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The oxidation of carbon monoxide with Hopcalite catalyst was studied in an isothermal recycling
reactor with special attention poid to the changes of gas phase compositions with time.
Conversion-time data exhibit significant departures from first-order behavior often ascribed to
this reaction. In early stages the reaction rate declines more rapidly than would a first-order
reaction; later the reverse is true. A mechanism, based on careful analyses of the literature
and of our observations, is proposed. A kinetic model based on this mechanism is shown to re-
produce the data of any run satisfactorily, but there is a considerable variation in values
of the constants from run to run.
The catalytic oxidation of carbon monoxide near ambient critically influenced by their preparation, their history, and
temperature is the subject of this study. The reaction is even their environment between runs. This has received
an interesting and challenging one because, when oxide little attention.
catalysts are used, interactions between gas and solid Although the heat of reaction is large, measurements of
phases beyond simple catalysis are often involved. The re- the catalyst temperature during reaction are generally ab-
action is of practical interest, as well, since carbon monox- sent; large temperature rises have been reported in some
ide is a common pollutant. investigatiops (1, 24, 25, 39, 41, 47, 5 7 ) . With such a
The catalyst used was commercial Hopcalite ( a mixture large heat effect, it is unlikely that isothermal conditions
of oxides of manganese and copper and small quantities of were attained in much of the previous work.
other oxides). The possible presence of fluid-film and catalyst pore con-
This reaction has been the subject of much previous centration and temperature gradients was rarely explored.
work, but its complexity and certain special circumstances, These can exhibit great rate influencing effects, particularly
for example, the large heat of reaction (67.6 kcal./g. mole in the often used static experiments.
carbon monoxide) have led to considerable disagreement. A notable shortcoming in many investigations is the de-
The basic objectives of the present work were to carry out pendence on total pressure measurements for determina-
experiments with careful regard to these complexities and tion of reaction extent in batch experiments. There is
to establish, if posible, a mechanism and kinetic model to ample evidence in the literature (see below) that the oxide
explain the results. catalysts undergo reaction in addition to acting as catalysts;
The reaction was carried out in a batch recirculation dif- thus, the reaction cannot be described so simply as CO +
ferential reactor. The range of variables was as follows: 1/2 O2 = C02, and total pressure measurements are in-
Temperature: 40°C. (majority of runs), sufficient. Analyses of the gas compositions in a region of
28"C., 50°C. known pressure and constant temperature are essential to
Initial carbon monoxide: 26 to 108mm. Hg. clarify this matter.
Initial oxygen: 0 to 376 m. Hg. For these reasons, this experimentation was designed to:
Initial carbon dioxide: 2' to 84 mm. Hg. 1. Specify as completely as possible the nature, history,
Total pressure: 800 to 833 mm. Hg. This was and storage of the catalyst
attained with diluent nitrogen 2. operate under such conditions that the reaction was
Catalyst weight: About 3 g. isothermal
Reactor gas volume: 3,194 cc. 3. minimize diffusional effects
4. permit measurements of gas compositions at known
* Since initial time was taken at a point somewhat after initial contact
with the catalyst, some product carbon dioxide was always present. See pressure and constant temperature so that the true course
section Operating Pressure. of the reaction could be followed. To this end, the whole
reactor (not merely the catalyst) was held at constant tem-
SUGGESTIONS FROM THE L I T E R A T U R E perature.
A comprehensive survey of the extensive literature on Cunsensus of Findings
this reaction is presented by Brittan ( 7 ) .Those references Notwithstanding differences and inconsistencies in
bearing on the aims and methods of the experimentation much of the previous work, there is general agreement on
will be touched on briefly here; those having to do with many points. The catalytic oxides are almost invariably
kinetics and mechanism will be deferred to appropriate nonstoichiometric in composition (36, 4S, 59, 69, 70, and
later sections. others). The catalyst activity appears to be dependent on
the amount of available oxygen in the oxide (1,9 to 12,21,
Experimental Problems
38, 39, 43, 47, 52, 53, 61, 6 2 , 6 5 ) . Reduction of the oxide
Shortcomings in experimental techniques are probably causes a lowering of its activity, ,and the data of some
responsible for some of the discrepancies in the literature. workers (11, 39) suggest a linear relationship between
For instance, the activity and behavior of the catalysts are the amount of oxygen removed and the decline in activity.
Several workers have reported that the activity of fresh
Michael I. Brittan is with the Anglo American Corporation of South catalysts is high but declines with use (11, 12, 42, 47, 6 5 ) .
Africa, Limited, Cmwn Mines, Johannesburg, South Africa. The activity is apparently also permamently impaired by
EXPERIMENTAL
The reaction was conducted by charging mixtures of carbon
monoxide, oxygen, and nitrogen (and, on occasion, carbon
dioxide) to a closed-loop reactor and circulating them con-
tinuously through a short bed of Hopcalite catalyst. The entire
reactor was immersed in a constant temperature bath. Gas
samples were withdrawn from the reactor at suitable time in-
tervah for analysis to monitor the progress of reaction. Runs
were usually continued to virtual1 100% conversion.
The reactor of Long ( 4 4 ) , moJfied for this work, was con-
structed of glass piping (Figure 1) and had a total volume of THERMOSTAT
3,194 f 5 cc. The assembly consists of a horizontal section of
Fig. 1. Reactor and support system.
4-in. pipe in which the blower is mounted in an annular Teflon
insert, a loop of 1-in. diameter ipe connecting the ends of the
blower section and containing i e catalyst ( a bed about % in.
in depth and supported on stainless steel wire mesh grid) and reaction components removed were insignificant.
a sam ling port sealed with chromatograph septums, a mani- At high reaction rates, the frequency of the gas sampling was
f
fold o copper tubing with provisions for adding and removing greater than the maximum frequency with which they could
be analyzed imposed by the 7 min. analysis time. Thorough
gases and for measurement of pressure, and a water bath with
temperature control to zk 0.05"C. Thermocouples are located sealing of the syringes permitted the storage of these sam-
in the catalyst bed, in the gas downstream from the blower and ples in the syringes prior to injection into the chromatograph.
in the water bath. Catalyst
The chromatographic analyses of the gases used in this work
are as follows: The Hopcalite used was the same as that employed in Mine
Percentage of Safety Appliances M-S-A All-Service Gas Mask Canisters. This
CO 02 N2 CO2 was stored in a dry atmosphere prior to use. The catalyst used
in A-series runs consisted of 3.05 g. of Hopcalite taken directly
Carbon monoxide 99.90 0.02 0.08 from storage. That used in B-series runs was pretreated by
Oxygen 99.75 0.25 heating in vacuo at 185°C. for 3 hr. The bed of B catalyst
Nitrogen 99.996 weighed 2.988 g.
Carbon dioxide 0.03 0.12 99.85 Analysis of the catalyst for metal components (60) indicated
manganese as the major component, copper as the minor, very
Since complete dryness of all gases was necessary, they (ex- small amounts of cobalt and silver, and traces of aluminum,
cept carbon dioxide) were passed through tubes packed with iron, nickel, magnesium, and barium. A recently reported anal-
Linde 5A molecular sieves. Since carbon dioxide is strongly re- ysis of Hopcalite from the same source is 78.3% manganese
tained b molecular sieves at ambient temperatures silica gel dioxide, 13.1% cupric oxide, traces of other elements, 7.9%
was usedlas the desiccant in this case. The gas feed lines formed loss on ignition ( 1 5 ) . The fresh catalyst was analyzed vol-
a manifold system connected to the reactor as shown in Figure umetrically for available oxygen content by methods described
1 enabling any of the five gases to be tapped as required. in such textbooks as that of Kolthoff and Sandell. The result
(13.30% available oxygen) is in the range of values reported
Gas Analysis System in the literature ( 1, 39).
A chromatographic technique was devised for all four gaseous The catalyst consisted of black granules of irregular shape
components using a Beckman GC-2 Chromatograph with both which can be characterized as to size by noting that the equiv-
a silica el and a 5A molecular. sieve column in conjunction alent sphere diameter would be 0.20 to 0.25 cm. Data on ni-
with a ~uaEcolumnvalve. The details of the technique are trogen adsorption and desorption at liquid nitrogen temper-
given elsewhere (7). The precision of the analysis was esti- atures indicated the BET surface area to be about 300 sq.m./g.
mated to be within & 0.2%. The method of Barrett, Joyner, and Halenda (3)was used to
Gas samples were withdrawn from the reactor with 5 cc. analyze the isotherm data and indicated an average micropore
hypodermic syringes equipped with 1% in. Huber point needles radius of approximately 30A.
which prevented plugging of the needle on penetration of the
septums. Since a complete analysis of all components was ob- Operating Procedure
tained, it was not necessary to know or duplicate accurately the With the thermostat at the re uired temperature, the reactor
sample volume. The sample volume withdrawn from the re- was evacuated, then charged wig nitrogen and oxygen ( i n the
actor was about 3 cc. and was purged until 2 cc. remained im- great majority of runs) in the desired proportions but in quan-
mediately preceding injection into the chromatograph. On tities somewhat in excess of those required for the run. A ball
average, about 1% of the gas in the reactor was lost to the valve at the reactor inlet was used to meter the gases to pro-
samples in the course of a run. The nitrogen diluent consti- vide the required partial pressures as indicated by the pressure
tuted the major proportion of the gas and thus the amounts of gauge. The blower was then switched on and the system left
In -
POCO
= Kt (.2 ,)
PCO
The plots for most of the runs are thus shown in Figures
2 to 6. The run conditions relevant to Figures 2 to 6 are
given in Table 1.
The activity of fresh catalysts was high but declined
in the course of experimentation. This is exemplified in
Figure 4 by the decline in slope of the first-order curves
in passing from run B1 to B11. Similar observations have
been made in previous investigations with manganese
oxides and Hopcalite (11, 12, 42, 47, 65) and also with
other oxides. The decrease in catalyst activity was found
to be accelerated by reducing gas-phase conditions (rela-
tively low 0xygen:carbon monoxide) and minimized by
oxidizing gas mixtures (relatively high oxygen:carbon
monoxide) corresponding with the degree of oxidation
of the catalyst. It was possible to attain reasonable plateaus
of activity (or even on occasion to enhance the activity)
t (min) by ensuring that oxidizing gas-phase conditions prevailed,
Fig. 2. First-order plot of carbon monoxide data, runs A l to A9. thereby preventing appreciable reduction of (or actually
MECHANISM
Previous Work
The literature survey revealed close similarity in the
behavior of Hopcalite and manganese dioxide and some
similarity between the behavior of Hopcalite and other ox-
ides such as those of copper and nickel. In this discussion,
20 40 60 80 100
t (min)
Fig. 4. First-order plot of carbon monoxide data, runs 81 to B1 1.
r
the presumed primar and rate-controlling adsorption step
can be written as fol ows: The reasons for indicating this reaction to be reversible
have been stated previously. However, carbon dioxide has
co + 0, + 0, [CO] (E) negligible effect on the overall rate (see Run A l l ) , indi-
Reduction of the catalyst to produce carbon dioxide can cating that the equilibrium lies far to the right. With
be represented as Reaction ( D ) written as irreversible, it will be seen that
the sum of ( D ) and ( H ) is ( G ) . It is thus not necessary
0, [ C O ] + coz +s (F) to consider this complex as a separate species.
where S is a vacant active site which can be regenerated During this stud it was observed that the amount of
as forlows: B
carbon dioxide pro uced was consistently slightly less than
+
s 1/202+0, (B) the amount of carbon monoxide consumed. This effect has
also been reported by Bruns ( 1 1 ) and others (27, 37, 46,
The experimental data provide evidence for reaction 49) and suggests that a small amount of carbon dioxide
steps ( E ) , ( F ), and (B). Qualitatively, one might expect must be very firmly retained and released very slowly:
reduction of the catalyst to occur when the carbon monox-
ide partial pressure is high at low conversions and oxida- co + o,+ cog, (K)
tion of the catalyst to occur when the carbon monoxide
partial pressure is low (provided sufficient oxygen is pres-
ent). Participation of the oxide catalyst in the reaction It is not likely that the desorption step is of importance
would influence the stoichiometry of the gas phase. This in a kinetic analysis. Experimental observations indicated
would be reflected in the value of ( 2 p 0 2 - p c o ) , a quan- a very slow release of carbon dioxide into the gas phase
0, [CO] + 1/2 0 2
k4
+ CO2 + 0, (GI - 2 - =dpOz
dt
(k4 e + k , S ) p ~ ~ ” ~
k5
s + 1/202+0, (B) Since ( E ) is a relatively slow reaction, 0, [CO] reacts
to form carbon dioxide according to ( F ) and (G) as fast
A KINETIC MODEL as it is formed. This conforms to the o‘bservation that the
The major reactions of the mechanism with the rate carbon dioxide produced is rapidly released to the gas
constants given permit the formulation of a model. It is phase and is substantiated by the experimental data which
based on the assumption that the rate is controlled by show that the partial pressure-time curve for carbon dioxide
the adsorption of carbon monoxide [reactions ( E ) and is virtually a mirror image of that for carbon monoxide
( K ) ] on 0, centers whose concentration is governed by (provided that the small quantity of carbon dioxide present
the scheme as a whole. It must be observed that the fact at t = 0 be accounted for). Consequently, a balance for
that a model may fit kinetic data only lends support to the 0, [CO] yields
mechanism on which it is based; it does not prove the
mechanism.
kl 0,pco = (k3 + kp pOz1/z) 0 (7)
The rate-controlling step of carbon monoxide adsorption It may be noted that this is tantamount to a quasistationary
is taken as first-order in the partial pressure of carbon state assumption for 8. Solving for e:
monoxide and proportional to the concentration of 0, kl 0 s pco
adsorption sites: e=
dpco
k3 + k4 PO,”
--=
dt
(kl + kz) 0 s pco Substituting for 0 in Equations (5) and (6) yields
4c dpco2
-= kl 0, pco
dt
pCO
1c
Integrating this equation, we get
e
0 s - Os0 = (pco - pcoO)- 2(pO, - p 0 2 O ) (12)
Let
e c1 = oso + 2pozO - pcoo (13)
then
0 s = c1 - - pco) (14)
4 Similarly, for S
dS dpcoz dp02
-.=- +2-- (15)
dt dt dt
Integrating this equation, we get
2
Let
S - So = ( P C O- +
~ ~ ~ 0 2 ’ ) ~ ( P o Z- ~ 0 2 ’ ) (16)
It may be noted that separate rate equations are required Though diffeient sets of constants are required for each
for each component since the reaction does not proceed run and each activity level, the good reproduction of the
stoichiometrically. The rate equations contain among them data by the kinetic model in all cases may be regarded as
the six constants, k, kl, k3/k4, kg, c1, and c2. some endorsement of the model.
The constant k is always very little larger than kl (the
Qualitative Behavior of the Model difference is k2). Thus the rate of adsorption of carbon
I t is interesting to examine the qualitative behavior of monoxide must be greatly in excess of the rate of reaction
the above system of rate equations. of carbon monoxide to form strongly held carbon dioxide.
Equation (19), in the limiting case that ( 2 ~ 0 -%~ C O ) It was observed that runs exhibiting particularly low
remains constant, reduces to a straightforward first-order values of k also exhibit low values of average slopes in
expression giving the kinetics most frequently reported in Figures 3, 4, and 6. This means, of course, that some of
previous studies. As discussed earlier, however, the value the discrepancies in values of the constants is real and not
of ( 2 ~ - 0 pco)
~ passes through a maximum in the course merely an inaccuracy in calculations. There must be some
of a run. Consequently, [cl - (2pOz - p C o ) ] traverses variation in intrinsic activity not accounted for in the
a minimum, and this is in accordance with the cubic shape model. Characterization of the activity decline was not
of the first-order curves of Figures 2 to 6. practical because the decline was dependent on the con-
Equation (20) indicates that the partial pressure-time ditions between runs. In the model an attempt was made
curve for carbon dioxide is almost a mirror image of that to account for changes in activity during a run due to
for carbon monoxide in agreement with the experimental reduction (and partial reoxidation) of the catalyst oxygen.
data. The difference between k and kl accounts for the This is apparently insufficient, however, and it is possible
slight disparity between carbon monoxide consumption that the reoxidized catalyst is of somewhat less active na-
and carbon dioxide production. ture than the original. It should be noted that it is unlikely
+
In Equation (21) the factor (k3/k4 poa’h) character- that oxygen removed from the catalyst can be replaced at
izes the competition between Reactions ( G ) and ( F ) de- low temperatures with the original binding energy.
termining whether 0, [CO] reacts with oxygen or breaks The proposed model, reactions ( E ) , ( K ) , ( F ), ( G ) , and
down into carbon dioxide and reduced catalyst. Higher
oxygen partial pressures would, of course, assist the former
reaction and thus decrease the degree of catalyst reduction. 120 I I I I
This is in accordance with the experimental results obtained
with conditions of relatively high O2 : CO as noted earlier. 0 EXPERIMENTAL DATA
A number of techniques have been used for the mea- ble region.
surement of dynamic surface tension of water-surfactant
solutions (1 to 3). One very simple method, utilizing the
THE EXPERIMENT
phenomena of gas bubble formation on a submerged orifice,
has been reported ( 4 ) but is difficult to apply because of The air bubbles were produced on an orifice which was
a complicated analytical model. The process of gas bub- submerged in a transparent plastic walled tank filled with
bling from a submerged orifice into a pure liquid has been either distilled water or water-surfactant solution. The
subdivided into three regions, namely, the constant volume particular solution used in this study was distilled water
(or single bubble) region, a transition zone, and a constant plus 0.08 vol. % of Ultra Wet 60L (Atlantic Refining
frequency region. The latter two taken together have also Company, Los Angeles, California) which exhibited an
been referred to as the regime of chain bubbling ( 5 to 7 ) . equilibrium surface tension of 33 dynedcm. as deter-
This note is based on observations made in the single bub- mined by the DeNouy Tensiometer method (maximum