AIChE Paper 220a

Top 5 Contaminants in Ethylene Production Unit Feedstocks

Mark Brayden, Dow Chemical

Dwight Hines, BASF Fina Petrochemicals

James Graham, ExxonMobil Chemical

Company

Thomas Pickett, Shaw Stone & Webster Inc.

Prepared for Presentation at the 2008 Spring National Meeting

New Orleans, Louisiana, April 6-10, 2008
 Contaminants
• Sulfur (42) • Ammonia (22)
• Methanol (41) • Phosphorus (18)
• Sodium (36) • Carbonyls (17)
• Chloride (35) • Iron (16)
• Carbon Dioxide (34) • Organic Acids (16)
• Mercury (34) • NOx (13)
• Fluorides (28) • Light Nitrogen
• Water (27) Compounds (11)
• Metals (26) • Silicon (11)
• Arsine (24) • Solvents (9)
• Radon (23) • Ethers (8)

Source: EPC 2004_55b "Feedstock Contaminants in Ethylene Plants -- An Update" 2

Sulfur
 Sulfur
• Sources: Feedstock, Sulfiding agents
• Partitions: All products
• Reactions: Decomposition in furnace, acid-base,
redox
• Removal: Amine treaters, Caustic scrubbers,
metal oxides.
• Analytical: various ASTM methods, including S-
selective detection, PbO tape.
• Impact on Specifications: H2S in ethylene, COS
in propylene, thiophene in benzene.
4
Methanol
 Methanol
• Sources: Feedstock, especially E/P (hydrate
breaking), breakdown of ethers.
• Partitions: Propylene, quench water, compressor
knockouts.
• Reactions: Decomposition in Furnace to CO.
• Removal: Water Wash, Adsorbents (13X,
alumina)
• Analytical: GC with specialized detectors.
• Impact on Specifications: Propylene
6
Coking
Sodium
 Sodium
• Sources: Brine / Seawater (Feedstock), caustic
soda added to quench.
• Partitions: Causes coking / corrosion of furnace
tubes.
• Reactions: Coke formation.
• Removal: Feed coalescer, knockout, amine for
pH control.
• Analytical: AA, AE, ICP.
• Impact on Specifications: Carbon Black
Feedstock.
8
Carbon Dioxide
 Carbon Dioxide
• Sources: Untreated LPG feedstocks.
• Partitions: Cracked gas, ethylene.
• Reactions: Acid-base.
• Removal: Amine treater, caustic tower,
adsorbent (13X).
• Analytical: GC w/ specialized detector, IR.
• Impact on Specifications: Ethylene.

10
 References
• Twenty-one listed in paper for further, more in-
depth coverage of these topics.
– Sulfur (4)
– Methanol (5)
– Sodium (7)
– Carbon Dioxide (5)
• Primary sources are from past EPC papers.
• Intend to be incorporated into contaminants
spreadsheet to be discussed in paper 220x.

11
 Future Plans
• Covered in 2008 – Ammonia (22)
– Sulfur (42) – Phosphorus (18)
– Methanol (41) – Carbonyls (17)
– Sodium (36) – Iron (16)
– Carbon Dioxide (34) – Organic Acids (16)
• Next Year? – NOx (13)
– Chloride (35) – Light Nitrogen Compounds
(11)
– Mercury (34)
– Silicon (11)
– Fluorides (28)
– Solvents (9)
– Water (27)
– Ethers (8)
– Metals (26)
– Arsine (24)
– Radon (23)
Source: EPC 2004_55b "Feedstock Contaminants in Ethylene Plants -- An Update" 12
 Disclaimer
• Neither the authors nor their respective employers represent,
warrant, or otherwise guarantee, expressly or impliedly, the
merchantability, fitness for a particular purpose, suitability, accuracy,
reliability, or completeness of the information contained in this
document or the products, materials, or processes described. The
user is solely responsible for all determinations regarding any use of
material or product and any process in its territories of interest. The
authors and their respective employers expressly disclaim liability
for any loss, damage, or injury directly or indirectly suffered or
incurred as a result of or related to anyone using or relying on any of
the information in this document. The authors and their respective
employers do not endorse any product or process, and expressly
disclaim any contrary implication.

13
 Top 5 Contaminants in in Ethylene Production Unit Feedstocks
Mark Brayden
Process Research Leader
Dow Chemical
Dwight Hines
Product and Process Technical Manager
BASF Fina Petrochemicals
James Graham
Staff Chemist
ExxonMobil Chemical Company
Thomas Pickett
Olefins Technology Manager
Shaw Stone & Webster Inc.

Abstract: Trace contaminants in feedstocks to ethylene production units cause various

processing issues and impact final product purity. This paper explores the top 5 feedstock
contaminants that were identified in the 2004 survey paper, "Feedstock Contaminants in
Ethylene Plants -- An Update". According to the survey, the top five contaminants, based on
number of respondents reporting issues with it, are sulfur, methanol, sodium, chlorides, and
carbon dioxide. Each impurity will be discussed in some detail as to the source of the
contaminant, how it partitions in the plant, any reactions that it may undergo, how it is
removed, analytical methods, and its impact on final product specifications.
 Sulfur
(Prepared by Thomas Pickett)

Sources
Sulfur generally enters olefins plants with the plant feedstock. It is also typically
injected in relatively small quantities upstream of the cracking furnaces to minimize coke
formation, manage CO & CO2 formation, and preserve furnace tube metal integrity.
Volumes can be written on the topic of sulfur due to the variety of sulfur species,
distribution of the various species within the plant’s recovery systems and the variety of
removal techniques.
This portion of the paper will touch on sulfur species most commonly encountered by
olefins producers.

Liquid Feeds
Liquid feedstocks will typically contain the higher sulfur concentrations. There is
generally a direct relationship between boiling point and sulfur content, assuming feeds have
not been hydrotreated. Following are typical or expected levels which might be encountered
for various feeds:

Total Sulfur
Light Naphtha 100-400 ppmw
Heavy Naphtha 200-800 ppmw
Middle-East Condensate 500-2500 ppmw
AGO 1000 ppmw-1 wt%

Gas Feeds (E/P/B):

Most LPG recovery plants providing feed to ethylene plants will remove sulfur and CO2
to meet pipeline transportation requirements. Many gas fed ethylene plants have sufficiently
low sulfur such that sulfur injection is required as indicated above. Ethane fed plants with
high CO2 levels (>1000 ppm) will often install amine treaters in the feed to reduce caustic
consumption costs. Amine treating will likewise remove H2S to very low levels.

Refinery Sourced Streams (FCC Gas/Propane/Propylene):

Light-end streams originating from refineries are especially troublesome with respect to
contaminants and will normally require special treatment for H2S, mercaptan, and COS, as well
as other non-sulfur bearing contaminants.

Sulfur Injection:
Furnace coils are fabricated with high nickel content. Nickel catalytically promotes
coking reactions with CO and CO2 forming in the coils as a by-product of the cracking process.
These side reactions can be “managed” in part via sulfur addition where sulfur is in-effect a
poison to the catalyst sites. Common sulfiding agents are DMS and DMDS. Mercaptan can
also be used if practically available. The sulfiding additive of choice is one which completely
vaporizes prior to entering the furnace coils (normally injected into the dilution steam) and one
which dissociates principally to H2S. Most operators strive to achieve from 20-200 ppmw total
sulfur in the furnace feed.

The table below summarizes various ways sulfur enters the ethylene plants:

Source Sulfur Type

Feedstock H2S, mercaptans, COS, disulfides
Furnace Injection H2S, mercaptan, DMS or DMDS, elemental
sulfur
Vent Gas Recycle Stream H2S, COS, mercaptans, CS2
from gasoline
hydrogenation units
FCC and Coker Off-gas H2S, COS, CS2, mercaptans, SOx, thiophenes
Vent and recycle streams H2S, mercaptans, solvents
from downstream units
Sulfur Compounds produced H2S, thiophenes, mercaptans, disulfides
in cracking furnaces
Sulfur added to front-end H2S, mercaptans
raw gas type reactors

Sulfur Partition
Many sulfur compounds will dissociate or partially convert to H2S in cracking furnaces.

H2S:
Hydrogen sulfide will follow the ethylene plant light-ends, and if breakthrough occurs in
the caustic tower, contamination will be seen in the ethylene and propylene product.

COS
COS will mostly convert to H2S (~90%) in the cracking furnace. It is normally more of
an issue for olefin plant operators receiving C3 or refinery off-gas streams which by-pass the
furnaces. If left untreated, COS will primarily follow propylene through the plant recovery
systems. A small portion will track with the C2’s, especially C2’s with high propylene content.

Mercaptans
Mercaptans must be examined in terms of methyl-, ethyl- and propyl-mercaptans.

• Methylmercaptan (CH4S) - Unconverted methylmercaptan exiting the cracking

furnace, if untreated, will partition partially with the C3’s and partially with C4’s in
the plant recovery system.
• Ethylmercaptan (C2H6S) - Unconverted ethylmercaptan exiting the cracking furnace,
if untreated, will partition with the C4’s with a small portion into the C5’s.
• Propylmercaptan (C3H6S) - Unconverted propylmercaptan exiting the cracking
furnace, will typically leave the plant’s quench system with the heavy pyrolysis
gasoline.
Reactions
Amine based systems:
2RNH2 + H2S → (RNH3)2S
(RNH3)2S + H2S → 2RNH3HS
Caustic based systems:
H2S + 2NaOH → Na2S + 2H2O
CH3S-H + NaOH → NaS-CH3 + H2O
C2H5S-H + NaOH → NaS-C2H5 + H2O
Metal Oxide Reactions:
H2S + PbO → PbS + H2O
H2S + CuO → CuS + H2O
COS + PbO → PbS + CO2
COS + CuO → CuS + CO2

Removal
The following table summarizes conventional removal methods for various sulfur species:

Species Removal Technique

H2S (Gas Cracker) Amine Treatment in Plant Feed system when
CO2 >1000 ppmw, followed by caustic treatment in
the cracked gas compression (CGC) system.
H2S (Gas Cracker) Caustic Treatment in the CGC system when
(CO2 <1000 ppmw)
H2S (Liquids Cracker) Caustic Treatment in Compression system. (For high
CO2 content systems, amine followed by caustic
treatment in the CGC system)
H2S (general) Molecular sieve (regenerable), activated alumina
(regenerable) or metal oxide catalyst (non-
regenerable) when < approx. 20 ppm
COS Amine treatment for partial removal. Molecular sieve,
activated alumina and/or metal oxides for final
purification.
Mercaptans Hydrocarbon vapor/liquid caustic – partial removal
Hydrocarbon liquid/liquid caustic – final purification
(large quantities)
Metal oxides when < approx. 20 ppm.
Analytical
Recommended analytical methods for analysis are as follows:

Species Laboratory Method

Total Sulfur ASTM D4468
H2S ASTM D4084/D5504
COS (general) ASTM D5504/UOP212
COS (in ASTM D5303
propylene)
Mercaptans ASTM D5504, D1988, UOP212

Impact on Product Specifications, Plant and Equipment

There are three major areass which are impacted by sulfur laden streams. These are:
1. Piping/Equipment – Corrosion,
2. Catalyst Protection
3. Product Specification

Piping/Equipment – Special considerations must be given to wet sulfur containing

streams for corrosion prevention. This applies to both piping and equipment. For example,
Cracked Gas and Wet Gas Compressors casings upstream of the sulfur removal units will
typically design for yield strength limits at 90,000 psi with maximum hardness factors of
Rockwell C-22. (API 617 recommendations)
Catalyst Protection – Modern palladium based catalysts are sensitive to sulfur and will
poison at levels less than 0.5 ppmw (total sulfur). Sulfur is generally considered an inhibitor to
the catalyst and will dissipate slowly once the contaminant is removed. Designers must
consider how sulfur tracks through the plant and include provisions to protect expensive
catalyst beds to ensure long catalyst life and performance. Nickel based catalysts are more
resistant to sulfur poisoning, but do not have the selectivity and lower operating temperature
advantages which palladium catalysts offer. Front-end C2 Hydrogenation systems have been
known to operate for 6+ years without regeneration when protected from poisons and
properly operated.
Product Specification – Polymer grade ethylene and propylene specifications have
continued to tighten in recent years. Less than 1 ppmw total sulfur is now commonly seen as
a requirement in ethylene production. Some specifications of COS in propylene, set by the
polymer producers, are now requiring levels below 10 ppb(v). Olefins producers are seeing
limits tightened even in the by-product streams from ethylene plants. For example, total
acceptable sulfur levels in raw C4’s, including mercaptans, are now sometimes required below
2 ppmw.

References for Additional Information

1. Reid, J. A., “Introduction to Sulfur Chemistry as Related to the Olefin Industry”, Presented
at the 1998 Spring National Meeting, 10th Ethylene Producers Conference.
2. Reid, J. A., “Introduction to Sulfur Compounds and Sulfur Removal as Applied to Olefin Unit
Design and Operation” Presented at the 1998 Spring National Meeting, 10th Ethylene
Producers Conference.

3. Kapur, Sanjeev, “Contamination Removal/Treating Technologies: an Overview”, Presented

at the 2001 Spring National Meeting, 13th Ethylene Producers Conference.

4. “Axial and Centrifugal Compressors and Expander-Compressors for Petroleum, Chemical and
Gas Industry Services”, American Petroleum Institute (API) Standard 617-7, July 2002

Methanol
(Prepared by James Graham)

This document provides a summary of Methanol (MeOH) contamination in steam

cracker feeds and steam cracking olefin plants as originally published in multiple AIChE papers
and surveys (5,6,7,8,9).

Sources of MeOH
MeOH has been reported at various levels in the following feed types:
• 1 - 50 ppm in seven Ethane/Propane mixes
• 14 – 258 ppm in seven propane rich samples
• 3 – 696 ppm in eleven raw natural gas liquid (NGL) rich samples
MeOH and alcohol mixtures including MeOH are purposefully added to olefin unit
processing equipment operating at low temperature to:
• Dry-out the equipment prior to chill down,
• Prevent hydrate formation, and/or
• Remove ice.
MeOH can be used as a pump seal fluid in C3 and lighter services, and during pump
switch over, small amounts of this seal fluid may enter and contaminant the process stream.
n-propanol can be used as a seal fluid to avoid possible MeOH contamination in such
applications.
MeOH can also be present in C4 raffinate feeds returned from methyl tert-butyl ether
(MTBE) production and C5 raffinate feed returned from tert-amyl methyl ether (TAME)
production as MeOH is used in slight excess in the production of these ethers to ensure
maximum feed conversion and limit Di-Methyl Ether production and MeOH must be effectively
removed in the product. MeOH can also be in vent gas from poly-propylene units. Cracking
feedstocks, containing MTBE or TAME (via direct introduction of the ethers or more likely cross
contamination of the feedstock with ether during logistic transport), also produces MeOH in an
olefin plant.
Partition of MeOH in Steam Cracking Olefin Plants
In the steam cracking furnace, 50 – 75% of MeOH in feedstock is converted to CO.
Higher cracking temperatures and longer residence time coils favor higher conversion.
The unconverted MeOH can concentrate in quench water systems and cracked gas
compressor suction drum liquid removal systems. If the plant does not have a dilution steam
generator, the MeOH can exit the plant with the quench water blowdown. In plants with a low
pressure stripper upstream of the dilution stream generator, the majority of the MeOH is
stripped and recycled to the water quench tower. If the plant does not have a stripper
upstream of the dilution steam generator, much of the MeOH is recycled to the cracking
furnaces with the dilution stream. If MeOH does not exit in quench water systems, it
concentrates in the cracked gas and travels with the C3 stream.
MeOH in the cracked gas entering a C3 splitter will concentrate over time and exit with
both the propylene product and C3 recycle stream. In a C3 splitter, MeOH will concentrate
just as methyl acetylene and propadiene at 15 - 30 trays above the reboiler close to the
propylene side-stream product outlet. As the concentration of MeOH builds in the tower, any
upset or operating change can result in MeOH traveling with the propylene product, exceeding
the capacity of any (if available) removal facilities, and producing off spec propylene product.
The CO, produced from cracking MeOH, fractionates with the tail gas in the cold
box/demethanizer systems. Spiking levels of CO from cracking MeOH may result in
operational upsets of:
• Front End acetylene converters,
• Back End acetylene reactor systems using raw hydrogen as a CO source,
• Hydrogen methanation systems, and
• Hydrogen PSA units being operated in a variable cycle mode for maximum hydrogen
as CO, commonly used as a catalyst moderator, is a temporary poison for metal loaded
hydrogenation/methanation catalysts and in addition can promote potential
methanator/acetylene converter runway reactions.

Reactions
The most common reaction for methanol is its decomposition in the furnace to form CO.
Nominally, 50 % converts to CO, while the remainder remains as methanol.

MeOH Removal Options

Water wash systems can reduce the level of MeOH and MTBE/TAME in feed and
process streams. MTBE can be removed from naphtha via a water wash where the solubility
of MTBE in water is ~ 4 wt% at 20°C. Gross amounts of MeOH (>250 ppmv) can be removed
via single and/or double water wash systems. If the washed feed is to be introduced directly
into a steam cracking furnace, it should be noted that the water quality should be clean cold
steam condensate or cold boiler feed water with low total dissolved solids to avoid negatively
impacting furnace operability.
Molecular sieves can remove trace amounts (< 50 ppmw) of MeOH in C3 streams.
While 3A molecular sieve is too small to absorb MeOH, the larger pore molecular sieves such
as 4A, 5A, or 13X will absorb MeOH when operated to avoid water breakthrough since water
will displace any absorbed MeOH. Since some molecular sieves can produce propylene dimers
and higher order polymers (green oil) during regeneration and each can have varying
capacities and regeneration requirements, it is recommend vendor input be obtained when
designing and/or using molecular sieves in a MeOH removal application.
Activated alumina systems can remove trace amounts of MeOH. Alumina systems, that
require regeneration gas temperatures of 500 – 550°F, have the highest MeOH removal
capacity of any system in terms of lbs per 1000 lbs of active bed material. Vendors offer
products for both MeOH and water removal that require different regeneration conditions and
offer varying MeOH removal capacities. As with molecular sieves, it is recommended vendor
input be obtained when designing and/or using activated alumina in a MeOH removal
application.

MeOH Removal Option Locations

MeOH process removal facilities can be located on the C3 splitter feed or the propylene
product stream. Advantages and disadvantages of these locations are summarized in Table 1
below:

Table 1. Location of MeOH Removal Facilities in Olefin Plants

(advantages and disadvantages)
Location C3 propylene product C3 splitter feed stream
stream
Advantages Reduced flow rates MeOH has no opportunity to
concentrate in C3 splitter resulting in
potential for a MeOH slug into
propylene product that may overload
downstream treatment facilities
Reduce MeOH load If CO or Green Oil is produced during
regeneration and enters the C3 splitter,
they will not concentrate in the
propylene product
Disadvantages Potentially introduce CO CO absorbed on the adsorbent from
from regen gases into the tail gas during a regeneration can
propylene product desorb into the C3 feed steam when
on-line and enter the C3 splitter. The
majority of the CO in the C3 splitter
exits with H2 and CH4 from the reflux
drum, but a small fraction of CO can
end up in the propylene product. This
may become an issue with lower
propylene product CO specs.
Potentially introduce green
oil from regen gases into
propylene product
MeOH Analytical
MeOH can be measured in hydrocarbons by standard GC techniques using various
quantitative detectors and polar separation columns. Various techniques may also require the
sample be extracted prior to analytical detection.
ASTM and UOP have published standardized test methods for the quantitative detection
of MeOH in various hydrocarbon matrices as listed below:

• ASTM D4815 - Standard Test Method for Determination of MTBE, ETBE, TAME,
DIPE, tertiary-Amyl Alcohol and C1 to C4 Alcohols in Gasoline by Gas
Chromatography
• ASTM D4864 - Standard Test Method for Determination of Traces of MeOH in
Propylene Concentrates by Gas Chromatography
• ASTM D7059 - Standard Test Method for Determination of MeOH in Crude Oils by
Multidimensional Gas Chromatography
• UOP 569-79 – Methanol in Petroleum Distillates and LPG by Gas Chromatography

MeOH Impact of Final Product Specifications

Off-spec MeOH in Propylene product is a major concern for downstream polymer plants
as MeOH and other oxygenates are significant poisons for the transition metal catalysts utilized
to generate polypropylene.

References

5. Nowowiejski, G. and Reid, J., “An Overview of Oxygenates in Olefins Units in Relation to
Corrosion, Fouling, Product Specifications, and Safety”, EPC Paper 56a, 2003.
6. Reid, J. and McPhaul, D., “Contaminant Rejection Technology Update”, EPC Paper 21c,
1996.
7. Graham, M., “Selected Ethylene Feedstock Impurities: Survey Data”, EPC Paper 15d,
1993.
8. EPC Discussion Panel, “Section 22 Questions and Answers”, EPC Document 22disc,
1996.
9. Stout, E., “MTBE as a Feedstock Contaminant”, EPC Paper 22b, 1996.
 Sodium
(Prepared by Dwight Hines)

Sources
The sodium compounds most often associated with contamination in steam crackers are
sodium chloride (NaCl) and sodium hydroxide (NaOH). However, drying agents such as
sodium sulfate (Na2SO4) could also be involved. Sodium chloride sources usually include brine
from feed caverns and ballast from barges and ships containing liquid feeds. Sodium
contamination is seen most often in liquid feeds containing water. However, entrained drier
material could also be found in liquid feeds, LPG’s or even gas feedstocks.
Sodium hydroxide is often used for pH control in quench water used to make dilution
steam. NaOH can then easily be entrained in dilution steam that is fed back to the furnaces.

Reactions
A variety of reactions are reported for sodium compounds in furnaces. Arguably, the
most common is the reaction of sodium with furnace tubes is the formation of volatile sodium
chromate. Parks and Schillmoller (10) report “Sodium is an especially bad actor as it breaks
down the protective oxide film by formation of volatile sodium chromates. Its concentration
should be controlled to below 500 ppb.” As the oxide film is removed surfaces are left
unprotected and iron/nickel catalytic surfaces are exposed. Catalytic coke is formed until the
exposed surface is covered and asymptotic coke begins to form from the gas phase
hydrocarbon. The asymptotic coke is a softer “tar-like, amorphous coke that dehydrates with
time and dries to a grayish brown color of very fine grain and high in chromium”.
In 1996 Ray Orriss (11) presented a paper at the EPC entitled “Effects of Contaminants
in Ethylene Plants: Sodium and Iron”. In this paper, he outlines a basic mechanism of sodium
attack. The mechanism begins with the sodium compound from the feed forming sodium
sulfate (Na2SO4) with the furnace sulfur in an oxidizing steam environment. It is then reduced
to sodium sulfide (NaS) at the metal sites on furnace radiant tubes. The sodium then reacts
with the chrome carbides to form chrome sulfide and carbon which results in a tube that is
“primed” for increase rates of catalytic coking. He reports that Kellogg has demonstrated such
coking in laboratory tests resulting in coking 50 to 100 times higher than normal levels. In a
prior presentation in 1994 (12), Ray Orriss further states that the initial reaction forming
Na2SO4, removes some of the sulfiding agent (added to coat tubes and prevent coking) and
therefore reduces the effectiveness of the sulfiding agent.
In the 1994 presentation (12), he further explains this “priming” mechanism. He states
iron and nickel (both available in bare radiant tubes) promote filamentous catalytic coke. He
cites a reference from Baker (13) et al that shows the rate of coking is directly proportional to
the available bare surface area of the tube and that Bernardo and Trimm (14) reported
enhanced coking on a nickel foil. Therefore, this is the reason for much of the work done on
protecting active sites with inert layers and presulfiding of furnace tubes.
Another mechanism reported for sodium attack on furnace tubes is molten salt
corrosion, (also called hot salt corrosion). Attack by sodium chloride on austenitic steels
including alloys such as 800 H used in the convection section shield coils with subsequent slag
formation and slag migration was first mentioned in the 1994 presentation (12). Molten salts
such as Na2SO4, NaCl and CaSO4, generally are good fluxing agents, effectively removing
oxide scale from a metal surface. The corrosion reaction proceeds primarily by oxidation,
which is then followed by dissolution of metal oxides in the melt. Oxygen and water vapor thus
accelerates the hot corrosion by re-oxidation of the surface metal, (especially during steam-air
decoking) and by oxidation of sulfur, (by steam) in a feedstock to create small amounts of
SO4.
As water evaporates when the liquid feedstock is heated to the dry point in the
convection section, salt crystals form, and stick to the tube surface. In time they build up and
form an insulating layer, resulting in increased metal temperatures. Once the tube material
attains the melting temperature of these salts, they cause hot corrosion. Commonly a lower
melting point eutectic is formed by a mixture of salts. The slag-like appearance of such
corrosion deposits results from a mixture molten salts with metal oxides dissolved in it slowly
moving or flowing in the affected tube. In addition, the melt is often sticky enough at
operating temperatures to capture coke and rust particles that impinge upon it, causing
further growth of the slag. Such slag deposits tend to accumulate in the U bends of the shield
coils causing the U bends to fail, but can migrate further downstream and cause flow
maldistribution problems as stated in the 1994 presentation (12).

How Sodium Compounds Partition

While most sodium can be captured on tube surfaces inside ethylene furnaces, removal
of sodium from a feedstock by its capture in the furnaces is not always complete. Sodium
compounds can exit the furnace quench exchangers and will usually partition with the heavy
streams from the gas fractionators such as tar or fuel oil. Should sodium be entrained with
other lighter streams, they would tend to partition with the quench water due to high water
solubility of most sodium compounds. These are removed in blowdowns from the water
system.
Sodium in the heavy streams posses a problem if these streams are used as carbon
black oil feedstocks. These have relatively low sodium specifications.

Removal
The first line of defense is water removal by draining feed tanks and equipment where
water accumulates, that of course requires sufficient settling time to allow adequate water
separation to occur. Heavier, higher viscosity feedstocks will require more settling time or may
require additional steps for water removal. Feedstock maximum haze and other maximum
water content specifications should be rigorously enforced since water in feed systems is rarely
benign and commonly contains salt.
Last year Mark Brayden from Dow Chemical presented a paper (15) summarizing the
merits of filtration and coalescence. In his paper he shows the benefits of high efficiency
coalescers to remove water and water soluble salts, while filtration removes particulates such
as iron and debris. He shows that sodium compounds are effectively removed using this
technology.
Many ethylene plants that take liquid streams from refineries use desalting technology
(11) to remove sodium salts from salt driers or ship ballasts.
 A recent patent (16) outlines a vessel that can be used upstream of the furnaces to
remove salts and particulates in very heavy feeds such as crude oil and heavy resids. This one
stage flash vessel operates at a temperature to allow lighter molecules into the cracking
furnace and heavy molecules with the solids and salts to exit in the bottoms stream back to
the refinery.

Analytical
Several analytical techniques are used to measure sodium. These include Atomic
Absorption (AA), Atomic Emission (AE) and Inductively Coupled Plasma Emission Spectroscopy
(ICPES). Each of these techniques can measure low levels of sodium even into the ppb levels.
Classic techniques use “dry ashing” (or sulfated dry ashing) to prepare the sample for analysis.
In these methods a suitable sample size is used to get the required detection limit. The
samples are weighed into a crucible and placed in a muffle furnace for a specified time in air
to vaporize the organic part of the sample. The resulting salt is dissolved in a dilute acid to be
measure by the above techniques. Less used for sodium are wet ashing techniques.
In the past few years the detection limits for analytical techniques have improved. This
allows the analyst to measure the hydrocarbon directly and maintain a low detection limit. To
do this the ICPES can be equipped with a Direct Injection Nebulizer (DIN) to atomize the
sample into the plasma.
Many labs simply water wash the sample to extract the sodium salts and use the above
techniques. This technique would not extract organo-sodium compounds, should they be
present, though no references for such compounds were found by this researcher.

Impact on Final Product Specification

As mentioned above, the primary specification impacted is any heavy streams such as
steam cracked tar that are used for carbon black feeds.

References

10. Parks, S. B. and Schillmoller, C.M., “Update in Alloy Selection for Ethylene Furnaces”,
EPC Paper 24a, 1995.
11. Orriss, R., “Effects of Contaminants in Ethylene Plants: Sodium and Iron”, EPC Paper
22ba, 1996.
12. Orriss, R., “Ethylene Plant Contaminants”, Opening address at 1994 EPC Conference,
Atlanta, Georgia.
13. Baker, R.T.; Harris, D.S.; Thomas, R.B. ; and Waite, R.J.; Catalysis, 30, 86 (1973)
14. Bernardo, C.; and Trim, D.L.; Carbon, 14, 225 (1976).
15. Brayden, M.; Wines, T.H.; and Del Giudice, K., “Improve Steam Cracking Furnace
Productivity and Emissions Control Through Filtration and Coalescence”, EPC Paper
218a, 2006.
16. McCoy, J.N,; DiNicolantonio, A. R.; Frye, J. M.; Stapleton, M. D.; and Stell, R. C.,
Patent WO/2005/113714, 2005.
 Chloride

Carbon Dioxide
(Prepared by Mark Brayden)

Sources
The primary sources of carbon dioxide (CO2) in the feed-streams to an ethylene
production plant are vapor feedstocks derived from natural gas liquids (NGL), primarily, ethane
and propane. In the 2004 Feedstock Impurities Survey (17), the presence of CO2 in ethane
was listed by 66 % of respondents as either a high or medium concern in ethane. Likewise, 37
% listed it as a high or medium concern for propane or other NGL’s, but no one listed it as a
problem in heavier feedstocks like raffinate or naphtha. Finally, 67 % of respondents listed
CO2 as a medium concern for refinery dry gas.
From this same survey CO2 was reported at various levels in these feed types:
ƒ 0-40,000 ppm range with 100 - 500 ppm (average) in 23 ethane or E/P mixes
ƒ 0-500 ppm range with < 100 ppm average in ten propane rich samples
ƒ 100-500 ppm range with 300 ppm average in two samples of refinery dry gas
Carbon dioxide is also formed in the pyrolysis or cracking furnace. Often, a sulfur
compound like dimethylsulfide (DMS), dimethyldisulfite (DMDS), or tert-butylpolysulfide (TBPS)
is used as an additive to passivate catalytic metal surfaces to suppress carbon monoxide (CO)
and CO2 formation. Even so, there will be a period of elevated CO and CO2 formation during
the initial startup of a freshly decoked furnace. Furthermore, even after the furnace is
passivated by the sulfur additive or by a coke layer, CO2 is produced by reforming reactions.
Secondary sources include natural gas containing high CO2 used for commissioning,
especially when starting up supported catalysts or adsorbents downstream of the acid gas
removal system. Carbon dioxide adsorbed during commissioning can be later released into the
cracked gas and end up primarily in the ethylene product.
CO2 in product can also come from COS removal beds, which convert COS to CO2 and
water. If a metal oxide bed is used for this purpose, generally a CO2 removal bed will also be
required. (18)
In 1999 Reid (19) reported on natural gas infiltration into salt dome caverns used for
storage. Reid reported two instances of ethylene contamination on the US Gulf Coast. Since
product ethylene specification for CO2 is generally a few ppm, only minor contamination by
natural gas infiltration can cause out of specification ethylene product. One might assume,
then, that if these same caverns are used for storage of cracker feedstocks, the natural gas
infiltration would probably not exceed levels that would be problematic for the plant.

How CO2 Partitions

CO2 typically follows the ethylene product, but can also be an impurity in other streams
in an ethylene plant as described in last year’s paper presented by Hood and Coleman,
specifically, as a bicarbonate salt in the C4 and C5 streams. This salt can then decompose
back to CO2. (20)
 Absorption of CO2 in quench water removes a fraction of the CO2 from the product gas,
forming carbonic acid in the water. Carbon dioxide is the most plentiful acid gas in the product
gas stream, as well as being a stronger acid than hydrogen sulfide, the other abundant acid
gas in pyrolysis gas. There are other acids that may be present in the gas, some even stronger
acids like acetic acid, but primarily the dissolution of CO2 into the quench water is the primary
cause of low pH of the quench water. This can lead to corrosion problems in the quench and
dilution steam systems.
CO2 can also surface adsorb on molecular sieve 3A, only to be displaced later by other
adsorbed species, most commonly water vapor. This can be affected by going to a larger pore
molecular sieve to allow the CO2 to penetrate the pores of the sieve, or to a selective
adsorbent that allows the CO2 to absorb / adsorb in the internal pore structure of the
adsorbent.

Reactions
Since CO2 is an acid gas, it can be absorbed into water and then reacted with a base to
form a bicarbonate or carbonate salt. In this manner, this marginally soluble gas compound
can be held in water as the bicarbonate or carbonate at percentage levels. This is the basis for
amine and caustic scrubbers. The acid-base reaction is rapid, and the rate-limiting step in an
absorber is the transfer of the CO2 from the gas to the liquid phase.
In the pyrolysis furnace, CO2 is formed by the reaction of formed CO with steam added
for coke suppression by the water-gas shift reaction and by reforming reactions. (21)
Carbon dioxide can surface adsorb onto molecular sieve 3A. It can be effectively
adsorbed by various treated aluminas or molecular sieve 13X.
Carbon dioxide will combine with hydrogen sulfide to form carbonyl sulfide in the
presence of 4A or larger pore molecular sieves. This reaction does not occur across 3A.

Removal
The primary method of removing CO2 from the feed is by an amine treater, using MEA,
DEA, MDEA, or any of various other formulated amines for this purpose. The amine treater is
typically located at the NGL fractionation plant. An amine treater can also be located at the
entrance to the ethylene plant prior to the pyrolysis furnaces, especially when the vapor
feedstock is untreated and contains high levels CO2. The amine can be regenerated and
reused, releasing the CO2 into a fuel gas stream or sent to a flare.
To remove CO2 in the pyrolysis gas, typically a caustic scrubber is employed. In some
plants, amine scrubbers are also used to remove the bulk of the acid gases. Since an amine
scrubber will not remove CO2 to sub-ppm levels, it is followed by a caustic tower as a
secondary absorber to get to sub-ppm levels. The spent caustic containing carbonate is
generally sent to a waste treatment system like a wet air oxidation unit before being sent on
for biological waste treatment. Like the amine scrubbers used for feed treatment, amine
scrubbers in cracked gas service are also regenerable.
In product ethylene trace levels of CO2 are removed with a selective adsorbent like 13X
or a treated alumina, usually at the block entrance to a user’s plant like a polyethylene
production unit.
Analytical
Since CO2 is at a low level in product and the response of CO2 is very poor on a flame
ionization dectector (FID) and non-responsive on other common lab GC detector, the
laboratory analysis that has been most commonly used is a gas chromatograph equipped with
a thermal conductivity detector or flame ionization detector (FID) in combination with a
methanizer, which utilizes a nickel catalyst to convert any CO2 in the stream to methane.
For several years now a commonly used method of detecting CO2 is a field infrared
analyzer. Sensitivity is gained by employing a long path length IR cell to see down to the sub-
ppm levels.
For some troubleshooting activities, sub-ppm analysis of CO2 is needed. One approach
was presented in 2007 using a GC equipped with a pulsed discharge detector. (22)

Impact on Final Product Specifications

The primary problem with CO2 in the product is as a catalyst poison for polyethylene
production. With new higher efficiency catalysts, the presence of even sub-ppm levels of
impurities can cause catalyst efficiency losses. Typically, an adsorption unit is in place to
protect these sensitive processes.

References

17. Baumgartner, A. J.; Blaschke, M. W.; Coleman, S. T.; Kohler, R.; and Paxson, T. E.,
“Feedstock Contaminants in Ethylene Plants – An Update”, EPC Paper 55b, 2004.
18. Polito, C., “Arsine and Carbonyl Sulfide Contaminants in Ethylene Plant Feedstocks”,
EPC Paper 22h, 1996.
19. Reid, J., “Natural Gas Infiltration into Salt Caverns - Attachment 4”, EPC Paper 69e,
1999.
20. Hood, D. and Coleman, S., “Minor Components, Major Issues: An Overview of
Contaminants in Ethylene Plants”, EPC Paper 51c, 2007.
21. Nowowiejski, G. and Reid, J., “An Overview of Oxygenates in Olefins Units in Relation
to Corrosion, Fouling, Product Specifications, and Safety”, EPC Paper 56a, 2003.
22. Sun, K., et al, “Analysis of ppb Levels of H2, O2, N2, CH4, CO and CO2 in Hydrocarbon
Feed Streams with a PDD Detector”, EPC Paper 51a, 2007.

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