWhr.
In summary, there is no natural resource in such short supply that
it would render the development of molten salt reactors unattractive.
World reserves of some materials required for the MSR Program are being
depleted, but new resources of these materials must be developed in
order to supply a wide variety of consumers. Several areas are indi-
cated where efficient recycle of materials within the MSR economy is
desirable, but such recycle is probably in the direction of lower fuel
cycle costg even at present market conditions, and will be included in
the MSR fuel cycle for reasons other than conservation of natural re-
SOUTrCesS.
23
T-0 REFERENCES
1. U.S. Bureau of Mines, Mineral Facts and Problems, 1970 edition.
2. U. S. Geological Survey, Geological Survey Professional Paper 60C,
"Mineral-Resource Appraisals"™ (1968).
3. P. R. Kasten and R. C. Robertson, ORNL Reactor Division, unpub-
lished MSRP data, April 1969.
L. W. L. Carter and E. L. Nicholson, Design and Cost Study of a Fluo-
rination-Reductive Extraction-Metal Transfer Processing Plant for
the MSBR, ORNL-TM-3579 (in press).
5. Potential Nuclear Growth Patterns, WASH-1098 (December 1970).
6. J. R. Hightower, L. E. McNeese, B. A. Hannaford, and H. D. Cochran,
Jr., Low-Pressure Distillation of a Portion of the Fuel Carrier
Salt from the Molten Salt Reactor Expériment, ORNL-L5TT (AuguSt"1971),
.........
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