Lecture No.

Physico-Chemical Processes
Chapter 9, p.447

 Includes technologies that can be used for:

- hazardous waste treatment
- soil remediation
 Each section includes:
- description of technology
- theory
- design

1. Air Stripping

A. Description

 Air stripping is a mass transfer process that enhances the volatilization of compounds
from water by passing air through water to improve the transfer between the air and
water phases.
 One of the most common remediation methods for VOCs.
 Suited for low concentrations < 200 mg/l.
 Packed towers, tray towers, spray systems, diffused aeration, mechanical aeration.
Packed towers are generally used for remediating ground water.
 Lecture No. 1, Hazardous Waste, Page No. 2

B. Process Description

 Process consists of counter-current flow of water and air through a packing material.
The packing material provides a high surface area for VOC transfer from the liquid to
the gaseous phase. F9-1, p.448.
 Typical packing material consists of plastic shapes with high surface to volume
ratios, specific volume.
R = H'(Qa/Qw) units p.449
R = stripping factor

C. Theory

 Two film theory. F9-2, p.449.

- Bulk film to liquid film
- Liquid film to air film
- Air film to bulk air
 Sherwood Holloway equation
KLa =  x DL x (305L/)1-n(/DL)0.5 eq.9-4 units p.450
 Also:
Z (depth of column) = HTU x NTU

L
HTU = M K
w La

R (Cin/Cout)(R-1) + 1
NTU = R-1 ln R eq.9-20 units p.455
 Different packing shapes are available. See T9-2, p.451


 Example: ** Problem 9-2, p.544

D. Design

 Stripping towers have diameters of .5-3m and heights of 1-15m.

 The air-to-water ratio is 5-several hundred and is controlled by pressure drop and
flooding considerations.
 Distribution plates should be placed every 5-diameters to avoid channeling around
the wall as opposed to the packing media
 It may be necessary to clean up the off-gas with activated carbon.
 Lecture No. 1, Hazardous Waste, Page No. 3

 The pressure drop in the tower should be between .25-.5 inches H2O/ft of tower to
avoid flooding.
 Use F9-5, p.458 to simplify calculations.

2. Soil Vapor Extraction

A. Description

 Soil Vapor Extraction (SVE) is a remedial technique to remove VOCs from soil in
the vadose zone or from stockpiled, excavated soil. The vadose zone is the zone
above the GWT.

 SVE consists of passing an air stream through the soil, thereby transferring the
contaminants fro the soil matrix to the air.
 SVE systems can be enhanced:
- Install ground water extraction pumps to increase the vadose zone and perhaps
simultaneously treat ground water.
- Impermeable barrier over the surface to minimize short-circuiting
- Install air recharge wells.
- Install wells into the ground water.

B. Theory

 The removal of VOCs from the vadose zone can be modeled as a 5-step process:
- Gases desorb from the soil particles.
- Transfer to the soil water.
- Volatize to the soil gas
- Gas migrates to surface
- Released to atmosphere
 Lecture No. 1, Hazardous Waste, Page No. 4

 The movement of contaminants in the soil gas through the soil media can be
described by two processes
- Advection. Movement with bulk airflow through the soil media and best
describes the flow through permeable soils with the unsaturated zone.
- Diffusion. Movement through the soil media via concentration gradients.
Diffusion tends to control in soils of low permeability.
 Provided the leak is of sufficient quantity, the VOC contamination will tend to
migrate downward through the unsaturated zone, leaving globules, films and small
droplets of the released material. Low density contaminants will tend to collect in the
capillary fringe or float on the ground water surface. Dense contaminants will tend to
pass through the ground water until encountering a impermeable layer.
 A release of contaminants will result in residual contamination the soil pores. This
residual material in the unsaturated zone is the target contamination for cleanup via
SVE.
 Diffusion may be the rate limiting step for mass transfer.
 Current practice is to utilize empirical models to select the most appropriate
mechanical system and then to use field data to refine system design.
 Movement of VOCs through the soil is controlled in part by diffusion and Fick's Law:
dC
J = -Dv dz eq.9-22 units p.464
 The partition coefficient refers to the preference of contaminant for soil or water. A
higher Kp indicates that a contaminant is more likely to remain on the soil and not be
transmitted through soil moisture movement and is:
X
Kp = C eq.9-26 units p. 465
 Example:
Given: Ethylene Dibromide and hexane.
Find: Based on H, which is a more likely candidate for SVE.

Assume T=20C, K=C+273.2=20+273.2

K=293.2

Ethylene Dibromide
From app. A, p.1046
A=5.70
B=3.24 x 103
p.1038 eq.A-2
H = exp {A-B/T}
H = exp{5.70-3.24x103/293.2}= exp{5.70-11.05}=exp{-5.35}= e-5.35
H = 4.748 x 10-3 atm.m3/mol

Hexane
 Lecture No. 1, Hazardous Waste, Page No. 5

From app. A, p.1046

A=25.3
B=7.53 x 103
p.1038 eq.A-2
H = exp {A-B/T}
H = exp{25.3-7.53x103/293.2}= exp{25.3-25.68}=exp{-0.382}= e-0.382
H = .682 atm.m3/mol

Since hexane, .682 atm.m3/mol > Ethylene Dibromide, 4.748 x 10-3 atm.m3/mol,
hexane would be best suited to vadose treatment by SVE.

 Hartley equation estimates the volatilization of chemicals from soil:

(1-h)
Asat

J= eq.9-32 units p.467
1  AsatM
2
D + kRT2
AsatM
The second term in the denominator, kRT 2 , indicates the resistance to volatilzation
due to thermal elements and may be neglected for compounds significantly less
volatile than water.
 Example: problem 9-11, 9-14

C. Design

 SVEs primary benefit is that it is an in situ method and as such does not require the
removal and transportation of the hazardous waste. Also SVE can remediate soil
beneath structures; does not require reagents and employs conventional equipment,
labor and materials.
 SVE is not appropriate for:
- low-permeability soil
- low vapor pressure contaminants
- high ground water table

D. Process Description

A typical SVE system:

 Infrastructure:
- vapor extraction wells, 6-11' deep
- piping
- monitoring wells
- gauges and valves
- impermeable cover
- vent wells

 Equipment
 Lecture No. 1, Hazardous Waste, Page No. 6

- vacuum/blower unit, .5-30" Hg.

- moisture knockout drum
- off-gas treatment
 Three variables control performance, pilot testing is essential:
- well spacing, critical
- air flow rate
- subsurface pressure

 Example:
Given: A radius of 25'
Find: The vacuum requirement

From F9-12, p.474

.05 monitoring point vacuum/well vacuum
From F9-11, p.473
.05 inches water @ 75cfm
.45 inches water @ 150cfm
.8 inches water @ 240cfm

Given: The above data

Find: How much vacuum is required.
From F9-10, p.472
.05 inches water @ 75cfm requires  9 inches water
.45 inches water @ 150cfm requires  20 inches water
.8 inches water @ 240cfm requires  34 inches water

3. Carbon Adsorption

 Adsorption is a process in which a soluble contaminant is removed from water by

contact with a solid surface typically activated carbon usually in granulated form
(GAC).

A. Process Description F9-14, p.477

 The activated carbon is placed in cylindrical vessel, contaminated water enters the
top, contacts the carbon and exits the bottom.
 Ancillary considerations include: a way to regenerate the carbon which is done
thermally.
 Extensively used in water and wastewater systems for the removal of non-
biodegradable organics and as a polishing step.

B. Theory

 Sorption is he process by which a component moves from one phase to another across
some boundary. In adsorption the process takes place at a surface.
 Movement of an organic molecule to a surface involves 4 transport phenomena:
- bulk fluid transport
 Lecture No. 1, Hazardous Waste, Page No. 7

- film transport
- pore diffusion
- actual physical attachment
 Driving forces that control adsorption:
- chemical affinity between the pollutant and the activated carbon.
- electrical attraction
- van der Waal's forces
- hydrophobic nature of the organic
 A plot of the amount of contaminant adsorbed per unit mass of carbon, X/M, against
the concentration of contaminant in the bulk fluid, C, is an adsorption isotherm. The
Freundlich isotherm is an empirical model mathematically expressed:
X/M = KCf1/n eq.9-33 units p. 479
 Example: **problem 9-16, 9-19

C. Design

 The design of adsorption units requires column tests that simulate the actual operation
of full scale units.
 In the lab, 2-inch diameter columns are filled with carbon and the contaminated
ground water is run through the columns. The effluent is monitored for the
contaminants of interest.
 The adsorption zone is where adsorption takes place. Breakthrough is the point where
a specified amount of the influent is detected in the effluent usually 5-10%.
 Hutchins provides a method for analyzing the results of multiple columns in series
F9-19, p.483, by evaluating the bed-depth service time (BDST). A horizontal line is
drawn where breakthrough =90% of the influent concentration, Cout/Cin = .9. The
Bohart-Adams equation represents 90% removal.
t = aX + b eq.9-35 units p.483

4. Steam Stripping

A. Process Description

 Steam stripping is the purging of contaminants from ground water by the use of
steam. Capable of reducing VOCs to very low concentrations.
 T9-6. p.487. EPA established Best Available Technology Economically Achievable
(BATEA) for Organic Chemical, Plastics and Synthetic Fibers (OCPSF). In some
cases, VOCs may be below detectable limits.

 The differences between steam stripping and air stripping:

- steam not air is the stripping gas
 Lecture No. 1, Hazardous Waste, Page No. 8

- the stripping gas, steam, is infinitely soluble in water

- much higher temperatures are used
- the organics in the water are recovered as a separate liquid phase
 Schematics F9-21,22, p.488. Based on distillation. The heated feed water is fed to the
tank and flows down where it encounters the steam which is flowing upward,
counter-current to the organics. The organics volatize and are carried upward; the
mixture is condensed and since the organics are supersaturated they separate and are
disposed of.

B. Design

 Too complicated based on:

- Thermodynamics
- Material Balance
- Mass transfer
- Process design selection
 Generalized material balance:
F+S=B eq.9-49 units p.496
 A steam stripper is designed as an equilibrium stage process; mass transfer
resistances are not directly considered in the design approach.
 Design considerations:
 The strippalitity of the organics
- Simple for a single organic, but for a mixture of organics, a computerized
process simulator to assess the thermodynamics of the interactions between the
various organics is required.
- Rule of thumb. Any priority pollutant that is analyzed by direct injection on a
gas chromatograph can be considered a good candidate for high-efficiency stream
stripping.
- Rule of thumb. Any compound with a boiling point <150C is a good candidate.
 Whether the organics will form a separate organic phase in the overhead decanter.
- If even one organic compound has a low solubility limit (<1%) then there is a
basis to expect a separate phase to form in the decanter. Some organics are infinitely
soluble in water and will not form a separate organic phase, by themselves, in the
overhead decanter and are therefore not good candidates for stream stripping.
- Only one sparingly soluble organic need be present to make stream stripping
feasible. As a general rule, the organics will preferentially partition to the organic
phase created by the single sparingly soluble organic.
 Mechanical design:
- random packing
- valve trays
- sieve trays

5. Chemical Oxidation
 Lecture No. 1, Hazardous Waste, Page No. 9

 The object is to detoxify waste by adding an oxidizing agent to chemically transform

waste components. An organic molecule might be converted to carbon dioxide and
water.
 Well established technology capable of treating a wide range of organics and
inorganics: chlorinated VOCs, mercaptans, phenols, cyanide.
 Principle oxidants: ozone, hydrogen peroxide, chlorine. The chemicals that are
reduced are the contaminants.
 Oxidation-reduction reactions occur in pairs to comprise an overall REDOX reaction.
Oxidizing agents are non-specific and will react with any reducing agents present in
the waste stream.

A. Process Description

 Completely mixed or plug flow.

 Mixing can be provided by :
- mechanical agitation
- pressure drop
- bubbling air
 Hydrogen peroxide and UV, ultraviolet light are generally used together.
 Common redox reactions T9-8, p.508, for example the reduction of hexavalent
chromium to tri-valent chromium using sulfur dioxide and ferrous sulfate.
 Example:
Given: A waste stream of 5000 gal/day containing 86 mg/l of hexavalent chromium.
Find: The stoichiometric amount of ferrous sulfate required to reduce it to trivalent chromium.
From T9-8, p.509
2CrO3 + 6FeSO4 + 6H2SO4  3Fe2(SO4)3 + Cr2(SO4)3 + 6H2O

From cover of book, atomic weights:

Cr = 51.996
O = 15.994
Fe = 55.847
S = 32.06
From the equation 6 moles of ferrous sulfate are required to reduce 2 moles of hexavalent
chromium or a ratio of 6/2=3.

Mass of hexavalent chromium reduced daily is:

lb/MG
lb/day = 86 mg/l x 8.34 mg/l x 5000/106 MGD
lb/day = .359 hexavalent chromium

Lb moles of CrO3 discharged daily:

CrO3
Cr = 51.996x1=51.996
O = 15.994x3=47.982
 Lecture No. 1, Hazardous Waste, Page No. 10

CrO3 = 99.978 lb/lb mole

.359 lb/day / 99.978 lb/lb mole = 3.59 x 10-3 lb mole/day

FeSO4 required daily:

Fe = 55.847x1=55.847
S = 32.06x1=32.06
O= 15.994x4=63.976
FeSO4 = 151.883
3 (molar ratio from equation) x 3.59 x 10-3 lb mole/day = .0108 lb mole FeSO4
= .0108 lb mole FeSO4 x 151.883 lb/lb mole
= 1.64 lb/day of FeSO4 required, theoretical or stoichiometric amount

 The power of an oxidizing or reducing agents is measure by it electrode potential. An

indication of how a reaction will proceed can be determined from the free energy
considerations:
G = -nFE = -RTlnK eq.9-52 units p. 510
E may be determined from T9-9, p.511.
 It is possible to measure ORP, Oxidation Reduction Potential, directly by means of a
galvanic cell made up of a gold or platinum anode and a reference electrode, the
cathode.
 Nernst equation:
E = E - (RT/nf)ln Q eq.9-53 units p.510

B. Design

 Ozone. Ozone is a blue gas with a pungent order and the most powerful oxidant
available. Ozone has a very high free energy which indicates that the oxidation
reaction may proceed to completion. Ozone dissociates to oxygen very rapidly and
must be generated on site.
 Example:
Given: Hexachlorobiphenyl
Find: The time required for 60% removal using ozone with and without UV.

From F9-29, p514

60% removal means 40% remaining or C/Co=.4
For no UV, Time=not doable
With UV, Time  50 min, UV make a significant difference

 Hydrogen peroxide. Hydrogen peroxide is effective in oxidizing organic in soil

through in situ treatment. As with ozone, hydrogen peroxide is greatly enhance when
used with UV.

 Example:
Given: It is desired to use hydrogen peroxide + UV to reduce chloroform to 90%.
Find: Time required.
From F-9-34, p.518
90% removal means 10% or .1 remaining
@ .1 on the graph for chloroform, time  150 minutes
 Lecture No. 1, Hazardous Waste, Page No. 11

 Chlorine. Chlorine and its various compounds are used extensively in water and
waste water treatment and is the principal chemical involved in disinfection.
However, when combined with organic material, chlorine forms THM,
TriHaloMethanes, which are carcinogenic. Chlorine is evaporated to a gas and mixed
with water to provide a hypochlourous acid (HOCl) solution.

6. Supercritical Fluids (SCF)

 Supercritical fluids (SCF) is an emerging technology and are materials at elevated

temperature and pressure that have properties between those of a gas and liquid.
 With SCF, organics in soils, sediments or water are dissolved in the fluid at elevated
temperatures and pressure conditions and released from the SCF at lower
temperatures and pressures.

A. Process Description

 F9-36, p.522. The contaminated stream is introduced into the extraction vessel,
heated and pressurized. The contaminant dissolves in the SCF which is then
expanded which lowers the solubility of the organic contaminant resulting in
separation of the organic contaminant from the extracting fluid.

B. Theory

 The critical point is a temperature/pressure where the material exhibits properties

between a liquid and gas; densities approaching the liquid phase, dffusivities and
viscosities approaching the gas phase. As a result of these properties, organic
compounds are highly soluble in SCFs and can easily transfer to the SCF from their
original medium.

C. Design

 Selection of the SCF, solvent. Re-use is important. CO2 is a good choice because of
lack of toxicity, also T9-13, p,529.

7. Membrane Processes

 Well established technology.

 Membrane which is usually a solid matrix or swollen gel refers to a barrier to flow
which will allow the passage of water, ions or small molecules. Not a conventional,
gravity, filtration process as the driving force may be electrostatic or high pressure.
 Lecture No. 1, Hazardous Waste, Page No. 12

 The membranes are subject to fouling and in hazardous waste management,

membranes are limited to extremely toxic materials that can not be removed by cost-
effective technologies.
 Processes include: electrodialysis, reverse osmosis and ultrafiltration.

A. Process Description

 Electrodialysis. F.9-42, p.530. Electrodialysis consists of the separation of ionic

species fro water by applying a direct-current electric field. By alternating cation and
anion exchange membrane between two electrodes, alternate dilute and concentrated
cells are created. The membranes are about .5mm thick and the spacers are 1mm
thick. Operated at 40-60psi and 90% of the feed is turned into product water, the
remainder is concentrate.
 Reverse Osmosis. F9-46, p.534. In reverse osmosis, a solvent is separated fro a
solution by applying a pressure greater than the osmotic pressure, thus forcing the
solvent through a semipermeable membrane. The membrane will allow the water but
not the salt, solvent, to pass. In reverse osmosis, a pressure is applied to force the salt,
solvent through the membrane, thus leaving product water.
 Ultrafiltration. F9-49. p.536. Ultrafiltration separates solutes from a solvent on the
basis of molecular size and shape by passing the solution through a membrane
module where a pressure difference is maintained across the membrane. Water
molecules pass through, heavy molecules are retained on the filter. Fouling is avoided
by high velocities which in turn yields a low efficacy requiring multiple passes.
Molecules of molecular weight greater than 500 and less than 500,000 can be
separated. Heavier molecules can be separated by conventional filtration, the lower
size reflects the opening size in commercially available membrane.

B. Theory

 Electrodialysis. Faraday's Law yield required current:

I = (FQN/n) x (E1/E2) eq.9-69 units p.537
Voltage, Ohm's Law:
E = IR eq. 9-70 units p.537
Power:
P = I2R eq. 9-71 units p.537
Current density, CD, is the current passing through a unit areas of membrane,
amp/m2.

 Reverse Osmosis. Osmotic pressure, solute rejections and flows are of interest.
Osmotic pressure determined by the van't Hoff equation:
 = cNCsRT eq.9-72 units p.539
 The flow is:
Jw = Wp x (P -  ) eq.9-75 units p.540
 Lecture No. 1, Hazardous Waste, Page No. 13

 Example:
Given: Manganous nitrate, Mn(NO3)2, salt solution at 8400 mg/l at 30C. =.87, The wastewater
has a flow rate of 100gpm. A vendor gives the following data:
Wp=2.0 x 10-6 gmol/cm2.sec.atm
Area of a bundle = 500ft2
65% recovery rate
Optimal pressure across the membrane 625 psi

Find:
1.) The Osmotic Pressure.
2.) Flow through the membrane, Jw
3.) Number of bundles required.

1.) Osmotic pressure.

eq 9-72, p.539
 = cNCsRT units p. 9-72

N= 3 (Mn(NO3)2, Mn=1, NO3=2)

Molecular weight
Mn=24.305x1=23.305
N= 14x 2=28
O=16x6=96
Mn(NO3)2=147.3 g/gmol

Cs = 8400 mg/l = 8.4 g/l / 147.3 g/gmol

Cs = .0570 gmol/l

K = C + 273.2 = 30 + 273.2
K = 303.2

 = cNCsRT = .87 x 3 x .0570 gmol/l x .082 atm.l/gmol.K (p.1080) x 303.2K

 = 3.698 atmospheres x 14.7psi/atm. = 54.35psi

2.) Flow, Jw
Jw = Wp x (P -  ) units p.540
Jw = 2.0 x 10-6 gmol/cm2.sec.atm x (625-54.35) (1atm/14.7psi)

Jw = 7.76 x 10-5 gmol/cm2.sec

3.) Number of bundles for 100gpm

Q = 100gpm x 3.79l/gal x 1min/60sec x 1000g/l x 1gmol/18g (AWof water) x cm2.sec/ 7.76 x 10-
5 gmol
Q = 4.52 x 106 cm2 of membrane

Each bundle contains 500 ft2.

 Lecture No. 1, Hazardous Waste, Page No. 14

Bundle (3.28ft)2 1 m2
No. of bundles = 4.52 x 106 cm2 x 500 ft2 x m 2 x (100)2cm
No. of bundles = 9.73 bundles use 10

 Ultrafiltration:
(P -  )
Jw = (R + R ) eq. 9-78 units p.542
g m

C. Design

 Concentration Polarization results in an increased power requirement without an

appreciable increase in performance and occurs in all membranes.

HOMEWORK
Read Chapter 9, Physico-Chemical Processes, pp. 447-554
Problems, p.544, 9-5, 9-7, 9-10, 9-14, 9-17, 9-18, 9-27, 9-29, 9-31, 9-32, 9-33, 9-34