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Chemical Engineering Science 57 (2002) 4831 – 4844

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Simulation of NOx gas absorption under adiabatic condition and comparison with plant data
J. A. Patwardhan, M. P. Pradhan, J. B. Joshi ∗
Institute of Chemical Technology, University of Mumbai, Matunga, Mumbai 400 019, India

Abstract A mathematical model has been developed for the absorption of NOx gases in aqueous solutions of NaOH. The present model is for adiabatic operation, which is an extension of the previous isothermal model of Pradhan and Joshi (Chem. Eng. Sci. 55(7) (2000) 1269). Heat e ects have been considered for gas phase reactions such as the oxidation of NO, dimerisation of NO2 , and formation of N2 O3 , HNO2 and HNO3 . Absorption of NO2 , N2 O3 , HNO2 (g), HNO3 (g), into NaOH solutions is accompanied by large heat e ects which have been incorporated in the model. Evaporation=condensation of water has also been considered. A comparison between isothermal and adiabatic operation has been presented. The model was validated using data from an operating small-scale plant which uses the process of absorption of NOx in NaOH and a good match between plant and simulation results was obtained. Minor modiÿcations were suggested in the existing plant which would improve the selectivity of the product NaNO2 . ? 2002 Elsevier Science Ltd. All rights reserved.

1. Introduction and mathematical model There are many strategies for NOx abatement such as dry processes, wet processes, preventive methods and greener processes (which circumvent NOx generation). Amongst wet processes, the reactive absorption of suitably oxidised NOx in alkalies such as NaOH, Ca(OH)2 , attenuates NOx pollution. Moreover, if their corresponding nitrites NaNO2 , Ca(NO2 )2 , are produced selectively (over nitrates) in this process, the nitrites can be marketed since they have value as corrosion inhibitor, antifreeze agents, reactive intermediates in diazotisation reactions, etc. By tailoring the process and conditions, the encumbrance of NOx abatement can be converted to a proÿtable activity. However, the genuine complexity of this NOx absorption process impedes the use of currently available industrial simulation software packages to simulate the NOx absorption phenomena in entirety. Pradhan and Joshi (2000) have presented a mathematical model for the multiple component gas absorption with multiple reactions for the case of NOx absorption in aqueous solutions of NaOH. They have given a stepwise procedure for the estimation of overall rate of absorption by consi∗ Corresponding author. Tel.: +091-22-414-5616; fax: +091-22-414-5614. E-mail address: jbj@udct.ernet.in (J. B. Joshi).

dering (i) the gas phase reaction of NO oxidation (ii) gas phase equilibria between the components NO, NO2 , N2 O3 , N2 O4 , HNO2 , HNO3 and H2 O, (iii) gas phase mass transfer of NO, NO2 , N2 O3 , N2 O4 , HNO2 , HNO3 and H2 O (iv) interfacial equilibria and (v) liquid phase mass transfer with chemical reaction for NO2 , N2 O3 , N2 O4 , HNO3 and HNO2 . They have also analysed the important issue of selectivity of nitrite against nitrate. The following are the overall liquid phase reactions: 2NO2 (l) + 2OH− (l) → NO− (l) + NO− (l) + H2 O(l); (1) 2 3 N2 O3 (l) + 2OH− (l) → 2NO− (l) + H2 O(l); 2 (2)

N2 O4 (l) + 2OH− (l) → NO− (l) + NO− (l) + H2 O(l); (3) 2 3 HNO2 (l) + OH− (l) → NO− (l) + H2 O(l); 2 HNO3 (l) + OH− (l) → NO− (l) + H2 O(l): 3 (4) (5)

It can be seen from Eqs. (1) to (5) that the nitric oxide (NO) does not react with NaOH on its own. One mole of NO needs one mole of NO2 to form either N2 O3 or HNO2 and the subsequent reactions are given by Eqs. (2) and (4), respectively. The decrease in NO concentration can also occur via the gas phase oxidation reaction: 2NO(g) + O2 (g) → 2NO2 (g): (6)

0009-2509/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 0 0 9 - 2 5 0 9 ( 0 2 ) 0 0 2 7 5 - 0

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J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844 Table 1 Reaction 2NO(g) + O2 (g)→ 2NO2 (g) 2NO2 (g)
K2 K1

The product NO2 reacts with NaOH according to Eq. (1). In addition to this reaction, NO2 gets converted to N2 O4 and HNO3 , which in turn react with NaOH according to Eqs. (3) and (5), respectively. Because of these reactions, the overall rate of NO2 absorption is much higher than NO absorption. However, the reactions that enhance the rate of NO2 absorption unfortunately result in poorer selectivity of nitrite (Eqs. (1) and (3)). Pradhan and Joshi (2000) have presented the e ects of pressure, temperature and NO=NO2 ratio on selectivity and rates of absorption. For this purpose, they considered isothermal conditions. More details have been given by Pradhan and Joshi (1999). This model needs to be augmented by including all the heat e ects due to gas and liquid phase reactions. Moreover, it is simpler to operate packed column sections in a plant in an adiabatic mode than isothermal mode. Hence, a model has been formulated to include heat e ects and simulation adiabatic operation. 1.1. Model for column performance A mathematical model was developed for the performance of a countercurrent packed column, the salient features of which are given below. The following assumptions were made: 1. Gas and liquid phases move in a plug ow manner. 2. Liquid hold-up is uniform throughout the column. Therefore, the values of e ective interfacial area, the mass and heat transfer coe cients are also uniform throughout the column. 3. Gases follow ideal gas behaviour. 4. No concentration and temperature gradients in the radial direction. 5. The column is operated under steady-state conditions. 1.1.1. Mass balance for the gas phase Let Yx denote the moles of gaseous component x per mole of inerts in the gas phase. Mass balance across a di erential height dh gives: 1. Balance of reactive divalent nitrogen:
∗ O O G dYNO = −S dhk1 (PNO )2 PO2 G

Kcal=gmol H1 = −27:22 H3 = −13:61
K4

N2 O4 (g)
K3

NO(g) + NO2 (g)

N2 O3 (g)

H4 = −9:55 2HNO2 (g) H7 = −9:80 H6 = −8:55 H8 = −49:82 H10 = −30:16 H9 = −36:13 H12 = −19:46 H11 = −31:00

NO(g) + NO2 (g) + H2 O(g)
K5

3NO2 (g) + H2 O 2HNO3 (g) + NO(g) 2NO2 (l) + 2NaOH → NaNO2 + NaNO3 + H2 O(l) 2N2 O3 (l) + 2NaOH → 2NaNO2 + H2 O(l) N2 O4 (l) + 2NaOH → NaNO2 + NaNO3 + H2 O(l) HNO2 (l) + NaOH → NaNO2 + H2 O(l) HNO3 (l) + NaOH → NaNO3 + H2 O(l)

represents the loss in the gas phase divalent nitrogen due to N2 O3 absorption. Term 4: Similarly the reaction of HNO2 formation in Table 1 shows that one mole of HNO2 corresponds to 0:5 mol of N2 O3 , which would in turn need 0:5 mol of NO. Term 4 is the loss of gas phase divalent N due to the HNO2 absorption. Term 5: The ÿfth equation in Table 1 shows the equivalence of 1 mol of HNO3 with 1:5 mol of NO2 and (−0:5) mol of NO. Hence, term 5 is incorporated in the divalent N balance. Eq. (7) is written compactly as
∗ dYNO S O O = − [k1 (PNO )2 PO2 dh G G

+ RgNO (8)

+ RgN2 O3 + 0:5(RgHNO2 − RgHNO3 )]: 2. Balance of total reactive nitrogen:
∗ S dYN = − [RgNO + RgNO2 + 2RgN2 O3 dh G

+ 2RgN2 O4 + RgHNO3 + RgHNO2 ]: 3. Balance of water (both reactive and free):
∗ dYH2 O S = − [RgH2 O + 1=2RgHNO3 + 1=2RgHNO2 ]: dh G

(9)

(10)

− S dhRgNO − S dhRgN2 O3 (Term 2) (Term 3)

4. Oxygen balance: dYO2 1 S O O =− [k1 (PNO )2 (PO2 ) G ]: dh 2 G 1.1.2. Mass balance for the liquid phase 5. Hydroxide ion balance: dXOH− S = [2(RaN2 O4 + RaN2 O3 ) + RgHNO3 dh L +RgHNO2 + RaNO2 ]: 6. Balance of nitrate ion: dXNO− dh
3

(Term 1)

(11)

−S dh0:5RgHNO2 + S dh0:5RgHNO3 (Term 4) (Term 5) (7)

Term 1: From Table 1 it can be seen that when NO is oxidised to NO2 , one divalent N is converted to a tetravalent species, hence term 1 in the above Eq. (7) represents the loss of divalent N due to NO oxidation. Term 2: It refers to the kmol=s of NO lost by the gas, due to mass transfer across the gas–liquid interface. Term 3: Table 1 shows that for 1 mol of N2 O3 to form, it needs one mole of NO (divalent nitrogen); hence term 3

(12)

S = − [RaN2 O4 + RgHNO3 + 1=2RaNO2 ]: L

(13)

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7. Balance of nitrite ion:
− dXNO2 S = − [RaN2 O4 + 2RaN2 O3 dh L

Table 1. It will be assumed that the heat liberated is taken up by the liquid phase and the interface is always saturated with water vapour. Contribution to the heat changes are due to the following reactions. (14) 1.3.1. Gas phase reactions (a) The rate of formation of N2 O3 in the gas phase, from NO and NO2 in the di erential element (dh) is given by Rate of N2 O3 formation = N2 O3 leaving at exit− (kmol=s) (kmol=s) N2 O3 entering at inlet + N2 O3 absorbed (kmol=s) (kmol=s) (N2 O3 )f = (N2 O3 )e − (N2 O3 )i + (N2 O3 )a ; (N2 O3 )f = G[(YN2 O3 )e − (YN2 O3 )i ] + RaN2 O3 S dh: (17) (18)

+ RgHNO2 + 1=2RaN O2 ]:

Eqs. (8) – (14) are coupled ÿrst-order di erential equations. The di erential balances are integrated over the height of the column from bottom to top. The starting point for the column design is the speciÿcation of the quantity and quality of the inlet gas stream. The problem deÿnition speciÿes the outlet gas composition from the column. It also speciÿes the inlet composition of liquid stream (which may be aqueous solution of NaOH with known amounts of nitrite and nitrate). As regards to the boundary conditions for the liquid phase, these were adjusted by trial–error. To start the integration of Eqs. (11) – (13), the values of XOH− , XNO− 3 and XNO− were guessed at the column bottom and adjusted 2 so as to satisfy the top boundary conditions. The simulation marched with respect to height of the column. At each height, the gas bulk concentration was run though a subroutine for calculating the equilibrium gas composition which would depict the equilibria shown in the gas phase reactions of Table 1 to be instantaneously attained. 1.2. Estimation of design parameters Values of design parameters such as e ective interfacial area and mass transfer coe cient are needed in the model. These were estimated by using correlations reported in the published literature. Details pertaining to these correlations have been given by Suchak, Jethani, and Joshi (1990). For the estimation of the rates of mass transfer with chemical reaction in the liquid phase for and NO2 , N2 O4 and N2 O3 , the values of physico-chemical parameter Hx (kD)x have been estimated by several workers. These results have been analysed by Joshi, Mahajani, and Juvekar (1985) and Suchak et al. (1990) and the set of values which are recommended by them have been used. Rax = Hx
I (kD)x Px a

The rate of heat generation due to N2 O3 formation is Q1 = [(N2 O3 )f ] H4 : (19)

(b) From the component balance of N2 O4 , the rate of formation of N2 O4 in the gas phase, from NO2 in the di erential element (dh) is given by (N2 O4 )f = (N2 O4 )e − (N2 O4 )i + (N2 O4 )a ; (N2 O4 )f = G[(YN2 O4 )e − (YN2 O4 )i ] + RaN2 O4 S dh: The rate of heat generation due to N2 O4 formation is Q2 = [(N2 O4 )f ] H3 : (22) (20) (21)

(c) From the component balance of HNO3, the rate of formation of HNO3 in the gas phase, in the di erential element (dh) is given by (HNO3 )f = (HNO3 )e − (HNO3 )i + (HNO3 )a ; (HNO3 )f = G[(YHNO3 )e − (YHNO3 )i ] + RaHNO3 S dh: The rate of heat generation due to HNO3 formation is Q3 = [(HNO3 )f ] H6 : (25) (23) (24)

where x = N2 O3 ; N2 O4 ; 2 I (kD)NO2 (PNO2 )3=2 a: 3

(15) (16)

RaNO2 = (HNO2 )3=2 1.3. Heat balance

(d) From the component balance of HNO3 , the rate of formation of HNO2 in the gas phase in the di erential element (dh) is given by (HNO2 )f = (HNO2 )e − (HNO2 )i + (HNO2 )a ; (HNO2 )f = G[(YHNO2 )e − (YHNO2 )i ] + RaHNO2 S dh: The rate of heat generation due to HNO2 formation is Q4 = [(HNO2 )f ] H7 : (28) (26) (27)

Oxidation of NO, formation of N2 O4 and N2 O3 in the gas phase, absorption of NO2 ; N2 O4 , N2 O3 and the liquid phase reactions are exothermic. The decomposition of HNO2 , however, is endothermic. Therefore, signiÿcant heat changes occur. The values of physico-chemical parameters, such as reaction rate constants, equilibrium constants, solubilities, vapour pressures and di usivities, depend upon temperature. The heat of reactions in the liquid phase are given in

(e) NO is used in the formation of HNO2 and N2 O3 and it is liberated during HNO3 formation. The rate of NO oxidised

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in the element of height dh is (NO)o = [(NO)i − (NO)e ] − (N2 O3 )f − (1=2)(HNO2 )f + 1=2(HNO3 )f ; A = G[(YNO )i − (YNO )e − (YN2 O3 )e + (YN2 O3 )i ]; B = G[ − 1=2(YHNO2 )e + 1=2(YHNO2 )i ]; C = G[1=2(YHNO3 )e − 1=2(YHNO3 )i ]; D = [[RaN2 O3 + 1=2RaHNO2 − 1=2RaHNO3 ]S dh]; (NO)o = A + B + C − D: by (30) (29)

The rate of heat generation due to NO oxidation is given (31)

Q5 = [(NO)o ] H1 :

1.3.2. Heat changes due to water evaporation From the component balance of H2 O, the rate of water evaporation in the di erential element dh was obtained by (H2 O)v = [(H2 O)e − (H2 O)i ] + 1=2(HNO3 )f + 1=2(HNO2 )f ; (32)

(F) = G[(YH2 O )e − (YH2 O )i + 1=2(YHNO3 )e − 1=2(YHNO3 )i ]; (I ) = (1=2)G[(YHNO2 )e − (YHNO2 )i ] + 1=2(RaHNO3 )S dh + 1=2(RaHNO2 )S dh; (H2 O)v = [(F) + (I )]; Q6 = [(H2 O)v ]
W:

(33) (34) (35)

The speciÿc heat of the gas being low compared to that of the liquid, the overall e ect is re ected by the rise in the bulk liquid temperature as it ows down the column. As mentioned before, it was assumed that there was plug ow and that there were no radial temperature gradients in the column. However, the exothermic reactions of hydrolysis of NO2 , N2 O3 , N2 O4 as well as neutralisation of HNO2 and HNO3 all occur within a small fraction of the liquid ÿlm, close to the interface. This will increase the temperature of the interface as compared to that of the liquid bulk. However, the conductivity of the liquid will try to disperse the heat to attain a uniform temperature. Most important of all, the rise in temperature of the interface will increase the vapour pressure of water at the interface and lead to mass transfer of water into the bulk gas. The evaporation of water will take up majority of the heat of the liquid phase reactions. The combined e ect of these factors (as well as the heat of gas phase reactions) will lead to the development of a temperature proÿle in the gas and liquid ÿlm, at steady state. Since it was assumed (for simplicity) that the temperature of the liquid is the same throughout the ÿlm in the current model, it was sought to check the assumption. The magnitude of the maximum expected temperature rise at the interface was estimated as follows. In the simulation of the plant case (which is described in detail in Section 2.3), the highest rates of NOx absorption are encountered at the bottom of the ÿrst column, since the gas phase NOx is the maximum there. Close to the column bottom, the speciÿc rate of heat evolution due to exothermic reactions in the liquid phase (QL =S dh) was found (from simulation) to be 305:08 kcal=s=m3 of reactor volume. If this heat were to be taken up by a rise in the liquid ÿlm temperature and the evaporation of water corresponding to the increased interfacial temperature (and hence vapor pressure), then
I O QL tC = kG; H2 O a[PH2 O − PH2 O ] WS

dhtC (38)

The total heat change in the gas phase is given by QG = Q 1 + Q 2 + Q 3 + Q 4 + Q 5 + Q 6 :

+

L (S

I O dha L )CP; L [TL − TL ]; W tC

QL I O tC = kG; H2 O a[PH2 O − PH2 O ] S dh +
I L a L CP; L [TL

1.3.3. Heat changes due to absorption with chemical reaction In the absence of information on heats of dissolution of gases, the information on heats of formation of reactants and products was used to compute the heats of reactions. Heats of reaction are given in Table 1. Hence, heat liberated due to absorption with chemical reaction in the liquid phase is expressed as QL = (RaNO2 H8 + RaN2 O4 H9 + RaN2 O3 H10 + RaHNO2 H11 + RaHNO2 H12 )S dh: (36) Total heat change in the di erential volume is the summation of all the heat changes: QT = QG + QL : (37)

O − TL ]:

(39)

In the above equation, tC = 0:19 s, kG; H2 O = 0:004258 kmol= O m2 s=(kN=m2 ), a = 112 m2 =m3 , PH2 O = 9:4511 kN=m2 , −6 m, CP; L ∼ W = 9720 kcal=kmol, L = 15: × 10 O I 1000 kcal=kg=K, TL = 317:91 K, the unknowns is TL since I I PH2 O = f(TL ). Upon solving the above equation, the value I of TL = 318:04 K. Thus, the interface temperature rise worked out to be (318:04 − 317:91) = 0:13 K. Thus, the maximum calculated temperature rise at the interface was itself negligible. Throughout the rest of the column too, it is expected to be lower due to lower absorption rates. This justiÿes the assumption of uniform liquid temperature in the liquid ÿlm. Since the Henry’ constant, kinetic rate constant as well as di usivity have dependency on the √ temperature, the overall dependence of Hx (kD)x has been

J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844

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expressed as Hx (kD)x = Bx e−
Ex =RT

Table 2

;

where x = NO2 ; N2 O3 ; N2 O4 :

(40)

Pradhan and Joshi (2000) have given the overall values of E=R for NO2 , N2 O3 , N2 O4 . The overall E for N2 O3 is −9128 kcal=kmol. If temperature of the interface is hotter than the bulk by say 0:13 K, then a change in the temperature from 317.91 to 318:04 K at the interface would a ect √ the value of Hx (kD)x by a factor of (1.011). Such a temperature change is not likely to change the regime of mass transfer accompanied by chemical reaction. 2. Results and discussion For simulation studies, a packed column was considered, the details of the design and operating parameters of which are given in Table 2. 2.1. Parametric sensitivity The results of simulation of adiabatic operation are presented here as also a comparison with the isothermal case. Fig. 1 shows the typical liquid side temperature proÿle attained in the column when the liquid enters at di erent inlet temperatures, and for di erent values of concentration of inlet NOx in the entering gas. In isothermal operation, the temperature had been assumed to be the same throughout the column and equal to the liquid inlet temperature, based on the assumption that the heat transfer was e cient. However, when the heat e ects were incorporated in the adiabatic model, it was found that there was a signiÿcant temperature gradient in the bottom section of the column. This was due to the fact that, in the bottom section, the gas entering with high concentration of NO was oxidised and NO2 was consumed by absorption=reaction rapidly within a short height. This led to a sharp increase in the liquid temperature due to the overall exothermicity. (Compare cases with liquid inlet ◦ temperature = 20 C, inlet NOx = 9:1 mol%, adiabatic and isothermal operation in Fig. 1). Further up the column, the large height was utilised only for removal of small amounts of NOx gases with small heat e ects. Hence, the temperature of the liquid increased slowly initially as it travelled from top to bottom and increased rapidly in the bottom section. The above analysis has two implications that interstage cooling is not required in the upper zone of absorption and the highest temperature attained in the lower section must be considered in the mechanical design. When the inlet NOx content is higher, then the heat e ects in the bottom section are even more prominent and lead to higher temperature peak or conversely, liquid inlet temperature should be lower. (Cases with inlet NOx = 20 mol%, liq◦ uid inlet temperature = 20 C and inlet NOx = 25 mol%, liq◦ uid inlet temperature = 5 C, in Fig. 1). When the gas stream

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12.

Column diameter = 1:9 m Type of packing: stainless-steel pall rings Diameter of packing = 12:7 mm Superÿcial liquid velocity = 4 mm=s Total NOx at the inlet of packed column = 91; 000 ppm Flow rate of inert = 0:0513 kmol=s Oxygen to total NOx ratio at the inlet of column = 0:82 Total H2 O at the inlet of packed column = 1; 06; 800 ppm Total moles of gas=kmol of inert = 1:37 Average molecular weight of the gas = 28:7 E ective interfacial area = 46:69 m2 =m3 True gas side mass transfer coe cient kG a = 5:105 × 10−4 kmol= (m3 =s(kN=m2 ))

contains high concentration of NOx (¿ 10 mol%) such as the gas stream from processes involving oxidation=nitration using nitric acid, which may contain higher than 50 mol% NOx , the initial heat e ects due to absorption make it unfavourable to use a packed column for the same. Hence the initial absorption should be carried out in a reactor such as mechanically agitated contactor or bubble column, which can take care of the heat removal requirements. In this way a lean gas containing about 10 mol%NOx may be attained, which is suitable for being treated in a packed column where the advantage of plug ow is utilised to e ectively reduce the NOx to very low levels. Fig. 2 shows the temperature proÿle attained by the liquid at di erent inlet temperatures of the gas, for adiabatic operation, with the same inlet water concentration. Since the gas enthalpy is very low compared to the liquid phase (under the present gas–liquid ow rates), the change in the inlet gas temperature has small heat e ects. It can be seen from Fig. 2 that beyond 0:1 m of packed height, the temperature proÿles of the liquid tend to be merged with one another. However, there is a drop in the liquid temperature close to ◦ ◦ the bottom. When the inlet gas is hotter (150 C=200 C), there is a large driving force for water to evaporate from liquid to gas. This evaporation leads to a cooling e ect and the liquid temperature falls at the bottom of the column. Fig. 3 shows the temperature proÿle attained by the liquid when the water content in the inlet gas is varied. Consider the case of very dry inlet gas (H2 O = 1000 ppm). As the liquid travels from top to bottom, its temperature increases very slowly initially (as explained previously). Then the heat evolved due the rapid absorption=reaction in the lower section leads to an increase in the temperature close to the bottom section. Further down towards the lowest section of the column, evaporation of water takes place so as to saturate the entering dry gas. This consumes heat and thus, the liquid temperature falls. The simulations were carried out to calculate the height of packed column required to attain the desired NOx composition for all of the above cases. Fig. 4 shows the ratio of height of packed column required for adiabatic operation to that for isothermal operation, for various exit concentrations of NOx . It can be seen that the isothermal operation

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Fig. 1. Liquid side temperature proÿle in the column: adiabatic and isothermal operation at various liquid inlet temperatures and inlet gas composition. ◦ NO∗ =NO∗ ratio = 10, H2 O = 106; 800 ppm, Pressure = 0:1 MPa, b = 0:82, Gas inlet temperature = 50 C, Outlet NOx = 2500 ppm. 2

Fig. 2. Liquid side temperature proÿle in the inlet temperature under adiabatic condition. total = 91; 000 ppm, NO∗ =NO∗ ratio = 10, 2 Pressure = 0:1 MPa, liquid inlet temperature = NOx = 2500 ppm.

column : e ect of gas Inlet concentration of H2 O = 106; 800 ppm, ◦ 30 C, b = 0:82, Outlet

Fig. 3. Liquid side temperature proÿle in the column: e ect of water content in the inlet gas, under adiabatic condition. Inlet concentration of total ◦ NOx = 91; 000 ppm, NO∗ =NO∗ ratio = 10, Gas inlet temperature = 50 C, 2 ◦ Liquid inlet temperature = 30 C, Pressure = 0:1 MPa, b = 0:82, Outlet NOx = 2500 ppm.

requires lower heights than adiabatic operation. The height required for isothermal operation is lower because oxidation of NO to NO2 is favoured at low temperature. Majority of the NOx removal takes place in the bottom section, in which the NOx concentration is very high, the rates are high and there is only slight di erence in the height required for removal upto a gas concentration of 10; 000 ppm NOx under adiabatic and isothermal condition. Beyond this concentration, the temperature proÿles in the adiabatic and the isothermal case almost coincide and so almost no di erence in the height for NOx removal is expected. This discussion highlights that the choice of operating the packed column adiabatically (which is simpler to operate in reality) will not lead to too much increase in height. Further results from simulation showed that the enthalpy of the gas phase being very low, the variation in the inlet temperature of the gas has little e ect on the column height requirement. Water content in the inlet gas has a marked e ect on the height required for adiabatic operation. Figs. 5 and 6 show the proÿles of NO and H2 O, respectively, in the gas phase, along the height of the column. When the inlet gas is relatively dry, as it enters the lower section of the column, evaporation of water leads to reduced temperature. Oxidation of NO is very rapid at low temperature. NO2 , once formed, is consumed rapidly by absorption=reaction. Also evaporation of water lowers the calculated value of NOx ppm in the gas phase, since additional moles of water enter the gas phase to increase the total number of moles. Hence, initially, the fall in NOx content of the gas is faster for the gas of relatively dry gas (inlet H2 0=1000 ppm) as compared to the case of wet gas (inlet H2 0 = 106; 800 ppm). However, it can be seen that further up the column the NO ppm falls faster in the case of (inlet H2 0 = 106; 800 ppm) than that of (inlet H2 O=1000 ppm) and the height required to attain 2500 ppm outlet NOx in the two cases is 76 and 93 m, respectively. This is explained as follows. From the proÿle of water ppm in Fig. 6, the water ppm moves towards a steady value and

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Fig. 4. Ratio of column height for adiabatic operation to that for isothermal operation at various outlet NOx concentrations. Inlet concentration of total ◦ NOx = 91; 000 ppm, NO∗ =NO∗ ratio = 10, Gas inlet temperature = 50 C, Pressure = 0:1 MPa, b = 0:82. 2

Fig. 5. Concentration proÿle of NO in the gas phase for various concentrations of water content in the inlet gas. Inlet concentration of total NOx =91; 000 ppm, ◦ ◦ NO∗ =NO∗ ratio = 10, Gas inlet temperature = 50 C, Liquid inlet temperature = 30 C, Pressure = 0:1 MPa, b = 0:82, Outlet NOx = 2500 ppm. 2

the three curves tend to merge. So, the e ect of water ppm is not really expected beyond the bottom section of the column. However, to the contrary, the NOx removal rate is higher in the case of wet gas. The answer lies in the corresponding temperature proÿles (shown in Fig. 3) which evolve as a consequence of water evaporation and heats of reactions. Above a height of 1 m, the liquid temperature proÿle for the case of dry gas (1000 ppm H2 O) is at a higher level than that for the wet gas (106; 800 ppm H2 O). Therefore, above 1 m height, the rate of NO oxidation is less and the partial pressure of NO remains at a higher level in the case of dry gas. 2.2. Optimisation Pradhan and Joshi (2000) have explained the dependence of selectivity and the rate of absorption on NO∗ =NO∗ 2

ratio, temperature, total pressure and partial pressure of NOx . High NO∗ =NO∗ ratio, high temperature and low 2 pressure are favourable conditions for better selectivity. However, under these conditions, the rates of oxidation are poor and result in huge equipment volumes. Therefore, it was thought desirable to establish optimum design strategy. 2.2.1. Simultaneous oxidation and absorption In this case, the packed volume is itself used for the gas phase oxidation as well as absorption in the liquid phase. For this case, the height required for the various exit NOx concentrations is shown in Fig. 7, Case 1. It can be seen that the column height increases with a decrease in the exit NOx concentration. Detailed study of the rates of oxidation

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Fig. 6. Concentration proÿle of water in the gas phase, for various concentrations of water content in the inlet gas. Inlet concentration of total ◦ ◦ NOx = 91; 000 ppm, NO∗ =NO∗ ratio = 10, Gas inlet temperature = 50 C, Liquid inlet temperature = 30 C, Pressure = 0:1 MPa, b = 0:82, Outlet 2 NOx = 2500 ppm.

Fig. 7. Comparison of column height required for various schemes: Case 1—simultaneous oxidation and absorption; Case 2—oxidation and absorption stages in series; Case 3—oxidation and absorption in parallel.

and absorption along the height of the column revealed that most of the volume is utilised for oxidation with relatively small volume required for absorption. This means that much of the packing is unnecessary. This leads to the idea of having interstage empty oxidation sections between packed volumes for absorption. This is discussed below. 2.2.2. Oxidation and absorption stages in series To achieve a desired selectivity, at a given set of temperature, pressure and NOx concentration, the oxidation volume should be adjusted in such a way that NO∗ =NO∗ ratio 2 does not exceed the permissible limit. This further necessitated the strategy of oxidation and absorption stages in series as shown in Fig. 8A. Some typical results are shown in

Table 3. For the selection of absorption heights, various levels of per cent absorption of NO2 have been considered. The oxidation volume was selected for getting the desired NO∗ =NO∗ ratio. From Table 3 it can be seen that for the ÿrst 2 packed section, the height required increases with increase in the percentage NO2 absorption. Higher percentage NO2 absorption in this section leads to lower NOx ppm and higher NO=NO2 ratio at the inlet to the next oxidation section. Hence the oxidation height increases. In this way, absorption and oxidation proceed in the alternate sections. However, when the speciÿed percentage NO2 absorption is high, say 99.9%, the NOx levels reduce rapidly in the packed sections and a few packed and empty sections are required to attain the same outlet NOx concentration of 2500 ppm. This leads

J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844

4839

Fig. 8. (A) oxidation and absorption stages in series: schematic diagram of column with alternate packed and empty sections; (B) oxidation and absorption in parallel: schematic diagram of packed column with oxidation chamber and side streams.

to a zigzag and non-uniform trend in the variation of the total height required, with the percentage NO2 absorption. For example, when the percentage NO2 absorption is 85%, the NOx content at the outlet of the second last packed section is 3202 ppm and 15:93 m are required for oxidation to the desired NO=NO2 ratio; but when the percentage NO2 absorption is 90%, the NOx content at the outlet of the second last packed section is 2570 ppm, which is close to the desired outlet NOx ppm and yet 23:64 m are required for oxidation to the desired NO=NO2 ratio. Thus the trends in the variation of the total height required, with the percentage NO2 absorption is zigzag. It can be seen from Table 3 that for the said conditions, a speciÿcation 99.9% NO2 absorption gave least total height of the column and also very few number of stages. This optimum depends on operating temperature, pressure and excess O2 ; refer to Fig. 7, Case 2. It can be seen that the packed height is a very small part of the total (packed + empty) height required for a desired outlet ppm. 2.2.3. Oxidation and absorption stages in parallel In the series mode of operation, the oxidation and absorption volumes are given in Table 3. It can be seen that the oxidation volume increases with a decrease in NOx concentration. The huge oxidation volumes increase the overall height of the column. In view of this, it was thought desirable to carry out oxidation separately and that too when the NOx concentration is the highest. Such a strategy has been schematically shown in Fig. 8B. The inlet gas stream is divided into two streams. One enters the packed column and the other is sent to an oxidiser. In the oxidiser, NO is oxidised to a high level (say 90%). The oxidised gas is used to adjust the NO∗ =NO∗ ratio at the inlet of each packed section 2 by mixing the oxidised gas with the gas leaving the liquid as shown in Fig. 8B. The height required for mixing has been

assumed to be 0:2 m. The results are given in Fig. 7. It can be seen that, the parallel strategy is relatively advantageous than the series strategy. It results in drastically lower heights and therefore, one can attain much lower outlet NOx levels (even 100 ppm or less) in low-volume columns. 2.3. Model validation with industrial data A small-scale manufacturing plant provided its operating data. Their main process consisted of oxidation of organic compounds using HNO3 . R–CH3 + 2HNO3 → R–COOH + 2NO + 2H2 O; R–CH3 + 6HNO3 → R–COOH + 6NO2 + 4H2 O; (41) (42)

where R is an aromatic group. The NOx gases were generated as a byproduct and posed a pollution hazard. The reactor of gases mainly consisted of NOx , CO2 (the carbon dioxide also being generated due to the oxidation) and water vapour. They were ÿrst cooled to condense out water vapour. For the purpose of pollution abatement as well as the recovery of NOx , three columns consisting of one oxidation column and two packed columns were used. The details pertaining to column dimensions and internals are given in Table 4. The two absorption columns were of 0:3 m ID and 4:04 m total height, with packed height of 3 m. The oxidiser for NO oxidation was of 0:4 m ID and 3:4 m height. The NOx recovery section of the plant is shown in Fig. 9. The NOx gas stream was passed through the ÿrst absorption column. A circulation loop was used for the liquid phase as shown in Fig. 9. The exit gas from the absorber was mixed with air and passed through the oxidiser. The oxidised stream was passed through the second absorption column. The initial concentration of NaOH fed to both the columns was in the

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J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844
packed empty height second last height (m) height (m) (m) packed section (A) (B) (A+B) outlet

NOx ppm at

Table 4 Details of small-scale industrial set-up
3202.0 2570.0 2621.0 2954.0 3259.7

Absorption column I Diameter, mm Packed height Total straight height, mm Packing type Size, mm Material Liquid distributor Heat transfer area of the heat exchanger, m2 Number of support plates 300 3000 4040 Pall rings 25 SS 316 1 2.1 1

Oxidiser 400 — 3400 — — — — — —

Absorption column II 300 3000 4040 Pall rings 25 SS 316 1 1.8 1

Outlet NOx = 2500 ppm

Total

9.13 12.03 15.93 1.53 11.65 15.71 23.64 1.73 15.93 24.68 1.85 22.95 2.08 6.34

13

14

63.47 82.49 81.65 72.95 57.80

Total

64.99 84.22 83.50 75.02 64.15

Total

range 20 –25 wt%. The liquid circulation was maintained in such a way as to wet the packings and continued till the NaOH was almost consumed. Heat exchanger was provided in the circulation loop for the removal of the heat of reaction. The product containing NaNO2 , NaNO3 and residual NaOH in water was then withdrawn from the liquor recirculation tank. The temperature and concentration of the gas phase was measured at the inlet and outlet of all the columns. The absorption in each column was carried out under adiabatic conditions. The concentration and temperature of the liquid phase was measured with respect to time. In the plant, the gas was owing continuously into and out of the column. With the liquid being recirculated, the NaOH concentration changed with time, indicating a semi-batch process. Only the liquid phase composition would change with time. However, Eqs. (15) and (16) show that the rate of absorption was independent of the liquid NaOH concentration as long as OH− was not the limiting reactant. Hence, the present steady-state model of the counter current absorber could predict the rate of NOx removal and selectivity of the plant set-up. The contact time being more than 50 fold of the typical di usion time, it was well to assume that a steady-state concentration proÿle is attained in the gas and liquid ÿlm at a given cross-section of the absorber. The rate of absorption was controlled by the gas composition, gas side and liquid side resistances, and chemical reactions in the liquid ÿlm (Pradhan & Joshi, 2000). Table 5 shows the detailed comparison of the plant data and the simulation results. It can be seen that there is a good agreement between the model predictions and the experimental observations. For the ÿrst absorption column, the observed and predicted values of NOx removal e ciency were 55.7% and 55.4%, respectively. The observed and predicted values of selectivity were 99.1% and 98.5% nitrite, respectively. For the second absorption column, the observed and predicted values of NOx removal e ciency were 99.9% and 99.99%, respectively. The observed and predicted values of selectivity were 85.4% and 86.1% nitrite, respectively. A further interesting observation from the simulation results was that, in the present case, in the ÿrst absorption column,

12

Gas inlet temperature = 50 C Pressure = 0:1 Mpa ◦ Liquid inlet temperature = 30 C

Empty section height (m)

Inlet NOx = 91; 000 pppm NO=NO2 ratio = 10 H2 O = 106; 800 ppm b = 0:82

Packed section height (m)

Table 3

absorption in packed section

%NO2

85 90 94 98 99.9

0.07 0.08 0.10 0.14 3.74

1

0.09 0.11 0.12 0.15 1.03

2

0.09 0.11 0.12 0.15 0.23

3

0.10 0.11 0.12 0.15 0.22

4

0.10 0.11 0.12 0.15 0.22

5

0.10 0.11 0.13 0.16 0.23

6

0.10 0.12 0.13 0.16 0.23

7

0.10 0.12 0.14 0.16 0.23

8

0.11 0.12 0.14 0.16 0.23

9

0.11 0.12 0.15 0.18

10

0.12 0.13 0.15 0.18

11

0.12 0.13 0.15 0.18

12

0.12 0.12 0.12 0.49 0.60 0.13 0.13 0.13 0.53 0.65 0.15 0.15 0.56 0.79 0.2 0.60 0.85 1.25 2.15

13

14

15

1

2

0.81 0.90 0.96 1.06 2.95

3

0.97 1.07 1.20 1.35 4.02

4

1.19 1.32 1.80 2.05 6.44

5

1.76 1.97 2.33 2.69 9.19

6

2.14 2.50 3.03 3.60 13.1

7

2.68 3.20 4.01 4.80 18.7

8

3.48 4.21 6.25 7.56

9

5.34 6.51 8.48 10.60

10

6.91 8.64 11.63 14.84

11

J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844

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Fig. 9. Schematic representation of small-scale industrial set-up.

most of the NOx removal takes place within a very small height (¡ 0:12 m) of the column. Beyond this height, only NO (among the NOx components) remains in the gas phase. NO being inert in the absence of O2 , no signiÿcant NOx removal takes place further in the remaining 2:8 m packed height, indicating redundancy of packings. The predicted ◦ top liquid temperature was 38:2 C, whereas the plant read◦ ing was 40 C. This di erence may be due to heat losses to the surroundings in the actual plant. For the second column, ◦ the predicted top liquid temperature was 41:1 C, whereas ◦ the plant reading was 42:5 C. 2.3.1. Suggestions for improving the plant performance The match between model and plant data being satisfactory, the following plant problem was addressed. From Table 5 it can be seen that the ÿrst column gives a product (nitrite) selectivity of 98.5% whereas the second column gives a selectivity of 86.1%. In the plant, the product of each column is crystallised to get high purity NaNO2 and some NaNO2 is lost with the NaNO3 . In the case of the product from the second column, signiÿcant loss occurs because of low selectivity. Hence, simulation was used to suggest a strategy to improve performance. The e ects of total NOx concentration, internal NOx composition (NO∗ =NO∗ ratio), tem2 perature and pressure on selectivity have been reported in detail by Pradhan and Joshi (1999). For any given total NOx concentration, temperature and pressure, there is a critical NO∗ =NO∗ ratio above which a selectivity greater than say 2 99% can be obtained. If the NO∗ =NO∗ ratio is lower than the 2 critical ratio, then the unfavourable reactions of nitrate formation occur and selectivity will be reduced. However, the

rate of NOx removal is high. Such is the case in the second absorption column of the plant. If the oxidation is adjusted to get higher NO∗ =NO∗ at the inlet of the second absorber, 2 then higher selectivity will be obtained, but the rate of NOx removal will be lower. The above-mentioned case is summarised as Case A in Table 6. The overall NOx removal efÿciency was 99.996% and the overall nitrite selectivity was 92.3%. This case ensured that the process became pollution free but product selectivity required improvement. To tackle the over-oxidation, the next simulation was carried out with all the inlet conditions same as in Table 3, except that the air supply was reduced such that the ratio of O2 =NO at the inlet of the oxidiser was reduced from 0.32 to 0.25. But it can be seen from Table 6, Case B, that though the selectivity in the second column increases to 95%, the NOx removal e ciency reduces and the ppm of NOx in the exit gas is 35; 841 ppm which is not at all acceptable by the norms of pollution. Hence, Case C was simulated in which the conditions were exactly the same as in Case A but only the oxidiser was bypassed and the mixture of air with the gas from the outlet of the ÿrst column was directly fed to the second column. The predictions were an NOx removal efÿciency of 94.3% and selectivity greater than 99.9% nitrite in the second column. Thus, improvement in the selectivity was possible but it was not feasible to implement since the outlet NOx of 19; 686 ppm from the second column would be out of pollution control norms. Hence, simulation D was carried out according to the strategy discussed in Section 2.2.3 and the scheme is represented in Fig. 10. The gas stream from the ÿrst absorber outlet was partly (50%) fed to the oxidiser and the rest (50%) was bypassed and fed

4842

Table 5 Comparsion of plant data and simulation results
Absorber I inlet streams

Absorber I outlet streams 40 0.0054 403995 0 63600 1 532404 1000000 38:2 50# 0.004# 99.1 55.7 55:4 98:5 42.5 41:1 0 0 0 210000 790000 1000000 250057 0 39366 80019 630558 1000000 97904 173895 42789 29 685383 1000000 97904 173895 42789 29 685383 1000000 50# 0.004# 85.4 99.9 86:1 99:9 38:2 30# 1.15E+05# 0.0034# 31:8 1:09E + 05 0:0088 0:057 59:1 1:09E + 05 0:0088 0:058 59:1 1:09E + 05 0:0088 0:102 42.5 41:1

Air to oxidiser

Oxidiser inlet gas

Oxidiser outlet gas

Absorber II inlet

Absorber II outlet stream

Gas ◦ Temperature, C Pressure, N=m2 Flow, kg=s velocity, m=s Compositon, ppm 50# 1.15E+05# 0.0091# 0.095# 429000# 171000# 47099# 0# 352901# 1000000 40

NO∗ NO∗ 2 H2 O O2 CO2

1 11 74822 38 925128 1000000

Liquid ◦ temperature, C velocity, m=s

Overall selectivity % [nitrite=(nitrite+nitrate)]

% NOx removal e ciencya

J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844

Numbers in bold indicate plant data and # indicates same value has been input to the simulation. Numbers underlined, indicate simulation output a 100 × (kmol=s NO at inlet- kmol=s NO at outlet)= kmol=s NO at inlet. x x x NO∗ = (NO + N2 O3 + 0:5HNO2 − 0:5HNO3 ). NO∗ = (NO2 + 2N2 O4 + N2 O3 + 0:5HNO2 + 1:5HNO3 ). 2

Table 6 Optimisation of Pilot plant performance: compromise between selectivity and NOx removal e ciency

Case Oxidiser in line= bypass In line In line Bypass 50% Bypass 50% Bypass 100 100 100 50 70 % Of the oxidised stream fed to the ÿrst pack section of second absorber

Absorber 1

Absorber 1

O2 =NO

Overall % NOx removal e ciency ¿99.99 90.7 94.34 90.24 92.25 86.1 95 ¿ 99:99 98.81 ¿ 99:99

Overall % selectivity of nitrite

NOx in exit gas ppm

Acceptable

% NOx removal e ciency

% selectivity of nitrite

ratio to oxidiser

Absorber 2 section 1 % NOx removal e ciency

Absorber 2 section 1 % selectivity of nitrite

Absorber 2 section 2 % NOx removal e ciency

Absorber 2 section 2 % selectivity of nitrite

A B C D E

55.4 55.4 55.4 55.4 55.4

98.5 98.5 98.5 98.5 98.5

0.32 0.25 0.32 0.86 0.86

¿ 99:99 ¿ 99:98

78.39 85.63

99.996 95.870 97.500 99.999 99.999

92.3 96.8 99.2 95.7 97.8

¡ 10 35841 19686 ¡ 10 ¡ 10

Yes No No Yes Yes

J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844

4843

Fig. 10. Suggested modiÿcation to small-scale industrial plant set-up.

directly to the second absorber. The second absorber was divided into two packed sections. The oxidised outlet stream was partly (50%) fed to the ÿrst section of the second absorber and the rest (50%) was fed to the second section. Refer Case D. Using this strategy, the overall NOx removal e ciency was 99.999% and the overall selectivity was 95%, both being an improvement over Case A. This scheme would require nominal piping modiÿcations in the plant, and the same were proposed to the industry and are being considered for implementation. To improve the selectivity of the second packed section further, the amount of NO2 -rich (oxidised) stream fed to the second packed section of the second column was decreased. This is shown in Case E which is similar to Case D except that the oxidiser outlet stream was divided into 70% and 30% streams and fed to the ÿrst and second packed section of the second absorber, respectively. Table 6 shows that Case E ÿnally yielded the overall NOx removal e ciency of 99.999% and the improvement in the overall selectivity to 97.8%. 3. Conclusions A mathematical model has been developed for the adiabatic operation of a packed column for absorption of NOx gases in aqueous NaOH solutions. All the heat e ects have been included in the mathematical model. A reasonable agreement has been shown between the model predictions and the performance of a small-scale industrial plant. As regards the optimum design, the stagewise oxidation=

absorption has been shown to be superior to the simultaneous oxidation=absorption. The parallel mode of operation, which results in much lower volume requirements, is far more superior. In this third strategy, there is a possibility of attaining very low exit NOx concentrations (as low as 25 ppm). The parallel strategy is, therefore, recommended for commercial operation.

Notation a b Bx CP dh Dx G E H Hx (kD)x Hi k1 kG kp Kn interfacial area, m2 =m3 molar ratio of oxygen to nitric oxide constant speciÿc heat, kcal=kg=K di erential height, m di usivity of component x, m2 =s ow rate of inerts, kmol=s energy of activation, kcal=kmol enthalpy kcal=kmol absorption factor for fast pseudo-ÿrst-order reaction for component x, kmol=[m2 (kN=m2 )s] heat of reaction i, kcal=kmol reaction rate constant, s−1 gas side mass transfer coe cient, kmol=[m2 s(kN=m2 )] rate constant for NO oxidation equilibrium rate constant for reaction n

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J. A. Patwardhan et al. / Chemical Engineering Science 57 (2002) 4831–4844

L LY NO∗ NO∗ 2 PI i Px
o Px

PT Q Rax Rgx S tC T XJ
∗ YN

∗ YNO

∗ YH2 O

YT Yx (Z) Greek letters

molar ow rate of water in liquid phase, kmol=s molar ow rate of liquid, kmol=s total mol fraction of divalent reactive nitrogen total mol fraction of tetravalent reactive nitrogen partial pressure of inerts, kN=m2 partial pressure of component x at the gas liquid interface partial pressure of component x in the bulk phase total pressure of gas, kN=m2 heat, kcal rate of absorption of component x into liquid phase, kmol=(m3 s) rate of gas phase mass transfer of component x, kmol=(m3 s) cross-sectional area of column, m2 contact time based on penetration theory, s ◦ temperature, K kmols of component ‘J ’ per kmol of water in the liquid phase, dimensionless total moles of reactive nitrogen per moles of inerts =YNO + YNO2 + 2YN2 O3 + 2YN2 O4 + YHNO2 + YHNO3 total moles of divalent reactive nitrogen per moles of inerts =YNO + YN2 O3 + 0:5YHNO2 − 0:5YHNO3 total equivalent moles of water per moles of inerts =YH2 O + 0:5YHNO2 + 0:5YHNO3 total moles of gas per mole of inerts moles of gaseous component x per mole of inerts kmol=s of component Z

G L G L

fractional gas holdup fractional liquid holdup heat of vaporisation, J=kmol density of gas, kg=m3 density of liquid, kg=m3

Subscripts a e f g i l o x w v Superscripts I O interface bulk absorption exit formation gas phase inlet liquid phas oxidation NO, NO2 , N2 O3 , N2 O4 , HNO3 , HNO2 , H2 O, O2 water vaporised

Acknowledgements JAP thanks Prof. M. M. Sharma Endowment & JNMF for the award of fellowship. MPP would like to thank University Grant Commission for the award of fellowship. References
Joshi, J. B., Mahajani, V. V., & Juvekar, V. A. (1985). Absorption of NOx Gases. Chemical Engineering Communications, 33, 1–90. Pradhan, M. P., & Joshi, J. B. (1999). Absorption of NOx gases in aqueous solutions: Selectivity and optimization. AIChE Journal, 45(1), 38–50. Pradhan, M. P., & Joshi, J. B. (2000). Absorption of NOx gases in plate column: Selectivity and manufacture of sodium nitrite. Chemical Engineering Science, 55(7), 1269–1282. Suchak, N. J., Jethani, K. R., & Joshi, J. B. (1990). Absorption of nitrogen oxides in alkaline solutions: Selective manufacture of sodium nitrite. Industrial and Engineering Chemistry Research, 29, 1492.

stagnant ÿlm thickness, m voidage