' 4 -

- -*

. .

. .

Thii document is

15th DOE NUCLEAR AIR CLEANING CONFERENCE

*-

NITROGEN OXIDE ABSORPTION I N T O WATER AND DILUTE N I T R I C ACID I N AN ENGINEERING-SCALE SIEVE-PLATE COLUMN WITH PLATES DESIGNED F O R HIGH GAS-LIQUID INTERFACIAL AREA*
R. M. Counce, W. S. Groenier, J. A. Klein, and J. J. Perona O a k Ridge National Laboratory

Oak Ridge, Tennessee 37830

Abstract
The absorption of gaseous NOx compounds i n t o water and d i l u t e HNO3 w a s studied i n a three-stage sieve-plate column with p l a t e s designed f o r high gasl i q u i d i n t e r f a c i a l area, The performance of t h e column w a s measured while s e v e r a l operating parameters were varied. The r e s u l t s of t h e study i n d i c a t e t h e importance of t h r e e mechanisms i n t h e absorption of gaseous NOx (NO2 + 2N2O4 + NO) compounds: (1) t h e absorption of NO$',(NO2 + 2N204) which r e s u l t s i n production of l i q u i d HNO3 and HN02; ( 2 ) t h e d i s s o c i a t i o n of t h e l i q u i d HN02 i n t o HNO3 and gaseous NO; and (3) t h e gas-phase oxidation of NO t o N02. A mathematical model based on t h e s e mechanisms was developed and i s presented t o explain t h e observed phenomena.
I.

Introduction

The removal of NOx compounds from gas streams i s important i n t h e reprocessing of nuclear f u e l s because many of t h e off-gas streams i n such a f a c i l i t y will contain t h e s e compounds i n concentrations t o i n t e r f e r e with f u r t h e r gas Composition of t h e feed-gas stream cleanup operations or exceed discharge l i m i t s . for t h e s e s t u d i e s was prepared t o simulate t h e product gas r e s u l t i n g from t h e f i e 1 d i s s o l u t i o n step. This product gas contains a l a r g e amount of steam as w e l l as a i r and NOx compounds. The mechanism of NOx removal considered i n t h i s study i s based on: (1)t h e absorption of NOZ/ (NO2 + 2N2O4) i n t o d i l u t e HNO3, which r e s u l t s i n t h e production of l i q u i d HNO3 -and HN02; ( 2 ) t h e d i s s o c i a t i o n o f l i q u i d HN02 i n t o l i q u i d HNO3 and gaseous NO; and ( 3 ) t h e gas-phase oxidation of NO t o N02. This method i s a t t r a c t i v e f o r t h e proposed a p p l i c a t i o n because t h e HNO3 produced could be recycled for use i n t h e plant. Commercial NOx scrubbing equipment, u s u a l l y bubble-cap columns, i s based on HNO3-industry experience. Since t h e absorption r e a c t i o n s a r e exothermic, commercial scrubbers g e n e r a l l y have cooling c o i l s i n t h e f r o t h of each column stage. The absorber under development i s intended f o r operation i n a r a d i o a c t i v e environment, and hence t h e design of t h e scrubber should be as simple as p o s s i b l e t o f a c i l i t a t e maintenance. The scrubber system under i n v e s t i g a t i o n meets t h i s requirement. I n t h i s system, d i l u t e HN03 i s r e c i r c u l a t e d through the column; t h e water input i s provided by condensing steam from t h e feed gas. The column under development i s designed t o operate a t high l i q u i d flow r a t e s , which eliminates the need f o r i n t e r n a l cooling. Heat a s s o c i a t e d w i t h the absorption r e a c t i o n s and condensing steam i s removed from t h e scrubber l i q u i d i n e x t e r n a l h e a t exchangers. *Research sponsored by t h e Nuclear Power Development Division, U.S. Department of Energy under c o n t r a c t W-7405-eng-26 with t h e Union Carbide Corporation.

DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency Thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.

15th DOE NUCLEAR AIR CLEANING CONFERENCE

I I

INFRARED ANALYZER

1 I

MOOD EXHAUST

PROCESS STEAM

AIR PROCESS

49
ROTAYETER

PRESSURE

VALVE

FIGURE 1 FLOWSHEET OF EQUIPMENT USED I N NOx SCRUBBING EXPERIMENT.

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1 1 .

ExDerimental Atmaratus and Procedure

. The N% scrubber i s a The flowsheet f o r t h e experiment i s shown i n Fig. 1 three-stage s i e v e - p l a t e column constructed of 0.076-m-ID by 0.254-m-long s e c t i o n s of Pyrex g l a s s pipe, The p l a t e s and downcorners, shown i n Fig. 2, a r e constructed of s t a i n l e s s s t e e l .

The f r e e a r e a per p l a t e .6%, i s r e l a t i v e l y low when compared with t h a t of a t y p i c a l s i e v e - p l a t e column. This i s because t h e column w a s designed f o r high r a t i o s of l i q u i d f l o w r a t e t o gas f l o w r a t e (L/G) i n an attempt t o d i s s i p a t e t h e heat generated from t h e absorption r e a c t i o n s and t h e condensation of t h e steam with increased l i q u i d f l o w r a t e s ; t h i s a l s o provides increased gas residence time i n t h e column.

7 ' (

Other equipment used i n t h e experiment include: $ scrubber l i q u i d holdup tank, pmp, rotameter, and h e a t exchanger; a gaseous N O 2 supply system; and progess The gas-handling equipment includes a N @ a i r , steam, and water supply systems. a i r rotameter, an e f f l u e n t gas holdup tank, an i n f r a r e d analyzer t o determine t h e concentrations o f N4, i n t h e feed and e f f l u e n t gas streams, a c a l i b r a t i o n gas supply system, and an exhaust gas system. The system i s normally operated by pumping t h e scrubber l i q u i d from t h e scrubber l i q u i d holdup tank and metering it through h e a t exchangers t o t h e column. Upon leaving t h e column, the e f f l u e n t l i q u i d stream flows by g r a v i t y t o t h e r e t u r n @ i s supplied t o t h e system by vaporizing commercially obtained tank. Gaseous N l i q u i d NO; i n a temperature-regulated water bath. Process a i r i s metered with t h e NO$ by a rotameter and i s blended with steam i n a comon feed stream t o t h e column. Steam f l o w i s c o n t r o l l e d by maintaining a constant d i f f e r e n t i a l pressure across a c a l i b r a t e d c a p i l l a r y tube. The system i s allowed t o reach steady-state conditions before d a t a are taken. The system i s considered t o be a t steady s t a t e when a l l gas and l i q u i d f l o w r a t e s , column temperatures, and N& concentrations i n The t h e feed and e f f l u e n t streams have shown no change over a 30-min i n t e r v a l . gas stream i s sampled before and a f t e r leaving each stage. The gas-sample streams, with t h e exception of t h e feed stream, a r e passed through a sample holdup tank t o provide s u f f i c i e n t time f o r t h e N & gases t o reach t h e N O ; state for
analysis.

The sample streams a r e then metered t o an i n f r a r e d analyzer ( L i r a Model

202), which i s s p e c i f i c for NO5 and r e q u i r e s a gas with a known a i r - N O 5 content f o r t h e purpose of c a l i b r a t i o n , Samples of t h e scrubber l i q u i d a r e taken e n t e r i n g and leaving t h e column. These l i q u i d samples a r e analyzed f o r HNO3 and HN02 by P l a t e and column e f f i c i e n c i e s a r e then calculated from t h e standard techniques. gas concentration differences.
TTT.

Theoretical Develoment

The o v e r a l l chemical r e a c t i o n s involved i n t h e s t e a d y - s t a t e absorption of N 4 ( compounds i n t o water or d i l u t e HNO3 appear t o be adequately represented as follms :

15th

DOE NUCLEAR AIR CLEANING CONFERENCE

W
P-

I'

I
(L

a
! -

>

15th DOE NUCLEAR AIR CLEANING CONFERENCE

3HNOz(R)

H 2 0 ( R ) + HN03(R)

+ 2NO(g)

(4)

where ( g ) and (R) i n d i c a t e gas and l i q u i d species respectively. A review of t h e l i t e r a t u r e i n d i c a t e s t h a t t h e following assumptions about t h e o v e r a l l r e a c t i o n s may be made:

1 . The NO2 and N204 a r e i n continuous gas-phase equilibrium.

2 .

(2-4)

Reaction of N2O4 with t e proceeds by means of a f a s t - f i r s t - o r d e r liquid-phase reaction.Y'-lg) (For NO5 p a r t i a l pressures >O. 01 atm, t h i s i s t h e predominant absorption r eaction). ~- __The HN02 decomposes exclusively by Eq.

3.

(4).(18-21)

4.

Oxidation o f NO occurs a s an o v e r a l l t h i r d - o r d e r gas-phase r e a c t ion. ( 22-27)

The following a d d i t i o n a l assumptions were made concerning t h e c h a r a c t e r i s t i c s of t h e column gas and l i q u i d phases:
1 .

The f r o t h on t h e s i e v e p l a t e s i s w e l l mixed.

. .

2 .

No baclanixing occurs i n t h e gas t r a v e l i n g through t h e s i e v e - p l a t e f r o t h .

The changes i n gas flow r a t e through t h e f r o t h and through t h e gas space between p l a t e s a r e considered t o be n e g l i g i b l e while i n t h a t p a r t i c u l a r phase. The gases behave i d e a l l y . The gas i n t h e gas space between t h e p l a t e s i s w e l l mixed.

3.

4 .
5.

i n t o water or The N02-N204 equilibrium and t h e absorption of gaseous ~ 2 0 4 diluteIHN03 a r e simulated mathematically and combined i n t o a31 equation f o r N204 absorption i n t h e f r o t h on t h e s i e v e plates. The d i s s o c i a t i o n of l i q u i d HN02 t o By using t h e gas-phase r e a c t i o n r a t e gaseous NO i s a l s o t r e a t e d mathematically. f o r NO oxidation, a mathematical expression i s developed f o r t h e extent of t h i s r e a c t i o n i n t h e gas space between t h e s i e v e plates. These t h r e e equations a r e combined i n an o v e r a l l mathematical model f o r NOx removal i n a multistage-plate colmt. The equilibrium between N2O4 and NO2 can be defined by

( 2 4 ) -

where

P, 1

= pressure equilibrium constant f o r r e a c t i o n (l), a t m ;

15th DOE NUCLEAR AIR CLEANING CONFERENCE

'NO,

p a r t i a l pressure of NO2,

atm; ahd

pN204

p a r t i a l pressure of N 0 atm. 2 4'

If a represents t h e degree of d i s s o c i a t i o n of N 2 0 4 and t h e p a r t i a l pressures of N 2 O 4 and N O 2 a r e expressed i n terms of NO; and a, then
\
1

'1

PN204

= (1 - a)PN0;/2

(7)

and
P

NO2

= aP

NO2

*
*
,$

where

P *

N02

'NO2

-i- 2pN204,

atm.
z

Combination and rearrangement of t h e above equations results i n t h e following equation f o r a:

-K
a =

+ K

1 + 8PNO* 2/KP, 1

4p~~z
*

(9)

neglecting gas-phase The l o c a l absorption r a t e f o r NO i n t o d i l u t e HNO 2 3' r e s i s t a n c e , can be expressed as:

where

= l o c a l absorption r a t e of NO

*
2

per u n i t area, kg.moles/m

sec,

D ~ 2 ~~ 4 ,2 0
k

= d i f f u s i v i t y of N204

2 i n H 0, m /sec,
2

pseudo-first-order r e a c t i o n r a t e constant, s e c - l ; and

He~2~4

= Henry's

law constant f o r t h e s o l u t i o n of N 0 i n H 0. 2 4 2

15th DOE NUCLEAR AIR CLEANING CONFERENCE

p * = p * N02 NO2,

in

(1 -

xNo*),
2

where
P * NO2
P
=

p a r t i a l pressure of NO

*
2'

atm; entering t h e f r o t h , a t m ; and

NO2, i n

= p a r t i a l pressure of NO

*
2

conversion of NO;, t h e r a t i o of t h e change in*the p a r t i a l O 2 entering the pressure of NO; t o t h e p a r t i a l pressure of N f r o t h of a given p l a t e ;

and t h e equilibrium r e l a t i o n s h i p between N204 and N O 2 i n t o t h e d i f f e r e n t i a l NO; balance. I n t e g r a t i n g over t h e volume of f r o t h per p l a t e , t h e following equation may be obtained:

4 1 + 20
(41 +

- 2$XN0*

2@ - 2@XN0Z -

rn 1) (m - 1)
-

= o ,

where

a
Ri

= gas-liquid i n t e r f a c i a l area per u n i t volume of f r o t h , m-'*

_ _ 1

gas constant, n3 atm/kg.mole K; _.

T ' F R
G

= f r o t h temperature, K;

f r o t h volume, m3 ; and s u p e r f i c i a l gas volumetric flow r a t e , m 3/see

Solution of t h i s equation involves finding t h e \root,

%oL,

.
between zero and ong.
I

The model f o r t h e decomposition of IN02 i n t h e f r o t h on t h e s i e v e p l a t e s presumes equilibrium of Eq. (4) a s indicated by:(18-21)

15th DOE NUCLEAR AIR CLEANING CONFERENCE

HNO2
where
__

P,4

=
=

pressure equilibrium constant for reaction liquid concentration of H+ , kg*mole/m3; liquid concentration of NO- kg-mole/m 3;

(k), m3 atm /kg.mole;

cH+
=

' N O -3
' N O

3 '

partial pressure of NO, atm; and liquid concentration of HNO

:cmo2
I

2'

3 kg-mole/m

. .
I

Because the froth is considered to be perfectly mixed,

where

NO^,

in

concentration of liquid NO2 resulting from the HN02 in the incoming liquid stream and production from absorption reactions, kge mole/m3; and conversion of HN02, the concentration decomposing per plate * divided 'by Cmo in'
2'

A mole of NO is produced for each 3/2 moles of HN02 decomposed; therefore, the following relationship may be used to predict the partial pressure of NO desorbed
per plate:

where
L
=

liquid flow rate, m 3/sec

Because equilibrium is approached by the decomposition of liquid HN02, Eq. (13) may be rearranged into the following form, using relationships given in Eqs. (14)and (15):

15th DOE NUCLEAR AIR CLEANING CONFERENCE

where
'NO,

in

p a r t i a l pressure of NO entering t h e f r o t h , atm ,

~~~

The solution of t h e equation involves finding t h e p o s i t i v e and r e a l root, xHN02) of t h i s third-degree polynomial. The model f o r NO oxidation i n t h e f r e e volume between t h e s i e v e p l a t e s i s based on t h e t h i r d - o r d e r gas-space r e a c t i o n of NO and oxygen. The r e a c t i o n r a t e i s expressed as:

NO

2 = k P P 5 NO 0,

.
( 5 ) , a t m m 2 sec-l;

(17)

where

r
k

NO

- l o c a l r e a c t i o n r a t e of t h e oxidation of NO, atm/sec; = r e a c t i o n r a t e constant f o r reaction

' N O
po2

- p a r t i a l pressure of NO, atm; and

-

- p a r t i a l pressure of 0

2'

atm

U t i l i z i n g Eq. (1.7) i n developing a NO balance around a d i f f e r e n t i a l element of f r e e space between t h e p l a t e s , and incorporating t h e following d e f i n i t i o n s :

and

where
'NO,

in

= =

t h e p a r t i a l pressure of NO e n t e r i n g t h e gas space, a t m ; t h e conversion of NO i n t h e f r e e space between t h e s i e v e p l a t e s , r a t i o of t h e p a r t i a l pressure of NO oxidized t o t h e p a r t i a l pressure of NO entering t h e gas space, dimensionless; and

) ( N O

15th DOE NUCLEAR AIR CLEANING CONFERENCE

in

t h e p a r t i a l pressure of 0

entering t h e gas space, a h .

I n t e g r a t i n g over the f r e e space between t h e p l a t e s y i e l d s :

where
7

t h e gas residence time between t h e s i e v e p l a t e s , sec.

The s o l u t i o n of t h i s equation involves finding t h e r e a l and p o s i t i v e root, ?NO of t h i s polynomial.

1 .

The o v e r a l l model f o r N4, removal i s based on themathematical simulations developed e a r l i e r f o r t h e NO$ absorption and HN02 decomposition i n t h e f r o t h on a s i e v e p l a t e and NO oxidation i n t h e gas spaces between t h e s i e v e plates.

NO$ and HN02 and t h e stoichiometry of Eqs. (1-4).-For c a l c u l a t i o n s involving---__ _ _ t h e recycle of t h e scrubber l i q u i d , t h e l i q u i d feed stream t o t h e col& w a s equal
i n concentration t o t h e effluent-scrubber l i q u i d stream. Steady-state acid concentrations a r e determined through repeated i t e r a t i o n s of t h e column model, beginning w i t h i n i t i a l a c i d concentrations of near zero. Reaching steady s t a t e i n t h e l i q u i d phase coincided w i t h e s t a b l i s h i n g steady s t a t e i n t h e gas phase f o r The model allows f o r adjustment of t h e gas d e n s i t y t h e described calculations. upon leaving t h e f r o t h and again upon leaving t h e gas space. The s u b s c r i p t s j and k are used t o i n d i c a t e t h e stage number i n a column and t h e position of t h e gas i n a p a r t i c u l a r s t a g e respectively. For gas e n t e r i n g t h e f r o t h of p l a t e j , k = 1; f o r gas leaving t h e f r o t h of p l a t e j , k = 2. The p a r t i a l pressures of NC$, NO, nitrogen, and oxygen of a gas stream e n t e r i n g t h e f r o t h on s t a g e j a r e indicated by P * and P respectively. The , N02,j, k = l NO,j,k=l: PN*,j,k=l 02,j , k = l model begins a t t h e f i r s t p l a t e and works upward. The p a r t i a l pressures of t h e components leaving t h e f r o t h a r e i n d i c a t e d by:

The s t e a d y - s t a t e a c i d m o l a r i t i e s were calculated using t h e conversions of

~. .

(23)

15th DOE NUCLEAR AIR CLEANING CONFERENCE

and

where

so x

conversion of NO,, t h e r a t i o of t h e change i n t h e p a r t i a l pressure of NO, e n t e r i n g t h e f r o t h of a given p l a t e .

Those leaving t h e gas space of s t a g e j or entering s t a g e j+l a r e i n d i c a t e d by:

* j ,k = 2 + PNO, j k = 2xN O I/( - Ei12XNo) NO;, j +1, k = l - [NOz,

(25)

N2,

j+ 1,k=l

( 1 N2, j , k=2/

and
\
; 02, j+l,k=l
I

02,

j ,k=2

(1 - NO, in
2p~2, in

- k=2 x NO ) .
-

The p a r t i a l pressures of t h e gas components as w e l l as t h e gas flow r a t e s a r e This correction may be corrected for bulk removal of t h e gas-phase components. where e i s t h e f r a c t i o n a l made by d i v i s i o n or m u l t i p l i c a t i o n by (1 - e), volume change due t o removal of t h e gas components (k = 1 f o r t h e f r o t h and k = 2 a r e found using Eqs. and f o r t h e gas space). The q u a n t i t i e s ?NO*, N0,j (12), (15), and (20). Solution of Eq. 715) r e q u i r e s p r i o r s o l u t i o n of Eq. (16). A multistage column may be modeled by l e t t i n g j assume values from one t o t h e number of required stages, provided t h e b a s i c removal mechanisms remain valid.

%o

IV.

Experimental Results

I n order t o c a l c u l a t e t h e column performance, it i s necessary t o have numerical values f o r t h e appropriate equilibrium, k i n e t i c , and t r a n s f e r constants. The values of K p , l used i n t h i s study were obtained from a c o r r e l a t i o n by Hoftyzer and K ~ a n t e n ( based ~) o n t h e work of Verhoek and Daniels. (3) --The values of used t o c a l c u l a t e t h e absorption of N204 were a l s o obtained from a c o r r e l a t i o n by Hoftyzer and Kwanten. (4) Abels equilibrium cons function of temperature w a s used t o describe t h e decomposition of HN02. The r a t e constant f o r t h e oxidaton of NO was derived as a function of temperature from t h e work of Greig and Hall.t27) The gas-liquid i n t e r f a c i a l a r e a was determined experimentally f o r t h e case with no steam i n t h e feed gas by u t i l i z i n g

15th DOE NUCLEAR AIR CLEANING CONFERENCE

t h e absorption of C02 i n t o N a O H solutions, a s described by Danckwerts. (28) These r e s u l t s a r e summarized i n Fig. 3. The i n t e r f a c i a l a r e a of t h e bottom t r a y f o r t h e case when steam i s present i n t h e feed gas was estimated u t i l i z i n g Eq. ( 1 2 ) , and / t h e experimental d a t a given i n Table I f o r nominal run conditions.\ The nominal run conditions were:
1 .

: '

scrubber l i q u i d flow r a t e , 0.175 x combined a i r and NO2 flow r a t e s , 2.0 x

o r 0.350 x
m3/sec;

m3/sec;

2.

3.

steam flow rate, 3.7 kg of steam per m3 of a i r and NO2; i n l e t scrubber temperature, 298 K; feed gas temperature, 363 K; scrubber molarity, " 2 . 0 ; feed gas p a r t i a l pressure of NO2, 0.31- a t m ; t o t a l pressure, 1.1 atm.
m.

4.
5.

6.
7.

8.

A s e r i e s o s experiments was performed, a s shown i n Table I, i n which t h e absorption of NO2 was s t u d i e d using a s i n g l e p l a t e i n order t o evaluate t h e v a l i d i t y of Eq. (11)and t h e s e l e c t e $ constants. This w a s accomplished by measuring t h e p a r t i a l pressure of N O 2 i n N 2 before and a f t e r it was passed through t h e sieve-plate f r o t h . The scrubber l i q u i d f o r these runs was water flowing i n a s i n g l e pass through t h e column. These r e s u l t s a r e given i n Table I. A * NO: representative experimental s e r i e s showing experimental and model-predicted absorption o r conversion i s shown f o r various feed p a r t i a l pressures of NO2 i n Fig. 4. I n general, NO; conversion increases w i t h increased p a r t i a l pressures of NO2 and increased l i q u i d f l o w r a t e s and decreases w i t h increased s u p e r f i c i a l gas f l o w r a t e s . The presence of steamwas shown t o g r e a t l y enhance the absorption of NO; i n t h e s e experiments, involving a s i n g l e s i e v e p l a t e .

The removal of gaseous NO, compounds depends not only on t h e absorption of but a l s o on t h e desorption and subsequent gas-phase oxidation of NO. "he model predictions f o r t h e three-stage column performance provide f o r t h e s e phenomena as i n d i c a t e d previously.
NO;,

The buildup of HN02 i n t h e l i q u i d phase for runs involving l i q u i d recycle i s shown i n Fig. 5. The attainment of steady s t a t e appears t o be c l o s e l y r e l a t e d t o reaching a s t e a d y - s t a t e concentration of H N 0 2 i n t h e r e c i r c u l a t i n g scrubber l i q u i d . As t h e concentration of HN02 increases i n t h e scrubber l i q u i d , t h e o v e r a l l scrubber e f f i c i e n c y or conversion of NOx i s shown t o decrease. The model-predicted conversion of NOx behaves s i m i l a r i l y as shown i n Fig. 6, i n which o t h e r conditions were approximately as experimental run 42 given i n Tables I1 and 1 1 1 . ! The model-predicted gaseous NO, p r o f i l e i n t h e column i s compared w i t h t h a t P l a t e s a r e numbered calculated from t h e experimental d a t a of run 53 i n Table IV. from bottom t o top. There w a s no steam i n t h e feed gas f o r t h i s experiment. The model-predicted p r o f i l e s are very close t o t h e experimentally determined p r o f i l e s .
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FIGURE 3 CORRELATION O F EXPERIMENTALLY DETERMINED GAS-LIQUID I N T E R F A C I A L
ARFA VS C A S PTOW RATF FOR A STNCTP-STACP STFTTF-PTATPP PnTliMM

P N O ~ I(atm) N
A

F I G U R E 4x EXPERIMENTAL AND MODEL PREDICTED NO2 ABSORPTION VS THE PARTIAL

F NO; PRESSURE O

ENTERING THE TRAY AT A TOTAL GAS FLOW RATE OF

1.86 x
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15th

DOE NUCLEAR AIR CLEANING CONFERENCE

Table I .
Run

Steady-state NO2 scrubbing data for a single sieve plate a n d a nonrecirculating scrubber liquid
TG,out

'NO;,in
(atm) 0.026 0.051 0.101 0.161 0.207 0.267 0.330 0.035 0.053 0.107 0.167 0.187 0.260 0.330 0.020 0.044 0.101 0.161 0.216 0.279 0.312 0.015 0.050 0.107 0.165 0.211 0.260
0.163

'NOh,out (atm) 0.012 0.020 0.040 0.059 0.081 0.103 Oil17 0.013 0.017 0.035 0.057 0.075 0.088 0.094 0.011 0.020 0.044 0.068 0.094 0.119 0.134 0.009 0.024 0.051 0.075 0.099 0.119 0.079 0.075 0.062 0.057 0.051 0.044 0.055 0.055 0.026 0.024 0.024 0.022 0.031 0.019 0.028

TG,in .

TL

G
( s t d m3/sec) 2.0 2.0 2.0 2.0 2.0 2.0 2.0
x
x

F~~~~

NO.
55a 55b 55c 55d 55e 55f 55g 56a 56b 56c 56d 56e 56f 5% 5 7a 57b 57c 5 7d 57e 57f 5 7g 58a 58b 58c 58d 58e 58f 59a 59b 59c
59d

(K)
293 294 294 294 294 294 294 294 294 294 294 294 294 294 294 294 294 295 295 295 295 295 295 295 295 295 295 294 294 294 294 299 297 294 294 348 35 5 362 365 368 359 369

(K)
297 297 297 297 297 297 297 298 298 298 298 298 298 298 297 298 298 298 298 298 298 298 298 298 298 298 298 296 296 296 296 297 298 298 298 302 304 306 309 316 300 322

(K)
292 292 292 292 292 292 292 293 293 293 293 293 293 293 293 293 293 292 292 292 292 293 292 292 292 292 292
292

(kg/sec)
0 0 0 0 0 0 0
0

(m3/sec)

(m2/1113

x x
x

x x

io-'+

1.5 x 1.5 x

1.5

1 . 5 x 1014 1 . 5 x 10 1.5 x io-" 1.5 x 2.5 2.5 2.5 2.5

x x x x x x x

0 0 0
0 0
-.

0
0

iod4

io-'+
io-"+

2.5
2.5 2.5 3.0 3.0 3.0 3.0 3.0

0 0 0 0 0 0 0 0 0 0 0
0
0

x x

x x x 3.0 x

io-'+

2.0 x

0.163 0.163 0.163 0.152 0.145 0.151 0.151 0.165 0.166 0.163 0.166 0.141 0.152 0.151

293 292 290 290 291 290 290 298 302 309 317 337 300 322

2.0 x 2.0 x 2.0 x 2.0 1.5 2.5 2.5 2.0 2.0 2.0 2.0
x x x x
x

io-'+

0
0

63a 63b 63c 63d 64a 64b 64c 64d 65a 65b 65c

io-'*

0 0

0
0

x
x x

io-'*

2.0 x 2.0 x 2.0 x

io-' io-'+ io-'

1.67 x 3.67 x 7.83 X 11.83 x IO-'+ 7.83 x 7.83 x 7.83 x

1 . 7 5 X lo-' 1.75 X lo-' 1.75 X 1.75 x 0.44 x 3.50 x 0.86 x

622 724 850 1200 1650 781 1120

lo-'

15th DOE NUCLEAR AIR CLEANING CONFERENCE

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Table 1 1 .
NO

Ste

, s t a t e NOx s c r u b b i n g d a t a for r e c i r c u l a t i n g s c r u b b e r l i q u i d

p a r t i a l p r e s s u r e (atm)

Gas t e m p e r a t u r e ( K )
feed stage 1 stage 2 stage 3

Liquid t e m p e r a t u r e ( K ) stage 1 stage 2 stage 3

A

Run no.

feed

stage 1

.stage
0.067 0.068 0.073 0.068 0.073 0.073 0.084 0.057 0.057 0.0 0.066 0,079 0.070 0.088 0.095 0.097 0.088 0.097 0.090 0.069 0.112 0.048 0.110 0.123 0.101 0.079 0.101 0.068

stage 3

Recirculating scrubber l i q u i d 9 10 11 12 13 15 16 17 18 19 20 31 32 42 44 45 46 47 48 49 50 51 52 53 54 60 61 62 0.308 0.312 0.299 0.295 0.273 0.341 0.310 0.293 0.332 0.0 0.310 0.341 0.352 0.306 0.295 0.301 0.301 0.301 0.350 0.301 0.312 0.145 0.215 0.317 0.321 0.293 0.400 0.308 0.106 0.114 0.114 0.110 0.012 0.128 0.141 0.100 0.103 0.0 0.117 0.125 0.117 0.141 0.136 0.150 0.125 0.143 0.141 0.107 0.171 0.066 0.127 0.183 0.132 0.129 0.174 0.114
0 .os1 0.053 0 .OS8 0 .OS3 0.062 0.051 0.070 0.040 0.042
0 .o

0.042 0.057 0 .os1 0.062 0.066 0.084 0.070 0.068 0.068 0.051 0.075 0.040 0.105 0.103 0.079 0.057 0.070 0.050

35 2 35 3 35 3 35 1 35 3 35 3 298 35 2 35 1 35 1 35 1 353 35 3 364 36 5 29 9 357 36 8 363 363 367 36 2 298 299 365 366 366 35 7

314 312 312 309 312 313 302 312

312 30 3 316 312 313 320 320 303 311 322 315 31 7 33 3 317 30 0 30 3 317 317 315 3 36

306 305 304 305 305 305 303 304 304 299 30 5 305 305 307 30 8 306 30 6 308 307 30 5 310 304 30 0 30 7 306 30 6 305 313

305 303 304 304 30 3 304 30 5 303 303 299 30 3 304 304 305 30 6 299 305 30 5 30 5 304 305 303 30 1 309 305 303 30 3 300

31 0 310 310 310 310 312 297 310 309 310 309 310 310 320 320 298 310 33 1 313 30 9 337 318 298 298 318 310 311 310

298 297 297 297 297 29 7 29 7 29 7 297 297 297 297 29 7 298 298 29 7 29 8 299 299 298 299 298 29 7 297 296 298 297 29 7

297 297 297 297 297 29 7 597 297 297 297 297 29 7 29 7 29 7 297 29 7 297 298 29 7 297 297 29 7 297 29 7 29 5 29 7 29 6 297

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15th DOE NUCLEAR AIR CLEANING CONFERENCE

O O O O O l n C ~ O C ~ O ~ O O G O C O C O O c o c O q q

0 0 c 0 0 N a r . b C N 0 N C c C C C C C o o c c o o o o
4

. . . . . . . . . . . . . . . . . . . . . . . . . .

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0 0 ~ 0 m b N C b N N M r - M u 3 r . O m ~ o ~ o ~ o .............................
d N M M M N M M N N N I - 4 N 4 N M N N N N N N M M I - N N

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15th DOE NUCLEAR AIR CLEANING CONFERENCE

Table IV. A comparison of s t e a d y - s t a t e NOx column p r o f i l e s c a l c u l a t e d from experimental d a t a versus NO, removal p r e d i c t e d by model f o r experiment 53
E x p e r i m e n t 5 3 (no steam i n f e e d g a s )

P
Gfeed

= 1.1 atm

= 3.07 x

m3/sec
m3/sec

L = 2.6 x lo-'

hkNO3 = 3.0
%NO
2

= 0.20 (experimental), 0.13 ( c a l c u l a t e d )

NO

P r o f i l e i n Column (atm)
% .

E x p e r i m e n t a1 Feed Stage 1 Stage 2 Stage 3 0.317 0.183 0.123 0.103

Calculated 0.317 0.181 0.134 0.116

Table V. Calculated p a r t i a l pressures of gaseous components f o r s t a g e , i, and p o s i t i o n , j , where j = 1 e n t e r i n g f r o t h and j = 2 leaving f r o t h f o r experiment 53 'NO:
(191) ( 1 9 2) (2,1> (292) (3911 (392) 0.317 0.095 0.135 0.051 0.087 0.037

'NO

02

P
N2

0.000
0.086 0.051 0.083 0.051 0.080

0.165 0.193 0.163 0.172 0.143 0.147

0.618 0.726 0.751 0.794 0.819 0.837

.?___

15th DOE NUCLEAR AIR CLEANING CONFERENCE

'

The steady-state HN02 concentration calculated by the model is slightly lower than that determined experimentally. The calculated partial pressures of the gaseous component are given for each plate (i) and for positions entering the froth (jd) and leaving the froth ( j = 2 ) in Table V .
ExFerimentally determined NO, conversions are compared with those predicted by the model in Fig. 7 for two different feed gas rates with no steam in feed gas. The N O , conversions predicted by the model are then compared with those experimentally determined for varying scrubber liquid flow rates, feed gas flaw rates, NO, partial pressure in feed gas, and stem component in feed gas at reference conditions in Figures 8-U. In almost all cases, the model used to predict NOx conversions in sieve plate columns is l o w with respect to absorption efficiencies. Consequently, the steady-state-predicted concentrations of HNO 2 (usually 0 . 1 kg.mole/m3): are always lower than the experimental values. The 2 . column overall NO, conversion for varying HNO molarities is given in Fig. 1

Some researchers have consolidated the forward rates of Eqs. (3) and (4) producing one-third of a mole of NO for every mole of NO; absorbed. No apparent difference in the revised model and the one described in this paper was detected when this mode was tested for the steady-state case involving recycle of the scrubber liquid. However, the use of this simple model does not account for the O , removal efficiency buildup of liquid HN02 in the system or for the reduced N that results from its presence in the scrubber liquid. -The model clearly demonstrates the observed phenomenon that the presence of HN02 in the scrubber liquid reduces the overall NO, scrubbing efficiency of the system.

V .

Conclusions

The following conclusions can be drawn from the results of this study:

1 . The model adequately represents the experimental results for the experimental system over the range of variables studied.
2.

The conversion of N O , varies directly with the gas and liquid f l o w rates and the partial pressure of . : O N
The model predicts a buildup of HN02 in the scrubber liquid and a corresponding decrease in scrubbing efficiency. This was verified in the experimental work,

'

3.

4 .

These finaings indicate that a method to destroy HN02 in the scrubber liquid before its recycle to the column will greatly increase the system N O , removal efficiency. Additional investigation will be necessary in order to verify the use of this model in predicting effluent-gas partial pressures of less than 0 . 0 1 atm.

5.

VI.

Acknowledgement

This work was performed in the Chemical Technology Division under the auspices of the Advanced Fuel Recycle Program of the Oak Ridge National Laboratory.

15th DOE NUCLEAR AIR CLEANING CONFERENCE

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FIGURE 9 EXPERIMENTAL NO, CONVERSIONS AND THOSE PREDICTED BY THE MODEL FOR VARYING FEED GAS FLOW RATES AT OTHERWISE REFERENCE CONDITIONS FOR STEADY-STATE THREE-STAGE COLUMN OPERATION.

FIGURE 10 EXPERIMENTAL NO, CONVERSIONS AND THOSE PREDICTED BY THE MODEL FOR VARYING PARTIAL PRESSURE O F NO, I N THE FEED GAS AT OTHERWISE REFERENCE CONDITIONS FOR STEADY-STATE THREE-STAGE COLUMN OPERATION.
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15th DOE NUCLEAR AIR CLEANING CONFERENCE

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15th DOE NUCLEAR AIR CLEANING CONFERENCE

VII.

L i s t of References

1 .
2.

R. H.

18-8,McGraw-Hill, New
M.

Perry and C. H. Chilton, "Chemical engineers' handbook," 5th ed., York (1973).

Bodenstein, "Formation and decomposition of n i t r o u s oxides of high volume," Z. Elektrochem. 100: 68-123 (1922).

3.

F. H. Verhoek and F. J. Daniels, "The d i s s o c i a t i o n constants of nitrogen t e t r o x i d e and of nitrogen t r i o x i d e , " J. Am. Chem. SOC. 53: 1250-63 (1931). P. J. Hoftyzer and F. J. G. Kwanten, "Process for a i r p o l l u t i o n c o n t r o l , " 2nd ed., 164-87,Chemical Rubber Co., Cleveland (1972).
K. G. Denbigh and A. J. Prince, "Kinetics of n i t r o u s gas absorption i n aqueous n i t r i c a c i d , " J. Chem. SOC. 53: 790-801 ( 1 9 4 7 ) .

4 .
5 . 6 .

P. G. Caudle and K. G. Denbigh, "Kinetics of t h e absorption of nitrogen peroxide i n t o water and aqueous s o l u t i o n s , " Trans. Faraday SOC., 49: 39-52

(1953) 7 .
M. M. Wendel and R. L. Pigford, "Kinetics of n i t r o g e n t e t r o x i d e absorption i n water," AIChE. J. 4: 249-56 ( 1 9 5 8 ) .I
k

. 8 . M

S. P e t e r s and J. L. Holman, "Vapor- and liquid-phase r e a c t i o n s between nitrogen dioxide and water," Ind. Eng. Chem. 47: 2536-39 (1955).
J. J. Carberry, "Some remarks on chemical equilibrium and k i n e t i c s i n t h e nitrogen oxides-water system," Chem. Eng. Sci. 9 : 189-94 (1959).

9 .

1 0 . W. A. Defier, E. Snoeck, and H. Kramers,. "The r a t e of absorption of NO 2 i n water," Chem. Eng. Sci. 1 1 : 61-71 ( 1 9 5 9 ) .

1 1 . E. S. Koval and M. S. Peters, "How does n i t r i c oxide a f f e c t r e a c t i o n s of aqueous n i t r o g e n dioxide?, Ind. Eng. Chem. 52: 1011-14 (1960).

12. M. J. Moll, "The r a t e of hydrolysis of nitrogen t e t r o x i d e , " Ph.D.

D i s s e r t a t i o n , Univ. of Washington

(1966).

13.

J. P. Detournay and R. H. J a d o t , "Determination of t h e r e a c t i v e phase during t h e absorption"of nitrogen oxides i n water," Chem. Eng. Sci. 28:-2099-2102

(1973).

1 4 .

M.

S. Peters, C. P. Ross, and J. E. Klein, "Controlling mechanisms i n t h e aqueous absorption of nitrogen oxides," AIChE. J. 1: 105-11 (1955).

15. H. Kramers, M. P. P. Blind, and 'E. Snoeck, "Absorption of nitrogen t e t r o x i d e

by water j e t s , " Chem. Eng. Sci.

14: 115-23 (1961).

__

1 6 .

Sherwood, R. L. Pigford, and C. R. Wilke, "Mass t r a n s f e r , " McGraw-Hill Book Co., N e w York (1975).
T. K.

346-361, I I

1 7 . S.

P. Andrews and D. Hanson, "The dynamics of n i t r o u s gas absorption," Chem. Eng. Sci. 14: 115-23 ( 1 9 6 1 ) .

-a

15th DOE NUCLEAR AIR CLEANING CONFERENCE

1 8 . E . 1 9 . E .

Abel and H. Schmid, "Kinetics of n i t r o u s acid," Z. Phys. Chem 132: 55-77 (1928).

Abel and H . Schmid, "Kinetics of n i t r o u s acid: k i n e t i c s of t h e decomposition of n i t r o u s acid," Z. Phys. C h m . 134: 279-300 (1928).

2 0 . E . Abel, H . Schmid, and S. Babad, "Kinetics of n i t r o u s acid: k i n e t i c s of t h e formation of n i t r o u s a c i d from n i t r i c acid and n i t r i c oxide," Z. Phys. Chem.

136: 135-45 (1928).

2 1 .

E . Abel, H . Schmid, and S. Babad, "Kinetics of n i t r o u s acid: k i n e t i c s of t h e n i t r o u s a c i d - n i t r i c a c i d - n i t r i c oxide reaction, " Z. Phys. Chem.

136: 419-36 ( 1 9 2 8 ) .
2 2 .
M. Bodenstein, "Velocity of r e a c t i o n between n i t r i c oxide and oxygen," Z. Elektrochem. 24: 183-201 ( 1 9 1 8 ) .
R. L . Hasche and W. A. Patrick, "Studies on t h e r a t e of oxidation of n i t r i c oxide; I1 t h e v e l o c i t y of t h e reaction between n i t r i c oxide and oxygen a t 0" and 30," J. Am. Chem. SOC. 47: 1207-14 (1925).

2 3 .

2 4 .

J . C . Treacy and F. Daniels, "Kinetic study of t h e oxidation of n i t r i c oxide with oxygen i n t h e pressure range 1-20 ran,'' J. Am.-I-Chem. SOC. 77: 2033-36

( 1 9 5 5 ) .
25.
P. G. Ashmore, M. G. Burnett, and B. J. Tyler, "Reaction of n i t r i c oxide and oxygen," Trans. Faraday SOC. 1 5 8 : 685-91 (1962).

2 6 . M . E .

Morrison, R. C, Rinker, and W. H. Corcoran, "Rate and mechanism o f gas-phase oxidation of parts-per-million concentrations of n i t r i c oxide," Ind. Eng. Chem. Fundam. 5: 175-81 (1966).
D. Greig and P. G, H a l l , "Thermal oxidation of n i t r i c oxide a t l o w concentrations, mans. Faraday soc. 63: 655-61 (1967).

2 7 . J.
28.

P. V. Danckwerts, "Gas-liquid reactions," McGraw-Hill, N e w York ( 1 9 7 0 ) .

96-150,117-118,227,