EP3241218B1

(19)
*EP003241218B1*
(11) EP 3 241 218 B1
(12) EUROPEAN PATENT SPECIFICATION
(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: G21C 1/02 (2006.01) G21C 7/22 (2006.01)
24.03.2021 Bulletin 2021/12 G21C 7/27 (2006.01) G21C 11/06 (2006.01)
(21) Application number: 15876187.4 (86) International application number:

PCT/US2015/067905
(22) Date of filing: 29.12.2015
(87) International publication number:
WO 2016/109565 (07.07.2016 Gazette 2016/27)
(54) MOLTEN NUCLEAR FUEL SALTS AND RELATED SYSTEMS AND METHODS
GESCHMOLZENE KERNBRENNSTOFFSALZE UND ZUGEHÖRIGE SYSTEME UND VERFAHREN

SELS COMBUSTIBLES NUCLÉAIRES FONDUS ET SYSTÈMES ET PROCÉDÉS ASSOCIÉS
(84) Designated Contracting States: • EL-DASHER, Bassem S.

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Bellevue,
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Washington 98008 (US)
PL PT RO RS SE SI SK SM TR • LATKOWSKI, Jeffrey F.
Bellevue,
(30) Priority: 29.12.2014 US 201462097235 P Washington 98008 (US)
31.12.2014 US 201462098984 P • KELLEHER, Brian C.
30.09.2015 US 201562234889 P Bellevue,
Washington 98008 (US)
(43) Date of publication of application: • PETROSKI, Robert C.
08.11.2017 Bulletin 2017/45 Bellevue,
(60) Divisional application: • WALTER, Joshua C.
20211581.2 Bellevue,
(73) Proprietor: TerraPower LLC
Bellevue Washington 98008 (US) (74) Representative: D Young & Co LLP
120 Holborn
(72) Inventors: London EC1N 2DY (GB)
• CHEATHAM, Jesse R. III
Bellevue, (56) References cited:
Washington 98008 (US) WO-A1-2014/128457 DE-B- 1 112 791
• CISNEROS, Anselmo T. Jr JP-A- 2014 119 429 US-A- 5 421 855
Bellevue, US-B1- 6 181 759
• KERLIN, William M. • MOUROGOV A ET AL: "Potentialities of the fast
Bellevue, spectrum molten salt reactor concept:
Washington 98008 (US) REBUS-3700", ENERGY CONVERSION AND
• CZERWINSKI, Ken MANAGEMENT, ELSEVIER SCIENCE
Bellevue, PUBLISHERS, OXFORD, GB, vol. 47, no. 17, 1
Washington 98008 (US) October 2006 (2006-10-01), pages 2761-2771,
EP 3 241 218 B1
• KRAMER, Kevin XP027957150, ISSN: 0196-8904 [retrieved on

Bellevue, 2006-10-01]
Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).
Printed by Jouve, 75001 PARIS (FR) (Cont. next page)

EP 3 241 218 B1
• TAUBE M ET AL: "Molten plutonium chlorides • A. MOUROGOV ET AL.: ’Potentialities of the fast
fast breeder reactor cooled by molten uranium spectrum molten salt reactor concept:
chloride", ANNALS OF NUCLEAR SCIENCE AND REBUS-3700’ ENERGY CONVERSION AND
ENGINEERING,, vol. 1, no. 4, 1 April 1974 MANAGEMENT vol. 47, no. 17, 30 March 2006,
(1974-04-01), pages 277-281, XP023636399, ISSN: pages 2761 - 2771, XP027957150
0302-2927, DOI: 10.1016/0302-2927(74)90045-2
[retrieved on 1974-04-01]
2
EP 3 241 218 B1
Description
RELATED APPLICATIONS
5 [0001] This application is being filed on 29 December 2015 as a PCT International application and claims the benefit
of U.S. Provisional Application Nos. 62/097,235, filed December 29, 2014, 62/098,984, filed December 31, 2014, and
62/234,889, filed September 30, 2015.
[0002] The present application is also related to U.S. Patent Application No. 14/981,512 [Attorney Docket No. 14-003-
UT1-USINN/365003USP1], entitled "Fission Reaction Control in a Molten Salt Fast Reactor" and filed December 28, 2015.
10
INTRODUCTION
[0003] The utilization of molten fuels in a nuclear reactor to produce power provides significant advantages as compared
to solid fuels. For instance, molten fuel reactors generally provide higher power densities compared to solid fuel reactors,
15 while limiting fuel fabrication processes, which are necessary in the construction of solid fuels. Molten fuel reactors may
also provide a higher level of burn-up in a given reactor, even in systems lacking salt cleanup. DE 11 12 791 B describes
fissile material for nuclear reactors, characterized by a content of 1) at least one of the elements: uranium, thorium and
plutonium in the form of oxides, halides and/or salts of oxygen-containing anions in an amount of about 0.01 to 50% by
weight of the total mass and 2) at least a constituent of the groups: a) sulphur in the form of oxides of sulphur, metal
20 sulphates, metal silicates, metal halosulphonates and/or acids of sulphur, b) halogen in the form of metal halides, metal
halosulphonates and/or metal halophosphates, c) phosphorus in the form of oxides of phosphorus, metal phosphates,
metal phosphites and/or metal halophosphates and d) at least one oxide of a non-metal and/or of a metal other than the
metals mentioned under 1), wherein the amount of halogen and/or sulphur is at least 1 atomic percent of the total sulphur,
halogen and phosphorus atoms in the total mass and the amount of components 2a), 2b) and 2c) are at least 60 weight
25 percent of the total weight of all components of the mass, which are free of uranium, thorium and plutonium.
[0004] Molten fluoride fuel salt suitable for use in nuclear reactors have been developed using uranium tetrafluoride
(UF4) mixed with other fluoride salts. For instance, a UF4 based fuel salt may include a mixture of LiF, BeF2, ThF4 and
UF4. It is noted that in such a family of UF4 based fuel salt compositions the heavy metal content may range from
approximately 40-45 % by weight and have a melting temperature of approximately 500 °C.
30
MOLTEN NUCLEAR FUEL SALTS AND RELATED SYSTEMS AND METHODS
[0005] This disclosure describes embodiments of nuclear fuel salts usable in certain molten salt reactor designs and
related systems and methods. Binary, ternary and quaternary chloride fuel salts of uranium, as well as other fissionable
35 elements, are described. In addition, fuel salts of UClxFy are disclosed as well as bromide fuel salts. This disclosure also
presents methods and systems for manufacturing such fuel salts, for creating salts that reduce corrosion of the reactor
components and for creating fuel salts that are not suitable for weapons applications.
[0006] In part, this disclosure describes a method of operating a nuclear reactor. The method includes supplying a
reactor core with a fissionable fuel salt containing an amount of UCl4 and one or more of UCl3F, UCl3, UCl2F2, UClF3,
40 and a non-fissile salt selected from NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4,
AmCl3, LaCl3, CeCl3, PrCl3, and NdCl3, wherein the fuel salt has a melting temperature below 800 °C and a uranium
content of approximately 61 % by weight. The method further includes initiating fission in the fissionable fuel salt and
maintaining breed-and-burn behavior in the fissionable fuel salt for a period of time, thereby creating an irradiated fuel
salt. The method may further include performing the initiating and maintaining operations at a temperature below 550
45 °C but above the melting temperature of the fissionable fuel salt. The method may also include removing irradiated fuel
salt from the reactor core; contacting the irradiated fuel salt from the reactor core with a carrier gas, thereby creating a
carrier/fission product gas mixture and a degassed fuel salt having a reduced amount of gaseous fission products relative
to the irradiated fuel salt; filtering the degassed fuel salt, thereby removing fission product solids, to obtain a filtered fuel
salt; and transferring the filtered fuel salt to the reactor core. Prior to initiating fission in the fissionable fuel salt, at least
50 one radioactive isotope may be added to the fissionable fuel salt in an amount sufficient to obtain a fissionable fuel salt
having a Figure of Merit that is less than 1.0. The chloride ions in the fissionable fuel salt may have a first ratio of 37Cl
to total Cl, the first ratio being different than a naturally occurring ratio of 37Cl to total Cl. The fissionable fuel salt may
contain UCl4 and one or more of UCl3 and NaCl and the molar fraction of UCl4 in the fissionable fuel salt is from 13 mol
% to 71 mol % UCl4.
55 [0007] In part, this disclosure describes a nuclear reactor facility for generating power from a nuclear reaction. The
reactor facility may include a reactor core containing a fissionable fuel salt, the fissionable fuel salt having at least 0.01
% by molar fraction UCl4 and wherein the fuel salt has a melting point of less than 800 °C and a uranium content of
approximately 61 % by weight. For example, the reactor facility may include a reactor core containing a fissionable fuel
3
EP 3 241 218 B1
salt having at least 5 % by molar fraction UCl4 and wherein the fuel salt has a melting point of less than 600 °C. The
reactor facility also may include a heat exchanger adapted to transfer heat from the fuel salt to a coolant. The molar
fraction of UCl4 in the fuel salt may be from 5 mol % to 100 % UCl4, from 13 % to 71 % UCl4, from 0 % to 34 % UCl3,
or from 12 % to 67 % NaCl. The melting point of the fuel salt may be from 330 to 550 °C, from 338 to 500 °C, or from
5 338 to 450 °C. In the nuclear reactor, the heat exchanger may be outside of the reactor core and the nuclear reactor
further includes first piping fluidly connecting an outlet of the reactor core to an inlet of the heat exchanger and allowing
fuel salt to flow from the reactor core to the heat exchanger. The nuclear reactor may further include second piping fluidly
connecting an inlet of the reactor core to an outlet of the heat exchanger and allowing cooled fuel salt to flow from the
heat exchanger to the reactor core. The nuclear reactor may include at least one pump adapted to move the fuel salt
10 when the fuel salt is in a molten state. The nuclear reactor may include a turbine adapted to convert thermal energy in
the coolant into mechanical energy and an electrical generator connected to the turbine adapted to convert mechanical
energy into electricity. Additional components, as illustrated in the attached FIGS., may also be included.
[0008] In part, this disclosure describes methods and fuel salts with modified amounts 37Cl. A method is disclosed for
operating a nuclear reactor using a molten chloride fuel salt. The method includes: identifying a target effective neutron
15 multiplication factor for the nuclear reactor; generating a modified molten chloride fuel salt having a first ratio of 37Cl to
total Cl in the modified molten chloride fuel salt that, when used in the nuclear reactor, achieves the target effective
neutron multiplication factor, the first ratio being different than the naturally occurring ratio of 37Cl to total Cl; and operating
the nuclear reactor with the modified molten chloride fuel salt. The method may further include: determining an initial
effective neutron multiplication factor for the reactor using an initial molten chloride fuel salt having a second ratio of
20 37Cl to total Cl in the fuel; comparing the initial effective neutron multiplication factor to the target effective neutron
multiplication factor; and calculating the first ratio based on results of the comparing operation. The modified molten
chloride fuel salt may include a plurality of different chloride compounds including a first fissile chloride salt compound
and a first non-fissile chloride salt compound and the generating operation of the method may further include: generating
the first fissile chloride salt compound having a second ratio of 37Cl to total Cl; generating the first non-fissile chloride
25 salt compound having a third ratio of 37Cl to total Cl; and combining the first fissile chloride salt compound and the first
non-fissile chloride salt compound in appropriate amounts to obtain the modified molten chloride fuel salt having the first
ratio of 37Cl to total Cl in the modified molten chloride fuel salt.
[0009] The plurality of different chloride compounds may include the first fissile chloride salt compound, the first non-
fissile chloride salt compound and a second fissile chloride salt compound and the method may further include: generating
30 the second fissile chloride salt compound having a fourth ratio of 37Cl to total Cl; and combining the first fissile chloride
salt compound, the first non-fissile chloride salt compound, and the second fissile chloride salt compound in appropriate
amounts to obtain the modified molten chloride fuel salt having the first ratio of 37Cl to total Cl in the modified molten
chloride fuel salt. The first fissile chloride compound may be selected from UCl4, UCl3, UCl3F, and UCl2F2. The first non-
fissile chloride compound may be selected from NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, ThCl4,
35 AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and/or NdCl3. The modified molten chloride fuel salt may be selected from
UCl4, UCl3, UCl3F, NaCl and any mixtures thereof. The modified molten chloride fuel salt may be selected from a mixture
of 34 mol % UCl3 and 66 mol % NaCl; a mixture of 47.7 % UCl4 and 52.3 % NaCl; a mixture of 71UCl4-17UCl3-12NaCl;
and a mixture of 40.5 % UCl4, 17 % UCl3 and 42.5 % NaCl.
[0010] A modified chloride fuel is also disclosed that includes a fissionable fuel salt having a ratio of 37Cl to total Cl in
40 the fuel salt of greater than 25 mol %.The modified chloride fuel salt may have a ratio of 37Cl to total Cl in the fuel salt
that is greater than 75 mol %. The modified chloride fuel salt may further have a ratio of 37Cl to total Cl in the fuel salt
that is greater than a value selected from (in mol %) 30 %, 35 %, 40 %, 45 %, 50 %, 55 %, 60 %, 65 %, 70 %, 75 %, 80
%, 85 %, 90 %, 95 % and 99 %.
[0011] In part, this disclosure also describes uranium chloride fluoride fuel salts. A molten salt reactor is described
45 that includes a reactor core containing a fuel salt, wherein the fuel salt is from 1-100 mol % UCl3F. The fuel salt may be
from 15-20 mol % UCl3 and the balance being from 35-45 mol % NaCl and 35-45 mol % UCl3F. The fuel salt may be at
least 5 mol % UCl3F. The fuel salt may further include one or more of UCl4, UCl3, UCl2F2, ThCl4, UBr3, UBr4, UClF3,
and a non-fissile chloride compound. The non-fissile chloride compound may be selected from NaCl, MgCl2, CaCl2,
BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3,PrCl3 and/or NdCl3.
50 [0012] The disclosure also describes a fuel salt for a molten fuel reactor consisting of at least a detectable amount of
UCl3F and one or more of UCl4, UCl3, UCl2F2, UClF3 and a non-fissile salt selected from NaCl, MgCl2, CaCl2, BaCl2,
KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and NdCl3, wherein the fuel salt has a
melting temperature below 800 °C. The fuel salt may have a melting temperature below 550 °C.
[0013] In part, this disclosure also describes thorium chloride fuel salts. A fuel salt for a molten fuel reactor is described
55 that includes at least a detectable amount of ThCl4 and one or more of UCl4, UCl3, UCl3F. The fuel salt may further
include one or more non-fissile salt selected from NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4,
AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and NdCl3. The melting point of the fuel salt may be below 550 °C. Comparative
examples of the fuel salt capable of supporting a breed-and-burn reaction while in the molten state are disclosed. A
4
EP 3 241 218 B1
breed-and-burn reaction refers to a reaction that creates (breeds) new fissile fuel from fertile fuels (e.g., Th, natural U
and/or depleted U) as it consumes (burns) fissile fuel. In some of the disclosed fuel salts the chloride in the fuel salt is
enriched with 37Cl.
[0014] The disclosure further describes a fuel salt for a molten fuel reactor consisting of at least a detectable amount
5 of ThCl4 and one or more of UCl4, UCl3, UCl3F and a non-fissile salt selected from NaCl, MgCl2, CaCl2, BaCl2, KCl,
SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and NdCl3, wherein the fuel salt has a melting
temperature below 800 °C.
[0015] In part, this disclosure also describes bromide fuel salts. A fissionable fuel salt is disclosed that includes a
detectable amount of at least one of UCl3F, UBr3 or UBr4. The fissionable fuel salt may be a mixture of UBr3, UBr4 and
10 NaBr. The bromide fuel salts may have a melting point above 330 °C and below 800 °C. At least one of the uranium
specie such as UBr3 and UBr4 may have a modified amount of 235U. Fuel salts are disclosed wherein at least one of
the UBr3 and UBr4 have uranium enriched above 19 % 235U. The fuel salt may be 17UBr3-71UBr4-12NaBr and uranium
in either or both of the UBr3 and UBr4 may be enriched to 19.99 % 235U. The bromide in the fuel salt may be enriched
with 79Br or 81Br. For example, greater than 90 %, 95 %, 98 %, 99 %, or 99.9 % of the bromide ions in the fuel salt may
15 be either 79Br or 81Br.
[0016] In part, this disclosure also describes UCl4 synthesis using ammonium chloride. A method is described for the
manufacture of uranium chloride fuel salt. The method includes: providing a mixture of UO2 and NH4Cl; exposing the
mixture to HCl under conditions sufficient to create at least some (NH4)2UCl6; and heating the (NH4)2UCl6 to a temperature
and for a period of time sufficient to convert at least some of the (NH4)2UCl6 into UCl4. The method may include heating
20 the mixture in the presence of HCl to a temperature and for a period of time sufficient to create at least some (NH4)2UCl6.
The method may further include heating the mixture in the presence of HCl to 100 °C for at least one hour. The method
may also include heating the (NH4)2UCl6 to from 200-500 °C. The method may further include heating the (NH 4)2UCl6
to from 250-350 °C or heating the (NH4)2UCl6 to a temperature above 200 °C but below a temperature that melts the
(NH4)2UCl6 or UCl4. The method may include contacting anhydrous CaCl2 with aqueous HCl under conditions sufficient
25 to create HCl gas. The method may include placing pellets of anhydrous CaCl2 in aqueous HCl in a reactor, the reactor
also containing the mixture and heating the reactor to 100 °C for at least one hour. In the method, one or more of the
HCl or the NH4Cl may have a ratio of 37Cl to total Cl of greater than 25 %.
[0017] In part, this disclosure also describes several UCl3-UCl4-NaCl manufacturing processes and systems. A method
is disclosed for manufacturing a uranium chloride fuel salt that includes: contacting a volume of UO2 with chlorine and
30 carbon monoxide under conditions that allow the formation of UCl4, thereby obtaining an amount of UCl4; contacting a
volume of Na2CO3 with chlorine and carbon monoxide under conditions that allow the formation of NaCl, thereby obtaining
an amount of NaCl; contacting a volume of Si with UCl4 under conditions that allow the formation of UCl3, thereby
obtaining an amount of UCl3; and mixing at least some of the NaCl with at least some of either or both of the UCl3, UCl4
as appropriate to achieve a desired uranium chloride fuel salt. The method may include using enriched chlorine in one
35 or more of the contacting operations. The enriched chlorine may have more than 24 mol % 37Cl isotope. The method
may include contacting a volume of solid UO2 with gaseous chlorine and gaseous carbon monoxide. The method also
may include contacting a volume of solid Na2CO3 with gaseous chlorine and gaseous carbon monoxide. The method
may include contacting a volume of solid Si with a liquid UCl4.
[0018] Another method is also disclosed for manufacturing a uranium chloride fuel salt. This method includes: preparing
40 a first vessel with UO2, second vessel with Na2CO3, and third vessel with Si; passing Cl2 and CO through the first and
second vessels thereby converting at least some of the UO 2 into UCl4 and at least some of the Na2CO3 into NaCl;
adjusting the pressure and/or temperature of the first vessel to sublimate at least some UCl4, while maintaining the UO2
as a solid; transferring at least some of the UCl4 gas into the second vessel; adjusting the pressure and/or temperature
of the second vessel to convert the UCl4 and NaCl into a liquid mixture, while maintaining the Na2CO 3 as a solid; and
45 transferring at least some of the liquid mixture of UCl4 and NaCl into the third vessel under the condition appropriate to
create at least some liquid UCl3 and gaseous SiCl4, thereby creating a liquid UCl3-UCl4-NaCl fuel salt mixture. The
method may further include using enriched chlorine in the passing Cl2 and CO operation. The enriched chlorine may
have more than 25 mol % 37Cl isotope. The method may be controlled to obtain desired relative amounts of UCl3, UCl4
and NaCl in the UCl3-UCl4-NaCl fuel salt mixture. In the method, all or most of the UO2 may be converted into UCl4
50 and/or all or most of the Si may be converted into SiCl4.
[0019] A system for manufacturing a uranium chloride fuel salt is also disclosed. The system includes: a UO 2-containing
vessel; a Na2CO3 -containing vessel; a Cl2 gas source; and a CO gas source; wherein the UO2-containing vessel and
the Na2CO3- containing vessel are connected to receive Cl2 gas and CO gas. The system may further include a Si-
containing vessel connected to one or both of the UO 2-containing vessel and the Na2CO 3 -containing vessel. An envi-
55 ronmental control system may also be included capable of adjusting the pressure and/or temperature in the UO2-con-
taining vessel sufficiently to sublimate UCl4 and the pressure and/or temperature of the Na2CO3 -containing vessel
sufficiently to melt UCl4 and NaCl. The UO2-containing vessel may further be connected to the Na2CO3 -containing
vessel so that gases may be controllably transferred from the UO2-containing vessel to the Na2CO3 -containing vessel
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EP 3 241 218 B1
and the Na2CO3 -containing vessel may be connected to the Si-containing vessel so that liquids may be controllably
transferred from the Na2CO3 -containing vessel to the Si-containing vessel. In the system, the Cl2 gas obtained from
the Cl2 gas source may be modified Cl2 gas having a ratio of 37Cl2 to total Cl2 different from 24 mol %. The modified Cl2
gas may have a ratio of 37Cl2 to total Cl2 greater than 25 mol % or the modified Cl2 gas may have a ratio of 37Cl2 to total
5 Cl2 less than 23 mol %.
[0020] In part, this disclosure also describes a fast spectrum molten salt nuclear reactor that includes a reactor core
section including a fuel input and a fuel output, in which the fuel input and the fuel output are arranged to flow a molten
chloride nuclear fuel salt through the reactor core section. The molten chloride nuclear fuel salt includes a mixture of
UCl4 and at least one of an additional uranium chloride salt or an additional metal chloride salt that has a UCl 4 content
10 greater than 5 % by molar fraction. In the nuclear reactor the uranium concentration in the mixture of UCl4 and at least
one additional metal chloride salt may be greater than 61 % by weight. The additional uranium chloride salt may be
UCl3. The mixture may have a composition of 82UCl4-18UCl3, 17UCl3-71UCl4-12NaCl, or 50 UCl4-50NaCl. The additional
metal chloride may include at least one of NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4,
AmCl3, LaCl3, CeCl3, PrCl3, or NdCl3. The mixture may have an additional metal chloride salt concentration at or below
15 the precipitation concentration for the additional metal chloride salt and/or may have a melting temperature below a
temperature of 800 degrees Celsius. The mixture may also have a melting temperature above a temperature of 330
degrees Celsius. Breed-and-burn behavior may be established within the molten chloride nuclear fuel salt with a uranium-
plutonium cycle. The chloride in the molten chloride nuclear fuel may be modified so that the molten chloride fuel salt
has a first ratio of 37Cl to total Cl in the molten chloride fuel salt that, when used in the nuclear reactor, achieves a target
20 effective neutron multiplication factor, in which the first ratio is different than the naturally occurring ratio of 37Cl to total Cl.
[0021] In part, this disclosure also describes a method of fueling a fast spectrum molten salt nuclear reactor. The
method includes: providing a volume of UCl4; providing a volume of at least one of an additional uranium chloride salt
or an additional metal chloride salt; mixing the volume of UCl4 with the volume of the at least one of an additional uranium
chloride salt or an additional metal chloride salt to form a molten chloride nuclear fuel salt having a UCl4 content greater
25 than 5 % by molar fraction; and supplying the molten chloride nuclear fuel salt having a UCl4 content greater than 5 %
by molar fraction to at least a reactor core section of the fast spectrum molten salt nuclear reactor. The additional uranium
chloride salt may include a volume of UCl3. The method may further include providing a volume of at least one of NaCl,
MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, -AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3, or NdCl3. The
mixing operation of the method may also include mixing the volume of UCl4 with the volume of the at least one of an
30 additional uranium chloride salt or an additional metal chloride salt to form a molten chloride nuclear fuel salt having a
UCl4 content greater than 5 % by molar fraction and a melting temperature from 330-800 °C. The mixing operation may
include forming a molten chloride nuclear fuel salt having a composition of 82UCl4-18UCl3, 17UCl3-71UCl4- 12NaCl, or
50 UCl4-50NaCl. The mixing operation may also include mixing the volume of UCl4 with the volume of the at least one
of an additional uranium chloride salt or an additional metal chloride salt inside of the fast spectrum molten salt nuclear
35 reactor and/or mixing the volume of UCl4 with the volume of the at least one of an additional uranium chloride salt or an
additional metal chloride salt outside of the fast spectrum molten salt nuclear reactor. The method may include controlling
a first ratio of 37Cl to total Cl in the molten chloride nuclear fuel salt that, when used in the nuclear reactor, achieves a
target effective neutron multiplication factor, the first ratio being different than the naturally occurring ratio of 37Cl to total
Cl. Molten chloride fuel salts for use in a fast spectrum molten salt nuclear reactor having a UCl4 content greater than
40 5 % by molar fraction prepared by the method described above are also described.
[0022] In part, this disclosure also describes a UCl3F fuel salt manufacturing process. The method includes: preparing
a first amount of UCl4; preparing a second amount of UF4; combining three parts UCl4 with one part UF4; and mixing
the combined UCl4 and UF4 for a period of time to obtain UCl3F. The mixing may further include mixing the combined
UCl4 and UF4 in one or more of a ball mill, rod mill, autogenous mill, SAG mill, pebble mill, roll grinder, and stamp mill.
45 The mixing may include mixing the combined UCl4 and UF4 in an inert gas environment. The UCl4 and UF4 may be
combined and mixed while in a solid state or while in a liquid state.
[0023] In part, this disclosure also describes another UCl3F manufacturing method. That method includes: providing
a mixture of UO2, NH4HF2 and NH 4Cl; exposing the mixture to HCl under conditions sufficient to create at least some
(NH4)2UCl5F; and heating the (NH4)2UCl5F to a temperature and for a period of time sufficient to convert at least some
50 of the (NH4)2UCl5F into UCl3F. In the method, exposing the mixture to HCl may include heating the mixture in the
presence of HCl to a temperature and for a period of time sufficient to create at least some (NH4)2UCl5F such as heating
the mixture in the presence of HCl to 100 °C for at least one hour. The method may include heating the (NH4)2UCl5F to
200-500 °C, or to 250-350 °C. The heating may include heating the (NH4)2UCl5F to a temperature above 200 °C but
below a temperature that melts the (NH4)2UCl5F or UCl4. In the method, exposing the mixture to HCl may include
55 contacting anhydrous CaCl2 with aqueous HCl under conditions sufficient to create HCl gas and may further include
placing pellets of anhydrous CaCl2 in aqueous HCl in a reactor, the reactor also containing the mixture and heating the
reactor to 100 °C for at least one hour. In the method, one or more of the HCl or the NH4Cl have a ratio of 37Cl to total
Cl of greater than 25 %.
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EP 3 241 218 B1
[0024] In part, this disclosure also describes various techniques for reducing corrosion from the salt fuels. A method
of reducing corrosion in a nuclear reactor is disclosed in which a nuclear fuel in the form of a salt having a first anion
and a fissionable cation is used. The method includes: identifying a material in the nuclear reactor that is in contact with
the molten salt; determining, based on the identified material, at least one material cation in the material; and including
5 in the nuclear fuel a corrosion inhibiting salt consisting of the first anion and the material cation. In the method, the
maximum amount of the corrosion inhibiting salt in the nuclear fuel that can be solubilized may be included. For example,
the material may be a molybdenum alloy and the material cation may be molybdenum. Alternatively, the material may
be a nickel alloy and the material cation may be nickel and/or the material may be an iron alloy and the material cation
may be iron. Likewise, the material may be a chromium alloy and the material cation may be chromium. In the method,
10 the first anion may be selected from Cl, F, and combinations thereof.
[0025] In part, this disclosure also describes fuel monitoring techniques. For example, a method of operating a molten
salt nuclear reactor is disclosed that includes: maintaining breed-and-burn behavior in molten salt in a reactor core of
the nuclear reactor; analyzing at least some molten salt using a speciation method to determine at least one concentration
of a molecule in the molten salt; and adjusting an operational parameter of the nuclear reactor based on the determined
15 at least one concentration. In the method, the analyzing may include analyzing the at least some molten salt using one
or more of Raman spectroscopy, absorbance spectroscopy, laser ablation spectroscopy, laser induced breakdown
spectroscopy, IR spectroscopy, and electrochemistry. The method further includes monitoring using a Raman probe
and the Raman probe may be located inside of or outside of the reactor core. The analyzing may further include: removing
the at least some molten salt from the reactor core; analyzing the at least some molten salt; and after analyzing, returning
20 the at least some molten salt to the reactor core. The operation parameter may be selected from one or more of a
temperature, a fuel salt replacement rate, a position of a displacement element, a reactivity of the fuel salt, and a feed
rate of an additive to the reactor core.
[0026] In part, this disclosure also describes techniques for using freeze plugs in molten salt nuclear reactors. The
disclosure describes a fast spectrum molten salt nuclear reactor that includes: a reactor core section adapted to contain
25 a nuclear fuel salt at a first temperature above a melting point of the nuclear fuel salt; an access port allowing access
to the reactor core; and a freeze plug in the access port preventing flow through the access port. The freeze plug is
made of a material that is solid, nonreactive with the nuclear fuel salt at the first temperature and the material further
has a melting point at a second temperature above the first temperature. A neutron poison supply may be connected to
the reactor core via the access port such that, when the freeze plug material melts, at least some of the neutron poison
30 flows through the access port into the reactor core section. The neutron poison supply may be located above the reactor
core section so that, upon melting of the freeze plug, neutron poison flows under gravity into the reactor core section.
A dump tank may be connected to the reactor core via the access port such that, upon melting of the freeze plug, molten
fuel salt flows into the dump tank. The dump tank may be located beneath the reactor core section so that, upon melting
of the freeze plug, molten fuel salt flows under gravity into dump tank. The nuclear fuel salt in the reactor core section
35 may be maintained at a first pressure and the dump tank maintained at a second pressure less than the first pressure
so that, upon melting of the freeze plug, molten fuel salt flows under pressure into the dump tank.
[0027] This disclosure also describes use of an actively-maintained freeze plug in a molten salt nuclear reactor. A fast
spectrum molten salt nuclear reactor is described having: a reactor core section adapted to contain a nuclear fuel salt
at a first temperature above a melting point of the nuclear fuel salt; an access port allowing access to the reactor core;
40 a safety material in the access port having a melting point from the first temperature and a second temperature less
than the first temperature; and a cooling component adapted to maintain the safety material in a solid form at the second
temperature, thereby preventing flow through the access port. The cooling component may be an active component that
requires power from a power supply to maintain the temperature of the safety material at the second temperature. The
reactor may include a controller that disconnects the power to the cooling component based on an analysis of the
45 temperature of the nuclear fuel salt or detection of some fault condition. A neutron poison supply may be connected to
the reactor core via the access port such that, upon melting of the safety material, neutron poison flows into the reactor
core section. The neutron poison supply may be located above the reactor core section so that, upon melting of the
safety material, neutron poison flows under gravity into the reactor core section.
[0028] In part, this disclosure also describes anti-proliferation techniques for use with fuel salts. A method of operating
50 a molten salt nuclear reactor is disclosed that includes: charging a reactor core section of the molten salt nuclear reactor
with an amount of nuclear fuel salt in a first activity per unit mass less than a threshold amount; prior to initiating a nuclear
reaction in the nuclear fuel salt, adding at least one radioactive isotope to the nuclear fuel salt so that the activity per
unit mass of the resulting mixture is equal to or greater than a predetermined threshold. The threshold may be 100
rads/hour at one meter or more, 500 rads/hour at one meter or more, or 1000 rads/hour at one meter or more. The
55 radioactive compound may include one or more of caesium-137 or iodine-121. In an alternative comparative example,
the selected lanthanide or lanthanides may be mixed with the molten fuel salt 108 in such proportions to achieve a
threshold FOM that is equal to or less than 1.0. More stringent FOM thresholds of less than 0.99, 0.98, 0.97, 0.96 or
0.95 may be selected and lanthanides or other ingredients altering the bare critical mass, M, the heat content, h, and
7
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the dose, D, factors of the FOM equation to achieve the desired threshold may be added. In some comparative examples,
an FOM threshold of less than 0.95 may be desired such as less than 0.9 or 0.8.
[0029] This disclosure also describes a fast spectrum molten salt nuclear reactor that includes: a reactor core section
including a fuel input and a fuel output, in which the fuel input and the fuel output are arranged to flow a mixture of molten
5 nuclear fuel salt and at least one lanthanide through the reactor core section at start-up of the fast spectrum molten salt
nuclear reactor. The at least one lanthanide may include one or more of La, Ce, Pr, or Nd. The mixture may be formed
by mixing the molten nuclear fuel salt with at least one lanthanide chloride. The at least one lanthanide chloride may
include at least one of LaCl3, CeCl3, PrCl3, or NdCl3. The mixture of molten nuclear fuel salt and at least one lanthanide
may have a lanthanide concentration from 0.1 to 10 % by weight, or from 4 to 8 % by weight. The mixture of molten
10 nuclear fuel salt and the at least one lanthanide may be formed outside of the fast spectrum molten salt nuclear reactor
or inside of the fast spectrum molten salt nuclear reactor. The fuel input and the fuel output may be arranged to flow a
mixture of molten nuclear fuel salt and at least one lanthanide through the reactor core section prior to achieving a
selected reactivity threshold in the fast spectrum molten salt nuclear reactor. The fuel input and the fuel output may be
arranged to flow a mixture of molten nuclear fuel salt and at least one lanthanide through the reactor core section prior
15 to achieving criticality in the fast spectrum molten salt nuclear reactor. The fuel input and the fuel output may be arranged
to flow a mixture of molten nuclear fuel salt and at least one lanthanide through the reactor core section prior to generation
of a selected amount of plutonium in the fast spectrum molten salt nuclear reactor. The molten nuclear fuel salt may be
a mixture of at least two of a first uranium chloride, a second uranium chloride or an additional metal chloride. The
additional metal chloride may include at least one of NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4,
20 AcCl3, NpCl4, or AmCl3. At least one of the first uranium chloride or the second uranium chloride may include UCl4, UCl3
or both UCl4 and UCl3. Specific fuel salt compositions are discussed including 82UCl4-18UCl3, 17UCl3-71UCl4-12NaCl,
50 UCl4-50NaCl, and 34 UCl3-66NaCl. The mixture of at least a first uranium chloride, a second uranium chloride and
an additional metal chloride includes at least 5 % by molar fraction UCl4. The mixture of at least a first uranium chloride,
a second uranium chloride and an additional metal chloride may have a uranium concentration of greater than 61 % by
25 weight and, independently, may have a melting point from 330-800 degrees Celsius.
[0030] This disclosure also describes a method of fueling a fast spectrum molten salt nuclear reactor that includes:
providing a molten nuclear fuel salt; providing at least one lanthanide; prior to start-up of the fast spectrum molten salt
nuclear reactor, mixing the molten nuclear fuel salt with the at least one lanthanide to form a lanthanide-loaded molten
nuclear fuel salt; and supplying the lanthanide-loaded molten nuclear fuel salt to at least a reactor core section of the
30 fast spectrum molten salt nuclear reactor. Providing a molten nuclear fuel salt may include providing a mixture of nuclear
reactor. Providing a molten nuclear fuel salt may include providing a mixture of at least two of a first uranium chloride,
an additional uranium chloride and an additional metal chloride or providing a mixture of at least two of UCl4, UCl3 and
an additional metal chloride. The additional metal chloride may be at least one of NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2,
VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, or AmCl3. The molten nuclear fuel salt may have at least 5 % by molar fraction
35 UCl4 and/or may have a uranium concentration of greater than 61 % by weight. The molten nuclear fuel salt may have
a melting point from 330 and 800 degrees Celsius. Providing at least one lanthanide may include: providing at least one
of La, Ce, Pr, or Nd; providing at least one lanthanide in the form of a lanthanide chloride; and/or providing at least one
of LaCl3, CeCl3, PrCl3 or NdCl3. Mixing the lanthanide-loaded molten nuclear fuel salt may include: mixing the molten
nuclear fuel salt with the at least one lanthanide to form a lanthanide-loaded molten nuclear fuel salt having a lanthanide
40 concentration from 0.1 to 10 % by weight or from 4 to 8 % by weight. The method may further include mixing the molten
nuclear fuel salt with the at least one lanthanide inside or outside of the fast spectrum molten salt nuclear reactor. The
method may further include, prior to achieving a selected reactivity threshold in the fast spectrum molten salt nuclear
reactor, mixing the molten nuclear fuel salt with the at least one lanthanide to form a lanthanide-loaded molten nuclear
fuel salt. The method may further include, prior to achieving criticality in the fast spectrum molten salt nuclear reactor,
45 mixing the molten nuclear fuel salt with the at least one lanthanide to form a lanthanide-loaded molten nuclear fuel salt.
The method may further include, prior to generation of a selected amount of plutonium in the fast spectrum molten salt
nuclear reactor, mixing the molten nuclear fuel salt with the at least one lanthanide to form a lanthanide-loaded molten
nuclear fuel salt. This disclosure further describes a molten fuel salt for use in a fast spectrum molten salt nuclear reactor
prepared by the method described above.
50 [0031] This disclosure also describes a method of polishing irradiated fuel salt containing gaseous and solid fission
products from a molten salt reactor. The method includes:
transferring at least some irradiated fuel salt from the molten salt reactor to a drain tank; contacting fuel salt obtained
from the drain tank with a carrier gas, thereby creating a carrier/fission product gas mixture and a degassed fuel
55 salt having a reduced degassed fuel salt, thereby removing fission product solids, to obtain a filtered fuel salt;
transferring the filtered fuel salt to the drain tank; collecting gaseous UCl4 during the filtering operation; condensing
the gaseous UCl4 into fuel salt obtained from the drain tank to create a high concentration UCl4 fuel salt; transferring
the high concentration UCl4 fuel salt to the drain tank; and transferring at least some now polished fuel salt from the
8
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drain tank to the reactor core. The method can be done continuously or as a series of batch operations. The various
operations may themselves be performed as continuous or batch operations in any order. The method may include
recovering the carrier gas, which may be helium, from the carrier/fission product gas mixture. This may further
include passing the carrier/fission product gas mixture through one or more vessels containing activated carbon.
5 The method may also or alternatively include holding the carrier/fission product gas mixture for a period of time until
a concentration of a selected gaseous fission product, such as 135Xe, falls to below a predetermined threshold.
[0032] These and various other features as well as advantages which characterize the systems and methods described
herein will be apparent from a reading of the following detailed description and a review of the associated drawings.
10 Additional features are set forth in the description which follows, and in part will be apparent from the description, or
may be learned by practice of the technology. The benefits and features of the technology will be realized and attained
by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
[0033] It is to be understood that both the foregoing general description and the following detailed description are
explanatory and are intended to provide further explanation of the invention as claimed.
15
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] The following drawing figures, which form a part of this application, are illustrative of described technology and
are not meant to limit the scope of the invention as claimed in any manner, which scope shall be based on the claims
20 appended hereto.
FIGS. 1A-1G generally describe novel comparative examples of a molten salt nuclear reactor for operating in a fast
spectrum breed-and-burn mode.
FIG. 2 describes a different configuration of a molten salt nuclear reactor.
25 FIG. 3 illustrates an comparative example of a method for creating a fuel tailored to a specific reactor.
FIG. 4 illustrates a ternary phase diagram calculated for UCl3-UCl4-NaCl fuel salts.
FIG. 5 illustrates keff modeled as a function of time for a larger reactor core section of the reactor illustrated in FIGS
1A-1F utilizing the 66NaCl-34UCl3 composition.
FIG. 6 illustrates a process flow representing example operations related to fueling a fast spectrum molten salt
30 nuclear reactor, in accordance with one or more comparative examples of the present disclosure.
FIG. 7 illustrates the (n,γ) capture cross section for the main Cl and Br isotopes.
FIG. 8 illustrates the modelling results for a breed-and-burn curve of the bromide fuel salt comparative example of
17UBr3-71UBr4-12NaBr and 19.99 % 235U enrichment.
FIG. 9 illustrates an comparative example a method of manufacturing a fuel salt containing UCl4.
35 FIG. 10 illustrates an comparative example of a coordinated method of manufacturing a fuel salt containing UCl4
based on the method of FIG. 9.
FIG. 11 illustrates a schematic of the contacting vessels and their connections suitable for use in performing the
method of FIG. 10.
FIG. 12 illustrates an comparative example of a method of reducing corrosion in a nuclear reactor using a molten
40 nuclear fuel.
FIG. 13 lists some alloys of potential applicability as fuel salt-facing materials in a molten salt nuclear reactor.
FIG. 14 illustrates a method of operating a molten salt nuclear reactor.
FIG. 15 illustrates an comparative example of a method for creating a fuel salt that has reduced weapons applications
by the addition of one or more radioactive isotopes.
45 FIG. 16 illustrates an comparative example of a method for the manufacture of UCl4 using ammonium chloride. In
the comparative example of the method 1600 shown, a mixture of solid UO2 and NH4Cl is created in a uranium
preparation operation 1602.
FIG. 17 illustrates an comparative example of method for manufacturing UCl3F.
FIG. 18 illustrates an comparative example of another method for manufacturing UCl3F.
50 FIG. 19 illustrates an comparative example of a polishing system for fuel polishing that utilizes a drain tank.
FIG. 20 illustrates an comparative example of an off gas treatment system suitable for use in treating gaseous fission
products produced by a molten salt reactor, for example as the off gas treatment system 1922 in FIG. 19.
FIG. 21 illustrates an comparative example of a method for polishing fuel salt based on the systems described in
FIGS. 19 and 20.
55
DETAILED DESCRIPTION
[0035] This disclosure describes embodiments of nuclear fuel salts usable in certain molten salt reactor designs and
9
EP 3 241 218 B1
related systems and methods. Binary, ternary and quaternary chloride fuel salts of uranium, as well as other fissionable
elements, are described. In addition, fuel salts of UClxFy are disclosed as well as bromide fuel salts. This disclosure also
presents methods and systems for manufacturing such fuel salts, for creating salts that reduce corrosion of the reactor
components and for creating fuel salts that are not suitable for weapons applications.
5 [0036] The present disclosure is directed to a fast spectrum molten salt breed-and-burn nuclear reactor fuel and
methods of fuel fabrication, management and use.
[0037] Much of the historical and current research related to molten salt nuclear fission reactors focused on uranium-
and thorium-based fluorine salts. The molten chlorides differ significantly from the fluoride based salts due to a couple
of key aspects. First, chlorides can be somewhat less moderating than the fluorides, particularly if the chlorides are
10 enriched with the 37Cl isotope. Second, the chlorides offer the possibility of very high heavy metal concentrations in
mixtures with reasonable melting points. This is an aspect which allows for the utilization of the uranium chlorine salt
mixtures in a fast neutron spectrum. Fluoride salts typically contain no more than 10-12 mol % heavy metal. Historically
proposed fluorine salt mixtures typically contained molar concentrations of 63-72 mol % LiF (enriched to 99.997 % 7Li),
16-25 mol % BeF2, 6.7-11.7 mol % ThF4, and only 0.3 mol % UF4 (heavy metal is 40-45 %, by weight). Such salts melted
15 at 500 °C. By contrast, one comparative example of a chloride salt proposed here has a composition of 17UCl3-71UCl4-
12NaCl (62 %, by weight, heavy metal), and it also melts at 500 °C, as discussed in greater detail below.
[0038] Some fuel embodiments and comparative examples of the present disclosure may provide for equilibrium or
quasi-equilibrium breed-and-burn behavior, while other embodiments and comparative examples provide for non-equi-
librium breed-and-burn behavior without reprocessing of the fuel salt. This is notable because prior molten salt reactor
20 designs could not achieve equilibrium breed-and-burn behavior without chemical separation of the fuel salt in the reactor
necessitating ongoing chemical reprocessing of the fuel salt. For example, the present disclosure discloses, but is not
limited to, a molten chloride fuel salts suitable for use in a fast spectrum reactor displaying equilibrium, quasi-equilibrium
and/or non- equilibrium breed-and-burn behavior. In embodiments and comparative examples, little or no reprocessing,
may be required and what little reprocessing that may be used may be physical reprocessing only (e.g., physical separation
25 of byproducts such as by gas sparging and/or filtering). Various embodiments and comparative examples of the molten
fuel salt of the present disclosure may include mixtures of a first uranium chloride salt, a second uranium chloride salt
and/or additional metal chloride salts. Some embodiments and comparative examples of the present disclosure provide
for a molten fuel salt having a uranium tetrachloride (UCl4) content level above 5 % by molar fraction, which aids in
establishing a high heavy metal content in the molten fuel salt (e.g., above 61 % by weight) while maintaining operable
30 melting temperatures. Embodiments and comparative examples including UCl4 may be formed through a mixture of
UCl4 and uranium trichloride (UCl3) and/or and additional metal chloride (e.g., NaCl) such that desirable heavy metal
content levels and melting temperatures (e.g., 330-800 °C) are achieved.
[0039] Due to the high level of fissile content achievable through molten fuel salts of the present disclosure and the
ease of access to the molten fuel salt, it is desirable to provide non-proliferation measures with respect to the fuel(s) of
35 the present disclosure. Some comparative examples of the present disclosure provide a molten fuel salt that is pre-
loaded (i.e., loaded prior to start-up) with one or more selected lanthanides to increase the activity of the initial salt. In
addition, unless subsequently separated, the lanthanides will act as a neutron poison in the fuel and, thus, reduce the
desirability of the lanthanide-loaded fuel for weapons-grade purposes.
40 Molten Salt Reactors
[0040] Prior to discussing the fuel salt embodiments and comparative examples in greater detail, a brief discussion
of the general components of molten fuel salt reactors suitable for using the fuel salt embodiments will be helpful. FIGS.
1A-1F generally describe a novel comparative example of a molten salt nuclear reactor 100 for operating in a fast
45 spectrum breed-and-burn mode. FIG. 2 describes a different configuration of a molten salt nuclear reactor 200. These
are just examples to provide context for discussion of the fuel embodiments and comparative examples described herein
and the reader should understand that potentially any molten fuel nuclear reactor could be adapted to use the fuel
embodiments and comparative examples described below. While various fluoride salts may be utilized in molten salt
nuclear reactors as described below, fluoride- based fuel salts typically display heavy metal concentrations significantly
50 below that which may be achieved with chloride-based and chloride-fluoride-based fuel salts described in the present
disclosure.
[0041] FIG. 1A illustrates a simplified schematic view of a molten salt fast spectrum nuclear reactor 100, in accordance
with one or more comparative examples of the present disclosure. In one comparative example, the reactor 100 includes
a reactor core section 102. The reactor core section 102 (which may also be referred to as the "reactor vessel") includes
55 a fuel input 104 and a fuel output 106. The fuel input 104 and the fuel output 106 are arranged such that during operation
a flow of the molten fuel salt 108 is established through the reactor core section 102. For example, the fuel input 104
and/or the fuel output 106 may consist of conical sections acting as converging and diverging nozzles respectively. In
this regard, the molten fuel 108 is fluidically transported through the volume of the reactor core section 102 from the
10
EP 3 241 218 B1
input 104 to the output 106 of the reactor core section 102. Although FIG. 1A shows fluid fuel flow with arrows, it is to
be appreciated that the direction of flow may be modified as appropriate for different reactor and plant configurations.
Specifically, FIG. 1A shows fluid fuel 108 flow from the ’bottom’ to the ’top’ in the central core region, and alternative
apparatuses may create and/or maintain a fluid fuel 108 flow from the top towards the bottom in the central core region.
5 [0042] The reactor core section 108 may take on any shape suitable for establishing criticality within the molten fuel
salt 108 within the reactor core section 102. By way of non-limiting example, the reactor 100 may include, but is not
limited to, an elongated core section, as depicted in FIG. 1A. In addition, the reactor core section 108 may take on any
cross-sectional shape. By way of non-limiting example, the reactor core section 108 may have, but is not required to
have, a circular cross-section, an ellipsoidal cross-section or a polygonal cross-section.
10 [0043] The dimensions of the reactor core section 102 are selected such that criticality is achieved within the molten
fuel salt 108 when flowing through the reactor core section 102. Criticality refers to a state of operation in which the
nuclear fuel sustains a fission chain reaction, i.e., the rate of production of neutrons in the fuel is at least equal to rate
at which neutrons are consumed (or lost). For example, in the case of an elongated core section, the length and cross-
sectional area of the elongated core section may be selected in order to establish criticality within the reactor core section
15 102. It is noted that the specific dimensions necessary to establish criticality are at least a function of the type of fissile
material, fertile material and/or carrier salt contained within the reactor 100. Principles of molten fuel nuclear reactors
are described in U.S. Patent Application No. 12/118,118 to Leblanc, filed on May 9, 2008.
[0044] The reactor core section 102 is formed from any material suitable for use in molten salt nuclear reactors. For
example, the bulk portion of the reactor core section 102 may be formed, but is not required to be formed, from one or
20 more molybdenum alloy, one or more zirconium alloys (e.g., ZIRCALOY™), one or more niobium alloys, one or more
nickel alloys (e.g., HASTELLOY™ N) or high temperature ferritic, martensitic, or stainless steel and the like. It is further
noted that the internal surface may coated, plated or lined with one or more additional materials in order to provide
resistance to corrosion and/or radiation damage, as discussed in additional detail further herein.
[0045] In the comparative example shown, the reactor 100 includes a primary coolant system 110 that takes heat from
25 the reactor core 102 and transfers that heat to the secondary coolant 126 in the secondary coolant system 120 via the
heat exchanger 119. In the comparative example illustrated in FIG. 1A, the molten fuel salt 108 is used as the primary
coolant 118. Cooling is achieved by flowing molten fuel salt 108 heated by the ongoing chain reaction from the reactor
core 102, and flowing cooler molten fuel salt 108 into the reactor core 102, at the rate necessary to maintain the
temperature of the reactor core 102 within its operational range. In this comparative example, the primary coolant system
30 110 is adapted to maintain the molten fuel salt 108 in a subcritical condition when outside of the reactor core 102.
[0046] The primary coolant system 110 may include one or more primary coolant loops 112 formed from piping 114.
The primary coolant system 110 may include any primary coolant system arrangement known in the art suitable for
implementation in a molten fuel salt context. The primary coolant system 110 may circulate fuel 108 through one or more
pipes 114 and/or fluid transfer assemblies of the one or more primary coolant loops 112 in order to transfer heat generated
35 by the reactor core section 102 to downstream thermally driven electrical generation devices and systems. For purposes
of simplicity, a single primary coolant loop 112 is depicted in FIG. 1A. It is recognized herein, however, that the primary
coolant system 110 may include multiple parallel primary coolant loops (e.g., 2-5 parallel loops), each carrying a selected
portion of the molten fuel salt inventory through the primary coolant circuit.
[0047] In an alternative comparative example (an example of which is shown in FIGS. 1G and 2), the primary coolant
40 system 110 may be configured such that a primary coolant 118 (different than the molten fuel salt 108) enters the reactor
core section 108 (e.g., main vessel). In this comparative example, the fuel salt 108 does not leave the reactor core
section, or main vessel, but rather the primary coolant 118 is flowed into the reactor core 102 to maintain the temperature
of the core within the desired range. It is noted that in this comparative example the reactor 100 may include an additional
heat exchanger (not shown) in the reactor core section 102, or main vessel. In this comparative example, the secondary
45 coolant system 120 may be optional, the usable thermal power can be derived directly from the primary coolant system
110. In this comparative example, the primary coolant may be a chloride salt with a suitable melting point. For example,
the salt may be a mixture of sodium chloride and magnesium chloride.
[0048] In the comparative example shown in FIG. 1A, the primary coolant system 110 includes one or more pumps
116. For example, one or more pumps 116 may be fluidically coupled to the primary coolant system 110 such that the
50 one or more pumps 116 drive the primary coolant 118, in this case the molten fuel 108, through the primary coolant/reactor
core section circuit. The one or more pumps 116 may include any coolant/fuel pump known in the art. For example, the
one or more fluid pumps 116 may include, but are not limited to, one or more mechanical pumps fluidically coupled to
the primary coolant loop 112. By way of another example, the one or more fluid pumps 116 may include, but are not
limited to, one or more electromagnetic (EM) pumps fluidically coupled to the primary coolant loop 112.
55 [0049] FIG. 1A further illustrates that the reactor 100 includes a secondary coolant system 120 thermally coupled to
the primary coolant system 110 via one or more heat exchangers 119. The secondary coolant system 120 may include
one or more secondary coolant loops 122 formed from piping 124. The secondary coolant system 120 may include any
secondary coolant system arrangement known in the art suitable for implementation in a molten fuel salt context. The
11
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secondary coolant system 120 may circulate a secondary coolant 126 through one or more pipes 124 and/or fluid transfer
assemblies of the one or more secondary coolant loops 122 in order to transfer heat generated by the reactor core
section 102 and received via the primary heat exchanger 119 to downstream thermally driven electrical generation
devices and systems. For purposes of simplicity, a single secondary coolant loop 124 is depicted in FIG. 1A. It is
5 recognized herein, however, that the secondary coolant system 120 may include multiple parallel secondary coolant
loops (e.g., 2-5 parallel loops), each carrying a selected portion of the secondary coolant through the secondary coolant
circuit. It is noted that the secondary coolant may include any second coolant known in the art. By way of example, the
secondary coolant may include, but is not limited to, liquid sodium.
[0050] It is further noted that, while not depicted in FIG. 1A, the reactor 100 may include any number of additional or
10 intermediate heating/cooling systems and/or heat transfer circuits. Such additional heating/cooling systems may be
provided for various purposes in addition to maintaining the reactor core 102 within its operational temperature range.
For example, a tertiary heating system may be provided for the reactor core 102 and primary coolant system 110 to
allow a cold reactor containing solidified fuel salt to be heated to an operational temperature in which the salt is molten
and flowable.
15 [0051] Other ancillary components 127 may also be utilized, as illustrated, in the primary coolant loop 112. Such
ancillary components 127 may include one or more filters or drop out boxes for removing particulates that precipitate
from the primary coolant 118 during operation. To remove unwanted liquids from the primary coolant 118, the ancillary
components 127 may include any suitable liquid-liquid extraction system such as one or more co-current or counter-
current mixer/settler stages, an ion exchange technology, or a gas absorption system. For gas removal, the ancillary
20 components 127 may include any suitable gas-liquid extraction technology such as a flash vaporization chamber, dis-
tillation system, or a gas stripper. Some additional comparative examples of ancillary components 127 are discussed
in greater detail below.
[0052] It is noted herein that the utilization of various metal salts, such as metal chloride salts, in reactor 100 may
cause corrosion and/or radiation degradation over time. A variety of measures may be taken in order to mitigate the
25 impact of corrosion and/or radiation degradation on the integrity of the various salt-facing components (e.g., reactor core
section 102, primary coolant piping 114, heat exchanger 119 and the like) of the reactor 100 that come into direct or
indirect contact with the fuel salt or its radiation.
[0053] In one comparative example, the velocity of fuel flow through one or more components of the reactor 100 is
limited to a selected fuel salt velocity. For example, the one or more pumps 116 may drive the molten fuel 108 through
30 the primary coolant loop 112 of the reactor 100 at a selected fuel salt velocity. It is noted that in some instances a flow
velocity below a certain level may have a detrimental impact on reactor performance, including the breeding process
and reactor control. By way of non-limiting example, the total fuel salt inventory in the primary loop 112 (and other
portions of the primary coolant system 110) may exceed desirable levels in the case of lower velocity limits since the
cross-sectional area of the corresponding piping of the primary loop 112 scales upward as flow velocity is reduced in
35 order to maintain adequate volumetric flow through the primary loop 112. As such, very low velocity limits (e.g., 1m/s)
result in large out-of-core volumes of fuel salt and can negatively impact the breeding process of the reactor 100 and
reactor control. In addition, a flow velocity above a certain level may detrimentally impact reactor performance and
longevity due to erosion and/or corrosion of the internal surfaces of the primary loop 112 and/or reactor core section
102. As such, suitable operational fuel salt velocities may provide a balance between velocity limits required to minimize
40 erosion/corrosion and velocity limits required to manage out-of-core fuel salt inventory. For example, in the case of a
molten chloride fuel salt, the fuel salt velocity may be controlled from 2-20 m/s, such as, but not limited to, 7 m/s.
[0054] FIGS. 1B and 1C illustrate a simplified schematic view of a molten salt fast spectrum nuclear reactor 100 with
a protective layer 128 disposed on one or more internal surfaces of the reactor 100, in accordance with one or more
comparative examples of the present disclosure.
45 [0055] In one comparative example, the protective layer 128 is disposed on one or more surfaces of the reactor 100
facing the fuel salt 108 of the reactor 100. The protective layer 128 may provide resistance to corrosion and/or radiation
degradation of one or more reactor salt-facing surfaces of the reactor 100. For the purposes of the present disclosure,
a material resistant to corrosion and/or radiation degradation is interpreted as any material displaying resistance to
corrosion and/or radiation degradation superior to the underlying bare surface of the reactor 100.
50 [0056] The protective layer 128 may include any material known in the art suitable for providing an internal surface of
a reactor with corrosion and/or radiation resistance to a corresponding nuclear fuel salt. Thus, the material of the protective
layer 128 may vary depending on the salt 108 used. In one comparative example, the protective layer 128 includes one
or more refractory metals. For example, the protective layer 128 may include, but is not limited to, one or more of niobium,
molybdenum, tantalum, tungsten or rhenium. In another comparative example, the protective layer 128 includes one or
55 more refractory alloys. For example, the protective layer 128 may include, but is not limited to, one or more of a molyb-
denum alloy (e.g., titanium-zirconium-molybdenum (TZM) alloy), a tungsten alloy, tantalum, a niobium or a rhenium. In
another comparative example, the protective layer 128 includes one or more nickel alloys. In another comparative
example, the protective layer 128 includes a carbide, such as, but not limited to, silicon carbide.
12
EP 3 241 218 B1
[0057] In an comparative example, the protective layer 128 is formed by plating the internal surface of the one or more
portions (e.g., piping 114 or primary loop 112) of the reactor 100 with the selected protective material. In another
comparative example, the protective layer 128 includes one or more coatings of the selected protective material disposed
on the internal surface of one or more portions of the reactor 100. In yet another comparative example, the bulk material
5 of the various components may be formed with one or more of the protective materials described above. For instance,
the piping 114 of the primary coolant loop 112 may include, but is not limited to, TZM piping.
[0058] In one comparative example, as shown in FIG. 1B, the internal salt-facing surface of the reactor core section
102 includes a protective layer 128. For example, the vessel of the reactor core section 102 may be formed from steel
or a zirconium alloy, with refractory alloy or nickel alloy plating disposed on the internal salt-facing surface of the reactor
10 core section 102 to form the protective layer 128. For instance, the reactor core section 102 may include, but is not
limited to, a molybdenum-based protective layer 128 having a thickness from approximately 5-7 mm, with the vessel of
the reactor core section 102 having a wall thickness of approximately 9-11 cm thick.
[0059] Similarly, as shown in FIG. 1C, the salt-facing surface of the piping 114 of the primary coolant loop 112 (which
may be the internal and/or external surface of piping or other components) includes a protective layer 128. For example,
15 refractory alloy or nickel alloy plating may be disposed on the salt-facing surface of the piping 114 of the primary coolant
loop 112 to form the protective layer 128.
[0060] FIG. 1D illustrates a schematic view of a reflector assembly 130 of the reactor 100. The reflector assembly 130
is suitable for reflecting neutrons emanating from the reactor core section 102 back into the fuel salt 108. In one com-
parative example, the reflector assembly 130 is disposed at the external surface of the reactor core section 102 such
20 that the reflector assembly 130 surrounds at least a portion of the reactor core 102. In the comparative example shown,
the neutrons reflected back into the reactor core section 102 by the reflector assembly 130 may contribute to maintaining
criticality within the reactor core section 102 and/or the breeding of fissile fuels from fertile feed materials. By reducing
such losses of neutrons, the amount of fuel salt necessary for criticality, therefore, the size of the reactor core 102, may
be reduced. The reflector assembly 130 may be formed from any material known in the art suitable for neutron reflection.
25 For example, the reflector assembly may include, but is not limited to, one or more of zirconium, steel, iron, graphite,
beryllium, tungsten carbide, lead, lead-bismuth and like materials.
[0061] FIGS. 1E and 1F illustrate the reflector assembly 130 constructed with multiple reflector modules 132, in
accordance with one or more comparative examples of the present disclosure. It is noted that at some operating tem-
peratures of the nuclear reactor 100 of the present disclosure a variety of neutron reflecting materials will liquefy. For
30 example, lead and lead-bismuth are both materials that provide good neutron reflecting characteristics. However, lead
melts at approximately 327 °C, while lead-bismuth alloys commonly have melting temperatures below 200 °C. As noted
elsewhere in this application, the reactor 100 may operate in a temperature range from approximately 330 to 800 °C,
above the melting points associated with lead and lead-bismuth alloys. In one comparative example, the reactor modules
132 include a reflector container to contain a liquid-phase of the selected neutron reflecting material 133, as shown in
35 FIGS. 1E and 1F. The reactor modules 132 may be formed from any material known in the art and may be selected
based on consideration of any one or more design functions including temperature resistance, corrosion resistance,
non-reactivity with other components and/or the fuel, radiation resistance, structural support, weight, etc. In some cases,
one or more reflector containers may be formed of a material which is substantially neutronically translucent with the
reflector material inside the container, and/or one or more reflector containers may be formed of a material which is
40 refractory. For example, the reflector modules 132 (such as the reflector containers) may be formed from one or more
refractory alloys, one or more nickel alloys or one or more carbides, or graphite compounds. For instance, the material
used to form the reflector modules 132 and/or reflector containers may include, but are not limited to, any one or more
components or combinations of one or more molybdenum alloys (e.g., TZM alloy), one or more tungsten alloys, one or
more tantalum alloys, one or more niobium alloys, one or more rhenium alloys, one or more nickel alloys, silicon carbide,
45 or graphite compounds, and the like. The reflector module may include (either contain or be formed from) one or more
moderating compounds that can exist at the operating temperatures (e.g., graphite and/or lead) and may consider
balancing a stronger moderator (e.g., graphite) and a weaker moderating material (e.g., lead) and may be used to
determine the overall reflector neutron spectrum.
[0062] In one comparative example, the reflector modules 132 are positioned at the external surface of the reactor
50 core section 102 and distributed across the external surface of the reactor core section 102. As shown in the examples
of FIGS. 1E and 1F, the reflector modules 132 are arranged azimuthally across the external surface of the reactor core
section 102. Each reflector module 132 contains a volume of neutron reflecting liquid (e.g., lead, lead-bismuth or the
like). In this regard, the discrete reflector modules 132 may be arranged to form a contiguous volume of neutron reflecting
liquid 133 of the reactor core section 102. While FIGS. 1E and 1F depict an azimuthal arrangement of reflector modules
55 132, such a configuration should not be interpreted as limiting. It is noted herein that any geometrical arrangement and
number of reflector modules 132 is suitable for implementation within the context of reactor 100 of the present disclosure.
For example, although not shown, the set of reflector modules 132 may take on a stacked-ring configuration, with each
module being a ring filled with the selected neutron reflecting liquid. In this regard, set of modules 132 may be stacked
13
EP 3 241 218 B1
so as to form a neutron reflecting volume about the core section 102. The volume may be spherically shaped, cylindrically
shaped, may be a rectangular-, hexagonal-, octagonal-, triangular-, pentagonal-, or other prism or otherwise be a volume
of any cross-sectional shape. In a comparative example, the reflector will utilize a 12.7-mm-thick (1/2"-thick) HASTEL-
LOY™-N or SiC plating on all exterior surfaces and the inner vessel will have a thickness of 2cm of the same plating
5 material. It is to be appreciated that the shape of the reflector modules may be formed as appropriate for the core design
and may include any appropriate shape including trapezoidal, rectangular, hexagonal, circular, ellipsoidal, and may even
include irregular shapes.
[0063] FIG. 1G illustrates a comparative example of a nuclear power plant for generating power from a nuclear reaction
using a molten chloride fast reactor (MCFR). For a power plant application, the heat generated by the MCFR will be
10 converted into electrical power by power conversion hardware. In the comparative example shown, Rankine cycle power
conversion hardware was used with water (steam) as the working fluid. The conversion efficiency of a Rankine cycle
plant is in large part determined by the temperature (and pressure) of the steam entering the turbines, where higher
temperatures correlate to higher efficiency. Performance is coupled to steam pressure as well as temperature and the
highest efficiency Rankine cycle plants use supercritical and ultrasupercritical steam.
15 [0064] The power conversion system encompasses all systems that come into contact with the power conversion
system working fluid. In the case of a steam Rankine cycle plant as illustrated, this includes a steam generator 152, a
turbine system 154, water circulation loop 162 including one or more water circulation pumps 156 and a cooling tower
158, electrical generation equipment 160 and a control system 162. In addition, a fuel storage system 166 for storing
new fuel salt and a reaction product storage system 168 to receive and safely contain used fuel salt are illustrated. As
20 illustrated in FIG. 1G, the power conversion system starts with a primary coolant transferring heat to the power cycle
working fluid through a heat exchanger (e.g. steam generator 152). A modelling of the system included simplified models
of the primary coolant salt loop 114, and steam generator 152, with more detailed treatment of the Rankine cycle system
components. Although a Rankine cycle steam turbine was used for modelling purposes, heat engines based on other
cycles are also feasible such as closed-cycle gas turbines (e.g., air, helium, or CO2) based on the Brayton cycle.
25 [0065] Inputs to the power conversion system used in the modelling come from primary coolant heat transfer fluid
mass flow rate, supply and return temperatures and pressures. The power cycle cost and performance are evaluated
for different rated thermal power output levels of 600 MW, 1200 MW, 1800 MW, 2400 MW, and 3000 MW. For the
baseline reactor design conditions, the primary coolant salt temperature is delivered to the steam generator 152 at 612
°C and is returned from the steam generator 152 at 498 °C. The analysis included modelling operation with 580 °C, 300
30 bar main steam conditions and 600 °C, 70 bar reheat steam conditions, although higher and lower temperature and
pressure operation may affect cost and performance.
[0066] The analysis use Thermoflow, Inc. software packages STEAMPRO™ and THERMOFLEX™ to provide cost
and performance data for the power cycle for steady state operation. The analysis used standard thermodynamic models
for turbine system 154 components, coupled with proprietary models for specific components in the power cycle. A large
35 body of water, like a river or lake, is assumed to be available for heat rejection (i.e. no cooling towers were modeled),
although a cooling tower 158 could be utilized as illustrated in FIG. 1G for heat rejection. Thermodynamic efficiencies
and component parameters are kept at the default values determined by STEAMPRO™ and THERMOFLEX™ sub-
models. For the modelling, a fuel salt of 17 % UCl3-71 % UCl4-12 % NaCl and primary coolant of 58 % NaCl-42 % MgCl2
were used. Fuel salt properties have been added to THERMOFLEX™ as lookup tables based on data curve fits. The
40 data used are shown in Table land Table 2 for fuel salt and primary coolant salt, below.
Table 1 - Fuel salt properties used in THERMOFLEX™ calculations

Temperature Density Specific Heat Thermal Cond. Dynamic Vise. Vapor Pressure
45 °C kg/m 3 kJ/kg-C W/m-C kg/m-s bar

1 400 4189 0.5732 0.972 0.0171 0
2 450 4077 0.5515 1.081 0.0117 0
3 500 3965 0.5297 1.19 0.00817 0
50
4 550 3853 0.5079 1.299 0.00585 0
5 600 3741 0.4861 1.409 0.00427 0
6 650 3629 0.4644 1.518 0.00317 0
55 7 700 3517 0.4426 1.627 0.00239 0

8 750 3406 0.4208 1.736 0.00183 0
9 800 3294 0.399 1.845 0.00142 0
14
EP 3 241 218 B1
(continued)
10 850 3182 0.3773 1.954 0.00111 0
5
11 900 3070 0.3555 2.064 8.83E-04 0
12 950 2958.3 0.3337 2.173 7.07E-04 0
13 1000 2846.5 0.3119 2.282 5.71E-04 0
10 14 1050 2734.6 0.2902 2.391 4.65E-04 0
15 1100 2622.8 0.2684 2.5 3.81E-04 0
16 1150 2511 0.2466 2.609 3.15E-04 0
17 1200 2399.1 0.2248 2.719 2.62E-04 0
15
18 1250 2287.3 0.2031 2.828 2.19E-04 0
19 1300 2175.5 0.1813 2.937 1.85E-04 0
20 1350 2063.6 0.1595 3.046 1.56E-04 0
20 21 1400 1951.8 0.1377 3.155 1.33E-04 0
22 1450 1840 0.116 3.264 1.14E-04 0
23 1500 1728.1 0.0942 3.374 9.74E-05 0
24 1550 1616.3 0.0724 3.483 8.40E-05 0
25
25 1600 1504.5 0.0506 3.592 7.27E-05 0
26 1650 1392.6 0.0289 3.701 6.32E-05 0
27 1700 1280.8 0.00709 3.81 5.51E-05 0
30
Table 2 - Primary coolant salt properties used in THERMOFLEX™ calculations

35 °C kg/m 3 kJ/kg-C W/m-C kg/m-s bar
1 444.8 1785 1.128 1.555 0.0023 0
2 498.6 1759 1.114 1.672 0.00201 0
3 552.2 1734 1.1 1.789 0.00176 0
40
4 606 1708 1.086 1.906 0.00154 0
5 659.6 1683 1.072 2.022 0.00134 0
6 713.2 1658 1.058 2.139 0.00118 0
45 7 766.8 1632 1.044 2.255 0.00103 0
8 820.8 1607 1.03 2.372 8.98E-04 0
9 873.8 1581 1.016 2.487 7.87E-04 0
10 927.8 1556 1.002 2.604 6.87E-04 0
50
11 981.8 1530 0.9874 2.721 6.01E-04 0
12 1035.8 1505 0.9732 2.838 5.25E-04 0
13 1088.8 1479 0.9593 2.952 4.60E-04 0
55 14 1142.8 1454 0.9452 3.069 4.02E-04 0
15 1196.8 1428 0.931 3.186 3.51E-04 0
15
EP 3 241 218 B1
(continued)
°C kg/m 3 kJ/kg-C W/m-C kg/m-s bar
5
16 1249.8 1403 0.9171 3.3 3.07E-04 0
17 1303.8 1378 0.9029 3.416 2.69E-04 0
18 1357.8 1352 0.8887 3.532 2.35E-04 0
10 19 1410.8 1327 0.8748 3.647 2.06E-04 0
20 1464.8 1301 0.8607 3.763 1.80E-04 0
[0067] The power conversion system receives thermal power from the reactor 100 and converts that heat into me-
15 chanical and then electrical power. The analysis specifically focused on using conventional steam Rankine cycle hardware
for power conversion. The analyzed configuration has three-turbines, with a high pressure turbine (HPT), intermediate
pressure turbine (IPT), and low pressure turbine (LPT), illustrated simply as the turbine system 154. FIG. 1G shows a
simplified cycle diagram for the 2400 MWth Rankine cycle analysis. The model in FIG. 1G is simplified in that it shows
only the major components of the power plant. In the model used, the HPT receives steam from the "main steam"
20 generation system that is heated by the primary cooling fluid carrying thermal energy from the reactor. Exhaust from
HPT is sent to the reheat steam generation system, where the primary cooling fluid transfers heat to the exhaust from
the HPT, and that heated steam is fed to the IPT. The exhaust from the IPT is fed directly to the LPT to extract additional
enthalpy. There are often multiple turbines in parallel, particularly for the LPT. In the model used, there are twin LPTs
that are used for the final expansion step. In the model, all turbines are on a common shaft and direct coupled to an
25 electrical generator 160. The outlet of the LPT flows to a condenser that cools the steam to near ambient temperature.
For this analysis, the LPT is assumed to be a once-through condenser that receives heat from a large body of water,
like a large lake or river. After the condenser, the water is pumped and sent through several feedwater heaters. The
feedwater heaters preheat the feedwater by mixing with steam extracted from various points on the turbines. The
preheated fluid from the feedwater heaters is then fed to the steam generator, where it is heated to temperature for the
30 main turbine.
[0068] The analysis process involves using STEAMPRO™ to specify the characteristics of the Rankine cycle system,
and then exporting that model to Thermoflex to investigate the interactions with the molten salt loops. STEAMPRO™ is
a purpose-built tool for configuring steam turbine components, while Thermoflex is considered a "fully-flexible" design
tool with more features and options. In STEAMPRO™, the plant is defined as having a "Black-box steam generator"
35 and "once-through open-loop water cooling." The steam cycle is defined as single-reheat condensing supercritical cycle
with an electric motor driven boiler feed pump. All turbines are specified to operate at 3600 RPM. The turbine group
characteristics, feedwater heaters, and pumps are determined by STEAMPRO’s default parameters and selection meth-
od. The cycle is then computed and exported to Thermoflex. STEAMPRO™ gives a detailed component layout of the
Rankine cycle plant selected for efficient operation at rated conditions.
40 [0069] In THERMOFLEX™, the black-box steam generator is replaced with molten-salt-to-steam heat exchangers for
the main and reheat steam generators. Simplified fuel salt and primary coolant salt loops are included in the model. The
fuel and primary coolant salt loops are included to provide the energy source and are not modeled in detail.
The modelling approach in THERMOFLEX™ is to specify outlet conditions of heat exchangers in the salt and steam
loops, and then adjust the steam flow rate to that the heat input into the fuel salt matches the rated conditions. Although
45 the component layout and performance characteristics of the plant was determined by STEAMPRO™, THERMOFLEX™
will further tune (resize) components (e.g. turbines, pumps, and heat exchangers) to achieve good performance for the
working fluid conditions. The heat input into the fuel salt loop represents the thermal power of the reactor. The gross
efficiency is the turbine shaft power output relative to the thermal power input. Net power is generator output power
subtracting pumping and auxiliary losses relative to thermal power input.
50 [0070] Table 3 below shows the performance and cost results for the supercritical Rankine cycle operated with thermal
power input of 600 MW, 1200 MW, 1800 MW, 2400 MW, and 3000 MW.
Table 3 - Performance and overall Thermoflex cost results for supercritical Rankine operation at thermal power levels
from 600MW to 3000MW
55 Heat input MW 600.0 1200.0 1800.0 2400.0 3000.1
Net power MW 276.1 560.9 845.5 1130.3 1415.2
16
EP 3 241 218 B1
(continued)
Heat input MW 600.0 1200.0 1800.0 2400.0 3000.1

Net electrical efficiency % 46.0 46.7 47.0 47.1 47.2
5
Fuel salt mass flow kg/s 14625 29251 43876 58501 73130
Primary coolant salt total kg/s 4774 9487 14231 18975 23719
mass flow
10 Primary coolant salt main kg/s 3800 7520 11244 14968 18691
steam generator mass
flow
Primary coolant salt kg/s 943.7 1967 2986.4 4006 5029
reheater mass flow
15
Main steam mass flow rate kg/s 224.5 452.8 677.1 901.3 1025
Reheat steam mass flow kg/s 195.2 403.7 610.9 818 1125.4
rate
Fuel salt heat source outlet °C 737 737 737 737 737
20
Fuel salt primary heat °C 645 645 645 645 645
exchanger outlet
Primary coolant primary °C 612 612 612 612 612
heat exchanger outlet
25
Primary coolant main °C 498 498 498 498 498
steam generator outlet
Primary coolant reheat °C 498 498 498 498 498
steam generator outlet
30
Main steam generator °C 580 580 580 580 580
steam outlet
Reheat steam generator °C 600 600 600 600 600
outlet
35
[0071] FIG. 2 illustrates another comparative example of a simplified schematic view of a molten salt nuclear reactor
200. The reactor 200 is a pool-type reactor in which in some examples the fuel salt 108 may be flowing/circulating through
the pool or in other cases contained or guided such as through piping. In the example shown in FIG. 2, the fuel salt is
contained in tubes 204 that are located at the center of a pool 210 of coolant 202 in a closed reactor vessel 206. The
40
top portion of the reactor vessel 206 may be filled with some inert gas 218 such as argon. The fuel tubes 204 are arranged
in an array similar to conventional solid fuel arrays in a light water reactor. The coolant 202 transfers heat from the center
of the pool 210 to heat exchangers 208 located on the periphery of the pool 210. In the comparative example shown,
the circulation of the coolant 202 (illustrated by the dashed arrows 212) within the pool 210, which may be natural or
induced by an impeller or other mechanism (not shown), convects heat away from the fuel tubes 204 to be removed by
45
the heat exchangers 208.
[0072] The heat exchangers 208 transfer heat from the pool 210 to a secondary coolant system 214. In a comparative
example, the secondary coolant is water that is boiled in the heat exchangers and the resulting steam 216 is used to
drive turbines (not shown) for the generation of power.
[0073] An optional set of reflector modules 232, such as reflector modules 132 discussed with reference to FIGS. 1E
50
and 1F, may be provided around the array of fuel tubes either within the reactor vessel as shown in FIG. 2 and/or external
to the reactor vessel similar to that of FIGS. 1E and 1F to increase the efficiency of the reactor. Optional shutdown rods
may be provided to maintain the reactor subcritical when needed.
[0074] Following its initial start-up with enriched (∼ 12 % 235U) fuel, an MCFR may not require the ongoing feed of
enriched fissile material. Instead, an MCFR can be fed depleted or natural uranium, among other fertile materials. During
55
normal operations, modelling shows that the reactor slowly breeds up in reactivity. To counter this increase in reactivity,
a small quantity of fully mixed fuel salt may be removed and replaced with fertile feed salt. The addition of fertile material
is, in effect, a control rod that reduces reactivity.
17
EP 3 241 218 B1
[0075] Rather than going to disposal, used MCFR fuel can be collected until a sufficient amount is available to start
a new reactor. Such a daughter reactor contains a chemically identical fuel salt, and thus, is able to be started without
any new enrichment. By transferring used fuel, in total, to a daughter plant for use as the initial fuel for that plant, creation
of a fleet of MCFRs significantly reduces the use of actinides and defers the vast majority of radioactive waste until the
5 end of fleet build-out. For ultimate disposal of actinide-bearing fuel salt, prior work found that the salt itself could be
packaged, without chemical conversion, into a suitable waste form.
Chloride-Based Fuel Salts
10 [0076] Nuclear fuel salts are generally described by E. H. Ottewitte, "Configuration of a Molten Chloride Fast Reactor
on a Thorium Fuel Cycle to Current Nuclear Fuel Cycle Concerns," Ph.D. dissertation, University of California at Los
Angeles, 1982. Uranium chloride compounds are also discussed generally by B. R. Harder, G. Long and W. P. Stanaway,
"Compatibility and Processing Problems in the Use of Molten Uranium Chloride-Alkali Chloride Mixtures as Reactor
Fuels," Symposium on Reprocessing of Nuclear Fuels, Iowa State University, 405-432, Aug. 1969. The novel fuel salt
15 embodiments describe below improve this work and have been developed through modelling and other theoretical
research.
[0077] It is noted that the molten chloride fuel salts of the present disclosure provide for the introduction of high heavy
metal concentration in the fuel salt 108 at reasonable temperatures. By way of a non-limiting example, one or more of
the chloride fuel salts of the present disclosure may provide a heavy metal concentration of greater than 61 % by weight,
20 with a melting temperature of approximately 500 °C. When operated using the fuel salts described below, embodiments
of a molten fuel salt reactor may have possible nominal operating temperatures from 200-800 °C. While each different
fuel will have a slightly different optimal operating temperature, reactors having an operational temperature range of
330-550 °C, 350-520 °C, 400-510 °C and 450-500 °C. The ability to achieve high uranium content levels allows for the
utilization of uranium chloride based fuel salt mixtures in the fast neutron spectrum breed-and-burn reactor of the present
25 disclosure. Furthermore, the fissile material may be enriched to any level desired such as 12.5 % 235U or 19.99 % 235U,
or any other suitable enrichment level.
[0078] It is also noted that the molten chloride fuel salts of the present disclosure have a relatively low vapor pressure
when heated to the operating temperatures described herein. While each different fuel will have a slightly different optimal
operating pressure to reduce the amount of vaporization of the fuel salt, reactors having an operational pressure range
30 of from 1-10 atm and from 2-5 atm are contemplated.
[0079] The following discussion presents various embodiments and comparative examples of molten chloride nuclear
fuel salt having a mixture of a metal chloride fuel salt with one or more additional metal chloride salts. For example, the
molten chloride nuclear fuel salt may include, but is not limited to, a mixture of a first uranium chloride salt, a second
uranium chloride salt and/or an additional metal chloride salt. It is noted that relative amounts of the various components
35 of the fuel salt 108 may be manipulated to control one or more thermal, chemical or neutronic parameters of the fuel
salt including, but not limited to, the melting point, thermal conductivity, corrosivity, actinide content level, reactivity,
effective neutron multiplication factor (keff) at equilibrium, and the like. For example, the relative amount of fissile uranium
(e.g. 235U) in a given fuel salt mixture may dictate the size of the reactor core section 102 necessary to provide a given
power density. By way of non-limiting example, a fuel salt having a 235U content of 10 mol % (except where specifically
40 stated otherwise, all % values for chemical compounds will be in molar %) may have a reactor core section volume of
approximately 67 cubic meters (m3) and produce a power density of 200 MW/m3, while a fuel salt having a 235U content
of 16 % may only require a reactor core section volume of approximately 11m3. Such a relationship shows the strong
dependence of the size of the reactor core section 102 (or number of fuel tubes 204) on the composition of the utilized
fuel salt 108.
45 [0080] In one embodiment, the salt mixture of the present disclosure may be selected so that the associated breeding
ratio, which is the ratio of the new fissile material created in a reactor during a nuclear reaction to the fissile material
consumed by that reaction, of the fuel salt 108 is greater than 1 (e.g., breeding ratio = 1.000001, 1.001, etc.), resulting
in a long reactor life, but with a breeding performance less than potentially achievable. In another embodiment, the salt
mixture of the present disclosure may be selected so that the associated breeding ratio of the fuel salt 108 is less than
50 1, resulting in burn off of enrichment for a given period of time. It is to be appreciated that selection of a specific fuel
composition is dependent on many different competing factors including the reactor design, nominal operating parameters
(e.g., temperature and pressure), and, not least of all, overall operational goals (e.g., reducing enrichment, reactor
longevity, breeding additional fissile material).
55 Chlorine-37 Modified Chloride Fuel Salt
[0081] In addition to enriching the fissile element(s) (such as uranium or thorium) used to create the fuel salts, em-
bodiments of the fuel salts described herein may be enriched so that some amount of the chloride ion in any one or
18
EP 3 241 218 B1
more of the chloride compounds contain a specific percentage of 37Cl. Chlorine has many isotopes with various mass
numbers. Of these, there are two stable isotopes, 35Cl (which forms 76 % of naturally-occurring chlorine) and 37Cl (24
% in naturally-occurring chlorine). The most common isotope, 35Cl, is a neutron moderator, that is, 35Cl reduces the
speed of fast neutrons, thereby turning them into thermal neutrons. The isotope 35Cl is also a strong neutron absorber,
5 and leads to formation of corrosive sulfur and long lived radioactive 36Cl. The isotope 37Cl, on the other hand, is relatively
transparent to fast neutrons.
[0082] One aspect of the present technology is to adjust the 37Cl content of any chloride-containing compounds to be
used as molten fuel salt 108. As discussed above, use of naturally occurring chloride ions to create a chloride compound
would result in roughly 76 % of the chloride ions being 35Cl and 24 % being 37Cl. However, in the comparative examples
10 described herein any ratio of 37Cl to total Cl may be used in any particular chloride fuel salt comparative example, and
in some cases may meet or exceed a selected ratio of 37Cl to total Cl. It is to be appreciated that any known or to be
developed enrichment techniques may be used to ensure the desired and/or selected 37Cl ratio concentration including
but not limited to centrifuges, ion exchange columns, etc.
[0083] In a comparative example all chloride-containing compounds may be created from as pure a feed of 37Cl as
15 possible. For example, chloride-based fuel salt compounds may be created so that greater than 90 %, 95 %, 98 %, 99
% or even 99.9 % of the chloride ions in the fuel salt are 37Cl. Alternatively, a chloride-based nuclear fuel may be
developed to achieve any target or selected percentage amount of 37Cl to other chloride ions in the fuel or in different
components of the fuel. For example, for a fuel designed for thermal reactions, the chloride-based fuel salt compounds
may be created so that less than 10 %, 5 %, 2 %, 1 % or even 0.1 % of the chloride ions in the fuel salt are 35Cl, the
20 remaining being 37Cl. For fuels tailored to fast reactions, the chloride-based fuel salt compounds may be created so that
greater than 10 %, 25 %, 30 %, 35 %, 40 %, 45 %, 50 %, 55 %, 60 %, 65 %, 70 %, 75 %, 80 %, 85 %, 90 %, or more
up to 100 % as described above of the chloride ions in the fuel salt are 37Cl. Modelling has indicated that MCFR
performance improves significantly with chlorine that is enriched to at least 75 % 37Cl. The use of enriched chlorine
reduces both neutron parasitic absorption and production of 36Cl, which is a long-lived activation product.
25 [0084] FIG. 3 illustrates a comparative example of a method for creating a fuel tailored to a specific reactor. This
adjustment of the relative amounts of 35Cl to 37Cl provides an additional method to control the reactivity of the fuel salt
in fast or thermal reactions. The method 300 begins with an identification operation 302. In the identification operation
302, the desired ratio of 37Cl to total Cl is determined. To determine the appropriate ratio, factors such as the reactor
design, the desired operating parameters of the reactor (e.g., temperature, pressure, etc.), and the chloride-based
30 compounds to be used in the fuel may be taken into account.
[0085] The fuel identification operation 302, for example, may include choosing an initial Cl salt having a second ratio
of 37Cl to total Cl in the fuel and determining an initial effective neutron multiplication factor (keff) for the reactor using
the initial molten chloride fuel salt, comparing the initial effective neutron multiplication factor to the target effective
neutron multiplication factor, and calculating the next or final ratio of 37Cl to total Cl based on results of the comparing
35 operation. A target effective neutron multiplication factor (keff) may be identified based on the desires of the manufacturer
or operator of the nuclear reactor. These techniques may be iterated and/or adjusted as appropriate to determine 302
the selected ratio of 37Cl to total Cl.
[0086] A fuel generation operation 304 is then performed. In the fuel generation operation 304, a fuel is created by
modifying the ratio of 37Cl to total Cl in the final fuel.
40 [0087] In a comparative example, the modified molten chloride fuel salt includes a mixture of different chloride com-
pounds including a first fissile chloride salt compound and a first non-fissile chloride salt compound. In this comparative
example, the fuel generation operation 304 may include generating the first fissile chloride salt compound and the first
non-fissile chloride salt compound so that they have different ratios of 37Cl to total Cl of the first fissile chloride salt
compound or first non-fissile chloride salt compound, respectively. The 37Cl to total Cl ratio of each compound is adjusted
45 so that upon combination of the two (or more) compounds to form the final modified fuel salt mixture, the modified molten
chloride fuel salt has the desired ratio of 37Cl to total Cl based on the mass balance of the compounds and their respective
37Cl to total Cl ratios.
[0088] The result of the fuel generation operation 304 is a modified molten chloride fuel salt having a first ratio of 37Cl
to total Cl in the modified molten chloride fuel salt that, when used in the nuclear reactor, achieves the target effective
50 neutron multiplication factor. The fuel salt is referred to as ’modified’ to recognize that the final ratio is different than the
naturally occurring ratio of 37Cl to total Cl. For example, a fuel salt may be a mixture of 33 % UCl4, 33 % UCl3 and 33
% NaCl and, in order to achieve a final modified fuel salt ratio of 40 % 37Cl to total Cl, the NaCl may be enriched to have
a ratio of 75 % 37Cl to total Cl while the naturally occurring ratio is used for the other two components. This results in a
final modified UCl4-UCl3-NaCl fuel salt having a ratio of 40 % 37Cl to total Cl.
55 [0089] The preceding example also shows that, for efficiency, it may be decided to enrich only one compound of a
multi-compound fuel salt mixture. For example, if a non-fissile chloride salts is included in the final fuel salt, a large
amount of high (or low) 37Cl to total Cl ratio salt may be created and maintained for later use in blending fuel. The refining
of 37Cl from naturally occurring chlorine is known in the art and any suitable method may be used. For example, centrifugal
19
EP 3 241 218 B1
or ion exchange column (IXC) methods of enrichment appear viable and extensible to the required quantities. Other
methods are also possible.
[0090] After the modified fuel has been generated, the reactor is charged with the modified fuel and the reactor is
operated using the modified fuel in a reactor operation 306. If it is determined during operation that the reactivity is not
5 optimal, new fuel may be generated using the method 300 to either replace the existing fuel or to be blended with the
existing fuel until the desired reactivity is achieved in a subsequent fuel generation and blending operation (not shown).
In yet another comparative example, the method 300 may be used to change or maintain the reactivity over time in a
reactor.
[0091] As discussed in greater detail below, chloride-containing fuel salts may include one or more of UCl4, UCl3,
10 UCl3F, UCl2F2, and UClF3 and/or any of the specific fuel salt comparative examples described herein may be modified
as described above. If a non-fissile chloride compound is used, such additional metal chloride salt may be selected from
NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and/or NdCl3.
UCl3-UCl4-[X]Cln Fuel Salts

15
[0092] Comparative examples of uranium salts suitable for use as nuclear fuel includes salts that are a mixture of from
0-100 % UCl3, 0-100 % UCl4 and 0-95 % of a metal chloride salt. Thus, these salts include 100 % UCl3 fuel salt, 100 %
UCl4 fuel salt, as well as fuel salts that are mixtures of UCl3 and/or UCl4 with or without an additional metal chloride salt.
Based on the results for NaCl as the additional metal chloride salt, fuel salts having a NaCl content less than 68 mol %
20 are considered suitable based on the modelling results. In another comparative example, uranium salts suitable for use
as nuclear fuel includes salts that are a mixture of from 0-100 % UCl3, 0-100 % UCl4 and 0-95 % of a metal chloride salt
having a melting point below 800, 700, 600, 500, 400 or 350 °C. For NaCl comparative examples, uranium salts suitable
for use as nuclear fuel include salts that are a mixture of from 0-100 % UCl 3, 0-100 % UCl4 and 0-68 % of NaCl having
a melting point of each of the constituent salts below 800, 700, 600, 500, 400 or 350 °C. In yet another comparative
25 example, NaCl content of the fuel salt may vary between 12 and 68% of NaCl.
[0093] The molten chlorides differ significantly from the historically used fluorides in two noteworthy aspects. First,
chlorides are less effective at moderating neutrons than the fluorides. This ensures a fast neutron spectrum, which is
essential to breed-and-burn operation. Second, and more importantly, the chlorides offer the possibility of very high
heavy metal concentrations in mixtures with reasonable melting points, which is important to obtain a compact fast
30 breeding reactor design. Fluoride salts typically contain no more than 10-12 mole % heavy metal with proposed salt
mixtures typically containing molar concentrations of 63-72 mole % LiF (enriched to 99.997% 7Li), 16-25 mole % BeF2,
6.7-11.7 mole % ThF4, and only 0.3 mole % UF4 (heavy metal is 40-45%, by weight).
[0094] FIG. 4 illustrates a ternary phase diagram calculated for UCl3-UCl4-NaCl fuel salts based thermodynamic
models. The diagram 400 shows the expected melting temperature for any mixture of UCl3-UCl4-NaCl. Of particular
35 interest are mixtures having a melting point less than 500 °C, which mixtures are illustrated in the shaded region 402 of
the diagram 400. The eutectic point 404 has a melt temperature of 338 °C and a composition of 17UCl3-40.5UCl4-
42.5NaCl (i.e., 17 mol % UCl3, 40.5 mol % UCl4 and 42.5 mol % NaCl). The shaded region 402 indicates a melting point
envelope of 500 °C. Moving to the far-right of this envelope 402 provides an comparative example, 17UCl 3-71UCl4-
12NaCl, but note that many possible compositions exist within the envelop 402 as comparative examples of fuel salt
40 mixtures having a melting point below 500 °C. Furthermore, if the melting temperature limit is slightly extended to 508
°C, a composition of 34UCl3-66NaCl provides an option that is free of UCl4. Likewise, the ternary diagram 400 allows a
range of specific UCl3-UCl4-NaCl fuel salt comparative examples to be identified for any given melting point limit from
800 °C and 338 °C. For example, ternary salts with melting points from 300-550 °C, 338-500 °C, and 338-450 °C may
be easily identified.
45 [0095] The specific composition of the mixture may include any formulation including two or more of UCl4, UCl3 or
NaCl such that the resulting uranium content level and melting temperature achieve desired levels. By way of non-
limiting example, the specific composition may be selected so that the corresponding melting temperature falls from 330
and 800 °C. By way of another non-limiting example, the specific composition may be selected so that the overall uranium
content level is at or above 61 % by weight. In addition to selecting the overall uranium content level the fuel composition
50 may also be determined to meet a selected amount of fissile uranium (as opposed to fertile). For example, the specific
composition of the fuel salt 108 may be selected such that the 235U content of the fuel salt 108 is below 20 %.
[0096] As part of initial concept development, a series of neutron transport and burn calculations have been completed
for a variety of fuel salts, fissile enrichments, sizes and powers. As would be expected, higher enrichments enable
smaller core sizes, but suffer from reduced breeding potential. Systems with some form of fission product removal can
55 reach equilibrium behavior, while others breed up and then are eventually overwhelmed by the build-up of fission products.
Multiple options exist for fuel salt selection, each with benefits and risks. The following discussion will identify particular
comparative examples of interest, however the following discussion does not limit the scope of the invention as claimed
to only the comparative examples described below, but rather, that any comparative examples identifiable from FIG. 4
20
EP 3 241 218 B1
are contemplated, as well as any comparative examples having different metal chlorides other than NaCl. Examples of
additional, non-fissile metal chlorides include NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3,
NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and/or NdCl3.
5 UCl4 Fuel Salt Comparative examples
[0097] In one comparative example, fuel salt 108 includes UCl4. For example, the fuel salt 108 may have a UCl4
content at or above 5 % by molar fraction. In another comparative example, the fuel salt 108 of the reactor 100 may
include a mixture of UCl4, an additional uranium chloride salt and/or an additional metal chloride salt (e.g., carrier salt)
10 such that the UCl4 content of the mixture is at or above 5 % by molar fraction. In other comparative examples, the UCl4
content of the mixture may be at or above 0.01 % by molar fraction, 0.1 %, 0.5 %, 1 %, 2 %, 3 % or 4 % UCl4. It is noted
that fuel salt 108 having a UCl4 content at or above 5 % by molar fraction may experience increased levels of corrosive
exposure. As discussed below, a variety of approaches may be implemented to mitigate corrosion caused by increased
chloride content.
15 [0098] In another comparative example, the fuel salt 108 of the reactor may include a mixture of UCl 4, an additional
uranium chloride salt and/or an additional metal chloride salt such that uranium concentration of the mixture is at or
above 61 % by weight.
[0099] In one comparative example, the additional uranium chloride salt includes UCl3, as is described in greater detail
below. In another comparative example, the additional metal chloride salt may include a carrier salt, a fission product
20 chloride salt, an actinide chloride salt and/or a lanthanide chloride salt. By way of non-limiting example, the additional
metal chloride salt may include, but is not limited to, NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4,
AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and/or NdCl3.
[0100] By way of non-limiting example, the fuel salt 108 of the reactor 100 may include a mixture of UCl4 and UCl3
(with no NaCl) such that the composition of the mixture corresponds to 82UCl4-18UCl3 (in molar %). It is noted that such
25 a fuel salt composition has a uranium content of approximately 65 % by weight and a melting temperature of 545 °C.
[0101] By way of another non-limiting example, the fuel salt 108 of the reactor 100 may include a mixture of UCl4,
UCl3 and NaCl such that the composition of the mixture corresponds to 17UCl3-71UCl4-12NaCl (in molar %). It is noted
that such a fuel salt composition has a uranium content of approximately 61 % by weight and a melting temperature of
approximately 500 °C.
30 [0102] By way of another non-limiting example, the fuel salt 108 of the reactor 100 may include a mixture of UCl4 and
NaCl (with no UCl3) such that the composition of the mixture corresponds to 50UCl4-50NaCl (in molar %). It is noted
that such a fuel salt composition has a melting temperature of approximately 368 °C. It is noted herein that, as the
lanthanides and/or plutonium build up within the fuel salt 108, they may act similar to UCl3, since lanthanides and
plutonium form trichloride compounds (as discussed above). In this event, the change in composition may cause the
35 behavior of the fuel salt 108 to shift toward that of the eutectic (as discussed above), thereby reducing the melting point
of the composition.
[0103] By way of yet another example, pure UCl4 may be used as a fuel salt. Pure UCl4 has a melting temperature
(as shown in FIG. 4) of 590 °C.
[0104] Due to the lower uranium content of the 66NaCl-34UCl3 composition, the binary salt requires a larger core than
40 the UCl4-containing compositions in order to achieve initial criticality. For example, the reactor core section 102 may
require a volume 3-4 times larger than required for a UCl4-Containing version of the fuel salt 108 to achieve initial criticality.
[0105] FIG. 5 illustrates keff modeled as a function of time for a larger reactor core section of the reactor illustrated in
FIGS 1A-1F utilizing the 66NaCl-34UCl3 composition. Curve 502 depicts a modeled keff curve for a power level of 5800
MW and curve 504 depicts a modeled keff curve for a power level of 3420 MW. It is noted that both curves 502, 504 are
45 modeled to operate with a depleted uranium (DU) feed and without specific lanthanide removal. As shown in FIG. 5, the
3420 MW case (curve 504) may operate for nearly 70 years before going subcritical, while the 5800 MW case (curve
502) may operate for approximately 41 years prior to going subcritical. In addition, the model shown in FIG. 5 also
predicted a fuel burnup of 43 % without any lanthanide removal during the years of operation. Thus, the modeling shows
that chlorine-based uranium fuel salt may be effective at reducing dependencies of prior molten salt reactors on enriched
50 uranium to maintain criticality.
[0106] FIG. 6 illustrates a process flow 600 representing example operations related to fueling a fast spectrum molten
salt nuclear reactor, in accordance with one or more comparative examples of the present disclosure. Although the
operations of FIG. 6 are presented in the sequence(s) illustrated, it should be understood that the various operations
may be performed in other orders than those which are illustrated, or may be performed concurrently.
55 [0107] Operation 602 of flow diagram 600 includes providing a volume of UCl4. By way of non-limiting example, a
selected volume of UCl4 may be provided in a substantially pure form. By way of another non-limiting example, a selected
volume of UCl4 may be provided in the form of a mixture of UCl4 with another salt, such as, but not limited to, a carrier
salt (e.g., NaCl).
21
EP 3 241 218 B1
[0108] Operation 604 of flow diagram 600 includes providing a volume of at least one of an additional uranium chloride
salt or an additional metal chloride salt. By way of non-limiting example, the additional uranium chloride may include,
but is not limited to, UCl3. In one comparative example, a selected volume of substantially pure UCl3 may be provided.
In another comparative example, a selected volume of UCl3 may be provided in the form of a mixture of UCl3 with another
5 salt, such as, but not limited to, a carrier salt (e.g., NaCl). By way of another non-limiting example, the additional metal
chloride includes, but is not limited to, one or more of NaCl, MgCl 2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4,
AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and/or NdCl3. In one comparative example, a selected volume of an additional
metal chloride may be provided. In another comparative example, a selected volume of an additional metal chloride may
be provided in the form of a mixture of the metal chloride with another salt, such as, but not limited to, a carrier salt.
10 [0109] Operation 606 of flow diagram 600 includes mixing the volume of UCl4 with the volume of the at least one of
an additional uranium chloride salt or an additional metal chloride salt to form a molten chloride nuclear fuel salt having
a UCl4 content greater than 5 % by molar fraction. By way of non-limiting example, the volume of UCl4 provided in
operation 602 may be mixed with the volume of operation 604 such that the resulting molten chloride salt mixture has
a UCl4 content greater than 5 % by molar fraction. In this regard, the volume of UCl4 of operation 602 and the volumes
15 of additional uranium chloride and/or an additional metal chloride may be selected such that the resulting molten chloride
salt mixture has a UCl4 content greater than 5 % by molar fraction. Additionally or alternatively, operation 606 includes
mixing the volume of UCl4 with the volume of the additional uranium chloride salt and/or additional metal chloride salt
to form a molten chloride salt mixture having a melting temperature from 330 to 800 °C.
[0110] In one comparative example, the volumes of operations 602 and 604 may be selected and mixed such that the
20 resulting molten chloride salt mixture has a chemical composition of (or approximately) 82UCl4-18UCl3. In another
comparative example, the volumes of operations 602 and 604 may be selected and mixed such that he resulting molten
chloride salt mixture has a chemical composition of (or approximately) 17UCl3-71UCl4-12NaCl. In another comparative
example, the volumes of operations 602 and 604 may be selected and mixed such that the resulting molten chloride
salt mixture has a chemical composition of (or approximately) 50 UCl4-50NaCl.
25 [0111] Operation 608 of flow diagram 600 includes supplying the molten chloride nuclear fuel salt having some amount
of UCl4 as described above (e.g., the UCl4 content of the mixture may be at or above 0.01 % by molar fraction, 0.1 %,
0.5 %, 1 %, 2 %, 3 %, 4 % or 5 %) to at least a reactor core section of the fast spectrum molten salt nuclear reactor. In
one comparative example, the mixture of operation 606 may be formed by mixing the volume of UCl4 with the volume
of the at least one of an additional uranium chloride salt or an additional metal chloride salt inside of the fast spectrum
30 molten salt nuclear reactor. In one comparative example, the mixture of operation 606 may be formed by mixing the
volume of UCl4 with the volume of the at least one of an additional uranium chloride salt or an additional metal chloride
salt at a location outside of the fast spectrum molten salt nuclear reactor, such as, but not limited to, a mixing vessel. In
this regard, following the mixture of UCl4 with the volume of the at least one of an additional uranium chloride salt or an
additional metal chloride salt, the molten chloride salt mixture may be loaded into the reactor 100. The reactor may then
35 be operated as described herein, for example by initiating fission in the fuel salt and then maintaining breed-and-burn
behavior in the reactor core for some period of time.
[0112] In one comparative example, the concentration of one or more of the additional metal chlorides (discussed
above) is selected to be at or below the precipitation concentration for precipitation of the additional metal chloride within
the nuclear fuel mixture. For instance, a fission product concentration may be kept below the concentration associated
40 with that fission product that would cause another constituent, such as Pu, of the fuel salt 108 to precipitate out of the
fuel solution.
[0113] It is again noted that the molten chloride salt compositions provided above are not limitations on the reactor
100 or associated methods of the present disclosure. Rather, the specific compositions are provided merely for illustrative
purposes. It is recognized that any molten chloride fuel salt may be implemented in the reactor 100 of the present
45 disclosure.
UCl3 Fuel Salt Comparative examples
[0114] In addition to the comparative examples described above that contained UCl3 in combination with UCl4, addi-
50 tional comparative examples of the fuel salts include UCl3 and lack any UCl4 content. These comparative examples and
their associated melting points are also identified on FIG. 4 along the left axis. It is noted that a fuel mixture free of UCl4
may be of particular interest in the event UCl4 corrosion concerns become significant and may lessen the need for
corrosion mitigation techniques (as described below). By way of non-limiting example, the fuel salt 108 of the reactor
100 may include a mixture of UCl3 and NaCl such that the composition of the mixture corresponds to 66NaCl- 34UCl 3
55 (in molar %). It is noted that such a fuel salt composition has a melting temperature of approximately 508 °C, but a
reduced uranium content level as compared to the UCl4-containing compositions (described above).
[0115] UCl3 fuel salt comparative examples also include pure UCl3, however, the melting point is slightly above 800
°C and thus this comparative example may not be suitable for certain reactor designs.
22
EP 3 241 218 B1
Mixed Chloride-Fluoride Fuel Salt Embodiments
[0116] Mixed chloride-fluoride salts of actinides, and particularly of uranium, may also be suitable fissionable salts for
use in a molten salt reactor. UCl3F is an embodiment of a potentially useful chloride-fluoride salt. UCl3F has a melting
5 point of from 410-440 °C which is less than the melting point of pure UCl4, which is 590 °C. Because of the molecular
symmetry and chemical composition of the UCl3F salt, it is also anticipated that UCl3F will have a lower volatility than
UCl4 making it even more attractive as a fuel salt in a low temperature (e.g., less than 800 °C, or even less than 550
°C) molten salt reactor.
[0117] Based on the above information, the calculated ternary diagram for UCl4 shown in FIG. 4, and the similarity
10 between UCl3F and UCl4, it is expected that UCl3F could be used to replace some or all of the UCl4 in a fuel salt mixture
to obtain fuel salt embodiments that have even better properties (e.g., lower melting point and lower volatility) while
having substantially the same reactivity. Although a ternary diagram of UCl3F, UCl3 and NaCl has not been calculated,
a ternary diagram for UCl3F, UCl3 and NaCl is anticipated to show a minimum melting point at a location near the
corresponding eutectic point 404 on FIG. 4 for the salt 17UCl3-40.5UCl4-42.5NaCl. That is, it is anticipated that such a
15 diagram for UCl3F, UCl3 and NaCl will show a similar trend in reduced melting point in a region from 15-20 mol % UCl 3
and the balance being from 35-45 mol % NaCl and 35-45 mol % UCl3F. Given that UCl3F normally has a melting point
substantially less than UCl4, replacing UCl4 with UCl3F in fuel salt embodiments is anticipated to result in fuel salts with
even lower melting points than those observed in FIG. 4.
[0118] Given this information, uranium embodiments of Cl3F fuel salts include salts having from 1-100 mol % UCl3F.
20 For example, embodiments of mixed chloride-fluoride fuel salts include salts with at least 5 %, 10 %, 15 %, 20 %, 25 %,
30 %, 35 %, 40 %, 45 %, 50 %, 55 %, 60 %, 65 %, 70 %, 75 %, 80 %, 85 %, 90 %, 95 %, and 99 % UCl3F. A fuel salt
of pure or substantially pure UCl3F is also possible, as the melting point is within the operational range of the reactors
described herein. In an alternative embodiment, a UCl3F fuel salt may have only a detectable amount of UCl3F. While
it is recognized that detection limits may change as technology improves, in an embodiment a detectable amount means
25 equal to or greater than 0.01 mol %.
[0119] Other salts that could be combined with UCl3F to make fuel salt embodiments include, UCl3, NaCl, and UCl4.
As discussed above salts of UCl3F-UCl3-NaCl are particularly contemplated including embodiments having from 15-20
mol % UCl3 and the balance being from 35-45 mol % NaCl and 35-45 mol % UCl3F. In addition, any other salts discussed
herein may be included, such as ThCl4, uranium fluoride salts, non-fissile salts, and uranium bromide salts.
30 [0120] In addition to UCl3F, other mixed actinide salts such as UCl2F2, and UClF3 may be suitable for use as a fuel
salt or a constituent of a fuel salt in a molten reactor. Mixed chloride-fluoride salts of plutonium or thorium may also be
suitable for use as molten fuel salts.
[0121] Embodiments of methods for creating UCl3F, UCl2F2, and UClF3 are described below including an experiment
in which UCl3F was created.
35 [0122] Modified chloride fuel salt embodiments having an altered ratio of 37Cl to total Cl are also possible and may be
used for molten fuel salts. In addition, mixed chloride fluoride fuel salt embodiments may include non-fissile chloride
compounds in addition to or instead of NaCl, such as MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3,
NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and/or NdCl3.
[0123] In use, mixed uranium chloride-fluoride salt embodiments will be used in a similar fashion to that described
40 above for the chloride salt embodiments. For example, the desired salt composition, such as from 15-20 mol % UCl3
and the balance being from 35-45 mol % NaCl and 35-45 mol % UCl3F, is created. This may be done remotely or by
adding the constituents directly into the reactor core. The constituents may be added in solid or liquid form. After charging
the reactor core with the fuel salt, the reactor is then brought to operating conditions to initiate a chain reaction, as
described above.
45
Thorium Chloride Fuel Salt
[0124] In one comparative example, the fuel salt 108 may include a selected amount of thorium. By way of example,
in the case of a chloride-based nuclear fuel salt, the thorium may be presented in the fuel salt 108 in the form of thorium
50 chloride (e.g., ThCl4). Methods for manufacturing ThCl4 are known in the art and any suitable method may be used.
[0125] The introduction of ThCl4 into chloride-salt systems has been shown to reduce the melt temperature of the
system by approximately 50 °C. Thus, based on the information from the ternary salt diagram of FIG. 4, ThCl4 comparative
examples should have a melting point at or below those found in the ternary system and should be capable of supporting
a breed-and-burn reaction while in the molten state. For example, melting points below 800 °C and even 550 °C should
55 be achievable based on the information from the ternary diagram.
[0126] A comparative example utilizing ThCl4 is UCl3F-UCl4-UCl3-ThCl4-[X]Cl where, as above, [X]Cl is any additional,
non-fissile salt. In these comparative examples, the mol ratios of the any of various chloride salt may be determined as
needed to obtain the desired melting point. In an comparative example, the amount of ThCl4 varies from a detectable
23
EP 3 241 218 B1
amount of ThCl4 and 80 mol % and the other components (i.e., UCl3F, UCl4, UCl3, and [X]Cl) vary independently from
0 to 80 %. Thus, comparative examples such as UCl3F-ThCl4-[X]Cl, and UCl3-ThCl4-[X]Cl are contemplated as are
UCl4-UCl3-ThCl4-NaCl.
5 Uranium Bromide Fuel Salt Comparative examples
[0127] In addition to the chloride fuel salt comparative examples described herein, bromide fuel salts are also possible
as an alternative or backup to a chloride fuel salt. A feature of a molten chloride fuel salt reactor is the ability to breed-
and-burn its own fissile fuel from fertile fuel because of the very fast neutron spectrum. This is enabled by the use of an
10 enriched chloride salt to bind the actinide atoms. Chlorine is generally a poor neutron moderator relative to other materials
like water, graphite or fluorine. It also has a relatively low neutron capture cross section for parasitic capture (wasted
neutrons). An well-performing salt constituent would create a strong chemical bond with actinides, exist with a low vapor
pressure, be high Z number to enable a fast spectrum, and have low (n,γ) capture cross section. 37Cl is an excellent
choice as discussed above. However, based on this analysis bromine may also be suitable.
15 [0128] Bromide salt (UBr3, UBr4) is in the same group and will have similar chemical properties to chloride salts.
Bromine is a higher Z material than Cl, so it should moderate neutrons less and result in a faster spectrum. Bromine’s
chemical bond should be similar to that of Cl. These features make it an attractive alternative to a Cl salt. UBr4 has a
reported melting temperature of 519 °C, lower than that of UCl4, and so should be suitable for use in the systems and
methods described herein. While the boiling point of UBr4 is reported as 791°C so operating at high temperatures is
20 likely not possible, this is not a limitation for nuclear reactors that are designed to operate in some of the lower ranges
identified herein, e.g., 330-550 °C, 338-500 °C and 338-450 °C.
[0129] FIG. 7 illustrates the (n,γ) capture cross section for the main Cl and Br isotopes, which illustrates that the (n,γ)
capture cross section of Br is higher than Cl in most of the energy spectrum. In fact, 37Cl (curve 708 of FIG. 7) has a
lower capture cross section throughout almost the entire spectrum when compared to 79Br (curve 706 of FIG. 7) and
25 81Br (curve 704 of FIG 7). The 35 Cl (curve 702 of FIG. 7) is also generally lower than the Br above 1x10-4 MeV.
[0130] In addition, the suitability of a bromide salt to actually support a breed-and-burn reaction was studied. This
study started with the same chemical makeup of salt and enrichment of the baseline chloride salt. These were 17UBr3-
71UBr4-12NaBr and 12.6 % 235U enrichment. This fuel salt was modeled in a standard 1 GWth molten chloride fast
reactor with no other changes. The resulting system was subcritical and required either increasing the reactor core size
30 or increasing the enrichment. Increasing the enrichment to 19.99 % (maximum allowed to be considered low enriched
fuel) in the model resulted in a breed-and-burn curve is shown in FIG. 8. The reactor starts at an artificially high keff,
burns down for a few decades, but eventually breeds enough Pu and minor actinides to increase keff again. Even without
being optimized for the bromide salt system, the results of the modelling in FIG. 8 illustrate that the bromide fuel salt
comparative examples do breed-and-burn and that a molten bromide salt reactor can operate. Thus, UBr3 and/or UBr4
35 containing fuel salts in which the fuel salts are enriched with 235U at levels greater than 19 % are suitable.
[0131] There exist a number optimization possibilities to maximize performance while minimizing volumes necessary
to support a breed-and-burn reaction. First, a minimum enrichment may be found to ensure breed-and-burn performance
without falling subcritical. Second, reflector sizing and material configurations could be used to tailor the spectrum in a
region that maximizes breeding. Third, consistent with the chloride comparative examples described above, different
40 fuel salt combinations (XXUBr3-YYUBr4-ZZNaBr) could be investigated to find the optimal comparative examples.
[0132] In addition, the bromide anions used in one or more components of the salt could be modified similar to that
described with chloride salts using 37Cl. As shown in FIG. 7, the two stable isotopes of bromine, 79Br and 81Br, have
different neutron capture cross sections. Thus, the capture characteristics of the salt can be tailored by modifying the
ratio of these isotopes used in the bromide salts. In a comparative example all bromide-containing compounds may be
45 created from as pure a feed as possible of either 79Br or 81Br. For example, bromide-based fuel salt compounds may
be created so that greater than 90 %, 95 %, 98 %, 99 % or even 99.9 % of the bromide ions in the fuel salt are either
79Br or 81 Br. Alternatively, a bromide-based nuclear fuel may be developed to achieve any target or selected percentage
amount of either 79Br or 81Br or a combination of the two to other bromide ions in the fuel or in different components of
the fuel. For example, in a comparative example, the bromide-based fuel salt compounds may be created so that less
50 than 10 %, 5 %, 2 %, 1% or even 0.1 % of the bromide ions in the fuel salt are 81Br, the remaining being 79Br. Alternatively,
the bromide-based fuel salt compounds may be created so that greater than 10 %, 25 %, 30 %, 35 %, 40 %, 45 %, 50
%, 55 %, 60 %, 65 %, 70 %, 75 %, 80 %, 85 %, 90 %, or more up to 100 % as described above of the bromide ions in
the fuel salt are 81Br.
55 Uranium Chloride Fuel Manufacturing Processes
[0133] Various methods of manufacturing of UCl4 and UCl3 are known in the art and any suitable method may be
used. For example, UCl4 may be manufactured by the chemical reaction:
24
EP 3 241 218 B1
UO3 +Cl3CCCl=CCl2 → UCl4 + byproduct

Likewise, UCl3 may be manufactured using either of the following reactions:
U + 3/2H2→UH3 and UH3 + 3HCl→UCl3 +3H2

5 UCl4 + Cs → UCl3 + CsCl
Using the above methods, any amount of UCl4 and UCl3 may be created and then blended to form any of the uranium
chloride fuel salt embodiments or comparative examples described above. In addition to the above methods, the following
describes another method that can efficiently and simply create a UCl4-UCl3-NaCl comparative example.
10 [0134] Synthesized salts will be subject to strict chemical control to minimize corrosion and precipitation of nuclear
material. These chemical controls revolve around eliminating the formation of oxides and hydroxides, especially asso-
ciated with the uranium cation, which are all more stable than their chloride counterparts. Therefore, once component
salts are manufactured they must not contact oxide layers, oxygen, or water, for the duration of their lifetime. To satisfy
this stringent requirement, one may purify and process salts under an inert atmosphere, in a closed container. When
15 component salts are required to be mixed, the operation should be performed without exposure to air, water, or oxygen.
Storage should be done within leak tight, oxide free, canisters with a positive partial pressure of inert gas. These strict
purity actions coupled with the isotopic enrichment and high temperatures lead to unique challenges.
[0135] While there are many simpler lab scale processes, it is proposed that a four-step process be used to create
high purity, chlorine-37 enriched, and chloride salt mixtures. First, uranium dioxide and sodium carbonate should be
20 reacted in tandem below liquidus temperatures, in vessels coupled in series, with a controlled mixture of chlorine and
carbon monoxide gas yielding uranium tetrachloride, sodium chloride, and carbon dioxide gas. Second, the uranium
tetrachloride is heated below its liquidus temperature and dry argon is slowly passed over it, facilitating its sublimation
and subsequent transfer through heated lines into the cooler bed of fresh sodium chloride. Third, a charge of silicon is
added to the UCl4-NaCl mixture and allowed to react in the liquid phase, producing silicon tetrachloride, which can be
25 sparged from the salt. Other reducing agents can be used instead of Si and will be examined if necessary. Fourth, the
salt is transferred into a storage container and cold stored under argon.
[0136] FIG. 9 illustrates a comparative example a method of manufacturing a fuel salt containing UCl4 based on the
process outlined above. In the comparative example shown, the method starts with a uranium dioxide contacting operation
902. In the uranium dioxide contacting operation 902, a volume of UO2 is brought into contact with gaseous chlorine
30 and carbon monoxide at a temperature that allows the formation of UCl4. In a comparative example, this operation may
be performed by providing an amount of solid UO 2. By providing the solid UO2 in a high surface area form that allows
easy contact with a gas, such as a powder, a particulate or a porous matrix, the reaction can be made more efficient.
The result of the contacting operation 902 is that at least some of the UO 2 that comes in contact with the gases is
converted into UCl4 via the carbochlorination reaction:
35 UO2 (s) + 2CO(g) + 2Cl2(g) = UCl4 (s) + 2CO2(g)
[0137] This reaction is unique as it contains both a reductant, carbon monoxide, and oxidizer, chloride. These two
components oscillate uranium’s oxidization state from IV to VI in order to satisfy the thermodynamics of producing
uranium tetrachloride from the much more stable oxide. The reaction is very complex in terms of partial reactions. It can
be thought of, in order, as
40
UO2(s) + 1/2Cl2(g) → UO2Cl; Oxidization,
UO2Cl+ 1/2Cl2(g) → UO2Cl2(s); Oxidation,
45 UO2Cl2(s) + CO (g) → UOCl2 + CO 2(g); Reduction,
UOCl2(s) + 1/2Cl2(g) → UOCl3(s); Oxidation,
UOCl3(s) + 1/2Cl2(g) → UOCl4; Oxidation,

50
UOCl4 + CO (g) → UCl4+ CO2(g); Reduction.
It is important to note that two reactions are predicted after the tetrachloride
55 UCl4 + 1/2Cl2(g) → UCl5 ; Oxidation,
UCl5 + 1/2Cl2(g) → UCl6; Oxidation.
25
EP 3 241 218 B1
[0138] Two oxidization reactions are known to produce uranium pentachloride and uranium hexachloride, but these
products are predicted to decompose to uranium tetrachloride at 250 °C. To avoid the production of uranium pentachloride
and uranium hexachloride, and the melting or sublimation of the uranium tetrachloride as well, the reaction may be kept
between the temperatures of 250 °C and 400 °C.
5 [0139] As described above, some or all of the chlorine may be 37Cl in order to achieve a target 37Cl to total Cl in the
resulting UCl4 or the Cl in the fuel overall as discussed above. Depending on the desired ratio, multiple sources of
different isotopes of Cl may be used to achieve the desired 37Cl to total Cl ratio, e.g., a source of pure 37Cl, a source of
natural Cl, a source of pure 35Cl and/or some other blend of 35Cl and 37Cl.
[0140] The method 900 also includes a sodium carbonate (Na2CO3) contacting operation 904. Similar to the UO2
10 contacting operation 902, the Na2CO3 contacting operation 904, includes contacting a volume of Na2CO 3 with gaseous
chlorine and carbon monoxide at a temperature that allows the formation of NaCl. In a comparative example, this
operation may be performed by providing an amount of solid Na2CO3. By providing the solid Na2CO3 in a high surface
area form that allows easy contact with a gas, such as a powder, a particulate or a porous matrix, the reaction can be
made more efficient. The result of the sodium carbonate contacting operation 904 is that at least some of the Na2CO3
15 that comes in contact with the gases is converted into NaCl. Again, as described above, the amount of Cl enrichment
(e.g., 37Cl enrichment) in the final NaCl can be controlled by controlling the enrichment in the chlorine gas used. The
equation for this reaction is as follows:
Na2CO3 (s) + CO(g) + Cl2(g) = 2NaCl (s) + 2CO2(g)
[0141] The method 900 also includes silicon contacting operation 906 in which liquid or gaseous UCl4 is contacted
20 with silicon metal. In a comparative example, the silicon contacting operation 906 may control the reaction conditions
to cause a specified UCl4-Si reaction or reactions to occur, whereby the amount of UCl3 generated is controlled by the
amount of Si used and UCl4 is provided in excess. This operation 906 may be performed by providing an excess amount
of liquid UCl4 and immersing a known amount of silicon in the liquid until all or substantially all the Si has reacted. The
result of the silicon contacting operation 906 is that at least some of the UCl4 that comes in contact with the gases is
25 converted into UCl3. The amount of UCl4 that is converted to UCl3 is stoichiometric with the amount of Si used as the
Si is highly reactive with UCl4 but not with UCl3. Therefore, with a known starting amount of UCl4, any desired mixture
of UCl4-UCl3 can be obtained simply by controlling the amount of Si placed into contact with the UCl4 gas and the amount
of UCl4. An equation for a suitable reaction that could be used in this comparative example of the operation 906 is as
follows:
30 4UCl4 (g or 1) + Si (s) = 4UCl3 (g) + SiCl4 (g)
Silicon tetrachloride boils at 57 °C, which at molten salt temperatures will readily vaporize and be carried away with the
argon. Once removed it can be collected or reacted with a neutralization bath. The naturally existing oxide layer, silicon
dioxide, is inert to the salt and will exist as a suspension or settle as a precipitate. Its presence will not affect the quality
of the salt.
35 [0142] Other reactions are also possible. For example, the silicon contacting operation 906 may involve using silane
(SiH4) or another silicon containing gas such as silicon dichloride (SiCl2) under the temperature and pressure conditions
to allow the formation of UCl3 and SiCl4 from the UCl4. The UCl4 may be either in gaseous or solid form during this
reaction, depending on the temperature and pressure conditions.
[0143] In an alternative comparative example, rather than using an excess of UCl4 the silicon contacting operation
40 906 may instead convert a known amount of UCl4 to the same stoichiometric amount UCl3 in an excess of Si. As the
goal is to generate a known amount of UCl3 and the resulting silicon chloride specie are unimportant, performing the
silicon contacting operation 906 in an excess of Si may be simpler than controlling the reaction conditions.
[0144] The contacting operations 902, 904, 906 may be performed using any suitable contacting vessels or equipment,
now known or later developed. For example, in a comparative example the solid material to be contacted is a loose
45 particulate or powder and the gaseous material is flowed or circulated under pressure through the contacting vessel
(e.g., flowed into a valve at one end of the vessel and removed from a valve at the other end of the vessel) such that
the vessel temporarily becomes a packed bed reactor or, if the flow rate through the container is sufficient, a fluidized
bed reactor. In these comparative examples, the contacting of the gases with the solid material is performed without
removing solid material from the vessel container.
50 [0145] The method 900 further includes mixing the generated UCl3, UCl4 and NaCl to obtain the desired fuel salt
comparative example. The mixing may be done while the UCl3, UCl4 and NaCl are, independently, in the gas, liquid or
solid phase. For example, the appropriate amount of each compound may be created separately, then the separate
compounds may be heated to the molten state and transferred into a single container where they are allowed to mix
and solidify. This creates a solid fuel salt comparative example that is easily transported. As previously noted, the
55 components can be mixed and/or melted within or external to the reactor vessel.
[0146] The method 900 may be performed as independent operations or may be performed in a way that the execution
of the operations is coordinated. For example, the same chlorine gas may be used in the UO2 contacting operation 902
and the Na2CO 3 contacting operation 904 by connecting the contacting vessels.
26
EP 3 241 218 B1
[0147] FIG. 10 illustrates a comparative example of a coordinated method of manufacturing a fuel salt containing UCl 4
based on the method of FIG. 9. In the coordinated method 1000, a first contacting vessel containing solid UO2, a second
contacting vessel containing solid Na2CO3 and a collection vessel containing element Si solid are provided in a system
preparation operation 1002. This operation 1002 also includes providing the Cl2 and CO as well as bringing all of the
5 components of the system up to the appropriate operating conditions, e.g., from 200-550 °C and 1-5 atm. In a comparative
example, the vessels may be prepared with an inert gas, such as argon, filling the gas space around the solid contents.
[0148] As discussed above, the Cl2 gas may have a modified amount of 37Cl (i.e., an amount different than the naturally
occurring amount of 24 % 37Cl) to change the neutron moderation and absorption of the Cl content in the final fuel salt.
For example, in one comparative example the modified Cl2 may have less than 23 % 37Cl. In another comparative
10 example, the Cl2 gas may have greater than 25 % 37Cl.
[0149] FIG. 11 illustrates a schematic of the contacting vessels and their connections suitable for use in performing
the method of FIG. 10. FIG. 11 shows a first contacting vessel 1102 holding solid UO2, a second contacting vessel 1104
with solid Na2CO 3, and a collection vessel 1106 containing silicon (Si) metal solid. The vessels 1102, 1104, 1106 are
connected such that gas can be flowed through the first vessel 1102 and then through the second vessel 1104. The
15 collection vessel 1106 is further connected to the second vessel 1104 so that it can receive one or both of a gas or liquid
from the second vessel 1104, such as via gravity or an induced pressure differential between the vessels 1104, 1106.
In an alternative comparative example, the Si may be added to the second vessel 1104 or provided in an intermediate
contacting vessel (not shown).
[0150] A Cl2 source 1108, a CO source 1110 and an inert gas source 1112 are shown as gas cylinders, although any
20 source may be used. In the comparative example shown, the CO and Cl2 are connected only to the first vessel 1102,
while the inert gas (illustrated as argon although any inert gas may be used) is connected to all three vessels so that
the environment in each vessel may be independently controlled.
[0151] Ancillary components such as valves, filters, check valves, pressure and temperature sensors, flow monitors
and flow controllers, heating and cooling equipment, pumps, and compressors are not illustrated, one of skill in the art
25 who ready recognize how to implement these components to achieve the results described herein. Likewise, fittings and
access ports, internal diffusion components and other elements may be used where needed and are not specifically
identified on FIG. 11.
[0152] Returning now to FIG. 10, after the system has been prepared in the preparation operation 1002, the Cl2 and
CO are flowed through the first vessel 1102 and the second vessel 1104 of FIG. 11 in a reactant gas flowing operation
30 1004. This serves to contact the UO 2 and the Na2CO3 with the Cl2 and CO so that UCl4 and NaCl are created, respectively,
in each vessel. The gases may be flowed through each vessel 1102, 1104 once (single pass) or recirculated for some
amount of time. For example, in a comparative example the reactant gas flowing operation 1004 may be performed until
all of the UO 2 has been converted into UCl4, until all of the Na2CO 3 or both. Alternatively, the reactant gas flowing
operation 1004 may be performed only for a fixed period of time sufficient to produce as much or more UCl4 and NaCl
35 as currently necessary to create the final fuel salt.
[0153] After flowing gases through the two vessels 1102, 1104, the gases may be collected for reprocessing and
reuse. In particular, if an enriched Cl2 gas is used, it may be cost effective to recover as much of the Cl gas as possible.
Alternatively, the gases could be treated and discharged to the environment, such as, for example, by passing the gases
through a copper oxide scrubber which will reduce the CO.
40 [0154] The amount of UCl4 and NaCl created will depend on the operating conditions and how long the gases are
flowed through the vessels 1102, 1104. Thus, the operator can easily control the system 1100 to get a desired amount
of each material. In addition, the relative size and shape of the vessels 1102, 1104 can be tuned so that a specific relative
amount of NaCl is created for a given amount of UCl4 from a single operation. This allows the system to be configured
to create any desired UCl4-NaCl fuel salt and, by extension as discussed in greater detail below with reference to
45 operation 1012, any UCl3-UCl4-NaCl fuel salt.
[0155] In the system comparative example shown in FIG. 11, the vessels are connected in series and the gases flow
first through the first vessel and then through the second vessel. In an alternative comparative example, the gases may
be flowed independently through each vessel. This alternative comparative example allows different sources (and there-
fore enrichments) of Cl2 to be used.
50 [0156] After flowing gases through the two vessels 1102, 1104, thereby creating at least some UCl4 in the first vessel
1102 and NaCl in the second vessel 1104, a UCl4 gasification operation 1006 is performed in which the temperature
and/or pressure of the first vessel 1102 is adjusted such that the UCl4 is converted from the solid phase to the gas phase.
In a comparative example, the conversion is through sublimation and the UCl4 does not go through a liquid phase. In
an alternative comparative example, the temperature and pressure conditions are adjusted so that the UCl4 is first
55 converted into a liquid before it is boiled into a gas. In a comparative example, the gasification operation 1006 may
maintain the sublimation conditions for a certain period of time selected so that most or all of the UCl4 is converted to
the gas phase.
[0157] In a comparative example the carbochlorination of uranium dioxide is run to completion. However, the extent
27
EP 3 241 218 B1
of the reaction does not matter except for efficiency purposes. Any mixture of powdered uranium dioxide and uranium
tetrachloride can be conveniently separated via uranium tetrachloride’s high vapor pressure. Uranium tetrachloride has
been found to sublimate at temperatures as low as 520 °C. By heating up the uranium tetrachloride, for example in a
comparative example to 520 °C (70 °C below its melting point), the UCl4 should be slowly volatilized and easily removed
5 from any unreacted UO2. The UCl4 gasification operation 1006 may be performed after flushing all or most of the reactant
Cl2 and CO gas from the first vessel 1102.
[0158] The gaseous UCl4 is then transferred to the second vessel 1104 in a UCl4 transfer operation 1008. This may
be achieved through any conventional means. Because UO 2 has a higher melting point (2,865 °C at 1atm) than UCl4
has boiling point (791°C), any UO2 remains in the first vessel as a solid. However, filters or dropouts may be provided
10 to prevent any particulate from being unintentionally removed from the first vessel 1102 during the gas transfer. In a
comparative example, all or substantially all of the UCl4 is transferred during this operation 1008. Alternatively, a known
amount of UCl4 may be transferred based on the desired amount and proportion of the final fuel salt desired. Real-time
flow meters and gas analyzers may be used to verify or control the amount transfers, as is known in the art.
[0159] After the selected amount of UCl4 gas has been transferred to the second vessel 1104, the environment of the
15 second vessel 1104 is adjusted so that the UCl4 gas is condensed and NaCl solid is melted, bringing both to a liquid
state in a fuel salt melting operation 1010. In a comparative example in which the second vessel is maintained at a
pressure of 1 atm, this environment corresponds to a temperature range of from 368 °C and 800 °C depending on the
relative amounts of UCl4 to NaCl (as shown on the lower axis of the ternary diagram of FIG. 4). As the melting point of
Na2CO3 is 851 °C at 1 atm, the environment can be easily adjusted to a point where the UCl4-NaCl mixture is liquid
20 while the Na2CO3 is maintained in the solid state. In a comparative example, for example, the sodium chloride will be
kept at 350 °C, or 20 °C below the eutectic of UCl4-NaCl.
[0160] After the fuel salt melting operation 1010, the some or all of the liquid UCl4-NaCl is then transferred into the
collection vessel 1106 in a UCl4-NaCl transfer operation 1012. This may be achieved by any conventional means, such
as pressurizing the second vessel 1104 with argon to displace the molten UCl4-NaCl mixture and drive it into the collection
25 vessel 1106. Alternatively, the liquid could simply be decanted using gravity into the collection vessel 1106. Again, care
and special equipment may be utilized to prevent any remaining Na2CO 3 from being removed from the second vessel
1104.
[0161] The system 1100 is further designed so that, upon entering the collection vessel 1106, the UCl4 in the liquid
will come into contact with the Si in the collection vessel 1106. In a comparative example, the conditions will be controlled
30 so that the Si reaction has the effect, described above, of stoichiometrically reacting with the UCl4 to form SiCl4 and
UCl3. The collection vessel is maintained at an operating condition so that the UCl3 remains a liquid, while the SiCl4 is
boiled off into a gas that can be easily removed. Therefore, by controlling the amount of Si in the collection vessel 1106,
the amount of resulting UCl3 can be controlled.
[0162] Because the system 1100 allows for easy control of the relative amounts of UCl4 and NaCl that ultimately are
35 transferred into the collection vessel 1106, and the amount of UCl4 converted into UCl3 can also be easily controlled,
any desired UCl3-UCl4-NaCl mixture can be made using the system 1100 and the method 1000.
[0163] After the UCl4-NaCl transfer operation 1112, a final collection operation 1012 may be performed. In this operation
1012, the SiCl4 may be removed and replaced with an inert gas. The fuel salt may be solidified for easy transportation
within the collection vessel 1106 or may be transferred into another container (in a liquid, solid or gaseous state) for
40 storage or transportation.
[0164] The kinetics of the reactions in the vessels 1102, 1104, 1106 will depend on the form of the solid UO2 and solid
Na2CO3 used, e.g., powder, particulate, porous matrix, block, etc., and the flow, temperature and pressure conditions
of the gases, as well as the internal configuration of the contacting vessels, e.g., they are configured to enhance contact
with the flowing gases through the use of internal baffles, diffusers or other components. While any solid form of UO2
45 and Na2CO 3 can be used, high surface area forms will enhance the kinetics of the reaction and be generally more
efficient. Likewise, while any type of vessel, now known or later developed, may be used, contacting vessel designs
specifically adapted to enhance solid-gas and liquid-gas contacting will be more efficient than simpler designs. In addition,
active components such as mixers or agitators may be used in any or all vessels to enhance contacting, gasification or
mixing during any of the operations of FIGS. 9 or 10.
50 [0165] While various comparative examples of the UCl3-UCl4-NaCl fuel salt generation system 1100 and methods
900, 1000 have been described for purposes of this disclosure, various changes and modifications may be made which
are well within the scope of the technology described herein. For example, one of skill in the art will recognize that many
minor alterations to the system 1100 or methods 900, 1000 may be made while still achieving the same control over the
final fuel salt mixture and final product. For example, solid silicon could be introduced into the second vessel 1104 or
55 the solid silicon could be kept in a flow-through chamber (not shown) between the second vessel 1104 and the collection
vessel 1106. Likewise, the first and second vessels could be operated independently, instead of serially, and the UCl 4
gas and NaCl liquid could be separately transferred into the collection vessel 1106.
[0166] In addition, the methods of FIGS. 9 or 10 may be further adapted if a UCl3-NaCl binary mixture is desired. In
28
EP 3 241 218 B1
this comparative example, the entire UCl4-NaCl mixture can be sparged with hydrogen for extended periods of time
initiating the reaction:
2UCl4 + H2(g) = 2UCl3 + 2HCl(g).
By providing the excess H2, all of the UCl4 may be converted to UCl3.
5
Synthesis of UCl4 from UO2 using Ammonium Chloride
[0167] FIG. 16 illustrates a comparative example of a method for the manufacture of UCl4 using ammonium chloride.
In the comparative example of the method 1600 shown, a mixture of solid UO2 and NH4Cl is created in a uranium
10 preparation operation 1602. The solid mixture may be created using any conventional means such as grinding, crushing,
or cutting with any suitable equipment such as a ball mill, rod mill, autogenous mill, SAG mill, pebble mill, roll grinder,
stamp mill, etc.
[0168] A first conversion operation 1604 is then performed, in which the solid mixture is exposed to HCl under the
conditions appropriate to generate (NH4)2UCl6 by the reaction:
15 UO2(s) + 2NH4Cl(s) + 4HCl(g) = (NH4)2UCl6 · 2H2O
In a comparative example, the conversion operation 1604 includes heating the solid mixture while exposing the mixture
to the HCl gas in an enclosed environment to 100 °C at 1 atm and maintaining the temperature until sufficient conversion
is obtained. Depending on the comparative example, the temperature may be maintained for at least one hour. However,
for full conversion additional time may be desirable, such as maintaining the temperature for two, three, four or more
20 hours. Depending on the concentration of HCl used, the temperature may be maintained just below the boiling point of
aqueous HCl and allows the HCl gas environment to be maintained by providing a pool of aqueous HCl in the enclosed
environment.
[0169] Alternative methods for achieving the conversion to (NH4)2UCl6 are also possible, such as passing HCl gas at
a higher temperature through a kiln, moving bed, cyclone, fluidized bed reactor, or any other gas-solid contacting tech-
25 nologies. Fuming HCl (aqueous HCl at greater than 40 % concentration) may also be used to generate HCl gas. In yet
another comparative example, the mixture may be contacted with aqueous HCl in liquid, rather than gaseous, form
under conditions that result in the (NH4)2UCl6.
[0170] Yet another comparative example involves creating HCl gas for the first conversion operation 1604 by using
calcium chloride (CaCl2) and aqueous HCl. In this comparative example, HCl gas is generated via the following reaction:
30 CaCl2 (s, anhydrous) + HCl (aq) = CalCl2 · 2H2O (s) + HCl (g)
[0171] In this comparative example, the first conversion operation 1604 includes providing anhydrous CaCl2 pellets
in the reaction environment and contacting the anhydrous CaCl2 with aqueous HCl. In a comparative example the
contacting may be done by placing the CaCl2 pellets in a pool of HCl. In the first conversion operation 1604, a reactor
vessel may be provided that can separately hold both the mixture and the pool of HCl with CaCl2 pellets so that only
35 the HCl gas can contact the mixture. In an alternative comparative example, the liquid HCl may be circulated or flowed
over a solid form CaCl2. Regardless of how the contacting is performed, as the water is removed from the aqueous HCl
to hydrate the CaCl2, the concentration of the HCl in the liquid increases until HCl gas is released into the environment.
This method for generating HCl gas can use a safer and more easily handled aqueous HCl concentration as the input
and may be preferred over using other sources of HCl gas. This method for making HCl may be adapted for use with
40 any of the methods described herein.
[0172] Furthermore, aqueous HCl and NH4Cl having a modified amount of 37Cl isotope as the anion may be used to
generate chloride fuel salts from the method 1600. As mentioned above, separation and collection of the 37Cl isotope
is possible by several methods. This 37Cl can then be used to generate hydrogen chloride which, when combined with
water, will generate modified aqueous HCl. There are many known methods for making hydrogen chloride and any
45 suitable method maybe used, including combining Cl2 gas with H2 gas and reacting NaCl with H2SO4. Likewise, modified
NH4Cl may also be generated using a source of 37Cl from any known method. The amount of modification of either of
both the HCl and the NH4Cl may be controlled to achieve any desired ratio of 37Cl to total Cl in the final fuel salt, such
as a final salt having a ratio of 37Cl to total Cl in the fuel salt of greater than 25 %.
[0173] After the first conversion operation 1604, a second conversion 1606 operation is performed in which the
50 (NH4)2UCl6 is maintained under the appropriate conditions to convert it into UCl4 by the reaction:
(NH4)2UCl6 = UCl4 + 2NH4Cl
In a comparative example, the second conversion 1606 includes removing the (NH4)2UCl6 · 2H2O from the HCl envi-
ronment, heating it to a temperature sufficient for the conversion until the desired amount of the (NH4)2UCl6 has been
converted to UCl4. Conversion is expected above 200 °C, but higher temperatures may speed the reaction. In a com-
55 parative example, the (NH4)2UCl6 · 2H2O may be heated to any temperature above 200 °C but below a temperature
that melts the (NH4)2UCl6 or UCl4, such as from 200-500 °C, from 250-350 °C or 400 °C. Alternative comparative
examples are also possible, including comparative examples that heat the (NH4)2UCl6 to temperatures that cause the
generated UCl4 to melt during the conversion operation 1606.
29
EP 3 241 218 B1
[0174] The comparative example of the method 1600 shown is suitable for producing UCl4 product in bulk. Furthermore,
since UCl3 can be easily obtained from UCl4 via reduction, such as described above, the method 1600 can be easily
used to create bulk quantities of UCl3 also, simply by adding an optional reduction operation 1608, as shown in FIG. 16.
[0175] A comparative example of method 1600 was performed to verify the method. In the experiment, 2 grams of
5 UO2 and 0.44 grams of NH4Cl (i.e., 10 % excess NH4Cl) were ground together and placed in a reactor with aqueous
HCl so that the environment had excess HCl gas. The reactor was heated to 100 °C and maintained at that temperature
for four (4) hours. The resulting product was then removed and placed in a decomposition tube under vacuum and
heated from 80 to 400 °C. The creation of UCl4 was verified through x-ray diffraction.
[0176] In the experiment, the HCl gas was produced using the CaCl2 method. The mixture of UO2 and NH4Cl was
10 placed in an open-topped glass vessel and the vessel placed within the reactor. A pool of aqueous HCl was provided
in the bottom of the reactor and pellets of CaCl2 were placed in contact with the aqueous HCl. An excess of HCl gas
was produced by the hydration of the CaCl2 and this gas reacted with the solid mixture in the vessel.
Uranium Chloride-Fluoride Fuel Manufacturing Processes

15
[0177] FIG. 17 illustrates a comparative example of a method for manufacturing UCl3F. The method 1700 is based
on the following reaction:
3UCl4 + UF4 = 4UCl3F
In the comparative example shown, the method 1700 starts with preparing amounts of UCl4 and UF4 in a precursor
20 preparation operation 1702. The UCl4 and UF4 may be prepared by any methods described herein or known in the art.
[0178] Solid UCl4 and UF4 are then combined in stoichiometric amounts in a combining operation 1704. In the com-
parative example shown, three parts UCl4 and one part UF4 are combined. The combining operation 1704 may be done
in a mixer (e.g., a ball mill) in anticipation for the mixing operation 1706, discussed next, or may be done an intermediate
vessel prior to transfer to a mixer.
25 [0179] The combined UCl4 and UF4 is then mixed for a period of time to obtain a solid UCl3F mixture in a mixing
operation 1706. The mixing operation 1706 may use any conventional solid mixing means such as grinding, crushing,
or cutting with any suitable equipment such as a ball mill, rod mill, autogenous mill, SAG mill, pebble mill, roll grinder,
stamp mill, etc. The mixing may or may not be performed at an elevated temperature or pressure. The time period of
mixing may be a fixed time, based on the mixing conditions (e.g., at a high temperature), selected from 15 minutes to
30 5 days, such as, for example, a quarter of an hour, half an hour, three-quarters of an hour, an hour, two hours, four
hours, six hours, eight hours, 12 hours or 24 hours. Alternatively, mixing may be performed for a time period sufficient
for completion of the reaction, which time period is determined based on real-time or prior testing.
[0180] In an alternative comparative example, the mixing operation 1706 may be performed with one or both uranium
salts in a molten state, instead of a solid state. In yet another comparative example, the mixing operation may be
35 performed in the reactor core of a reactor, such that the UCl3F salt is created within the reactor core.
[0181] Any and all of the operations 1702-1706 may further be performed in an oxygen free environment, such as by
mixing under argon or some other inert gas.
[0182] An experiment was performed to validate the method 1700. As performed, 700 mg of UCl4 was mixed with 193
mg of UF4 in a ball mill for one hour under argon. After the one hour mixing time x-ray diffraction analysis of the precursors
40 prior to mixing and the product of the experiment indicated that none of the precursor UCl4 or UF4 was present in the
final product. Based on this, it is presumed that the reaction went to completion and the final product was UCl3F.
[0183] Note that the method 1700 can be adapted to produce UCl2F2 and UClF3 by varying the stoichiometric amounts
of the precursor salts. As discussed above, these salts may also have suitable properties for use as nuclear fuel, or as
a constituent of a nuclear fuel salt, in a molten salt reactor.
45 [0184] FIG. 18 illustrates a comparative example of another method for manufacturing UCl3F. This method 1800
generates UCl3F from UO2 based on the following reactions:
2UO2(s) + 3NH4Cl(s) + NH4HF2(s) + 7HCl(g) = 2[NH4]2UCl5F·2H 2O(s)
50 [NH4]2UCl5F·2H2O(s) = 2NH 4Cl + UCl3F + 2H2O
This reaction is similar to that described with reference to FIG. 16.

[0185] In the comparative example of the method 1800 shown, a mixture of solid UO2, NH4Cl, and NH4HF2 is created
in a precursor preparation operation 1802. The solid mixture may be created using any conventional means such as
55 grinding, crushing, or cutting with any suitable equipment such as a ball mill, rod mill, autogenous mill, SAG mill, pebble
mill, roll grinder, stamp mill, etc.
[0186] A first conversion operation 1804 is then performed, in which the solid mixture is exposed to HCl under the
conditions appropriate to generate (NH4)2UCl5F by the reaction:
30
EP 3 241 218 B1
2UO2(s) + 3NH 4Cl(s) + NH4HF2(s) + 7HCl(g) = 2[NH4]2UCl5F·2H2O(s)

In a comparative example, the first conversion operation 1804 includes heating the solid mixture while exposing the
mixture to an excess of HCl gas in an enclosed environment to 100 °C at 1 atm and maintaining the temperature until
sufficient conversion is obtained. Depending on the comparative example, the temperature may be maintained for at
5 least one hour. However, for full conversion additional time may be desirable, such as maintaining the temperature for
two, three, four or more hours. Depending on the concentration of HCl used, the temperature may be maintained just
below the boiling point of aqueous HCl and allows the HCl gas environment to be maintained by providing a pool of
aqueous HCl in the enclosed environment.
[0187] Alternative methods for achieving the conversion to (NH4)2UCl5F are also possible, such as passing HCl gas
10 at a higher temperature through a kiln, moving bed, cyclone, fluidized bed reactor, or any other gas-solid contacting
technologies. Fuming HCl (aqueous HCl at greater than 40 % concentration) may also be used to generate HCl gas. In
yet another comparative example, HCl gas for the first conversion operation 1804 may be created using calcium chloride
(CaCl2) and aqueous HCl as has been previously described with reference to FIG. 16.
[0188] After the first conversion operation 1804, a second conversion 1806 operation is performed in which the
15 (NH4)2UCl5F is maintained under the appropriate conditions to convert it into UCl3F by the reaction:
[NH 4]2UCl5F·2H2O(s) = 2NH4Cl + UCl3F + 2H2O
In a comparative example, the second conversion 1806 includes removing the (NH4)2UCl5F· 2H2O from the HCl envi-
ronment, heating it to a temperature sufficient for the conversion until the desired amount of the (NH4)2UCl5F has been
converted to UCl3F. Conversion is expected above 200 °C, but higher temperatures may speed the reaction. In a
20 comparative example, the (NH4)2UCl5F· 2H 2O may be heated to any temperature above 200 °C but below a temperature
that melts the (NH4)2UCl5F or UCl3F, such as from 200-500 °C, from 250-350 °C or 400 °C. Alternative comparative
examples are also possible, including comparative examples that heat the (NH4)2UCl5F to temperatures that cause the
generated UCl3F to melt during the second conversion operation 1806.
[0189] The method 1800 may also be used to generate modified 37Cl salts by using aqueous HCl and NH4Cl having
25 a modified amount of 37Cl isotope as the anion, as has been discussed elsewhere. The amount of modification of either
of both the HCl and the NH4Cl may be controlled to achieve any desired ratio of 37Cl to total Cl in the final fuel salt, such
as a final salt having a ratio of 37Cl to total Cl in the fuel salt of greater than 25 %.
Fuel Salt Examples

30
[0190] Various fuel salt comparative examples were manufactured in the laboratory and tested to confirm the ternary
phase diagram of FIG. 4.
[0191] A number of UCl3 batches were prepared. One batch, which was typical of the preparations, was prepared as
follows. A 1.895 g sample of uranium metal was washed with hexanes and treated with nitric acid to remove oxides.
35 The uranium metal was placed in a quartz crucible, loaded into a tube furnace and held at 250 °C for 30 minutes under
flowing H2, producing UH3. The UH3 was observed as a higher surface area product, morphologically different than the
uranium metal starting material. The furnace temperature was increased to 350 °C, the flowing gas switched to HCl,
and held at that temperature for 90 minutes, producing UCl3. The atmosphere was change to H2 and the furnace brought
to room temperature. The tube furnace was held under H2 atmosphere and transferred to an Ar glovebox. The UCl3 was
40 characterized by x-ray diffraction, with a total recovered mass of 2.47 g
[0192] A number of UCl4 batches were also prepared. One batch, which was typical of the preparations, was prepared
as follows. A 1.50 g sample of UO3 was added to a Schlenk flask and charged with Ar. Hexachloropropene was added
under inert conditions in 10 times molar excess. The flask temperature was increased to 75 °C and held for 30 minutes.
The temperature was increased to reflux around 165 °C and held for 3 hours. The product was brought to room temperature
45 and washed with carbon tetrachloride, toluene, and hexane. After the hexane wash the product was dried and identified
as UCl4 by x-ray diffraction. The procedure yielded 1.9 g of UCl4.
[0193] The binary and ternary mixtures were created by melting appropriate amounts of the constituent compounds
in a Mo crucible at 650 °C for 2 hours under an Ar atmosphere. A sample of 66NaCl-34UCl3 was prepared and charac-
terized in the same manner using 3.761 g UCl3 and 1.239 g NaCl. A typical batch for the 71UCl4-17UCl3-12NaCl contained
50 0.6188 g of UCl4, 0.1331 g of UCl3 and 0.0158 g of NaCl. The three components were added to a Mo crucible and
treated as described above. The mixed salt products were analyzed by differential scanning calorimetry.
[0194] An embodiment of UCl3F was created using the synthesis reaction between UCl4 and UF4 as described above.
In that experiment, 700 mg of UCl4 was mixed with 193 mg of UF4 in a ball mill for one hour under argon. After the one
hour mixing time x-ray diffraction analysis of the precursors prior to mixing and the product of the experiment indicated
55 that none of the precursor UCl4 or UF4 was present in the final product. Based on this, it is presumed that the reaction
went to completion and the final product was UCl3F.
[0195] The following fuel salts were created and their melting points determined as shown in Table 3.
31
EP 3 241 218 B1
Table 3 - Fuel Salt Embodiments and comparative examples

Fuel Salt Melting Point (°C)
5 71UCl4-17UCl3-12NaCl 491-512
66NaCl-34UCl3 508
17UCl3-40.5UCl4-42.5NaCl 351
47UCl4-53NaCl 343
10
UCl3F NA
Fuel Modification to Reduce Corrosion
15 [0196] Management of molten salt corrosion may dictate the use of advanced materials, such as nickel and molybdenum
alloys, for fuel salt-facing components, such as reflectors, PHX and vessel. In some comparative examples, because
of the design and operating conditions of suitable reactors components may only need to be clad or coated using these
advanced materials, while the bulk of such components can be constructed from more traditional materials such as
stainless steels and other materials with existing ASME code cases. Additionally, if components will be replaced on a
20 regular basis, it is not necessary to provide exceptional clad performance or to demonstrate perfect coatings.
[0197] In a comparative example, a compatible corrosion resistant cladding (CRC) will be utilized in conjunction with
ASME Code compliant base material on all fuel salt-facing surfaces. ASME Section III, Division V "High Temperature
Reactors" permits the use of CRC. Careful selection of materials, joining processes, and nondestructive examination
allows for the construction of a robust composite metallic reactor enclosure with multiple layers of defense against
25 corrosion, radiation damage, and high temperature service. In the comparative example, the CRC is the first barrier
against uncontrolled release of radionuclides. It is comprised of corrosion resistant cladding on pressure vessel plate,
piping, primary heat exchanger tubing and tube sheets and is designed for positive pressure.
[0198] In a comparative example, the fuel salt is adapted to prevent or reduce corrosion by providing one or more
chloride salts that correspond to the salts that would have been created through corrosion. By providing such a salt as
30 one of the (or the only) additional, non-fissile chloride salt, this will reduce or prevent the corrosion of the salt-facing
mechanical components.
[0199] FIG. 12 illustrates a comparative example of a method of reducing corrosion in a nuclear reactor using a molten
nuclear fuel. The method 1200 is suitable for any fuel salt anion including Cl, F, or combinations such as Cl3F, Cl2F,
Cl2F2, etc. In the comparative example shown, the method 1200 starts with an identification operation 1202 that deter-
35 mines what material or materials will be salt-facing in the reactor. For example, as discussed above it is anticipated that
nickel and molybdenum alloys may be used for various salt-facing components.
[0200] The identification operation 1202 is then followed by a determination of the cation or cations in the identified
material that is most likely to corrode in an analysis operation 1204. The analysis operation 1204 may be a purely
theoretical analysis, for example, based on a comparison of the relative free energies of salt formation for each of the
40 elements in the material. Alternatively or in addition, the analysis operation 1204 may include corrosion testing using
different representative salts in order to experimentally identify the likely corrosion chemistry.
[0201] After the cation or cations subject to salt corrosion have been determined, a fuel salt may be generated spe-
cifically for that reactor that includes in the nuclear fuel salt a corrosion inhibiting salt consisting of the salt anion (e.g.,
chloride in a MCFR) and the material cation (e.g., Mo, if the analysis operation 1204 determines Mo corrosion is an
45 issue with that particular alloy). The amount of the corrosion inhibiting salt may be determined experimentally or may
be selected based on the amount of salt necessary to eliminate the corrosion reaction by bringing amount of the corrosion
inhibiting salt in the fuel salt to the amount necessary to achieve equilibrium under the reactor’s operational conditions
(pressure, temperature, etc.). Alternatively, the maximum amount of the corrosion inhibiting salt in the nuclear fuel that
can be solubilized in the nuclear fuel.
50 [0202] For example, in a comparative example of the method 1200 it may be determined in the analysis operation
1204 that Cr corrosion will likely occur. In response, a corrosion resistant fuel may be created that includes at least some
CrCl2.
[0203] FIG. 13 lists some alloys of potential applicability. The figure lists the alloy, the major element or elements (>1
% by mass) of each alloy, and the minor elements (<1 % by mass) of each alloy.
55 [0204] Experiments were performed on some of the alloys in FIG. 13 using both 71UCl4-17UCl3-12NaCl and 66NaCl-
34UCl3 fuel salt comparative examples under representative conditions. The alloys tested included 316SS stainless
steel. In these experiments, a coupon of alloy was inserted into a volume of the fuel salt and the conditions were
32
EP 3 241 218 B1
maintained at 650 °C for 100 hours. The coupons were then inspected using energy dispersive spectroscopy. Inspection
of the stainless steel showed significant depletion of the chromium and measurable depletion of the Fe from the alloy
coupon. This validated the results of theoretical analysis based on the relative free energies of the cations in the alloy
(see below) that indicated that Cr would be more corroded by Cl salt, Fe relatively less, and Ni and Mo even less.
5 ΔHCrCl2 < ΔHCrCl3 < ΔHFeCl2 < ΔHNiCl2 < ΔHMoCl2
In response to this analysis, a corrosion inhibiting salt could include one or more of CrCl2, CrCl3 and FeCl3 for the 316SS
alloy. Some or all of these corrosion inhibiting salts could be added to a chloride fuel salt to reduce or eliminate the
corrosion of this alloy.
10 Fuel Monitoring
[0205] During operation, the fuel salt in a molten salt reactor may be monitored. This monitoring may be done in order
to determine when sufficient breeding has occurred so that some of the fuel may be removed and replaces with new
fuel in order to keep the reactivity down. Such monitoring may take many forms but includes monitoring at least one
15 concentration of a molecule in the molten salt that is indicative of the overall quality of the salt. In response to the results
of the monitoring, e.g., a result indicating sufficient breeding has occurred, some action may be taken such as changing
an operational parameter or replacing some fuel salt with new fuel salt.
[0206] Monitoring may be performed using any type of suitable speciation method or equipment including spectroscopic
methods or tools, now known or later developed. For example, in a comparative example, the monitoring is performed
20 in real-time using Raman spectroscopy, or laser ablation methods. Raman spectroscopy provides information from
molecular vibrations that can be used for sample identification and quantitation. The technique involves shining a mon-
ochromatic light source (i.e. laser) on a sample and detecting the scattered light. Some amount of fuel may be removed
from the reactor core, such as in a side stream, and passed through a monitoring cell that includes a ’window’ through
which the spectroscopy can be performed. Examples of Raman windows materials are fused quartz, fused silica, sapphire,
25 diamond, and some glasses. Laser ablation methods excited the compound to high energy states. The excited material
can be evaluated with a mass spectrometer or optically to determine element composition and possibly molecular
species. Any material may be used as long as it can meet the operational parameters of the reactor and monitoring
system. In some comparative examples, the removed fuel from the core for monitoring may be all of or a portion of a
side stream of fuel removed for fuel polishing/processing as described further below, a side stream for control purposes
30 to be replaced with fertile fuel, and/or a side stream off of the primary coolant loop 110 described above with respect to
FIG. 1A.
[0207] Other sampling configurations than a side-stream sampling configuration may also be used. For example, in
a comparative example a window may be provided somewhere in the reactor core, through which the speciation equip-
ment (e.g., Raman spectrograph or ablation system) may transmit light to the fuel, or the headspace, if any, above the
35 fuel. Alternatively, the speciation equipment may be a remote instrument that is wirelessly- or wire-connected to a
monitoring system outside of the reactor and that is capable of being inserted into the fuel salt or a fuel salt stream, such
as through a wall of the reactor core or piping. In another comparative example, the spectrograph may be included within
a heat exchanger apparatus or other component physically within the reactor core in order to sample fuel salt directly.
In yet another comparative example, the spectrograph or ablation system may be an ancillary component 127 as described
40 with reference to FIG. 1A.
[0208] In yet another comparative example that is not real-time, samples may be periodically removed from the reactor
core and analyzed. Such samples may then be returned or collected for later use. For example, in a comparative example
some amount of fuel salt is replaced in an operating MCFR on a schedule and the removed fuel salt is analyzed by laser
ablation, optical methods, or with a Raman probe. The results of this analysis are then used to modify one or more
45 parameters such as to modify the schedule for replacing fuel salt. Examples of other operation parameters that may be
adjusted include reactor core temperature, fuel salt replacement quality, a position of a displacement element, a reactivity
of the fuel salt, and a feed rate of an additive to the reactor core.
[0209] FIG. 14 illustrates a method of operating a molten salt nuclear reactor. In the comparative example shown, the
method 1400 starts with maintaining breed-and-burn behavior in molten salt in a reactor core of the nuclear reactor in
50 operation 1402.
[0210] During operation, at least some of the molten salt is analyzed in a real-time analysis operation 1404. In a
comparative example, the analysis is done using speciation methods such as a Raman spectroscopy or laser ablation
methods to determine at least one concentration of a molecule in the molten salt. Alternatively, the speciation may be
done to determine most if not all of the molecules in the fuel and their relative amounts allowing for a complete or near-
55 complete chemical makeup of the fuel salt at that location to be known. In yet another comparative example, radiation
detectors such as gamma detectors may be used to monitor the energy or activity of the molten salt, and determinations
of the partial or complete chemical makeup of the fuel salt at that location may be made based on the salt makeup and
measurements.
33
EP 3 241 218 B1
[0211] Based on the resulting knowledge of the chemical makeup of the fuel salt, an adjustment operation 1406 may
be performed if the chemical makeup or a particular concentration exceeds some predetermined threshold. The adjust-
ment may include adjusting one or more operational parameter of the nuclear reactor or performing specific tasks such
as fuel replacement.
5 [0212] Raman spectroscopy is but one of the speciation techniques that could be used to monitor fuel salt quality
and/or other safety or design considerations, e.g., accumulation of fission products, viscosity, etc. Other techniques
include absorbance spectroscopy, laser ablation spectroscopy, laser induced breakdown spectroscopy, infrared (IR)
spectroscopy, and electrochemistry to determine the relative concentrations of different salt constituents (e.g., UCl3,
UCl4 and NaCl). As discussed above, any technique, now known or later developed, may be used for monitoring.
10
Freeze Plugs
[0213] Another aspect of molten fuel salt reactors includes the possible use of frozen material plugs for different
purposes. A frozen material plug, referred to herein as a freeze plug, is a volume of material that at intended operational
15 conditions is solid, nonreactive with the fuel salt, and has a sufficiently strong solid structure that it can be used to prevent
the movement of fuel salt within the reactor but that also, upon reaching a desired activation temperature, melts to allow
mixing with and movement of the fuel salt.
[0214] Freeze plugs may be used for many different purposes and, in some comparative examples, for multiple
purposes at one time. For example, in a simple comparative example a freeze plug may be used to prevent fuel salt
20 from flowing out of the reactor core into a dump tank when at operational temperatures, but that melts if the reactor core
temperature exceeds that plug’s activation temperature, thereby allowing the fuel salt to exit into the dump tank. This
may be achieved by locating the dump tank below the reactor core so that the fuel salt can flow by gravity or by maintaining
the reactor core and the dump tank at different pressures so that, upon melting of the freeze plug, molten fuel salt flows
under pressure into the dump tank.
25 [0215] In some cases, the freeze plugs may be detectable within the fuel upon melting. For example, the freeze plug
may be made of some material that is a neutron poison so that if the reactor core exceeds the activation temperature
the poison material melts and is subsequently distributed throughout the reactor core reducing reactivity. In this com-
parative example, the freeze plug is the neutron poison. Achieving a similar function, in another comparative example
the freeze plug is used to prevent a quantity of neutron poison held in a vessel separate from the reactor core from
30 mixing with the fuel salt. Upon reaching the activation temperature, the freeze plug melts and releases the poison into
the reactor. As with the dump tank comparative examples, the vessel of poison may be located above the reactor core
so that it flows under gravity into the reactor core or alternatively, may be maintained under pressure so that the poison
is forced into the reactor core. In this manner, activation or melting of the freeze plug is highly detectable in the neutronic
reactions of the reactor core. In additional or alternative comparative examples, the freeze plug may contain or separate
35 one or more elements that are detectable in other suitable manners, such as by the fuel monitoring system (e.g., Ramen
Spectroscopy), other sensors within the reactor, etc. Many other configurations of safety-related freeze plugs are possible.
[0216] Freeze plugs may be passively maintained by providing a freeze plug material that has the appropriate melting
point tailored to the desired activation temperature. In an alternative comparative example, freeze plugs may be actively
maintained by providing an actively cooled component, such as a cooling jacket, around the location of freeze plug.
40 Actively maintained freeze plugs may be used, for example, to allow for operator control of activation (through control
of the cooling) or as a safety measure that activates upon loss of external power or control. Active control also allows
for the use of fuel salt as a freeze plug, simplifying the use of freeze plugs in the operation of the reactor.
[0217] Suitable freeze plug materials include salts that are miscible in the fuel salt and that have the appropriate
melting temperature higher than that of the reactor’s operational temperature. In some cases, it may be appropriate to
45 include a chemical barrier between the freeze plug and fuel salt to reduce the occurrence of inadvertent dissolution of
the plug. For example, in a comparative example of an MCFR using a ternary fuel salt such as those described above,
a suitable freeze plug may be any chloride salt, which has a melting point higher than that of the ternary salt comparative
examples.
[0218] For moderating purposes, a comparative example of a freeze plug that acts as a neutron poison includes freeze
50 plugs made with 35Cl. As discussed above, 35Cl is a neutron moderator and absorber and salts of 35Cl when dissolved
into the fuel salt will reduce the salt’s reactivity. Other potential freeze plugs suitable for use in an MCFR include chloride
salts of fission products with high absorption cross sections such as 133Cs, 101Ru, 103Rh, 99Tc and 105Pd.
[0219] In some comparative examples, the freeze plug material may not be a fuel salt or even a salt with the same
anion as the fuel salt. Suitable freeze plug materials include those materials with a melting temperature that is targeted
55 for the safety melting point for an action to occur and likely not react negatively with the fuel salt. Modified fuel salt with
a higher melting temperature is just one example of this. Thus, a freeze plug potentially may be made of any material.
[0220] In yet another comparative example, the freeze plug material may be a neutron reflective material such that,
upon reaching the activation temperature, the reflective freeze plug melts and provides less reflection of neutrons,
34
EP 3 241 218 B1
thereby changing the overall reactivity of the reactor. In this comparative example, the freeze plug may further expose,
release or uncover a neutron poison upon melting. For example, a reflective freeze plug may cover a neutron absorber
and thus operate as a reflector component that self-destructs upon reaching an activation temperature.
5 Ongoing Fuel Polishing
[0221] In a comparative example, during normal operations MCFR fuel salt only receives minor treatments other than
periodic replacement of an amount of nuclear fuel salt with fresh fuel salt. In some cases, the removed fissile fuel will
be replaced with fertile fuel salts. Some possible minor treatments for fuel polishing include mechanical filtering of fission
10 products such as the noble metals and minimal removal of noble gases. In a comparative example, the treatment includes
removal of noble gases that are created during the ongoing nuclear reaction. Such gases will include various isotopes
of Kr, Xe and Ar. These gases may be removed by sparging of the fuel salts. Sparging will also have the effect of
removing any other gaseous volatile fission products that may be created.
[0222] In a comparative example, fissile materials are not separated in any portion of the MCFR fuel cycle. Rather,
15 bred plutonium is mixed in operation with fertile uranium and created fission products, including lanthanides, which are
chemically similar and expected to be soluble in the fuel salt comparative examples. In this manner, fuel polishing may
be simplified in MCFR over typical fuel processing of prior fluoride molten salt reactors since the lanthanides in the
MCFR will not need to be removed.
[0223] Fuel polishing may further include mechanical filtering to remove any precipitates that may be generated by
20 the ongoing nuclear reaction and/or operation of fluid flow and moving components. Both filtering and sparging may be
performed by conventional means including those presented above with reference to FIG. 1A.
[0224] Fuel polishing may further include mechanical filtering to remove any precipitates that may be generated by
the ongoing nuclear reaction and/or operation of fluid flow and moving components. Both filtering and sparging may be
performed by conventional means including those presented above with reference to FIG. 1A.
25 [0225] FIG. 19 illustrates a comparative example of a polishing system for fuel polishing that utilizes a drain tank 1904.
In a comparative example, the system 1900 is designed to remove most, if not all, insoluble fission products, corrosion
products, and other compounds that have the potential to alter the fuel salt stoichiometry beyond design specifications.
The system 1900 may also clean the fuel salt to acceptable specifications under normal and off-design operation. In the
system 1900 illustrated, gas phase contaminants may evolve into the void space above the reactor core. These con-
30 taminants could contain fission products, noble gases, UCl4, etc. The off-gas system includes the equipment for safely
handling this off gas stream and recovering the UCl4. The system 1900 includes equipment to dissipate the heat, collect
and store/dispose of stable and long-lived gases, recovery of the UCl4, and recompression/recycling of the inert gases.
The system 1900 further may have the ability to reduce the concentration of corrosion elements such as oxygen and
sulfur. In addition, the system 1900 may remove dissolved noble gases, such as 135Xe.
35 [0226] In the comparative example shown, the system is comprised of several different unit operations to facilitate the
cleanup of the fuel salt. These include: Filtration of insoluble fission products; helium bubble generation to aid in the
removal of noble gas fission products from the fuel salt prior to reinsertion in the reactor core; degassing of the helium
bubbles/noble gases from the molten salt prior to reinsertion in the reactor core; passing the degassed helium bub-
bles/noble gases through a long delay chemical trap system where the isotopes will decay to insignificant levels; and
40 recycling of the helium. In a comparative example, any vent gases from the reactor system would be vented to this
system 1900. These gases would pass through a scrubber where it would be contacted with cooled fuel salt to remove
any UCl4 in the gas stream.
[0227] In the comparative example shown, the drain tank 1904 is located at a level lower than the fuel salt level 1912
in the reactor core 1902 to allow molten fuel salt from the reactor core 1902 to flow under gravity into the drain tank 1904
45 for polishing. The fuel 1906 may be removed from one or more locations in the reactor core by gravity flow or siphon.
The transfer of gas between the reactor core head space 1920 and the drain tank headspace 1921 may be controlled
to maintain the desired level 1916 of fuel salt in the drain tank 1904. In a comparative example, to preserve the integrity
of the reactor core, a dip tube 1910 is provided from the top of the reactor core 1902 to the depth within the fuel salt
1906 from which removal is desired. The flow rate may be controlled by valves or by selection of discharge pipe diameter
50 and pressure differential between the reactor core 1902 and drain tank 1904.
[0228] The treatment system 1900 can be operated in continuous of batch fashion. The system may be sized to treat
any desired throughput, such as for example 1 % per minute or 0.1 % per minute of the total fuel salt 1906 in the system.
In a comparative example, the drain tank 1904 may be maintained at the same operating temperature and pressure as
the reactor core. In an alternative comparative example, drain tank and treated sidestream of fuel salt may be maintained
55 under different conditions selected to improve treatment or handling characteristics of the fuel salt. For example, in a
comparative example the fuel salt 1906 in the drain tank 1904 may be maintained at a temperature from 800-900 °C,
such as 850 °C. A heater exchanger 1908 is illustrated in the drain tank 1904 for temperature control, however any
suitable technology may be used such as heated jacket around the drain tank. In yet another comparative example, the
35
EP 3 241 218 B1
relative operating conditions of the reactor core 1902 and the drain tank 1904 may allow treatment to occur without
actively heating the drain tank 1904, in which case the tank 1904 may only be insulated rather than actively heated.
[0229] In some comparative examples, the number of valves may be reduced or eliminated to reduce the amount of
maintenance needed. For example, in a comparative example the system is operated in batch fashion and valves are
5 eliminated. The drain tank 1904 is filled from and discharged back into the reactor core 1902 by adjusting the pressure
in the drain tank 1904 relative to the reactor core 1902, e.g., by pumping gas into the drain tank 1904 or by physically
raising/lowering the drain tank 1904 relative to the fuel salt level 1912 in the reactor core 1902. In an alternative com-
parative example, one or more pumps 1914, such as the VTP™ variable speed molten salt pump by Flowserve Corpo-
ration, may be provided to transfer treated fuel salt 1906 back to the reactor core 1902. In a comparative example, it
10 would be undesirable to have level control valves in the return line, so the level 1916 of salt 1906 in the drain tank 1904
could be controlled by the speed of the pump 1914. The level 1916 could be measured by either a non-intrusive nuclear
level detector, by thermocouples in the drain tank or by any suitable level sensing technique.
[0230] The system 1900 includes three different fuel salt treatment components that can receive fuel salt from the
drain tank 1904: a degassing system 1924 that includes a helium contactor 1926 and a separation vessel 1928; a filtration
15 system illustrated as filter 1930; and a UCl4 condenser 1932. In the comparative example illustrated, the degassing
system 1924 and filtration system 1930 are connected serially so that fuel salt exiting the degassing system flows through
the filtration system and the UCl4 condenser 1932 is a parallel treatment component. However, in alternative comparative
examples the three components may be connected in any configuration either serially or in parallel. Each component
1924, 1930, 1932 will be discussed in greater detail below.
20 [0231] In the degassing system 1924 illustrated, fuel salt 1906 from the drain tank 1904 is transferred into a degassing
vessel that acts as a helium contactor 1926 where helium would be added in the presence of strong agitation. In a
comparative example, a rotary degasser may be used as the helium contactor 1926. As a result of the contacting, the
135 Xe and other noble gases diffuse from the fuel salt 1906 to the helium gas. The helium gas, now a He mixture with
135 Xe and other noble gases, would separate from the fuel salt 1906 and vent to the off gas treatment system 1922,
25 either directly or indirectly by being routed first through the headspace 1921 in the drain tank 1904. The fuel salt 1906
from the helium contactor 1926 is transferred, for example via overflow by gravity or by pumping, to a separation vessel
1928 to provide more residence time for the helium to separate from the fuel salt 1906. In a comparative example, the
helium contactor 1926 and separation vessel 1928 are located at a higher elevation than the drain tank to provide the
pressure drop necessary for the fuel salt to "overflow" from the helium contactor, through the separation tank and to the
30 filter 1930 without a second pump. Alternative comparative examples may also be used in which pumping or differential
pressure transfer may be used. In yet another comparative example, the separation vessel 1928 may be omitted in favor
of a larger helium contactor 1926 or a series of parallel contactors 1926 that are independently and alternately operated
in a batch mode to provide sufficient helium contacting and separation time.
[0232] In the comparative example shown, the degassing system 1924 may be operated continuously such that a
35 constant flow of fuel salt is maintained through both vessels and out the bottom of each 1926, 1928. On benefit of the
gravity flow and draining each vessel from the bottom is to avoid the accumulation of solids in the bottom of either vessel.
Accumulated solids would be a radioactive waste that would have to be removed and disposed. The separation vessel
1928 drains into the filter system 1930, which removes any particulate prior to returning the fuel salt 1906 to the drain
tank 1904.
40 [0233] In a comparative example, some treatment chemicals may be added to the fuel salt prior to its introduction into
the degassing system 1924 or the filter system 1930 or both. The purpose of such treatment chemicals would be to
chemically modify contaminants in the fuel salt in order to more efficiently remove the contaminants by the degassing
system 1924 or the filter system 1930. For example, injecting liquid NaAlCl4 may assist in oxide removal.
[0234] In an alternative comparative example, the degassing system 1924 may be incorporated into the reactor core
45 1902. In this comparative example, helium gas is delivered into the reactor core 1902. While some gas will leave the
fuel salt and collect in the headspace 1920 where it can be removed and treated by the off gas system 1922 as described
above (with or without being passed through the drain tank 1904), some helium will cause cavitation in the circulation
pumps. In this comparative example, the helium may be collected from the pumps and likewise removed and treated
by the off gas system 1922 as described above.
50 [0235] In a comparative example, the filter system 1930 may be directly connected to the top of the drain tank 1904.
Any suitable type of filter may be used. For example, in a comparative example the filtration system may include a tube
sheet supporting a number of individual tube filter elements inside of a filter vessel 1930. In a comparative example,
filter elements would not be cleaned in service. Solids will accumulate on the filter material surface over time until the
filter vessel 1930 is taken out of service and the filter elements either discarded as waste or regenerated. The filter
55 vessels 1930 may be sized for any desired nominal lifetime based on the design throughput of the system 1900.
[0236] In a comparative example, the filter elements are made from either sintered molybdenum powder or fiber to
reduce corrosion. The initial pressure drop of the filter system will be very low. The filter elements could be installed
"upside down", that is with the tube sheet at the bottom of the vessel 1930 and the filter elements extending vertically
36
EP 3 241 218 B1
upwards above the tube sheet, so that the vessel would continually drain into the tank 1904. The filter inlet may be
located as close to the tube sheet as possible to minimize the holdup of molten salt in the filter vessel. As particulate
accumulates on the filter surface and the pressure drop increases, the liquid level will rise in the filter vessel.
[0237] The UCl4 condenser 1932 is designed to condense gaseous UCl4 and return it to the drain tank 1906. In the
5 comparative example illustrated, the UCl4 condenser 1932 is connected so that it receives and treats gas from the filter
system 1930 and the drain tank 1904. In an alternative comparative example, the UCl4 condenser 1932 may be connected
to other gas streams from other components such as the reactor core 1902.
[0238] In a comparative example, the condenser 1932 is a countercurrent contacting heat exchanger using cooled
fuel salt 1906 from the drain tank 1904 as the coolant. The melting point of pure UCl4 is 590 °C and the boiling point is
10 791 °C, so a portion of the fuel salt 1906 from the drain tank 1904 may be cooled, using any conventional heat exchanger
such as a shell and tube heat exchanger 1934 illustrated , to below the boiling point of UCl4, such as 700 °C, and flowed
through nickel or molybdenum structured packing countercurrent to the vent gases. The condenser 1932 may be a
packed column of containing random nickel and/or molybdenum packing elements. This would condense any UCl4 in
the vent gas. Because the exchanger is a contacting vessel, condensed UCl4 would combine with the cooled fuel salt
15 and be returned to the drain tank 1904. The gaseous output of the condenser 1932 may be cooled prior to delivery to
the off gas treatment system 1922.
[0239] As shown in FIG. 19, the discharge flow from the drain tank 1904 may be transferred to the reactor core 1902,
the degassing system 1926, or to the UCl4 condenser 1932 as the coolant. These flows may be actively controlled by
valving (not shown) or restricting orifices may be placed in the various lines to balance the fuel salt flows and avoid the
20 requirement for valves. Sizing of these restricting orifices will depend on the actual routing of the piping and ensuing
hydraulic calculations.
[0240] The off gas treatment system 1922 receives fission product gases and holds them for a sufficient time to allow
some radioisotopes to decay. In the comparative example shown, vent gases 1918 are removed from the void space
1920 above the fuel salt level 1912 in the reactor core 1902 and flow into the drain tank 1904. The gas flow leaving from
25 the drain tank 1904 would flow, either directly or as illustrated in FIG. 19 indirectly via the UCl4 condenser 1928, through
an off gas treatment system 1922. In addition, in the comparative example illustrated the off gas treatment system 1922
receives gas directly from the degassing system 1924. In a comparative example, the flowrate of gases through the
entire system including the reactor core 1902, drain tank 1904 and the off gas treatment system 1922 are controlled by
valving and instrumentation located at the exit of the off gas treatment system 1922 where the temperature is cool and
30 there is little to no radiation. This comparative example avoids the need for a compressor/blower between the reactor
and the drain tank. It is anticipated that the total yield of tritium will flow out through the off gas system 1922.
[0241] FIG. 20 illustrates a comparative example of an off gas treatment system 2000 suitable for use in treating
gaseous fission products produced by a molten salt reactor, for example as the off gas treatment system 1922 in FIG.
19. The system is designed to receive the gaseous fission products in a carrier gas such as helium although other gases
35 are possible. In the comparative example shown, the flow through the off-gas treatment system 200 primarily consists
of two recycle loops, a short delay holdup loop 2002 and a long delay holdup loop 2004.
[0242] Inlet gas to be treated may first be cooled and filtered before entering the recycle loops as illustrated in FIG.
20 by cooler 2006 and filter 2008. In a comparative example, the filter 2008 is designed to remove any gas borne
particulate, metals, salts, or fission products that may be in the gas. Based on the molten salt chemistry, the primary
40 constituents of the filtered inlet gas will be Kr, Xe and tritium.
[0243] The short delay holdup loop 2002 includes one or more vessels containing activated carbon. In the comparative
example shown, the short delay holdup loop 2002 has three parallel activated carbon vessels 2006, each nominally
sized to handle 50% of the anticipated Xe load. In a comparative example, the short delay holdup loop 2002 is a holdup
loop designed to retain the received gases for a period sufficient to allow the 135Xe to decay to less than 5% of the inlet
45 concentration. This period may be actively controlled and determined by monitoring the inlet and outlet concentrations
of 135Xe or the loop 2002 may be designed with a fixed residence time based on the half-life of 135Xe, such as for example
from 45 to 49 hours or 40 to 60 hours.
[0244] The activated carbon vessels 2006 may be maintained in a shielded enclosure or may be individually shielded
vessels to attenuate any radiation escaping the system 2000. A vessel cooling system 2008 may also be provided, such
50 as a thermal bath of water or other heat transfer fluid in which the vessels 2006 are immersed, to mitigate the decay
heat. In a comparative example, waste heat from the vessels 2006 may be used to generate low pressure steam, thus
recovering energy from the cooling system 2008.
[0245] Gas exiting the short delay holdup loop 2002 may be transferred to the long delay holdup loop 2004, may be
transferred to a carrier gas recovery system or both. In the comparative example shown, gas exiting the short delay
55 holdup loop 2002 is divided into two streams, one stream going to the long delay holdup loop 2004 and the other stream
to a helium gas recovery system 2010. In a comparative example, some flow of gas greater than 50 % of the total outflow
of the short delay holdup loop 2002 (e.g., 70-90 %) is passed through one or more chemical traps 2012 and radiation
alarms 2014 before entering a surge tank 2016 at the inlet of a carrier gas compressor 2018. The helium is compressed
37
EP 3 241 218 B1
and then stored in the accumulator tank 2020. In a comparative example, helium from this accumulator tank 2020 is
metered and recycled for use as new carrier gas, such as by being fed into degassing system 1924.
[0246] Any outlet gas from short delay holdup loop 2002 not treated by the carrier gas recovery system 2010 will be
transferred to the long delay holdup loop 2004. The long delay holdup loop 2004 is designed to retain the Kr and Xe
5 long enough for the radioisotope concentration to drop to an acceptable discharge threshold. In a comparative example,
similar to the short delay holdup loop 2002, the long delay holdup loop 2004 includes one or more vessels containing
activated carbon. In the comparative example shown, the long delay holdup loop 2004 has three parallel activated carbon
vessels 2006, each nominally sized to handle 50% of the anticipated Xe load for the specified period, in this case 90
days but which may be from 50-150 days depending on the desired discharge threshold. The activated carbon vessels
10 2006 may be maintained in a shielded enclosure or may be individually shielded vessels to attenuate any radiation
escaping the system 2000. A vessel cooling system 2008 may also be provided, as described above.
[0247] Exiting the long term Xe holdup system, the gas may be transferred through a preheater 2022 which raises the
gas temperature to 800 °C or higher. The gas may then be passed through a catalyst vessel 2024 where the tritium is
oxidized with air. The gas then flows through a water cooled aftercooler 2026 or set of aftercoolers 2026, as shown, that
15 reduces the temperature to reduce the heat load on the final charcoal packed absorber 2028. In a comparative example,
the absorber 2028 is designed to operate at to -20 °C. The tritium, Kr and Xe are retained on the charcoal while the
helium gas passes thorough the bed. After leaving the refrigerated absorber, the helium is compressed and can be
recycled to the reactor purge system for pump seals, etc. In the comparative example shown, there are three refrigerated
absorbers 2028 sized for 50% of the anticipated load with two of the three in service at all times. At any given time, the
20 out-of-service absorber 2028 will be regenerated by heating the absorber electrically and flowing a small heated helium
stream through the absorber in the reverse direction. This regenerated gas stream containing Kr, Xe, and 3H2O would
flow into a liquid nitrogen cooled receiver cylinder 2030 for permanent storage.
[0248] FIG. 21 illustrates a comparative example of a method for polishing fuel salt based on the systems described
in FIGS. 19 and 20. In the comparative example shown, the method 2100 starts with transferring irradiated fuel salt from
25 the operating reactor core 1902 to the drain tank 1904 in a transferring operation 2102.
[0249] The fuel salt is then degassed in a degassing operation 2104 in which a carrier gas, such as helium, is contacted
with the irradiated fuel salt, thereby removing gaseous fission products from the fuel salt. In a comparative example, the
degassing operation 2104 may include contacting the fuel salt with the carrier gas in a contacting vessel then transferring
the fuel salt to a second vessel for some residence time to allow additional time for the separation to occur. This operation
30 2014 creates a carrier/fission product gas mixture and a degassed fuel salt having a reduced amount of gaseous fission
products relative to the irradiated fuel salt.
[0250] After the degassing operation 2104, the degassed fuel salt may be filtered in a filtration operation 2106. In a
comparative example of the filtration operation 2106, degassed fuel salt passes through a filter 1930 under gravity and
the filtered fuel salt effluent drains into the drain tank 1904. As presumably any solids in the fuel salt at operational
35 temperature are some form of contaminant (either a fission product solid, corrosion product, or some other contaminant),
any filtered solids are unwanted and are removed and disposed of in this operation 2106.
[0251] The polishing method 2100 further includes treating the carrier/fission product gas mixture generated by the
degassing operation 2104 in a carrier gas treatment and recovery operation 2108. This operation 2108 includes collecting
the carrier gas/fission product mixture from the system and transferring it to an off gas treatment system, such as the
40 system 1922 described above. The carrier gas treatment and recovery operation 2108 may include storing the carrier
gas/fission product mixture for a first period of time, then recovering the carrier gas from the mixture by passing the
carrier gas through a separator, carbon filter, ion exchanger, or other chemical trap that removes Kr and Xe from the
carrier gas and otherwise cleans the carrier gas sufficiently to allow it to be reused.
[0252] The polishing method 2100 may further include collecting gaseous UCl4 that evaporates from the fuel salt and
45 re-condensing it in a UCl4 condensation operation 2110. Recovered UCl4 condensate is returned to the fuel salt by
dissolving it into a fuel salt stream and returning the stream, which may be considered a high concentration UCl4 fuel
salt, to the drain tank or reactor core.
[0253] The method 2100 includes returning the filtered, degassed fuel salt to the reactor core. In a comparative example
for the system 1900 in FIG. 19, the method 2100 is continuously operated on a sidestream taken from the reactor core
50 1902. In this comparative example the drain tank 1904 is continuously receiving both irradiated fuel salt from the reactor
core 1902 and filtered fuel salt from the filtration system 1930. In addition, fuel salt with condensed UCl 4 is also received
from the UCl4 condensor. Simultaneously, polished fuel salt from the drain tank is being transferred to the reactor core.
In alternative comparative examples, the operations of the method 2100 described above may be performed concurrently
as continuous or batch processes. In addition, the various operations may be performed serially as continuous or batch
55 processes.
38
EP 3 241 218 B1
Fuel Salt Post-Processing
[0254] Fuel salts removed from an operational reactor will include fission products in addition to the fuel salt constituents
described herein. While some fission products may be easily removed by sparging, settling or differential precipitation,
5 others, particularly the lanthanides as described above, may be difficult to remove. Note that such used fuel salt purification
may not be necessary in the fast spectrum of the chloride fuel salts, as used fuel salt may be suitable for use ’as is’ as
startup material for another molten salt reactor. However, if purification is desired, a fission product removal system may
be utilized.
[0255] A removal system may be configured to remove one or more lanthanides from the nuclear fuel salt. A fission
10 product removal system may include one or more plasma mass filters. By way of non-limiting example, the one or more
plasma mass filters may include an Archimedes-type plasma mass filter. The use of an Archimedes-type plasma mass
filter is described by R. Freeman et al. in "Archimedes Plasma Mass Filter," AIP Conf. Proc. 694, 403 (2003).
[0256] In another comparative example, an Archimedes filter plant (AFP) may act to remove one or more lanthanides
from fuel salt from one or more reactors. In one comparative example, the AFP may include two plasma mass filters.
15 By way of non-limiting example, each of the two plasma mass filters is capable of processing approximately a ton of fuel
salt per day. In another comparative example, the first plasma filter is tuned so as to separate out the heavy elements
from the fuel salt, with the second filter being tuned to separate the salt constituents from the fission products. In this
configuration, the AFP could support a fleet of approximately 100-200 molten salt nuclear reactors (e.g., molten chloride
salt fast reactors). In another comparative example, the fleet could utilize Archimedes-type filtering in a batch-type
20 process. By way of non-limiting example, in a batch- type process, each reactor may send a portion (e.g., 10-20 %) of
its salt to the AFP every 1-3 years. Further, the salt may either be returned to the original reactor, swapped with the salt
from another reactor, or replaced with depleted uranium loaded salt in the original reactor. The lanthanide-cleaned salts
may be used to start up additional molten salt nuclear reactors without the need for ongoing enrichment, as discussed
above.
25 [0257] It is noted that the reactor 100 of the present disclosure is not limited to the Archimedes-type filter described
above, which is provided merely for illustrative purposes. It is recognized herein that the separation requirement of the
reactor 100 of the present disclosure may be significantly less than system typically used in the context of an Archimedes-
type system. For example, the reactor 100 of the present disclosure may only require a separation efficiency required
of approximately 0.99 or 0.9. As such, a significantly simplified plasma mass filter design may be used in the context of
30 reactor 100 of the present disclosure.
[0258] In another comparative example, the fission product removal system includes a significantly smaller plasma
mass filter capable of cleaning 30-50 kg of salt each day. By way of a non-limiting example, a small bypass flow (∼10-8
of the flow) may be sent to the filter for cleaning and immediately sent back to the core without the need for off-site
transport. It is noted herein that, while small plasma mass filters may lose some economy of scale, they are affordable
35 and significantly less expensive than procurement of fresh fuel that has been enriched in fissile material.
Anti-Proliferation Technologies
[0259] Since molten nuclear fuel salt may be removed from the reactor 100, it is desirable to provide anti-proliferation
40 safeguards to the molten fuel salt 108 of the present disclosure. In one comparative example, the molten fuel salt 108
is pre-loaded or initially created with one or more materials, such as lanthanides or other elements, that can be difficult
to separate from the fuel salt but improve the proliferation resistance and which serve as a neutron absorber in the
molten fuel salt 108. This diminishes the capacity of the fuel salt for use in weapons applications if it were to be intercepted
prior to its use as a nuclear fuel in a molten salt reactor but does not substantially affect the criticality of the MCFR due
45 to its fast spectrum. The addition of lanthanides also make the fuel salt more dangerous to handle, thereby also reducing
its attractiveness for use in weapons applications.
[0260] One method of determining the attractiveness of a material for weapons use is referred to as the Figure of Merit
(FOM). The FOM is a calculation that takes into account the mass of a material (or materials), its dose and its decay
heat. One equation for the FOM is as follows:
50
55
where M is the bare critical mass in kg of the metal component of a compound (i.e., does not include the weight contribution
of oxides, chlorides, other anions, etc.), h is the heat content or decay heat in W/kg, and D is the dose of 0.2∗M at 1 m
from the surface in rad/hr. For non-proliferation purposes, an FOM of < 1.0 is deemed to be unattractive for weapons
39
EP 3 241 218 B1
purposes. Thus, in a comparative example, lanthanides are added to the fuel salt to the extent necessary to obtain an
FOM of < 1.0.
[0261] In one comparative example, when pre-loaded into a molten chloride-based fuel, the one or more pre-loaded
lanthanides act to form one or more lanthanide trichlorides. It is noted that these compounds are similar, in at least a
5 chemical sense, to PuCl3, which is present in the molten fuel (e.g., Pu- 239 is formed during enrichment and may form
PuCl3). The presence of the one or more lanthanide trichlorides makes PuCl3 less usable for weapons applications.
[0262] The presence of lanthanide trichlorides in the molten fuel salt 108 reduces the usability of the Pu present in
the molten fuel salt 108 in the event one attempts to apply a chemical process to separate the Pu from the rest of the
molten fuel salt. In this sense, the lanthanides "ride along" with the Pu during some forms of chemical separation. This
10 feature provides at least three benefits. First, the lanthanides cause the ultimate Pu sample to become more radioactive,
making it more difficult to handle, shield and etc. Second, the lanthanides increase heat generation within the Pu sample,
again, making the Pu more difficult to handle, shield and etc., as it may reach temperatures above the Pu melting point.
Three, the presence of lanthanides change the critical mass of the material such that the reaction process within a given
Pu sample is far less efficient than a lanthanide-free sample. As such, in the case of a lanthanide-loaded Pu sample,
15 more Pu material would be required for weapon device purposes, making weapons use more difficult and unwieldy.
[0263] Further, uranium chemically separated from the mixture is not suitable for weapons applications as it is low
enrichment uranium (LEU).
[0264] It is noted that while some lanthanides may be formed in the fuel salt 108 as fission products during operation
of the nuclear reactor 100, it is contemplated herein that the lanthanides of the present comparative example are pre-
20 loaded into the nuclear fuel salt 108 prior to start-up of the reactor 100 and, thus, prior to the production of any significant
amount of plutonium. After operation has begun, the fuel salt will naturally become less suitable for weapons applications
as lanthanide fission products are created and build up due to the chain reaction.
[0265] In one comparative example, the one or more lanthanides are pre-loaded into the molten fuel salt 108 prior to
start-up of the reactor 100. In one comparative example, the one or more lanthanides are pre-loaded into the molten
25 fuel salt 108 prior to the reactor 100 reaching a selected reactivity threshold. By way of non-limiting example, the one
or more lanthanides are pre-loaded into the molten fuel salt 108 prior to the reactor 100 reaching criticality or a sub-
critical threshold.
[0266] In another comparative example, the one or more lanthanides are pre-loaded into the molten fuel salt 108 prior
to the generation of a selected threshold of plutonium (e.g., Pu-239) within the reactor (e.g., generated by enrichment
30 of uranium in a uranium-plutonium breed-and-burn operation). By way of non-limiting example, the one or more lantha-
nides are pre-loaded into the molten fuel salt 108 prior to the generation of a selected amount of plutonium within the
reactor. For instance, the one or more lanthanides are pre-loaded into the molten fuel salt 108 prior to the generation
of 8 kg of plutonium within the reactor 100. In another instance, the one or more lanthanides are pre-loaded into the
molten fuel salt 108 prior to the generation of 4 kg of plutonium within the reactor 100. In yet another instance, the one
35 or more lanthanides are pre- loaded into the molten fuel salt 108 prior to the generation of 2 kg of plutonium (and so on)
within the reactor 100. It is noted that the above plutonium masses are not limitations on the present comparative example
and are provided merely for illustrative purposes as any plutonium threshold may be implemented in the context of the
present comparative example.
[0267] In another comparative example, the one or more lanthanides may be mixed with the molten fuel salt 108 such
40 that the resulting lanthanide-loaded fuel salt has a lanthanide concentration from 0.1 and 10 % by weight. In another
comparative example, the one or more lanthanides may be mixed with the molten fuel salt 108 such that the resulting
lanthanide-loaded fuel salt has a lanthanide concentration from 4 and 8 %. In yet another comparative example, the
selected lanthanide or lanthanides may be mixed with the molten fuel salt 108 in such proportions to achieve a threshold
FOM that is < 1.0, such as for example, an FOM threshold of less than 0.99, 0.98, 0.97, 0.96 or 0.95. In some comparative
45 examples, an FOM threshold of less than 0.95 may be desired such as less than 0.9 or 0.8.
[0268] In one comparative example, the one or more lanthanides may include one or more of La, Ce, Pr, or Nd. In
another comparative example, in the case of a chloride-based molten nuclear fuel salt 108, the one or more lanthanides
may be mixed into the molten nuclear fuel salt 108 by mixing the molten fuel salt 108 with one or more lanthanide
chlorides. By way of example, the one or more lanthanide chlorides may include one or more of LaCl3, CeCl3, PrCl3 or
50 NdCl3. In another comparative example, in the case of a chloride-based molten nuclear fuel salt 108, the one or more
lanthanides (or one or more lanthanide chlorides) may be mixed into the molten nuclear fuel salt 108 by mixing the
molten fuel salt 108 with one or more carrier salts (e.g., NaCl) loaded with one or more lanthanides or lanthanide chlorides.
[0269] In another comparative example, the mixture of molten nuclear fuel salt and the at least one lanthanide is
formed outside of the fast spectrum molten salt nuclear reactor. By way of non-limiting example, the mixture of molten
55 nuclear fuel salt 108 and the one or more lanthanides may be formed by mixing a volume of molten nuclear fuel salt
108 (prior to loading into reactor 100) and the one or more lanthanides (or lanthanides chlorides) in a separate mixing
station external to the reactor core section 102 of the reactor 100 or after a predetermined period of time after start up
when an expected amount of Pu is modeled to be bred up in the core.
40
EP 3 241 218 B1
[0270] In another comparative example, the mixture of molten nuclear fuel salt and the at least one lanthanide is
formed inside of the fast spectrum molten salt nuclear reactor. By way of non-limiting example, the mixture of molten
nuclear fuel salt 108 and the one or more lanthanides may be formed by mixing a volume of one or more lanthanides
(or lanthanides chlorides) into the molten nuclear fuel salt 108 contained within the primary circuit (e.g., reactor core
5 section 102, primary coolant system 110 and the like) prior to start-up of the reactor 100.
[0271] FIG. 15 illustrates a comparative example of a process flow 1500 representing example operations related to
fueling a fast spectrum molten salt nuclear reactor with nuclear fuel pre-loaded with one or more lanthanides, in accord-
ance with one or more comparative examples of the present disclosure. In FIG. 15, discussion and explanation may be
provided with respect to the above-described examples of FIGS. 1A-1F, and/or with respect to other examples and
10 contexts. It should be understood that the operational flows may be executed in a number of other environments and
contexts, and/or in modified versions of FIGS. 1A-1F. Also, although the operations of FIG. 15 are presented in the
sequence(s) illustrated, it should be understood that the various operations may be performed in other orders than those
which are illustrated, or may be performed concurrently.
[0272] In operation 1502, the process 1500 includes providing a molten nuclear fuel salt. By way of non-limiting
15 example, a selected volume of a molten nuclear fuel salt may be provided. For instance, the molten nuclear fuel salt
may include, but is not limited to, any chloride-based fuel salt described throughout the present disclosure. In another
instance, the molten nuclear fuel salt may include, but is not limited to, any fluoride-based fuel salt described throughout
the present disclosure.
[0273] In operation 1504, the process 1500 includes providing at least one lanthanide. By way of non-limiting example,
20 one or more lanthanides, such as, but not limited to, one or more of La, Ce, Pr, or Nd are provided. In one comparative
example, the one or more lanthanides are provided in the form of a lanthanide salt. For example, the one or more
lanthanides may be provided in the form of a lanthanide salt chemically compatible with the molten nuclear fuel salt of
operation 1502. For instance, in the case of a chloride-based molten nuclear fuel salt, the one or more lanthanides may
be provided in the form of one or more lanthanide salts, such as, but not limited to, LaCl3, CeCl3, PrCl3 or NdCl3. In
25 another comparative example, a selected volume of one or more lanthanides (or one or more lanthanide salts) may be
provided in the form of a mixture of one or more lanthanides (or one or more lanthanide salts) with an additional salt,
such as, but not limited to, a carrier salt compatible with the molten nuclear fuel salt of operation 1502.
[0274] In operation 1506, the process 1500 includes mixing the molten nuclear fuel salt with the at least one lanthanide
to form a lanthanide-loaded molten nuclear fuel salt prior to start-up of the fast spectrum molten salt nuclear reactor or
30 after a determined amount of Pu has been bred up. In one comparative example, the volume of molten fuel salt provided
in operation 1502 is mixed with the one or more lanthanides (or one or more lanthanide salts) of operation 1504 such
that the resulting molten salt mixture has a lanthanide content level from 0.1-10 % by weight. By way of non-limiting
example, the volume of molten fuel salt provided in operation 1502 may be mixed, but is not required to be mixed, with
the one or more lanthanides (or one or more lanthanide salts) of operation 1504 such that the resulting molten salt
35 mixture has a lanthanide content level from 4-8 % by weight.
[0275] In operation 1508, the process 1500 includes supplying the lanthanide- loaded molten nuclear fuel salt to at
least a reactor core section of the fast spectrum molten salt nuclear reactor. In one comparative example, the mixture
of operation 1506 may be formed by mixing the volume of molten fuel salt with the one or more lanthanides (or one or
more lanthanide salts) inside of the fast spectrum molten salt nuclear reactor 100. In one example, the lanthanides may
40 be added to the molten fuel salt within the reactor core. In another comparative example, the mixture of operation 1506
may be formed by mixing the volume of molten fuel salt with the one or more lanthanides (or one or more lanthanide
salts) outside of the fast spectrum molten salt nuclear reactor 100, such as, but not limited to, a mixing vessel. In this
regard, following the mixture of the molten fuel salt with the one or more lanthanides (or one or more lanthanide salts),
the lanthanide loaded salt mixture may be loaded into the reactor 100.
45 [0276] As discussed above, a goal of the method 1500 is to make the fuel salt less attractive for use as feedstock for
weapons development. An aspect of comparative examples of the method 1500 is that the dose, that is the radiation
exposure from the lanthanide-loaded fuel salt, is increased. The amount of lanthanides added may be determined based
on a target dose. For example, the Department of Energy and other regulatory bodies have published recommended
thresholds for what are referred to as "self-protecting limits" at or beyond which that body believes the material is no
50 longer attractive for weapons use. One such attractiveness measure may be dose, which may be made so high that a
recipient is exposed to so much radiation that the recipient is prevented from completing an intended task by the damage
caused by the exposure. One such dose limit is 100 rads per hour (rads/hr), another is 500 rads/hr and a third is 1,000
rads/hr, all measured at a distance of one meter. However, limits as high as 10,000 rad/hr have been proposed and
may be used. Comparative examples of the method 1500 can be adapted to provide a fuel salt having any desired dose.
55 [0277] Another such attractiveness measure is the FOM, as described above. As described, based on that measure,
initial fuel salts artificially modified to have an FOM of less than 1.0 are deemed unattractive for weapons use. In a
comparative example, the selected lanthanide or lanthanides may be mixed with the molten fuel salt 108 in such pro-
portions to achieve a threshold FOM that is < 1.0. In alternative embodiments, more stringent FOM thresholds of less
41
EP 3 241 218 B1
than 0.99, 0.98, 0.97, 0.96 or 0.95 may be selected and lanthanides or other ingredients altering the bare critical mass,
M, the heat content, h, and the dose, D, factors of the FOM equation to achieve the desired threshold may be added.
In some embodiments, an FOM threshold of less than 0.95 may be desired such as less than 0.9 or 0.8.
[0278] The lanthanides used may be any lanthanide, however, particularly high dose and long-lived lanthanide isotopes
5 are most suitable. In addition to lanthanides, radioactive isotopes of other elements may be used to increase the dose
of a fuel salt. These include caesium-137 and iodine-121.
Conclusion
10 [0279] While particular aspects of the present subject matter described herein have been shown and described, it will
be apparent to those skilled in the art that, based upon the teachings herein, changes and modifications may be made
without departing from the subject matter described herein. It will be understood by those within the art that, in general,
terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended
as "open" terms (e.g., the term "including" should be interpreted as "including but not limited to," the term "having" should
15 be interpreted as "having at least," the term "includes" should be interpreted as "includes but is not limited to," etc.). It
will be further understood by those within the art that if a specific number of an introduced claim recitation is intended,
such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present.
[0280] For example, as an aid to understanding, the following appended claims may contain usage of the introductory
phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not
20 be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular
claim containing such introduced claim recitation to claims containing only one such recitation, even when the same
claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g.,
"a" and/or "an" should typically be interpreted to mean "at least one" or "one or more"); the same holds true for the use
of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim
25 recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to
mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, typically means
at least two recitations, or two or more recitations).
[0281] The term "about" is not intended to either expand or limit the degree of equivalents which may otherwise be
afforded a particular value. Further, unless otherwise stated, the term "about" shall expressly include "exactly," consistent
30 with the discussions regarding ranges and numerical data. The term "about" in the context of the present disclosure
means a value within 15% (615 %) of the value recited immediately after the term "about," including any numeric value
within this range, the value equal to the upper limit (i.e., + 15%) and the value equal to the lower limit (i.e., - 15%) of this
range. For example, the value "100" encompasses any numeric value that is between 85 and 115, including 85 and 115
(with the exception of "100%", which always has an upper limit of 100%).
35 [0282] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are
approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any
numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in
their respective testing measurements.
[0283] Furthermore, in those instances where a convention analogous to "at least one of A, B, and C, etc." is used,
40 in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g.,
" a system having at least one of A, B, and C" would include but not be limited to systems that have A alone, B alone,
C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances
where a convention analogous to "at least one of A, B, or C, etc." is used, in general such a construction is intended in
the sense one having skill in the art would understand the convention (e.g., " a system having at least one of A, B, or
45 C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together,
B and C together, and/or A, B, and C together, etc.). It will be further understood by those within the art that typically a
disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings,
should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms
unless context dictates otherwise. For example, the phrase "A or B" will be typically understood to include the possibilities
50 of "A" or "B" or "A and B.
[0284] In some instances, one or more components may be referred to herein as "configured to," "configurable to,"
"operable/operative to," "adapted/adaptable," "able to," "conformable/conformed to," etc. Those skilled in the art will
recognize that such terms (e.g., "configured to") can generally encompass active-state components and/or inactive-state
components and/or standby-state components, unless context requires otherwise.
55 [0285] With respect to the appended claims, those skilled in the art will appreciate that recited operations therein may
generally be performed in any order. Also, although various operational flows are presented in a sequence(s), it should
be understood that the various operations may be performed in other orders than those which are illustrated, or may be
performed concurrently. Examples of such alternate orderings may include overlapping, interleaved, interrupted, reor-
42
EP 3 241 218 B1
dered, incremental, preparatory, supplemental, simultaneous, reverse, or other variant orderings, unless context dictates
otherwise. Furthermore, terms like "responsive to," "related to," or other past-tense adjectives are generally not intended
to exclude such variants, unless context dictates otherwise.
[0286] It will be clear that the systems and methods described herein are well adapted to attain the ends and advantages
5 mentioned as well as those inherent therein. Those skilled in the art will recognize that the methods and systems within
this specification may be implemented in many manners and as such is not to be limited by the foregoing exemplified
embodiments and examples. In this regard, any number of the features of the different embodiments described herein
may be combined into one single embodiment and alternate embodiments having fewer than or more than all of the
features herein described are possible.
10 [0287] While various embodiments have been described for purposes of this disclosure, various changes and modi-
fications may be made which are well within the scope of the technology described herein. For example, although not
explicitly stated Raman spectroscopy may be but one of many techniques used to monitor fuel salt quality during operation
of a molten salt reactor and, likewise, multiple Raman probes may be used in order to get an understanding of the
variations in fuel salt quality at different locations within the reactor.
15
Claims
1. A fuel salt for a molten fuel reactor consisting of:

20
at least a detectable amount of UCl3F;
one or more of UCl4, UCl3, UCl2F2, UClF3 and a non-fissile salt selected from NaCl, MgCl2, CaCl2, BaCl2, KCl,
SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and NdCl3; and
wherein the fuel salt has a melting temperature below 800 °C.
25
2. The fuel salt according to claim 1, wherein at least:
the fuel salt is from 15-20 mol % UCl3 and the balance is from 35-45 mol % NaCl and 35-45 mol % UCl3F or
the fuel salt includes at least 5 % UCl3F or
30 the fuel salt includes at least 5 % UCl3F and further includes one or more of UCl4, UCl3, UCl2F2, ThCl4, UBr3,
UBr4, UClF3, and a non-fissile chloride compound or
the fuel salt includes at least 5 % UCl3F and the non-fissile chloride compound is selected from NaCl, MgCl2,
CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 and/or NdCl3; or
the chloride in the fuel salt is enriched with 37Cl.
35
Patentansprüche
1. Brennstoffsalz für einen Flüssigbrennstoffreaktor, bestehend aus:

40
wenigstens einer nachweisbaren Menge UCl3F;
einem oder mehreren aus UCl4, UCl3, UCl2F2, UClF3 und einem nicht spaltbaren Salz, das aus NaCl, MgCl2,
CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl2, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 und NdCl3 aus-
gewählt ist, und
45 wobei das Brennstoffsalz eine Schmelztemperatur unterhalb von 800 °C aufweist.
2. Brennstoffsalz nach Anspruch 1, wobei wenigstens:
das Brennstoffsalz zu 15-20 mol-% UCl3 ist und der Rest zu 35-45 mol-% NaCl und zu zu 35-45 mol-% UCl3F
50 ist oder das Brennstoffsalz wenigstens 5 % UCl3F enthält oder das Brennstoffsalz wenigstens 5 % UCl3F und
ferner eines oder mehrere aus UCl4, UCl3, UCl2F2, ThCl4, UBr3, UBr4, UClF3 und eine nicht spaltbare Chlorid-
verbindung enthält oder
das Brennstoffsalz wenigstens 5 % UCl3F und die nicht spaltbare Chloridverbindung aus NaCl, MgCl 2, CaCl2,
BaCl2, KCl, SrCl2, VCl3, CrCl2, TiCl4 ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 und/oder NdCl3 ausgewählt
55 ist; oder
das Chlorid in dem Brennstoffsalz mit 37Cl angereichert ist.
43
EP 3 241 218 B1
Revendications
1. Sel de combustible pour un réacteur à combustible fondu constitué de :
5 au moins une quantité détectable de UCl3F ;

l’un ou plusieurs parmi UCl4, UCl3, UCl2F2, UClF3 et un sel non fissile choisi parmi NaCl, MgCl2, CaCl2, BaCl2,
KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3, PrCl3 et NdCl3 ; et
le sel de combustible possédant une température de fusion inférieure à 800 °C.
10 2. Sel de combustible selon la revendication 1, dans lequel au moins :
le sel de combustible est composé de 15 à 20 % en moles d’UCl3 et le reste est de 35 à 45 % en moles de

NaCl et 35 à 45 % en moles d’UCl3F ou
le sel de combustible comprend au moins 5 % d’UCl3F ou
15 le sel de combustible comprend au moins 5 % d’UCl3F et comprend en outre l’un ou plusieurs parmi UCl4, UCl3,
UCl2F2, ThCl4, UBr3, UBr4, UClF3, et un composé de type chlorure non fissile ou
le sel de combustible comprend au moins 5 % d’UCl3F et le composé de type chlorure non fissile est choisi
parmi NaCl, MgCl2, CaCl2, BaCl2, KCl, SrCl2, VCl3, CrCl3, TiCl4, ZrCl4, AcCl3, NpCl4, AmCl3, LaCl3, CeCl3,
PrCl3 et/ou NdCl3 ; ou
20 le chlorure dans le sel de combustible est enrichi en 37Cl.
25
30
35
40
45
50
55
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REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.
Patent documents cited in the description
• US 62097235 PCT [0001] • US 98151215 [0002]

• US 62098984 PCT [0001] • DE 1112791 B [0003]
• US 62234889 PCT [0001] • US 11811808, Leblanc [0043]
Non-patent literature cited in the description
• Configuration of a Molten Chloride Fast Reactor on • Compatibility and Processing Problems in the Use of
a Thorium Fuel Cycle to Current Nuclear Fuel Cycle Molten Uranium Chloride-Alkali Chloride Mixtures as
Concerns. E. H. OTTEWITTE. Ph.D. dissertation. Reactor Fuels. B. R. HARDER ; G. LONG ; W. P.
University of California at Los Angeles, 1982 [0076] STANAWAY. Symposium on Reprocessing of Nu-
clear Fuels. Iowa State University, August 1969,
405-432 [0076]
• R. FREEMAN et al. Archimedes Plasma Mass Filter.
AIP Conf. Proc., 2003, vol. 694, 403 [0255]
70

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(19)

(45) Date of publication and mention (51) Int Cl.:

(21) Application number: 15876187.4 (86) International application number:

GESCHMOLZENE KERNBRENNSTOFFSALZE UND ZUGEHÖRIGE SYSTEME UND VERFAHREN

(84) Designated Contracting States: • EL-DASHER, Bassem S.

• KRAMER, Kevin XP027957150, ISSN: 0196-8904 [retrieved on

Printed by Jouve, 75001 PARIS (FR) (Cont. next page)

40 Molten Salt Reactors

Table 1 - Fuel salt properties used in THERMOFLEX™ calculations

45 °C kg/m 3 kJ/kg-C W/m-C kg/m-s bar

55 7 700 3517 0.4426 1.627 0.00239 0

Table 2 - Primary coolant salt properties used in THERMOFLEX™ calculations

Heat input MW 600.0 1200.0 1800.0 2400.0 3000.1

Chloride-Based Fuel Salts

55 Chlorine-37 Modified Chloride Fuel Salt

UCl3-UCl4-[X]Cln Fuel Salts

5 UCl4 Fuel Salt Comparative examples

UCl3 Fuel Salt Comparative examples

Mixed Chloride-Fluoride Fuel Salt Embodiments

5 Uranium Bromide Fuel Salt Comparative examples

55 Uranium Chloride Fuel Manufacturing Processes

UO3 +Cl3CCCl=CCl2 → UCl4 + byproduct

U + 3/2H2→UH3 and UH3 + 3HCl→UCl3 +3H2

UO2Cl+ 1/2Cl2(g) → UO2Cl2(s); Oxidation,

45 UO2Cl2(s) + CO (g) → UOCl2 + CO 2(g); Reduction,

UOCl2(s) + 1/2Cl2(g) → UOCl3(s); Oxidation,

UOCl3(s) + 1/2Cl2(g) → UOCl4; Oxidation,

55 UCl4 + 1/2Cl2(g) → UCl5 ; Oxidation,

UCl5 + 1/2Cl2(g) → UCl6; Oxidation.

Uranium Chloride-Fluoride Fuel Manufacturing Processes

2UO2(s) + 3NH4Cl(s) + NH4HF2(s) + 7HCl(g) = 2[NH4]2UCl5F·2H 2O(s)

50 [NH4]2UCl5F·2H2O(s) = 2NH 4Cl + UCl3F + 2H2O

This reaction is similar to that described with reference to FIG. 16.

2UO2(s) + 3NH 4Cl(s) + NH4HF2(s) + 7HCl(g) = 2[NH4]2UCl5F·2H2O(s)

Fuel Salt Examples

Table 3 - Fuel Salt Embodiments and comparative examples

Fuel Modification to Reduce Corrosion

5 Ongoing Fuel Polishing

Fuel Salt Post-Processing

1. A fuel salt for a molten fuel reactor consisting of:

1. Brennstoffsalz für einen Flüssigbrennstoffreaktor, bestehend aus:

2. Brennstoffsalz nach Anspruch 1, wobei wenigstens:

1. Sel de combustible pour un réacteur à combustible fondu constitué de :

5 au moins une quantité détectable de UCl3F ;

10 2. Sel de combustible selon la revendication 1, dans lequel au moins :

le sel de combustible est composé de 15 à 20 % en moles d’UCl3 et le reste est de 35 à 45 % en moles de

REFERENCES CITED IN THE DESCRIPTION

Patent documents cited in the description

• US 62097235 PCT [0001] • US 98151215 [0002]

Non-patent literature cited in the description

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