Case Study

Butadiene Unit Run Length Extended with Popcorn

Polymer Inhibitor and Monitoring Program
Background
A Western European N-methylpyrrolidone (NMP)
process butadiene plant failed to achieve its targeted run length of 6 years for the columns and exchangers in the purification section.
Polybutadiene, in the form of popcorn polymer,
was forcing unscheduled plant shutdowns every 1
to 2 years for manual cleaning. The fouling material
is a highly cross-linked butadiene polymer, called
popcorn polymer, due to its very rapid and expansive nature when formed. Each shutdown resulted
in a month or more of extremely costly production
loss, in addition to increased maintenance costs
and safety concerns. At the same time, the finishing
column overhead condensers required cleaning
and passivation every 3 months.

GE monitored the performance parameters that

would indicate fouling of the de-propynizer and finishing columns using Multiple Regression Analysis
(MRA) and Statistical Process Control (SPC). MRA/SPC
helped monitor the fouling tendency on a weekly
basis by modeling the columns delta Pressure (dP)
as a function of independent parameters (time,
flowrates, pressures, temperatures, etc.), normalized
to start-up conditions.
The monitoring and its frequency helped GE and the
plant operators evaluate the efficiency of the
treatment, and provided ample warning when fouling began to increase, due to oxygen entering the
system.

Results

Under normal operating conditions in the tower and

the overhead condensers, oxygen intrusion leads to
peroxide formation, which in turn can catalyze and
create polymer. From a fouling perspective, its formation can dramatically diminish unit performance,
but it can also cause significant damage to equipment.

A prescheduled regulatory shutdown occurred 1

year after initiating the GE treatment program. At
that time, both columns were found to be very
clean after 15 months of run. Since the restart of
the unit in November 2010 and 3 years of treatment, no unplanned shutdown has occurred and
the program is ongoing.

At this plant, TBC (Tertiary Butyl Catechol) was being

injected in different parts of the finishing section to
help prevent rapid growth of popcorn polymer.

One year after restarting the unit, the MRA/SPC assisted monitoring program identified, in real time, a
slight increase in the dP trend. To address the issue,
it was decided to temporarily increase the inhibitor
dosage rate to provide extra inhibition and passivate any polymers that might form. This corrective
action helped avoid a costly throughput reduction,
or worse, a unit shutdown.

Solution
In 2010, GE began injecting Butaclean* 4610, a
polymerization inhibitor, in conjunction with the existing TBC treatment program. The inhibitor was fed
to the vapor line overhead of the de-propynizer column to prevent popcorn polymer formation in the
upper part of the column and in the condensers.
Additionally, the treatment program also helped
reduce polymer formation in the finishing column.

MRA/SPC confirmed that the dP of the depropynizer column was under control and remained
very stable at less than 5 mbar per year.

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* Trademark of General Electric Company; may be registered in one or more countries.
2013, General Electric Company. All rights reserved.
CS1448EN.doc Dec-13

Passivation
Working closely with a cleaning company, GE developed a complete passivation treatment program
designed to protect the columns, reboilers and condensers.
The passivation process combines Butaclean 4603,
a metal passivator, with Butaclean 4604, a multifunctional polymerization inhibitor, capable of neutralizing active polymer seeds and scavenging
oxygen. This passivation process is now standard
procedure before each restart of the entire unit or
section of the unit.
In addition to passivation, proper monitoring, and
appropriate inhibitor selection, GE also recommends the continuous flushing of dead legs on
transfer lines. Measures should be taken to reduce
dead spaces in vessels (stagnant areas and underneath column trays near the walls) to avoid oxygen
contamination and subsequent polymerization as
well as reduce the possibility of stagnant butadiene
accumulation.

Conclusion
Controlling popcorn polymer formation is a very
critical matter in a butadiene unit. Its formation can
be very quick and can cause a shutdown after significant disruption of unit performance. Consequently, reliable monitoring of operating
parameters in real time, combined with appropriate
chemical selection and the ability to adjust treatment programs quickly in response to performance
deviations is essential to the efficient, safe, and
profitable operation of the butadiene unit.

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