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Chapter 3
Isotope Separation Methods for Nuclear Fuel

Shuichi Hasegawa




Glossary

Isotope                    Nuclei of a chemical element which have the same number
                           of protons but different number of neutrons. Some isotopes
                           are stable; some are radioactive.
Separation factor          A ratio of a mole fraction of an isotope of interest to that of
                           non-interest in an enriched flow divided by that in
                           a depleted flow from a separation unit. The factor should
                           be larger than unity for the unit to result in isotopic
                           enrichment.
Separation capability      A measure of separative work by a cascade per unit time.
Mean free path             An average distance of a moving gas molecule between its
                           collisions.
Molecular flow              Low-pressure phenomenon when the mean free path of
                           a gas molecule is about the same as the channel diameter;
                           then a molecule migrates along the channel without inter-
                           ference from other molecules present.




This chapter was originally published as part of the Encyclopedia of Sustainability Science and
Technology edited by Robert A. Meyers. DOI:10.1007/978-1-4419-0851-3
S. Hasegawa (*)
Department of Systems Innovation, School of Engineering, The University of Tokyo,
7-3-1 Hongo Bunkyo-ku, Tokyo, Japan
e-mail: hasegawa@sys.t.u-tokyo.ac.jp

N. Tsoulfanidis (ed.), Nuclear Energy: Selected Entries from the Encyclopedia               59
of Sustainability Science and Technology, DOI 10.1007/978-1-4614-5716-9_3,
# Springer Science+Business Media New York 2013
60                                                                       S. Hasegawa


Definition of the Subject

Isotope separation, in general, means enrichment of a chemical element to one of its
isotopes (e.g., 10B in B; 6Li in Li, 157Gd, etc). In the case of uranium, isotope
separation refers to the enrichment in the isotope 235U, which is only 0.711% of
natural uranium; today’s nuclear power plants require fuel enriched to 3–5%
in 235U. Uranium enrichment is the subject of this article.
    Efficiencies of sorting out different isotopes of the element (separation factor)
are usually very low. For practical enrichment plants, a gaseous diffusion process
has been successfully employed to obtain enriched uranium. A gas centrifugation
process is the preferred method of enrichment today due to reduced energy con-
sumption. A new process using lasers, which can have a high efficiency of separa-
tion, is under development and has the potential to replace the current enrichment
methods.



Introduction

The fuel used today by commercial nuclear power plants is the fissile isotope 235U.
Unfortunately, 235U is only 0.711% of natural uranium, the rest of which is,
essentially, 238U. Light water reactors (LWR) operating dominantly all over the
world require isotope enrichment processes because the isotopic ratio of 235U for
their fuels should be 3–5%. The processes used to elevate the 235U content from
0.711% to 3–5% are called isotope separation or enrichment processes. Table 3.1
shows the current trends of isotope separation capabilities of the world. The main
countries performing the process are Russia, France, US, and URENCO (Germany,

Table 3.1 World Enrichment capacity (thousand SWU/year) [1]
Country                                  2010          2015           2020
France (Areva)                           8,500*        7,000          7,500
Germany, Netherlands, UK (Urenco)        12,800        12,200         12,300
Japan (JNFL)                             150           750            1,500
USA (USEC)                               11,300*       3,800          3,800
USA (Urenco)                             200           5,800          5,900
USA (Areva)                              0             >1,000         3,300
USA (Global Laser Enrichment)            0             2,000          3,500
Russia (Tenex)                           23,000        33,000         30–35,000
China (CNNC)                             1,300         3,000          6,000–8,000
Pakistan, Brazil, Iran                   100           300            300
Total approx.                            57,350        69,000         74–81,000
Requirements (WNA reference scenario)    48,890        55,400         66,535
Source: WNA Market Report 2009; WNA Fuel Cycle: Enrichment plenary session WNFC April
2011
*Diffusion
3 Isotope Separation Methods for Nuclear Fuel                                      61


Netherland, and UK). A number of separation processes have been studied so far,
but the principles of the current isotope separation processes mainly use gaseous
diffusion or gas centrifugation. The diffusion process was commercialized first but
the centrifugation is taking over because of less energy consumption. This article
following mainly [2, 3] describes the principles of the two processes and cascade
theory, which explains why it is required to repeat the process many times (using
successive stages/cascades) to obtain a certain desired enrichment fraction such as
3–5% because a single step provides only a small incremental enrichment. The new
enrichment technology using lasers will be described at the end.



Principles of the Separation Processes

Gaseous Diffusion

Figure 3.1 shows the schematic diagram of the gaseous diffusion process. Consider
a chamber divided into two compartments by a porous membrane. When dilute
gases are introduced into the bottom compartment of the chamber, the pores of the
membrane (membrane) make dependency of the transmission of the gases on their
molecular masses.
   If we have a mixture of two molecules in a gas with the same kinetic energy
(kinetic energy is determined by kT, k = Boltzmann constant; T = temperature in K;
(1/2 mv2 $ kT)), the lighter molecule is faster than the heavier one. Therefore, their
frequencies of hitting the membrane is higher for the lighter than for the heavier
molecule. However, the mass preference phenomena occur only when
the mean free path of the gas molecule is longer than the diameter of the pores 2r
and the thickness of the membrane l. The mean free path, l of the molecule can be
written as [2]

                                         kT
                                    l ¼ pffiffiffi                                     (3.1)
                                       4 2ps2 p

where k is the Boltzmann constant, T is the absolute temperature, s is the radius of
the molecule, and p is the gas pressure in the chamber. In this condition, a molecule

                                                                              Product

                                                   p′




                                Feed                                           Waste
                                                   p′′
Fig. 3.1 A single gaseous
diffusion stage
62                                                                          S. Hasegawa


cannot collide with others during the transmission through the membrane so that its
dynamics can be considered as a single molecule process. This process is called
molecular flow. The flux of the molecular flow through the flow path with circular
cross section is derived by Knudsen as [3]

                                               8rDp
                                  Gmol ¼      pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi                    (3.2)
                                            3l 2pmRT

where Gmol is the molecular flow velocity, m is the molecular mass, R is the gas
constant, and Dp ¼ p00 À p0 is the pressure difference between the bottom and top
compartments of the chamber. Equation 3.2 shows that the flow velocity depends
on the mass of the gas molecules so that the ratio of the molecules in the mixture
transmitted to the upper compartment of the chamber is changed compared with
that of the feeding gas. The opposite condition where flows do not depend on the
molecular mass is called viscous flow.
   We will derive the ideal separation factor in the case of 235UF6 and 238UF6 [3],
the gas molecules used for uranium enrichment. On the ideal condition where p00 is
very small and p0 can be neglected compared with p00 , when we have a binary
mixture of gases which consist of 235UF6 (molecular mass: m235 = 349, mole
fraction: x) and 238UF6 (molecular mass: m235 = 352, mole fraction: 1 À x), the
molecular flow velocities of 235UF6 and 238UF6 are
                                       00                        00
                                                          ð1ÀxÞ
                          G235 ¼ pffiffiffiffiffiffiffi ;
                                 ap x
                                  m235          G238 ¼ ap ffiffiffiffiffiffiffi
                                                        p
                                                          m238                    (3.3)

where the constant a includes factors in Eq. 3.2. The ratio of the molecular flow of
235
  UF6 to the whole can be written as

                                    pffiffiffiffiffiffiffiffiffi
                                         x                  x
                     G235               m235              1 À x ffiffiffiffiffiffiffiffiffi
               s¼            ¼                        ¼      r                    (3.4)
                                x          1Àx
                  G235 þ G238 pffiffiffiffiffiffiffiffiffi þ pffiffiffiffiffiffiffiffiffi   x þ m235
                               m235            m238 1 À x
                                                                m238

   Therefore, the ideal separation factor a0 of the gaseous diffusion process can be
derived as the separation factor of the molecular flow of the porous media

                             s      rffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffi
                                     m238       352
                     a0 ¼   1Às
                             x    ¼           ¼          ¼ 1:00429                (3.5)
                            1Àx      m235       349

   The separation factor depends on the ratio of the molecular masses so that this
method is more effective for the isotope separation of lighter elements. For heavier
elements, a larger number of repeated processes is required to obtain sufficiently
enriched products.
   However, in reality, the real value of the separation factor is smaller than that
given by Eq. 3.5 due to reverse molecular flow from the upper compartment to the
3 Isotope Separation Methods for Nuclear Fuel                                       63


bottom one and viscous flow not depending on the molecular mass; these two
phenomena work in a direction negating the enrichment process. Furthermore
operating conditions (porous media performance, working pressures, etc.) affect
the value of the separation factor. The energy consumption to run the process is
very high due to pressure controlling of the gases, small separation factors and so on
(see discussion about Separative Work Unit). Because of the relatively high energy
consumption, uranium enrichment by gaseous diffusion is on the way out and is
replaced by the gas centrifugation method.




Gas Centrifugation

The principle of gas centrifugation is based upon centrifugal forces that are created
inside a rotating cylinder containing two different gas molecules, forces that depend
on the molecular mass. Let’s see how it works in detail [2]. When we have a mixture
of two gas molecules in a rotating cylinder (centrifuge), pressure gradients develop
with respect to the radial direction. The pressures can be written as

                                       dp
                                          ¼ o2 rr                                (3.6)
                                       dr

where p is the pressure, r is the radial distance, o is the angular frequency of
rotation, and r is the density of the gases. By substituting the equation of state r
¼ pm=RT into the differential equation, we can derive the following equation,

                                     dp mo2
                                        ¼    rdr                                 (3.7)
                                      p   RT

   When we integrate this differential equation from the radial distance r (pressure
pr) to the inner radius of the cylinder a (pressure pa), we can obtain this expression,
                                           &     r  2 '!
                          pr         1 mv2
                             ¼ exp À     a
                                             1À                                  (3.8)
                          pa         2 RT        a

where the speed of the outer circumference of the cylinder na = oa This equation
shows that the ratio of the pressure at radius r to that of radius a depends on the
molecular mass of the gases.
   If we have the gases which consist of 235UF6 (molecular mass: m235 = 349, mole
fraction: x) and 238UF6 (molecular mass: m235 = 352, mole fraction: 1 À x), their
ratios of the partial pressures at the radius r to the radius a can be derived as
                                                      r 2 '!
                        pr x r         1 m235 v2
                               ¼ exp À         a
                                                   1À                            (3.9)
                        pa x a         2 RT            a
64                                                                               S. Hasegawa


Table 3.2 The local separation factor of 235UF6 and 238UF6 at r/a with T = 300K, ua = 700m/s
r/a        0         0.5        0.8        0.9         0.95        0.98       0.99        1.0
a          1.343     1.247      1.112      1.058       1.029       1.012      1.006       1.0


                                                           r  2 '!
                       pr ð1 À xr Þ         1 m238 v2
                                    ¼ exp À         a
                                                        1À                            (3.10)
                       pa ð1 À xa Þ         2 RT            a

      Therefore, the local separation factor at radial distance r of radius a is given by
                          xr                               r  2 '!
                        1 À xr       ðm238 À m235 Þv2
                   a¼     xa   ¼ exp                a
                                                        1À                            (3.11)
                                           2RT              a
                        1 À xa
which depends on the difference of their molecular masses, Dm = m238Àm235 = 3.
Values of the local separation factor of 235UF6 and 238UF6 with T = 300 K and na =
700 m/s are given in Table 3.2. This feature is superior to the gaseous diffusion
method when the difference of the masses is large, (e.g., for heavier elements). The
separation factor increases as the speed of the outer circumference increases.
However, the maximum speed vmax is limited by stresses created to the cylinder
from the force of the centrifugation and can be written as [2]
                                             rffiffiffi
                                              s
                                     vmax ¼                                   (3.12)
                                              r

where r is the density of the material of the cylinder, and s is the tensile strength.
Although most molecular gases are localized at a % 1 because of the centrifugation,
                                                 r

the values of the separation factor could be higher than those obtained from the
gaseous diffusion method. These values can be enhanced if we make use of
a countercurrent flow in the vertical direction. Figure 3.2 shows the schematic
diagram of countercurrent centrifugation method. Gernot Zippe performed
pioneering work on the development of the centrifugation first in the Soviet
Union during 1946–1954, and from 1956 to 1960 at the University of Virginia.
The countercurrent flow can be induced by heating and cooling centrifuges, or pipes
drawing off flows in centrifuges. The temperature control can adjust the flow
deliberately but the equipment becomes more complicated than that of the flow
control by the pipes (Fig. 3.2). This countercurrent flow makes enrichment of the
lighter isotopes at inner radius as the flow descending along the axis direction, and
the heavier isotopes are being enriched at the circumference as the flow ascending.
These enriched gases are collected at different radial positions of the both ends (at
outer radius for heavier isotope and at inner radius by baffle for lighter isotope).
When the centrifuge has a length L, the maximum separative power dUmax can be
derived as [2, 4]
                                                    2
                                         p     Dmv2
                                dUmax   ¼ LrD      a
                                                                                      (3.13)
                                         2      2RT
3 Isotope Separation Methods for Nuclear Fuel                                                       65


Fig. 3.2 Schematics of gas
centrifuge with                                                                Heads (Product)
countercurrent flow
                                                                                     Feed
                                                       Tails (Waste)




                                                         238UF                        238UF
                                                              6                            6




                                                        238
                                                          UF6     235
                                                                    UF6        235          238
                                                                                                  UF6
                                                                                 UF6




                                                         235UF                        235UF
                                                              6                               6




where D is diffusion coefficient. The maximum separative power is proportional to
the height of the centrifuge. It is preferable to have a taller centrifuge in the vertical
direction, but the length is imposed on the resonant vibration of the centrifuge. The
resonant conditions can be written as [3]
                   pffiffiffiffirffiffiffiffiffiffiffi
                  L        4  E
                      ¼ li         li ¼ 22:0; 61:7; 121:0; 200:0; 298:2;Á ÁÁ                  (3.14)
                  a i        2s0

where E is coefficient of elasticity. A taller centrifuge can give a larger separative
power although excellent mechanical properties are required to overcome the
resonant conditions.




Cascade Theory

The present isotope separation plants make use of these principles of enrichment
with small separation factors. In order to obtain high enrichment ratios, cascade
theory is necessary [3]. According to the theory, we can enhance the ratios by
iterating a single physical stage many times. Figure 3.3 shows a simple scheme
66                                                                            S. Hasegawa


                   Heads P1       Feed Fi        Heads Pi   Feed Fn
                      xP
                       1             i
                                    xF               i
                                                    xP         n
                                                              xF
      Feed F                                                             Product P
                stage1                      stage i            stage n
     Feed xF                                                             Product xP

                Waste W1                 Waste Wi             Waste Wn
                  xW1                      xWi                  xWn



Fig. 3.3 Simple scheme of the cascade

of a cascade. An original material “feed” is provided to the system. The isotope of
interest is enriched as going through many separation stages and a final output
“product” is obtained. Another output which mainly contains unnecessary isotopes
is called “waste.” Each flow F, P and W should have the following equation

                                        F¼PþW                                        (3.15)

and with mole fractions of the isotope of interest in each flow xF , xP , xW , we can
obtain

                                  FxF ¼ PxP þ WxW                                    (3.16)

   In this system, we have four independent parameters to define. In order to obtain
necessary flow of Product “P ” and mole fraction “xP” of the isotope of interest, we
need the design methodology to construct stages of separation units. The product of
a single stage (unit) is called heads and the waste of that is tails. The ratios of the
isotope of interest in the product are usually most important. If, for instance, we
have two isotopes “1” and “2,” and want to enrich the “1” isotope, we would focus
on the variation of the mole fraction ratio of the two isotopes, x1 , which can be
                                                                     x2
               x1
rewritten as 1Àx1 . The capability of each enrichment unit is described as separation
factor a. This factor is defined as the ratios of the isotopes of interest to that of
not-interest in the heads (product) divided by those in the tails (waste)

                                             xP
                                           1 À xP
                                        a ¼ xW                                       (3.17)
                                           1 À xW

   In a similar way, we can define the ratio of the heads (product) to the feed as
heads separation factor b, and that of the feed to the tails as tails separation factor g,

                                xP          xF
                              1 À xP      1Àx
                         b¼     xF   ; g ¼ xW F and a ¼ bg                           (3.18)
                              1 À xF      1 À xW
3 Isotope Separation Methods for Nuclear Fuel                                                     67


                 Feed Fi             Heads Pi                Feed Fi                Heads Pi
                    i
                   xF                    i
                                        xP                    xF+ 1
                                                               i                      xP+ 1
                                                                                       i


                                                                           stage
                           stage i
                                                                            i+1



                         Waste Wi                                        Waste Wi
                           xWi                                            xW+ 1
                                                                            i



Fig. 3.4 Simple cascade of the i and i + 1 th stages



   The ratio of the product to the feed is called “cut” y and defined as

                                                  P xF À xw
                                             y    ¼                                           (3.19)
                                                  F xP À xW

   The simplest design to accomplish enrichment is to accumulate separation stages
in a single line such as Fig. 3.4. This scheme is called simple cascade.




Simple Cascade

In this scheme, the heads and the mole fraction of the i th stage are equal to the feed
flow and the mole fraction of the i + 1 th stage (Fig. 3.4).

                                       Fiþ1 ¼ Pi ;           xiþ1 ¼ xiP
                                                              F                                (3.20)

   This cascade disposes of the tails of all stages so that the total amount of the
isotope of interest in the waste should be given sufficient attention. This can be
evaluated by means of the recovery rate of the i th stage ri

                                                                           xiW
                                                                         1À
                        Pi xiP         xi        xiF   À   xiW   xiP        xiF  a i À bi
                 ri ¼            ¼   yi P    ¼                         ¼     i ¼ a À1          (3.21)
                        Fi xiF         xiF       xiP   À   xiW   xiF       x        i
                                                                         1À W
                                                                            xiP

   When we have n stages in the cascade, the total recovery rate r can be expressed as

                     P xP Pn xn P1 x1 P2 x2 Pn xn
                r¼       ¼    P
                                ¼   P     P
                                            ¼   P
                                                  ¼ r1 r2 Á Á Á rn                             (3.22)
                     F xF F1 x1 F1 x1 F2 x2 Fn xn
                              F     F     F     F

   The over-all separation factor of the cascade o can be derived as
68                                                                          S. Hasegawa


Fig. 3.5 Countercurrent
recycle cascade

                                                     Stage n

                                          Heads Pi
                                            xP+ 1
                                             i                   Feed Fi
                                                                  xF+ 1
                                                                   i
                                                      Stage i               Heads Pns +1
                                          Tails Wi
                                                                              xP s+ 1
                                                                                n
                                           xW+ 1
                                              i

                               Feed F                                  Stage
                                 xF                                    ns + 1
                                        Heads Pns
                                            n
                                          xP s                              Tails Wns+1
                                                     Stage ns                 xW s + 1
                                                                                 n
                                                                Feed Fns
                                        Tails Wns                  n
                                                                  xF s
                                             n
                                          xW s


                                                     Stage 1




                                   xn
                                    P
                                 1 À xn
                              o¼      P
                                        ¼ b1 b2 Á Á Á bn                         (3.23)
                                   x1
                                    F
                                 1 À x1
                                      F

   Therefore, if a, b do not depend on each stage, the total recovery rate can be
rewritten as
                                                    !n
                                           a À o f ng
                                                   1
                               aÀb n
                         r¼            ¼                                    (3.24)
                               aÀ1           aÀ1

   When the feed itself is available without any special cost, the simple cascade is
effective. But in case the wastes from each stage should not be disposed because,
for instance, it is valuable or the recovery rate has to be increased, the waste flows
are recycled as feed flow, which is called countercurrent recycle cascade (Fig. 3.5).


Countercurrent Recycle Cascade

Since the simple cascade cannot improve the recovery rate, the tail flow is recycled
into either stage to use it efficiently, which is called recycle cascade (Fig. 3.5). If b
(heads separation factor) is equal to g (tails separation factor) in all stages, we can
obtain xiþ2 ¼ xiþ1 ð¼ xiP Þ. So the tails flow of the i + 2 th stage can be merged to the
         W      F
3 Isotope Separation Methods for Nuclear Fuel                                          69


heads flow of the i th stage and fed into the i + 1 th stage without any mixing loss.
We will consider the case that the tails flow of the second upper stage is refluxed to
the i th stage.
   The flows and the fractions of the isotope of interest in each stage of enriching
sections should have the following relationships.

                     Pi ¼ Wiþ1 þ P;      Pi xiP ¼ Wiþ1 xiþ1 þ PxP
                                                        w                          (3.25)

   In a similar way, those in stripping sections can be expressed as

                     Wjþ1 ¼ Pj þ W; Wjþ1 xjþ1 ¼ Pj xjP þ WxW
                                          W
                                                                                   (3.26)

   Let’s estimate the number of stages. From these equations, we can derive

                                                xP À xiP
                                 xiP À xiþ1 ¼
                                        W         Wiþ1                             (3.27)
                                                   P


   At total reflux, where the reflux ratio is infinity,

                                       Wiþ1
                                            !1                                     (3.28)
                                        P

the mole fraction of the heads flow at the i th stage xiP becomes equal to that of the
tails flow at the i + 1 th stage xiþ1 and the number of the stages is minimal.
                                 W


                   xiþ1        xiþ1      xi       xiÀ1
                    P
                          ¼ a W iþ1 ¼ a P i ¼ a2 P iÀ1 ¼ Á Á Á                     (3.29)
                 1 À xiþ1
                      P      1 À xW    1 À xP   1 À xP

gives the following equation,

                                    xP          xW
                                         ¼ an                                      (3.30)
                                  1 À xP      1 À xW

and the minimum number of the stages at total reflux can be derived as
                                                    
                                  1        xP 1 À xW
                             n¼      ln                                            (3.31)
                                ln a     1 À xP xW

   On the contrary, the reflux ratio becomes minimum when the mole fraction of
the heads at the i + 1 th stage is equal to that of the heads at the i th stage ðxP ¼ xPÞ.
                                                                                  iþ1  i
70                                                                         S. Hasegawa


Ideal Cascade

Ideal cascade satisfies the condition that the values of b (heads separation factor) at
all stages are constant and the mole fraction of the heads flow at the i + 1 th stage is
equal to those of the tails flow at the i À 1 th stage and of the feed flow at the i th
stage ðxiþ1 ¼ xiÀ1 ¼ xiF Þ . In this instance, each separation factor satisfies the
          p      W
following relationship.
                                          pffiffiffi
                                     b¼    a¼g                                  (3.32)

   In a similar way to the previous section, we can obtain the total number of the
stages for an ideal cascade
                                                   
                              1         xP   1 À xW
                         n¼      ln                   À1
                            ln b      1 À xP   xW
                                                                              (3.33)
                              2         xP   1 À xW
                          ¼      ln                   À1
                            ln a      1 À xP   xW

   The number of stages in stripping nS and enriching nE = n À nS sections can be
derived as
                                                    
                                1        xF   1 À xW
                         nS ¼      ln                  À1                       (3.34)
                              ln b     1 À xF   xW
                                                             
                                       1          xP   1 À xF
                      nE ¼ n À nS ¼        ln                                   (3.35)
                                      ln b      1 À xP   xF

     The reflux ratio Eq. 3.27 can be rewritten using xiP ¼ xiþ1 and b as
                                                            F

                                                         '
                   Wiþ1   xP À xiP   1    xP    bð1 À xP Þ
                        ¼ i        ¼          À                                 (3.36)
                    P    xP À xiþ1 b À 1 xiþ1
                               W          W      1 À xiþ1
                                                      W




Mccabe–Thiele Diagram

It is useful to draw McCabe–Thiele diagram to investigate the design of the
cascade, the mole fractions of the stages and so on. Figure 3.6 shows a typical
McCabe–Thiele diagram. In this graph, the horizontal and vertical axes correspond
to the mole fractions of the heads flow xiP and of the tails flow xiW , respectively.
3 Isotope Separation Methods for Nuclear Fuel                                                                                            71


                                   1
                           xP

                                                  Equilibrium line
                           x P+1
                             i

                                           x iP                 x iW
                                                      = α
                                       1      x iP          1      x iW
                            x iP


                                                                                                     Operating line
     Heads mole fraction




                                                                                                                     i
                                                                                                                 xP
                                                                                                             1           x iP
                           x P−1
                             i
                                                                                                                          i +1
                                                                                                                         xW
                                                                                                         =   α
                                                                                                                             i +1
                                                                                                                 1          xW




                                                                          i +1  i −1
                                                                         xW = x P




                            xW
                                   0
                                       0                                                                                             1
                                        xW           xW−1
                                                      i
                                                                  x iW                 xW+1
                                                                                        i
                                                                                                  xW+2
                                                                                                   i                            xP

                                                                            Tails mole fraction

Fig. 3.6 McCabe-Thiele diagram



   First, the following equation is satisfied at the enrichment process of the i th
stage because of the definition of the separation factor

                                                       xiP         xiW
                                                           i ¼ a         ðEquilibrium lineÞ                                          (3.37)
                                                     1 À xP      1 À xiW

    Second, the condition that the tail (waste) flow at the i + 1 th stage is the feed of
the i th stage ðxiF ¼ xiþ1 Þ defines the relationship between the mole fractions of the
                       W
tail (waste) and head (product) flows at different stages as follows

                                          xiP         xiF     pffiffiffi xiþ1
                                              i ¼ b       i ¼  a W iþ1 ðOperating lineÞ                                              (3.38)
                                        1 À xP      1 À xF        1 À xW
72                                                                         S. Hasegawa


   And third, the feed flow at the i th stage consists of the tails flow of the i + 1 th
stage and the heads flow of the i À 1 th stage and their mole fractions are the same.

                                     xiþ1 ¼ xiÀ1
                                      W      P                                  (3.39)

   These three formulae can be shown in the McCabe–Thiele diagram as shown in
Fig. 3.6. We can estimate the number of necessary stages, mole fractions of the
stages, and overview the total processes through the graphical construction.




Separative Work Unit

The total flow in the cascade can be derived as

             X                                                    
                                 bþ1                          xW
                   ðPi þ Wi Þ ¼             Wð2xW À 1Þ ln
               i
                             ðb À 1Þ ln b                   1 À xW
                                                                  !
                                       xP                       xF
                    þPð2xP À 1Þ ln           ÀFð2xF À 1Þ ln                     (3.40)
                                     1 À xP                   1 À xF

    The first term of Eq. 3.40 including b indicates the difficulty of the separation
and increases as the value of b approaches to unity. The second term corresponds to
the amount of work for separation, and it has the same dimension as flow rates and
is called separative capacity or separative power. This value is important because it
is considered to be proportional to the initial cost of the plant. When we use the unit
of the amounts of material (mole, kg, etc.) instead of flow rates, this is called
separative work. The sum of the annual investment and operation costs can be
expressed by the product of the separative work SW (kg SWU/year) and unit price
of separative work cs ($/kg SWU). SWU is the abbreviation of Separative Work
Unit. The separative work is defined as

                        SW ¼ WfðxW Þ þ PfðxP Þ À FfðxF Þ                        (3.41)

where f(xi) is called separation potential and written as

                                                       xi
                             fðxi Þ ¼ ð2xi À 1Þ ln                              (3.42)
                                                     1 À xi

   When we use kg SWU/year for the separative work, the unit of W, P, and F
should be kg/year.
   For operating the plant, we need the raw materials, the amount of which is F (kg/
year) and unit price of the raw materials cF ($/kg). The total cost per year c ($) can
be written as

                                  c ¼ SWcS þ FcF                                (3.43)
3 Isotope Separation Methods for Nuclear Fuel                                        73


   When the amount of the product per year is P (kg), the unit cost of the product
cP ¼ P : could be derived as
     c


                                                                '
       SWcs FcF                                  fðxF Þ À fðxW Þ
  cP ¼     þ    ¼ ðfðxP Þ À fðxF ÞÞ À ðxP À xF Þ                   cs
        P    P                                      xF À xW
                            
                    xP À xW
                 þ            cF                                                 (3.44)
                    xF À xW




Example

With the ideal cascade of the gaseous diffusion method (a = 1.00429), the mole
fraction of the feed flow 0.711% (xF = 0.00711) would be enriched to 3% (xP = 0.03)
and the mole fraction of the waste is planned to be 0.3% (xW = 0.003). In this case, the
necessary moles of the feed and the waste to obtain the product of 1 [mol] are

                      PðxP À xW Þ 1 Â ð0:03 À 0:003Þ
                 F¼              ¼                   ¼ 6:569½molŠ
                       xF À xW     0:00711 À 0:003

                          PðxP À xF Þ 1 Â ð0:03 À 0:00711Þ
                      W¼             ¼
                           xF À xW       0:00711 À 0:003
                        ¼ 5:569ð¼ 6:569 À 1Þ½molŠ



   The total number of stages n and the number of stages in stripping section nS and
in enriching section nE are calculated as



Stripping Section

                                          
                      2        xF 1 À xW
                nS ¼     ln                  À1
                     lna     1 À xF xW
                                                       
                          2           0:00711 1 À 0:003
                   ¼            ln                        À 1 ¼ 404
                     ln 1:00429     1 À 0:00711 0:003
74                                                                      S. Hasegawa


Enriching Section

                                              
                       2          xp    1 À xF
                nE ¼       ln
                      ln a     1 À xp     xF
                                                          
                         2             0:03    1 À 0:00711
                 ¼              ln                           ¼ 683:5
                   ln 1:00429        1 À 0:03    0:00711

The total number of stages
                                           
                    2         xp     1 À xW
               n¼      ln                     À1
                  ln a      1 À xp     xW
                                                      
                      2              0:03    1 À 0:003
               ¼              ln                         À 1 ¼ 1087:5
                 ln 1:00429        1 À 0:03    0:003

     The heads flow rate in the enriching section can be written as

                Pi ¼ P þ Wiþ1
                          P
                   ¼Pþ        fxp ð1 À biÀn Þ þ ð1 À xp ÞbðbnÀi À 1Þg
                         bÀ1

and that in the stripping section

                           W È                                    É
                   Pi ¼        xW bðbi À 1Þ þ ð1 À xW Þð1 À bÀi Þ
                          bÀ1

   These flows as a function of the number of the stages can be shown as Fig. 3.7 in
this example.
   When we need higher concentration, such as 5%, F = 11.436[mol], W = 10.436
[mol], n = 1336 and nE = 932.



Laser Isotope Separation (LIS)

The photon absorbing frequencies of isotopes show small differences caused by
shifts of atomic electron energies due to the differences in the number of neutrons
among isotopes. This is called isotope shift. The invention and development of
lasers enable to resolve the isotope shift sufficiently and make isotope-selective
photo-chemical reaction possible. Laser Isotope Separation may lead to almost
100% isotope separation in a single stage. Mainly, two methods such as Atomic
Vapor Laser Isotope Separation (AVLIS) and Molecular Laser Isotope Separation
(MLIS) were intensively studied. AVLIS uses uranium atomic vapor that is struck
by lasers of such wavelength that only 235U atoms are excited and then ionized;
3 Isotope Separation Methods for Nuclear Fuel                                                     75


                                               Feed
                                           xF = 0.00711

                  1600

                  1400

                  1200
Heads flow rate




                  1000

                   800

                   600

                                                                                      Product
                   400         Waste                                                  xP = 0.03
                             xW = 0.003
                   200

                     0
                         0   100   200    300   400   500 600 700        800   900 1000 1100 1200
                                                      number of stages

Fig. 3.7 Heads flow rate




once ionized, the 235U ions are collected by an electromagnetic field. MLIS uses
UF6, and vibrationally excites and multiphoton-dissociates only 235UF6 into
235
    UF5 by infrared lasers. The research to commercialize them has faded on
a global scale.
    A new process called Separation of Isotopes by Laser Excitation (SILEX) is
under development. All details are not out in the open yet; but SILEX is considered
to be a kind of molecular LIS using UF6. The method only isotope-selectively
excites but not dissociates 235UF6. The separation factor announced by the company
has been 2–20 [5]. Silex Systems Ltd was originally established as a subsidiary of
Sonic Healthcare Limited of Australia in 1988. In 2007, the SILEX Uranium
Enrichment project was transferred to GE’s nuclear fuel plant in the United States.
Global Laser Enrichment (GLE) was formed as a subsidiary of GE-Hitachi in 2008
[5]. In June 2009, GE-Hitachi submitted a license application to construct a
commercial laser enrichment plant in Wilmington, NC. The NRC staff is currently
reviewing that application. They announced that they succeeded the initial mea-
surement program at Test Loop in 2010 and proceeded to evaluate the program to
decide the commercialization of the process [6].
76                                                                              S. Hasegawa


Future Directions

As of today, the gaseous diffusion and centrifuge processes have been used on a
commercial scale. For the future, it seems that laser enrichment (the SILEX
process) may be the successor to current enrichment methods. Preliminary results,
based on enrichment by lasers, are encouraging. However, considerable
improvements are needed before this method achieves commercial competitive
status. Every uranium enrichment process is linked to nuclear proliferation issues.
It would be very beneficial for the world if a method of enrichment is devised
which inherently offers non- proliferation safeguards for nuclear materials.




Bibliography

1. World Nuclear Association, Uranium Enrichment, World Enrichment capacity - operational and
   planned. http://www.world-nuclear.org/info/inf28.html
2. Villani S (1976) Isotope separation. American Nuclear Society, Hillsdale
3. Benedict M, Pigford TH (1957) Nuclear chemical engineering. Mcgraw-Hill, New York;
   Benedict M, Pigford TH, Levi HW (1981) Nuclear chemical engineering (second edn.),
   (trans: by Kiyose R into Japanese)
4. Kemp RS (2009) Gas centrifuge theory and development: a review of U.S. programs. Science
   and Global Security 17, 1; Wood HG, Glaser A, Kemp RS (2008) The gas centrifuge and
   nuclear weapons proliferation. Physics Today 40
5. Silex Systems Limited home page. http://www.silex.com.au/
6. World Nuclear News (2010) Initial Success from SILEX test loop, 12 April 2010. http://www.
   world-nuclear-news.org/NN-Initial_success_from_SILEX_test_loop-1204104.html

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Nuclear energy

  • 1. Chapter 3 Isotope Separation Methods for Nuclear Fuel Shuichi Hasegawa Glossary Isotope Nuclei of a chemical element which have the same number of protons but different number of neutrons. Some isotopes are stable; some are radioactive. Separation factor A ratio of a mole fraction of an isotope of interest to that of non-interest in an enriched flow divided by that in a depleted flow from a separation unit. The factor should be larger than unity for the unit to result in isotopic enrichment. Separation capability A measure of separative work by a cascade per unit time. Mean free path An average distance of a moving gas molecule between its collisions. Molecular flow Low-pressure phenomenon when the mean free path of a gas molecule is about the same as the channel diameter; then a molecule migrates along the channel without inter- ference from other molecules present. This chapter was originally published as part of the Encyclopedia of Sustainability Science and Technology edited by Robert A. Meyers. DOI:10.1007/978-1-4419-0851-3 S. Hasegawa (*) Department of Systems Innovation, School of Engineering, The University of Tokyo, 7-3-1 Hongo Bunkyo-ku, Tokyo, Japan e-mail: hasegawa@sys.t.u-tokyo.ac.jp N. Tsoulfanidis (ed.), Nuclear Energy: Selected Entries from the Encyclopedia 59 of Sustainability Science and Technology, DOI 10.1007/978-1-4614-5716-9_3, # Springer Science+Business Media New York 2013
  • 2. 60 S. Hasegawa Definition of the Subject Isotope separation, in general, means enrichment of a chemical element to one of its isotopes (e.g., 10B in B; 6Li in Li, 157Gd, etc). In the case of uranium, isotope separation refers to the enrichment in the isotope 235U, which is only 0.711% of natural uranium; today’s nuclear power plants require fuel enriched to 3–5% in 235U. Uranium enrichment is the subject of this article. Efficiencies of sorting out different isotopes of the element (separation factor) are usually very low. For practical enrichment plants, a gaseous diffusion process has been successfully employed to obtain enriched uranium. A gas centrifugation process is the preferred method of enrichment today due to reduced energy con- sumption. A new process using lasers, which can have a high efficiency of separa- tion, is under development and has the potential to replace the current enrichment methods. Introduction The fuel used today by commercial nuclear power plants is the fissile isotope 235U. Unfortunately, 235U is only 0.711% of natural uranium, the rest of which is, essentially, 238U. Light water reactors (LWR) operating dominantly all over the world require isotope enrichment processes because the isotopic ratio of 235U for their fuels should be 3–5%. The processes used to elevate the 235U content from 0.711% to 3–5% are called isotope separation or enrichment processes. Table 3.1 shows the current trends of isotope separation capabilities of the world. The main countries performing the process are Russia, France, US, and URENCO (Germany, Table 3.1 World Enrichment capacity (thousand SWU/year) [1] Country 2010 2015 2020 France (Areva) 8,500* 7,000 7,500 Germany, Netherlands, UK (Urenco) 12,800 12,200 12,300 Japan (JNFL) 150 750 1,500 USA (USEC) 11,300* 3,800 3,800 USA (Urenco) 200 5,800 5,900 USA (Areva) 0 >1,000 3,300 USA (Global Laser Enrichment) 0 2,000 3,500 Russia (Tenex) 23,000 33,000 30–35,000 China (CNNC) 1,300 3,000 6,000–8,000 Pakistan, Brazil, Iran 100 300 300 Total approx. 57,350 69,000 74–81,000 Requirements (WNA reference scenario) 48,890 55,400 66,535 Source: WNA Market Report 2009; WNA Fuel Cycle: Enrichment plenary session WNFC April 2011 *Diffusion
  • 3. 3 Isotope Separation Methods for Nuclear Fuel 61 Netherland, and UK). A number of separation processes have been studied so far, but the principles of the current isotope separation processes mainly use gaseous diffusion or gas centrifugation. The diffusion process was commercialized first but the centrifugation is taking over because of less energy consumption. This article following mainly [2, 3] describes the principles of the two processes and cascade theory, which explains why it is required to repeat the process many times (using successive stages/cascades) to obtain a certain desired enrichment fraction such as 3–5% because a single step provides only a small incremental enrichment. The new enrichment technology using lasers will be described at the end. Principles of the Separation Processes Gaseous Diffusion Figure 3.1 shows the schematic diagram of the gaseous diffusion process. Consider a chamber divided into two compartments by a porous membrane. When dilute gases are introduced into the bottom compartment of the chamber, the pores of the membrane (membrane) make dependency of the transmission of the gases on their molecular masses. If we have a mixture of two molecules in a gas with the same kinetic energy (kinetic energy is determined by kT, k = Boltzmann constant; T = temperature in K; (1/2 mv2 $ kT)), the lighter molecule is faster than the heavier one. Therefore, their frequencies of hitting the membrane is higher for the lighter than for the heavier molecule. However, the mass preference phenomena occur only when the mean free path of the gas molecule is longer than the diameter of the pores 2r and the thickness of the membrane l. The mean free path, l of the molecule can be written as [2] kT l ¼ pffiffiffi (3.1) 4 2ps2 p where k is the Boltzmann constant, T is the absolute temperature, s is the radius of the molecule, and p is the gas pressure in the chamber. In this condition, a molecule Product p′ Feed Waste p′′ Fig. 3.1 A single gaseous diffusion stage
  • 4. 62 S. Hasegawa cannot collide with others during the transmission through the membrane so that its dynamics can be considered as a single molecule process. This process is called molecular flow. The flux of the molecular flow through the flow path with circular cross section is derived by Knudsen as [3] 8rDp Gmol ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi (3.2) 3l 2pmRT where Gmol is the molecular flow velocity, m is the molecular mass, R is the gas constant, and Dp ¼ p00 À p0 is the pressure difference between the bottom and top compartments of the chamber. Equation 3.2 shows that the flow velocity depends on the mass of the gas molecules so that the ratio of the molecules in the mixture transmitted to the upper compartment of the chamber is changed compared with that of the feeding gas. The opposite condition where flows do not depend on the molecular mass is called viscous flow. We will derive the ideal separation factor in the case of 235UF6 and 238UF6 [3], the gas molecules used for uranium enrichment. On the ideal condition where p00 is very small and p0 can be neglected compared with p00 , when we have a binary mixture of gases which consist of 235UF6 (molecular mass: m235 = 349, mole fraction: x) and 238UF6 (molecular mass: m235 = 352, mole fraction: 1 À x), the molecular flow velocities of 235UF6 and 238UF6 are 00 00 ð1ÀxÞ G235 ¼ pffiffiffiffiffiffiffi ; ap x m235 G238 ¼ ap ffiffiffiffiffiffiffi p m238 (3.3) where the constant a includes factors in Eq. 3.2. The ratio of the molecular flow of 235 UF6 to the whole can be written as pffiffiffiffiffiffiffiffiffi x x G235 m235 1 À x ffiffiffiffiffiffiffiffiffi s¼ ¼ ¼ r (3.4) x 1Àx G235 þ G238 pffiffiffiffiffiffiffiffiffi þ pffiffiffiffiffiffiffiffiffi x þ m235 m235 m238 1 À x m238 Therefore, the ideal separation factor a0 of the gaseous diffusion process can be derived as the separation factor of the molecular flow of the porous media s rffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffi m238 352 a0 ¼ 1Às x ¼ ¼ ¼ 1:00429 (3.5) 1Àx m235 349 The separation factor depends on the ratio of the molecular masses so that this method is more effective for the isotope separation of lighter elements. For heavier elements, a larger number of repeated processes is required to obtain sufficiently enriched products. However, in reality, the real value of the separation factor is smaller than that given by Eq. 3.5 due to reverse molecular flow from the upper compartment to the
  • 5. 3 Isotope Separation Methods for Nuclear Fuel 63 bottom one and viscous flow not depending on the molecular mass; these two phenomena work in a direction negating the enrichment process. Furthermore operating conditions (porous media performance, working pressures, etc.) affect the value of the separation factor. The energy consumption to run the process is very high due to pressure controlling of the gases, small separation factors and so on (see discussion about Separative Work Unit). Because of the relatively high energy consumption, uranium enrichment by gaseous diffusion is on the way out and is replaced by the gas centrifugation method. Gas Centrifugation The principle of gas centrifugation is based upon centrifugal forces that are created inside a rotating cylinder containing two different gas molecules, forces that depend on the molecular mass. Let’s see how it works in detail [2]. When we have a mixture of two gas molecules in a rotating cylinder (centrifuge), pressure gradients develop with respect to the radial direction. The pressures can be written as dp ¼ o2 rr (3.6) dr where p is the pressure, r is the radial distance, o is the angular frequency of rotation, and r is the density of the gases. By substituting the equation of state r ¼ pm=RT into the differential equation, we can derive the following equation, dp mo2 ¼ rdr (3.7) p RT When we integrate this differential equation from the radial distance r (pressure pr) to the inner radius of the cylinder a (pressure pa), we can obtain this expression, & r 2 '! pr 1 mv2 ¼ exp À a 1À (3.8) pa 2 RT a where the speed of the outer circumference of the cylinder na = oa This equation shows that the ratio of the pressure at radius r to that of radius a depends on the molecular mass of the gases. If we have the gases which consist of 235UF6 (molecular mass: m235 = 349, mole fraction: x) and 238UF6 (molecular mass: m235 = 352, mole fraction: 1 À x), their ratios of the partial pressures at the radius r to the radius a can be derived as r 2 '! pr x r 1 m235 v2 ¼ exp À a 1À (3.9) pa x a 2 RT a
  • 6. 64 S. Hasegawa Table 3.2 The local separation factor of 235UF6 and 238UF6 at r/a with T = 300K, ua = 700m/s r/a 0 0.5 0.8 0.9 0.95 0.98 0.99 1.0 a 1.343 1.247 1.112 1.058 1.029 1.012 1.006 1.0 r 2 '! pr ð1 À xr Þ 1 m238 v2 ¼ exp À a 1À (3.10) pa ð1 À xa Þ 2 RT a Therefore, the local separation factor at radial distance r of radius a is given by xr r 2 '! 1 À xr ðm238 À m235 Þv2 a¼ xa ¼ exp a 1À (3.11) 2RT a 1 À xa which depends on the difference of their molecular masses, Dm = m238Àm235 = 3. Values of the local separation factor of 235UF6 and 238UF6 with T = 300 K and na = 700 m/s are given in Table 3.2. This feature is superior to the gaseous diffusion method when the difference of the masses is large, (e.g., for heavier elements). The separation factor increases as the speed of the outer circumference increases. However, the maximum speed vmax is limited by stresses created to the cylinder from the force of the centrifugation and can be written as [2] rffiffiffi s vmax ¼ (3.12) r where r is the density of the material of the cylinder, and s is the tensile strength. Although most molecular gases are localized at a % 1 because of the centrifugation, r the values of the separation factor could be higher than those obtained from the gaseous diffusion method. These values can be enhanced if we make use of a countercurrent flow in the vertical direction. Figure 3.2 shows the schematic diagram of countercurrent centrifugation method. Gernot Zippe performed pioneering work on the development of the centrifugation first in the Soviet Union during 1946–1954, and from 1956 to 1960 at the University of Virginia. The countercurrent flow can be induced by heating and cooling centrifuges, or pipes drawing off flows in centrifuges. The temperature control can adjust the flow deliberately but the equipment becomes more complicated than that of the flow control by the pipes (Fig. 3.2). This countercurrent flow makes enrichment of the lighter isotopes at inner radius as the flow descending along the axis direction, and the heavier isotopes are being enriched at the circumference as the flow ascending. These enriched gases are collected at different radial positions of the both ends (at outer radius for heavier isotope and at inner radius by baffle for lighter isotope). When the centrifuge has a length L, the maximum separative power dUmax can be derived as [2, 4] 2 p Dmv2 dUmax ¼ LrD a (3.13) 2 2RT
  • 7. 3 Isotope Separation Methods for Nuclear Fuel 65 Fig. 3.2 Schematics of gas centrifuge with Heads (Product) countercurrent flow Feed Tails (Waste) 238UF 238UF 6 6 238 UF6 235 UF6 235 238 UF6 UF6 235UF 235UF 6 6 where D is diffusion coefficient. The maximum separative power is proportional to the height of the centrifuge. It is preferable to have a taller centrifuge in the vertical direction, but the length is imposed on the resonant vibration of the centrifuge. The resonant conditions can be written as [3] pffiffiffiffirffiffiffiffiffiffiffi L 4 E ¼ li li ¼ 22:0; 61:7; 121:0; 200:0; 298:2;Á ÁÁ (3.14) a i 2s0 where E is coefficient of elasticity. A taller centrifuge can give a larger separative power although excellent mechanical properties are required to overcome the resonant conditions. Cascade Theory The present isotope separation plants make use of these principles of enrichment with small separation factors. In order to obtain high enrichment ratios, cascade theory is necessary [3]. According to the theory, we can enhance the ratios by iterating a single physical stage many times. Figure 3.3 shows a simple scheme
  • 8. 66 S. Hasegawa Heads P1 Feed Fi Heads Pi Feed Fn xP 1 i xF i xP n xF Feed F Product P stage1 stage i stage n Feed xF Product xP Waste W1 Waste Wi Waste Wn xW1 xWi xWn Fig. 3.3 Simple scheme of the cascade of a cascade. An original material “feed” is provided to the system. The isotope of interest is enriched as going through many separation stages and a final output “product” is obtained. Another output which mainly contains unnecessary isotopes is called “waste.” Each flow F, P and W should have the following equation F¼PþW (3.15) and with mole fractions of the isotope of interest in each flow xF , xP , xW , we can obtain FxF ¼ PxP þ WxW (3.16) In this system, we have four independent parameters to define. In order to obtain necessary flow of Product “P ” and mole fraction “xP” of the isotope of interest, we need the design methodology to construct stages of separation units. The product of a single stage (unit) is called heads and the waste of that is tails. The ratios of the isotope of interest in the product are usually most important. If, for instance, we have two isotopes “1” and “2,” and want to enrich the “1” isotope, we would focus on the variation of the mole fraction ratio of the two isotopes, x1 , which can be x2 x1 rewritten as 1Àx1 . The capability of each enrichment unit is described as separation factor a. This factor is defined as the ratios of the isotopes of interest to that of not-interest in the heads (product) divided by those in the tails (waste) xP 1 À xP a ¼ xW (3.17) 1 À xW In a similar way, we can define the ratio of the heads (product) to the feed as heads separation factor b, and that of the feed to the tails as tails separation factor g, xP xF 1 À xP 1Àx b¼ xF ; g ¼ xW F and a ¼ bg (3.18) 1 À xF 1 À xW
  • 9. 3 Isotope Separation Methods for Nuclear Fuel 67 Feed Fi Heads Pi Feed Fi Heads Pi i xF i xP xF+ 1 i xP+ 1 i stage stage i i+1 Waste Wi Waste Wi xWi xW+ 1 i Fig. 3.4 Simple cascade of the i and i + 1 th stages The ratio of the product to the feed is called “cut” y and defined as P xF À xw y ¼ (3.19) F xP À xW The simplest design to accomplish enrichment is to accumulate separation stages in a single line such as Fig. 3.4. This scheme is called simple cascade. Simple Cascade In this scheme, the heads and the mole fraction of the i th stage are equal to the feed flow and the mole fraction of the i + 1 th stage (Fig. 3.4). Fiþ1 ¼ Pi ; xiþ1 ¼ xiP F (3.20) This cascade disposes of the tails of all stages so that the total amount of the isotope of interest in the waste should be given sufficient attention. This can be evaluated by means of the recovery rate of the i th stage ri xiW 1À Pi xiP xi xiF À xiW xiP xiF a i À bi ri ¼ ¼ yi P ¼ ¼ i ¼ a À1 (3.21) Fi xiF xiF xiP À xiW xiF x i 1À W xiP When we have n stages in the cascade, the total recovery rate r can be expressed as P xP Pn xn P1 x1 P2 x2 Pn xn r¼ ¼ P ¼ P P ¼ P ¼ r1 r2 Á Á Á rn (3.22) F xF F1 x1 F1 x1 F2 x2 Fn xn F F F F The over-all separation factor of the cascade o can be derived as
  • 10. 68 S. Hasegawa Fig. 3.5 Countercurrent recycle cascade Stage n Heads Pi xP+ 1 i Feed Fi xF+ 1 i Stage i Heads Pns +1 Tails Wi xP s+ 1 n xW+ 1 i Feed F Stage xF ns + 1 Heads Pns n xP s Tails Wns+1 Stage ns xW s + 1 n Feed Fns Tails Wns n xF s n xW s Stage 1 xn P 1 À xn o¼ P ¼ b1 b2 Á Á Á bn (3.23) x1 F 1 À x1 F Therefore, if a, b do not depend on each stage, the total recovery rate can be rewritten as !n a À o f ng 1 aÀb n r¼ ¼ (3.24) aÀ1 aÀ1 When the feed itself is available without any special cost, the simple cascade is effective. But in case the wastes from each stage should not be disposed because, for instance, it is valuable or the recovery rate has to be increased, the waste flows are recycled as feed flow, which is called countercurrent recycle cascade (Fig. 3.5). Countercurrent Recycle Cascade Since the simple cascade cannot improve the recovery rate, the tail flow is recycled into either stage to use it efficiently, which is called recycle cascade (Fig. 3.5). If b (heads separation factor) is equal to g (tails separation factor) in all stages, we can obtain xiþ2 ¼ xiþ1 ð¼ xiP Þ. So the tails flow of the i + 2 th stage can be merged to the W F
  • 11. 3 Isotope Separation Methods for Nuclear Fuel 69 heads flow of the i th stage and fed into the i + 1 th stage without any mixing loss. We will consider the case that the tails flow of the second upper stage is refluxed to the i th stage. The flows and the fractions of the isotope of interest in each stage of enriching sections should have the following relationships. Pi ¼ Wiþ1 þ P; Pi xiP ¼ Wiþ1 xiþ1 þ PxP w (3.25) In a similar way, those in stripping sections can be expressed as Wjþ1 ¼ Pj þ W; Wjþ1 xjþ1 ¼ Pj xjP þ WxW W (3.26) Let’s estimate the number of stages. From these equations, we can derive xP À xiP xiP À xiþ1 ¼ W Wiþ1 (3.27) P At total reflux, where the reflux ratio is infinity, Wiþ1 !1 (3.28) P the mole fraction of the heads flow at the i th stage xiP becomes equal to that of the tails flow at the i + 1 th stage xiþ1 and the number of the stages is minimal. W xiþ1 xiþ1 xi xiÀ1 P ¼ a W iþ1 ¼ a P i ¼ a2 P iÀ1 ¼ Á Á Á (3.29) 1 À xiþ1 P 1 À xW 1 À xP 1 À xP gives the following equation, xP xW ¼ an (3.30) 1 À xP 1 À xW and the minimum number of the stages at total reflux can be derived as 1 xP 1 À xW n¼ ln (3.31) ln a 1 À xP xW On the contrary, the reflux ratio becomes minimum when the mole fraction of the heads at the i + 1 th stage is equal to that of the heads at the i th stage ðxP ¼ xPÞ. iþ1 i
  • 12. 70 S. Hasegawa Ideal Cascade Ideal cascade satisfies the condition that the values of b (heads separation factor) at all stages are constant and the mole fraction of the heads flow at the i + 1 th stage is equal to those of the tails flow at the i À 1 th stage and of the feed flow at the i th stage ðxiþ1 ¼ xiÀ1 ¼ xiF Þ . In this instance, each separation factor satisfies the p W following relationship. pffiffiffi b¼ a¼g (3.32) In a similar way to the previous section, we can obtain the total number of the stages for an ideal cascade 1 xP 1 À xW n¼ ln À1 ln b 1 À xP xW (3.33) 2 xP 1 À xW ¼ ln À1 ln a 1 À xP xW The number of stages in stripping nS and enriching nE = n À nS sections can be derived as 1 xF 1 À xW nS ¼ ln À1 (3.34) ln b 1 À xF xW 1 xP 1 À xF nE ¼ n À nS ¼ ln (3.35) ln b 1 À xP xF The reflux ratio Eq. 3.27 can be rewritten using xiP ¼ xiþ1 and b as F ' Wiþ1 xP À xiP 1 xP bð1 À xP Þ ¼ i ¼ À (3.36) P xP À xiþ1 b À 1 xiþ1 W W 1 À xiþ1 W Mccabe–Thiele Diagram It is useful to draw McCabe–Thiele diagram to investigate the design of the cascade, the mole fractions of the stages and so on. Figure 3.6 shows a typical McCabe–Thiele diagram. In this graph, the horizontal and vertical axes correspond to the mole fractions of the heads flow xiP and of the tails flow xiW , respectively.
  • 13. 3 Isotope Separation Methods for Nuclear Fuel 71 1 xP Equilibrium line x P+1 i x iP x iW = α 1 x iP 1 x iW x iP Operating line Heads mole fraction i xP 1 x iP x P−1 i i +1 xW = α i +1 1 xW i +1 i −1 xW = x P xW 0 0 1 xW xW−1 i x iW xW+1 i xW+2 i xP Tails mole fraction Fig. 3.6 McCabe-Thiele diagram First, the following equation is satisfied at the enrichment process of the i th stage because of the definition of the separation factor xiP xiW i ¼ a ðEquilibrium lineÞ (3.37) 1 À xP 1 À xiW Second, the condition that the tail (waste) flow at the i + 1 th stage is the feed of the i th stage ðxiF ¼ xiþ1 Þ defines the relationship between the mole fractions of the W tail (waste) and head (product) flows at different stages as follows xiP xiF pffiffiffi xiþ1 i ¼ b i ¼ a W iþ1 ðOperating lineÞ (3.38) 1 À xP 1 À xF 1 À xW
  • 14. 72 S. Hasegawa And third, the feed flow at the i th stage consists of the tails flow of the i + 1 th stage and the heads flow of the i À 1 th stage and their mole fractions are the same. xiþ1 ¼ xiÀ1 W P (3.39) These three formulae can be shown in the McCabe–Thiele diagram as shown in Fig. 3.6. We can estimate the number of necessary stages, mole fractions of the stages, and overview the total processes through the graphical construction. Separative Work Unit The total flow in the cascade can be derived as X bþ1 xW ðPi þ Wi Þ ¼ Wð2xW À 1Þ ln i ðb À 1Þ ln b 1 À xW ! xP xF þPð2xP À 1Þ ln ÀFð2xF À 1Þ ln (3.40) 1 À xP 1 À xF The first term of Eq. 3.40 including b indicates the difficulty of the separation and increases as the value of b approaches to unity. The second term corresponds to the amount of work for separation, and it has the same dimension as flow rates and is called separative capacity or separative power. This value is important because it is considered to be proportional to the initial cost of the plant. When we use the unit of the amounts of material (mole, kg, etc.) instead of flow rates, this is called separative work. The sum of the annual investment and operation costs can be expressed by the product of the separative work SW (kg SWU/year) and unit price of separative work cs ($/kg SWU). SWU is the abbreviation of Separative Work Unit. The separative work is defined as SW ¼ WfðxW Þ þ PfðxP Þ À FfðxF Þ (3.41) where f(xi) is called separation potential and written as xi fðxi Þ ¼ ð2xi À 1Þ ln (3.42) 1 À xi When we use kg SWU/year for the separative work, the unit of W, P, and F should be kg/year. For operating the plant, we need the raw materials, the amount of which is F (kg/ year) and unit price of the raw materials cF ($/kg). The total cost per year c ($) can be written as c ¼ SWcS þ FcF (3.43)
  • 15. 3 Isotope Separation Methods for Nuclear Fuel 73 When the amount of the product per year is P (kg), the unit cost of the product cP ¼ P : could be derived as c ' SWcs FcF fðxF Þ À fðxW Þ cP ¼ þ ¼ ðfðxP Þ À fðxF ÞÞ À ðxP À xF Þ cs P P xF À xW xP À xW þ cF (3.44) xF À xW Example With the ideal cascade of the gaseous diffusion method (a = 1.00429), the mole fraction of the feed flow 0.711% (xF = 0.00711) would be enriched to 3% (xP = 0.03) and the mole fraction of the waste is planned to be 0.3% (xW = 0.003). In this case, the necessary moles of the feed and the waste to obtain the product of 1 [mol] are PðxP À xW Þ 1 Â ð0:03 À 0:003Þ F¼ ¼ ¼ 6:569½molŠ xF À xW 0:00711 À 0:003 PðxP À xF Þ 1 Â ð0:03 À 0:00711Þ W¼ ¼ xF À xW 0:00711 À 0:003 ¼ 5:569ð¼ 6:569 À 1Þ½molŠ The total number of stages n and the number of stages in stripping section nS and in enriching section nE are calculated as Stripping Section 2 xF 1 À xW nS ¼ ln À1 lna 1 À xF xW 2 0:00711 1 À 0:003 ¼ ln À 1 ¼ 404 ln 1:00429 1 À 0:00711 0:003
  • 16. 74 S. Hasegawa Enriching Section 2 xp 1 À xF nE ¼ ln ln a 1 À xp xF 2 0:03 1 À 0:00711 ¼ ln ¼ 683:5 ln 1:00429 1 À 0:03 0:00711 The total number of stages 2 xp 1 À xW n¼ ln À1 ln a 1 À xp xW 2 0:03 1 À 0:003 ¼ ln À 1 ¼ 1087:5 ln 1:00429 1 À 0:03 0:003 The heads flow rate in the enriching section can be written as Pi ¼ P þ Wiþ1 P ¼Pþ fxp ð1 À biÀn Þ þ ð1 À xp ÞbðbnÀi À 1Þg bÀ1 and that in the stripping section W È É Pi ¼ xW bðbi À 1Þ þ ð1 À xW Þð1 À bÀi Þ bÀ1 These flows as a function of the number of the stages can be shown as Fig. 3.7 in this example. When we need higher concentration, such as 5%, F = 11.436[mol], W = 10.436 [mol], n = 1336 and nE = 932. Laser Isotope Separation (LIS) The photon absorbing frequencies of isotopes show small differences caused by shifts of atomic electron energies due to the differences in the number of neutrons among isotopes. This is called isotope shift. The invention and development of lasers enable to resolve the isotope shift sufficiently and make isotope-selective photo-chemical reaction possible. Laser Isotope Separation may lead to almost 100% isotope separation in a single stage. Mainly, two methods such as Atomic Vapor Laser Isotope Separation (AVLIS) and Molecular Laser Isotope Separation (MLIS) were intensively studied. AVLIS uses uranium atomic vapor that is struck by lasers of such wavelength that only 235U atoms are excited and then ionized;
  • 17. 3 Isotope Separation Methods for Nuclear Fuel 75 Feed xF = 0.00711 1600 1400 1200 Heads flow rate 1000 800 600 Product 400 Waste xP = 0.03 xW = 0.003 200 0 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 number of stages Fig. 3.7 Heads flow rate once ionized, the 235U ions are collected by an electromagnetic field. MLIS uses UF6, and vibrationally excites and multiphoton-dissociates only 235UF6 into 235 UF5 by infrared lasers. The research to commercialize them has faded on a global scale. A new process called Separation of Isotopes by Laser Excitation (SILEX) is under development. All details are not out in the open yet; but SILEX is considered to be a kind of molecular LIS using UF6. The method only isotope-selectively excites but not dissociates 235UF6. The separation factor announced by the company has been 2–20 [5]. Silex Systems Ltd was originally established as a subsidiary of Sonic Healthcare Limited of Australia in 1988. In 2007, the SILEX Uranium Enrichment project was transferred to GE’s nuclear fuel plant in the United States. Global Laser Enrichment (GLE) was formed as a subsidiary of GE-Hitachi in 2008 [5]. In June 2009, GE-Hitachi submitted a license application to construct a commercial laser enrichment plant in Wilmington, NC. The NRC staff is currently reviewing that application. They announced that they succeeded the initial mea- surement program at Test Loop in 2010 and proceeded to evaluate the program to decide the commercialization of the process [6].
  • 18. 76 S. Hasegawa Future Directions As of today, the gaseous diffusion and centrifuge processes have been used on a commercial scale. For the future, it seems that laser enrichment (the SILEX process) may be the successor to current enrichment methods. Preliminary results, based on enrichment by lasers, are encouraging. However, considerable improvements are needed before this method achieves commercial competitive status. Every uranium enrichment process is linked to nuclear proliferation issues. It would be very beneficial for the world if a method of enrichment is devised which inherently offers non- proliferation safeguards for nuclear materials. Bibliography 1. World Nuclear Association, Uranium Enrichment, World Enrichment capacity - operational and planned. http://www.world-nuclear.org/info/inf28.html 2. Villani S (1976) Isotope separation. American Nuclear Society, Hillsdale 3. Benedict M, Pigford TH (1957) Nuclear chemical engineering. Mcgraw-Hill, New York; Benedict M, Pigford TH, Levi HW (1981) Nuclear chemical engineering (second edn.), (trans: by Kiyose R into Japanese) 4. Kemp RS (2009) Gas centrifuge theory and development: a review of U.S. programs. Science and Global Security 17, 1; Wood HG, Glaser A, Kemp RS (2008) The gas centrifuge and nuclear weapons proliferation. Physics Today 40 5. Silex Systems Limited home page. http://www.silex.com.au/ 6. World Nuclear News (2010) Initial Success from SILEX test loop, 12 April 2010. http://www. world-nuclear-news.org/NN-Initial_success_from_SILEX_test_loop-1204104.html