Source: A Working Guide to Process Equipment

CHAPTER

28

Catalytic Effects:
Equilibrium and
Kinetics

hen I discuss a process problem, Ill frequently qualify my

views by stating, Lets assume equilibrium conditions
have been reached. What Im doing is choosing to ignore
the effect of time on changes in composition. Im ignoring the effects
of kinetics on the process. Ill make such assumptions to simplify
complex discussions. Its a bad habit, which sometimes gets me into
trouble.

28.1

Kinetics vs. Equilibrium

A reaction that is limited by equilibrium is finished. Waiting longer
will make no difference. An example of this is the absorption of H2S
from refinery fuel gas into an amine solution. Depending on the
concentration of the H2S in the fuel gas, the amine solution will
become saturated with H2S. Mixing the fuel gas and the amine
solution for a longer period of time will not push more of the H2S into
the amine solution. The reaction is complete, and we say the
absorption of H2S by amine is limited by equilibrium.
On the other hand, a reaction that is limited by kinetics is not
finished. Waiting longer will help to complete the reaction. An
example of this is the absorption of CO2 from refinery fuel gas into an
amine solution. The CO2 will react with the amine to produce a
stronger chemical bond than would the H2S and amine. CO2 reaction
with amine goes slower than the H2S reaction with amine. Mixing
the fuel gas and the amine solution for a longer period of time will
push more of the CO2 into the amine solution. The reaction is
incomplete, and we say the absorption of CO2 by amine is limited by
kinetics or time.

349
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CO2 lean
fuel gas

Vented
CO2

C
O2

C
O2
Cooler

A
b
s
o
r
b
e
r

S
t
r
i
p
p
e
r

CO2 rich
fuel gas

Heat
Lean
Rich
Amine solution

FIGURE 28.1

Recovery of CO2 with amine solution.

In the plant, then, we have two problems:

H2S absorption is limited by equilibrium.
CO2 absorption is limited by time.
We deal with these two problems by:
To extract the residual H2S from fuel gas, we circulate more
amine solution.
To extract the residual CO2 from fuel gas, we have more
contacting trays in the absorption tower.
A similar problem occurs in the amine solution regenerator or
stripper (see Fig. 28.1). The H2S strips out easily. Residual CO2, which
is more tightly bound to the amine molecule, requires lots of trays
and lots of steam to strip out.

28.2 Temperature vs. Time

If a reaction is too slow, there is a simple way to make the reaction go
faster: higher temperature. Milk goes sour even in my 38F refrigerator
after a few months. The milk will go sour much faster if I leave it on
our kitchen table at 74F for a few days. Typically, for a nonbiological

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Catalytic Effects: Equilibrium and Kinetics

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351

reaction, the rate of reaction might very roughly double for every
30F increase in temperature.
Regarding the example of CO2 absorption in amine solution, I
said the CO2 absorption was limited by time or kinetics or reaction
rate and not equilibrium. Perhaps I could increase the amount of CO2
absorption in the amine solution by increasing the absorber
temperature shown in Fig. 28.1.
Maybe yes, but maybe no. Maybe yes, because the reaction will
go faster with higher temperature. But maybe no, because a higher
temperature reduces the amount of CO2 that, at equilibrium, can be
absorbed by the amine solution.

28.3

Purpose of a Catalyst
Increasing temperature to speed up a reaction is often a bad idea. If I
have a plant that is desulferizing diesel oil with hydrogen, so as to
convert the sulfur in the diesel to H2S, I can achieve the required
percent of sulfur removal in two ways:
Mix the hydrogen and diesel together and wait a very long
time.
Mix the hydrogen and diesel together at a very high
temperature (850F).
At 850F, desulferization will proceed quickly, but the diesel oil will
also thermally crack to coke and gas and be useless as a fuel for trucks.
What is wanted is a way to accelerate the conversion of the sulfur molecules
attached to the diesel to H2S at a moderate temperature (about 700F).
Thats what a catalyst does. It does not change the equilibrium, it just
makes the reaction go faster without having to increase the temperature.
For a catalyst to be effective in accelerating the rate of reaction, it
has to come into contact with the molecules of the stuff thats reacting.
Thats why catalysts have lots of surface area. Most of the surface area
of a pellet of catalyst can only be seen with a microscope. As we try to
desulferize diesel oil, some small fraction of the hydrocarbon will
turn to coke. The coke covers a tiny portion of the surface area of the
catalyst. This slows down the rate of reaction between the hydrogen
and sulfur molecules converting to H2S in the diesel oil. The sulfur
content of the diesel product goes above spec. To reduce the sulfur
content of the diesel below spec, the operator raises the temperature
of his reactor. This makes the reaction go faster, which is good. But it
also increases the rate at which coke deposits on the surface of the
catalyst, which is bad. The extra coke blinds-off more catalyst area.
The reaction rate drops. More sulfur is left in the diesel. The operator
increases his reactor temperature to speed up the reaction, which
leaves more coke on the catalyst. When this game is over, we are at
the end-of-run condition.

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28.4

A Working Guide to Process Equipment

Lessons from Lithuania

Sometimes my bad habit of assuming equilibrium gets me into
trouble. A few years ago I was hired by a refinery in Lithuania to
redesign their hydrogen production plant, to increase plant capacity
by 25 percent, and to reduce the CO2 content of the hydrogen product.
The CO2 content of the hydrogen was 2 percent, and the new
specification was 0.5 percent CO2 in hydrogen product.
The process for CO2 absorption is the same as shown in Fig. 28.2.
The only difference is that a potassium salt solution is used instead
of the amine solution to absorb the CO2 from the hydrogen product.
The potassium salt solution is called Catacarb, as shown in Fig. 28.2.
To accelerate the rate of absorption and deabsorption of CO2, a
catalyst called LRS-10 is added to the Catacarb. I had ordered a fresh
supply of LRS-10 catalyst for start-up. When I arrived in Lithuania, I
was informed that the LRS-10 catalyst was stuck in customs and
would be delivered any day now. I decided not to worry about the
LRS-10 catalyst for two reasons:
1. The plant operations chief informed me that there was already
a catalyst in the Catacarb solution that would be used for
start-up. It was a di-ethanol amine catalyst, not LRS-10, but
still it was a catalyst.
2. You cant worry about everything.

CO2 Vent
to ATM

H2 Product
145F
300 psig

5.0 psig

140F
60
Air cooler

Absorber

Deabsorber

Lean
Catacarb
solution

110F

20% CO2
80% H2

Steam
Reboiler
160F

FIGURE 28.2

230F

Circulating Catacarb solution absorbs CO2 from hydrogen.

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As lower temperatures favor the absorption of CO2 by the Catacarb

solution, I had expanded the capacity of the circulating Catacarb
solution aerial fin-fan cooler to cool the absorber tower and thus reduce
CO2 in the H2 product. Liz stood next to me at the panel when we started
the Catacarb circulation pumps. I was totally confident.
I forgot to mention that the operators in Lithuania didnt like
me. Nothing personal. It was just that they didnt like Americans.
So when the cooled Catacarb solution began to circulate, they were
overjoyed. The CO2 content of the hydrogen product lined out at
3.5 percent CO2, well above the previous level of 2 percent, and far
above my target of 0.5 percent CO2 in the hydrogen product. Its
nice to make people happy.
Liz said that I went deathly pale. I was soaked with sweat in the
chilly control room. The operations chief and panel room operators
beamed with pleasure. Confused, I asked them to turn on the last
fan on the aerial fin-fan solution cooler. The absorber temperature
dropped by 10F and the CO2 in the hydrogen product went up
from 3.5 to 4 percent CO2.
Any further instructions, Comrade Lieberman? the unit chief
happily inquired. I didnt answer. I couldnt breathe.
For the next three weeks I engaged in a titanic battle with the
hydrogen plant. Fourteen hours a day, seven days a week:
I raised the absorber pressure by 15 psi, which helped a bit.
I lowered the deabsorber pressure by 3 psi, which helped a bit.
I maximized the steam flow to the deabsorber reboiler, which
helped a bit.
I had open stripping steam piped up to the reboiler return
nozzle, which helped a bit.
I increased the circulation rate of the Catacarb solution, which
helped a bit.
I shut off one of the four aerial cooler fans on the lean Catacarb
solution (see Fig. 28.2), which helped a lot.
So I shut off, one by one, over a period of days, all the aerial
cooler fans. The absorber became quite hot and the CO2 dropped to
0.5 percent in the H2 product. None of this made any sense. CO2
absorption in Catacarb solution should be favored by lower, not
higher, temperatures. Equilibrium conditions for CO2 absorption are
always improved by cooling the circulating absorption liquid.

28.4.1 The Celebration Dinner

The general director of the plant, Nelson English, (an American),
invited Liz and me to a dinner to celebrate the 0.5 percent CO2.
Waiting for the main course, I thought about the problem. Why would

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A Working Guide to Process Equipment

raising the absorber temperature, clearly bad for equilibrium, reduce
CO2 in hydrogen? Certainly absorption efficiency is improving, not
because of equilibrium, but because of kinetics. It must be reaction
rate or time limited. Otherwise, the higher temperatures in the
absorber would never help.
Mr. English, I asked, what about the LRS-10 catalyst? Has it
cleared customs in Klipiada yet? (the old German port of Memel)

28.4.2

Catalytic Effect

The catalyst was like a cold drink on a hot summers day. I put all the
variables I had changed in three weeks back to normal conditions.
I turned on all the aerial cooler fin fans. The CO2 dropped below
0.2 percent in the hydrogen product.
The lesson is, if raising reaction temperature in a reactor promoting
an exothermic reaction makes the reaction proceed further, the reactor
is limited by kinetics and not equilibrium. The term exothermic
means that heat is liberated in the reaction. How can one tell if the
absorption of CO2 in the Catacarb solution is exothermic (gives off
heat), rather than endothermic (absorbs heat)? Refer to Fig. 28.2. Note
that both the hydrogen gas and the Catacarb liquid are being heated
in the absorber. They are being heated by the heat of reaction between
the CO2 and the potassium salt in the Catacarb solution.

28.5

Zero Order Reactions

Not all reactions are exothermic. Thermal cracking is an endothermic
reaction. Heat is absorbed. Good thing, too. If thermal cracking of
crude oil was exothermic, all the earths crude would by now have
turned to coal and natural gas. Delayed cokers, visbreakers, and fluid
catalytic cracking units are processes that are primarily endothermic
in nature. A delayed coker operates with a zero order reaction. This
means the rate of reaction depends on time in the coke drum and the
temperature in the coke drum. The composition of the products of
reaction have no effect.
On the other hand, hydrocracking is exothermic. The consumption
of hydrogen liberates heat in the hydrocracking reaction.

28.6

Runaway Reaction
In 1968, a 3000 psig vessel exploded. This unhappy event occurred at the
ESSO Refinery in Bayway, New Jersey. The cause was a runaway reaction.
Tar was being hydrocracked in a emulated bed of catalyst. The reactor
got hotter, more hydrogen was consumed, and more exothermic heat
of reaction was generated, which increased the rate of hydrogen
consumption, which released more exothermic heat of reaction. I suppose
if hydrogen feed had been stopped sooner, the runaway reaction could
have been controlled. But it wasnt and the reactor blew apart.

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I had a similar, but less dramatic experience on a liquid-filled

reactor converting propylene to viscous polypropylene (a gasoline
additive). The catalyst was aluminum chloride added continuously
with a small pump. The pump malfunctioned. During its outage we
failed to stop feed to the reactor. The propylene content of the reactor
increased. Finally, we restored the catalyst flow, but the liquid-filled
reactor became very warm, very fast. Fortunately, an alert operator
stopped the propylene feed to the reactor in time.

28.7

Common Chemical Plant and Refinery

Catalytic Processes
28.7.1

Naphtha Reforming

This is an endothermic reaction in a hydrogen environment taking place

in the vapor phase. The catalyst is the size of grains of rice and contains
very costly platinum (which sells for twice the price of gold). The
objective is to produce aromatics benzene, toluene, or xylene. Benzene
and xylene are the basic building blocks of the chemical industry.

28.7.2

Steam-Hydrocarbon Reforming

This is also an endothermic process. The reaction takes place inside

catalyst-filled furnace tubes. Heat is supplied to the tubes by furnace
firing. Almost any hydrocarbon can be usednatural gas, propane,
butane. The objective is to make hydrogen. Most of the worlds
hydrogen is produced in this way. Half the hydrogen comes from
steam and the other half from hydrocarbons. All of the carbon in the
feed is converted to CO2 and vented. How hydrogen powered cars
will help global warming, I do not grasp.

28.7.3 Alkylation
This is a very exothermic reaction. Iso-butane and light olefines react
to form iso-octane, a gasoline blending component with a 100 octane.
Thats where the word octane comes from. Reaction takes place at
50F, in a liquid phase of either H2SO4 or HF acid.

28.7.4

Polymerization

This is an old process using a solid bed of phosphoric acid. Reaction

takes place in the vapor phase. Feed is normally propylene. Products
are hexane and nonane. Polymerization is a very exothermic process.

28.7.5

Sweetening

This is slightly exothermic process. Mercaptains are converted to

disulfides by adding air. Catalyst is a blue powder (Merox), which
impregnates a bed of charcoal saturated with caustic. Converting

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A Working Guide to Process Equipment

mercaptains to disulfides reduces the bad smell of gasoline and jet
fuel. The process takes place at about 100F. Sulfur content of the
product is not changed.

28.7.6 White Oil Hydrogenation

Motor oil is hydrotreated at 3000 psig and 450 to 650F to remove
all aromatic compounds by contact with hydrogen. The resulting
white oil is used for baby oil, mineral oil, and ladies cosmetics. The
white oil costs $3 per gallon to make and is sold for $30 an ounce in
face creams.

28.7.7

Fluid Catalytic Cracking

Reaction takes place at 1000F and low pressure in a riser pipe.

The catalyst looks like white sand but is actually made of zeolites.
The catalyst picks up coke from the endothermic cracking reaction. The
coke is burned off of the circulating catalyst with air. The catalyst gets
hot (1200F) and this supplies the endothermic heat of reaction. Half
the gasoline sold in the United States is produced in this way. The
original catalyst for this process was actually beach sand.

28.7.8

Sulfuric Acid

Sulfuric acid is produced by burning sulfur and H2S to SO2 with air.
Then more air is added and reacted in a catalyst bed of vanadium
pentoxide to produce SO3. The SO3 is mixed with water to make
sulfuric acid. The reaction is exothermic and takes place in the vapor
phase. Sulfuric acid is, by weight, one of the main chemicals produced
in the world. I spent 1974 to 1976 in charge of a sulfuric acid plant in
Texas City. In 1975, I had 34 shutdowns and start-ups. Ive kept a piece
of lead wire, part of that awful plant, in my desk drawer. When things
seem bad, that memento reminds me that it could be a lot worse.

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