Int. J. Hydrogen Energy, Vol. 14, No. 4, pp. 241-256, 1989.

Printed in Gr eat Britain.

0360-3199/89 $3.00 + 0.00
Pergamon Press plc.
1989 International Association for Hydrogen Energy.
MODE LLI NG, SI MULATI ON AND SENSI TI VI TY ANALYSI S OF STEAM -
M E T H A N E RE FORME RS
I. M. ALATIQI, A. M. MEzi ou a nd G. A. GASMELSEED
Applied Systems Depart ment , Techno-Economics Division, Kuwait Institute for Scientific Research, P.O. Box 24885,
1 3 1 0 9 -S a f a t , Kuwait
(ReceivedJbrpublication 14 November 1988)
Abst r act - - A mathematical model to calculate temperature, conversion and pressure profiles for static operations in
st eam- met hane reformers was simulated. A rigorous kinetic model describing st eam-met hane reactions was
compared to a first order one and an empirical heat distribution model was fitted to describe heat absorbed along the
reactor length. A control interface was simulated to allow sensitivity analysis with different control schemes. The
kinetic models were tested with data from industrial steam-gas reformers. Simulation results agreed with actual
plant data for conversion, tcmperature and pressure. Nevertheless, the first order kinetic model gave unrealistic
sensitivity results to pressure and steam-to-carbon ratio variations. The rigorous mode[ could confidently be used for
design analysis, control, and economic evaluation purposes.
A
Cv
D
Dp
F
(H2)n
AH
h
K
K i
K~
K3
k
ko
k~
[nCH4]i
F/T
P
Pr
Q
N OME N C LA TURE R
Rep
s ur f ace ar ea (ft 2) S
aver age specific heat of gas mi xt ur e ( Bt u
l b J mol eF) S/ C
d i a me t e r (ft)
e qui va l e n t par t i cl e d i a me t e r [6 x vol ume of
SG
par t i cl es ( t ot al par t i cl e sur f ace ar ea) i (ft) T
act i vat i on e ne r gy i n first or de r mode l e qua -
t i on (cal mol t) u
f eed gas mi xt ur e flow r at e (l b h 1) v
f uel gas flow r at e (scf h i) wt
mol e of i ni t i al hydr oge n per mol e of x
me t ha n e equi v. ( mol e mol e ~) Y
heat of r eact i on ( Bt u lb - l mol e) Z
heat t r a ns f e r coef f i ci ent [Bt u ft- F h) I] ZT
c onduc t i vi t y of gas mi xt ur e [Bt u (OF h ft )_ 1] d Z
e qui l i br i um c ons t a nt for r eact i on ( l a ) e
( a t m 2) t::
e qui l i br i um c ons t a nt for r eact i on ( l b ) Subscripts
1
(arm2) 2
e qui l i br i um c o n s t a n t f or r eact i on ( l c ) 3
( di me ns i onl e s s ) G
n u mb e r of c a r bon at oms i n t he mol ecul e of
in
s a t ur a t e d hy d r o c a r bo n gas i n t he f eed
speci fi c r at e c ons t a nt f or r eact i on ( l b ) ,
ba s e d on a ppr oxi ma t e mode l
specific r at e c o n s t a n t for r eact i on ( l b ) ,
bas ed on r i gor ous mode l flow r at e of com-
p o n e n t k ( mol e h i)
flow r at e of me t ha n e e qui va l e nt fed ( mol e
h ~)
t ot al mol e flow r at e (t ool h --~)
t ot al pr e s s ur e (ar m)
Pr a ndt l n u mb e r
r at e of he a t t r a ns f e r pe r uni t ar ea of r ef or -
me r t ube sur f ace [ Bt u ft 2 h ) - l ]
gas c o n s t a n t
par t i cl e Re ynol ds n u mb e r
t ot al n u mb e r of mol es i n t he gas mi xt ur e pe r
mol e of me t ha n e e qui va l e nt (t ool t o o l - ' )
r at i o of i ni t i al s t eam r at e to me t ha n e
e qui va l e n t f ed ( mol e mol e 1)
f uel gas specific gr avi t y
t e mp e r a t ur e (F)
ma ni pul a t i ve var i abl e
voi d f r act i on
wei ght i ng f act or f or e qua t i o n (33)
f r act i on of me t ha n e e qui va l e nt c onve r t e d
cont r ol var i abl e
di s t ant f r om i nl et of t ube (ft)
t ot al r e f or me r t ube l engt h (ft)
i nt e gr a t i on s t ep size (ft)
dens i t y of gas mi xt ur e (l b ft 3)
uni t effi ci ency
r eact i on ( l a )
r eact i on ( l b )
r eact i on ( l c )
fuel gas
i ns i de wal l of r e f or me r t ube
I N TRODUC TI ON
A c ons i de r a bl e a mo u n t of hydr oge n is pr oduc e d by
s t e a m r e f or mi ng of na t ur a l gas. Pr evi ous l y, mos t of t he
hy d r o g e n was us ed i n p e t r o l e um r ef i ni ng t o t r eat l i ght
n a p ht ha s a nd mi ddl e di st i l l at es for des ul f ur i zat i on a nd
pr oduc t st abi l i t y. Re c e nt l y, a mor e s ever e t ype of
hy d r o g e n t r e a t i ng was a d d e d t o r ef i ner y pr oces s i ng
syst ems: heavy di st i l l at es (gas oi l ) a nd r es i due ar e
hy d r o t r e a t e d t o r e mo ve s ul f ur a nd t o c onve r t t hese
241
242 1. M. ALATIQ1, A. M.
heavi er hydr ocar bons to product s with lower mol ecul ar
weights. The use of these hydrocracki ng and hyd-
rodesul furi zat i on processes has become increasingly
i mpor t ant as the demand for light distillates i ncreased.
Cur r ent r equi r ement s for hydrogen are in pet r ol eum
refining, manuf act ur e of ammoni a, met hanol and che-
micals, welding, etc. St eam reformi ng of nat ural gas in
the mai n process for hydrogen product i on. The reform-
ing process is carri ed out in mul t i t ubul ar reactors
suppor t ed with Ni-catalysts at t emper at ur es varyi ng
from 1300 to 1600C, pressures rangi ng from 300 to 600
psi and mol ar st eam to car bon ratios bet ween 2.00 and
9.00.
Because the oper at i on is i mpor t ant , process cont rol
must be i mproved cont i nual l y. The fired heat er and
r ef or mer mul t i t ubul ar reactors are subject to fluctua-
t i ons that di st urb the pr oduct i on rate, the qual i t y of
hydrogen and the level of the st eam dr um downst ream
from the reformer. The objective of this study is to
devel op a st eady state mat hemat i cal model that can be
used to investigate the per f or mance of existing plants.
MODEL DEVELOPMENT
The mul t i t ubul ar react or to be si mul at ed is placed
vertically in a gas-fired heater. The heat t ransfer is by
r adi at i on and convect i on from the fuel gas and flames to
the r ef or mer mul t i t ubul ar react or and from ext ended
t ube surfaces to the process gas. The r ef or mer t ubes
were si mul at ed as one di mensi onal het er ogeneous reac-
tor model this is appl i cabl e for this case where the
r ef or mer t ube l engt h- t o- di amet er ratio is large (great er
t han 100). Axial di spersi on is compl et el y i gnored at all
flow velocities al ong the length of the reactor. A
met hane equi val ent to the feed is cal cul at ed at the
react or ent ry; this is based on the assumpt i on that higher
hydr ocar bons are very rapidly conver t ed to met hane. It
is t herefore assumed that met hane is the pri mary
r eact ant in the r ef or mi ng process. Heavi er hydrocar-
bons are rapi dl y hydrocracked to met hane in a very
short l engt h of time at the ent r ance of the t ubul ar
reactor. Consequent l y, the react i on system inside the
r ef or mer t ubul ar react or is described by the ki net i c rate
expressi on for s t e a m- me t ha ne react i on, irrespective of
the hydr ocar bon fed.
MEZIOU AND G. A. GASMELSEED
(7) All hydr ocar bons higher t han met hane are hyd-
rocracked to met hane at the ent r ance section of the
t ubes.
St oi chomet ry
The following react i ons are commonl y assumed to
take place in the r ef or mer t ubes: -
reformi ng:
CH4 4- H20 = CO 4- 3 H2 ( l a)
the overall react i on:
CH4 + 2 H20 = CO2 + 4 H2 ( l b)
watershift:
CO 4- H20 = C02 + H2 (l c)
hydrocracki ng:
CkH2k+2 + (k - 1)H2-+ k CH4. ( l d)
Let nk be the mol es of Ck H2k+2 (k = 1,2 . . . . ) per hour,
t hen
CH4 equi val ent = Y. knk tool h -1. (all k) (2)
The amount of hydrogen avai l abl e after cracking be-
comes
( H2 ) 0 = original H 2 - Y ~ ( k - 1 ) n k . ( k > l ) ( 3 )
Let x be the fraction of mol es of met hane (i.e. equi val ent
met hane) convert ed. Then the following equat i ons give
the number of moles of each component pr esent in the
reacting gas mi xt ure per mole of met hane fed:
(CH4) = 1 - x (4)
( H20) = S/ C - x - (CO2) (5)
(H2) = (H2)0 + 3x + (CO2) (6)
(CO) = x - (CO2) (7)
( c o ~ _ ) = ( c o 2 ) ( 8 )
(N2) = (N2) (9)
total:
S = (H2)o + 1 + S/ C + 2x + (N2). (10)
As s umpt i ons
(1) Axi al plug flow for the reformi ng gases in the
t ubes is assumed.
(2) Radi al t emper at ur e profile is neglected.
(3) Catalyst particle t emper at ur e is uni form and is the
same as that of the process gas.
(4) Heat t ransfer is by r adi at i on and convect i on.
(5) All the t ubes in the r ef or mer are consi dered to
behave similarly.
(6) No car bon deposi t i on is assumed to occur in the
reformer.
The t erm S/ C denot es st eam to car bon rat i o, measur ed
in met hane equi val ent , mole mole ~. S is the sum of
moles present in gas mi xt ure per mole of met hane
equi val ent fed, mole mole t.
Material bal ance and rate equat i ons
Let r be the rate of met hane conversi on in st andar d
cubic feet (scf) per hour per cubic foot of bul k catalyst
and [ncn~]i be the mol es of met hane fed per hour.
Then
STEAM - METHANE REFORMERS
r/379
[nc.Ji
is mol e of met hane conver t ed per mol e of met hane fed
per cubic foot of catalyst. If Ai , d z is an i ncrement al d(CO2)
vol ume of bulk catalyst, t hen dZ
r
dx -- Ain dz (11)
D~. k
and divide by 379 (the mol ar gas vol ume at st andar d
conditions) t o convert t o mol e units,
d x Ai n
dx Ain r - - -
(12) dZ
dZ 379 [n(, ~]
z )x
(CO2) = (0.666 - 0.10
(a) (b) ZT
Z dx 0.10
- - - ( 0 . 6 6 6 - 0 . 1 0 ~ - T) ( _ - - ~ ) - (-~--v)x.
2 4 3
(20)
(21)
The rat e of met hane conversi on can be expressed in a
compact form if we combi ne equat i ons (12) t hr ough t o
(21), which gives:
3 7 9 [ n c , j i
k _ ~
X
(H2) o + 1 + S I C + 2 [ x + (N2)] 3
[n('H~]i = CH4equiv = Z knk.
all k (13)
Among the many rate expressions, t he one published
by Moe and Ger har d [1] was pr oven t o give reasonabl y
accurate results. Thus, it was accommodat ed here.
Accor di ng t o the react i on ( l b) , t he rat e of met hane
conversi on can be expressed as:
r = rCH 4 = k2 [K2Pc'Hap21t:o - P4H, Pc%]. (14)
Hiroshi [2] used a similar kinetic expressi on t o simulate a
heat exchanger t ype st eam reformer.
The partial pressures can be expressed in t erms of
mol e fractions t o give:
k2/~t (H2) 4 (CO2)
r 2 = ~--ff~-- [K2(CH4) (H2O) 2 S 2 P2].(15)
The p3 t erm can be arbi t rari l y set t o 1 in or der t o
correl at e dat a for t he kinetic and equilibrium constants.
These were det er mi ned by t he following expressions:
7_ _
x [ K2 ( l - x) { S/ C - x - (0.666 - 0.1 "~)x} 2
ZT
Z Z
- { (H2)o + 3x + (0.666 - 0. lG--)x} 4 (0. 666-0. 1G--)x P2 I
LT LT
[(H2) 0 + 1 + S / C + 2x + (N2)] 2
(22)
Due t o t he compl i cat ed f or m of t he react i on rat e
resulting from t he model assumed in equat i on (14), it
woul d be desirable t o check if a simpler kinetic model is
satisfactory. The most popul ar simple model assumes a
first or der dependence of r with met hane partial
pressure:
rCH~ = ko e- e~mrPcn4 (23)
i gnori ng ot her react ant s and pr oduct pressures [4--6].
More recent l y [7], it was cl ai med t hat this first or der
kinetics is sufficiently accurat e for engi neeri ng calcula-
tions. Thus, equat i on (23) will be t est ed along with t he
model given by equat i on (14) for compari son.
K 3 = exp
I 31720 ]
k, = exp T+ 460 7.912 (16)
- 49435 ]
- - + 30.707 (17)
KI = exp T+ 46(1
7351.24 3.765 1 for T/ > 1100F
T + 460
d
(18a)
I 8240 1
K3 = exp - 4.33 for T< 1100F (18b)
r + ~ o
K2 = KI K3. (19)
Hyman [3] consi dered t he CO2 concent r at i on t o be
proport i onal t o met hane conversi on. The pr opor t i onal -
~ty fact or was t aken as a linear funct i on of distance.
Energy balance
The t ransfer of heat f r om r ef or mer tubes i nner wall t o
t he process gas is given by Beek [8]:
hi, = __K [2.58 (Rep) 1/3 (Pr) 1/3 + 0.094 (Rep)S(Pr)4].
Dp (24)
This equat i on is valid for pellet catalysts. For ring-
shaped catalysts, the heat t ransfer coefficient is about
40% of the val ue given by equat i on (24) [3].
The t emper at ur e profile along t he r ef or mer t ube is
r epr esent ed by t he following equat i ons [3, 9]:
d T ( AHi t ri Ai n ~ Dinhin ( T i n _ T)
d -~- = Z C p / ~ + nT C------~ ( 2 5 )
where n x = [ncHJiS is t he total mol e flow rat e per hour
(mol e h- l ) .
244
d T ( - AH1 )
d Z S Cp
I. M. ALATIQ1, A. M. MEZIOU AND G. A. GASMELSEED
dx ( - AH3 ) d(C02)
d Z S C'p d Z
~ Din hi, ( Ti, - 7)
[nCH4] i S C'p
MP
- - + ~ = R T ( 3 2 )
whi ch can be put in t he equi val ent form
d T ( - A H 0 dx ( - AH3 ) Z d2c
- s C p ~ d Z p ~ [ ( 0 ' 6 6 6 S - 0 . 1 - - ) - - -
d Z
ZT d Z
(26)
0.1 ~ Din hin (Tin - T)
Z-T xl + [nCH4]i S (~p (27)
wher e (~p is t he mol a r heat capaci t y of t he mi xt ur e and
Di , is t he i nsi de di a me t e r of t he t ube.
Tin ma y be cal cul at ed from t he fol l owi ng equat i ons
[91:
Qi n = 0 . 4 hi n ( Ti n - T) ( 2 8 )
Qin = Q (O(/ Oi n). (29)
Si nce t he i nner wal l t e mpe r a t ur e Ti, is a second or de r
pol ynomi al in Z, Q will be a pol ynomi al of t he same
or der . On t he ot he r hand, t he heat flux de pe nds on t he
net heat l i be r a t e d by t he fuel whi ch var i es l i near l y wi t h
t he pr oduc t of fuel gas flow r at e (FG), fuel gas specific
gr avi t y ( SG) and uni t effi ci ency ( e) . Thi s pr oduct can
easi l y be i ncl uded in a he a t flux pol ynomi al equat i on t o
obt ai n a si mpl e empi r i cal equat i on whi ch cal cul at es t he
r at e of heat t r ans f er pe r uni t a r e a of r e f or me r t ube
surface:
Q = F G SG (a + b Z + c Z 2) e (30)
wher e t he coeffi ci ent s a, b and c ar e de t e r mi ne d usi ng
mul t i pl e r egr essi on pr oc e dur e . Thi s equat i on gi ves t he
heat di s t r i but i on al ong t he t ube l engt h Z.
The use of equat i on (30) el i mi nat es t he ambi gui t y of
ext ensi ve r adi at i on and convect i on cal cul at i ons. I t al so
el i mi nat es t he need for any as s umpt i on r egar di ng t he
pr evai l i ng mode of heat t r ansf er and gives fl exi bi l i t y in
cal cul at i ng heat di s t r i but i on at any r e f or me r t ube
l engt h.
Pressure drop and physi cal properties
The pr ocess gas pr es s ur e dr op in r e f or me r t ubes was
cal cul at ed by t he f ol l owi ng equat i ons [10}:
( G 2 1 1 - v )
+ 1.751 ( - U) ( - - ~) ( - St - 3 )
(31)
d P 150 ( I - v )
- - 2 - - [
dZ Rep
32. 2(144)(14. 7)(3600) 2
wher e v is t he voi d f r act i on in t he cat al yst bed, which can
be cal cul at ed gi ven t he cat al yst par t i cl e size and t he r at i o
of pa c ke d be d bul k densi t y t o a sol i d cyl i nder densi t y.
Equa t i on (32) is val i d for mode r a t e pr essur es and high
t e mpe r a t ur e s t hat ar e t ypi cal in t he r ef or mi ng pr ocess.
Physi cal pr ope r t i e s such as vi scosi t y, t her mal conduc-
t i vi t y and heat capaci t i es wer e cal cul at ed from s t andar d
f or mul ae and aver age val ues wer e cal cul at ed accor di ng
t o t he compos i t i on of t he r eact i ng mi xt ur e at each
i t er at i on sect i on. Det ai l s on physi cal pr ope r t i e s ar e
gi ven i n t he appendi x.
Met hod o f solution
The met hane conver si on t e mpe r a t ur e and pr es s ur e of
t he r eact i ng gas mi xt ur e at any poi nt of t he r e f or me r
t ube were obt a i ne d by i nt egr at i ng equat i ons (22), (27)
and (31), st ar t i ng f r om t he i nl et of t he r e f or me r t ube t o
its end.
The 38 ft l ong r e f or me r t ube was di vi ded i nt o 380
sect i ons. St ar t i ng wi t h t he known i nl et gas mi xt ur e
condi t i ons, t he physi cal and t he r modyna mi c pr ope r t i e s
wer e cal cul at ed. Fr o m t hese pr ope r t i e s and t he act ual
gas mi xt ur e flow r at e, t he pr es s ur e in t he first sect i on was
eval uat ed, t hen me t ha ne conver si on and out l et t emper -
at ur e of t hi s sect i on wer e cal cul at ed. Usi ng t hese new
condi t i ons of compos i t i on, t e mpe r a t ur e and pr es s ur e,
t he physi cal and t he r modyna mi c pr ope r t i e s were re-
cal cul at ed. Thes e pr ope r t i e s wer e, in t ur n, used t o
cal cul at e pr es s ur e, conver si on and t e mpe r a t ur e for t he
second i t er at i on sect i on. The pr oc e dur e was r e pe a t e d
unt i l t he end of t he r e f or me r t ube.
The f our t h or de r Run g e - Kut t a me t hod was used t o
s o l v e for conver si on and t e mpe r a t ur e profi l es. The
execut i on t i me was 5 s on t he I BM 4371 c omput e r and 7 s
on a PC/ AT 386 r unni ng at 16 MHz.
RESULTS AND DI SCUSSI ON
Kinetic model s
The model was t est ed for t wo di f f er ent i ndust r i al scal e
r ef or mer s. The first is in a r ef i ner y hydr ogen pl ant and
t he second is a pr i mar y r e f or me r in an a mmoni a pl ant .
Tabl e 1 shows t he ope r a t i on var i abl es of t he t wo uni t s on
t wo di f f er ent days. Tabl es 2 and 3 c ompa r e t hese base
cases and t he model pr edi ct i ons. Devi at i ons bet ween
pr edi ct ed and act ual r e f or me r pr oduct t e mpe r a t ur e ,
conver si on and pr es s ur e show excel l ent accur acy.
These r esul t s were i dent i cal for t he t wo model s t es t ed,
t he r i gor ous model and t he first or de r mode l bas ed on
equat i ons (14) and (23), r espect i vel y. Thi s mi ght t empt
one t o concl ude t hat t he t wo model s ar e c ompa r a bl e , but
t he conver si on and t e mpe r a t ur e pr of i l es al ong t he t ube
l engt h showed t hat t he t wo model s do not give i dent i cal
STEAM - METHANE
profi l es (see Fi gs 1 a nd 2). The c onve r s i on r at e was
hi gher f or t he r i gor ous mo d e l t ha n f or t he a p p r o xi ma t e
mode l (Fi g. 1), t he r ever s e was o bt a i n e d f or t he
t e mp e r a t ur e pr of i l e, wi t h a c ons i de r a bl e di f f er ence
be t we e n t he t wo mode l s especi al l y i n t he e n t r a n c e
s ect i on (Fi g. 2). The r i gor ous mo d e l shows a dr op i n
t e mp e r a t ur e of a bo ut 25F n e a r t he e n t r a n c e of t he t ube .
Thi s is due t o t he e ndot he r r ni c n a t ur e of t he s t e a m
r e f or mi ng r e a c t i on t hat gi ves a hi gh c onve r s i on r at e at
t he e n t r a n c e as s hown i n Fi g. 1. Ho we ve r , t he appr oxi -
ma t e mode l does not s how t hi s be ha vi or . The i nl et a nd
out l e t c ondi t i ons wer e t he s a me f or bot h model s . The
ki net i c p a r a me t e r s i n t he a p p r o xi ma t e first o r d e r mode l
wer e set t o gi ve t he bes t fit t o t ube exi t c ondi t i ons (100 l b
mol h at m l bm) J f or k0 a nd 17050 cal mo l i f or E~).
Bot h val ues ar e wi t hi n t he r a nge c o mmo n l y r e p o r t e d
[11]. I n t e r me d i a t e me a s ur e me n t s wer e n o t avai l abl e for
c ompa r i s on. The t wo mode l s wer e f ur t he r c o mp a r e d for
sensi t i vi t y of coi l out l e t t e mp e r a t ur e a nd c onve r s i on t o
var i ous s t ep changes . The r es ul t s ( Ta bl e 4) s how t hat t he
t wo mode l s a gr e e d f ai r l y wel l f or s ens i t i vi t i es t o f uel r at e
REFORMERS 245
or dens i t y a nd f eed i nl et t e mp e r a t ur e a nd flow r at e.
Ho we v e r , ups et s i n f eed pr es s ur e a n d S/ C r at i o l ead t o
c ont r a di c t or y r esul t s, especi al l y i n c onve r s i on. The
r i gor ous mo d e l pr e di c t e d t hat c onve r s i on is f a vor e d at
l ower pr es s ur es , whe r e a s t he first o r d e r mo d e l pr e di c t e d
t hat i ncr eas i ng t he pr es s ur e f a vor e d c onve r s i on. I n t he
a bs e nc e of e xp e r i me n t a l ver i f i cat i on, one mi ght ar gue
t hat , un d e r t he e qui l i br i um c ont r ol l e d c ondi t i ons cons i -
de r e d ( S/ C = 5. 5), t he s t oi c hi ome t r y gi ven by t he
r ef or mi r . g r eact i on ( e qua t i o n l a ) cal l s f or hi gher con-
ver s i on at l ower pr es s ur es . Ac c o r d i n g t o t hi s a r g ume n t ,
t he r i gor ous mode l gave a mo r e r e a s o n a bl e effect .
The a s s umpt i on t hat t he pr ocess is e qui l i br i um con-
t r ol l ed al so expl ai ns t he r esul t s o bt a i n e d f or S/ C ups et s ,
whe r e t he r i gor ous mo d e l pr e di c t e d a negl i gi bl e ef f ect
on c onve r s i on for smal l S/ C upset s.
Thes e a r g ume n t s i ndi cat e t hat t he r i gor ous ki net i c
mode l is mor e r el i abl e t ha n t he first o r d e r mode l . Eve n
t hough t he l at t er gave a n accur at e fit t o t he t ube exi t
c ondi t i ons , it gave unr eal i s t i c s ens i t i vi t y effect s f or i nl et
pr es s ur e a nd S/ C r at i o. The e xp l a n a t i o n f or t hi s is t hat
Table l(a). Steam reformer operating condi t i ons--Refi nery hydrogen plant
Operating condition June 30, 1987 December 12, 1987
(100% capacity) (58% capacity)
Feed gas flow rate (MMSCFD)*
Feed gas density (air = 1)
Steam flow rate (Mlb h ~)
Fuel gas flow rate (MMSCFD
Fuel gas density (air = 1)
Steam-to-carbon ratio
Inlet feed temp. (F)
Inlet feed pressure (psi)
Feed gas composition (vol %)
H2
C1
C2
C3
i -C4
n- C4
i-C5
n-C5
C6+
Catalyst specifications
Shape, dimensions (inches): ring, 5/8 5/8 1/4
Bulk density (Ib ft-3): 55 5
29.516 17.107
0.381 0.374
197.736 149.532
8.275 6.092
0.930 0.799
5.320 7.111
921.5 902.0
325.0 293.0
53.9O 56.30
32.61 28.16
l 0.85 1 3 . 9 6
1.30 0.54
0.55 0.27
0.79 0.58
0.00 0.09
0 . 0 0 O. 1 0
0.00 0.00
* MMSCFD--Mi l Ii on standard cubic foot per day.
246 I. M, ALATI QI , A. M. ME ZI OU AND G. A. GASME LSE E D
Tabl e l ( b) . St eam r e f or me r oper at i ng c o n d i t i o n s - - Ammo n i a pl ant
Ope r a t i ng condi t i ons Feb 09, 1988 Feb 10 1988
Fe e d gas flow r at e ( MMSCFD) 13.96 12.24
Fe e d gas dens i t y (ai r = 1) 0.732 1/.749
St eam flow r at e ( Ml b h- ~) 213.85 202.16
Fuel gas flow r at e ( MMSCFD) 6.738 6. 199
Fuel gas dens i t y (ai r = 1) I).744 1/.8/)
St e a m- t o- c a r bon rat i o 5.825 6.117
I nl et f eed t emp. (F) 948./) 964.4
I nl et f eed pr es s ur e (psi ) 455.0 400.0
Feed gas composition (vol %)
H2 5.67 5.57
CI 61.33 57.66
C2 27.61 27.31
C3 0.77 0.91
i - C4 0.03 0.08
n - C4 0.06 0.24
i - C5 2.44 2.13
n - C5 0.18 0.16
C~, + 0.07 0.04
N2 1.84 5.9
Catalyst specifications
Shape, di me ns i ons (i nches): ring, 0. 7 11.6 x 0.35
Bul k dens i t y (lb f t - 3) : 57
Tabl e 2. Compa r i s on of model pr edi ct i ons wi t h act ual pl ant dat a ( s t e a m- r e f or me r )
Run dat e Me a s ur e d Pr edi ct ed f r om % e r r or
s i mul at or
(a) Reformer product average temperature (F)
30. 06. 87 1455.5 1450.15 - 0 . 3 7
12.12.87 1413.0 1414.06 - 0 . 0 8 "
(b) Mol % of Hz in reformer product
30. 06. 87 77.911 77.60 - 0 . 3 9
12.12.87 78.00 78.94 1.21
(c) Tube outlet pressure (psi)
30.116.87 305.00 31}3.6 0.5
12.12.87 281.00 281.2 11.07
STEAM - METHANE REFORMERS 247
r~
0
r'
0
r~
,.c:
1.13 I~
G.~9
13.~ ]
13.7
13-5
I~1.4
13.3
13.2
, i , / "
"
i
i s
s "
i "
~ t
j J
l I
J
F
~ J
, /
rigorous
first o r d e r
3.8 7.6 11.4 15.2 19.13 2 2 .8 2 6 .6 313.4 34.2
. 1. 13
13.2
13.S
13.S
13 .4
13.3
13.2
13 .1
. -
13 . G
3 8.13
T u b e L e n g t h ( f t )
Fig. 1. Methane convers ion p rofile: rigorous and firs t ord er mo d el s .
p a rt i a l p res s ures f o r s ubs t a n c e s o t he r t ha n C H4 we r e n o t
i n c l ud ed i n t he k i n e t i c e qua t i o n o f t he f i rs t o rd er mo d e l .
Heat and temperature profiles
Ne w f a c et s o f t hi s wo r k a re t he c o n s i d e r a t i o n s a n d
c o n n e c t i o n o f hea t t ra n s f er by ra d i a t i o n a n d c o n v e c t i o n
f r o m t he f l a mes a n d f uel ga s s i mul t a n e o us l y t o t he
r e f o r me r t ubes . At t he s a me t i me , t he f uel a n d r e f o r me r
f e e d qua l i t i es a n d p hys i c a l p ro p ert i es we r e c a l c ul a t ed
a c c o rd i n g t o p reva i l i n g c o n d i t i o n s . The r e f o r me r ga s
p hys i c a l p r o p e r t i e s we r e i n c o n t i n uo us c ha n ge a l o n g t he
t ubes a s t he c o n d i t i o n s o f t he r e f o r me r mi ght requi re.
Hy ma n [ 3] c o n s i d e r e d o n l y hea t t ra n s f er f r o m t ube wa l l
i n t o t he ref o rmi n g ga s wi t ho ut i n c o rp o ra t i n g t he hea t
t ra n s f er f r o m t he f uel ga s a n d f urn a c e burn ers a n d
t he r e by o v e r l o o k e d t he f uel qua l i t y a n d qua n t i t y. S i n gh
a n d S a ra f [ 9] c o n s i d e r e d t ha t ra d i a t i o n wa s t he p reva i l -
i n g mo d e f o r he a t t ra n s f er by f urn a c e ga s a n d f l a mes a n d
t ha t hea t t ra n s f er by c o n v e c t i o n wa s n egl i gi bl e. In
a d d i t i o n , t he y a s s ume d t he f l a mes a n d t he f urn a c e ga s a s
t wo d i s t i n c t s o ur c e s o f ra d i a t i o n . Al t ho ug h t he n egl i -
g e n c e o f c o n v e c t i o n c a n be j us t i f i ed f o r s i d e-f i red
f urn a c es , t hi s a s s ump t i o n ma y n o t ho l d f o r t o p -f i red o r
f l o o r-f i red r e f o r me r s , whi c h a re c ha ra c t eri zed by c o -
c urren t a n d c o un t e r c urren t f uel ga s - ref o rmer ga s f l o ws ,
r e s p e c t i ve l y.
248 I. M. ALATI QI , A. M. MEZI OU AND G. A. GASMELSEED
Table 3. Compari son of model predictions with actual ammonia plant data (primary
reformer)
Run date Measured Predicted from % error
simulator
(a) Reformer product average temperature (F)
09.02.88 1345.6 1345.2 - (l . 3
10,02.88 1342.4 1339.7 - 0 . 2
(b) Mole % of H 2 in reformer product
09.02.88 69.31 69.99 0.98
10.02.88 70.33 7l . 13 1.14
(c) Tube outlet pressure (psi)
09.1)2.88 Not recorded 437.1
10.02.88 Not recorded 381.6
)-4
4J
@
E~
1S80
1488
1388
128B
1 1 0 8
1880
/ /
s 8 8 L
8OO
8.0
r i g o r o u s
. . . . . f i r s t o r d e r
t i I I I I i J
3.8 7. S 11.4 1S.2 19.8 22.S 2S.6 38.4
T u b e Le n g t h ( f t )
Fig. 2. Temperat ure profile: rigorous and first order models.
I
34.2
1588
1480
1380
12 88
1108
.1888
SO~t
3 8 . O
STEAM - METHANE REFORMERS 249
140 0 0
130 0 0
12 0 0 0
ii0 0 0
l OGO0
%
~ 9 0 0 0
m
8 0 0 0
-M
"" 70 0 0
X
6 0 0 0
50 0 0
4 0 G G
30 0 0
0 .0 3.8 7.S 11.4 15.2 19.0 2 2 .8 2 5.6 30 .4 34.2 38.0
Tube L e n g t h (ft)
Fig. 3. Heat flux profile.
The relative accuracy of the results obt ai ned by this
st udy is compar ed with st udi es done previ ousl y in Tabl e
5 [3, 9, 11]. The fact t hat Mur r ay [11] did not include
radi at i ve heat t ransfer effects caused significant devia-
t i ons from the ot her r epor t ed results, which confirms the
i mpor t ance of r adi at i on in r ef or mer furnaces. It is clear
that the i ncor por at i on of r adi at i on and convect i on
effects of the fuel gas and flames, the qualities and
condi t i ons of fuel gas and feed r ef or mer gas cont r i but ed
to our model ' s accuracy. The i ncr ement al consi derat i on
of r ef or mer gas propert i es al ong the t ube react or also
cont r i but ed to model accuracy.
The use of equat i on (30) allowed heat di st ri but i on to
be cal cul at ed in the simplest possible way, yet allowing
flexibility in vari abl e fuel rate or densi t y and react or t ube
l engt h. Fi gure 3 shows the heat di st ri but i on al ong the
r ef or mer t ube according to equat i on (30). The fact that
equat i on (30) is empi ri cal l y det er mi ned does not effect
its general applicability, since two di fferent reformers
were accurat el y si mul at ed. Var i at i on in t hermal efficien-
cy is t aken care of by the par amet er ~.
Fi gure 4 illustrates the t emper at ur e profile of the
r ef or mer i nner t ube wall for the two different oper at i ng
condi t i ons cited in Tabl e l (a). Heat t ransfer coefficients
are shown as a funct i on of t ube l engt h (Fig. 5). It is clear
t hat higher t hr oughput s favor hi gher rates of heat
t ransfer, due to the increase of Rer at higher space
velocities. An increase in hin is not i ced towards the end
2 5 0 I . M. A L A T I Q I , A. M. ME Z I O U A N D G. A. G A S ME L S E E D
E

e-

, 4
e-
b-
c q ~1 , ~ c q ~., r , ~ .,,c ., ~ ~"~1 c ,~'- , ~ ~.~ ~.~
> > > > + 1 + 1 + 1 + ~ 1 ~
~ + 1 + 1
16 0 0
o
~J
~J
rd
k~
~J
~4
@
r~
H
rd
D
IS00
1400
1 3 0 0
1200
1100
I000
~ o o
s/Ill I//''"
i 0 0 c a p a c i t y
~t
. . . . 5 8 % c a p a c i t y
~ o o
o.1
i IS80
1S00
I I I I | I I | I
2 . 8 7. f i 1 1 . 4 1 5 . 2 1 9 . O 2 2 . 8 2 6 . S 3 0 . 4 3 4 . 2 3 8 . 0
1 4 0 0
1300
1200
11OO
STE AM - ME TH A N E RE FORME RS 251
9 0 0
8 0 0
T u b e L e n g t h ( f t )
Fig. 4. Tu b e wall i nne r t e mp e r a t ur e pr of i l e.
Ta bl e 5. Co mp a r i s o n wi t h o t he r s t udi e s
St udi e s Co n ve r s i o n ( % er r or ) Te mp e r a t u r e ( % er r or )
Thi s s t ud y 0. 39- 1. 21 0. 084) . 37
M. H. Hyman (1968) [3] 1. 3- 3. 5 0 . 5 - 2 . 7
C. P. P. Si ngh a n d
D. N. Sa r a f (1979) [9] 0 . 2 - 2 0. 04- 1. 3
A. P. Mur r a y a n d
T. S. Sn y d e r (1985) [1l ] 12-36 6 . 5 - 9 . 6
25 2 I. M. ALATIQ1, A. M. MEZ IOU AND G. A. GASMELSEED
o
4J
~Q
a3
~3
.,-4
r3
-,.4
q q
0
U
q4
n
,3
4J
190 0
180 0
12 0 0
1S0 0
I SO0
140 0
130 0
12 0 0
I I 0 0
I 0 0 0
0 . I
/
I I I I I
3.8 7.5 11.4 15.2 19.0
. _..~---"
. . . . - . . . . . . . . .
1 0 0 % c a p a c i t y
. . . . 5 8 % c a p a c i t y
I I I I
2 2 . 8 2 6 . 6 3 0 . 4 3 4 . 2
1 9 OO
180 0
12 0 0
150 0
150 0
140 0
130 0
12 0 0
110 0
I 0 0 0
38.0
T u b e L e n g t h (ft)
Fig. 5 . Heat trans fer coefficient p rofile.
o f t he t ube, d ue t o t he l a rger s p a c e vel o c i t i es c a us ed by
t he p res s ure d ro p a c ro s s t he t ubes . The l a rger s p a c e
ve l o c i t i e s a re a l s o a t t ri but ed t o t he i n c rea s e i n t he
n umbe r o f mo l e s p res en t i n t he ga s mi xt ure.
Control interface
The s t ea d y s t a t e s i mul a t o r c a n be very hel p f ul f o r
s up ervi s o ry a n d a ut o ma t i c c o n t ro l d es i gn . By i n c l ud i n g
a c o n t ro l i n t erf a c e, t he c o mp ut e r p ro gra m c a l c ul a t es t he
f uel requi remen t s t o ma i n t a i n a c o n s t a n t c o i l o ut l et
t emp era t ure ( C OT) o r c o n ve r s i o n whe n d i s t urba n c es
l i k e f e e d ga s mi xt ure t hro ughp ut o r s t ea m-t o -c a rbo n
ra t i o o c c urs . Wh e n i n s t a l l ed o n - l i n e , t he s i mul a t o r c a n
be us ed t o mo d i f y t he f uel c o n t ro l l er s et p o i n t t o gi ve t he
c o rrec t s i gn a l t o t he f uel va l ve t o d el i ver t he requi red
f uel ra t e.
The c o n t ro l i n t erf a c e i s a n i t era t i ve l o o p t ha t c hec k s
f o r t he t a rget , e. g. t emp era t ure s et p o i n t ( 7 ~et) o r
c o n ve r s i o n s et p o i n t ( A ~ et ) a n d c ha n ges s o me ma n i p ul a -
t i ve Va ri a bl e t o a p p ro a c h t he t a rget c o n d i t i o n . An y
a l gebra i c f un c t i o n s o l ver, s uc h a s Ne wt o n ' s o r S ec a n t
me t ho d s , c o ul d be us ed . To a vo i d s t a bi l i t y p ro bl ems a n d
c ut c o n ve r ge n c e t i me, ho we ve r , a n a l t ern a t i ve a p p ro a c h
i s us ed . Thi s a p p ro a c h t a k es a d va n t a ges o f t he s en s i t i vi -
t i es o f t he t a rget va ri a bl e ( y ) t o t he ma n i p ul a t i ve
va ri a bl e ( u) , ( s e e Ta bl e 4 ) , Fro m t hes e s en s i t i vi t i es , a
wei ght i n g f a c t o r (wt) c a n be es t i ma t ed a n d us ed i n t he
rec urs i o n f o rmul a :
STEAM - METHANE REFORMERS 253
/2
O
g
o
8 0 .
79.
7 8
7 1 .
76.
A : F u e l
: % H 2
75
I I I / I I
- 5 0 - 4~ - 3 e - 2 8 - 10 0 l e
I ( s e t ) /
g a s r a t e
in r e f o r m e r p r o d u c t
2 8 3 40 5 ~
% C h a n g e i n R e a c t i n g G a s M i x t u r e F l o w R a t e
-E
r.)
4 J
Fig. 6. Percentage of hydrogen and fuel plotted against reacting mixture flow at constant T.
ui+l = ui 11 + w t ( y ~ t - Yi)] (33)
t hat can be regarded as l i near i nt er pol at i on accel erat ed
by wt . Exper i ment s with fuel rate as u and COT or
conver si on as y resul t ed in convergence to the r equi r ed
amount of fuel in two to four i t erat i ons. As a result, the
closed loop si mul at i on will have an execut i on time equal
to t hat of the open loop si mul at i on mul t i pl i ed by the
numbe r of i t erat i ons. This subst ant i at es the need for the
fast efficient numer i cal pr ocedur e empl oyed.
The cont rol i nt erface allows process si mul at i on in a
closed loop mode, i.e. at fixed val ues of the cont rol l ed
vari abl e. Thus, many al t er nat i ve cont rol systems can be
st udi ed and anal ysed. Fi gure 6 shows the r el at i onshi p
bet ween tuel r eqmr ement F G and t hr oughput F (with a
const ant S / C ratio) at cont r ol l ed COT. The conversi on
was relatively const ant in the range st udi ed, i ndi cat i ng
that cont rol l i ng COT gives a good command of conver-
sion in the absence of ot her di st urbances. Fi gure 6 also
shows that the feed forward gain bet ween fuel rate and
feed rate is const ant (the slope of the line).
The effect of a vari abl e S / C rat i o can be shown for
di fferent oper at i ng strategies. For exampl e, under con-
t rol l ed out l et t emper at ur e, fuel r equi r ement and thus
conversi on increases with the S / C rat i o (Fig. 7). Since
this is not economi cal , energy consumpt i on can be
reduced by varyi ng the out l et t emper at ur e set poi nt .
Figure 8 shows that the out l et t emper at ur e increases as
254 I.M. AI,A'I'IQI. A. M. MEZIOU AND (;. A. GASMELSEED
I
,9 _
,8 .
O
C
,7.
o
8 .6.
. 5.
, 4 1
A
T(set):L45g.15
( 1 1 3 8 z c a p a c i t~ )
: M e t h a n e c o n v e r s i o n
: F u e l g a s r a t e
S / C R a t i o
J. 0
R
(.)
4~
d
,-q
Fig. 7. Variation of conversion and fuel gas rate with S/C ratio for fixed COT.
the S/C ratio is reduced. Ther ef or e, a mi n i mum. S/ C
rat i o can be selected, based on the maxi mum al l owabl e
t emper at ur e t hat will not det er i or at e catalyst activity or-
service life.
CONCLUSI ONS
A steady state model for i ndust ri al scale s t e a m-
met hane reformers was devel oped. Compar i son of a
rigorous ki net i c model and a simplified model showed
t hat bot h model s can accurat el y predi ct t he r ef or mer
exit condi t i ons. Sensitivity analysis, confi rmed with
pl ant exper i ment s, showed t hat the model based on the
react i on (equat i on l b) and equat i on (equat i on 14)
predi ct ed conver si on bet t er in t erms of pressure and S/C
upsets. I n fact, the appr oxi mat e model based on
met hane pressure resul t ed in a response opposi t e to t hat
expected from an equi l i br i um cont r ol l ed react i on.
Heat t ransfer from fuel flames and gases to the
reformi ng gases was model l ed via an empi ri cal quadr at i c
equat i on, rel at i ng heat di st r i but i on to t ube l engt h. This
rel at i onshi p allows one to i ncl ude the effects of r adi at i on
and convect i on and to fit exactly the bur ner s l ocat i on
and di st ri but i on effects. Ref or mer out l et t emper at ur e
and conversi on mat ched closely with pl ant records.
A cont rol i nt erface was connect ed to the r ef or mer
model. The i nt erface cont ai ns an i t erat i ve loop that
converges to the r equi r ed heat dut y for cont rol of
conversi on, COT or any ar bi t r ar y object i ve, in the face
of any arbi t rary di st ur bance.
Acknowledgement--This study v~as done under KISR Project
ASD-18 "Adaptive Control of Selected Processes at KNPC: A
Pilot Study", which was supported by the Kuwait National
Petroleum Company (KNPC). The authors thank KNPC and
the Petrochemical Industries Company (PIC) for permission to
publish this article.
STEAM MI.:,TllANE I~,F, FOI~,MIH~,S 255
C
O
u]
C
O
>
C
S
r ~
e -
4~
. 8
,7~
. 6
(100z c apac i t f f )
: Me t h a n e c on v e r s ion
A : T e mp e r a t u r e ( COT)
S / C R a t i o
Fig. 8. Variation of conversion a n d C O T with S/C ratio.
I g @ 8
1798
16W~
1 5 8 8
[400
L309
1288
t l
4 J
b~
RE FE RE N C E S
1. J. M. Moe and E. R. Ger har d, Chemi cal react i on and
heat t r ansf er rat es in t he st eam met hane react i on.
A. 1. Ch. E. Symposium, 56th National Meeting, San Fran-
cisco, Cal i forni a (1965).
2. Hi roshi Yogi, Si mul at i on model of st eam r ef or mer he-
at ed by high t emper at ur e hel i um. Paper pr esent ed at
SCSC 81, Washi ngt on D. C. (1981).
3. M. H. Hyman, Si mul at e met hane r ef or mer react i ons.
Hydrocarbon Process 47, 131 (1968).
4. W. W. Aker s and D. P. Camp, A.1.Ch.E.J. 1, 471
(1955).
5. I. M. Bodr ov, L. O. Apel baum and M. I. Ti mki n,
Kinetics and Catalysts 5, 618 (1964).
6. D. W. Al l en, E. R. Ger har d and M. R. Likins, Jr. , Ind.
Engng Chem. Process Des. Dev. 14, 256 (1975).
7. M. E. Agnel l i , E. N. Ponzi and A. A. Yer ami an, Cat al y:
tic deact i vat i on on met hane st eam r ef or mi ng catalysts. 2.
Ki net i c study. Ind. Engng Chem. Res. 26, 1707-1713
(1987).
8. J. Beek, Advances in Chemical Engineering, Vol 3, p.
234, Academi c Press, New York (1962).
9. C. P. P. Singh and D. N. Saraf, Si mul at i on of side fired
s t eam- hydr ocar bon reforms. J. Ind. Engng Chem. Pro-
cess Des. Dev. (1979).
10. S. Er gun, Chem. Engng Progr. 48, 89 (1952).
11. A. P. Mur r ay and T. S. Snyder, St e a m- me t ha ne refor-
mer ki net i c comput er model with heat t r ansf er and
geomet r y opt i ons. Ind. Engng Chem. Process Des. Dev.
24, 286-294 (1985).
12. M. O. Tar han, Catalytic Reactor Design, pp. 79, 116-
117, McGraw-Hi l l , New York (1983).
13. R. H. Perry and C. H. Chi l t on, Chemical Engineers
Handbook, 5th ed. , pp. 10-12 to 10-17, McGraw-Hi l l ,
New York (1973).
A P P E N DI X
Physi cal propert i es
1. Vi scosi t y Th e vi s c os i t y of t he r e c t i o n mi x t u r e was
c a l c ul a t e d us i n g t he C. R. Wi l ke e q u a t i o n [12]. Thi s is
256
neces s ar y becaus e n e i t he r s t e a m n o r hy d r o g e n c onf or ms
t o s i mpl er r el at i ons hi ps . The e qua t i o n is:
Pi
~mi x = n
i = 1 Z n
i =~x j
- - q~6
Xi
wher e,
I. M. ALATI QI . A. M. MEZIOU AND G. A. GASMELSEED
[1 + ( FI / / ~j) 1/2 ( M j / M i ) 1/4]
q0ij = {8(1 + ( Mi / Mj ) ] } 1/2
The vi scosi t y of t he pur e gas c o mp o n e n t can be det er -
mi n e d us i ng r e f or me r Tho d o s a nd co- wor ker s cor r el a-
t i ons [13].
(a) No n pol a r gases:
# ~ = 4. 610 Tr 0. 618 - 2. 04 e 0. 449 Tr +
1.94 e 4sS7'r + 0.1
(b) Pol ar gases, hy d r o g e n - bo n d i n g Tr < 2. 0:
/ ~ = (0. 755 T~ - 0. 055) Zc 5/4
(c) Pol ar gases, n o n hy d r o g e n - bo n d i n g Tr < 2. 5:
/~ff = (1. 9 Tr - 0. 29) 4/5 Z ~ el3
wher e,
= TIc/6 M - I n pc2/3
M - mol e c ul a r wei ght of pur e gas c o mp o n e n t
n = n u mb e r of c o mp o n e n t s i n t he r eact i on
gas mi xt ur e
Tc = cri t i cal t e mp e r a t ur e , K
Tr = r e duc e d t e mp e r a t ur e
Pc = cr i t i cal pr es s ur e, ar m
Pr = r e duc e d pr es s ur e
xi, x/ = mol e f r act i on of c o mp o n e n t s i a nd j
/~ = vi scosi t y, p p ( mi cr opoi s e)
a nd t he s ubs cr i pt s , i, j = c o mp o n e n t , mi x = mi xt ur e.
2. He a t c a p a c i t y
Cp,,,,~ = Y X i C , , ,
whe r e
Co, = he a t capaci t y of c o mp o n e n t i [Bt u (l b
mol eOF) - i]
Cp,,,,~ = heat capaci t y of r eact i on gas mi xt ur e [bt u
(l b mol eF) -1]
Xg = mol e f r act i on of c o mp o n e n t i.
3. T h e r ma l c o n d u c t i v i t y
~'mix = Z X i ~i
whe r e ,
J.iMi
- 1 . 1 5 C ~ , , + 4 . 0 4
a nd Cv, = Co, - R
wher e
Co,, Cv~ = heat capaci t y of c o mp o n e n t i [cal (gmol
K) -' ]
Mi = mol e c ul a r wei ght of c o mp o n e n t i
R = gas l aw c o n s t a n t [1. 987 cal ( gmol K) 1]
/~i = vi scosi t y of c o mp o n e n t i (/ t p)
)-i = t he r ma l c onduc t i vi t y of c o mp o n e n t i
[cal (cm s K) - i ]
)t,lix = t he r ma l c onduc t i vi t y of gas mi xt ur e
[cal (cm s K) l].