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4.3 Effective Heat and Mass Transport Properties Where available you should always use experimentally measured values for thermal conductivity and diffusivity. For first estimates and where experimental data are not available, several correlations are suggested below. 4.3.1 THERMAL CONDUCTIVITY Suppose you have a slurry of solid particles having a thermal conductivity, ks, and a continuous fluid phase with conductivity kf. At zero flow conditions, as a first approximation, you might expect that the thermal energy will pass through the slurry with an effective thermal conductivity that is proportional to the volume fraction of the materials. This is analogous to saying that in the ideal model, as shown in Figure 4-11 that the total heat flux, Q is the sum of the total heat fluxes through the separate phases, Qs and Qf, as given by Q = = = Q f + Qs T Af k f x + As k s T x T x (4-31)

A(k f + (1 )k s )

It is assumed in this idealized case that the temperature profiles through the differential element are linear and that the heat flux is only in the x-direction. Hence we conclude that the effective thermal conductivity is given by

k 0 = k f + (1 )k s

T0

Area of Fluid Phase Af Fluid Phase Area of Solid Phase As Solid Phase

x Figure 4-11 . A thin differential element of a slurry with differential thickness x . The temperature change across the differential element is given by T = T1 T0 . The surfaces of the two phases in contact with the boundaries at each side of the differential element are Af and As. The ratio of fluid area to total area equals the porosity, = A f A .

4-17

If the solid phase is non-conducting then one would expect the effective thermal conductivity to be related to the porosity by

ko = kf

(4-33)

as deduced from Eq.(4-32) by setting ks equal to zero. Maxwell (J.C. Maxwell, A Treatise on Electricity and Magnetism, Vol. 1, 3rd ed., Dover, New York, 1954) experimentally tested the analogous electrical conductivity problem and derived the correlation

k o 2 = kf 3

(4-34)

Equations (4-33) and (4-34) are plotted in Figure 4-12. From the plot we see that the idealized case from Eq.(4-33) follows the same trend as determined from Maxwell and over predicts by about 20% in the 0.4 to 0.6 porosity range. In many engineering applications Eq.(4-33) may be adequate.

k 0/k f

Ideal Maxwell

Porosity,

Figure 4-12. Effective conductivity versus porosity based on Eqs.(4-33) and (4-34).

4-18

4.3.2 MASS DIFFUSIVITY Mass diffusivity in a multiphase system is analogous to thermal conductivity. By replacing the thermal conductivity terms with diffusivity terms in Eqs.(4-31) and (4-34) you have the analogous expressions relating effective diffusivity to the porosity and the diffusivities of the individual phases. 4.3.3 HEAT TRANSFER COEFFICIENT For gas phase flow through a packed bed of solids, the wall heat transfer coefficient, h, is estimated by the following empirical equation (McCabe and Smith, ibid).

Nu = hd p kg

0 = 1.94 Rep.5 Pr0.33

(4-35)

Gd p

(mass per area of bed per time). Unfortunately, this expression is limited to packed beds of porous inorganic materials such as alumina and silica gel with a porosity of approximately 0.3. Other correlations are needed to take into account the wide range of porosities that are possible with slurries. For dilute slurries, the Sieder Tate equation can be used as an approximation, for turbulent flow in a tube. In the Sieder Tate equation, the bulk slurry properties are substituted for the fluid properties:

N u = 0.023R P

0.8 e

0.333 r

0 0 w

0.14

(4-36)

0 Cp 0 0VD hD , Re = , and Pr = . The bulk density and viscosity were k0 0 k0 discussed previously. The bulk heat capacity is given by

where N u =

0 C p = C pf + (1 )C ps

(4-37)

4.3.4 MASS TRANSFER COEFFICIENT By analogy, the slurry mass transfer coefficients at the wall are analogous to those given by Eqs.(4-35) and (4-36) for heat transfer coefficients. The heat transfer Nusselt number Nu is replaced by the mass transfer Sherwood number Sh, and the Prandtl number Pr is replaced by the Schmidt number Sc. These numbers are defined by

Sh =

kx D cDAB

(4-38)

4-19

Sc =

DAB

(4-39)

4.3.5 DISPERSIVITY (FLOW EFFECTS) Numerous correlations are available in references and textbooks. For example, in McCabe and Smith (ibid) for a porous inorganic material such as alumina, silica gel, or an impregnated catalyst, the effective thermal conductivity of the bed is proportional to the gas phase thermal conductivity, kg, given by

k0 5 + 0.1Rep Pr kg

(4-40)

This shows that the effective thermal conductivity is affected by the flow rate, due to a dispersion mechanism. Dispersion is caused by the fluid following tortuous paths and becoming intermixed in the lateral directions normal to the prevailing direction of flow. 4.4 Hindered Settling What happens when particles settle in concentrated solutions? As each particles falls it displaces fluid which in turn must move upward. In a concentrated system this causes an upward fluid motion which interferes with the motion of other particles. This is shown in Figure 4-13.

DISPLACED FLUID

FALLING PARTICLES

Figure 4-13. Hindered settling: as a particle falls its displaced fluid moves upward and slows the observed settling rate of neighboring particles.

4-20

The net effect is a slower, hindered, settling rate for the group of particles as compared to the free settling terminal velocity of one particle by itself. Coe and Clevenger (Trans. Am. Inst. Min. Met. Eng. 55, 356, 1916) observed that during a batch settling operation, the sedimenting fluids develop several zones (Figure 4-14). In zone A the particles are in low concentration and settle at their terminal velocity. In zones B and C the particles are in hindered settling. In zone D the sediment has particles in contact with each other; the particles are no longer settling though the sediment may compact due to the weight of the overburden. The concentration of the particles in zone D near the C - D interface is approximately that of loose packing as given by the correlation in Figure 4-5. Not all four zones are present in all settling processes.

A B

Zone A = clear liquid zone. Zone B = constant composition zone. Zone C = variable composition zone. Zone D = sediment.

C D

Figure 4-14. Zones of settling observed by Coe & Clevenger. T. Allen (Particle Size Measurement, Volume 1, 5th ed, Chapman & Hall, London, 1997, page 224) notes that zone B settles in mass and the relative motion of fluid to particles is analogous to flow through a packed bed, hence Eq. (4-25) could be used here to model the motion of zone B. Maude & Whitmore (Br. J. Appl. Phy. 9, 477-482, 1958) modeled the hindered settling process as a power law in the concentration (volume fraction of the liquid phase) us = ut n (4-41) where for dilute solutions 1 and us ut . Here u t is calculated as in Chapter 3 for a single particle falling through a clear fluid and n accounts for the hindered settling effects. The parameter n is determined experimentally. Unfortunately n is not a constant but varies as a function of the particle geometry and the Reynolds number. Perrys Handbook (6th ed, pg 5-68) shows that n varies from 2.3 to 4.5 for spherical particles and has a dramatic effect on the calculated values for the hindered settling velocity.

4-21

In the section that follows a rational approach to hindered settling is described in which the particle settles through the slurry instead of the clear fluid. This approach is a preferred alternative to the Maude & Whitmore approach. 4.4.1 RATIONAL ANALYSIS OF HINDERED SETTLING The primary reasons for the phenomena of hindered settling are: (a) Large particles fall at a different rate relative to a suspension of smaller particles so that the effective density and viscosity of the fluid are increased, (b) In high concentrations, larger volumes of fluid are displaced causing an upward fluid velocity. The settling velocity to an external observer is different than the effective velocity difference be the two phases, and (c) Velocity gradients in the fluid near the particle surfaces are increased as a result of the concentration of the particles. Terminal velocity of a single particle is correlated through the drag coefficient CD as given by the defining equation relating the kinetic force acting on the particle and the particles kinetic energy,

Fk

= C d A KE 2 d p 1 2 = CD 4 2 ut

(4-42)

where ut is the observed velocity of the particle relative to the stationary vessel walls. ut actually represents the velocity difference between the particle and the stationary fluid phase, ut = v s v f . (4-43)

When settling occurs in a large vessel of cross-sectional area A the displaced fluid velocity is negligible. Let the z-direction be the direction of gravity; then the particles have a positive velocity in the z-direction and the fluid has a negative velocity opposite to the direction of gravity. At steady state the volume rate of flow of particles downward must equal the volume rate of flow of fluid upward. We can write this as

2 d p s f 4 v = Av

(4-44)

where A is large and hence v f is small compared to v s . In hindered settling the volume rate of flow of particles is related to the fluid phase velocity through the solid phase volume fraction (1 ) and the vessel cross sectional area, A, by

(1 )Av s = Av f

or

(4-45)

4-22

vf =

(1 )

vs.

(4-46)

Since the terminal velocity is the relative velocity difference between the solid particle downward motion and the fluid phase upward motion, then

ut = vs v f (1 ) s = vs + v = vs

(4-47)

v s = ut . (4-48)

This is consistent with the extreme case of dilute solutions. In the limit when only one particle is present, 1, the observed velocity approaches the terminal velocity, v s ut . For more concentrated solutions the particles interfere with the drag coefficients on each other. Davis and Hill (J. Fluid. Mech, 236, 513-533, 1992) studied hindered settling with spheres falling through slurries of neutrally buoyant particles. Their work assumes Brownian motion and interparticle attractive/repulsive forces are negligible. The results of their work show the velocity effects are nearly independent of particle size ratio. Geankoplis (Transport Processes and Unit Operations, 3ed, Prentice Hall, Englewood Cliffs, 1993, pg 820) suggests that we replace the fluid phase density and viscosity, and in the hindered settling correlations with the slurry bulk density and bulk viscosity, o and o , where

0 = + (1 ) p

and

(4-49) (4-50)

0 = f ( )

where f ( ) is a function of the fluid phase volume fraction, , as related through Eqs.(4-3) to (4-9). Effectively we are saying that the fall of a single particle in a slurry is the same as if all of the other particles in the slurry are part of the surrounding fluid phase. For neutrally buoyant particles in the slurry (but the falling particle is not neutrally buoyant), in the Stokes Law range the observed velocity is given by the modifying Stokes Law, Eq.(3-61) to be

v =u =

s o t

2 gd p p 0

18 0

).

(4-51)

If all of the particles in the surrounding slurry are also setting, then we must take into account the upward motion of the fluid phase as done in Eq.(4-40) which gives

4-23

v s = u to =

2 g d p ( p 0 ) . 18 0

(4-52)

This assumes all of the particles are approximately the same size and density. How can we approach this problem if the particles have a variation in size and density? If there is a variation in the size or density of the particles, then the different types of particles will settle at different rates. Let v is be the observed velocity of the ith type of particles (of size d pi and density i ) which occupy a solid phase volume fraction is (volume of all ith particles divided by total volume). The bulk density becomes

0 = + is i

(4-53)

where is = s = (1 ) is the total volume fraction occupied by the solid phase. We have no additional information on the bulk viscosity so we use the same models as given in Eqs.(4-3) through (4-9). Since the velocities are different, we must relate all of the velocities to the volumetric rate of displacement,

Qs

= A s v s

= A is v is

(4-54)

We are not interested in a mass average solid phase velocity. The drag coefficient correlation reflects the fact that we are accelerating the fluid around the particle, hence we are actually interested in the volumetric flow rate so we can relate it to the fluid phase mass. The terminal velocity of the ith size particle is uti = v is v f which can be manipulated as (4-56)

4-24

uti

= v is + =v

s i

A +

s i

Qs A

s i

v is

(4-57)

s j

= v is 1 + +

ji

v sj

uti js v sj

v is =

s i

+ )

ji

(4-58)

which is the expression that applies to settling Zone C. In estimating values for u ti in Eq.(4-58) one may use the modified forms (substitute bulk density and bulk viscosity for the fluid properties) of Stokes Law, Newtons Law or intermediate range, depending upon the Reynolds number for the particle size. Since Eq.(4-50) is the most general form we can apply it to several example cases to demonstrate its utility.

4.4.2 CASE STUDY COMPARISONS IN HINDERED SETTLING

CASE 1: One particle in free settling. This is the simplest case. Since there is only one particle, there is only one particle size. The fluid occupies a significantly greater volume hence = 1 and 1s = 0 , the fluid density is the same as the bulk density, = 0 , and the fluid viscosity is the same as the bulk viscosity, = 0 . Equation (4-58) reduces to

v1s = (1)u t1 0 = u t1 (0 + 1)

(4-59)

ji

s j

Eq.(4-58) reduces to the solids velocity equals the terminal velocity, as expected. CASE 2: One particle settling in a slurry of neutrally buoyant particles. In this case, the neutrally buoyant particles affect the bulk viscosity of the slurry, but not the bulk density. The neutrally buoyant particles are of a concentration represented by volume fraction 2s 0 which is non zero. The settling particle, as in Case 1, has a volume fraction of essentially zero, 1s 0 .

4-25

Since all of the volume fractions must sum to 1, we get = (1 2s ) . Equation (4-58) gives the estimated velocities to be v1s =

ut1 2s 0 = ut1 (0 + )

(4-60)

Where the velocity of the neutrally buoyant particles is zero because the remain motionless with the fluid phase. This tells us that the particle settles at its modified terminal velocity rate where u t1 = u t1 ( 0 , 0 ). As a consistency check, Eq.(4-58) gives

s the velocity of the neutrally buoyant particles to be zero, v 2 = 0 .

CASE 3: Group of particles of same size all settling at the same rate. This case is more complex than Case 2 because now there are many particles settling, not just one particle. There are no neutrally buoyant particles present in this system. The volume fraction, 1s occupied by the particles is not zero. This results in 1 = + 1s . Since only one type of particle is present in the system, the summation term in the numerator of Eq.(4-50) summed over j i is identically zero. The observed velocity becomes v1s = ut 1 where the terminal velocity is a function of the bulk density and viscosity. CASE 4: Two sizes of particles settling at different velocities. This is the most complex case that will be considered here. In this case there are two particle sizes, denoted 1 and 2. Neither of the particles are neutrally buoyant. The volume fractions are related by 1 = + 1s + 2s . The observed velocities are determined from Eq.(4-58) to be

s ut1 2s v2 v = (1 2s ) s 1

(4-61)

(4-62)

(4-63) (4-64)

and

s v2 =

ut 2 1s v1s (1 1s )

where we see that the two velocities are interdependent. If we use Eq.(4-64) to eliminate the velocity of particle 2 from the right side of Eq.(4-63) then we get the velocity of particle 1 as a function of the terminal velocities of both particles, v1s = (1 1s ) ut1 2s ut 2 . (4-65)

4-26

With Eq.(4-65) we can calculate the observed settling velocities for the two types of particles present in the slurry. The limitations of the results are reiterated here for emphasis. These results assume laminar, slow flow conditions. If there are any disturbances in the slurry then the eddy currents will disrupt the flow patterns. Also, these results only hold as long as the volume fractions are constant. The settling process is inherently unsteady hence these results only hold at the moment in time that the concentrations are those used in the equations; the concentrations will vary with time and position. Sedimentation of multicomponent mixtures has been the subject of numerous papers in literature. See for example: J. F. Richardson, and R.A. Meikle, Sedimentation and Fluidization Part III, The Sedimentation of Uniform Fine Particles and of TwoComponent Mixtures of Solids, Trans. Inst Chem. Engr, 39, 348-356, 1961. EXAMPLE 4-3. Calculate the observed settling velocities of a mixture of latex spheres and sand in water. Suppose a mixture of latex spheres (39 microns, intrinsic density of 1.18 g/cm3) and sand (1 mm, intrinsic density of 2.5 g/cm3) are settling in water at room temperature. Estimate the observed velocities of the latex and the sand.

s s . The mixture is uniformly mixed (initially) with latex = 01 and sand = 0.05 as the volume fractions occupied by each type of particle. The water volume fraction is s s given by = 1 latex sand = 0.85 . The water viscosity is 1.0 cP and using Eq.(4.4) the slurry bulk viscosity is estimated to be 1.409 cP. With the water density of 1000 kg/m3, the bulk density is calculated using Eq.(4-2) to be 1093 kg/m3.

Assuming Stokes law range, the terminal velocity of the latex particles is calculated to be 4.394x10-5 m/s using Eq.(3-61) modified with the bulk density and viscosity

u latex =

2 gd latex ( latex 0 )

18 0

(4-66)

The Stokes Law assumption is checked by the Reynolds number which calculates to be 0.0013 using

Re =

0 u latex d latex 0

(4-67)

Similarly, the terminal velocity for the sand is estimated from Stokes Law to be 0.462 m/s but the Reynolds number is 421 which places the sand in the intermediate range. A check of Newtons Law range, given by Eq.(3-62) modified with the bulk density and viscosity gives a terminal velocity of 0.1649 m/s and Reynolds number of 150, also indicates the intermediate range. Hence, the intermediate range Eq.(3-60) must be used, which is modified as

4-27

u sand =

4 3

d sand g sand 0 CD 0

(4-68)

3 C D = 18.5 / Rep/5

(4-69)

from Figure 3-12. Since the terminal velocity in Eq.(4-68) depends upon itself, through the Reynolds number, then an iterative solution is needed. Using successive substitution a guess for the terminal velocity is used to calculate the Reynolds number, calculate the drag coefficient, and calculate a new guess for the velocity. This set of calculations is easily computed using a computer spreadsheet.

guess u Re Cd calc u 0.35 271.5046 0.64107 0.16204 0.16204 125.6987 1.017591 0.128614 0.128614 99.76932 1.16889 0.120002 0.120002 93.08867 1.218523 0.117532 0.117532 91.17311 1.23382 0.116802 0.116802 90.60617 1.238446 0.116583 0.116583 90.43677 1.239837 0.116518 0.116518 90.38602 1.240255 0.116498 0.116498 90.37079 1.24038 0.116492 0.116492 90.36623 1.240418 0.11649 0.11649 90.36486 1.240429 0.11649

Hence the terminal velocity of the sand is u sand = 0.11649 m/s. Using Eq.(4-57) the observable velocities of the latex and the sand are s s v sand = 0.11066 m/s and v latex = 0.00578 m/s. The negative value for the observed latex velocity indicates that the velocity is upward! The observable velocity of the water may be determined from Eq.(4-58) with some manipulation as

vf =

s s i i

= 0.00617 m / s

(4.70)

for which the minus sign indicates upward flow. Flotats (Hungarian J. Indust. Chem, 23, 215, 1995) argues that in sedimentation the smallest particles may move upward with this fluid motion as indicated by the negative fluid and latex velocities.

4-28

4.5 Slurry Flows Cheremisinoffs book (N.P. Cheremisinoff and R. Gupta, Handbook of Fluids in Motion, M.C. Roco ed., Ann Arbor Science, Ann Arbor, Michigan, 1983) and the Encyclopedia of Fluid Mechanics are two examples of good references that discuss slurry flows. Many concentrated suspension display non-Newtonian flow behavior, even when the suspensions are spherical. Therefore the bulk viscosity correlations described previously in Section 4.2 must be used with some caution.

Some slurries can be influenced by electrical and magnetic forces that change their flow behavior. Electrorheological fluids (H. Conrad, Structure and Mechanisms of ElectroRheological (ER) Fluids,Chapter 12, in Particulate Two-Phase Flow, Butterworth, Boston, 1993) are fluids that change properties under the influence of electrical fields. With no electrical field the fluid flows like a Newtonian; with the electrical field the fluid flows like a yield-stress fluid. The ER fluid is made up of a non-conducting liquid phase and a conducting or semiconducting particulate phase. The mechanism by which this works is due to the particles lining up when an electrical field is applied. This is shown in Figure 4-15. This is one example of how slurry behavior is not a simple extension of the carrier fluids properties.

Figure 4-15. Alumina particles in a silicone oil line up in fibers when an electrical field of 1000 volts per centimeter is applied.

Another way that slurry behavior differs from the carrier fluid is when phase separation occurs. This is especially true for gas-liquid systems. Kao (D.T.Y. Kao, Rheology of

4-29

Suspensions, Chapter 33, in Handbook of Fluids in Motion, N.P. Cheremisinoff and R. Gupta eds., Ann Arbor Science, Ann Arbor, Michigan, 1983) classifies suspension flow behavior as: Single Phase Fine Dispersions Coarse Dispersions Macro-mixed Stratified Homogeneous Pseudo-Homogeneous Heterogeneous Heterogeneous Heterogeneous

A single phase by definition is homogeneous, because its material content does not vary with position. Fine dispersions are termed pseudo homogeneous because even though two phases are present, at a local scale the two phases are well among each other. Coarse dispersions are typically those with large particles (relative to the size of the slurry pipeline) and the larger particles may have a tendency to settle quickly. Macro-mixed dispersions have regions of high concentration of particles and regions of low concentrations of particles, and these regions are located somewhat randomly throughout the slurry. Stratified flows have regions of high concentrations of particles in a layer located at the bottom of a pipe, for example, and low concentration at the top of the pipe.

4-30

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