Controlling Exothermic Reaction

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How Can We Better Control an

Exotherm? | Chemical Processing
Oct 23, 2003
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We have to hold tight temperature control on a highly exothermic suspension polymerization

process in order to maximize reaction rates. We tried using PID on the catalyst flow, but
temperature fluctuation was too high. We added PID control to the cooling water and can now
control the temperature within +/-5 Degrees C, but now the batch time is too long. What can
we do to achieve tighter control on this kind of process?
,"From August Chemical Processing
Focus on heat transfer
where subscript R refers to the reactor conditions and subscript c refers to the coolant
conditions. It is critical to note that in polymerization reactions the rate of reaction, R,
is typically a highly nonlinear function of both TR and the catalyst feed rate, C, while
the cooling capacity is determined by the flow of coolant. In addition, the ability to cool
the reactor is limited by the reactor surface area and the overall heat transfer
coefficient.
There are a number of options to improve reactor cooling.
First, one may marginally improve the overall heat transfer coefficient by increasing
agitation speed. Since the main purpose of the agitation is to maintain the suspension,
a higher agitator speed should not hurt the process, although it might improve the
mass transfer from the bulk liquid into the reaction sites and result in a higher reaction
rate. Higher turbulence at the wall will enhance the heat transfer slightly, but I believe
that this would not be sufficient to improve control and reduce batch time.
Second, one can change to a cooling media with a higher heat capacity. This option
will be capital intensive in that a new system is required.
Third, by adding a pump-around loop to the reactor vessel one can add additional heat
exchange surface by either jacketing the pump around or putting a heat exchanger in-
line. This option might not be practical due to increased maintenance resulting from
fouling the heat exchange area.
Fourth, find a suspending fluid that will boil at the appropriate reaction temperature to
take advantage of the latent heat effects. The vapors should be condensed and
returned to the vessel. This will require an intensive development effort.
Fifth, scale down the process. A smaller reaction vessel will have a larger surface area
to volume ratio. This will have the effect of increasing the heat transfer capability of the
reactor, and ultimately allow shorter batch times with better temperature control. In
addition, two smaller reactors will probably provide more throughput than a single
reactor of equivalent size. This option might be difficult to sell to management due to
capital investment and the potential for higher operational cost brought on by
increasing the number of operators.
Keith Dackson, Ph.D., Engineering Scientist
Henkel Technologies/Loctite Electronics, Olean, N.Y.We
successfully scaled up a highly exothermic
and "unusual" batch isomerization reaction from 1 liter in a calorimeter to a 30-gal.
pilot-scale batch and from there to a 500-gal. full-scale reaction. We were able to
abandon a $20-MM plant modification based on a continuous reactor and substituted a
$5-MM (1980s $$) modification based on a couple of batch reactors.
Learn From a scale up
I would proceed as follows:
Run the reaction in a batch-heat-flow/heat-compensation calorimeter. This let's you run

the reaction under conditions where the heat-transfer surface to reaction-volume ratio
is very large. You can run the reaction in batch or semibatch mode; you can add the
catalyst all at once, or add it slowly, i.e., you can explore heat evolution (and yields) as
a function of time under various conditions. Since heat evolution is always some
function of reaction rate, you're actually getting a real-time view of the reaction
kinetics.
Once you have these data, first determine how large a surface-to-volume ratio you
need to prevent a runaway reaction. (Remember - batch reactions are always potential
bombs, since during an upward temperature excursion, the heat transfer capability
increases linearly with cooling media
Add even more heat transfer area so that you can run at a relatively small
Even if you only have a jacket, you must pump the cooling media around - so that it is
essentially isothermal. The cooling loop acts as big flywheel. Cooling media
temperature is adjusted by adding coolant to the pump-around loop and bleeding off
an equivalent amount.
Should the cooling media become too cold (e.g., during a process interruption), you
need the capability of heating the pump around loop to get the reaction started again.
Initially, when our ChEs tried to run the isomerization on a 10 gal. scale, they ended up
with two runaways out a total of four reactions. And even for the successful ones, it
was like balancing an egg on a pin.
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Oct 23, 2003
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There was a real incentive to go batch,"it was much cheaper. I finally built my own heat-
compensating calorimeter in one afternoon (a 1 liter resin kettle, submerged in a temperature-
controlled bath, with an electric immersion heater in the reactor for temperature control). It was
1980, before commercial calorimeters were available. During the first run, we found that the
reaction was not 1st order (as we had suspected). Here is what we observed: Initially, heat
release was quite slow. Then, after about 30 min., the heat release started to pick up, but then
diminished exponentially (as expected). It was that 30 min. phenomenon that caused the
runaway reactions.
There was obviously an "initiation" period, where an intermediate compound was formed, which
then further reacted to complete the isomerization. We never determined the mechanism (it
wasn't really important) because we now knew why we had the runaway reactions. We scaled up
directly to a 30 gal. pilot-plant reactor, with a pump-around loop. We actually started out at a
higher temperature, to get the reaction going, and as the heat release increased, we lowered the
reaction temperature to maintain a constant heat evolution.
On the second 30-gal. run, we only made a single temperature adjustment to the cooling
loop,"and the reaction ran perfectly. When we then scaled up 500 gal. commercial batches
(which required an external heat exchanger), we never had any problems with temperature
control.
Gary Knapp, President GFK Consulting Ltd.,
San Clemente, Calif.Subject
to limitations due to reactor volume or agitation requirements, use a high-
heat-capacity inert such as tabular alumina spheres to dampen temperature swings. Tabular
alumina spheres of 1/2 to 3/4-in. diameter would provide a significant heat sink, a high void
fraction and would not significantly impede flow from the reactor at the end of a cycle.
Bill Norman, Technology Manager
Porocel Corp., wnorman@porocel.comI
think you meant solution polymerization. In the past, I have used
an external cooler (heat exchanger) installed in the reactor circulation line. Depending on
polymer properties and cleaning considerations, monomer injection can be on the inlet
(preferred) or outlet of the cooler.
It's the media's fault
Add external cooling
Monomer injection should be interlocked with high/low temperature on the reactor to prevent run-
away exotherm and accumulation of unreacted monomer. Circulation pump and cooling should
also be interlocked.
Robert Bryant II, Manufacturing Engineer
Valent USA, Walnut Creek, Calif.For
a tight temperature control we often use a loop with a relative high-
flow-capacity pump (about 5 to 10 times the vessel content per hour) and feed the loop with fresh
cooling water over a PID-controlled three-way valve. This is a good and reliable solution in case
the amount of heat to be removed gives a relatively small temperature rise in the cooling water.
That's why this flow has to be as large as possible. The background of the story is that the heat
buffer capacity of the cooling water is so large that the response time becomes also large. This
gives the control loop the time to adjust the temperature before it runs away. I hope you can do
something with this suggestion. However, the mixing action of the agitator is also a very
important variable in this problem and in most cases the bottleneck.
Alan Ferraro, V.P. Engineering
Jongia Mixing/MPE Group USA, Pennsauken, N.J.The
reader is right about PID control. You can get rapid
response, but have too much overshooting and swings or you can control the overshooting and
swings but have long process times and very sluggish response. Most exothermic reactions only
allow a very narrow temperature band but require a rapid response to "catch" and control the
reaction when it occurs. Allowing the exothermic reaction to get too hot or too cold can ruin the
product batch. It is a significant issue with polymers.
Lots of water flow buffers response time
Consider vacuum steam
We have a patented system that can control to +/- 1.8 Degrees F (1 Degrees C) and provide
instant response to process fluctuations and temperature profiles. It is especially well-suited for
exothermic reactions since it provides both heating and cooling capabilities. The heating system
provides vacuum steam as low as 10 Degrees F. A pressure control valve uses proprietary
control algorithms to allow rapid, measured response with minimal overshooting and swings. The
cooling system uses an atomized water spray, which vaporizes under vacuum conditions to take
advantage of the latent heat transfer at a much lower temperature (below 32 Degrees F if using
brine solution). Product cooling times can be reduced by about 25%. Additionally, these systems
provide energy and space savings when replacing hot water systems.
By the way, did you know that vacuum steam has more BTU/lb. to transfer in latent heat? Just an
added bonus.
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Oct 23, 2003
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Steve Kortheuer
TLV Corp., Charlotte N.C.Initially
this sounds like the temperature setpoint (PID control) on the cooling
water is too low. But I'm sure there is more to it than that. I suspect there is more than one
process parameter that controls the reaction time.
Vary the setpoint
Perhaps the process requires maintaining one temperature when in steady state but could be
allowed to raise a given amount when the catalyst is added. If this is the case, the controller
could switch to a higher setpoint when triggered that the catalyst is being added. The setpoint
could go back to the initial value after a set time period. Some PID controllers can store more
that one setpoint and switch them based on time or logic.
For other situations, consider an over-ride controller. This consists of two PID controllers on one
box that share an output (or set of outputs if both heating and cooling are controller). A simple
rule set determines which PID controller had control of the output. Usually this is based on which
controller output is calling for the lowest output, but this is configurable. Over-ride allows one
output to be independently controlled by two parameters via two PID controllers.
Jim Overturf, VP of Marketing,
Eurotherm Inc., Leesburg, Va.The
problem is that a tight temperature control is difficult to achieve by
indirect cooling through a jacket of the vessel ," because of the high energy produced by the
reaction, the heat to be removed is also high. The limitation to removing that heat will be mainly
on the product side (not in the jacket).
Improve the stirring
One simple way to improve the heat transfer is stirring. But in order to stir, the solution or
suspension has to be diluted. Thus the concentration of active substance is lower and so too is
conversion and reaction speed. If the suspension is particularly dense, the agitator will not move
or, using a tougher, kneader type unit, the induced energy will be eventually even higher through
mechanical dissipation.
One appropriate method to overcome this problem is evaporative cooling. This means the
operating pressure is adjusted so that one of the components in the reaction mixture (likely the
solvent or suspension media) simply boils. You will need a closed design of the equipment and
pressure control. The evaporated solvent can be recycled internally through a simple heat
exchanger. You have to check if there is danger that one of the active substances of the reaction
is stripped out and chose your solvent accordingly.
Daniel Witte, Senior Process & Sales Engineer,
List USA Inc., Charlotte, N.C.If
a liquid is exposed to a pressure lower than its steam pressure, it starts
evaporating and radiating heat through the developing vapors until the steam pressure is equal
to the ambient pressure. In this process, the liquid cools down to the temperature corresponding
to the prevailing pressure.
Vacuum recirculation cooling
If the homogeneous mix of the product is exposed to underpressure, water will evaporate from
the mix until the pressure of the water is equal to the interior pressure in the mixer. With the
developing vapor, a heat stream is dissipated from the paste in the form of evaporative heat. At
this point, the paste cools down to the temperature corresponding to the prevalent pressure
according to the water vapor chart.
With our vacuum cooling method, the cooling is generated in the product itself, independent from
cooling surfaces (contact cooling) or from environmental conditions (evaporative cooling).
A rotating mixing pan and rotary mixing tool keeps the product constantly moving, thus
supporting the evaporation process.
The temperature of the prepared product in the mixer is determined by the generated vacuum
(underpressure), because pressure and temperature are related according to the water vapor
chart. With a pre-selected defined pressure value, it is possible to automatically control the
product temperature by means of the process controller.
Occurrence of partial temperature differences in the product is impossible. The product quantity
is entirely exposed to the vacuum, so that the water evaporates evenly throughout.
The water vapor originated during the product cooling process is evacuated through a surface
condenser, which consists of a bundle of thin-walled tubes with external circulation of cooling
water. The developing condensate flows immediately back into the mixer, again being mixed
homogeneously into the product. The processes of evaporation, condensation, and recirculation
are occurring simultaneously during the cooling phase.
Nick Semitka
Eirich Machines, Gurnee, Ill.
The problem does not lie in the method of control (PID in this case) or the tuning of the
controllers. It is a heat transfer issue. Consider the enthalpy balance:
DT, while heat generated increases exponentially with reaction temperature). If your reactor has
insufficient jacket area, incorporate a pump-around loop to get sufficient heat exchange area.DT
between cooling media and reactants. By doing this, the cooling media temperature essentially
determines the reaction temperature. By operating at low DT, when the batch temperature rises
slightly, heat evolution increases, but the delta T increases more significantly, thus removing the extra
heat and driving the reaction temperature back to the target temperature.

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Controlling Exothermic Reaction

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Controlling Exothermic Reaction

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How Can We Better Control an

We have to hold tight temperature control on a highly exothermic suspension polymerization

,"From August Chemical Processing

Focus on heat transfer

There are a number of options to improve reactor cooling.

Learn From a scale up

I would proceed as follows:

Run the reaction in a batch-heat-flow/heat-compensation calorimeter. This let's you run

How Can We Better Control an

Add external cooling

Lots of water flow buffers response time

Consider vacuum steam

How Can We Better Control an

Vary the setpoint

Improve the stirring

Vacuum recirculation cooling

3 of 3 < 1 | 2 | 3 > View on one page

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