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Process design of waste gas treatment from Emirates Gold Refinery

Article  in  Clean Technologies and Environmental Policy · June 2011

DOI: 10.1007/s10098-010-0323-3

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Clean Techn Environ Policy
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

Ó Springer-Verlag 2010

Abstract In this case study, the process modifications SuperPro Designer simulation and Aspen HYSYS simu-
and improvement to the existing process at the Emirates lation.
Gold refinery (in order to meet the United Arab Emirates
(UAE) nitrogen oxides air emission regulations) is pre- Keywords NOx  Tail gases  Gold refining 
sented. In the past, Emirates Gold refinery used a single Oxidation and absorption
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 Introduction
second scrubber is needed. The waste gas is mixed with air
at a fixed ratio before entering the oxidizer which is Emirates Gold is the largest gold and silver refinery in the
designed to obtain the optimum degree of NO oxidation Arabian Gulf, equipped with hi-tech refinery facilities with
(about 50%).To keep the oxidation reactions in the desir- a capacity of 2,500 kg/day. The most important step in the
able direction the temperature should be kept between 15 gold refining process is dissolving the scrap gold in aqua
and 20°C There for an internal cooler was required. The regia (Latin for royal water); it is a highly corrosive solu-
gas mixture from the Oxidizer enters the first scrubber tion that is fuming yellow or red in color. Due to this
(existing) where most of the NOx, mainly as N2O3, are corrosive nature, QVF glassware was used as the material
absorbed by a NaOH solution (15–20%). The remaining of construction in all units. The solution is formed by
NOx, mainly as N2O3 is absorbed in the second scrubber by mixing concentrated nitric acid and concentrated hydro-
a NaOH solution (8–10%). The mass transfer area of the chloric acid, usually in a volumetric ratio of 1:3 (Massucci
packing in the two scrubbers, the solution circulation rate, et al. 1999). Nitric acid is a strong oxidizer, which will
and the cooling duty were designed to reach the desired dissolve gold completely, forming Au3?. The hydrochloric
degree of absorption of N2O3 and NO2. This ensures that acid provides the needed Cl-, which reacts with gold to
the recommended NOx residual value of 500 mg/m3 produce chloraurate anions as shown in reaction (1).
(250 ppm) is reached. All reactions occur simultaneously Au þ HNO3 þ 4HCl ! 2H2 O þ NO þ H½AuCl4  ð1Þ
was calculated using EQ4WIN software. The data obtained
for different temperatures was processed with Stat View, 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
A. Aidan (&)  R. Alnaizy  O. Abdelrahman 90 min. Nitrogen oxide (NO) is formed by the basic
Department of Chemical Engineering, American University
of Sharjah, PO Box 2666, Sharjah, United Arab Emirates
reaction of the scrap gold dissolution. In addition, nitrogen
e-mail: [email protected] dioxide (NO2) is produced, if oxygen is present in the gas
phase. Nitrogen oxide compounds (NOx, i.e., NO and NO2)
V. Nenov are known to be major atmospheric pollutants. NO is one of
Department of Water Treatment Technology,
Bourgas University, Bourgas, Bulgaria
the most harmful air pollutants. NOx contributes to acid
e-mail: [email protected] rain and greenhouse effects, which are of great concern.

123
 A. Aidan et al.

Concentrations of NOx in the air have also been linked to Several new studies employs bio-treatment for NOx con-
mortality rates, where it was found that an increase in taminated gas by the application of denitrification (Flana-
concentration by 10 lg/m3 lead to, on average, a 0.4% gan et al. 2002; Barnes et al. 1995; Du Plessis et al. 1998).
increase in mortality (Qian et al. 2010).
Regulations concerning limitation of air emission of
NOx from industrial processes differ from one country to Objective
another. The UAE regulatory limits NOx emissions,
including averaging times, to a maximum of 500 mg/m3 The existing treatment process for the waste gas at Emir-
NOx (without abatement systems) (Dubai Municipality ates Gold employs a single scrubbing column using sodium
2008). Due to the change in the UAE regulation of air hydroxide (NaOH) as scrubbing solution (Fig. 1). The
pollutant emission, it was necessary that the Emirates Gold chemistry controlling the treatment process is as follows:
refinery improve its waste gas treatment process to meet the NO þ 0:5O2 , NO2  62 kJ=mol ð2Þ
stringent requirement. There are several methods for con-
trolling NOx emissions such as selective catalytic reduction NO þ NO2 , N2 O3  40:1 kJ=mol ð3Þ
(SCR) or selective non-catalytic reduction (SNCR) (Lietti 2NO2 , N2 O4 þ 59:6 kJ=mol ð4Þ
1996; Heidenreich et al. 2008). The most common forms of
N2 O3 þ 2NaOH ! 2NaNO2 þ H2 O þ 188:7kJ=mol ð5Þ
NOx treatment is via gas scrubbing using an alkaline solu-
tion (Chironna and Altshuler 2009; Thomas and Vander- 2NO2 þ 2NaOH ! NaNO2 þ NaNO3 þ H2 O
schuren 2000; Patwardhan and Joshi 2004; Coates 1987). þ 231:8 kJ=mol ð6Þ
Conventional gas scrubbing usually utilizes five alkaline
scrubbers in series (Günther 2010). Other scrubbing solu- Nonetheless, the process is inefficient and does not meet
tions are available, such as hydrogen peroxide and ammonia the UAE regulations for NOx air emissions. Since the ratio of
(Wallin et al. 2003; Economidis et al. 1998). In the case of NO to NO2 in the exhaust stream is significant and a high NO
the hydrogen peroxide, it acts as an oxidizer as well as the removal efficiency is required, multiple scrubbing stages are
absorber of the NOx (Thomas and Vanderschuren 1996). essential. In this paper, improvements and modifications to

6 12 Purified gas to fan

Waste gas Valve mixer

1 3 Fresh
NaOH solution
(15-20%)
5
Air
Cooler
2

Cooler Cooling Cooling

First Second water
water
Oxidizer scrubber Scrubber
(Existing)

11
8
Cooling
water
Valve mixer

4 13
10
7

9
Existing 14

Fig. 1 Flow sheet of the waste gas treatment system. 1 Waste gas first scrubber to the second scrubber, 10 Recycled NaOH from the
from gold scrap dissolution process, 2 Air to be mixed with stream second scrubber, 11 Recycle stream to the second scrubber (8–10%
(1), 3 Mixed gas feed to oxidizer (see Table 9), 4 Effluent gas from NaOH), 12 Purified gas from the second scrubber (see Table 9), 13
oxidizer (see Table 9), 5 NaOH (15–20%) feed to the first scrubber, 6 Liquid outlet from the second scrubber, 14 Purge stream from second
Treated gas effluent from the first scrubber, 7 Liquid outlet from the scrubber
first scrubber, 8 Recycle stream of NaOH, 9 Recycled NaOH from the

123
Process design of waste gas treatment

the current treatment system that is utilized at the Emirates residence time for the gas mixture to reach a 50% con-
Gold refinery in order to meet the UAE air emission version of NO to NO2 (reaction 1). The oxidizer is
regulations are presented. equipped with an internal heat exchanger (with large sur-
face area) to control the temperature (below 200°C) given
that reaction (2) is highly exothermic and NO2 will convert
The modified process back to NO at a temperature above 200°C. Reactions (3)
and (4) are very fast and the equilibrium state is reached in
As stated above, sodium hydroxide is used as the scrubbing 10.2–10.3 s. Both reactions are highly exothermic and thus
solution for NOx treatment. The absorption rate constants they are commonly carried out at low temperatures and
are higher if diluted NaOH solutions are used. To reach a high pressures. At atmospheric pressure and relatively low
high degree of absorption as well as very low residual temperatures, the concentrations of both N2O3 and N2O4
concentrations of NOx in the treated gas mixture, dual are very low (no more than several percent); however, the
alkali scrubbers (absorption columns) packed with raschig concentration of N2O3 is always lower than N2O4. The
rings in series, different concentrations of the alkali solu- second step of the process is the absorption of the NOx and
tions were proposed. A schematic diagram of the modified N2Ox by the alkali solution. The gases from the oxidizer are
process to treat NOx is shown in Fig. 1. The proposed fed into the first scrubber wherein the alkali solution is
modification includes an oxidizer, first scrubber, and sec- added to the first scrubber to maintain the oxidative con-
ond scrubber. The oxidizer is the first operation and the ditions. The second scrubber will remove the remaining
second scrubber is the last step. NO has a very low solu- NOx and N2Ox from the gas stream. The concentration of
bility in NaOH, hence posing a significant problem for its the alkali solution is about 15 to 20% by weight.
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 Process kinetics and equilibrium
overcome this issue of insolubility, such as ClO2 or Ozone
(Chien and Chu 2000). However, such chemical additives The NO oxidation to NO2 is a rate limited third-order
are quite costly and pose a potential hazard in storing and gaseous reaction and the rate equation is (Lietti 1996):
when used in operating equipment. Therefore, the oxidizer
dPNO2
is added since it can oxidize NO to other NOx, which are ¼ k1 : p2NO : pO2 ð7Þ
more soluble, as well as avoid using chemical additives. ds
The modified process for removing NOx from the gas The integrated form of the above Eq. 1 (Thomas and
stream compromises of the following steps: Vanderschuren 2000) is:
1. Mixing the flue gas with air and feeding it into the a 1 vð1  aÞ
k  a2  P 2  s ¼ þ  ln
oxidizer, ðv  1Þ ð1  aÞ ðv  1Þ2 va
2. Feeding the effluent gas from the oxidizer into the first ð8Þ
scrubber where it comes in contact with an aqueous
alkali solution, where k is the rate constant mol l-1 s-1; a a half of the
3. Feeding the gas stream from the first scrubber into the initial concentration of NO, mole fraction; v initial con-
second scrubber where it comes in contact with the centration of O2, mole fraction; a degree of oxidation of
recycled alkali solution from first scrubber. NO; s residence time, s; and P pressure, atm
The values of the rate constant, k, for temperatures range
In the first scrubber, the gas mixture is treated by an from 0 to 390°C were statistically processed with Stat
alkali solution of higher concentration (15–20% NaOH) View statistic software and the following equation was
and in the second scrubber with a weaker solution (8–10% obtained:
NaOH). In both columns, an intensive circulation of the
1370
absorption solution is used in order to reach a high intensity ln k ¼  0:747 ð9Þ
of mass transfer. The oxidizer is needed prior to scrubbing T
to oxidize NO to NO2 since NO is insoluble in water and in The formation N2O3 from NO and NO2 via reaction (3)
alkali solutions. and N2O4 formation (NO2 dimerization) via reaction (4)
Prior to entering the oxidizer, the flue gas stream 1 are limited by chemical equilibrium. The equilibrium
(Fig. 1) which is mainly composed of NOx is mixed with composition of the gas mixture when both reactions occur
air so that the desired O2/NO ratio is achieved. The oxi- simultaneously was calculated using EQ4WIN software.
dation reaction is normally very slow. Therefore, a large The data obtained for different temperatures was processed
hollow vessel oxidizer is needed to maintain the necessary with Stat View and the following equations for the

123
 A. Aidan et al.

dependence of the equilibrium constants on temperature In the alkali scrubber NO oxidation (reaction 2) as well
were obtained: as reactions (3) and (4), occur simultaneously with the
N2O3 formation absorption reactions (5) and (6). If both processes are to
4874 take place simultaneously, the total process rate is lower
ln K ¼  17:081 ð10Þ than when the oxidation and absorption occur consecu-
T
tively. Consequently, in the modified process an oxidation
N2O4 formation reactor was included ahead of the absorption column so
6876 that the optimum degree of oxidation (50%) is attained. If
ln K ¼  21:127 ð11Þ
T an oxidation reactor is not included prior to the absorption
The alkali absorption rate was calculated by the column, then the NO oxidation will run solely in the
following equation: absorption column(s). In this case, the packing of the
absorption column must provide enough space to ensure a
lnð1  yÞ ¼ k  q  s ð12Þ sufficient residence time for the oxidation of NO. In the
where y degree of absorption; k absorption rate constant new design, the gas space in the absorbers is not of
mol l-1 s-1; q specific mass transfer area of the packing, importance. Hence, less packing may be used, reducing the
m2/m3; and s absorption time, s size of the absorbers. The modified scheme also includes an
For the required degree of absorption and the selected external heat exchanger to absorb heat that is generated
kind and size of packing, the absorption time was from reactions (5) and (6) (highly exothermic) in the
calculated. 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
Results and discussion the capacity of the reactor (125 kg of scrap gold). In
addition, average flow rates per hour based on a cycle time
The optimum absorption rate of NOx by the alkali solution of 1.5 h are calculated and shown in Table 1. Table 2
(NaOH) is attained at a NO to NO2 ratio of 1:1, which shows the material balance calculation in the oxidizer with
corresponds to the formation of N2O3 via reaction (3). respect to only reaction (2) at several different O2:NO
Hence, an oxidation reactor (oxidizer) is installed ahead of ratios. The O2:NO ratio in the oxidizer is controlled by the
the absorption column to ensure that an optimum degree of amount of air mixed with the waste gas prior to entering the
NO oxidation in the gaseous mixture is achieved before it oxidizer. In Table 3, the compositions of the various NOx
enters the first scrubber (Fig. 1). The oxidation of NO to at the outlet of the oxidizer are shown at a O2:NO ratio of 1
form NO2 proceeds according to the gaseous reaction (2). with respect to only reaction (2). The heat evolved by the
The equilibrium state depends strongly on temperature, reaction is also assumed to be completely removed, hence
pressure, and excess oxygen. If the reaction occurs under maintaining the temperature at 20°C.
adiabatic conditions, a large quantity of heat is released and Tables 4, 5, 6, and 7 show results from the material
the temperature will increase significantly, depending on balance on the oxidizer where a basis of 125 kg scrap gold
the concentration of NO in the gaseous mixture. For is assumed; the calculations are based on the degree of NO
example, if NO content is 10% by volume and the degree oxidation as well as the assumption that the equilibrium
of oxidation reaches 50%, the temperature will rise to states of reactions (3) and (4) are attained. The quantities
about 100°C. At a temperature higher than 200°C, the and compositions of the gaseous mixtures are shown in
reverse reaction of the NO oxidation (reaction 2) will be mass (kg), volume (m3), and molar units (kmol). All results
observed, i.e., NO2 decomposes to NO. On the other hand, in Tables 4, 5, 6, and 7 are calculated based on the optimal
low temperature, high pressure, and excess oxygen shift the degree of NO oxidation (50%). As no data on the vacuum
equilibrium towards NO2. In addition, as stated above, in this system is available, the absolute pressure in the
reaction (2) is a third-order reaction, and therefore, depends whole waste gas treatment system is assumed to be 0.5 atm
strongly on NO and O2 concentrations. Therefore, the rate and the pressure drop is neglected. Tables 4, 5 and 6 show
of reaction is very low at low NO concentrations. Reactions the quantities and compositions of the gaseous mixture
(3) and (4) are very fast and the equilibrium state is reached after the oxidizer when the equilibrium state of reactions
within 0.01 s. As these reactions are very fast, they do not (3) and (4) is attained, given a basis of 125 kg scrap gold.
affect the alkali absorption process. N2O3 and NO2 The difference between these results is the assumed per-
absorption by the alkaline solution (reactions 5 and 6) are centage of reaction heat removed and the respective tem-
irreversible. The degree of absorption depends mainly on perature calculated after the oxidizer. Shown in Table 7 are
the absorption rate constants and is nearly independent of some of the basic parameters of the oxidizer, calculated
the N2O3 and NO2 partial pressures. based on the results shown in Tables 4, 5, and 6. The

123
Process design of waste gas treatment

Table 1 A stoichiometric
Feed stocks and products Amount required per
material balance based on
reactions (1) through (6) (cycle 1 kg scrap 125 kg scrap 1h
duration = 1.5 h)
HNO3 (68% mass, specific 1.4046 175.57 117.05
gravity 1.4046 at 200°C), kg
HNO3 (100%), kg 0.9551 119.3875 79.592
H2O, kg 0.4495 56.1825 37.455
NO yield (reaction 1)
kmol 0.01515 1.89375 1.2625
m3 0.33936 42.42 28.28
NO2 yield (reaction 2, 100% NO oxidation)
kmol 0.01515 1.89375 1.2625
m3 0.33936 42.42 28.28
N2O3 yield (reaction 3, 50% NO oxidation)
kmol 0.007575 0.946875 0.63125
m3 0.16968 21.21 14.14
NaOH (100% solution) (reactions 5 or 6)
kmol 0.01515 1.89375 1.2625
kg 0.6060 75.75 50.5
kg (20% solution) 3.030 378.75 252.5
NaNO2 yield (reaction 5)
kmol 0.01515 1.8938 1.2625
kg 1.045 130.67 87.11
NaNO2 yield (reaction 6)
kmol 0.007575 0.9469 0.6312
kg 0.5227 65.34 43.56
NaNO3 yield (reaction 6)
kmol 0.007575 0.9469 0.6312
kg 0.5227 65.34 43.56

oxidizer volume is calculated for the three cases with dif- Excess air was fed to the reactor (O2:NO = 1) with the
ferent percentage removals of reaction heat by cooling reaction heat completely removed. The process was carried
water. The calculations are based on the average gas out at a constant temperature (20°C) and pressure
flowrate. The results in Table 7 show that if the oxidizer is (0.5 atm). The heats of the reaction were removed com-
adiabatic, the size of the oxidizer will be unacceptable. On pletely by cooling water. The composition of the final
the contrary, if the reaction heat is completely removed, the effluent (stream 12) after the second scrubber is also
reactor size is significantly smaller. Yet this decrease in shown. The calculations are based on the assumption that
size due to heat removal will have an adverse effect on the the residual concentration of NOx (recalculated as NO2)
internal heat exchanger area required, therefore the opti- after the second absorber is decreased down to the rec-
mum choice should be economically based. In addition, ommended limit of 500 mg/m3 (250 ppm). To meet this
some specific characteristics of the existing system could requirement, the total degree of absorption must be equal to
be decisive factors, e.g., system arrangement, fan duty, etc. or greater than 99.9% (Table 10). Based on the size and
In Table 8, the quantity and composition of the treated other parameters of the existing scrubber, the residence
waste gas after scrubbing is shown. The calculations are time was calculated to be 13.2 s per cycle using Eq. 6. An
based on the assumption that the residual concentration of average value of the absorption rate constant was used
NOx (recalculated as NO2) after the second absorber is (Thomas and Vanderschuren 2000). The optimum distri-
decreased down to the recommended limit of 500 mg/m3 bution of the absorbed N2O3 between the two scrubbers
(250 ppm). may be calculated based on the real data available on the
Table 9 shows the oxidation reactor feed (stream 3) and packing and sizes of both columns. Table 11 shows a few
effluent (stream 4) composition per 125 kg scrap gold at basic parameters of the oxidation reactor that are calculated
50% NO oxidation in the reactor. It is assumed that the on the basis of the results. The calculations are based on the
equilibrium states of reactions (3) and (4) are attained. average gas flowrate.

123
 A. Aidan et al.

Table 2 Quantities and

NO, oxygen, and air inlet waste Per 1 kg Per 125 kg Average
compositions of the gas and air
gas treatment system scrap scrap per 1 h
mixture inlet NO oxidation
reactor in the waste gas NO oxidation stoichiometry (O2:NO = 0.5:1)
treatment system at various
O2:NO ratios NO yield (stoichiometric) by the reaction (1):
kmol 0.01515 1.89375 1.2625
3
m 0.33936 42.42 28.28
O2 needed (stoichiometric) for the reaction (2):
kmol 0.007575 0.946875 0.63125
m3 0.16968 21.21 14.14
Air needed for the reaction (2) m3 0.8277 103.46 68.97
NO oxidation by excess air (O2:NO = 1:1)
O2 added for the reaction (2):
kmol 0.01515 1.89375 1.2625
m3 0.33936 42.42 28.28
Air added for the reaction (2), m3 incl.: 1.6570 207.12 138.08
O2 0.33936 42.42 28.28
N2 and others 1.31764 164.70 109.80
Total gas and air mixture, m3 1.9964 249.54 166.36
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
3
Air added for the reaction (2), m incl.: 2.4855 310.69 207.12
O2 0.5090 63.63 42.42
N2 and others 1.9765 247.06 164.71
Total gas and air mixture, m3 2.8249 353.11 235.40
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 2.525
m3 0.6787 84.84 56.56
Air added for the reaction (2), m3 incl.: 3.314 414.25 276.17
O2 0.6787 84.84 56.56
N2 and others 2.6353 329.41 219.60
Total gas and air mixture, m3 3.3653 456.67 304.45
Gas and air mixture composition, %:
NO 9.29
O2 18.58
N2 and others 72.13

The basic flowchart of the modified treatment system of ratio to ensure the optimum degree of NO oxidation. The
the waste gas is shown in Fig. 1. The modifications are gas mixture goes into the oxidizer, which is a hollow
based on the grounds of basic principles and experimental column with an internal heat exchanger (cooler). The
work. The waste gas needs to be mixed with air at a fixed oxidizer is designed to give the optimum degree of NO

123
Process design of waste gas treatment

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 20°C; pressure 0.5 atm
vol.% m3 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 0.0000 0.0000 0.0000 0.0000 0.0000
N2O4 0.0000 0.0000 0.0000 0.0000 0.0000
O2 13.3159 31.8164 1.4204 45.4519 14.0535
N2 and others 68.9295 164.6964 7.3525 205.9881 63.6904
Total 100.0000 238.9346 10.6667 323.4208 100.0000
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 20°C; 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 0.1586 0.3723 0.0166 1.2635 0.3907
N2O4 1.6256 3.8160 0.1704 15.6755 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
Total 100.0000 234.7462 10.4797 323.4208 100.0000
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 111.7°C; pressure 0.5 atm
vol.% m3 kmol kg mass%

NO 8.8736 21.1968 0.9463 28.3961 8.7799

NO2 8.8362 21.1074 0.9423 43.3531 13.4046
N2O3 0.0059 0.0141 0.0006 0.0479 0.0148
N2O4 0.0187 0.0447 0.0020 0.1835 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
Total 100.0000 238.8758 10.6641 323.4208 100.0000
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 composition and temperature. The gas mixture from the
process, but the waste gas treatment system is a continuous reactor enters the first scrubber (existing) where most of the
system. The oxidizer will play the role of an equalization N2Ox, mainly as N2O3, is absorbed by a 15–20% NaOH
unit and thus help dampen the fluctuations of the gas solution. The remaining N2Ox, also mainly as N2O3, is

123
 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 203.4°C; pressure 0.5 atm
vol.% m3 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 0.0038 0.0090 0.0004 0.0305 0.0094
N2O4 0.0044 0.0105 0.0005 0.0430 0.0133
O2 13.3170 31.8164 1.4204 45.4519 14.0535
N2 and others 68.9351 164.6964 7.3525 205.9881 63.6904
Total 100.0000 238.9151 10.6659 323.4208 100.0000
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

NO oxidation reactor parameters Oxidation without Removed oxidation
parameters in the waste gas
heat removing heat, % of total
treatment system
Degree of NO oxidation 50%; ratio O2:NO = 1:1; pressure 0.5 atm
Removed heat, % 0 50 100
Removed heat, kJ per 1 kg scrap 0 234.8 469.6
Removed heat, kJ per 125 kg scrap 0 23953 58,706
Removed heat, kJ/h (average) 0 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
Average gas mixture flow rate:
m3/h 166.36 166.36 166.36
m3/s 0.04621 0.04621 0.04621
m3/s 0.15999 0.12957 0.09919
3
Oxidation reactor volume, m 6.272 2.560 0.644
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 None 0.312 0.624
(water temperature rise DT = 150°C)
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 20°C; 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 0.0000 0.0000 0.0000 0.0000 0.0000
O2 16.1866 31.8164 1.4204 45.4519 18.0709
N2 and others 83.7894 164.6964 7.3525 205.9881 81.8974
Total 100.0000 196.5600 8.7750 251.5198 100.0000

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Process design of waste gas treatment

Table 9 Oxidation reactor feed and effluent composition per 125 kg scrap at 50% NO oxidation
Component Reactor feed Reactor effluent Final effluent (Second absorber)
3 3
vol.% m vol.% m vol.% m3

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 0.0000 0.0000 1.6256 3.8160 0.0000 0.0000
O2 17.0000 42.4218 13.5535 31.8164 16.1866 31.8164
N2 and others 66.0000 164.6964 70.1593 164.6964 83.7894 164.6964
Total 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 20°C; Pressure 0.5 atm

Table 10 Basic parameters

Parameters Value
of the NOx absorption by
NaOH solution Per 125 kg scrap Average per hour

Final effluent (NO and NO2) as NO2 240 ppm

493 mg/m3
Total degree of absorption of NOx 99.9%
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 8.8
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 Detailed design specifications for the waste gas treat-
Reactor parameters ment system were performed using Aspen Tech simulation
software (HYSYS, Fig. 2) as well as Super Pro designer
Removed heat, kJ per 1 kg scrap 469.6 (Fig. 3), in accordance with hand calculations. The units
Removed heat, kJ per 125 kg scrap 58,706 were manufactured and added to the existing treatment
Removed heat, kJ/h (average) 39,137 system. Samples were taken by Emirate Gold DMCC
Temperature before oxidation, °C 20 chemist and Dubai municipality personnel, where both
Temperature after oxidation, °C 20 parties found that the modified and improved process meets
-1 -1
Reaction rate constant mol l s 50.723 the regulation standards.
Residence time, s 6.49
Average gas flow rate (m3/h) 166.36
Oxidation reactor volume, m3 0.644
Conclusion
Average chilled water flow, m3/h (water temperature rise 0.624
DT = 150°C)
The above recommendations were considered by the
Excess air was fed to the reactor (O2:NO = 1) with reaction heat Emirates Gold DMCC administrators in order to meet the
completely removed; Temperature 20°C; Pressure 0.5 atm
UAE air emission regulations. Based on the analysis of
removed from the gas in the second scrubber by an 8–10% environmental laboratory of Dubai municipality, Emirates
NaOH solution. The mass transfer area of the scrubbers Gold DMCC were able to meet the required UAE regula-
packing, the solution circulation rate and the cooling duty tions for NOx emission. It was also found that using an
were selected in order to attain the desired degree of N2O3 oxidizer prior to the scrubbing system, required a smaller
and NO2 absorption to achieve the regulation residual number of scrubbers in comparison to the conventional
value of NOx of 500 mg/m3 (250 ppm). method of a treatment system consisting only of scrubbers.

123
 A. Aidan et al.

Fig. 2 Aspen HYSYS simulation of Oxidizer

Fig. 3 SuperPro designer simulation of modified process

123
Process design of waste gas treatment

Acknowledgments The authors are grateful to Mr. Mohamed Günther L (2010) NOx separation from drawn off air: a method of
Shekarchy, Director of Emirates Gold DMCC, and Engineer Faisal recovery of a high-quality substance from drawn off air without
Dawood for their continuous support. any waste formation. DGE- Nox-Entfernung aus Abluft. http://
www.dge-wittenberg.de/english/produkte/waescherprogramm/
nox.html. Accessed 20 April 2010
Heidenreich S, Nacken M, Hackel M, Schaub G (2008) Catalytic filter
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