H2O2-UV-Treatment - Cal Poly San Luis Obispo

A ENVE 436 Course Project
Presented to Dr. Sczechowski of
California Polytechnic State University
San Luis Obispo
Melanie Kito
Hi Nguyen
John Tran
December 1998
Ever since the industrial evolution, the number factories and industries have been
growing like mushrooms to produce merchandise to improve our quality of life.
However, during the manufacturing process, many chemicals and other toxic wastes have
been produced as part of the by-product. Most of the toxic wastes and contaminants have
been disposed of improperly into the earth or a body of water. Today, the contaminants
from the past has ended up in the groundwater we drink and in the soil we plant our
crops. Several processes of degradation of contaminants have been discovered to
alleviate the problem. One process used to degrade several kinds of organic contaminants
in groundwater and soil is hydrogen peroxide and UV treatment.
Both hydrogen peroxide and UV can be used alone to facilitate the degradation of certain
contaminants. Hydrogen peroxide is a very strong oxidizing agent that is capable of
destroying some halogenated compounds and most nonhalogenated compounds in
aqueous media (Anderson, 3.21). UV light itself is also very capable of degradation by
initiating bond cleavage. However, the range of contaminants UV can degrade by itself is
limited. The time for the degradation to occur can also be very slow. The combination of
the two treatments, hydrogen peroxide and UV can create a very fast and efficient process
for remediation.
Hydrogen peroxide and UV together, form two free hydroxyl radicals (OH) which are
potent oxidizing agents.
H2O2 + hv  2OH
The free hydroxyl radicals are an excited state species since they are characterized by a
one-electron deficiency and are therefore extremely unstable. Because of their instability,
they tend to react with the first chemical it comes in contact with (Watts, 358). Hydroxyl
radicals (OH ) also tend to completely oxidize dissolved organic contaminants in
aqueous media and produce carbon dioxide, water and salts as by products (Heeks, Smith,
and Perry 1991). Hydrogen peroxide is catalyzed with UV irradiation and ozone to create
highly reactive radicals which react and cleave a wide variety of organics (Anderson,
The efficiency is dependent on several factors. These factors consists of the optical path
length of medium (turbidity of the water sample), molar extinction coefficient (dependent
on wavelength which is most commonly 220 nm), concentration of the substrate
(contaminant) and the intensity and wavelength of the light source used (Anderson, 3.57).
The formation of the free radicals is favored by: UV light, high pH and a low bicarbonate
concentration (Stowell and Jensen 1991).
The hydrogen peroxide and UV process can be implemented by using a stainless steel
reactor called a Ultrox System (Figure 1), that can range from 1,100L to 14,800L. The
reactor “contains vertical, low temperature mercury lamps inside quartz tubes. Four to
eight reactors can be staged in series, the number depending on treatment conditions”
(Anderson, 3.26). The process can be operated as a batch, continuous, or intermittent and
may be fully automated. The hydrogen peroxide is injected directly into the influent
wastewater stream. The contaminated water is then passed through several columns of
UV lamps before it is discharged. Ozone can also be added to facilitate the reaction.
Figure 1
The entire process is shown in Figure 2 on the following page. Generally the treatment
process is divided into three steps that can be identified as 1) the sulfide oxidation phase,
2) the VOC treatment phase, and 3) the discharge phase. In the sulfide oxidation phase,
sulfide in the groundwater is oxidized to sulfate by the addition of hydrogen peroxide at a
pH of 9.2. The pH is lowered to prepare for the VOC treatment phase. In the VOC
treatment phase, VOCs are either destroyed in an UV oxidation system or removed by
carbon adsorption. In the discharge phase the pH is raised so that the treated water is
suitable for discharge.
The following are possible tested contaminants that have been successfully degraded by
using the Ultrox system:
methylene chloride
methyl isobutyl ketone
polychlorinated biphenyls (PCBs)
1,2 -dichloroethylene
perchlorethylene (PCE)
polynuclear aromatics (PNA)
pentachlorophenol (PCP)
1,1,1 - trichloroethane (1,1,1-TCA)
trichloroethylene (TCE)
vinyl chloride
methyl-butyl ether (MTBE)
Freon 113
Industrial wastewater containing the following compounds are also effectively treated
(Anderson, 3.29):
chlorinated solvents
methylene chloride
complex cyanides
Royal Dutch Explosive, cyclo-1,3,5-
hydrazine compounds
trimethylene-2,4,6-trinitramine, or
cyclonite (RDX)
methyl ethyl ketone
trinitrotoluene (TNT)
methyl isobutyl ketone
Any hindrance of the transmission of UV light to the water sample can decrease the
efficiency of the process. In other words, a dirty lamp with rust or other interferences
cannot emit as much light as a clean one, therefore the efficiency will decrease. It is
necessary to clean the lamps periodically to avoid this problem. With cleaning in
consideration, the maintenance, labor and downtime should be included into the operating
costs (Anderson, 6.4).
If the pH needs to be adjusted to become basic, sodium hydroxide (NaOH) should be
used instead of dissolved carbonate (CO3-2) or bicarbonate (HCO3-). Both carbonate and
bicarbonate ions react with the free hydroxyl radicals as scavengers. With the increased
competition of the organic contaminants with the scavengers, the rate of degradation will
be drastically effected for the worse.
The reaction of hydrogen peroxide with UV light is a very effective treatment. Although
UV can be very inexpensive (one can use sunlight), the cost of hydrogen peroxide can be
very expensive. Costs for the peroxide range from $0.03 to $3.00 per 1,000 liters. For a
treatment facility operating at 200,000 gpd operation costs can reach as high as $200,000
per day or around $1.00 for every gallon of treated wastewater. Other factors that
influence the costs to implementing the UV/oxidation. These include 1) types and
concentration of contaminants, 2) degree of contaminant destruction required, and 3)
requirements for pre-treatment and/or post-treatments.
One of the big advantages of this process is the resonance time. For example, an initial
concentration of 75 mg/L of 2,4-DNT in water with a mole ratio of 13:1 of H2O2:2,4DNT was degraded to a concentration of 1 mg/L in 45 minutes or less (Ho 1986). With
such a rapid process, maybe there is hope for a fast cleanup for many of the highly
contaminated superfund sites!