Clean Techn Environ Policy (2011) 13:447457

DOI 10.1007/s10098-010-0323-3

REVIEW

Process design of waste gas treatment from Emirates

Gold Refinery
Ahmed Aidan Raafat Alnaizy Valentin Nenov
Omar Abdelrahman

Received: 2 June 2010 / Accepted: 21 September 2010 / Published online: 16 October 2010
Springer-Verlag 2010

Abstract In this case study, the process modifications

and improvement to the existing process at the Emirates
Gold refinery (in order to meet the United Arab Emirates
(UAE) nitrogen oxides air emission regulations) is presented. In the past, Emirates Gold refinery used a single
small scrubber to treat waste gases. In order to treat the
waste gas efficiently, it was found that a cooled oxidation
reactor (oxidizer) before the existing scrubber, as well as a
second scrubber is needed. The waste gas is mixed with air
at a fixed ratio before entering the oxidizer which is
designed to obtain the optimum degree of NO oxidation
(about 50%).To keep the oxidation reactions in the desirable direction the temperature should be kept between 15
and 20C There for an internal cooler was required. The
gas mixture from the Oxidizer enters the first scrubber
(existing) where most of the NOx, mainly as N2O3, are
absorbed by a NaOH solution (1520%). The remaining
NOx, mainly as N2O3 is absorbed in the second scrubber by
a NaOH solution (810%). The mass transfer area of the
packing in the two scrubbers, the solution circulation rate,
and the cooling duty were designed to reach the desired
degree of absorption of N2O3 and NO2. This ensures that
the recommended NOx residual value of 500 mg/m3
(250 ppm) is reached. All reactions occur simultaneously
was calculated using EQ4WIN software. The data obtained
for different temperatures was processed with Stat View,
A. Aidan (&)  R. Alnaizy  O. Abdelrahman
Department of Chemical Engineering, American University
of Sharjah, PO Box 2666, Sharjah, United Arab Emirates
e-mail: [email protected]
V. Nenov
Department of Water Treatment Technology,
Bourgas University, Bourgas, Bulgaria
e-mail: [email protected]

SuperPro Designer simulation and Aspen HYSYS simulation.

Keywords NOx  Tail gases  Gold refining 
Oxidation and absorption

Introduction
Emirates Gold is the largest gold and silver refinery in the
Arabian Gulf, equipped with hi-tech refinery facilities with
a capacity of 2,500 kg/day. The most important step in the
gold refining process is dissolving the scrap gold in aqua
regia (Latin for royal water); it is a highly corrosive solution that is fuming yellow or red in color. Due to this
corrosive nature, QVF glassware was used as the material
of construction in all units. The solution is formed by
mixing concentrated nitric acid and concentrated hydrochloric acid, usually in a volumetric ratio of 1:3 (Massucci
et al. 1999). Nitric acid is a strong oxidizer, which will
dissolve gold completely, forming Au3?. The hydrochloric
acid provides the needed Cl-, which reacts with gold to
produce chloraurate anions as shown in reaction (1).
Au HNO3 4HCl ! 2H2 O NO HAuCl4 

The dissolution of gold takes place in a semi-batch

reactor with a normal-operating capacity of 125-kg scrap
gold. The cycle time of each batch is approximately
90 min. Nitrogen oxide (NO) is formed by the basic
reaction of the scrap gold dissolution. In addition, nitrogen
dioxide (NO2) is produced, if oxygen is present in the gas
phase. Nitrogen oxide compounds (NOx, i.e., NO and NO2)
are known to be major atmospheric pollutants. NO is one of
the most harmful air pollutants. NOx contributes to acid
rain and greenhouse effects, which are of great concern.

123

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A. Aidan et al.

Concentrations of NOx in the air have also been linked to

mortality rates, where it was found that an increase in
concentration by 10 lg/m3 lead to, on average, a 0.4%
increase in mortality (Qian et al. 2010).
Regulations concerning limitation of air emission of
NOx from industrial processes differ from one country to
another. The UAE regulatory limits NOx emissions,
including averaging times, to a maximum of 500 mg/m3
NOx (without abatement systems) (Dubai Municipality
2008). Due to the change in the UAE regulation of air
pollutant emission, it was necessary that the Emirates Gold
refinery improve its waste gas treatment process to meet the
stringent requirement. There are several methods for controlling NOx emissions such as selective catalytic reduction
(SCR) or selective non-catalytic reduction (SNCR) (Lietti
1996; Heidenreich et al. 2008). The most common forms of
NOx treatment is via gas scrubbing using an alkaline solution (Chironna and Altshuler 2009; Thomas and Vanderschuren 2000; Patwardhan and Joshi 2004; Coates 1987).
Conventional gas scrubbing usually utilizes five alkaline
scrubbers in series (Gunther 2010). Other scrubbing solutions are available, such as hydrogen peroxide and ammonia
(Wallin et al. 2003; Economidis et al. 1998). In the case of
the hydrogen peroxide, it acts as an oxidizer as well as the
absorber of the NOx (Thomas and Vanderschuren 1996).

Waste gas

Objective
The existing treatment process for the waste gas at Emirates Gold employs a single scrubbing column using sodium
hydroxide (NaOH) as scrubbing solution (Fig. 1). The
chemistry controlling the treatment process is as follows:
NO 0:5O2 , NO2  62 kJ=mol

NO NO2 , N2 O3  40:1 kJ=mol

2NO2 , N2 O4 59:6 kJ=mol

N2 O3 2NaOH ! 2NaNO2 H2 O 188:7kJ=mol

2NO2 2NaOH ! NaNO2 NaNO3 H2 O

231:8 kJ=mol

Nonetheless, the process is inefficient and does not meet

the UAE regulations for NOx air emissions. Since the ratio of
NO to NO2 in the exhaust stream is significant and a high NO
removal efficiency is required, multiple scrubbing stages are
essential. In this paper, improvements and modifications to

Valve mixer
3

Several new studies employs bio-treatment for NOx contaminated gas by the application of denitrification (Flanagan et al. 2002; Barnes et al. 1995; Du Plessis et al. 1998).

Purified gas to fan

12

Fresh
NaOH solution
(15-20%)

Air

Cooler

Cooler

Cooling
water

First
scrubber
(Existing)

Oxidizer

Cooling
water

Second
Scrubber

11
8

Cooling
water

Valve mixer

13

7
Existing

Fig. 1 Flow sheet of the waste gas treatment system. 1 Waste gas
from gold scrap dissolution process, 2 Air to be mixed with stream
(1), 3 Mixed gas feed to oxidizer (see Table 9), 4 Effluent gas from
oxidizer (see Table 9), 5 NaOH (1520%) feed to the first scrubber, 6
Treated gas effluent from the first scrubber, 7 Liquid outlet from the
first scrubber, 8 Recycle stream of NaOH, 9 Recycled NaOH from the

123

10

14

first scrubber to the second scrubber, 10 Recycled NaOH from the

second scrubber, 11 Recycle stream to the second scrubber (810%
NaOH), 12 Purified gas from the second scrubber (see Table 9), 13
Liquid outlet from the second scrubber, 14 Purge stream from second
scrubber

Process design of waste gas treatment

the current treatment system that is utilized at the Emirates

Gold refinery in order to meet the UAE air emission
regulations are presented.

The modified process

As stated above, sodium hydroxide is used as the scrubbing
solution for NOx treatment. The absorption rate constants
are higher if diluted NaOH solutions are used. To reach a
high degree of absorption as well as very low residual
concentrations of NOx in the treated gas mixture, dual
alkali scrubbers (absorption columns) packed with raschig
rings in series, different concentrations of the alkali solutions were proposed. A schematic diagram of the modified
process to treat NOx is shown in Fig. 1. The proposed
modification includes an oxidizer, first scrubber, and second scrubber. The oxidizer is the first operation and the
second scrubber is the last step. NO has a very low solubility in NaOH, hence posing a significant problem for its
absorption. However, if the NO is oxidized to other NOx it
becomes much more soluble (Thomas and Vanderschuren
1996). Several chemical additives have been suggested to
overcome this issue of insolubility, such as ClO2 or Ozone
(Chien and Chu 2000). However, such chemical additives
are quite costly and pose a potential hazard in storing and
when used in operating equipment. Therefore, the oxidizer
is added since it can oxidize NO to other NOx, which are
more soluble, as well as avoid using chemical additives.
The modified process for removing NOx from the gas
stream compromises of the following steps:
1.
2.

3.

Mixing the flue gas with air and feeding it into the
oxidizer,
Feeding the effluent gas from the oxidizer into the first
scrubber where it comes in contact with an aqueous
alkali solution,
Feeding the gas stream from the first scrubber into the
second scrubber where it comes in contact with the
recycled alkali solution from first scrubber.

In the first scrubber, the gas mixture is treated by an

alkali solution of higher concentration (1520% NaOH)
and in the second scrubber with a weaker solution (810%
NaOH). In both columns, an intensive circulation of the
absorption solution is used in order to reach a high intensity
of mass transfer. The oxidizer is needed prior to scrubbing
to oxidize NO to NO2 since NO is insoluble in water and in
alkali solutions.
Prior to entering the oxidizer, the flue gas stream 1
(Fig. 1) which is mainly composed of NOx is mixed with
air so that the desired O2/NO ratio is achieved. The oxidation reaction is normally very slow. Therefore, a large
hollow vessel oxidizer is needed to maintain the necessary

449

residence time for the gas mixture to reach a 50% conversion of NO to NO2 (reaction 1). The oxidizer is
equipped with an internal heat exchanger (with large surface area) to control the temperature (below 200C) given
that reaction (2) is highly exothermic and NO2 will convert
back to NO at a temperature above 200C. Reactions (3)
and (4) are very fast and the equilibrium state is reached in
10.210.3 s. Both reactions are highly exothermic and thus
they are commonly carried out at low temperatures and
high pressures. At atmospheric pressure and relatively low
temperatures, the concentrations of both N2O3 and N2O4
are very low (no more than several percent); however, the
concentration of N2O3 is always lower than N2O4. The
second step of the process is the absorption of the NOx and
N2Ox by the alkali solution. The gases from the oxidizer are
fed into the first scrubber wherein the alkali solution is
added to the first scrubber to maintain the oxidative conditions. The second scrubber will remove the remaining
NOx and N2Ox from the gas stream. The concentration of
the alkali solution is about 15 to 20% by weight.

Process kinetics and equilibrium

The NO oxidation to NO2 is a rate limited third-order
gaseous reaction and the rate equation is (Lietti 1996):
dPNO2
k1 : p2NO : pO2
ds

The integrated form of the above Eq. 1 (Thomas and

Vanderschuren 2000) is:
k  a2  P 2  s

a
1
v1  a

 ln
v  1 1  a v  12
va
8

where k is the rate constant mol l-1 s-1; a a half of the

initial concentration of NO, mole fraction; v initial concentration of O2, mole fraction; a degree of oxidation of
NO; s residence time, s; and P pressure, atm
The values of the rate constant, k, for temperatures range
from 0 to 390C were statistically processed with Stat
View statistic software and the following equation was
obtained:
ln k

1370
 0:747
T

The formation N2O3 from NO and NO2 via reaction (3)

and N2O4 formation (NO2 dimerization) via reaction (4)
are limited by chemical equilibrium. The equilibrium
composition of the gas mixture when both reactions occur
simultaneously was calculated using EQ4WIN software.
The data obtained for different temperatures was processed
with Stat View and the following equations for the

123

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A. Aidan et al.

dependence of the equilibrium constants on temperature

were obtained:
N2O3 formation
ln K

4874
 17:081
T

10

N2O4 formation
ln K

6876
 21:127
T

11

The alkali absorption rate was calculated by the

following equation:
ln1  y k  q  s

12

where y degree of absorption; k absorption rate constant

mol l-1 s-1; q specific mass transfer area of the packing,
m2/m3; and s absorption time, s
For the required degree of absorption and the selected
kind and size of packing, the absorption time was
calculated.

Results and discussion

The optimum absorption rate of NOx by the alkali solution
(NaOH) is attained at a NO to NO2 ratio of 1:1, which
corresponds to the formation of N2O3 via reaction (3).
Hence, an oxidation reactor (oxidizer) is installed ahead of
the absorption column to ensure that an optimum degree of
NO oxidation in the gaseous mixture is achieved before it
enters the first scrubber (Fig. 1). The oxidation of NO to
form NO2 proceeds according to the gaseous reaction (2).
The equilibrium state depends strongly on temperature,
pressure, and excess oxygen. If the reaction occurs under
adiabatic conditions, a large quantity of heat is released and
the temperature will increase significantly, depending on
the concentration of NO in the gaseous mixture. For
example, if NO content is 10% by volume and the degree
of oxidation reaches 50%, the temperature will rise to
about 100C. At a temperature higher than 200C, the
reverse reaction of the NO oxidation (reaction 2) will be
observed, i.e., NO2 decomposes to NO. On the other hand,
low temperature, high pressure, and excess oxygen shift the
equilibrium towards NO2. In addition, as stated above,
reaction (2) is a third-order reaction, and therefore, depends
strongly on NO and O2 concentrations. Therefore, the rate
of reaction is very low at low NO concentrations. Reactions
(3) and (4) are very fast and the equilibrium state is reached
within 0.01 s. As these reactions are very fast, they do not
affect the alkali absorption process. N2O3 and NO2
absorption by the alkaline solution (reactions 5 and 6) are
irreversible. The degree of absorption depends mainly on
the absorption rate constants and is nearly independent of
the N2O3 and NO2 partial pressures.

123

In the alkali scrubber NO oxidation (reaction 2) as well

as reactions (3) and (4), occur simultaneously with the
absorption reactions (5) and (6). If both processes are to
take place simultaneously, the total process rate is lower
than when the oxidation and absorption occur consecutively. Consequently, in the modified process an oxidation
reactor was included ahead of the absorption column so
that the optimum degree of oxidation (50%) is attained. If
an oxidation reactor is not included prior to the absorption
column, then the NO oxidation will run solely in the
absorption column(s). In this case, the packing of the
absorption column must provide enough space to ensure a
sufficient residence time for the oxidation of NO. In the
new design, the gas space in the absorbers is not of
importance. Hence, less packing may be used, reducing the
size of the absorbers. The modified scheme also includes an
external heat exchanger to absorb heat that is generated
from reactions (5) and (6) (highly exothermic) in the
absorption column (Fig. 1). Table 1 shows a stoichiometric
material balance based on reactions (1) through (6). The
calculations are performed for 1 kg of scrap gold and for
the capacity of the reactor (125 kg of scrap gold). In
addition, average flow rates per hour based on a cycle time
of 1.5 h are calculated and shown in Table 1. Table 2
shows the material balance calculation in the oxidizer with
respect to only reaction (2) at several different O2:NO
ratios. The O2:NO ratio in the oxidizer is controlled by the
amount of air mixed with the waste gas prior to entering the
oxidizer. In Table 3, the compositions of the various NOx
at the outlet of the oxidizer are shown at a O2:NO ratio of 1
with respect to only reaction (2). The heat evolved by the
reaction is also assumed to be completely removed, hence
maintaining the temperature at 20C.
Tables 4, 5, 6, and 7 show results from the material
balance on the oxidizer where a basis of 125 kg scrap gold
is assumed; the calculations are based on the degree of NO
oxidation as well as the assumption that the equilibrium
states of reactions (3) and (4) are attained. The quantities
and compositions of the gaseous mixtures are shown in
mass (kg), volume (m3), and molar units (kmol). All results
in Tables 4, 5, 6, and 7 are calculated based on the optimal
degree of NO oxidation (50%). As no data on the vacuum
in this system is available, the absolute pressure in the
whole waste gas treatment system is assumed to be 0.5 atm
and the pressure drop is neglected. Tables 4, 5 and 6 show
the quantities and compositions of the gaseous mixture
after the oxidizer when the equilibrium state of reactions
(3) and (4) is attained, given a basis of 125 kg scrap gold.
The difference between these results is the assumed percentage of reaction heat removed and the respective temperature calculated after the oxidizer. Shown in Table 7 are
some of the basic parameters of the oxidizer, calculated
based on the results shown in Tables 4, 5, and 6. The

Process design of waste gas treatment

Table 1 A stoichiometric
material balance based on
reactions (1) through (6) (cycle
duration = 1.5 h)

451

Feed stocks and products

Amount required per

1 kg scrap

125 kg scrap

1h

HNO3 (68% mass, specific

gravity 1.4046 at 200C), kg

1.4046

175.57

117.05

HNO3 (100%), kg

0.9551

119.3875

79.592

H2O, kg

0.4495

56.1825

37.455

kmol

0.01515

1.89375

1.2625

m3

0.33936

42.42

28.28

NO yield (reaction 1)

NO2 yield (reaction 2, 100% NO oxidation)

kmol
0.01515

1.89375

1.2625

0.33936

42.42

28.28

kmol

0.007575

0.946875

0.63125

m3

0.16968

21.21

14.14

kmol

0.01515

1.89375

1.2625

kg

0.6060

75.75

50.5

kg (20% solution)

3.030

378.75

252.5

kmol

0.01515

1.8938

1.2625

kg

1.045

130.67

87.11

0.007575

0.9469

0.6312

0.5227

65.34

43.56

kmol

0.007575

0.9469

0.6312

kg

0.5227

65.34

43.56

m3
N2O3 yield (reaction 3, 50% NO oxidation)

NaOH (100% solution) (reactions 5 or 6)

NaNO2 yield (reaction 5)

NaNO2 yield (reaction 6)

kmol
kg
NaNO3 yield (reaction 6)

oxidizer volume is calculated for the three cases with different percentage removals of reaction heat by cooling
water. The calculations are based on the average gas
flowrate. The results in Table 7 show that if the oxidizer is
adiabatic, the size of the oxidizer will be unacceptable. On
the contrary, if the reaction heat is completely removed, the
reactor size is significantly smaller. Yet this decrease in
size due to heat removal will have an adverse effect on the
internal heat exchanger area required, therefore the optimum choice should be economically based. In addition,
some specific characteristics of the existing system could
be decisive factors, e.g., system arrangement, fan duty, etc.
In Table 8, the quantity and composition of the treated
waste gas after scrubbing is shown. The calculations are
based on the assumption that the residual concentration of
NOx (recalculated as NO2) after the second absorber is
decreased down to the recommended limit of 500 mg/m3
(250 ppm).
Table 9 shows the oxidation reactor feed (stream 3) and
effluent (stream 4) composition per 125 kg scrap gold at
50% NO oxidation in the reactor. It is assumed that the
equilibrium states of reactions (3) and (4) are attained.

Excess air was fed to the reactor (O2:NO = 1) with the

reaction heat completely removed. The process was carried
out at a constant temperature (20C) and pressure
(0.5 atm). The heats of the reaction were removed completely by cooling water. The composition of the final
effluent (stream 12) after the second scrubber is also
shown. The calculations are based on the assumption that
the residual concentration of NOx (recalculated as NO2)
after the second absorber is decreased down to the recommended limit of 500 mg/m3 (250 ppm). To meet this
requirement, the total degree of absorption must be equal to
or greater than 99.9% (Table 10). Based on the size and
other parameters of the existing scrubber, the residence
time was calculated to be 13.2 s per cycle using Eq. 6. An
average value of the absorption rate constant was used
(Thomas and Vanderschuren 2000). The optimum distribution of the absorbed N2O3 between the two scrubbers
may be calculated based on the real data available on the
packing and sizes of both columns. Table 11 shows a few
basic parameters of the oxidation reactor that are calculated
on the basis of the results. The calculations are based on the
average gas flowrate.

123

452
Table 2 Quantities and
compositions of the gas and air
mixture inlet NO oxidation
reactor in the waste gas
treatment system at various
O2:NO ratios

A. Aidan et al.

NO, oxygen, and air inlet waste

gas treatment system

Per 1 kg
scrap

Per 125 kg
scrap

Average
per 1 h

kmol

0.01515

1.89375

1.2625

0.33936

42.42

28.28

kmol

0.007575

0.946875

0.63125

m3

0.16968

21.21

14.14

0.8277

103.46

68.97

0.01515
0.33936

1.89375
42.42

1.2625
28.28

1.6570

207.12

138.08

NO oxidation stoichiometry (O2:NO = 0.5:1)

NO yield (stoichiometric) by the reaction (1):
m

O2 needed (stoichiometric) for the reaction (2):

Air needed for the reaction (2) m3

NO oxidation by excess air (O2:NO = 1:1)
O2 added for the reaction (2):
kmol
m3
Air added for the reaction (2), m3 incl.:
O2

0.33936

42.42

28.28

N2 and others

1.31764

164.70

109.80

1.9964

249.54

166.36

Total gas and air mixture, m3

Gas and air mixture composition, %:
NO

17.00

O2

17.00

N2 and others

66.00

NO oxidation by excess air (O2:NO = 1.5:1)

O2 added for the reaction (2):
kmol

0.02272

2.8406

1.894

m3

0.5090

63.63

42.42

2.4855

310.69

207.12

0.5090
1.9765

63.63
247.06

42.42
164.71

2.8249

353.11

235.40

2.525

Air added for the reaction (2), m incl.:

O2
N2 and others
Total gas and air mixture, m3
Gas and air mixture composition, %:
NO

12.01

O2

18.02

N2 and others

69.97

NO oxidation by excess air (O2:NO = 2:1)

O2 added for the reaction (2):
kmol

0.0303

3.7875

m3

0.6787

84.84

56.56

3.314

414.25

276.17

Air added for the reaction (2), m3 incl.:

O2

0.6787

84.84

56.56

N2 and others

2.6353

329.41

219.60

3.3653

456.67

304.45

Total gas and air mixture, m3

Gas and air mixture composition, %:
NO
O2

9.29
18.58

N2 and others

72.13

The basic flowchart of the modified treatment system of

the waste gas is shown in Fig. 1. The modifications are
based on the grounds of basic principles and experimental
work. The waste gas needs to be mixed with air at a fixed

123

ratio to ensure the optimum degree of NO oxidation. The

gas mixture goes into the oxidizer, which is a hollow
column with an internal heat exchanger (cooler). The
oxidizer is designed to give the optimum degree of NO

Process design of waste gas treatment

453

Table 3 Quantities and composition of the gas and air mixture after NO oxidation by excess air (O2:NO = 1:1)
Mass balance (per 125 kg scrap)
Components

Point no. 2: waste gas after oxidation; temperature 20C; pressure 0.5 atm
m3

vol.%

kmol

kg

mass%

NO

8.8773

21.2109

0.9469

28.4150

8.7858

NO2

8.8773

21.2109

0.9469

43.5657

13.4703

N2O3
N2O4

0.0000
0.0000

0.0000
0.0000

0.0000
0.0000

0.0000
0.0000

0.0000
0.0000
14.0535

O2

13.3159

31.8164

1.4204

45.4519

N2 and others

68.9295

164.6964

7.3525

205.9881

63.6904

100.0000

238.9346

10.6667

323.4208

100.0000

Total

Degree of oxidation 50%. Oxidation reaction heat completely removed

Table 4 Quantities and composition of the gas and air mixture after NO oxidation reactor
Mass balance (per 125 kg scrap)
Components

Point no. 3: waste gas after NO oxidation reactor; temperature 20C; pressure 0.5 atm
vol.%

m3

kmol

kg

mass%

NO

8.8771

20.8386

0.9303

27.9162

8.6316

NO2

5.6259

13.2066

0.5896

27.1254

8.3870

N2O3
N2O4

0.1586
1.6256

0.3723
3.8160

0.0166
0.1704

1.2635
15.6755

0.3907
4.8468

O2

13.5535

31.8164

1.4204

45.4519

14.0535

N2 and others

70.1593

164.6964

7.3525

205.9881

63.6904

100.0000

234.7462

10.4797

323.4208

100.0000

Total

Equilibrium state of reactions (3) and (4) attained. NO oxidation by excess air (O2:NO = 1:1). Degree of oxidation 50%. Oxidation reaction heat
completely removed

Table 5 Quantities and composition of the gas and air mixture after NO oxidation reactor
Mass balance (per 125 kg scrap)
Components

Point no. 4: waste gas after NO oxidation reactor; temperature 111.7C; pressure 0.5 atm
vol.%

m3

NO

8.8736

21.1968

NO2

8.8362

N2O3
N2O4

0.0059
0.0187

kmol

kg

mass%

0.9463

28.3961

8.7799

21.1074

0.9423

43.3531

13.4046

0.0141
0.0447

0.0006
0.0020

0.0479
0.1835

0.0148
0.0567

O2

13.3192

31.8164

1.4204

45.4519

14.0535

N2 and others

68.9465

164.6964

7.3525

205.9881

63.6904

100.0000

238.8758

10.6641

323.4208

100.0000

Total

Equilibrium state of reactions (3) and (4) attained. NO oxidation by excess air (O2:NO = 1:1). Degree of oxidation 50%. 50% of the oxidation
reaction heat removed

oxidation (about 50%). Emirates Gold refinery uses a batch

process, but the waste gas treatment system is a continuous
system. The oxidizer will play the role of an equalization
unit and thus help dampen the fluctuations of the gas

composition and temperature. The gas mixture from the

reactor enters the first scrubber (existing) where most of the
N2Ox, mainly as N2O3, is absorbed by a 1520% NaOH
solution. The remaining N2Ox, also mainly as N2O3, is

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A. Aidan et al.

Table 6 Quantities and composition of the gas and air mixture after NO oxidation reactor
Mass balance (per 125 kg scrap)
Components

Point no. 5: waste gas after NO oxidation reactor; temperature 203.4C; pressure 0.5 atm
m3

vol.%

kmol

kg

mass%

NO

8.8742

21.2019

0.9465

28.4030

8.7821

NO2

8.8655

21.1810

0.9456

43.5042

13.4513

N2O3
N2O4

0.0038
0.0044

0.0090
0.0105

0.0004
0.0005

0.0305
0.0430

0.0094
0.0133
14.0535

O2

13.3170

31.8164

1.4204

45.4519

N2 and others

68.9351

164.6964

7.3525

205.9881

63.6904

100.0000

238.9151

10.6659

323.4208

100.0000

Total

Equilibrium state of reactions (3) and (4) attained. NO oxidation by excess air (O2:NO = 1:1). Degree of oxidation 50%. Oxidizing reaction heat
not removed

Table 7 NO oxidation reactor

parameters in the waste gas
treatment system

NO oxidation reactor parameters

Oxidation without
heat removing

Removed oxidation
heat, % of total

Degree of NO oxidation 50%; ratio O2:NO = 1:1; pressure 0.5 atm

Removed heat, %

50

100

Removed heat, kJ per 1 kg scrap

234.8

469.6

Removed heat, kJ per 125 kg scrap

23953

58,706

Removed heat, kJ/h (average)

19,569

39,137

Temperature before oxidation, C

20

20

20

Temperature after oxidation, C

203.40

111.70

20

Reaction rate constant

8.396

16.657

50.723

Residence time, s

39.20

19.76

6.49

166.36
0.04621

166.36
0.04621

166.36
0.04621

0.15999

0.12957

0.09919
0.644

Average gas mixture flow rate:

m3/h
m3/s
m3/s
Oxidation reactor volume, m

6.272

2.560

Oxidation reactor diameter, m (estimation)

1.00/1.20

0.80/0.90

0.50/0.60

Oxidation reactor height, m (estimation)

8.00/5.60

5.10/4.00

3.30/2.30

Average chilled water flow, m3/h

(water temperature rise DT = 150C)

None

0.312

0.624

Internal heat exchange area, m2 (estimation)

None

15.6

31.2

Table 8 Quantities and composition of the treated waste gas after second NOx absorber
Mass balance (per 125 kg scrap)
Components

Point no. 7: waste gas after second scrubber; temperature 20C; pressure 0.5 atm
vol.%

m3

kmol

kg

mass%

NO

0.0120

0.0236

0.00105

0.0315

0.0125

NO2

0.0120

0.0236

0.00105

0.0483

0.0192

N2O3

0.0000

0.0000

0.0000

0.0000

0.0000

N2O4
O2
N2 and others
Total

123

0.0000

0.0000

0.0000

0.0000

0.0000

16.1866

31.8164

1.4204

45.4519

18.0709

83.7894

164.6964

7.3525

205.9881

81.8974

100.0000

196.5600

8.7750

251.5198

100.0000

Process design of waste gas treatment

455

Table 9 Oxidation reactor feed and effluent composition per 125 kg scrap at 50% NO oxidation
Component

Reactor feed

Reactor effluent
3

vol.%

vol.%

Final effluent (Second absorber)

m

m3

vol.%

NO

17.0000

42.4218

8.8771

20.8386

0.0120

0.0236

NO2

0.0000

0.0000

5.6259

13.2066

0.0120

0.0236

N2O3

0.0000

0.0000

0.1586

0.3723

0.0000

0.0000

N2O4
O2
N2 and others
Total

0.0000

0.0000

1.6256

3.8160

0.0000

0.0000

17.0000

42.4218

13.5535

31.8164

16.1866

31.8164

66.0000

164.6964

70.1593

164.6964

83.7894

164.6964

100.0000

249.5400

100.0000

234.7462

100.0000

196.5600

Excess air was fed to the reactor (O2:NO = 1) with reaction heat completely removed; Temperature 20C; Pressure 0.5 atm

Table 10 Basic parameters

of the NOx absorption by
NaOH solution

Parameters

Value
Per 125 kg scrap

Final effluent (NO and NO2) as NO2

Average per hour

240 ppm
493 mg/m3

Total degree of absorption of NOx

Absorption rate constant (average estimation)

0.001 m/s

Specific mass transfer area of absorber packing

500 m2/m3

Residence time total (s)

13.2

Total absorption heat to be removed (kJ)

178,480

118,990

NaOH (100%) consumption (kg)

75.7

50.5

NaNO2 and NaNO3 (kg)

130.6

87.06

Table 11 Oxidizer parameters at 50% NO oxidation

Reactor parameters
Removed heat, kJ per 1 kg scrap

469.6

Removed heat, kJ per 125 kg scrap

58,706

Removed heat, kJ/h (average)

39,137

Temperature before oxidation, C

20

Temperature after oxidation, C

20

Reaction rate constant mol l

-1

99.9%

-1

50.723

Residence time, s

6.49

Average gas flow rate (m3/h)

166.36

Oxidation reactor volume, m3

0.644

Average chilled water flow, m3/h (water temperature rise

DT = 150C)

0.624

Excess air was fed to the reactor (O2:NO = 1) with reaction heat
completely removed; Temperature 20C; Pressure 0.5 atm

removed from the gas in the second scrubber by an 810%

NaOH solution. The mass transfer area of the scrubbers
packing, the solution circulation rate and the cooling duty
were selected in order to attain the desired degree of N2O3
and NO2 absorption to achieve the regulation residual
value of NOx of 500 mg/m3 (250 ppm).

8.8

Detailed design specifications for the waste gas treatment system were performed using Aspen Tech simulation
software (HYSYS, Fig. 2) as well as Super Pro designer
(Fig. 3), in accordance with hand calculations. The units
were manufactured and added to the existing treatment
system. Samples were taken by Emirate Gold DMCC
chemist and Dubai municipality personnel, where both
parties found that the modified and improved process meets
the regulation standards.

Conclusion
The above recommendations were considered by the
Emirates Gold DMCC administrators in order to meet the
UAE air emission regulations. Based on the analysis of
environmental laboratory of Dubai municipality, Emirates
Gold DMCC were able to meet the required UAE regulations for NOx emission. It was also found that using an
oxidizer prior to the scrubbing system, required a smaller
number of scrubbers in comparison to the conventional
method of a treatment system consisting only of scrubbers.

123

456

Fig. 2 Aspen HYSYS simulation of Oxidizer

Fig. 3 SuperPro designer simulation of modified process

123

A. Aidan et al.

Process design of waste gas treatment

Acknowledgments The authors are grateful to Mr. Mohamed
Shekarchy, Director of Emirates Gold DMCC, and Engineer Faisal
Dawood for their continuous support.

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