An Overview of Oxygenates in Olefins Units

In Relation to Corrosion, Fouling,

Product Specifications, and Safety

by

George Nowowiej ski

and
John A. Reid

of
Stone & Webster Inc., A Shaw Group Company

Prepared for Presentation at

American Institute of Chemical Engineers

2003 Spring National Meeting

New Orleans, LA

Copyright© Stone & Webster Inc., A Shaw Group Company

March 31, 2003
"Unpublished"

AIChE shall not be responsible for statements or opinions in papers or

printed in its publications.

DISCLAIMER OF RESPONSIBILITY

Neither Stone & Webster Inc., A Shaw Group Company nor any of the contributors to this document makes any warranty or representation (expressed
or implied) with respect to the accuracy, completeness, or usefulness of the information contained in this document.
Stone & Webster Inc., A Shaw Group Company assumes no responsibility for liability or damage which may result from the use of any of the
information contained in this document.

165
 An Overview of Oxygenates in Olefins Units
In Relation to Corrosion, Fouling,
Product Specifications, and Safety

Abstract
_ _

The focus of this paper and presentation is on greater understanding of corrosion and fouling issues
within the olefins unit due to elemental oxygen and/or oxygen containing compounds. Organic acids
within the quench water system and cracked gas compressor train are frequently secondary reaction
products of CO and CO2 produced in the furnace cracking coil by steam-carbon water gas shift
chemistry. Many of these acids promote olefin compound cross-linking reaction. Oxygen and/or sulfur
containing compounds in ~ olefin unit feedstocks or vent recovery streams frequently increase
downstream corrosion and fouling rates. A short summary of olefin unit corrosion and fouling
experience will be presented with the related process chemistry to illustrate potential process design and
operating issues.

Introduction

Trace amounts of oxygen and/or oxygen containing compounds have been reported to promote
corrosion and/or fouling within olefins units and other process units.

Organic acids containing oxygen are well known corrosion issues in olef'm production units and refinery
process units. Elemental oxygen in contact with butadiene or cracked gasoline is known to promote
polymer or gum formation and increase the risk of process fouling.

A number of regenerative sulfur treating process designs use air injection. Two common sulfur treating
processes, used for naphtha boiling range fractions, that add air are Bender Sweetening and
Mercapfining.

During transportation or storage of liquid C5-plus cracking feed stocks contamination with elemental
oxygen and/or oxygen containing compounds, such as, methanol, ethanol, MTBE and similar may
occur. The entry of sea water or rain water or fiver water into liquid cracking feed stocks also allows
entry of dissolved elemental oxygen.

A trace amount of elemental oxygen (02) is soluble in water and most hydrocarbons. Some oxygen
containing compounds naturally occur in crude oil and to a lesser extent in oil field condensate.
Elemental oxygen in cracking feeds or vent streams routed into the olefins unit for recovery section may
also result in processing problems. The entry of cooling water into process equipment operating at low
pressure is another common potential source elemental oxygen.

On-Specification Produc.~

Ethylene and propylene product specifications typically limit elemental oxygen content to less than 5

166
ppmv, A few product specifications limit elemental oxygen content to less than 2 ppmv. During routine
unit operation these oxygen limits are not an issue. Problems related to on-line and laboratory analysis
for elemental oxygen content in ethylene and propylene product streams are frequently more an issue
than oxygen being present.

Several olefms units have experienced off specification polymer grade propylene (PGP) due to trace
amounts of methanol in the C3 Splitter feed. Methanol removal systems have been installed in some
olefms unit to minimize the risk of off specification PGP.

Some of these methanol removal systems create new fouling and safety issues during routine operation.
These fouling and safety issues will be discussed with methanol removal considerations in Appendix A
and B.

Frequently a sales specification for crude mixed C4, butadiene, and/or mixed butenes will limit carbonyl
and methanol content.

Feedstock Impurities Survey

Information reported in "Selected Ethylene Feedstock Impurities: Survey Data" (1) shows that eight
producers routinely analyzed for methanol in feedstocks. Data published through the Gas Processors
Association (GPA) titled "Trace Contaminants in Natural Gas Liquids" shows:

a. Methanol varied from:

1 to 50 ppm in the seven selected E/P mixes (2) and
14 to 258 ppm in the seven selected propane rich samples and
3 to 696 ppm in the 11 selected raw NGL rich samples.

bB Methanol in GPA "Natural Gasoline"

was less than I ppm for five samples, and
78 ppm in one sample than contained 240 ppm of C5 olefms.

C. Acetone varied from:

1 to 12 ppm in seven selected iso-butane samples.
7 to 94 ppm in six selected n-butane samples.

dQ Testing of 11 NGL "raw make" samples showed oxygenates such as:

methanol, acetone, and t-butanol.

Methanol - A Maior Oxygenate Issue

Methanol is sometimes present:

a. E/P feedstocks,
b. C4 raffinate returned from MTBE production,
c. vent gas from some poly-propylene units.

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21 Methanol is also produced in the fia'naces by cracking MTBE or TAME present in feedstocks.

@ Methanol is sometimes added to olefins unit equipment operating at low temperature for dry-out
prior to chill down or directly into the process as corrective action to remove hydrates or ice.

In the olefins unit cracking furnaces, somewhere from 50 to 75 percent of the feedstock methanol is
typically converted into CO and water. High cracking temperatures and long residence time coils favor
a high methanol conversion.

If methanol is received as a concentrated slug into the tin, aces, increased CO production may result in
operating upsets of:

a= Front-end acetylene reactors

b. Hydrogen methanation systems
C. Back-end acetylene reactor system using raw hydrogen as a CO source.
d. Hydrogen PSA units being operated in a variable cycle mode for maximum hydrogen.

Oxygenate Compound Formation and Reactions

The presence of oxygenated compounds in olefins units based on gas only and liquid feed cracking has
been documented. The presence of carbonyl compounds and specifically acetaldehyde in the cracked gas
feed to caustic wash towers was presented in an EPC paper several years ago (21).

Oxygenated Compounds from Ethane and Oxygen

Extensive laboratory and small semi-scale test work has been done on the production of ethylene from
auto-thermal dehydrogenation of ethane using oxygen. In the auto-thermal dehydrogenation process, the
"heat of cracking" energy input is provided by ethane partial combustion. Secondary reaction by-
products include: formic acid, acetic acid, and formaldehyde formed by ethane oxidation (17). High
mole weight organic acids are also typically present in the quench water used for direct contact cracked
gas cooling.

Thermal - Steam Cracking for Olefins

The "cracked gas" produced in an Olefins Unit by thermal cracking of ethane through C10+
hydrocarbons in the presence of steam contains several very reactive compounds. These reactive
compounds include acetylene, butadiene, carbon monoxide, ethylene, hydrogen, methyl-acetylene, and
styrene. Some oxygenates in cracking feedstocks will be converted into secondary products; but this
conversion is frequently less than complete. Methanol conversion during co-cracking with E ~ feeds has
been discussed at several EPC meetings in relationship to methanol contamination of product propylene.
Methanol is also produced during cracking MTBE or TAME present in some feedstocks. Solvents such
as acetonitdle (ACN) used for butadiene recovery will produce NH3 and HCN during cracking.

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CO and CO2 from Thermal Crocking Reactions

Carbon dioxide (CO2) and carbon monoxide (CO) are produced during hydrocarbon stream cracking
due to steam reforming reactions. Sulfur compounds such as DMS, D M D S , or mercaptans will
frequently be added to E ~ and low sulfur recycle stream feeding the steam cracking furnaces to
minimize C O and C O 2 formation from reactivemetals, such as nickel,used to manUfacture the cracking
coil.

Carbonic Acid

Cracked gas cooling by direct water contact in the quench water tower results in CO2 being dissolved
into the water with formation of carbonic acid. This may be shown as: CO2 + H20 --> H2CO3. The
term carbonic relates to a -COOH group in a hydrocarbon chain. A carbonic acid (aliphatic acid) has the
general form of R-COOH.

C o m m o n Chemical Names and Properties

Figure 1 shows names and chemical structures for one through four carbon alcohols and organic acids.
Table 1 shows some common "carboxylic acid" names, chemical structure, and normal boiling points.
The organic compounds described in this paper are of the following types:

a. Aliphatic acids: R-COOH (where R is a straightor branched chain).

b. Aromatic acids: Ar-COOH (where Ar is a benzene ring or tings).
c. Naphthenic acids" X-COOH (where X is a cyclo-paraffinicring).
d. Phenols: R-Ar-OH (where Ar is a benzene ring, R is typicallya straightor branched
paraffin chain).

Light naphtha and raw pyrolysis gasoline boiling ranges are frequently between 90 and 375 degrees F.
The following paraff~c acid compounds also boil between 90 and 375 degrees F; formic, acetic,
propionic, n-butyric, and iso-butyric.

It has generally been concluded that the carboxylic acids in petroleum with fewer than eight carbon
atoms per molecule are almost entirely aliphatic in nature; mono-cyclic acids begin at C6 and
predominate above C I4. This indicatesthat the structuresof the carboxylic acids correspond with those
of the hydrocarbons with which they are associated in the crude oil; that is, in the range in which
p~s are the prevailing type of hydrocarbon, the aliphatic acids may be expected to predominate;
similarly,in the ranges in which mono-cyclo-paraffins and di-cyclo-paraffinsprevail,one may expect to
find principally mono-cyclic and di-cyclic acids, respectively.

Organic Acids and W_ater pH Values

Table 2, shows the effect of 100 ppm of an acid on water pH, at 77 degrees F (14). Common organic
acids with reduce water pH from neutral (7 pH) to about a 3.7 pH. Inorganic acids, such as sulfin'ic,
hydro-chloric, or hydrofluoric acid are required to lower water pH below 3.

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Oxygenate Compound Formation

Many olefin units built between 1950 and 1965 used front-end, raw cracked gas hydrogenation reactors
for acetylene (C2H2) reduction or near total removal. The hydrogenation catalyst used in these reactors
was frequently nickel sulfide based or nickel in combination with cobalt. Many of these early
hydrogenation reactors produced propionic acid and similar organic acids, through CO addition
reactions.

One of the text book reactions for making propionic acid is:

C2H4 + H20 + CO .... > CH3-CH2-COOH

Optimum reaction conditions given for the above reaction are 650 degrees F and over 10,000 psig with a
nickel or similar metal surface. But, propionic acid has been found downstream and not upstream of wet
raw gas acetylene reactors operating below 400 degrees F and less than 250 psig.

Oxygenate. ComPounds and Process Chemicals

Several solvents used for aromatic recovery units use process chemicals, such as ethylene glycol or
sulfolane that contain oxygen. Some of the solvents used in butadiene recovery units contain oxygen.
Recycle cracking of a raffinate from an aromatic or butadiene recovery unit may result in feeding a trace
amount of oxygen to the olefm unit.

Ethylene glycol is used in many natural gas treating units to aid gross water removal. A trace of ethylene
glycol may be present in the mixed ethane-propane product from some older LPG or NGL recovery
units that do not use low temperature or cryogenic technology.

Ethylene glycol is sometimes used in DP insmanents as a seal fluid. A process upset or seal failure may
result in ethylene glycol entering an olefins unit process stream.

The solvent MEK is used in some lube oil treating units. Heavy boiling material not suitable for lube oil
production is sometimes sent to the steam cracking furnace in an olefins unit.

Isopropyl alcohol is used in some olefins units as a pump seal fluid, instead of methanol. A pump seal
problem can therefore result in Isopropyl alcohol entering the process or loss to the environment.

Morpholine is a water treating chemical commonly used for pH adjustment. Morpholine contains both
oxygen and nitrogen.

The chemical structure of these compounds is shown in Figure 5.

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Other Oxygenate Coml~unds

In addition to the carboxylic acids, alkaline extracts from petroleum contain phenols. Phenols (phenol,
cresols, xylenols) may be present in cracked distillates from which they are sometimes isolated and sold.
Aldehydes are also found in cracked distillates and are believed to be responsible for much of the gum
formation. Alcohols, ketones, and other oxygenated compounds occur in oils oxidized at relatively high
temperatures.

Acetone

A small number of olefins units use acetone as a solvent for recovery of acetylene or MAPD. Very few
olefins units have reported acetone related operation issues.

A primary industrial method for production of acetone (2-propanone) is the dehydrogenation of

isopropyl alcohol. Isopropyl alcohol normally made by the hydrolysis of propylene. Acetone is also
made on a large scale as a co-product of making phenol from cumene. Cumene is produced on a large
scale by alkylation of benzene with propylene.

Phenol Compounds

Phenols occur to an appreciable extent in crude oil and in the appropriate fractions of refinery products.
The commercial mixtures of higher boiling phenolic materials are called cresylic acids from a
predominance of the cresol compounds. The chemical structures for Phenol and major cresol compounds
are shown in Figure 4.

Tertiary-butyl,alcohol

An industrial method for making Tertiary-butyl-alcohol (TBA or t-butyl-alcohol is the hydrolysis of iso-
butene. Iso-butene is the primary product oft-butyl-alcohol dehydrogenation.

Organic Acids Produced by Fermentation

Some of the minor products of sugar fermentation include the following compounds (29):
Formic Acid Propionic Acid Ethyl Butyrate
Acetic Acid Butyric Acid Ethyl Acetate

The above compounds are also found in:

ao hydrocarbons flowing from oil and/or gas wells, and

b. olefm unit quench water and raw gasoline.

Natural sugar compounds are produced extensively by plants as a biological energy conversion and storage
method. Some plant fi~tit, for example grapes, is used to make wine. Fermentation of carbohydrates and

171
starch produced by plants (for example, corn, rice, and wheat) are used to made ethanol and secondary
compounds that are distilled to make drinking alcohol products.

The two primary products of fermentation are ethyl alcohol and carbon dioxide. Early work by Lavoisier
(1789) expressed the following the formulation:

ao Hexose to Ethyl Alcohol and Carbon Dioxide, or

b. C6H1206-> 2C2H5OH + 2CO2

Pasteur (1857) reported that this formulation accounts only for about 95% of the sugar comurned.
Glycerin, organic acids and traces of other by-products account for the balance. These other by-products,
are now known to include 5 fusel oil (higher alcohols), some acetaldehyde and other aldehydes and some
esters.

Pasteur report the actual yield from the fermentation of 100 pounds of sugar was as follows (29):

Compound Pounds
Alcohol 48.55.
Carbon 46.74.
Glycerol 3.23
Organic Acids 0.62
Miscellaneous 1.23
Total 100.37

The total weight of fermentation products exceeds slightly the weight of sugar fermented is explained by
the absorption and fixation of small amounts of water to make certain of the by-products. According to
Pasteur some sugar is also utilized by the yeasts in building new yeast cells.

Oxygenated Compounds in Petroleum

Oxygenated compounds found in petroleum or its distilled products may be present in the crude oil, or
they may be formed in the distillation or in contacting oils with atmospheric oxygen. In crude petroleum
the "total" quantity of oxygen seldom exceeds 0.5 per cent (22).

Higher mole weight and higher boiling temperature fraction of crude oil typically contain more oxygen
than lighter fractions. Some heavy fuel oils (bunker C) are reported to contain 5 to 6.5 percent elemental
oxygen (22).

Figure 6, is a based on IFP information showing an increasing oxygen content with boiling fraction until
the sample specific gravity is above about 0.95. The shape this oxygen curve is similar in shape to sulfur
content data versus sample specific gravity. Boiling fractions with a specific gravity approaching 1.0
have typically been processed at high temperatures during distillation, cracking, or coking units. During
high temperature processing some weaker chemical bonds are broken resulting in the formation of some

172
lower mole weight fragments rich in oxygen and sulfur and formation of higher mole weight compounds
with more carbon to carbon bonding.

In general, petroleum or its products may contain various types of acids, aldehydes, aleoh01s, or phenols,
as well as compounds of as yet undetermined chemical structure. Acids are the most important of these
constituents of the oil, and as a rule, they are naphthenie or poly-naphthenic in type. Only small
quantities of fatty acids are present in crude oil, such as formic, acetic, isoaniyl-aeetie, diethyipropionie,
or other low-boiling members of the series. However, some crude oils contain some high molecular
weight fatty acids, such as palmitic, stearie, myristie, and araehidic.

Naphthenic acids, are by far the most important oxygenated compounds found in the crude petroleum.
These acids are frequently isolated from the oil during refining operations and used for manufacturing
by-products, such as soaps.

Oils containing these acids are corrosive to distillation equipment and may have undesirable
characteristics after they are refined unless the acids are completely removed. Crude oils rich in
naphthenie acids are usually of naphthenie type, such as those of the Gulf Coast or of California.

The oxygenated compounds in petroleum oils are usually eliminated in the course of refining. They are
easily attacked during hydrotreating, or by sulfuric acid, solvents, clay treater, and particularly by
solutions of alkali. In exceptional cases, however, their removal presents a serious difficulty and may
require certain changes in the scheme of refining.

Naphthenic Acids

The presence of acid substances in petroleum first appears to have been reported in 1874. It was
established 9 years later that these substances contained earboxyl groups and were earboxylie acids.
These were termed naphthenic acids. Although alieyelie (naphthenic) acids appear to be the more
prevalent, it is now well known that aliphatie acids are also present.

The naphthenie acids of commerce interest are a mixture having a molecular weight range of 180 to 350.
They are dark in color and have an unpleasant odor. They are principally used in the form of their metal
salts. The lead, cobalt, and manganese salts are used as paint driers, and lead naphthenates are also
components of extreme pres sure lubricants. Other salts are used in greases and to jelly gasoline.

Butadiene Reactions and Fouling

Butadiene is a reactive compound and is frequently a fouling issue in olefin units. During storage "pure"
butadiene will slowly react (dimerazation) to make 1-vinyl-3-eyelo-hexene. This dimerization of two
butadiene molecules to make a C8 compound occurs in both the liquid and vapor phase. Table 6 shows that
the butadiene dimerization rate is strongly a function of temperature. The butadiene dimerization reaction
rate is reported not to be catalyzed by peroxides or by steel surfaces.

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The dimer, 1-vinyl-3-cyclo-hexene, is miscible with butadiene at normal process temperatures.
Conventional distillation is commonly used to separate butadiene from the dimer. The boiling temperature
of butadiene is -4.4 degrees C, at 760 mm of mercury versus a dimer boiling temperature of 127 degrees C.

Butadiene in contact with air will form peroxides. These peroxide compounds promote long chain polymer
formation to produce plastic or rubber like materials. Table 7 shows butadiene polymer formation rate as a
function of oxygen concentration. Table 8 shows butadiene polymer formation rate as a function of
temperature for a constant oxygen concentration.

Butadiene Peroxides

Butadiene on contact with air forms peroxides quite readily. Peroxide formation can be prevented by the
exclusion of air or by the use of inhibitors, such as tertiary-butyl-catechol (TBC), hydroquinone, di-
n-butylamine, phenyl-a-naphthylamine, phenyl-bunaphthylamine or aqueous sodium nitrite. Inhibitors
protect only the liquid butadiene in which they are dissolved. Peroxide may be destroyed by heating
butadiene with alkali, or ferrous salts.

Highly diluted solutions of peroxides are quite stable. When concentrated at elevated temperature, they
become dangerous because of their tendency to decompose violently. This may be overcome, especially
in batch distillation, by dilution with high-boiling liquid hydrocarbons.

Butadiene, free of inhibitor, may be obtained by distillation. TBC (Tertiary-Butyl-Catechol) may also be
removed by caustic washing. Solid butadiene absorbs enough oxygen at a sub-atmospheric pressure to
make it detonate violently upon slight heating above its melting point.

The peroxide in butadiene formed from contact with air promotes the formation of polymers in storage.
The formation of plastic polymers depends upon the peroxide content and temperature.

Butadiene "Popcorn" Polymer

The "plastic type" polymers are not soluble in butadiene. They may separate out and be troublesome in
many operations. Their formation can be minimized by maintaining minimum temperature, by avoiding
contact with oxygen and by the use of inhibitors.

The formation of "popcorn" polymer is initiated by peroxide or air. Rusty iron and water will cause it to
form even in the absence of air. When it is formed, it will grow slowly either in the presence or absence
of air and in contact with liquid or gaseous butadiene. The usual inhibitors do not prevent the growth of
"popcorn" but will probably inhibit its formation provided no seeds of this polymer are present.

Aqueous sodium nitrite has been proposed and effectively used as a control agent for "popcorn"
polymer. "Popcorn" may be deactivated with NO2 or N203 gas. One way to remove "popcorn" polymer
is by soaking with a dilute solution of caustic soda or sodium bisulfite.

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Butadiene Thermal Polymer and Fouling

Butadiene is a highly reactive molecule and will form dimer and higher mole weight compounds during
storage, without a catalyst being present. If oxygen or a metal oxide catalyst is present the butadiene
polymer formation rate will be greater than a sample in an inert container at the same temperature.

Butadiene ,F,
ou!ing and Dcpropanizer Design

Butadiene related fouling frequently occurs in both front-end and back-end flow sheet concepts used for
olefms units. Frequently this fouling is related to time at temperature for butadiene and similar materials
being processed. Many olefin units have spare depropanizer reboilers to allow a 3 to 5 year on-line plant
cycle with a reboiler cycle time 6 to 18 months.

Depropanizer fouling is typically greatest within the reboiler. If process anti-fouling chemicals are not used,
after 1 to 2 years fouling of the lower trays in the depropanizer will sometimes limit the olefin unit C4 plus
processing capacity.

A few olefin units have been built with both spare reboilers and spare tower bottom sections to maximize
the olefin unit on-line cycle. In some units, the cost of this spare tower section is sometimes off-set by a
reduced need for process anti-fouling chemicals.

Using a process design that lowers the depropanizer reboiler temperature by lowing the tower operating
pressure is one of the classic methods to decrease tray and reboiler fouling. Using propylene refrigeration
instead of cooling water for the depropanizer condenser results in a higher energy usage and frequently a
higher related operating cost.

A dual pressure (tower) depropanizer is another option to lower the depropanizer reboiler temperature by
lowing the tower operating pressure while still using cooling water for bulk heat removal. Stone &
Webster's US patent number 3,783,126 illustrates this process design for a classic back-end depropanizer
design.

A dual pressure front-end depropanizer system has been utilized on several recent Stone & Webster process
designs. Figure 10, illustrates one version of this dual tower concept with both a high and lower pressure
and LP) tower system used to make 3 streams.

Figure 10 shows both a dual pressure depropanizer concept and an application of distributed distillation.
The high pressure (HP) depropanizer is designed to make a split between ethane and butadiene. In this
design C3 compounds are allowed to go into both overhead and bottom streams from the HP depropanizer.

The low pressure (LP) dcpropanizer is fed by the bottoms of the HP depropanizer and finishes the
separation between C3 and C4 plus compounds. To minimize the reboiler operating temperature, the
warmest level of propylene refrigerant is normally utilized in the overhead condenser thereby reducing the
tower system operating pressure and the bottoms temperature.

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The C3 product drawn from the LP depropanizer tower overheads is pumped to the C3 hydrogenation unit
thus completely bypassing the demethanizer and the deethanizer system. This design greatly reduces the
potential for fouling in the deethanizer. The operating temperatures and thus the pressure of deethanizer can
now be adjusted consistent with available refrigerant levels without regard to fouling considerations.
Removal of heavy ends (C4+) upstream of the deethanizer typically results in colder reboiler inlet
temperatures than in traditional designs. This typically allows use of quench water heat for the deethanizer
reboiler with a reasonable sized heat exchanger and LMTD.

.Quench Oil Composition and Fouling

High temperature thermal cracking of naphtha or gas oil makes some compounds can react to form
polymefized products. Compounds that have both an olefin and aromatic nature, such a styrene, have a
faster polymerization rate than an pure olefm or aromatic compound. These polymerized products normally
have a higher specific gravity and viscosity than the compounds that they were produced from. The rate of
polymer formation increases greatly with tempemttae.

Compounds such as carbonlys and sulfur in the naphtha or gas oil feeds may increase the rate of quench oil
polymer formation. A naphtha feed rich in aromatic and naphthenie type compounds will produce more
fuel oil and more compounds that can form polymers in the quench oil than a naphtha rich in light paraffinic
compounds.

As the boiling point of aromatic compounds increases so does the viscosity and density. Highly poly-
aromatic compounds, (commonly used for asphalt) that are solids in a pure state at ambient temperature can
be dissolved in the lighter aromatic compounds present in quench oil and RPG. Removing light aromatic
compounds by boiling this quench oil will result in the concentration of heavy ends into tar or solid residue
depending on the amount of heat used.

Adding low viscosity RPG or imported oil to high viscosity quench oil will reduce the quench oil mixture
viscosity. Mixing equal amounts of high and low viscosity oil will not result in an oil mixture with the
average of the two oil viscosities. The oil mixture will have a higher viscosity than the calculated average.

It is critical to remember that operating the Quench Oil Tower at a high bottoms temperature results in a
higher oil viscosity by the combination of stripping lighter compounds from the oil and a higher rate of
polymer formation.

Figure 7, shows a high temperature oil quench system with two fuel oil strippers. Producing both a light and
heavy fuel oil product (LFO and HFO) allow more control of the quench oil viscosity and boiling curve
than using one stripper to make a fuel oil purge stream.

The HFO stripper is operated to purge the higher mole weight compounds from the circulating quench oil.
The LFO stripper is frequently operated to purge the C9 to C 12 compounds from the circulating quench oil
and gasoline reflux produced in the water quench system. Removing C9 plus compounds through the fuel
oil system reduces the amount of "heavy-ends" in the pyrolysis gasoline hydrotreater feed. Reducing these
heavy-ends normally results in a longer hydrotreater on-line cycle.

176
Gasoline Hydrogenation Reactor Foulin~
=.

During raw gasoline processing, dissolved oxygen is a major cause of gum (polymer) fouling.
Preventive measures practiced by olef'm units and refiners are gas-blanketing feed tanks, use of
floating-roof tanks, direct rundown of feedstocks from process unit to unit, instead of always through
day tanks, and use of antifoulants. These methods help minimize polymer deposits but seldom eliminate
them.

The first stage "Gasoline Hydrogenation Reactor" in an olef'ms unit may experience both physical
fouling and catalyst fouling. Carbon laydown, or coking, of the catalyst covers active sites, so
temperatures must be raised. Coking during normal unit operation is a gradual process. Sudden coking
of catalyst can be a result of loss of hydrogen o r of inclusion of large amounts of high-boiling
hydrocarbons in the feed.

Hydrogenation Reactor Feed Heater Fouling

The second stage "Gasoline Hydrogenation Reactor" in an olefins unit may require use of a high
temperature steam heater or fh'ed furnace for reactor feed temperature control.

Many of these second stage hydrogenation reactors operate in the vapor phase. In the reactor feed heater,
a gasoline and oil mixture will be passing through the "dry point", at which the feed becomes completely
vaporized.

This final vaporization zone is where deposits (fouling) frequently occur. Deposits in heat exchanger or
fired heater tubes reduce heat transfer rate. The high tube skin temperature necessary to compensate for
loss of heat transfer rate. A local hot zone in a fired heater may lead to tube failure and fire with the
reactor feed entering the heater firebox. Some olefins units and/or refiners make certain the feed is
completely vaporized by heat exchange before the feed enters the fired heater. This moves the deposits
from the heater to the shell and tube heat exchangers.

One refinery HDS unit that suffered repeated heaterombe failures solved this problem by deoiling the
naphtha, thus removing a high-boiling polymer-forming material before the HDS unit.

The boiling range of the "wash oil" injected into the cracked gas compressor may have a large effect on
the boiling curve of gasoline and oil mixture going to the first and second stage hydrogenation reactors.
Figure 8, shows a common cracked gas compressor with heavy gasoline exiting through a "distillate
stripper". Some organic acids present in the cracked gas system will also exit through the "distillate
stripper" and flow into the first stage gasoline hydrogenation reactor system.

Organic acid related corrosion in a depentanizer located between the first and second stage gasoline
hydrotreating reactors is discussed in Appendix C.

177
Silica

Silica is a name commonly applied to silicon dioxide (SiO2). Quartz crystals are an example of high
purity silicon dioxide that occurs in nature. ~Sand and sandstone are largely composed of silicon dioxide.
Many clay materials contain a combination of aluminum oxides and silicon oxides.

A common silica source is antifoam carried in cok~r naphtha. Another silica source is antifoam used in
fractionators. The poly-siloxane antifoam agent breaks down on contact and deposits silica on the
catalyst (23).

A suggested remedy is to reduce the amount of antifoam used in cokers and fractionators. Another
suggested remedy is the use on top of the catalyst bed of support balls containing a low concentration of
nickel-moly. The activity imparted to the support balls facilitates anti-foam-agent breakdown and
deposits silica on the support instead of on the catalyst.

Silica is only one of many materials known to foul the top of the catalyst bed in HDS reactors. Catalyst
fines, scale, coke, polymer, and caustic are some materials that deposit in the top layer of the catalyst.
They result in poor flow distribution and an increase in pressure differential across the reactor. The
fouling can be either blockage by fines in spaces between catalyst particles or crusting of the top layer of
catalyst.

After a time, the reactor must be opened and the top layer of the catalyst bed removed by skimming.
Since skimming requires entry into the top of the reactor, inert entry must be made under a nitrogen
atmosphere. The catalyst is broken up and vacuumed off to remove the crusted layer. Polymers are
deposited, not only on top of the catalyst but also in the exchangers and in the feed heater tubes.

178
 Appendix A
Methanol Considerations

MTBE and Methanol

O l e ~ units sometimes crack C4 streams that have been previously processed through units making
MTBE (Methyl Tertiary-Butyl Ether). If trace amounts of MTBE are present in the olefins unit cracking
feedstock it will be converted to CO and methanol.

Ships or storage tanks previous used for motor gasoline containing MTBE or similar materials are
sometimes used in naphtha service without cleaning. Several olefins units have been surprised with
varying amounts of MTBE or similar materials in cracking feedstocks.

MTBE is produced by reacting iso-butene (present in a mixed C4 stream) with methanol over a fixed
bed of catalyst. The MTBE synthesis reaction is an equilibrium reaction which highly favors MTBE
production at moderate temperatures. An Iso-butylene conversions of 96%-97% is commonly obtained
using a single pass reactor.

During MTBE production secondary by-products formation is normally minimal, but is a source of trace
compounds. Tertiary butyl alcohol (TBA) is formed from hydration with the water content of the feed.
Dimerization of isobutylene produces di-iso-butylene (DIB). DIB make increases as the ratio of
methanol to isobutylene drops to or below the stoichiometric value. Some dimethyl ether (DME) is also
formed from methanol dimerization.

Depending upon the MTBE process design used, varying amounts of methanol will be present in mixed
C4 stream exiting the MTBE unit. During MTBE production, a slight excess of methanol is used to
ensure maximum isobutylene conversion and to limit DME production. This excess methanol may be
recovered by a water wash or mole sieve adsorption. Water wash systems are less expensive to build
and are generally used.

TAME and Methanol

Olefins units sometimes recycle crack C5 olefin rich streams that have been previously processed
through units making TAME (Tertiary-Amyl-Ether). TAME is produced by reacting iso-pentene
(present in a mixed C5 olefins stream) with methanol.

MTBE and TAME as Nap,h,.thaFeedstock Contaminants

Barges, lines and/or storage tanks used for naphtha feedstocks may previously have been used in product
motor gasoline service or blend product service. Compounds such as MTBE and TAME are added to
gasoline to increase the octane value and provide a moderately cleaner combustion by adding oxygen.
In the olefins unit cracking fiarnaces MTBE and TAME are converted to olefins, CO, and methanol.

179
Mixed C4 Purification

One method for making "high-purity iso-butene" is by making MTBE from a mixed C4 steam using
methanol,then MTBE isolation, followed by MTBE cracking to make iso-butene and minor amounts of
DME, TBA, and dimers.

Methanol within an Olefins Unit

Within the olefins unit, methanol will concentrate in the C3/C4 streams. Methanol entering a C3
Splitter, producing a PGP product, will over an extended time period exit with both the PGP and C3
recycle. In the C3 Splitter, methanol will concentrate just as MAC/PD will concentrate 15 to 30 trays
above the reboiler. Methanol tends to concentrate in the C3 Splitter where the 90 to 95 percent
propylene zone exists. If methanol levels in the C3 Splitter build up over time, a minor upset or change
in operating conditions may result in 10 to 50 ppmv of methanol at the PGP product draw from the C3
Splitter.

180
 Appendix B

Methanol Reduction and Removal Issues

MTBE Removal with Water Washin~

The solubility of MTBE in water is about 4 weight percent at 20 degrees C or 68 degrees F. Water
washing is therefore, an option for reducing the MTBE level in naphtha. If an MTBE problem is limited
to one feed tank, then MTBE contaminated feed may be frequently used at a low rate to minimize
olef'ms unit CO related problems and the m o u n t of methanol in the propylene system.

Methanol Bulk Removal with Water Washing

Gross m o u n t s of methanol, over 250 ppmv, present in C4 raffinate returned from an MTBE unit are
best reduced by water washing. This washing may be single or multiple depending upon waste water
treating issues. The wash water used should be clean cold steam condensate or cold BFW. Wash water
with a low TDS (Total Dissolved Solids) value is critical if the C4 raffinate will be vaporized in the
cracking furnace convection section.

If C4 feedstocks are vaporized upstream of the furnaces, then equipment fouling judgements will
determine water quality requirements. Trace amounts of water in a C4 cracking feedstock should not be
a serious issue. Liquid water collection flow transmitter tubing does have the potential to cause furnace
flow meter errors.

Methanol- Trace Removal

Methanol at low levels (less than 50 ppmw) is typically removed from either the PGP product or the C3
Splitter feed using molecular sieve or activated alumina products. Large pore molecular sieves such as
4A, 5A and 13X will adsorb methanol when not operated to water breakthrough. Methanol on a 4A or
5A sieve will be displaced by water and enter the E ~ furnace feed if the pipeline feed dryer is operated
to water breakthrough.

Methanol Removal - Molecular Sieve Products

Some molecular sieve products may produce propylene dimers and higher order polymers (green oil)
during regeneration. The 4A sieve obtained from different vendors may vary greatly in the amount of
green oil formation. Some of this green oil will be flushed from the sieve and enter the flowing PGP
product or C3 Splitter feed stream. Vendor references for this sieve application should be checked prior
to bid list development. UOP markets an OG-491 sieve specifically for methanol from "reactive
hydrocarbons" such as propylene. Other vendors can supply a suitable sieve that is less reactive than the
generic 4A used for natural gas water removal.

181
The choice of molecular sieve or activated alumina products will depend upon the amount of methanol
to be removed and the regeneration gas temperature available. Optimum bed loads and regeneration
energy efficiency are obtained with a lead and guard bed operating mode for both molecular sieve or
activated alumina products.

Methanol Removal - Activated Alumina Products

Activated alumina products that require regeneration gas temperatures of 500 to 550 degrees F have the
highest methanol removal capacity in terms of pounds per 1000 pounds of active bed material. Both
molecular sieve or activated alumina products are available that will operate with a regeneration gas
temperature of about 425 degrees F, but a regeneration gas temperature of 500 to 550 degrees F is
preferred for both 4A molecular sieve or activated alumina products. Alcoa's general purpose 'F-200' is
a good product for both methanol and water removal if regeneration gas is only available at 400 degrees
F. While it is possible to regenerate 'F-200' using tail gas at 400 degrees F the methanol removal
capacity is less than other products.

Alcoa°s 'Selexsorb CD' is a promoted activated alumina product good for methanol removal. The
'Selexsorb CD' product will pick up about 2.2 weight percent methanol on a routine basis with a
regeneration gas temperature of 450 degrees F. Alcoa's 'Selexsorb COS' product will pick up less than
1.5 weight percent methanol. But with 'Selexsorb COS' both COS and methanol may be removed. A
major advantage of using 'Selexsorb COS' is that methanol and COS do not compete for the same active
adsorption sites, since methanol is physisorbed and COS is chemisorbed. Layers or beds of 'Selexsorb
CD' and 'Selexsorb COS' may also be used in a single vessel to optimize COS and methanol loadings.

Methanol Removal Location

The advantage of doing PGP product treating is a reduced flow rate and methanol load. The
disadvantages of PGP treating includes the risk of CO from regeneration gases and green oil produced
during regeneration entering the PGP product. Methanol removal from the C3 Splitter feed has the
advantage that the methanol will not concentrate in the C3 Splitter to produce a surprise slug that may
over load a PGP product treating system. Also if CO or green oil enter the C3 Splitter, they will not
concentrate in the PGP.

The olefins unit tail gas used for bed regeneration is typically rich in CO. During bed cool down with a
CO rich gas some CO may be adsorbed on the molecular sieve binder. Once the treater is on-line, trace
amounts of CO can bleed into the flowing liquid C3 stream. A very high percentage of the CO entering
the C3 Splitter will exit with the reflux drum vent stream with H2 and CH4. Therefore CO in PGP is
only a problem when a level of less than 2 ppmv is required.

182
 Appendix C

Corrosion in a Depentanizer Located Between the

First and Second Stage Gasoline Hydrotreating Reactors

Summary

Severe, localized weld metal corrosion in the heat affected zone (HAZ) was observed in portions of an
olefin plant Depentanizer in December, 1988. Investigation indicates that the likely cause is aqueous
sulfide corrosion is the responsible corrosion mechanism. Although organic acid corrosion could not be
ruled out.

Age and Design

The Depentanizer tower was made of carbon steel. This tower was apparently eight years old and had
not been originally stress-relieved. As a result of localized corrosion in the upper section, this tower was
cut and a new upper section of carbon steel was welded onto the existing tower. The new section was
stress-relieved prior to placing the tower back into operation.

Inspection

Internal examination of the Depentanizer tower revealed severe preferential weld metal (HAZ) corrosion
in upper areas of this vessel. It is believed that this was the first internal inspection of the tower. This
tower had been in intermittent service for approximately eight years. The carbon steel tower is
approximately 110 feet high and operates at a design temperature and pressure of 190 degrees F and 60
psig at the top and 325 degrees F and 70 psig at the bottom. There are 50 trays in this tower. Vessel
trays and hardware (valves) were not corroded. These were reportedly Type 410 stainless steel.

Vessel wall sections, internal attachments, and welds were submitted to a testing laboratory. All testing
confirmed metal to be carbon steel. All components were examined for possible sulfide stress-corrosion
cracking. No such cracking was observed following visual examination or wet fluorescent magnetic
particle testing of selected areas.

Corrosion Theory

Carbon steel that has not been stress-relieved can become susceptible to accelerated corrosion around
welds (HAZ) and other areas of high residual stress when exposed to acidic media. The pH of deposits
found in corroded areas inside the tower were all acidic indicating a low pH corrosion mechanism.
Aqueous sulfide and/or weak organic acids could both promote the type of corrosion witnessed. The
presence of corrosion at the top of the tower versus the bottom of the tower was believed to be a
function of temperature profile. In this tower liquid water could be present at the top tower section as a
result of a wet feed stream from tankage or small reboiler steam leak.

183
This unit's pyrolysis gasoline and quench water was shown to contain small amounts of organic acid (eg.
Acetic acid, butyric acid, propionic acid, etc). A sampling program showed that the Raw Pyrolysis
Gasoline (RPG) contained:

Concentration
Compound micro-grams/ml
Formic acid 35.4
Acetic acid 63.7
propionic acid 659 (approx.)
pentanoic acid 1189 (approx.)

The specific form or forms of the propioni¢ and pentanoic acids were not determined. The
concentration of the propionic and pentanoic acids is approximate due to use of a different test method
and reference standard.

184
 Appendix D

Pyrophoric Polymer in Deethanizer and De prgpanizer Colmnm

Naphtha and petroleum distillates are used as raw materials in the production of ethylene by pyrolysis.
The rapid build-up of pyrophoric polymer in the deethanizer and depropanizer distillation columns can
result in costly, unscheduled shutdowns in ethylene production due to plugging of equipment.

These shut-downs can last for weeks or months. This article briefly describes the work done to identify
and study the polymer formed, and to find methods for reducing its rate of formation. A more complete
account of the work can be found in the original article: "Rapid Build-up of a Pyrophoric Polymer in
Ethylene Plant Deethanizer and Depropanizer Columns", The Canadian Journal of Chemical
Engineering, Vol 32, June 1984.

The gaseous products from the pyrolysis of the naphtha or petroleum distillates feed stock in the
furnaces pass through a series of distillation columns. Methane, hydrogen and carbon monoxide are
taken off overhead from the demethanizer, while the bottoms go to the deethanizer. Ethylene, ethane,
and acetylene are recovered overhead from the deethanizer while C3's and heavier compounds are
removed as bottoms and fed to the depropanizer. Propylene, propane, methyl acetylene and propadiene
are distilled overhead from the depropanizer while C4's and heavier compounds are drawn off as
bottoms and sent to the debutanizer.

A mixture of butenes and butadiene is distilled overhead in the debutanizer while raw pyrolysis gasoline
is drawn off as bottoms. The heaviest polymer build-up has been experienced in the depropanizer and, to
a lesser extent, in the deethanizer.

Polymer Composition..,and Formation

Six sets of polymer samples were taken from the deethanizer and depropanizer. They were preserved by
storage in glass jars filled with freshly boiled-out and cooled distilled water. Some exposure to air
during sampling was unavoidable.

Less than 40% of the polymer was soluble in chloroform. Infrared spectra of the chloroform soluble
material from both columns indicated that the main components were trans-l,4-polybutadiene and
1,2-polybutadiene. Low concentrations of terminal acetylene groups were also detected.

Absorptions at 730 cm-1 (cis CH deformation) were too weak to establish the presence of significant
concentrations of cis-l,4-polybutadiene. There was no indication of the presence of polypropadiene,
polypropylene or polybutene. Nuclear magnetic resonance (NMR) spectra of the carbon tetrachloride
soluble portion of the polymer were similar to published spectra for polybutadiene produced by free
radical initiated polymerization.

185
Both the IR and NMR Spectra indicated that the trans-l,4 form of polybutadiene predominated over the
1,2- form. The spectra also indicated the presence of less abundant components.

Untreated, fresh samples of polymer ignited on exposure to air. After several days, none of the samples
collected were pyrophoric at less than 65-70 degrees C. Attempts to detect free radicals by electron spin
resonance on month-old samples were unsuccessful. Iodo-metric titration to determine peroxide content
were unsuccessful. This may be due to low solubility of samples, however other investigators have been
unable to detect peroxides in synthesized polymers.

These observations do not preclude the presence of peroxides. The presence of small quantities of
oxidation products (carbon monoxide, acetic and propionic acids, aromatic carbonyl compounds)
indicate that some oxygen enters the plant system. It is known that butadiene reacts with air to form
polymeric peroxides and that these are sensitive to heat and shock. Free radicals formed by
decomposition of butadiene peroxides are likely initiators of polymer formation.

Thermogravimetric (TGA) and differential thermal analysis (DTA) were carried out in nitrogen and in
air. Commercial Taktene 1220 polybutadiene (high cis-l,4 form) was also analyzed as a reference. The
polymer samples from this study decomposed more rapidly in nitrogen than Taktene, and absorbed
oxygen more rapidly and at a lower temperature.

Since metals are known to catalyze polymerization, samples from various points in the process during
both normal and rapid polymer build up were burned into an ash and analyzed for metals. Iron was the
chief component of the ash samples. A consistent relationship between metal concentrations and rate of
polymer build up could not be determined. Some popcorn-like polymer, whose formation is promoted
by iron, was observed in some areas. This is likely due to iron rust promoted polymerization.

Deactivation of pyrophodc polymer in plants

A range of deactivants were tested for their ability to decrease the oxygen absorption capacity, increase
the thermal stability and increase ignition temperature of the samples by destroying peroxide or other
groups on the polymer. Of the deactivants tested, sodium hydroxide was found to be the most effective.

When build up of polymer becomes suf~ciently great to necessitate a shut down of the deethanizer and
depropanizer, the following steps are taken to increase periods between forced shut downs to more than
one year:

• The columns are drained and depressurized to flare

• Columns are then filled with water, drained and deactivated with a 2 to 3 % sodium hydroxide
solution. The solution is circulated through the column for several hours to deactivate the polymer.
• The excess sodium hydroxide is neutralized with hydrochloric acid to pH 7 and the column drained.
• Air is drawn into the column and the trays removed.
• The trays and column surfaces are cleaned using brushes and sand-blasted to remove all polymer and
rust. During cleaning the polymer is kept wet to prevent possible auto-ignition of any deposit which
may have been in contact with the sodium hydroxide solution.

186
• The trays are replaced and all surfaces pacified by circulating an agent such as sodium nitrite for
several hours. This is necessary because the fresh metallic surfaces formed by mechanical cleaning
have increased surface area and catalytic activity.
• The pacifying solution is drained off.
• Oxygen free boiler water is added to the top of the column to wash the equipment and drained off
with the introduction of nitrogen to exclude air.
• The column is pressure purged with nitrogen until the oxygen content is sufficiently low.
• The column is then ready to go onstream.

Table 1

Physical Properties of Common Carboxylic Acids

Boiling Pt.
Acid Structure Deg C Deg F
formic HCO2H 100.7 213.3
acetic CH3CO2H 118.1 244.6
propionic CH3CH2CO2H 141.1 286.
n-butyric CH3CH2CH2CO2H 165.5 241.7
isobutyrie (CH3)2CHCO2H2020 154.5 310.1
palmitie CH3(CH2)14CO2H 390. 734.
stearic CH3(CH2)16CO2HO 360. 680.
vinylacetic CH2=CHCH2COaH 163. 325.4
benzoic C6H5CO2H 249. 480.2
phenylacetic C6H5CH2CO2H 265. 609.

Table 2

Effect of Acids on Pure Water pH

Acid oH
Formic 3.9
Acetic 4.2
Propionic 4.4
Butanoic 3.8
Sulfuric 3.0

Notes: The data shown above is at 77 degrees F.

The acid content is 100 ppm (14).

187
 Table 3

Naphthenie Acids Content in

Various American Crude Oil Fractions

Naphthenic
Crude Oil Type Fraction acid (%)

Pennsylvania Paraftinic Kerosene 0.006

Pennsylvania Paraffinic Gas oil 0.010
East Texas Intermediate Kerosene 0.009
Texas heavy Naphthenie Gas oil 0.35
Midcontinent Intermediate Kerosene 0.009
Naphtha 0.01
California Naphthenic Kerosene 0.06
Gas oil 0.36

Table 4

Effect of Bases on Pure Water pH

Chemical ........... pH

NaOH 12.0
MEA 10.4
DEA 10.2
Cyelohexylamine 10.3
Morpholine 9.2
Ammonia 7.4

Notes: The data shown above is at 77 degrees F

The acid content is 100 ppm (I 4).

Table 5

Boiling Points of Pure Amines & Treating Chemicals

Chemical Deg F
MEA 339
DEA 515
Cyclohexylamine 274
Morpholine 263
Ammonia -28

188
 Table 6

Effect of Temperature on
Butadiene Formation Dimer Rate

Temperature % Butadiene
Deg C Deg F polymerized
Per hour
20 68 0.00015
40 104 0.0014
60 140 0.013
80 176 0.12
100 212 1.1

Table 7

Effect of Peroxide
on Rate of Plastic
Polymer Formation
at 45 Deg C

Active % Butadiene
Oxygen polymerized
ppm. Per hour
0 0.00
25 0.0040
100 0.0076
225 0.00120
400 ,
0.0165
625 0.0200
900 0.0240
1600 0.0320

Table 8

Effect of Temperature on Rate

of Plastic Polymer Formation
at 1200 ppm of Active Oxygen

Temperature % Butadiene
Deg C Deg F polymerized
Per hour
20 68 0.0012
40 104 0.014
60 140 0.17
80 176 1.9

189
References

Q "Ethylene Producers Committee - Feedstock Issues Subcommittee Questionnaire Survey Data:

Selected Ethylene Feedstock Impurities" by Mark A. Graham of Chevron Chemical Company.
Presented at the Spring National Meeting, 1993,

11, "A Survey of Trace Contaminants in Natm~ Gas Liquids" by S. M. Wharry and N. J. Sung of
Phillips Petroleum Co., Bartlesville, Oklahoma; Published in the Proceedings of the Seventy-Fourth
GPA Annual Convention and in GPA TP-21.

Q GPA Technical Publication TP-21; "Trace Contaminants in Naatml Gas Liquids" from GPA
Technical Section C, July 24, 1996

Q D. R. McPhaul and J. A. Reid, "Ethylene Plant Feedstock Contaminants Treatment" in Proceedings

of the 7th Ethylene Producers Conference, Session 20, March 1995 combined AIChE and EPC
meeting.

0 "Methanol Contamination of Polymer Caade Propylene Product at the Union Texas Petrochemicals
Geismar Olefins Plant by L. Bayer; Presented at the 1996 AIChE Spring National Meeting,
published in the Proceedings of the 8th Annual Ethylene Producers Conference.

0 "MTBE as a Feedstock Contaminant" by E. Stout; Presented at the 1996 AIChE Spring National
Meeting, published in the Proceedings of the 8th Annual Ethylene Producers Conference.

0 Methanol in Cracking Furnaces; Presented at the 1996 AIChE Spring National Meeting, published
in the Proceedings of the 8th Annual Ethylene Producers Conference.

Q Panel Discussion: Effect of Contaminants in Ethylene Plants; SESSION 22" Published in the
Proceedings of the 8th Annual Ethylene Producers Conference.

0 D. J. Artrip, C. Herion and R. Meissner of BASF was presented on "Safeguarding Olefins Purity for
Polyolef'm Plants", Proceedings of the 5th Ethylene Producers Conference, Session 15, March 1993
combined AIChE and EPC meeting.

10. D.L. Smith, "Olefin and Comonomer Purification Via Selective Adsorption to Assure Metallocene
Catalyst Activity", Presentation at MetCon, Houston 1993.

11. Solubility of air (mole fraction) in kerosine or higher boiling petroleum oils (Henry's Law) by W. L.
Nelson, Technical Editor and Petroleum Consultant in the "Oil and Gas Journal; July 11, 1966

12. "Chemical Refuting of Petroleum", American Chemical Society, Monograph Series; Reinhold
Publishing Corporation, 1942

190
13. "Inhibiting Gum Formation in Modem Gasolines" by M.W. Schrepfer and C.A. Stansky of the UOP
Process Division, UOP Inc.; Presented at the 1980 UOP Process Division Technology Conference

14. Quench Area Tutorial 3, Dilution Steam Feedwater Conditioning & Generation, PAPER NO. 97C
by Greg Dunnells, ABB Lummus Global, Inc.; AIChE 2002 Spring National Meeting March 2002;
New Orleans, Louisiana

15. Quench Water Pretreat in Ethylene Plant by Sabah Kuntkchi; PAPER NO. 97D, AIChE 2002
Spring National Meeting, March 2002; New Orleans, Louisiana, Ethylene Producers Conference
2002

16. Quench Water tutorial presented at the Ethylene Producers Conference in 2002.

17. Mono-olefins Chemistry and Technology by F. Asinger and Translated by B. J. Hazzatd; Published
by Pergamon Press.

18. Petroleum Ref'ming, Vol 1; Crude Oil, Petroleum Products, Process Flowsheets; Institut Francais du
Potrole Publications; Edited by Jean-Pierre Wauquier, Translated from the French by David H.
Smith; Distributed in the United States by Gulf Publishing Company; 1995, Editions Teehnip-
Paris, ISBN 2-7108-0685-1 and Series ISBN 2-7108-0686-X

20. "What are the amounts of nitrogen and oxygen in U.S. products?", by W. L. Nelson the Technical
Editor and Petroleum Consultant in The Oil and Gas Journal of February 4, 1974.

21. Control of Carbonyl Polymer Fouling in Caustic Towers By

David Mullenix Vista Chemical Company
Mike Jordan Eastman Chemical Company
Hermie Bundick Huntsman Corporation
Fred Martin Betz Process Chemicals
Vince Lewis Nalco/Exxon Energy Chemicals
presented at the 8th Ethylene Producers' Conference and
published by AIChE in 1996.

22. "An Overview of Olefin Unit Accidents and Safety Lessons Learned" by John A. Reid of Stone &
Webster presented at American Institute of Chemical Engineers, 1999 Spring National Meeting and
published in the Proceedings of the 1lth Ethylene Producers Conference.

22. 2000 NPRA Q & A Session on Refining and Petrochemical Technology; pages 188-187.

23. Catalytic Reforming by Donald M. Little; PennWell Publishing Company of Tulsa, Oklahoma.

24. The Chemistry of Petrochemical Reactions By Lewis F. Hatch, Ph.D., Professor of Chemistry, The
University of Texas; Gulf Publishing Company, Houston, Texas, 1955; The text of this book, was

191
 presented originally as a seventeen-part series of articles during 1953 and 1954 in Petroleum
Refiner magazine, published by Gulf Publishing Company.

25. Petroleum Refinery Engineering by W. L. Nelson; Consulting Petroleum and Chemical Engineer,
Professor of Petroleum Refining, University of Tulsa; Fourth Edition, McGraw-Hill Book
Company, 1958.

26. The Causes and Control of Fouling in Hydrodesulfurization Units, A Tutorial by Bruce E. Wright,
P.E.; BetzDearbom, Inc., A Division of Hercules, Inc.; The Woodlands, TX; Copyright: December
2001, Prepared for presentation at the AICHE 2002 Spring National Meeting as Paper No. 57a.

27. Reduce Olefin Plant Fouling by J.F. Martin of Betz Process Chemicals, Inc., The Woodlands, TX;
in Hydrocarbon Processing, November, 1988.

28. Pyrophoric Polymer in Ethylene Plant Deethanizer and Depropanizer Columns by Karl Georgieff of
Gulf Canada Ltd.; in The Canadian Journal of Chemical Engineering, Vo132, June 1984.

29. Chemistry and Technology of Wines and Liquors By Karl M. Herstein, F.A.I.C.; Consulting Chemist
and Thomas C. Gregory; Consulting Chemist; Published by D. Van Nostrand Company, Inc. in 1935.

30. INERT GAS + POOR PIPING = EXPLOSION; D. S. Alexander and C. M. Finigan, Polymer
Corporation, Ltd; Petroleum Refiner, May 1959, pages 285-290

31. Petreeo Manual - Impurities In Petroleum - Occurrence, Analysis, Significance to Ref'mery and
Petrochemical Operations; Prepared by the Staff of Petrolite Corporation Laboratories and Published
by Petreco.

32. Significance of ASTM Tests for Petroleum Products; Prepared by ASTM Committee D-2 on
Petroleum Products and Lubricants in 1955; Special Technical Publication No. 7-B; Published by the
American Society for Testing Materials

33. Exxon Chemical's Guide on Storing/Handling Ol¢fins/Diolefins.

192
 Figure 1

Acids (CnH2n+l COOH) Alcohols (CnH2n+l OH)

HCOOH formic acid CH30H methanol

H
H--C~ O J
OH H-C-O-H

CH3COOH acetic acid C H OH ethanol

25

H H H
I //o i t
H-C--C H- C - C - O - H
I \ OH l l
H H H

C H COOH propionic acid C3HTOH propanol

2 5

H H H H H
I I ~o I I I
H-C--C-C\ H-C- C-C- O-H
I I OH I I I
H H H H H

C3H7COOH butyric acid C4H90H butanol

H H H H H H H
J I I //O a i i i
H-C- C-C-C \ H-C-C-C-C-O- H
I l J OH j I t l
H H H H H H H

193
 Figure 2
.-.

R--COOH H=C--CHC00H OH
I I
H,C (CH:).
\/
CH, ---R

Alipl,atic acids Naphthenic acids Pllenols

(C,'esylic acids)

Figure 3

H=C--CHC00H H~C--CHCH=COOH
I I I I
H=C CH= I-I,C CH,
\/ \/
CH= CH=
Cyclopentanecarboxylic acid Cyclopentylacetic acid

Figure 4

OH CH, CH, CH,

I

Phenol
1 • ]~0H 't
/

OH
ortho-Cresol recta-Cresol para-Cresol

194
 Figure 5
Morpholine

/O \
CH, CH,
I I
CH= CH=
\N/

Vinyl Acetate Sulfolane

0
U
CH=- C-O-CH=CH2
CH= CH=

Ethylene Glycol Ns ,/
0 0
H0- CH=- CH~ - O H

Isopropyl Alcohol MEK

CH~-CH- CH= 0
I II
OH CH=-C-C=CH

Figure 6
Distribution of the acid content as a function of the
specific gravity of successive distillation fractions.

T Moles of acid per

mole of hydrocarbon
05 . . . . . .

0.4
/
0.3
/"
0.2

0.1

0.8
J 0.9
11
Specific gravity

195
 Quench Oil System
, To
Water
Oil Reflux Quench
Heat
Heat Recovery
Recovew
p-

(.o
From t •~ - - Steam
03
Cracking Quench
Furnaces Oil
Coke Tower LFO
Rejection
Recycle
Furnace
~ ,,,>I
Effluent Steam --~ Fuel
HFO
"=, Oil
Product

Figure 7
 DISTILLATE & CONDENSATE STRIPPERS

, to
Recovery
acid gas Section
removal
_
|

!
from
quench
section

(.0 ( ~ oil-water I -|
separator [ / J
oil ~ - . . . . . . |
reflux ~ ~.1
.... • ~..

o
Q.
o.
,m
in

ut

1 ~ to d e b u t a n i z e r to ,depropanizer

Figure 8
 Compression
To
Cracked Gas Compressor
Recovery

.,lIII I lIlII

(.o
Qo
From

Quench
__._.~ ~__,N-1
. . . . . . .

.J=

I
,~,
QW Spent

Caustic Tower
Figure 9
 Front n d Depropanizer/Hydro genation

Heat Pump C2H2 Hydrogenation

RX
To Cold Fractionation
Cracked Gas Feed
mm

(.o
from Dryers
(.o
_) To C3 Hydrogenation

I .

f C4+

Figure 40