Example 10-9

The oxidatiion of dilute aqueous solutions of acetic acid was studied: in a trickle-bed reactor using
a commercial, iron oxide catalyst. Air and solutions of acetic acid saturated with oxygen (by
bubbling air through the solution at atmospheric pressure) flowed at 252oC and 67 atm downward
over 0.0541 cm catalyst particles (packed to a depth of 2.2 cm) in a 2.54 cm ID reactor. The flow
rates are QL = 0.66 cm3/s and Qg = 3.5 cm3/s. At the reactor entrance the concen tration CL,O2, of
oxygen in the liquid is 2.40 x 10-7 g mol/cm3 , that for acetic acid is CL,HA = 33.7 x 10– 7 g mol/cm3,
and the gas is air, saturated with water at 252oC. The bulk density of the catalyst bed is ρn= 1.17
g/cm3, while the particle density is, ρp = 2.05 g/cm3.

For the reaction, CH3COOH(aq) + 2O2(aq)-> 2CO2(aq) + 2H2O, the intrinsic rate for the
disappearance of oxygen is given by (A)

21000 1/2
9.9 𝑥 109 [exp (− 𝑅 𝑇 )] 𝐶𝑠,𝐻𝐴 𝐶𝑠,𝑂2
𝑔𝑚𝑜𝑙 𝑔
𝑟𝑂2 ( )(𝑠) =
𝑔𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 1 + 7.2 𝑥 105 𝐶𝑠,𝐻𝐴

where the concentrations are those at the outer surface of the catalyst particle and T is given in
degrees Kelvin. Henry's law constant for oxygen in liquid water at 252oC is 0.89 [g mol/(cm3 gas
at 25oC, 1 atm)]/[g mol/cm3 liquid). Other physical properties at 252°C and 67 atm for liquid water
are estimated to be :

𝑔
𝜌𝐿 = 0.81
𝑐𝑚3
𝑔
𝜇𝐿 = 1.18 𝑥 10−3
𝑐𝑚(𝑠)

−4
𝑐𝑚2
𝑃𝑂2 = 2.1 𝑥 10
𝑠

−4
𝑐𝑚2
𝑃𝐻𝐴 = 1.2 𝑥 10
𝑠

A. From this information calculate the global rate at the reactor entrance.
B. B. Also calculate the ra te of mass transfer of oxygen from the gas to the liquid.
SOLUTION

The reaction occurs by oxygen and acetic acid in the liquid diffusing to the catalyst particles and
reacting. Simultaneously, oxygen (but not nonvolatile acetic acid) is transferred from the air stream
to replenish the oxygen in the liquid. Since oxygen is but slightly soluble in water, the overall
transfer from gas to liquid may be safely assumed to be governed by the liquid-side coefficient
(kLαg)O2. Then the rate of oxygen transfer, per unit volume of reactor, from gas to liquid is (B)

𝑔 𝑚𝑜𝑙 𝐶𝑔,𝑂2
𝑁𝑂2 [ 3
] = (𝑘𝐿 𝑎𝑔 )𝑂2 ( − 𝐶𝐿,𝑂2 )
(𝑠)(𝑐𝑚) 𝐻

The concentration difference in this expression is large since CL,O2 in the feed corresponds to
saturation with air at a tmospheric pressure, while Cg,O2 in the feed is for air at 67 atm. Similarly,
the rate of oxygen and acetic acid transfer from liquid to particle are given by the express ions (C)
and (D)

(𝑟𝑣 )𝑂2 = (𝑘𝑐 𝑎𝑐 )𝑂2 (𝐶𝐿,𝑂2 − 𝐶𝑠,𝑂2 )

(𝑟𝑣 )𝐻𝐴 = (𝑘𝑐 𝑎𝑐 )𝐻𝐴 (𝐶𝐿,𝐻𝐴 − 𝐶𝑠,𝐻𝐴 )

A. At steady state the rates of mass transfer from liquid to particle are equal to the rates of
reaction. These expressions relate surface and bulk liquid concentrations. Equating Eqs.
(A) and (C), and (A), and (D), yields (E) and (F)

21000 1/2
9.9 𝑥 109 [exp (− 𝑅 𝑇 )] 𝐶𝑠,𝐻𝐴 𝐶𝑠,𝑂2
𝑔
𝑟𝑂2 = (𝑘𝑐 𝑎𝑐 )𝑂2 (𝐶𝐿,𝑂2 − 𝐶𝑠,𝑂2 ) =
1 + 7.2 𝑥 105 𝐶𝑠,𝐻𝐴

21000 1/2
9.9 𝑥 109 [exp (− 𝑅 𝑇 )] 𝐶𝑠,𝐻𝐴 𝐶𝑠,𝑂2
1 𝑔
𝑟𝐻𝐴 = (𝑘𝑐 𝑎𝑐 )𝐻𝐴 (𝐶𝐿,𝐻𝐴 − 𝐶𝑠,𝐻𝐴 ) = 𝜌𝐵
2 1 + 7.2 𝑥 105 𝐶𝑠,𝐻𝐴

Equations (E) and (F) may be solved for the two surface concentrations after (kcαc)O2 and
(kcαc)HA are estimated.

From the data given

0.66 (0.81)
𝐺𝐿 = 𝜋 = 0.11 𝑔/(𝑐𝑚)2 (𝑠)
( 4 ) (2.54) 2
 0.66
𝜇𝐿 = 𝜋 = 0.13 𝑐𝑚/𝑠
( 4) (2.54)2

𝑑𝑝 𝑢𝐿 𝜌 0.0541 (0.13)(0.81)
𝑅𝑒𝐿 = = = 4.8
𝜇𝐿 1.18 𝑥 10−3

𝜇𝐿 1.18 𝑥 10−3
𝑃𝑂2 = = 6.9
𝜌𝐿 0.81 (2.1 𝑥 10−4 )

𝜇𝐿 1.18 𝑥 10−3
𝑃 = = 12.1
𝜌𝐿 𝐻𝐴 0.81 (1.2 𝑥 10−4 )

for spherical particles,

𝜋𝑑𝑝2 𝜌𝐵 6 1.17 𝑐𝑚2

𝑎𝑡 = = ( ) = 63
(𝜋𝑑𝑝3 /6)𝜌𝑝 0.0541 2.05 𝑐𝑚3

Substituting these values in Eqs. Equations below

𝑗𝐷 = 1.64(𝑅𝑒𝐿 )−0.331 for (0.2 < ReL < 2400)

Where

2
𝑘𝑐 𝑎𝑐 𝜇𝐿 3
𝑗𝐷 = ( )
𝑢𝐿 𝑎𝑡 𝜌𝐿 𝐷𝐴

𝑢𝐿 = superficial velocity of liquid

𝑎𝑐 = total external area of particles per unit volume of reactor

𝑅𝑒𝐿 = reynold number

Below

2
𝜇𝐿 − 3
(𝑘𝑐 𝑎𝑐 )𝑂2 = 𝑗𝐷 (𝑢𝐿 𝑎𝑡 ) ( )
𝜌𝐿 𝐷𝐴

(𝑘𝑐 𝑎𝑐 )𝑂2 = 0.97 (0.13)(63)(0.28) = 2.2 𝑠 −1

(𝑘𝑐 𝑎𝑐 )𝐻𝐴 = 0.97 (0.13)(63)(0.19) = 1.5 𝑠 −1

 With these mass-transfer coefficients, T = 252 + 273 = 525 K, and CL,O2 = 2.40 X 10-7 g
mol/cm3 and CL,HA = 33.7 X 10-7, all quantities in Eqs. (E) and (F) are known except Cs,HA
and Cs,O2. Numerical solution yields

𝐶𝑠,𝐻𝐴 = 2.35 𝑥 10−7 𝑔𝑚𝑜𝑙/𝑐𝑚3

𝐶𝑠,𝑂2 = 33.6 𝑥 10−7 𝑔𝑚𝑜𝑙/𝑐𝑚3

The global rate is then obtained by using these surface concentrations in Eq. (A):

21000
9.9 𝑥 109 [exp (− )] (33.6 𝑥 10−7 )(2.4 𝑥 10−7 )1/2
𝑟𝑂2 = 525 𝑅
1 + 7.2 𝑥 105 (33.7 𝑥 10−7 )

𝑟𝑂2 = 8.4 𝑥 10−9 𝑔𝑚𝑜𝑙/(𝑠)(𝑔 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡)

In this example, the external liquid-particle mass-transfer resistance is relatively small;

(CL.O2 – Cs,O2)/CL,O2 = 0.05/2.4 = 0.02 or 2%. For this particular case bulk concentrations
could have been used in Eq. (A), to calculate the rate. This is because the intrinsic rate is
slow.

B. Equation (B) is applicable for evaluating the oxygen-transfer rate from gas to liquid. The
coefficient (kLαg)O2 , is determined from Eq. below
1
𝑘𝐿 𝑎𝑔 𝐺𝐿 𝜑𝐿 𝜇𝐿 2
= 𝑎𝐿 ( ) ( )
𝐷𝐴 𝜇𝐿 𝜌𝐿 𝐷𝐴
gives
0.4
0.11 1
(𝑘𝑐 𝑎𝑔 )𝑂2 = 2.1 𝑥 10−4 (7) ( −3
) (6.9)2 = 0.024 𝑠 −1
1.18𝑥10
Note that this coefficient is about two orders of magnitude less than kcαc. Both kLαg and
kcαc would be much higher at the higher liquid rates normally found in industrial trickle-
bed reactors. The concentration of oxygen in the gas at 67 atm and 252°C is
𝑝𝑂2 0.21(26.2)
𝐶𝑔 = = = 1.3 𝑥 10−4 𝑔𝑚𝑜𝑙/𝑐𝑚3
𝑅𝑔 𝑇 82(525)
Henry's law constant is HO2 = 0.89 when the gas volume of pure oxygen is measured at
25°C and 1 atm. At pO2 = 0.21(26.2) = 5.50 atm and t = 252°C
 5.5 298
𝐻𝑂2 = 0.89 ( ) ( )
1 252 + 273
𝑔𝑚𝑜𝑙/(𝑐𝑚3 𝑔𝑎𝑠 𝑎𝑡 5.5 𝑎𝑡𝑚, 252𝑜 𝐶)
𝐻𝑂2 = 2.78
𝑔𝑚𝑜𝑙/𝑐𝑚3 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑

Then, from Eq. (B)

1.3 𝑥 10−4
𝑁𝑂2 = 0.024 [ − 2.4 𝑥 10−7 ]
2.78
𝑁𝑂2 = 0.024(4.59 − 0.02)𝑥 10−5 = 1.1 𝑥 10−6 𝑔𝑚𝑜𝑙/(𝑠)(𝑐𝑚)3

Per unit mass of catalyst this is 1.1 x 10-5/ρB = 9.4 x 10-7 g mol/(s)(g catalyst). Since this
rate is much greater than the rate of reaction, rO2, at the particle surface, the oxygen
concentration in the liquid would tend to be augmented at this location in the reactor. This
was observed by Levec; the oxygen concentration in the liquid increased in the direction
of flow through the reactor. ln a similar study for the more rapid oxidation of formic acid,
the intrinsic rate was much higher. For that situation the rate of depletion of oxygen from
the liquid due to reaction was greater than the rate of transfer from gas to liquid in some
parts of the reactor. It was observed that CL,O2 , decreased in the direction of flow through
the reactor. Also in that case the concentration d ifference (CL,O2 – Cs,O2) was significant,
in contrast to the results of this example for acetic acid oxidation.