Chapter 6 7
Chapter 6 7
Chapter 6 7
The system will attain a new equilibrium state, i.e. it will have a different set of liquid and vapor
concentrations and a new total pressure in the vapor space
Under a given set of conditions, the equilibrium vapor composition is related to the liquid
composition
V-L equilibria constitute the physical basis of separation of a mixture by distillation. The higher
concentration of the more volatile component(s) in the vapor phase compared to the liquid phase
makes separation by distillation possible
Relative Volatility
Relative volatility of a component A in a mixture indicates the ease of its separation from another component B.
It is defined as the concentration ratio of A to B in the vapor divided by the same ratio in the liquid phase. It is
usually denoted by
If A is the more volatile component in the mixture, is larger than 1 (this is not applicable over the entire range of
concentration if the system is azeotropic)
Using Equations (7.5) and (7.7), the relative volatility (= AB) in an ideal binary solution can be expressed in
terms of the vapor pressures of the components
In a multicomponent mixture, the relative volatility of component i with respect to component j is given by:
The quantity ij gives a measure of the degree of enrichment of component i in the vapor compared to component
j when a liquid mixture is partially vaporized. Its definition has been extended to other equilibrium separation
processes as well
In mass transfer operations like extraction, membrane separation, etc. a quantity similar to is called the
separation factor
A mixture of 40% mol% benzene and 60 mol% toluene is being flash-distilled at a rate of 10 kmol/h at 1 atm
total pressure. The liquid product should not contain more than 30 mol% benzene. Calculate the amounts
and the compositions of the top and the bottom products . The relative volatility of benzene in the mixture is
2.5
Solution:
Algebraic solution
Total material balance: F = D + W; given F = 10, zF = 0.4 10 = D + W
-------- Eqn 1
------- Eqn 2
In equilibrium flash distillation, the distillate (vapor) and the bottom products (liquid) are in equilibrium,
i.e. xD and xW are in equilibrium, and are related through the relative volatility as follows:
------ Eqn 3
xW/(1 xW)
Equation 1, 2 and 3 can be solved for the three unknowns to get D = 4.61, W = 5.39 mol/h xD = 0.517
A tray column and the flow rates and the concentrations of the vapor and the liquid phases at
different trays are schematically shown in the figure.
The feed (it may be a liquid, a vapor/ a two-phase mixture containing components A and B; A
is the more volatile component) enters the column at a suitable location. The liquid stream
flows down the column from one tray to the next lower tray; the vapor stream flows up
bubbling through the liquid on the trays
The vapor from the top tray is condensed and the condensate is collected in a reflux drum. A
part of this liquid is drawn as the top product and the other part is fed back to the top tray
(the top tray is marked tray no. 1) as reflux
The top product contains the more volatile component A and a little of the less volatile B. The
liquid from the bottom tray goes to a reboiler where it is partly vaporized, the vapor is fed
back to the tower and the liquid part is continuously withdrawn as the bottom product
The bottom product is rich in the less volatile component B and has only a small amount of A
in it. A close contact btwn the liquid and the vapor phases occurs on a tray, facilitating rapid
exchange of mass btwn them
Transport of the more volatile component A occurs from the liquid to the vapor phase, while
transport of the less volatile B occurs from the vapor to the liquid phase
CHAPTER 7: SOLID
LIQUID EXTRACTION
Introduction
The process of separation of soluble constituents of a solid material using a suitable solvent.
Usually the soluble material is the target product and the inert solid residue a byproduct or just
a solid waste (e.g., in extraction of oils from oil seeds: the oil is the product and the solid
residue/ cake is a byproduct)
The overall process of liquid-solid extraction basically involves four steps: (i) close contact btwn
the solid feed with the solvent (ii) separation of the solution (or extract) from the exhausted solid
(iii) separation of the solvent (and the entrained solid, if any) from the extract followed by
purification of the product (iv) recovery of the solvent from the moist solid (by squeezing/
pressing and drying to get a dry cake)
Solid-liquid extraction is also called leaching, a substantial part of the solid does not dissolve
and the soluble matters diffuse out through the solid during solid-liquid contact
Solid-liquid extraction is widely used in the food industries
If the particle size of the solid is not small, there may be substantial diffusional resistance to
transport of the solute within the solid. Whenever possible, the solid is broken down or
disintegrated into particles or flakes to enhance the rate of extraction
Sometimes, an acidic, alkaline or a complexing solution may be used for solubilization of the target
substances
Some categories of commercial solid-liquid extraction:
Diffusional extraction
For example, the extraction of sugar from sugar beet. Sugar beets are cut into small pieces which
are treated with warm water (70-75C). Diffusion within the solid occurs through denatured cell
walls and through the intersticial liquid. The solvent (water) also diffuses in the opposite direction,
thus diluting the solute within the cells.
The rate and time of extraction depend mainly upon the thickness of the pieces, the effective
diffusivity of the solute in the solid and the concentration of sugar in the extracting liquor
Washing extraction
If the solid particle size is pretty small, the solid-phase diffusional resistance becomes negligibibly
small. In such a case, extraction virtually becomes a process of washing the solid with the solvent.
An example is extraction of oil from flakes of oil seeds. Flakes are pretty thin. During the flaking
process, much of the cells are ruptured and the diffusional resistance for transport of the solute
within the solid becomes small.
In washing extraction, a substantial amount of solvent is retained in the slurry after washing
Chemical extraction
Functionally similar to leaching but usually refers to recovering solutes from solids
of organic nature. Example, recovery of gelatin from animal bones using an alkaline
solution is an example of chemical extraction
Solvent
A solvent in which the solute has a high solubility is preferred. But it should not dissolve the undesired solids
The solvent should have a low viscosity, a low boiling point and should be non-toxic and reasonably cheap
It is easier to remove a low-boiling solvent from the product liquor by flash vaporization
Temperature
Diffusivity of the solute in the solid as well as its miscibility with the solvent increases with temperature. Also,
the viscosity of the solvent becomes less at an elevated temperature and it can penetrate into the interstices of
the solid more easily. So the extraction rate increases with temperature
Heat sensitivity of the solute, volatility of the solvent and possible thermal effects on the inert or residual solid
(e.g., solubility, degradation, change in consistency, etc.) limit the temperature of extraction
Agitation
Intense agitation increases the solid-liquid mass transfer coefficient and increases the rate of extraction but
may disintegrate the solid as well, causing a settling problem
However, if the solid phase offers the controlling resistance, the effect of agitation on the rate of extraction is
not pronounced
In any situation involving fluid flow, it is possible to consider the drag on the solid surface as being due
to two phenomena; skin friction (viscous drag) and form drag.
Viscous drag is a result of the stationary layer of liquid that occurs at the surface of the solid object,
the drag or pressure loss is therefore due to friction btwn solid and liquid
Form drag is due to the turbulent eddies which occur at higher flow rates and fluctuate in intensities
and direction. Form drag leads to additional pressure losses over that of skin friction and a breakdown
of linearity btwn flow rate and pressure drop
Most filtration occurs at low flow rates through the porous media.
Permeability
The ease with which liquid will flow within a porous medium, including filter cakes.
Factors which affect permeability include the size of particles making up the porous medium
and the porosity
In practice, filter cake permeability is a function of porosity, particle shape and packing, particle
size and distribution, rate at which the cake was formed, concentration of the slurry being
filtered, etc.
Cake Filtration
It is generally accepted that filtration resulting in a filter cake takes place by a bridging mechanism over the
surface pores within a filter medium, cloth, septum or support. This helps to prevent the medium from clogging
with fine particles
The filter medium plays a crucial role in initiating the filtration, and the medium can have long-lasting effects on
the filter cake structure and properties throughout the filtration cycle
During filtration the cake depth increases due to deposition of solids at the filter cake surface. The change in
cake depth is accompanied by changes in fluid flow rate and pressure differential, as filtration time increases
A material which displays constant cake permeability usually does so as consequence of a constant filter cake
concentration. This is consistent with the permeability equations which showed that this is a function of the
solids type (size) and porosity (or concentration)
A material displaying constant cake concentration is incompressible and this type of filtration is known as
incompressible cake filtration
Cake Filtration
For incompressible filtration, the cake concentration remains constant, thus for each
unit volume of suspension filtered the filter cake volume increases by a uniform and
constant amount. Likewise, the filtrate volume is uniform and constant with respect to
each volume of suspension filtered
However, when filtering at constant pressure, the rate of cake deposition with respect
to time will not be uniform because each new element of filter cake increases the total
resistance to the passage of filtrate from the new cake layer. Thus the rate of filtration
declines
The constant of proportionality can be used to give an equation for cake depth, at
any instant in time:
Cake Filtration
Clearly, the volume ratio of cake to filtrate still needs to be calculated before the previous equation
can be evaluated. This is achieved by means of a mass balance on the solid and liquid entering the
filter system
Mass of solids in the filter cake (kg): C A L s
1 (1)
Use of above Equation assumes knowledge of two constants (excluding densities): slurry
concentration by mass fraction and filter cake concentration by volume fraction. The slurry
concentration (by mass fraction) is readily obtained by means of sampling, weighing, drying and
reweighing. Meanwhile, the filter cake concentration by volume fraction from mass fraction can be
obtained by converting the data to volume fraction from mass fraction
Filter Media
The role is to cause a clean separation of particulate solids from a flowing fluid with a minimum
consumption of energy
Media may be broadly classified as (a) those designed to recover a valuable solid product and (b)
those used in the clarification of a fluid, e.g., deep-packed beds of sand in water clarification
The wide range media received early attention in descriptions of wire cloth, metal edge filters,
fused metallic fibers, ceramics and impregnated cellulose
Of particular interest is the recent massive expansion in the use of ceramics in (a) conventional
solid-liquid filtration and dewatering processes and (b) membrane operations. The latter
development points to important economic gains in the use of small- pore, highly resistant media
and membranes created from ceramics
For textile filter fabrics, both woven and nonwoven filter cloths constructed from polymeric
materials (polypropylene, polyethylene, polyester, polyamides, polyvinyl chloride etc)
(a) Plain-weave monofilament (b) reverse-plain-dutch weave monofilament (c) Twill-weave monofilament
(d) Plain-weave, multifilament, continuous fiber (e) Plain-weave, multifilament, staple fiber
Media Classification
Filter Media
Retention of particulates depends on many process variables and lower minima than reported in the table can be
realized in practical separations. Thus in woven fabrics, changes in particulate concentration can produce particle
capture much below 10 m
It is vital to have information on the particle size range to be processed in view of the interaction between the solids and
the pores during the first few moments of cake growth
Cloth Stretching
Shrinkage of the cloth can produce severe problems particularly with plate and frames and the larger recessed plates.
Repeated cloth washing/drying cycles aggravate the shrinkage problems, particularly polyamides
Preshrinkage can be effected in a number of ways:
Heat setting in an oven, with fabric under tension in warp and weft direction. This will maintain the original levels of
cloth porosity, permeability, etc.
Absorption of liquids causes swelling of fibers and yarn. The increase in fiber diameter and length causes dimensional
change in the cloth, with serious consequences for closely fitted plates.
Recessed plates are preferred to plate and frames, in order to facilitate mechanization.
Discharge of cakes is usually of high priority and is generally easier in recessed plate filters; cake discharge from a plate
and frame unit does not necessarily follow immediately after the opening of the filter
Adequate cake release is a fundamental prerequisite in efficient pressing operations, in maintaining a low downtime in
overall batch time
An understanding of the failure of the release mechanism follows consideration of the balance btwn the forces causing
adhesion
Microfiltration
Are mainly Dead End Filtration (DEF) plate and frame and Tangential Flow Filtration (TFF)
In TFF, the membrane is pleated and then folded around a permeate core. Many module
types are inexpensive and disposable. A typical disposable cartridge is 2.5 inch in
diameter and 10 inch long, with 3 ft2 of membrane area
The cartridge may include a prefilter to extend filter life by removing larger particles,
leaving the microporous membrane to make the required separation.
Compared to TFF, DEF has a lower capital cost, a higher operating cost and a simpler
operation. DEF is most suitable for dilute solutions, while TFF is preferred for
concentrated solutions
In Dead End Filtration (in-line) filtration (DEF), which is suitable for batch or semicontinuous
filtration of dilute solutions, the entire solvent is forced under pressure through the membrane,
in a manner similar to conventional filtration of solid-liquid slurries.
With time, as retained material accumulates on or within the membrane, the pressure
required to maintain a desired flow rate must increase or permeate flux will decrease. Thus,
DEF may operate at constant pressure, constant flux or a combination of both
Significant attempts to improve tangential-flow filtration (TFF) have evolved into high-performance
tangential flow filtration (HPTFF) for separation of macromolecular species. In a study, significant
improvements in yield and purification factors were achieved in the separation of protein mixtures of
close molecular weights with HPTFF
Clarifier Design
Design methods for dilute sedimentation are based on the principle of providing enough
residence time for the separation to take place
Estimates can be made using Stokes Law especially for well- defined homogenous system,
but due to allowance must be made for deleterious effects due to convection, air- induced
surface waves, inlet and outlet turbulence etc.
Batch Settling: Dilute Systems
The residence time required for the batch settling of a suspension that is composed of a
size distribution of particles of the same material can be calculated easily using the size of
the smallest particle to estimate the time it will take to settle the full height of the vessel
from surface to base
Some of the particles of the smallest size to be settled out must have travelled the full
height of the suspension and
Continuous Settling
These processes can be described most simply by an ideal continuous sedimentation tank
model which equates the residence times derived from the vertical settling motion of the
particle and the horizontal plug flow movement brought about by the drag of the liquid. Thus for
a residence time t the vertical equation is:
t = H/ut
And the horizontal equation is:
t = AH/Q
Where H is the tank depth, A is the area, Q is the volumetric flow rate of liquid through the tank
and ut is the terminal settling velocity of the particle. Clearly the depth of the tank is eliminated
from the equation and the relationship becomes:
A = Q/ut
Continuous Settling
Continuous settling: Hindered Systems/ Thickening
This process is usually conducted in a raked cylindrical tank with a loping conical
base leading to a central outlet for the sludge, an overflow launder around the
periphery of the tank for the clear liquid and a central feed point.
Continuous Settling
Continuous Settling: Special Designs
In the usual design of a sedimentation process the chemical pretreatment
stage is expected to take place separately before the settling step and in many
cases this may be appropriate
However there are applications where this approach is not particularly
successful owing to low solids concentrations in the feed, long flocculation
times and the formation of low-strength or small flocs
Floatation
The use of air or gas bubbles to separate mineral particles by preferential attachment and
subsequent floatation has been a feature of the mineral processing industry for many decades
In mineral floatation, it is more common to use chemicals to enhance the collection of the
particles and the stability of the froth and to produce the bubbles by beating air into suspension,
but in solid liquid separation it is more usual to dissolve air into the liquid under pressure, allowing
the gas to expand out of solution under the lower pressure of the separation chamber, producing
bubbles for the preflocculated particles to collect on without the need for further chemical
addition
Alternatives to pressure dissolution of air have been tried during the development of the process
technique. These methods of bubble generation include:
Dispersed Air Floation (DAF): beating air into the suspension, using a high-speed agitator and
air entrainment system
Electroflotation: passing an electric current between electrodes immersed in the suspension
and producing bubbles by electrolysis of the liquid which is usually water
Vacuum Filtration: saturating the suspension with air at atmospheric pressure and
transferring the suspension to an expansion chamber where the pressure is reduced to less
than atmospheric; the dissolved air rapidly comes out of its supersaturated solution,
producing bubbles
The next stage of growth involves the precipitation of dissolved air onto the newly formed bubbles
and the third and final stage of development is coalescence which increases bubble size and
reduces numbers
Edzwald et al [1991] suggest that treating the saturated water as a dilute solution of air in water,
allows Henrys Law to be used in the form:
c=f p
K
Where c is the concentration of air in the saturated liquid, p is the absolute pressure, K is the
Henrys Law constant and f is an efficiency factor
Values are given for f of about 0.7 for unpacked saturators and up to 0.9 for packed systems; for K
at 0 and 25C figures are 2.72 and 4.53 kPa/mgL respectively
For 100% efficiency at 70 psig (482.3 kPa), the air concentration is 25 mg/L at 0C and 129
mg/L at 25C.
The bubble volume concentration is obtained by dividing the concentration by the density of
saturated air; typical values for this are given as 1.29 and 1.17 g/L for 0 and 25C
respectively. These give typical values for an 8% recycle at 70 psig and for 40m bubbles per
milliliter. They suggest that for a typical application such as DAF treatment of water containing
an algae this would represent about 1 bubble per particle of contaminant
b = cr
sat