AI ChE Paper Number 33a

Feed Contamination With Sodium And I ts I mpact On

Ethylene Furnaces



Bala S. Devakottai *
Consulting Process Engineer
Equistar Chemical Company, LP, a LyondellBasell Company

Pinakin B. Mistry *
Consulting Materials Engineer
Lyondell Chemical Company, a LyondellBasell Company


Robert Pritchett
Principal Reliability Engineer
Equistar Chemical Company, LP, a LyondellBasell Company



Prepared for Presentation at the 2011 Spring National Meeting
Chicago, Illinois
March 14, 2011



* Presenter

AIChE and EPC shall not be responsible for statements or opinions contained in
papers or printed in its publications.
Feed Contamination with Sodium and I ts I mpact on Ethylene
Furnaces


Bala S. Devakottai *
Consulting Process Engineer
Equistar Chemical Company, LP, a LyondellBasell Company

Pinakin B. Mistry *
Consulting Materials Engineer
Lyondell Chemical Company, a LyondellBasell Company


Robert Pritchett
Principal Reliability Engineer
Lyondell Chemical Company, a LyondellBasell Company


Abstract


Sodium is a known contaminant in feedstock to ethylene furnaces. This paper
describes an incident involving the contamination of a natural gasoline feedstock
with sodium. The incident resulted in aggressive hot-salt corrosion which
impacted the radiant tubes and convection tubes. Analysis of coke at different
locations showed the presence of hexavalent chrome, which led to the
implementation of several health and safety precautions as well as environmental
monitoring during the clean-up process. Metallurgical failure analysis and
subsequent repairs are also discussed.


Introduction

LyondellBasell relies on stringent specifications on all feedstock brought into its
olefins plants to avoid process upsets and / or damage to equipment. Ethylene
plant feedstock contamination has been widely discussed in past Ethylene
Producers Conferences. This paper addresses sodium contamination issues
associated with natural gasoline, the C
5
and heavier bottoms product from
natural gas liquids fractionation facilities. Natural gasoline is typically marketed
as a gasoline blend stock. Because it contains mercaptan sulfur, natural gasoline
is typically treated to convert the mercaptan sulfur to disulfides, a process called
sweetening, to pass a Doctor Sweet specification required by gasoline blenders.
This process involves the addition of air and caustic to the gasoline, which is
then passed over a catalyst bed where the sulfur conversion takes place.
Sodium contamination from caustic not completely removed from the treated
natural gasoline is a potential threat to furnace components. Another source of
sodium is brine contamination of natural gasoline stored in salt caverns. This
paper discusses the impact of sodium contamination on the cracking furnace and
subsequent cleanup efforts during an incident at one of LyondellBasell ethylene
plants.


Symptoms of Damage

When feedstock is introduced into a cracking furnace after decoke, it is not
unusual a see a spike in CO/CO2 due to the exposure of catalytic nickel surface
of radiant tubes. This phenomenon is typical of a gas feed if a sulfiding agent
such as dimethyl sulfide (DMS) or dimethyl disulfide (DMDS) is not used to
passivate the exposed radiant coil metal surface.

As feed was introduced to the furnace in one of LyondellBasells plants following
a regular decoke, the caustic tower inlet analyzer showed a sudden increase in
concentration of CO
2
as shown in Figure 1. This increased CO
2
level lasted days
before subsiding to the base level.


1 Day

Figure 1: CO
2
spike in Caustic Tower Feed


While all furnaces did not exhibit this symptom, multiple furnaces showed an
abnormal increase in CO
2
levels upon reintroduction of feed following decoke, as
shown in Figure 2.



7 Days

Figure 2: CO
2
spike in Caustic Tower Feed during Multiple Furnace Feed-in


Root Cause Analysis

A cross functional team was formed to gather data and perform a root cause
analysis of the cracking furnaces exhibiting this unusual behavior, develop a plan
to clean up any contaminated equipment and recommend corrective actions to
prevent future recurrence.

Analysis of the data showed several uncharacteristic behaviors. Pre-sulfiding
these furnaces prior to reintroduction of feed did not change the CO
2

concentration. The CO
2
increase was observed regardless of the feed type
ethane, naphtha or condensate. Also, while the CO
2
concentration increased as
feed was introduced, there was no appreciable change in CO levels, as indicated
by methanator temperatures. Furnace operation started to deteriorate in these
furnaces.

The root cause analysis indicated one common factor among all of the furnaces
they processed natural gasoline feed just prior to and during the initial incident.
Furnaces that did not see this feed did not exhibit high CO
2
behavior. Sodium in
natural gasoline was suspected to be a causal factor for this abnormal behavior.


Evidence of Damage

When one of the affected furnaces experienced a radiant tube leak, a thorough
inspection of the furnace was performed to understand the extent of the damage.

Coke with green deposits were found on the TLE inlets, as shown in Figure 3.
Figure 4 shows green and brown deposits on the coke found at the TLE inlet.





Figure 3: Green deposits on inlet tube sheet of TLE




Figure 4: Green and brown deposits on coke from TLE inlet


Extent of Damage

The radiant coil failure at the bottom return bend is shown in Figure 5, which
was not a typical radiant coil failure mechanism.



Figure 5: Radiant coil failure

A boroscope of the radiant coil and crossover piping was conducted to assess the
damage. Figure 6 shows the inside wall of the radiant coil and Figure 7 shows
the crossover piping from radiant section to convection section.



Figure 6: Green Deposits in Radiant Coil


Figure 7: Green Deposits in Crossover Pipe

Radiant coil outlet piping bend showed large amounts metal deposits, as shown
in Figure 8.




Figure 8: Deposits in radiant coil outlet pipe


Lab results

Table 1 shows the analysis of coke by XRD and XRF analysis.



Table 1: Analysis of TLE inlet coke

The presence of a significant amount of sodium in coke alluded to sodium hot
salt corrosion. The absence of chloride confirmed that the sodium was not from
rine (sodium chloride), but most likely from caustic.
nd will
isintegrate into Cr
+3
and Cr
+6
, both of which are known carcinogens.
t coil. Sulfur in
e coke is presumed to have come from the feedstock or DMS.
iscussion of Hot Salt Corrosion
e presence of nickel catalyses
the reforming of steam and the water gas shift.

O + H
2
O CO
2
+ H
2
These reactions increase CO
2
formation dramatically.
ickel
ulfide eutectics at about 1175F, and corrodes and reduces the thickness.
in the formation of additional (Na
2
O) (Cr
2
O
3
), thus
creasing chromium loss.
since
hromium will only slowly migrate from the bulk alloy to the tube surfaces.

b

Since the formation of burkeite requires a very high temperature, this confirmed
the suspicion that the coke on the TLE inlet must have migrated from the radiant
coil. A literature survey revealed that Cr
+4
valency is quite unstable a
d

The presence of Ni, Fe and Cr in the coke, which are components of radiant coil
metallurgy, confirmed the damage to the inside surface of radian
th


D

Sodium prevents formation of protective oxide film on the inside diameter of the
radiant tubes. Lack of protective oxide film and th

C + H
2
O CO

+ H
2
C + 2H
2
O CO
2
+ 2H
2
C


The interaction of Na with chromium leads directly to sodium chromate (Na
2
CrO
4
)
which will peel off from tube walls. Presence of sulfur also forms Nickel-N
S

The presence of vanadium in the feed forms vanadium pentoxide (V
2
O
5
) which
acts as a catalyst in these reactions. A complex reaction scheme involving these
three compounds results
in

The loss of chromium at the tube surface results in additional coke formation.
The coking rate will be higher than normal for several furnace cycles,
c
Cleanup Effort and Recovery

The cleanup effort was time consuming due to the major extent of the damage.
There are 6 convection passes, with 6 crossover pipes and multiple tubes in each
of the 6 radiant coils, as shown in Figure 9.

1 | www.lyondellbasell.com |
| www.lyondellbasell.com | 1
Typical Furnace Layout
Burners
Fuel Gas
(Wall)
Burners
Hydrocarbon Feed
BFW
1500 PSIG Steam
Radiant Coil (6/furnace)
Heater B
(common st`ack
for 2 htrs)
HC Preheat
Mixed Preheat
BFW Preheat
Heater
A
Steam
Drum
TLE
(3/furnace)
Diluti on
Steam
Deposits


Figure 9: Extent of Damage

Extra precautions had to be taken during the cleanup effort due to the presence
of hexavalent chrome. The investigation team developed several steps for the
cleanup and restoration of the furnaces to restore them to their normal, clean
condition. The TLEs were filled with demineralized water and flushed several
times until the sodium concentration in the water samples was low. The water
from these flushes was handled as toxic waste and disposed of accordingly. The
TLEs were then hydroblasted using typical TLE cleaning practices.

The decoking drum area was barricaded and the atmosphere monitored for the
presence of chromium during decoking of the affected furnaces. Fortunately,
there was no measurable presence of chromium in the air, and potential risks
were not found to be significant.

A plan was developed to water wash the convection tubes, crossover piping and
radiant coil as a complete loop. Again, the water from this cleaning was sampled,
handled as toxic waste and disposed of accordingly.

Several radiant coil bottom return bends showed significant wall loss and leaks.
The damage to the base metal also caused significant weldability issues. The
picture below (Figure 10) shows a temporary repair to a radiant coil to enable
the water flush of the inside surface.




Figure 10: Weld overlay temporary weld repair for cleaning of inside coil

Radiography (X-ray) of the bottom return bends after the water flushes showed
metal deposits which could not be cleaned and significant wall losses. Many of
these bends and lower portions of the tubes could not be welded and had to be
replaced. In some furnaces, the entire radiant coil had to be replaced. Later,
after multiple cycles, one of the furnaces had a convection tube leak which was
traced back to sodium damage. This was followed by more similar failures on
other heaters. Repairs for this issue are ongoing.

Conclusion

As shown in this paper, hot salt corrosion due to sodium attack in multiple
furnaces can affect different components of the furnace. Extreme damage to the
protective chromium oxide layer in a radiant coil may not only lead to furnace
performance deterioration but to a toxic form of hexavalent chromium as well.
Care should be taken to deal with the possibility of hexavalent chrome when
handling coke and cleaning the TLEs.

Acknowledgements

This paper is the result of countless hours of investigation and cleanup effort by
various groups of people. The authors would like to thank the people in
production, environmental, maintenance, reliability, R&D and laboratory for their
diligent help in dealing with this issue.


References

1. Damaging Mechanisms in Ethylene Plant, Pinakin Mistry and Bala Devakottai ,
20
th
Ethylene Producers Conference, AIChE, 2008
2. An Overview of Self-Inflicted Contaminants Stephen De Haan, Vice President,
Plant Performance Improvement, ABB Lummus Global 18
th
Ethylene
Producers Conference, AIChE, 2008
3. Top 5 Contaminants in Ethylene Production Unit Feedstocks Mark Brayden,
Dow Chemical, Dwight Hines, BASF Fina Petrochemicals, J ames
Graham, ExxonMobil Chemical Company, Thomas Pickett, Shaw Stone &
Webster Inc. , 20
th
Ethylene Producers Conference, AIChE, 2008
4. ASM Handbook Vol. 11, Failure Analysis and Prevention
5. ASM Handbook Vol. 13, Corrosion
6. LyondellBasell Internal Failure Analysis reports from Olefins Plants