CHAPTER NO.

WET AIR OXIDATION OF ALKANOLAMINES

WET AIR OXIDATION OF ALKANOLAMINES

3.1 Literature review
3.1.1 Wet Air Oxidation of Nitrogenous organic compounds
Industrial waste comprises the nitrogen in the organic (e.g., amines, nitrites, and
nitroaromatics) or inorganic form (e. g., ammonia, HCN, and NOx) The organic nitrogen
bearing waste can be broadly classified into three classes, viz. ammonia nitrogen, nitrite nitrogen
and nitrate nitrogen. Wet air oxidation is a candidate technique for the treatment of waters
contaminated by nitrogen-containing compounds. In wet air oxidation of N bearing
compounds, mineralization of the N to N2 is most desirable. However, the N in amino group
also gets converted to NH4+, NO3- and NO2-. Ammonia is the most refractory product of
nitrogen-containing compound oxidation (Pifer et al., 1999; Oliviero et al., 2003). The low
molecular weight acids formed during wet air oxidation are combined with NH4+ to form
ammonium acetate, oxalate and so on. Due to environmental specification for ammonical
nitrogen in effluent, the dissolved ammonia in the form of salts of acids, which are products of
incomplete mineralization, is not desired in the waste stream.
Oliviero et al. (2003) presented an excellent review on WAO of nitrogen-containing organic
compounds. Mishra et al. (1994) studied the kinetics of WAO of diethanolamine and morpholine
and found that the reaction order with respect to COD and substrate concentration was one and
order with respect to oxygen varied from 0.3 to 0.9. Ingale and Mahajani (1995) studied the
effectiveness of the hybrid system like sonication followed by WAO to treat refractory waste.
and Gunale and Mahajani (2008) found that Ru/TiO2 is very effective for WAO of nitrogenous
organic compounds. Ruthenium promotes the destruction of low molecular weight organic acids
(e.g., acetic acid), which are often formed as intermediates during the oxidation process. Gunale
and Mahajani (2008) reported complete degradation of morpholine and the highest selectivity to
N2 over a Ru/TiO2 catalyst. Vaidya and Junghare (2011) studied the kinetics of catalytic wet air
oxidation of piperazine over heterogeneous Ru/TiO2 catalyst and found a very efficient TOC
destruction upto 91%. Lee (2003) observed that decreased pH during reaction shifts the reaction
equilibrium more towards the formation of NH4+.

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WET AIR OXIDATION OF ALKANOLAMINES

3.1.2 Model compound studies of amines
Organic amines such as aniline, morpholine, N-ethylethanolamine and various alkanolamines
representing aromatic, heterocyclic and aliphatic amines are important environmental
contaminants because of their combined effect of their high potential toxicity and
carcinogenicity. Their loss to the environment during production processes or incomplete
treatment of industrial effluents results in heavy loss of aquatic life. Ethanolamines are widely
used as intermediates in the production of surfactants, textile and leather chemicals and
emulsifiers. Gunale and Mahajani (2008) studied the wet air oxidation of mono, di and
triethanolamines with TOC reduction 97, 90, 96 % respectively. Passakel and Pimenova (1988)
have studied a biochemical degradation of mono, di and triethanolamine. Hutchison et al. (1984)
have studied the mechanism of oxidation of amino alcohols by pentavalent vanadium as oxidant
in aqueous perchloric acid medium. William et al. (1967) have described oxidative fragmentation
of amines with ClO2 and NaClO. Later Kawabata and Urano (1985) have studied the wet air
oxidation of all three alkanolamines at 423 K over Mn/Ce composite oxide to improve
biodegrability of other refractory organic compounds. Libralato et al. (2008) have studied
evaporation and air-stripping to assess and reduce ethanolamines toxicity in oily waste water.
Mishra et al. (1994) have studied non-catalytic wet air oxidation of DEA. Ali khan et al. (1981)
have studied catalytic (Pd/Al2O3) oxidation of DEA by gaseous oxygen to N-(2-hydroxyethyl)
glycine in an aqueous solution containing NaOH over 0.5% Pd/Al2O3 in the temperature range of
323-523 K and at ambient pressure in a slurry reactor. Gunale and Mahajani et al. (2008) have
given an insight into catalyzed wet air oxidation of N-ethylethanolamine in an aqueous solution.

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WET AIR OXIDATION OF ALKANOLAMINES

3.2 Reaction pathway
The following reaction proposed is divided into three steps; the basis is the free radical
formation, which is given as chain initiation, chain propagation and chain termination. Also
the reaction mechanism for amine oxidative degradation can be given as, where * denotes
active sites of catalyst.
+

NH4

NH3 (aq) + O*
NH* + O*

NH3 (aq) + H
NH* + H2O

(3.1)
(3.2a)

NHO* + *

(3.2b)

HNO2 +2*

NHO* + O*
HNO2
+
NO2 + NH4
-

NO2 +O*

(3.2c)

H + NO2

(3.3)

N2 + 2H2O
NO3 + *

(3.4)
(3.5)

Reddy and Mahajani (2005) proposed the following reaction mechanism for wet air oxidation
of nitrogenous organic compounds.

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WET AIR OXIDATION OF ALKANOLAMINES

3.3 N,N-diethyl Monoethanolamine (DEMEA) and N-methyl Diethanolamine (MDEA)
model nitrogenous compounds.
MDEA is a tertiary alkanolamine widely used for CO2 capture from industrial gases, whereas
DEMEA represents a further candidate tertiary amine which is potentially attractive for gas
sweetening applications. Its discharge has been a concern for chemical industries. Their loss to
the environment during production processes or incomplete treatment of industrial effluents
results in heavy loss of aquatic life. These alkanolamines are toxic in nature. Further when they
are used for gas purification purposes, they may undergo oxidative degradation and may form
toxic compounds. They form respective N-nitrosoamine under suitable conditions on reaction
with nitrous acid and nitric acid. N-nitrosoamines are carcinogenic in nature (Frauenkron et al.,
2003). These compounds are toxic and LD50 of DEMEA is 884 mg/kg and that of MDEA is 478
mg/kg respectively (DOWTM, 2001). Ethanolamines are widely used as intermediates in the
production of surfactants, textile and leather chemicals and emulsifiers. Currently there is no
literature reported on the WAO of DEMEA and MDEA, hence it was decided to carry on the
WAO of these model compounds, Gunale and Mahajani (2008) have reported the best selectivity
for Ru/Ti02 hence 5% Ru/TiO2 was used as the catalyst.

Table 3.1 Various catalysts for CWAO of nitrogenous organic compounds.

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WET AIR OXIDATION OF ALKANOLAMINES

Catalyst
Application

Reference

Active Phase

Carrier

Co-Ce

None

Ammonia

Imamura et al. (1985)

Co

None

Alcohols, Amines

Ito et al. (1989)

Ru

TiO2

Ammonia

Lee (2003)

Pd

TiO2

Ammonia

Taguchi and Okuhara (2000)

Ru

TiO2

Morpholine

Gunale and Mahajani (2008)

Ru

SiO2

Aniline

Reddy and Mahajani (2005)

Pt

TiO2

Ammonia

Ukropec et al. (1999)

MoO3

SiO2

Ammonia

Lietti et al. (2000)

Ru

CeO2

Aniline

Barbier et al. (2002)

Ru Pd

CeO2

Ammonia

Barbier et al. (2002)

Cu

MCM-41

Aniline

Gomes et al. (2005)

Ru

TiO2

Piperazine

Vaidya and Junghare (2011)

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