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BOD and COD Removal Hydrogen Peroxide

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Hydrogen peroxide (H2O2) has been used to reduce the BOD and COD of industrial wastewaters for many
years. While the cost of removing BOD and COD through chemical oxidation with hydrogen peroxide is typically Contact Us Today
greater than that through physical or biological means, there are nonetheless specific situations which justify the
use of hydrogen peroxide. These include: Predigestion of wastewaters which contain moderate to high levels of Read about our
compounds that are toxic, inhibitory, or recalcitrant to biological treatment (e.g., pesticides, plasticizers, resins, solutions that may also
coolants, and dyestuffs); benefit you:
Pretreatment of high strength / low flow wastewaters – where biotreatment may not be practical – prior to
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discharge to a Publicly Owned Treatment Works (POTW);
Enhanced separation of entrained organics by flotation and settling processes; and
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Supply of supplemental Dissolved Oxygen (DO) when biological treatment systems experience temporary
overloads or equipment failure.

As indicated by these examples, H2O2 can be used as a stand-alone treatment or as an enhancement to

existing physical or biological treatment processes, depending on the situation.

Discussion of H2O2 Applications and Mechanisms

Direct Chemical Oxidation Using Hydrogen Peroxide
Hydrogen peroxide can be used alone or with catalysts – such as iron (Fe2+ or Fe3+), UV light, ozone (O3) and
alkali – to oxidize BOD/COD contributing compounds in wastewaters. The type of oxidation needed depends on
the type of BOD/COD present. This relationship is present in the figure below.

Chemical Oxygen Demand

Oxidant System Type A Type B Type C
(Sulfide, Thiosulfate, Sulfite) (Phenols, Cyanides, Amines) (BTEX, TOCl, Paraffins)
Type A
H2O2 X
Type B
H2O2 / OH- X X
H2O2 / M+ X X
H2O2 / H+ X X
Type C
H2O2 / Fe X X X
H2O2 / O3 X X X
H2O2 / UV X X X

Note: Whether an oxidant system will degrade a specific pollutant (i.e., affect its COD) will depend on the oxidant system and the
pollutant. Type A oxidants react only with Type A pollutants; whereas, Type C oxidants, being more reactive, react with most any
pollutant. However, Type C oxidants generally react preferentially with Type A pollutants.

If a large fraction of the BOD and COD is contributed by inorganic reduced sulfur compounds such as sulfides,
sulfides, or thiosulfate, then hydrogen peroxide alone is typically effective. Depending on the wastewater pH, the
oxidation of these compounds by H2O2 yields sulfate or colloidal sulfur, neither which contribute to BOD and
COD. If the primary contributors to BOD and COD are dissolved organics, then a more reactive oxidation system
is needed. Moderate activation of hydrogen peroxide can be achieved by: 1) alkali (generating the perhydroxyl
ion , OOH- – the active agent in peroxide bleaching systems); 2) certain transition metals (e.g., tungstate,
vanadate, molybdate) which form reactive peroxometal complexes in-situ; and 3) certain mineral acids (e.g.,
sulfuric) which form reactive peroxyacid derivatives such as peroxymonosulfuric acid (Caro’s Acid) ex-situ. For
the more recalcitrant organics such as chlorinated solvents, extremely reactive free radical systems (termed
Advanced Oxidation Processes) are needed. A generalized reaction using Fenton’s Reagent for reducing BOD
and COD can be expressed as follows:

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7/10/2017 BOD and COD Removal Using Hydrogen Peroxide H2O2 | USP Technologies

With Fe+2
Step-1: BOD/COD + H2O2 ---> partially oxidized species
With Fe+2
Step-2: partially oxidized species + H2O2 ---> CO2 + H2O + inorganic salts

The extent of oxidation (and therefore the degree of direct BOD/COD reduction) typically depends on the
amount of hydrogen peroxide used. The theoretical hydrogen peroxide requirement is about 2.1 lbs (as 100%)
per lb-BOD and COD oxidized. In many cases, however, complete digestion of the organic compounds to carbon
dioxide and water is not needed. Partial oxidation to intermediate compounds minimizes chemical consumption
and often results in substantial reductions in BOD and COD and toxicity.

Enhanced physical separation of BOD and COD with Hydrogen Peroxide

Enhanced physical separation of BOD and COD with hydrogen peroxide may occur is two ways. In the first
case, partial oxidation of organic contaminants results in more polar (charged) substances which are more
amenable to adsorption onto coagulants and flocculants. As illustrated in the example below, this allows BOD
and COD removal efficiencies with less than stoichiometric hydrogen peroxide doses.

In the second case, enhanced physical separation (flotation) of fats, oils and greases (FOG) is provided by
H2O2. This occurs by the natural decomposition of hydrogen peroxide to oxygen and water, i.e., hydrogen
peroxide will supersaturate the wastewater with oxygen, which results in the formation of evenly dispersed
microbubbles which scavenge FOG constitutents as they rise to the surface of the water. In some cases, this
can increase BOD removal through dissolved air flotation cells from e.g., 50% to 90-95%. Typical doses are 25-
100 mg/L H2O2, the cost for which can often be offset against savings in coagulant use – a polyelectrolyte
polymer is generally still needed.

Hydrogen Peroxide (H2O2) as a supplemental oxygen source

The BOD removal efficiency of aerobic biological treatment processes depends on a number of factors including
(but not limited to): influent BOD loading, F:M ratio, temperature, nutrient levels, and dissolved oxygen (DO)
concentrations. Many biological treatment facilities use hydrogen peroxide to supplement DO levels when
oxygen limited conditions in aeration basins or lagoons result in poor BOD removal. These conditions can be
brought about by unexpected peaks in influent BOD loading; seasonal variations in BOD loading (e.g., fruit and
vegetable processing); and hot weather – which reduces the efficiency of oxygen transfer by mechanical
aeration equipment (i.e., O2 solubility decreases as temperature increases). These conditions may or may not
be accompanied by filamentous bulking (see Municipal Wastewater Applications : Filamentous Bulking Control).

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7/10/2017 BOD and COD Removal Using Hydrogen Peroxide H2O2 | USP Technologies
When hydrogen peroxide is used to supplement DO, it is metered directly into the aeration basin of a biological
treatment system to provide an immediate source of DO. The conversion of hydrogen peroxide to DO in an
activated sludge mixed liquor proceeds according to the following reaction:

(Catalase enzyme)
2 H2O2 ---> O2 + 2 H2O

Theoretical hydrogen peroxide requirement: 0.48 lbs H2O2 (100%) per mg/L DO

Catalase enzyme is a natural decomposition catalyst for hydrogen peroxide, and is found in all activated sludge
mixed liquors, being produced by most aerobic organisms. Because this enzymatic decomposition of hydrogen
peroxide is very rapid, the oxygen supplied by hydrogen peroxide is immediately available for uptake by the
aerobic organisms.

The above reaction shows that two parts of hydrogen peroxide will yield one part of DO. Therefore, the amount
of hydrogen peroxide required to oxygenate the wastewater is surprisingly small. For example, the theoretical
amount of hydrogen peroxide required to increase the DO by 1 mg/L in a treatment plant that averages 5 MGD
flow is about 17 gpd-50%. In actual practice, the requirement may be higher due to inefficiencies in oxygen
uptake and side reactions with oxidizable compounds.

Note: When measuring the BOD or COD of hydrogen peroxide treated wastewaters, it is important to determine
the residual hydrogen peroxide concentration (if any) prior to analysis. This is because H2O2 will interfere with
both of these analytical methods. In the standard BOD test, residual hydrogen peroxide in the sample will
liberate oxygen over the test period, resulting in a "false low" BOD value (1 mg/L H2O2 = 0.5 mg/L DO). In the
standard COD test, residual hydrogen peroxide will react with the potassium dichromate reagent, resulting in a
"false high" COD value. For methods to remove residual hydrogen peroxide prior to BOD and COD analysis, or
to mathematically account for the residual H2O2, see Interferences with Analytical Methods.

References

Cole, C.A., et.al., J.Water Pollut. Contr. Fed. 46:2579-2592 (1974).

Cole, C.A., et.al., J.Water Pollut. Contr. Fed. 45:829-836 (1973).
Houtmeyers, J. et.al. "Hydrogen Peroxide as a Supplemental Oxygen Source for Activated Sludge:
Microbiological Investigations", European. J. Appl. Microbiol. 4:295-305 (1977).
Steiner, Norbert, et.al. "Plant Experience using Hydrogen Peroxide for Enhanced Fat Flotation and BOD
Removal", Environ. Progress 11(4):261-264 (Nov. 1992).
Perley, William J., et.al. "Use of Hydrogen Peroxide to Control Upsets in the Treatment of Combined Sugar
Refining and Sanitary Wastewater", presented at Calif. Water Pollut. Contr. Fed., 64th Annual Conf.,
Sacramento, Calif. (Apr. 9, 1992).

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