Engineering Encyclopedia

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Exxon Chemical And Mechanical Cleaning Manual

12) Fouling Control By Prepassivation

Note: The source of the technical material in this volume is the Exxon Research
and Engineering Company Chemical and Mechanical Cleaning Manual.
Warning: This Exxon Research and Engineering Company Chemical and
Mechanical Cleaning Manual is made available exclusively for the use of
Saudi Aramco for its own use and for no other purpose. The disclosure of its
content are subject to the provisions of the Contract No. 30934/00 dated
November 1, 1986. The material in this manual may not be copied,
reproduced, sold, given, or disclosed to third parties or otherwise used in
whole or part without the written permission of the Vice President,
Engineering Services, Saudi Aramco.

Chapter : Fouling Control By Prepassivation For additional information on this subject, contact
File Reference: Section 12 R.S. Sarathy on 875-3520
Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

TABLE OF CONTENTS

I. HYDROCARBON, FREE RADICAL POLYMERIZATION FOULING ......................... 1

Chemistry of Fouling ................................................................................................ 1

Steam Cracker Light Ends Fouling............................................................................ 2

Nitric Oxide is Good Inhibitor for Free Radical Reactions......................................... 3

NO Passivation Procedures ....................................................................................... 3

Safety Considerations When Using NO Procedures................................................... 4

Comparison of NO Versus Other Methods ................................................................ 5

II. PASSIVATION OF COOLING WATER SYSTEMS ..................................................... 7

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Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

I. HYDROCARBON, FREE RADICAL POLYMERIZATION FOULING

Chemistry of Fouling

The chemistry of process side fouling is very complex and insufficient work has been done to
unravel the intricate chemical reaction paths. Fouling manifests itself through formation of
carbonaceous deposits on heat transfer surfaces and reduces the rate of heat transfer. It is
assumed that these deposits are formed via a polymerization mechanism and subsequent coking,
since the temperatures prevailing are too low for carbon formation through a direct cracking
mechanism.

Polymerization reactions proceed in three distinct steps, as shown below:

• Radical formation and chain initiation:

XH Õ X + H • •

R - CH = CH2 + X Õ R - CH - CH2X
•

• Chain propagation:
R R
 
R - CH + R - CH = CH2 Õ R - CH - [CH2 - CH - ] n - CH2 - CH
• •

 
CH2X CH2X

• Chain termination:
R R
 
R - CH - [CH2 - CH - ] n - CH2 - CH + H Õ
• •


CH2X
H R R
  
R-C [CH2 - C - ] n - CH2 - CH + CH2
•


CH2X

The rate of each step and the length of the chains formed depend on the concentration and
activity of the reaction partners.

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Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

Oxygen, halides, sulfides, nitrogen compounds and certain metals or metallic compounds are all
known to be able to initiate polymer formation. The extent of involvement depends on the
operating temperature as well as on the stability of the ensuing radical at this temperature. Thus
oxygen, for instance, can be involved in the chain initiation at one temperature while it sustains
the termination reaction at another.

It is thought that, at certain temperatures, mercaptans and sulfides can undergo reactions with the
metal surface according to the equation below:

R - SH Õ FeSH + R •

Corrosion reactions of this nature can yield hydrocarbon radicals which, in turn, may initiate
polymerization.

Steam Cracker Light Ends Fouling

Steam cracker light ends fouling (SCLEF) is caused mainly by thermally initiated free radical
polymerization of butadiene and isoprene. Fouling deposits grow by polymerization on the wall
rather than polymer being deposited from the bulk. Further information on the fouling and its
inhibition by means of Nitric Oxide passivation is contained in CRMB 10L.76, Steam Cracker
Light Ends Fouling - Mechanism and Prevention, by T. Lode. The fouling increases with:

• increasing butadiene or isoprene concentration according to a second order relationship

• increasing C4 acetylene concentration with a higher order relationship
• increasing temperature; it doubles every 10°C
• rusty surfaces; rust catalyzes polymerization reactions

Two basic forms of fouling material occur, popcorn polymer and rubber-like polymer. Both are
formed via a free radical mechanism.

• Polymer popcorn is, as the name implies, brittle, popcorn-like.

It forms only in a relatively pure diene atmosphere, liquid or vapor. It is self-catalytic; i.e.,-it
grows by monomer diffusing into the bulk which is "alive" with free radicals. Rapid,
exponential growth occurs, often developing several thousand atmospheres pressure in
restricted areas and causing tube ruptures. If popcorn is not 100% removed from equipment
or deactivated, the remaining particles will act as seeds often causing recurrence of the
popcorn polymer problem.

• Rubbery, elastic polymer is normally encountered in depropanizers, etc. It grows from the
walls and the rate of fouling build-up is usually quite regular. This type of polymer also
occurs in butadiene and isoprene plants.

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Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

Nitric Oxide is Good Inhibitor for Free Radical Reactions

Butadiene polymerization is radically initiated. Free radicals initiate chain growth of butadiene,
and this is self propagating. Because of that mechanism, nitric oxide is functionally a good
passivation agent for the following reasons:
• as a free radical, it is extremely reactive towards hydrocarbon free radicals. Even at the parts
per billion level it intercepts and terminates a growing free chain of butadiene units to stop
polymer formation.
• NO as such adsorbs strongly on iron surfaces, and is subsequently released very slowly when
equipment is operated. Thanks to this mechanism, NO will be present at the wall where the
fouling would be initiated.

This means that when NO is charged to a vessel with a partially oxidized surface, the NO, if not
in excess, will be adsorbed almost quantitatively. The rate of adsorption is high and the most
easily accessible surface areas are probably saturated with NO after a few minutes. Further
adsorption involving diffusion in the solid should be slower. The equipment then remains
passivated until all the NO is stripped off or otherwise destroyed. The rate at which NO is
stripped off depends on the temperature. It is believed that protection will last for months at
temperatures less than 80°C. Above 160°C the protection may need to be renewed every few
days.

NO Passivation Procedures

NO passivation procedures have evolved over several years. The procedures as now practiced at
Baton Rouge, Fawley, and Notre Dame de Gravenchon are safe to people and equipment.
Further optimization should make the procedure simpler, faster, and cheaper. This section will
deal with safety concerns and the actual passivation procedure.

There was about a four-year delay from the time when the effectiveness of NO was determined
to its general acceptance in commercial applications. This was due to safety concerns which are
now satisfactorily settled.

NO is a toxic gas with Threshold Limit Value (TLV) of 25 vppm. The NO is readily oxidized to
nitrogen dioxide (NO2) which has a TLV of 3 vppm. The TLV is the maximum level permitted
for continuous 8 hour exposure in U.S. industry. NO2 has been identified as one of several
components which together caused serious explosions in two ammonia plants. To have an
explosive mixture, the temperature must be below -130°C. Several other factors, none of which
is possible in SC operation, would also have to occur. No danger is foreseen for properly
executed NO passivation.

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Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

The first general report on NO passivation guidelines was released in early 1974. Port Jerome
was the first plant to develop a detailed NO passivation procedure. By now olefin plants at
Baton Rouge, Kawasaki and Port Jerome have developed a number of procedures. Each plant
has developed specific passivation procedures suited for their special conditions. The following
guidelines are still in effect:
• All procedures must ensure that personnel are not exposed to breathing NO. This is
accomplished by suitable use of fresh air masks and monitoring of the NO level in the air
with Drager tubes or similar devices.
• NO passivation should be carried out only on equipment which has been mechanically
cleaned, dried, and found essentially free from lumps of polymer when inspected.
• The equipment must be flushed by inert gas to ensure that the oxygen content is well below
one percent.
• NO is introduced to the inerted tower, with or without additional nitrogen.
• Reboilers are heated or other agitation should be used to ensure good mixing of NO in the
gas phase.
• Where the metal is exposed to NO, the passivation is believed to be completed in 30 min.,
i.e., after this, no further NO will be adsorbed.
• Typically, a tower or reboiler will adsorb 2-4 grams of NO per square meter of internal metal
surface area. Any NO added beyond this must subsequently be flushed from the -unit and is
essentially wasted. All early passivations used 10 grams of NO per square meter with excess
NO being flushed afterwards. Additional plant tests are needed to establish the minimum
NO charge needed.
• After passivation, the equipment is flushed with inert gas until the NO concentration is below
5 ppm. This is readily checked with Drager tubes or similar.
• The passivated equipment can now be put on stream or blocked off until needed.

Safety Considerations When Using NO Procedures

Like hydrogen sulfide, nitric oxide is a poisonous gas, and certain safety precautions have to be
taken in handling. NO is readily oxidized by oxygen to NO2, which reacts with air moisture to
form nitric acid in the lungs. The greatest hazard of exposure to NO comes from the fact that its
serious effects are not felt until several hours after the exposure.

To avoid any possibility of accident or explosion, the following precautions are recommended in
using NO:
a) Self contained breathing apparatus should be available, and used when opening the NO
bottles, and controlling the operation, until the excess of nitrogen monoxide is finally vented.

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Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

b) Area surrounding the equipment should be delimited with safety chains and access to the area
should be prohibited for non-authorized people.
c) Plugs and blinds should be installed on the top of every valve opened to the atmosphere and
under pressure to NO during the passivation. Piping should be preferentially welded.
d) Dragger tubes should be available to check NO and NO2 content of the atmosphere when
required.
e) If a chimney is used to vent the excess of nitrogen oxide, it is necessary to take care of the
dispersion of NO in the atmosphere. The chimney height could be checked with the plant
environmental engineer.
f) No system may be passivated which cannot be or has not been totally visibly inspected prior
to passivation. The visual inspection must ensure:
1) that deadlegs are free from trapped hydrocarbon liquid, vapor and polymer
2) butadiene popcorn polymer (except for that which may be plugging a few exchanger
tubes *) has been totally removed from the system.
* It is acceptable to passivate exchangers and reboilers which have polymer plugged tubes. This assumes
that (1) the polymer in the tube is so tightly packed that NO cannot penetrate far into the polymer i.e.,
that the polymer surface area presented to the NO is small and (2) that if sufficient tubes are plugged so
as to present a significant polymer surface area to NO, then no incentive would exist to recommission
that exchanger.
g) All parts of the system, including the NO passivation equipment, must be systematically and
effectively N2 purged. Hydrocarbons must be essentially eliminated and oxygen levels must
be less than 0.5%.
h) Residual NO at the end of passivation must NOT be purged to flare (although it would be
permissible to purge to a furnace stack).
i) The NO passivation equipment must be physically isolated from all process equipment at the
end of passivation such that no hydrocarbons can backflow into the passivation system.

Comparison of NO Versus Other Methods

Several tower reboilers have been passivated previously with aqueous NaNO2 which is a
common practice with SHELL butadiene plants. A 5% NaNO2 solution was circulated at 120°C
for about 20 hours before pressuring the system with hydrocarbons. Using this method, average
reboiler run length was extremely short, 44-50 days. Fouling appeared probably as soon as the
reboiler was onstream. After NO passivation a test run lasted 123 days, which is about thrice the
run length obtained with NaNO2 before. Nitric Oxide passivation is faster, cheaper, more
convenient, and longer lasting than the alternate aqueous NaNO2 procedure.

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Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

Recently the NO procedure has been de-emphasized somewhat in favor of process methods to
reduce fouling:
• Reduce tower bottoms temperature
• Minimize reboiler outlet temperature
• Minimize temperature of reboiler heating medium
• Modify tower internals (sieve trays, downcomer clearances, etc.)
• Test commercial light ends antifoulants
• Reduce C4 acetylene concentration in light ends towers.

A description of these methods can be obtained from the Olefins Technology Division of Exxon
Chemical Co.

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Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 12
Fouling Control By Prepassivation

II. PASSIVATION OF COOLING WATER SYSTEMS

The method is described in Section VI - Precommission Cleaning. In addition to passivating

new systems, passivation is recommended after an acid spill, bundle cleaning and extended
turnarounds in order to minimize corrosion and subsequent corrosion-related fouling. This is
discussed in Section 8 - Coolers and Condensers.

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