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