PA Site Process Safety Concept

Port Arthur Safety Concept Rev.
3
BASF Corp. October 2018
PORT ARTHUR SITE

PROCESS SAFETY CONCEPT
Master:
 Revision Number: 1
 Effective Date: December 2010
Authors:
Eric Christman - Petrochemicals Technology Manager

Robert Copland – Director, Olefins Technology
David Smith – EHS Specialist
Larry Zych – Process Engineer
Document Revision Change Table

Revision Revision Description Revised By Revision
Number Date
Included Design Codes and Standard Employed Pages 6 & 7 DLS 12/10
01
02 General Review-No Changes BLM 02/16
03 General Review-Minor Changes BLM 10/18
PA Site Process Safety Concept.doc 1 of 49

Port Arthur Safety Concept Rev. 3
Introduction
BASF Corporation operates the NAFTA Region Olefins Complex (NROC) at Port Arthur,
Texas. Functionally, the site consists of a naphtha cracker and a C4 olefins complex.
The cracker produces ethylene, propylene, benzene, and toluene. The C4 olefins
complex consists of a butadiene plant, a UOP indirect alkylation (InAlk) unit, and the
Olefins Conversion Unit (OCU), which includes the PAR BB Unit. InAlk converts
butenes into gasoline blending stock; the OCU produces propylene from ethylene and
butenes. The BASF Total Petrochemicals LLC (BTP) owns the Cracker, OCU,
Butadiene and InAlk plants, along with their associated utilities.
This Process Safety Concept has been written to document the hazards and safeguards
associated with the operation of the Port Arthur Site. The report focuses on the
hydrocarbon-handling areas. It does not cover widely-used, standardized systems such
as packaged boilers, non-flammable utilities, or low-hazard equipment such as water
purifying and wastewater treating processes.
While this report is extensive and represents the knowledge and experience of the
authors, it does not claim to be complete. If a particular operation or function is not
mentioned, it cannot be assumed to be free of hazard. Employees responsible for
operating and maintaining the site‘s processes must be involved in identifying and
resolving the associated hazards.

Contents
1.0 General Hazards
1.1 Preventing Fires and Explosions
1.1.1 Preventing Leaks and Spills

1.1.2 Excluding Air from Process Equipment
1.1.3 Eliminating Uncontrolled Ignition Sources
1.2 Chemical Hazards
1.2.1 Carcinogens
1.2.2 Highly Toxic Chemicals
1.2.3 Pyrophoric Materials
1.2.4 Other
2.0 Process Specific Hazards -- BTP
2.1 Hot Section
2.1.1 Feed Preparation

2.1.2 Pyrolysis Section
2.1.3 Gas Fractionation
2.1.4 Quench Tower/Quench Water Settler
2.1.5 Process Water Stripper and Dilution Steam Generator
2.2 Cold Section
2.2.1 General Cold Section Hazards

2.2.2 Charge Gas Compressor
2.2.3 Acid Gas Removal
2.2.4 Spent Caustic Oxidation
2.2.5 Dryer Feed Drum, Condensate Stripping and Drying
2.2.6 Charge Gas Dryers
2.2.7 Charge Gas Chilling Train
2.2.8 Methanator and Hydrogen Dryer
2.2.9 Demethanizer
2.2.10 Deethanizer and Acetylene Converter
2.2.11 Ethylene Dryer and Ethylene Fractionator
2.2.12 Depropanizer, MAPD Converter, and C3 Fractionator
2.2.13 Debutanizer and C4 Hydrogenation
2.2.14 Ethylene and Propylene Refrigeration

2.3 Aromatics Recovery Plant (Pygas)
2.3.1 General
2.3.2 Hydrogenation Section
2.3.3 Predistillation
2.3.4 Extractive Distillation
2.3.5 Benzene/Toluene Splitter Tower
2.4 BTP Flare System
3.0 Process Specific Hazards – C4 Complex
3.1 Butadiene Extraction Unit (BEU)
3.1.1 General
3.1.2 Prefractionator Tower
3.1.3 Feed Vaporization System
3.1.4 Main Washer System and Solvent Cooler
3.1.5 Rectifier Column System
3.1.6 Afterwasher Column System
3.1.7 Degasser System
3.1.8 Recycle Gas Compressor
3.1.9 Acetylene Washer
3.1.10 C4-Acetylene Condenser and TBC Removal Column
3.1.11 Crude Butadiene Cooler and Coalescer
3.1.12 Butadiene Column System
3.1.13 Solvent Regenerators
3.1.14 Regenerated Solvent Recovery System
3.1.15 Tert-Butyl Catechol (TBC) Injection System
3.1.16 Solvent Inhibitor System
3.1.17 Antifoam System
3.1.18 Butadiene Drain Drum and NMP Slop Vessel
3.1.19 Solvent Surge Tank
3.1.20 Raffinate Chilling and Coalescing
3.1.21 Bisulfite Wash System
3.1.22 Tank Farm
3.2 Indirect Alkylation Unit (InAlk)
3.2.1 General
3.2.2 Feed Dryer System
3.2.3 C4 Selective Hydrogenation Unit (Selop I)
3.2.4 Polymerization Reactors
3.2.5 Debutanizer Tower
3.2.6 Hydrotreater Reactor
3.2.7 Product Separator Drum and Recycle Gas Compressor
3.2.8 Product Stripper Tower

3.3 Olefins Conversion Unit (OCU)
3.3.1 General
3.3.2 C4 Selective Hydrogenation Unit (Selop II)
3.3.3 Feed Treatment
3.3.4 Feed Preheat System for the Disproportionation (DP) Reactors
3.3.5 Disproportionation (DP) Reactors and Regeneration System
3.3.6 Recovery Section
3.4 C4 Flare Systems
4.0 References
5.0 Block Flow Diagrams

1.0 General Process Hazards

In the discussion below, the general hazards at the Port Arthur Site are arbitrarily split between
fires and explosions and chemical hazards.
1.1 Preventing Fires and Explosions
By its very nature, a modern petrochemical facility such as the Port Arthur Site contains large
voumes of flammable materials and many potential sources of ignition. Consequently, fire and
explosion precautions must be a part of all operations. Generally, these precautions consist of:
 Preventing leaks and spills.

 Excluding air from process equipment.
 Eliminating uncontrolled ignition sources.
Leaks and spills are controlled through equipment design, mechanical integrity programs, and
housekeeping. Air is eliminated from the process stream through operating procedures,
equipment design, and mechanical integrity procedures. Ignition sources are controlled through
static control and the permitting process.
1.1.1 Preventing Leaks and Spills
1.1.1.1 General Design and Maintenance Practices
The Port Arthur Site maintains an Inspection, Testing, Preventative Maintenance (ITPM) program,
a Management of Change (MOC) program, and a Mechanical Integrity (MI) program. These
efforts conform to Federal, State, and local legal requirements, BASF requirements, and
Recognized and Generally Accepted Good Engineering Practices (RAGAGEP). The Site also
adheres to the applicable codes and standards for piping and equipment in petrochemical
facilities. The following is a comprehensive, but not all inclusive, list of Design Codes and
Standard Employed within the site:
The BASF TOTAL Petrochemicals/C4 Petrochemicals Site purchases equipment designed and
fabricated to Codes and Standards. Buildings, structures, facilities and piping are designed and
constructed to Codes and Standards. The Codes and Standards employed at the BASF TOTAL
Petrochemicals/C4 Petrochemicals site include but are not limited to the following:
Foundations
ACI (American Concrete Institute)
Structural Steel
AWS (American Welding Society)
AISC (American Institute of Steel Construction)
Pressure Vessels and Relief

ASME (American Society of Mechanical Engineers) Boiler and
Pressure Vessel Code Section VIII
Piping
ASME B31.3 (American Society of Mechanical Engineers)
Instruments and Controls

ISA (Instrument Society of America)
NEC (National Electric Code)

Electrical Systems
NEC (National Electric Code)
NFPA (National Fire Protection Association)
Storage Tanks
API (American Petroleum Institute)
Ventilation
NFPA (National Fire Protection Association)
ASHRAE (American Society of Heating Refrigeration and Air
Conditioning Engineers)
Process Equipment
TEMA (Tubular Exchanger Manufacturers Association)
AGMA (American Gear Manufacturers Association)
ANSI (American National Standards Institute)
Details about codes, standards and GEP (Good Engineering Practice) for particular equipment
are found in project and equipment files.
Current projects that are carried out at BASF TOTAL Petrochemicals/C4 Petrochemicals
implement designs based on the BASF Mechanical, Electrical and Civil Technical Standards. The
Technical Standards are kept up to date with references to the latest versions of Design Codes
and Standards. In addition, the Technical Standards incorporate GEP that is recognized in the
chemical industry, along with GEP from the Global Technical Community of BASF.
Specific practices followed by the Port Arthur Site to ensure containment include:
 Welded piping is used wherever possible to minimize leak points.

 Flange gaskets are specified to withstand process materials, pressures, and
temperatures.
 All terminal valves, drain lines, and bleed points in hydrocarbon service are capped,
plugged or blocked with a blind flange when not in use
 Pipe flanges are torqued to recommended value and pattern applicable to the joint for
new and repaired installations.
 Piping which can be subject to low temperatures (< - 40 F) AND high pressures is
fabricated of low temperature carbon steel or stainless steel. 100 % x-ray of all piping
and vessel welds is required.
 Piping and pump seals are designed to withstand pump deadhead or relief pressure.
 Pumps in hydrocarbon service are built with double mechanical seals. The seal system
will contain a barrier fluid and, if vented, be vented to a flare. Where practical, pumps
may also be of seal-less design.
 All piping and vessels are inspected at appropriate intervals to assure integrity and fitness
for service.
 Integrity of all new piping and vessels is verified through appropriate RAGAGEP
procedures before being put into service.
 Design requirements for all new or modified equipment are determined by a process
engineer with appropriate knowledge, certification, and experience.
 Any changes to the process are evaluated through the Management of Change (MOC)
system, or, for capital projects, BASF’s Step Review system.
1.1.1.2 Pressure Relief

A release can also result when equipment is overpressured. To prevent such incidents, the Site
installs and maintains appropriate pressure relief devices. Specific practices to prevent a release
due to overpressure include:
 All process equipment is protected from overpressure by relief devices sized for the worst
case overpressure scenario. The worst case scenario is determined by comparing the
relief requirements for fire exposure, run-away reaction, blocked outlet, wide-open valve
failure, and any other relevant causes.
 Relief devices in hydrocarbon service discharge to a flare header or other containment.
The goal is to eliminate any hydrocarbon releases to the atmosphere.
 Administrative procedures are followed to ensure pressure relief devices are not blocked
in when equipment is in service.
 Specific procedures ensure equipment is not over pressured while purging/de-
inventorying using steam or nitrogen. Relief or flare header lines must be open and
adequate to exhaust the purging gas volume without building excess pressure in the
equipment.
 Steam purging is not begun until the equipment is confirmed clear of all liquid
hydrocarbons. This is done to prevent overpressure from to the boil-up of any residual
liquid.
1.1.1.3 Emergency Isolation
Since a leak might occur despite all the precautions described here, remotely-operated isolation
valves are provided in flammable fluid services to limit the size of the potential release. The
valves are located between large inventories of flammables and likely leak points such as pump
and compressor seals, fired heater coils, etc. The detailed criteria vary for different potential leak
sources, but in general, isolation valves will be provided for inventories exceeding 10,000 lb.,
where the material is above either its normal boiling point or auto-ignition temperature.
The Quick Isolation and Shutdown System (QISS) systems make it possible to simultaneously
shut or open many remotely-operated isolation valves at once in the event of a major release or
plant upset. BTP has two separate QISS’s, one for Pygas, the other for the balance of the plant.
Equivalent systems exist in the C4 plants.
1.1.2 Excluding Air from Process Equipment
Preventing explosive mixtures from forming inside process equipment and piping is crucial.
Practices employed by the Port Arthur Site to achieve this goal include:
 Equipment is properly inerted, or other measures are taken to prevent a flammable

atmosphere forming.
 Any tank in liquid hydrocarbon service without floating roof must be continuously
padded/purged with nitrogen as per the BASF Process Safety/Explosion guidelines.
 All process lines and equipment must be cleared of hydrocarbon material using nitrogen,
steam, or other non-flammable material before opening to the atmosphere.
 All new or repaired equipment that has been opened to the atmosphere must be purged
free of oxygen before hydrocarbon material is introduced.
 Relief devices discharging directly to the atmosphere should reseat once the
overpressure is relieved, to prevent backflow of air into the vessel.
 To prevent air infiltration, most equipment is maintained at positive pressure during both
normal operation and clearing. The few vessels that operate under vacuum are properly
inerted; if appropriate, they may also have continuous O2 monitors. Since off-gases from
vacuum vessels may contain oxygen, they are handled separately. This prevents a
vacuum leak from ever creating a combustible gas mixture in the main flare gas systems.
1.1.3 Eliminating Uncontrolled Ignition Sources

As it is possible to have a leak of combustible material in most of the Site’s operating areas,
uncontrolled ignition sources must be eliminated from them. This applies to both electrostatic
sources and transitory sources of ignition.
1.1.3.1 Electrostatic energy sources
 All conducting equipment must be properly grounded and/or bonded.

 Avoid spraying of liquid droplets, e.g. make sure that all fill pipes are dipped.
 When using steam to clean a system, a minimum flow should be used to prevent static
sparks which may be generated due to the high velocity of steam through a wide open
steam hose.
 Avoid electrostatic charging of liquids, e.g. the maximum fill rate must be reduced
depending on the geometric conditions of the considered vessel; the minimum fill rate
may not be below 1m/s, because of the possibility of laminar flow which also can create
electrostatic charges.
1.1.3.2 Transitory ignition sources
 Hot Work/spark producing activities will be done outside process areas whenever
possible.
 All Hot Work/spark producing activities will be permitted following guidelines developed
for the facility.
 Uncontrolled vehicular traffic must be limited to areas of the facility that are not
susceptible to leaks. Powered vehicles that do not meet the area electrical classification
must be escorted “walked” to the location using a LEL/O2 meter and the atmosphere
monitored while the engine remains running.
 Electronic Equipment (cameras, cell phones,) that does not meet the electrical
classification for the area must be permitted. Radios used within the process area must
be approved for Class 1 Division 1 areas.
 Establish smoking areas and provide low energy lighters. No personal lighters are allowed
in the facility.
1.2 Chemical Hazards
Most chemicals are potentially hazardous, and if handled improperly, can endanger personnel
and/or property. Maintaining containment of process fluids is the site’s basic strategy for
preventing injury and property loss. It also complies with all regulations and good practices for
protecting personnel against exposure to chemicals. These measures include enforcing safe
work procedures and requirements for personal protective equipment (PPE). The site maintains a
PPE Matrix, which lists the equipment required for specific chemicals and procedures. It also
follows a routine monitoring program to ensure that employee exposure to chemicals does not
exceed safe limits.
Some of the principal chemical hazards at the Port Arthur Site are:
1.2.1 Carcinogens
Benzene, butadiene, quench oil, pyrolysis side stream, and pyrolysis tar are widely distributed
around the site. Most of the butadiene comes to the site in C4’s pipeline feed; benzene and the
carcinogens in the other streams are largely created in the cracking furnaces. Benzene and
butadiene are products; there is no practical way to eliminate the other carcinogens from the site’s
processes, either. Preventing personnel exposure is the only available safeguard. This is
accomplished by maintaining containment, and by enforcing work procedures and PPE

requirements that protect personnel from any releases that may occur. The site’s control
measures for carcinogens comply with industry’s Responsible Care guidelines for specific
chemicals, and all applicable regulations.
1.2.2 Highly Toxic Chemicals
Anhydrous Ammonia. Liquid ammonia is stored under its own vapor pressure at two locations on
site. It is used in the selective catalytic reduction (SCR) units that control the NOx emissions from
various fired heaters. Ammonia is chemically stable, but flammable and highly toxic. Therefore,
the principal hazard is loss of containment. The engineering safeguards in place include
secondary containment and multiple specific gas monitors at each storage tank for leak detection.
PPE requirements are enforced through safe work permits. Special operating procedures are
also enforced, especially for truck deliveries. Ammonia equipment and procedures are
periodically audited to ensure compliance with relevant regulations.
Hydrogen Sulfide. This well-known poison is a by-product of the cracking furnaces and some of
the hydrogenation reactors. It is produced from the heavy organosulfur compounds in the Site’s
feed stocks and processing additives. The control measures are maintaining containment, and
enforcing proper work procedures and the use of appropriate PPE. Compound-specific sensors
monitor the ambient air at strategic locations and actuate alarms in the control room on high H2S
concentration.
Nickel Carbonyl. This compound is a particular concern because it is toxic, even fatal, at very low
concentrations. (The OSHA exposure limit is 1 ppb in air.) At temperatures below 400 F, CO
reacts with nickel catalyst to form nickel carbonyl. To prevent this, the catalyst must be thoroughly
purged with nitrogen while still hot (above 400 F) to remove all traces of CO.
1.2.3 Pyrophoric Materials
Reduced nickel catalyst is typical of the pyrophoric catalysts and adsorbents handled on site. Any
such material known or suspected to be pyrophoric is handled under inert gas. For more
information, refer to Health and Safety Procedure PA-020-0052, Inert Confined Space Entry.
Iron sulfide deposits are common in the lower section of gas fractionator towers. This compound
is also pyrophoric, and can readily ignite trapped hydrocarbon deposits when air is admitted into
these towers. Port Arthur uses a cleaning method common in the industry to control this hazard.
First, a surfactant is used to remove the combustible material. Second, a mild oxidizer is used to
convert the iron sulfide and other sulfur compounds to inert forms. Various oxidizers can be used
for this purpose; Port Arthur has used sodium carbonate peroxyhdrate. In addition, iron oxide
deposits have occurred in fuel gas storage, which can smolder and generate heat on contact with
air. Ensure those services are properly cleaned and entry plans include submerging vessel with
water or other means prior to maintenance activities.
Spent cartridges from the Naphtha Feed Filters have been known to smolder. Iron sulfide is
assumed to be the pyrophoric agent in this area, too. The operating procedures for the Naphtha
Feed Filters specify the following measures for controlling this hazard:
 Maintain a nitrogen purge on the filter between steam-out and opening.

 Store spent cartridges in special containers where they are kept wet with water.
 Monitor spent cartridges until they are removed from the site.

1.2.4 Other
Activated carbon. This material is used for emissions control whenever hydrocarbon-containing
process equipment is vented to the atmosphere. Examples of such operations include upsets of
the Thermal Oxidizer, and clearing equipment for maintenance. There is an exotherm due to the
adsorption of the hydrocarbon that may (in the presence of oxygen) cause a fire in the carbon bed.
Before a carbon canister is put into vapor service, it must be purged with nitrogen to inert it. Other
measures include clearing to other control devices (flares) until residual hydrocarbon is as low as
reasonably practical and follow site administrative controls for utilizing activated carbon.

2.0 Process Specific Hazards -- BTP
2.1 Hot Section
2.1.1 Feed Preparation
Two parallel feed systems provide light naphtha and heavy naphtha to the cracking furnaces.
Feed storage is off-site in the Total Refinery, and outside the scope of this discussion. Each
naphtha feed system consists of filters, a coalescer, and a feed pre-heater. The filters and
coalescers operate at ambient temperature and up to ca. 230 PSIG. The preheaters operate at
up to ca. 220 PSIG, with a design outlet temperature of 140 F. Both feed systems contain a
significant amount of hydrocarbons. The principal hazard in this area is loss of containment,
which could result in a flammable vapor cloud or large pool fire. Automated isolation valves at the
battery limits will limit the volume of escaping hydrocarbon should containment be lost.
2.1.2 Pyrolysis Section (Heaters 0100-1000)
In the Pyrolysis Section hydrocarbon inventories are very low. Operating pressure is low but
operating temperatures are severe. The greatest hazard on the process (coil) side of the pyrolysis
heaters is mechanical failure due to over temperature. The greatest hazard on the firebox side of
the heaters is possible deflagration due to faulty burner light-off, burner flameout in a hot firebox,
or firing with insufficient air.
Over-temperature of heater convection section and radiant section coils can be caused by a
number of failures including:
 Low or no flow rate in selected coils.

 Excessive firing rate.
 Excessive oxygen partial pressure during decoking.
Low or no flow is addressed with process monitoring, alarming and automatic heater shutdown
where appropriate.
Loss of dilution steam will not immediately result in coil over temperature but will cause an
excessive radiant coil coking rate. Dilution steam flow is monitored, and low flow rate is alarmed
allowing operating personnel to take corrective action. To enhance dilution steam reliability, the
system is backed up with direct injection of medium pressure steam, all block in the dilution steam
path will be car sealed open, and dilution steam control valves are assigned to fail in the open
position upon loss of instrument air.
The complete loss of heater feed requires a more rapid response, since the heat absorption of the
cracking reaction comprises a large portion of the fired duty. However, a total trip of the furnace
from full production rates to zero heat input has the potential to cause spalling of coke from
radiant coils. Therefore, provisions will be made to maintain partial heat input to the radiant coil.
Low feed flow will result in only a partial heater trip. In this shutdown mode, the feed isolation
valve is closed, and firing of wall burners is stopped by closing the isolation valve in the fuel gas
system.
The hearth burners will be staged fuel type, and a segregated shutoff valve will isolate the
secondary fuel header. The firing in the hearth burners is immediately reduced to the capacity of
the primary spuds. Dilution steam flow continues at a preset rate to provide protection for, the
radiant coil in this situation. The induced draft (ID) fan is maintained in operation under draft
control with the hearth burner primary fuel spuds and pilots lighted. This status enables rapid
restart when the feed supply problem is resolved, and limits the temperature excursion
experienced by the radiant tubes.

The boiler feed water preheat coil and the steam superheat coil in the convection section can also
experience over temperature if insufficient flow occurs. To protect these coils, the BFW control
valve will have a minimum stop, and heater trip is automatically initiated if low-low boiler feed
water flow or high-high steam superheater coil outlet temperature is detected. In this trip situation,
hydrocarbon feed is isolated, and fuel is also isolated to all burners. Dilution steam continues at a
preset rate, hearth burner pilots remain on, and the ID fan is kept operating at the normal setting.
Additional protection will be provided for loss of steam drum water supply in the form of a low-low
steam drum level switch which also initiates heater trip as described above. However, in this
situation, the ID fan damper is set to the full open position to provide maximum cooling of the
firebox and convection section coils. This switch will also protect against loss of steam drum water
due to other causes such as excessive blowdown. Heater shutdown upon detection of low steam
drum level is critical to avoid operating the transfer line exchangers (TLEs) without the cooling
resulting from steam generation. In the absence of cooling, rapid over temperature and damage
to the TLEs can occur. For this reason, significant surge volume is provided in the steam drums to
allow for upsets without complete water loss. If the TLEs are in danger of operating without boiler
feed water, recommended operating action is to stop dilution steam flow. This will discontinue
heat input and protect the TLEs from overheating, but may result in radiant coil damage.
Damaging the radiant coil is the preferred "lesser of two evils" in this situation.
Coil over temperature can also occur at normal process flow rates as a result of excessive burner
heat input. Excessive firing rate may result from firing control, system failure or an increase in the
fuel heating value. To minimize control system error due to faulty coil outlet temperature
measurement, each coil is provided with four upscale burnout thermocouples and a "smart
average" function in the control system will average the four readings, but ignore any reading that
is out of the range of the other three. Firing control is based on the "smart average". Possible
over-firing due to a relatively rapid fuel heating value increase is addressed by a density meter
which adjusts the firing rate via a feed forward action. Any significant high temperature deviation is
indicated by high temperature alarms located at the coil cross-overs, the radiant coil outlets, the
convection section just below the steam superheater coil, and the heater stack outlet.
Over temperature of piping downstream of the heater quench fittings may occur upon loss of
quench oil injection. To protect downstream piping from over temperature, an interlock is provided
to trip the heater upon detection of high temperature downstream of the quench fittings. For
reliability and to prevent spurious heater trips, three temperature sensors with upscale burnout are
provided in a two-out-of-three voting arrangement. To enhance quench oil reliability, the following
design features are incorporated:
 Multiple quench oil pumps will be provided.

 Motor-driven quench oil pumps are automatically started on low-low quench oil header
pressure.
 Quench oil temperature control valves fail open on loss of instrument air.
 The piping manifold downstream of the quench fittings is designed to accommodate loss
of quench oil to any single fitting on a short term basis.
The heater process coils (excluding boiler feed water preheat and steam superheat) and the TLE
tubes will be protected from over pressure by safety relief valves located downstream on the
overhead of the Quench Tower. Since the transfer line valve when closed can isolate the heater
coils and TLEs from their safety relief devices, a mechanical interlock is provided which ensures
that an open relief path via the decoking line is opened as the transfer line valve is closed. As the
transfer line valve is closed, the linked decoking valve is opened in a manner which maintains the
pressure balance avoiding possible backflow of cracked gas from the main transfer line into the
heater decoking line.

The transfer line valve not only provides a means to isolate individual heaters from the main
transfer line for decoking operations but also allows the heater to be isolated in the unlikely event
of a heater radiant coil rupture. In this situation cracked gas can backflow from the main transfer
line into the heater firebox prolonging the fire and increasing the extent of heater damage. To
minimize heater damage due to coil failure, the operator closes the transfer line valve concurrently
with a total heater shutdown, which also isolates hydrocarbon feed and quench oil.
Interlocks will be provided to ensure proper positioning of various heater valves during the
transition between normal running and decoking, and vice versa.
Incorrect valve line-up can result in cracked gas or quench oil being admitted to the heater firebox
through the decoking line, resulting in a heater fire. The basic interlock function is as follows:
 Before the transfer line valve can begin to close, the hydrocarbon feed isolation valve(s)
and the quench oil isolation valve must be proved closed.
 The main decoking valve cannot be opened until the transfer line valve is proved closed.
 The hydrocarbon feed isolation valve(s) and the quench oil isolation valve cannot be
reopened until the transfer line valve proves
 The transfer line valve cannot be reopened until the main decoking valve and the
decoking air isolation valve are proved closed.
To also avoid the admission of plant air into the cracked gas, the above interlock requires the
decoking air isolation valve to prove closed before the transfer line valve can be opened. To
provide additional security against air entry, the plant air is normally isolated from the heater by
swing elbows and hose disconnection.
The heater steam drum, the boiler feed water preheat coil, and the steam superheat coil may be
over pressured if the steam outlet flow path is blocked. To protect against over pressure safety
relief valves are provided on the steam drum and at the outlet of the steam superheat coil
following ASME Code Section I rules. The set pressures of the safety relief valves are staggered
so that relief first occurs at the outlet of the steam superheater coil providing sufficient steam flow
through the coil to avoid excessive coil temperature.
To take advantage of the very high temperature of the cracked gas leaving a heater’s coils, steam
is raised in its steam drum at a design pressure of 1580 PSIG. It is subsequently super-heated to
950 F in the convection section. The recovery of this high-temperature waste heat is
economically important; it provides the motive force needed to run the site’s three largest
compressors, and other large equipment. However, loss of containment of this super-high
pressure (SHP) steam is a significant potential hazard. To control the hazard, SHP steam
equipment is built to Section I of the ASME Code or other relevant standards; SHP piping is built
to a specially-developed specification. In addition, written operating procedures and a Mechanical
Integrity (MI) program are followed to maintain containment. Despite these measures, the SHP
steam meter at the Charge Gas Compressor failed on July 12, 2009. The root causes were poor
design (a weld between dissimilar metals exposed to extreme temperature and pressure) and
poor weld quality. In response to this incident, the site is carrying out an action plan to identify and
correct any additional deficiencies in the system. See AIM report 0126-CLD-09-0102 and
associated documents for further details.
On the heater firebox side the greatest potential hazard is deflagration resulting from faulty burner
light-off, burner flame-out or a large disturbance in the fuel-air ratio during normal operation. The
risk is greatest during burner light-off. It is at this point that fuel gas leakage into the firebox
and/or insufficient air purging are most likely to produce a flammable mixture in the firebox. The
following safeguards and operating precautions manage this risk:
 Prior to light-off fuel gas is isolated via redundant isolation/block valves.

 Adequate firebox purging is accomplished by operating the induced draft (ID) fan with the
stack damper open for a prescribed period of time.
 Loss of hearth burner pilots during light-off (i.e., heater in decoke / standby mode) results
in heater trip with isolation of fuel gas.
 During a heater trip both the fuel firing valve and isolation valve are closed to provide
redundant fuel isolation. The ID fan is always maintained on-line to provide air purge of
the firebox.
These control measures are enforced either by written procedures or by DCS permissive
interlocks that prevent light-off from proceeding until safe conditions for the next step have been
proved.
It is critical to the safe operation of the heater that positive heater firebox pressure be avoided.
The heater’s draft pressure controller maintains heater draft by manipulating the stack damper.
During normal operation of the heater the response of the draft pressure controller is adequate to
prevent positive heater box pressure.
However, during rapid increases in combustion air flow, the normal tuning response may be
inadequate; therefore, the heater draft pressure controller will be equipped with output feed
forward compensation to rapidly open the ID damper when the draft pressure approaches unsafe
limits. Local alarm horns will be provided to advise operators of unsafe conditions in the firebox.
Medium-pressure steam distributors are installed in trenches along the north and west sides of
the heaters’ structure. This steam curtain installation is intended to blow steam vertically upward,
creating an updraft to divert a combustible gas cloud away from the heaters, where it might be
ignited. An operator manually actuates each section of the steam curtain with a pushbutton on
the fire and gas panel in the control room. The pushbuttons also actuate warning lights and horns
in the field to warn personnel to clear the steam curtain area. Additional steam curtain distributors
extend along the north side of the Cogen area.
2.1.3 Gas Fractionation
This section is characterized by moderate operating temperatures and low operating pressure.
The major process hazard is a potential liquid pool fire due to a spill of quench oil (QO). The large
inventory of quench oil contained in the bottom of the Gasoline Fractionator could support a major
pool fire in the event of a spill.
The most likely mechanical failure that could result in a quench oil spill is failure of a shaft seal at
one of the Quench Oil Circulation Pumps. To mitigate such a failure, the pump suction valves will
be provided with motor operators which can be started or stopped from a remote location
permitting isolation of the quench oil inventory from the point of leakage. Remote isolation is not
provided on the suction side of the Pyrolysis Fuel Oil (PFO) Product Pumps due to the relatively
small liquid inventory in the Pyrolysis Fuel Oil Stripper.
Over pressure protection for the Gasoline Fractionator, Pyrolysis Gas Oil (PGO) Stripper, and
Pyrolysis Fuel Oil Stripper is provided by relief valves located on the overhead line of the
downstream Quench Water Tower.
Water can condense in the upper section of the Gasoline Fractionator if its overhead temperature
is allowed to drop below the water dew point. In principle, liquid water can collect on trays and
then pour downward, causing a water-hot oil explosion. Persistent accumulations of water in the
upper section can lead to corrosion. The most likely cause of low overhead temperature is
excessive reflux. A DCS alarm on the overhead temperature sensor alerts the operator to reduce
the reflux rate.

2.1.4 Quench Tower/ Quench Water Settler
The Quench Tower operates at low temperature and very low positive pressure. The major
process hazard is a liquid pool fire resulting from a spill of pyrolysis gasoline. The large inventory
of gasoline in the Quench Water Settler could support a major pool fire in the event of a loss of
containment accident.
The most likely mechanical failure that could result in a gasoline spill is failure of a shaft seal at
one of the Gasoline Fractionator Reflux Pumps. The suction block valves of these pumps are
provided with motor operators to permit remote isolation of a seal failure.
Over pressure protection of the Quench Tower is provided by safety relief valves located on the
overhead line. Major relief scenarios considered in the sizing of these safety relief valves include
trip of the Charge Gas Compressor, loss of cooling water to the Quench Water Coolers, and loss
of quench water circulation. To minimize the likelihood of loss of quench water circulation, the
motor driven pumps are automatically started on low-low quench water header pressure. Loss of
flow to the Quench Tower while the Charge Gas System is still operating can result in vacuum
conditions below the design limit of the Quench Tower. An SIS Interlock provides underpressure
protection if these conditions are met.
Quench water is circulated through a network of process heat exchangers to recover quench
heat. It is then further cooled with cooling water before being returned to the Quench Tower.
Relief valves are not provided on the quench water side of these heat exchangers. Over pressure
protection of the quench water side is provided by the relief valves on the overhead line of the
Quench Tower. To ensure an unobstructed relief path from the various quench water exchangers
to the Quench Tower, block valves are eliminated where possible or a hole is drilled in the valve
disks. During detailed engineering it shall be verified that the quench water flow path can provide
adequate over pressure protection for any credible relief scenario, including but not limited to
external fire exposure and tube rupture.
2.1.5 Process Water Stripper and Dilution Steam Generator
The extent of hazards in the process water stripping area is low due to the mild operating
conditions and the absence of flammable materials. Although there are failure modes that can
cause over pressure of the Process Water Stripper, relief valves have not been provided for this
vessel. Instead, over pressure protection is provided by the safety relief valves on the Quench
Tower overhead. The overhead of the Process Water Stripper flows directly to the Quench Tower.
Dilution steam is generated by heat recovery from circulating quench oil. Over pressure protection
via safety relief valves is provided for the dilution steam side of the Quench Oil/Dilution Steam
Reboilers. Safety relief devices are not provided for the quench oil side. However, adequate over
pressure protection is provided by designing the quench oil side for the shutoff pressure of the
Quench Oil Circulation Pumps. Over pressure cannot result from tube rupture since the operating
pressure on the dilution steam side is below the quench oil side's design pressure. Fire exposure
can theoretically result in over pressure but the temperature required to generate a vapor
pressure exceeding the design pressure would result in failure of the exchanger due to over
temperature. Therefore, the provision of a safety relief valve to relieve vapor provides no
additional protection. However, if the quench oil side is blocked in during a fire, liquid thermal
expansion could cause over pressure before severe temperature failure occurs. To avoid this
occurrence, the outlet block valve on the quench oil side of each exchanger is locked open to
reduce the likelihood of the exchanger being blocked in. Lummus operating instructions require
that these exchangers be de-inventoried when blocked in on the oil side.

2.2 Cold Section
2.2.1 General Cold Section Hazards
The basic nature of operating this area of the facility includes hazards associated with cryogenic
temperatures as well as hydrocarbon flammability. Additional hazards include equipment hazards
i.e. Charge Gas Compressors and exothermic reactions.
2.2.1.1 Low Temperature Embrittlement
Conventional carbon steel maintains its ductility down to about -20 F. Below this temperature, it is
vulnerable to brittle fracture. Various sections of the Cold Section operate at temperatures from
-20 F down to -265 F; they require special materials of construction. For temperatures down to
about -50 F, impact-tested carbon steel is adequate; below this, stainless steel is necessary.
Piping made of conventional steel that operates at normal temperatures, but connects to a low-
temperature system, may be cooled below its minimum allowable temperature (MAT) by a
process upset. The consequences could include loss of containment due to brittle fracture. Such
piping is protected from this hazard by a safety instrumented system (SIS) that shuts off flow into
the line when low-low inlet temperature is detected. A two-of-three voting arrangement is used to
reduce spurious trips.
In general, equipment in Port Arthur is constructed of materials selected for normal operating
temperatures, but not for complete depressurization in the presence of refrigerant liquids such as
C1-C5 hydrocarbons. Therefore, such equipment can be cooled below the MAT when emptied of
or filled with these liquids. Special procedures are followed to prevent temperature excursions
during these transfer operations. The basic strategy is to prevent the refrigerant liquid from
vaporizing at pressures that will produce low temperatures. Refer to site procedures and Ethylene
Producers’ Conference papers for additional information.
2.2.1.2 Mercury Embrittlement
If feedstocks contain trace quantities of mercury, there is a potential for mercury embrittlement of
aluminum alloy piping and equipment. (Several exchangers in the C2 and C3 distillation areas
have aluminum cores, but most such equipment is found in the Charge Gas Chilling Train.) Port
Arthur uses a layer of silver-impregnated molecular sieve in the Charge Gas Dryers to prevent
mercury from entering the Chilling Train.
The site also enforces a mercury specification on liquid cracker feeds, and routinely samples the
cracker’s feed streams for mercury. However, the feed spec and sampling are done to control air
emissions, not for mechanical integrity. Mercury is stripped into the fuel gas used to regenerate
the Charge Gas Dryers, and winds up in flue gas.
Lummus originally recommended a silver guard bed in the Condensate Dryers, but BLFP has
found this not to be necessary.
2.2.1.3 Moisture
Temperatures at various points in the cold section are so low that even small amounts of water
could cause equipment to plug with water ice or hydrates. (Hydrates are solids, formed by the
association of water and light hydrocarbons at low temperature and elevated pressure.) To
prevent such plugging, beds of molecular sieve are used to dry cold section feeds to ppm levels of
water. On-line analyzers monitor the water content of these beds’ outlet streams. Water ice and
hydrates are not a major process hazard, but in principle they could block flow, leading to a
process upset and a release to the BTP flare system.

2.2.2 Charge Gas Compressor
Operating conditions in this section are generally moderate, with the fifth stage discharge
pressure approaching 585 PSIG. The major hazard is the leakage of the charge gas (cracked
gas). Protection of the compressor from mechanical damage is also a major concern. Benzene
is present at concentrations which require attention for personnel protection.
Leakage of cracked gas at the seals of the Charge Gas Compressor could result in a flammable
vapor cloud or a gas jet fire. Remotely operated isolation valves are provided at the suction of the
first stage and at the discharge of the fifth stage to allow rapid block-in of the compressor should a
major seal leak occur. To facilitate rapid isolation a seal leak gas detection system is provided.
Protection of the compressor from mechanical damage is of paramount importance. The greatest
hazard is perhaps carryover of liquid from the liquid disengaging drums into the compressor
suction. To provide protection, all suction drums are provided with high-high level trips which
initiate compressor shutdown. To ensure a high degree of reliability, each suction drum utilizes
three transmitters with two-out-of-three voting. To provide protection from loss of inter-stage
cooling, compressor trip is also initiated upon detection of high-high temperature at the discharge
of each compressor stage. Three upscale burnout thermocouples with two-out-of-three voting are
provided to ensure reliability and prevent spurious trips. The compressor is also provided with
additional protective instrumentation per normal vendor practice for a large, multistage centrifugal
compressor steam turbine driver. Such instrumentation typically includes minimum flow
bypass/anti-surge controls, and machine shutdown on over speed, excessive vibration, shaft
excessive axial displacement, and loss of seal or lube oil.
2.2.3 Acid Gas Removal
The Acid Gas Removal and Spent Caustic Pretreatment systems operate at mild temperatures
and low pressure. Inventories of liquid hydrocarbons are small and the resulting hazard of a liquid
pool fire is very low. Leakage of cracked gas can result in a flammable vapor cloud or gas jet fire.
There are no unusual process hazards in this section. Hydrogen sulfide is a significant personnel
hazard in this area; it is controlled by the safeguards discussed in Section 1.2.2 of this report.
2.2.4 Spent Caustic Oxidation
The spent caustic produced in the Acid Gas Removal section is an aqueous solution containing
NaOH, Na2CO3, NaHS, NaSR, and traces of hydrocarbons. To prepare the spent caustic for bio-
treating, the Spent Caustic Oxidation (SCO) Unit converts the sulfides, which are toxic to biomass,
to sulfates. The oxidation is an uncatalyzed reaction carried out at design conditions of 400 PSIG
and 395 F. It is exothermic, and at normal feed concentrations, produces a modest temperature
rise. A reciprocating compressor is used to supply atmospheric air to the reaction. Two special
hazards are mentioned in the vendor’s operating manual: loss of liquid flow, and reaction
chemistry. Both might lead to loss of containment. If the air compressor continues to run after
liquid flow has stopped, local dry spots may result. Organic material in such a dry spot may burn,
and in an extreme case produce enough heat to damage equipment. An interlock is provided to
shut the compressor down on loss of liquid feed. The spent caustic feed is alkaline, but the
oxidation lowers its pH. At reactor conditions, an acid solution would corrode carbon steel. This
corrosion hazard is controlled by utilizing Inconal Alloy cladding.
The vent gas from the SCO reactor normally contains oxygen, which might create a combustible
mixture in BTP’s wet flare header. This hazard is eliminated by directing the off-gas to the
Thermal Oxidizer through a dedicated header. The header is protected from back-flashing by a
pair of detonation arrestors fitted with high-temperature alarms.

The SCO unit normally contains an insignificant amount of hydrocarbons. A loss of containment
in this area is very unlikely to create a fire hazard.
2.2.5 Dryer Feed Drum, Condensate Stripping and Drying (Cold Box)
The Dryer Feed Drum operates at low temperature and moderately high pressure (ca. 545 PSIG).
The vessel contains a relatively small inventory of light hydrocarbons. The concentration of
benzene in the bottoms stream from the Condensate Stripper is fairly high; this potential hazard is
controlled as discussed in Sect. 1.2.1. The bottoms stream from the Condensate Stripper is dried
to prevent water from reaching the C3 system, where it would freeze or produce hydrates.
2.2.6 Charge Gas Dryers
The Charge Gas Dryers operate at moderately high pressure (ca. 545 PSIG) but at essentially
ambient temperature. During regeneration elevated temperatures are experienced but at low
pressure. The major hazards involved in this area are possible over pressure of the regeneration
system due to incorrect valve positioning and over temperature of the gas-filled dryers during a
fire.
The periodic regeneration of the dryers is carried out automatically by a triple modular redundant
programmable logic controller (TMR/PLC). If the regeneration path is opened to a dryer before
the dryer has been depressured, the regeneration system may be exposed to a pressure almost
five times its design pressure. Ordinarily this type of failure scenario would be addressed by
providing relief valves or the like on the low pressure system. However, due to the extremely high
pressure difference (ca. 425 PSIG) and the low flow resistance of the regeneration system, the
required relief rate is so high that this approach is impractical.
To protect the regeneration system from over pressure, a highly reliable interlock system
independent from the control is provided. This interlock system monitors the position of valves in
charge gas, regeneration and depressuring service, and dryer pressure. The regeneration system
cannot be opened to a dryer until the charge gas inlet and outlet valves are proved closed, and
the dryer pressure is proved to be below the design pressure of the regeneration system. To
ensure suitable reliability the interlock system instrumentation is based on triple modular
redundant architecture. Valves and process sensors are duplicated as necessary.
The dryers are gas-filled and fire exposure can result in rapid over-temperature of the vessel wall.
To protect against possible vessel failure, the dryers can be depressured via the normal
regeneration depressuring path. Reducing pressure lessens the possibility of dryer failure and
reduces the consequences of failure should rupture occur. Depressuring capacity allows the
normal operating pressure of 545 PSIG to be reduced to 100 PSIG in about 15 minutes.
2.2.7 Charge Gas Chilling Train
The Charge Gas Chilling Train is a cryogenic auto-refrigeration process that uses the Joule-
Thompson effect to condense the methane and heavier components out of the charge gas. The
chilling is done in a series of steps; its net effect is to separate hydrogen, methane, and several
liquid streams. The liquids are processed further to recover pure products. Due to the extremely
low temperatures it generates, the Chilling Train is contained in a heavily-insulated enclosure
known as a cold box. Operating pressures are moderately high (400-500 PSIG) and
temperatures are in the cryogenic range, as low as -285 F. These cryogenic temperatures require
special materials of construction for piping and vessels; stainless steel for the very lowest, impact-
tested carbon steel for the less extreme. Heat exchangers in the cold box are built from
aluminum plate; this design provides low-temperature strength and tolerates thermal cycling.
Process upsets can result in low temperature deviations in piping leaving the cold box. To control
costs, not all of this downstream piping is rated for cryogenic temperatures. SIS’s are provided to

protect the vulnerable piping from being cooled below its minimum allowable temperature and
possibly failing due to low-temperature embrittlement. For enhanced reliability, three downscale
burnout temperature sensors are provided at each sensing point with two-out-of-three voting to
prevent spurious trips. This practice is followed throughout the cold section where an upset may
embrittle materials not designed for cryogenic service.
It is difficult to completely remove nitric oxide (NO) and oxygen from the charge gas. Traces of
these compounds react under chilling train conditions to produce nitrogen trioxide (N2O3), which
can condense or solidify in the coldest sections of the chilling train. N2O3 further reacts with
unsaturated hydrocarbons, especially diolefins such as butadiene. The NOx gums thus formed
are not entirely stable even at normal chilling train operating conditions, and are likely to
decompose violently if the system’s temperature rises or its pressure drops. In normal operation,
the chilling train condenses and separates olefins from the charge gas before significant amounts
of nitrogen trioxide are formed, minimizing the potential for forming NOx gums. Olefins are more
likely to reach the areas where N2O3 collects during warm-up, shut-down, or upset. Operating
procedures are written to control these risks.
N2O3 can also react with ammonia under chilling train conditions to form ammonium nitrate and
nitrite. These solids may collect in the same areas as the NOx gums, or in the warmer sections of
the chilling train where condensed liquids are flowing to the Demethanizer Tower. The ammonium
salts are more stable than the NOx gums, but may detonate at room temperature or higher.
Accumulations of NOx gums or ammonium salts may be revealed by sampling; larger deposits
may cause a noticeable rise in pressure drop. The deposits are removed by washing the affected
equipment with alcohol.
BTP’s chilling train was damaged by a NOx gum detonation during an unplanned shut-down in
March 2008. Improved procedures have been implemented to prevent both the accumulation and
explosive decomposition of NOx compounds. These include weekly sampling for NO in the
chilling train feed, and blowing down the low points in the coldest section of the train once a
month. The new procedures also call for more thorough and more frequent alcohol washing.
(See AIM Report 0126-CLD-08-0059 and associated documents for details.)
Lummus’s original NROC Supervisory Operating Manual includes a warning that it is possible, in
principle, for acetylene to freeze out in the coldest parts of the chilling train. An accumulation of
frozen acetylene would be a hazard; it is very unstable and shock sensitive. The manual suggests
some instrument indications of frozen acetylene, and countermeasures to dissipate it harmlessly.
But Lummus qualifies this warning with the statement that it “has never known this phenomenon
to have occurred in the many plants operating at conditions nearly identical to those anticipated in
this design.” See Section 5 of the manual (NROCOPS5.doc) for details. Frozen acetylene does
not seem to be a credible hazard, and Port Arthur currently does not maintain any specific
safeguards against it.
2.2.8 Methanator and Hydrogen Dryer
The Chilling Train’s hydrogen product normally contains on the order of 0.5 mol % carbon
monoxide. Operating at design conditions of ca. 430 PSIG and up to 615 F, the Methanator
converts this catalyst poison to methane to protect downstream reactors. With normal feed
composition, there is a modest temperature rise across the reactor. However, the desired
reaction and potential side reactions are strongly exothermic on a molar basis. Compared to
other sections of the cracker, the system’s volume and inventory of flammable gas are not
especially large.
The principal process hazard is a runaway reaction in the Methanator, which is most likely to be
caused by high carbon monoxide or ethylene concentrations in the feed. The safeguard is a SIS
that blocks in the reactor on high-high outlet or bed temperature. The SIS also blocks the reactor

on high-high inlet temperature to D-3005X, as this implies excessive ethylene in the Methanator
feed. It also shuts off Methanator feed on low-low temperature in the high pressure methane
outlet from the cold box. The reactor block valves can also be closed remotely to limit the size of
the flammable gas cloud that would result from a loss of containment in this area.
At elevated temperature and pressure, hydrogen can infiltrate into steel, eventually causing it to
crack. The phenomenon, known as high-temperature hydrogen attack (HTHA), is prevented by
using suitable alloy steels and by stress relieving the equipment. In Port Arthur, the Methanator,
the Second Stage Hydrogenation Reactor in Pygas, and InAlk’s Hydrotreating Reactor operate at
the most extreme conditions with respect to HTHA. The Pygas reactor is made of 321 stainless;
equipment in the other two areas is typically made of SA387 alloy steel. The site’s other
hydrogen-service equipment operates at milder conditions, for which carbon steel is adequate.
Guidelines for selecting materials of construction for hydrogen service appear in API
Recommended Practice RP-941. ABB Lummus Global issued its Technical Safety Bulletin ALR-
ETH-002 in February 2004 to report hydrogen-induced cracking in two SS reactor heads at an
ethylene plant in Singapore. Charlie Smith, Port Arthur TES, followed up on this report and
concluded that none of the Site’s hydrogen-service equipment was at risk.
2.2.9 Demethanizer
The Demethanizer operates at relatively low pressure and at cryogenic temperatures. Given the
Demethanizer’s large hydrocarbon inventory, its most significant hazard is the potential for a large
flammable vapor cloud due to loss of containment. The Demethanizer Bottoms Pumps are
provided with remote isolation on the suction side to limit the amount of material released by a
seal failure.
Seal failure at the Methane Refrigerant Compressor can also result in a flammable vapor cloud.
This hazard is mitigated by remote isolation valves on the suction and discharge which allow rapid
block-in of the compressor. To facilitate rapid isolation, a seal leak gas detection system is
provided. Additional instrumentation protects the compressor from mechanical damage.
Compressor trip is initiated on high-high temperature at the discharge of each compressor stage.
Three upscale burnout thermocouples with two-out-of-three voting are provided to ensure
reliability and prevent spurious trips. The compressor is also provided with other protection per
normal vendor practice. Such instrumentation typically includes minimum flow bypass/anti-surge
controls and interlocks that shut the machine down on high shaft speed, excessive vibration,
excessive shaft displacement, and loss of seal or lube oil.
Like the Charge Gas Chilling Train, the Demethanizer operates at cryogenic temperatures.
Stainless steel and impact-tested carbon steel are used to prevent brittle fracture at these low
operating temperatures. Where connected equipment operates at normal temperatures but could
be chilled below its MAT by a Demethanizer upset, it is protected by an SIS that closes an
isolation valve on low-low process temperature.
2.2.10 Deethanizer and Acetylene Converter
The Deethanizer operates at moderately elevated pressure (ca. 315 PSIG) and mild
temperatures. The largest hazard in the Deethanizer system is a flammable vapor cloud due to a
leak from the large volatile liquid inventory. To address this hazard the Deethanizer Reflux Pumps
are provided with suction side remote isolation to protect against a major seal failure. The
Deethanizer is also protected by a SIS that stops the flow of heating media to its reboilers and
isolates the tower on high-high overhead pressure.
The Acetylene Converters operate at ca. 285 PSIG and low temperatures. The acetylene
conversion reaction takes place in the vapor phase, and the converter inventory is therefore very
low. The greatest hazard in operation of the Acetylene Converters is an uncontrolled exothermic
reaction. This is typically caused by an excessive hydrogen to ethylene feed ratio which results in

hydrogenation of the ethylene. This exothermic reaction leads to localized over temperature or
"hot spots" in the catalyst bed. If left uncontrolled, localized over temperature can initiate ethylene
polymerization and possibly decomposition. These reactions are also exothermic, and the
additional heat release can cause severe over temperature which can threaten the physical
integrity of the converters.
To protect against such temperature excursions, each catalyst bed is provided with an array of
nine duplex thermocouples distributed in the bed and triple thermocouples in the effluent stream.
Thermocouples are upscale burn-out type, and provide high temperature alarming and automatic
shutdown on high-high temperature.
Upon detection of high temperature, operators can take corrective actions to avoid uncontrolled
reaction. Actions include adjustment of hydrogen flow rate and converter feed temperature. If
operating personnel fail to respond, the interlock system will automatically shut down the system
by:
 Isolating the hydrogen feed.

 Isolating the ethylene feed,
 Blocking the converter effluent line, and
 Depressuring the converters to the flare.
This isolation and depressuring strategy will prevent converter failure due to severe over-heating
of the vessel wall. To avoid spurious trips, shutdown is activated based on two-out-of-three voting
of the duplex thermocouples.
Uncontrolled exothermic reaction can also result from faulty start-up. It is possible to initiate
ethylene decomposition by introducing ethylene feed into a converter filled with hydrogen or a
converter containing a hot spot. This hazard must be controlled by strict adherence to operating
procedures which require thorough purging of the converter before the introduction of ethylene
feed. It is also recommended that, after a shutdown initiated by a high temperature trip, the
deethanizer overhead be switched to the standby (cold) converter to ensure hot spots will not be
present. High temperatures which may be conducive to ethylene polymerization/decomposition
can also result from reintroducing ethylene feed into a converter which hasn't been cooled after
regeneration. Also rapid repressurization with ethylene of a nitrogen-filled converter may produce
high temperature by compression. These hazards need to be controlled by strict adherence to
prescribed start-up procedures.
Another hazard involving converter operation is possible over pressure of the low design pressure
regeneration system. During normal converter operation, the regeneration system is protected
from the converter high operating pressure by secure isolation using blinds. Before the
regeneration system can be safety commissioned to regenerate a converter, the converter must
be depressured and isolated (blinded) from the high pressure ethylene feed and hydrogen
systems. Strict adherence to isolation/blinding procedures is necessary to avoid severe over
pressure of the regeneration system.
During regeneration the catalyst is steam stripped to remove adsorbed hydrocarbons. The
stripped hydrocarbons and steam are routed to the Quench Tower for recovery. Subsequently,
plant air is introduced to steam-air decoke the catalyst. Before this is done, the regeneration off-
gas is diverted from the Quench Tower to atmosphere. The regeneration system is used to
distribute steam, methane, hydrogen, and air to various vessels, and send the regen offgas to
several different destinations. Given this service, it is a likely location for creating a combustible
mixture. This hazard is controlled by using removable piping spool pieces in the regeneration
manifold and the regen offgas line. The spool pieces, when used as directed by written

regeneration procedures, provide positive isolation to prevent the creation of a combustible

mixture.
2.2.11 Ethylene Dryers and Ethylene Fractionator
The Ethylene Dryers operate at about 255 PSIG and -15°F. Ethylene is dried in the vapor phase,
so the inventory of hydrocarbons is very small. The greatest hazard in dryer operation is possible
ethylene polymerization/decomposition due to high temperature. High temperature can be
experienced due to the reintroduction of ethylene into a dryer which hasn't been sufficiently cooled
after regeneration. Also rapid re-pressurization with ethylene of a nitrogen-filled dryer may
produce high temperature by compression. These hazards are controlled by strict compliance with
appropriate start-up procedures.
The Ethylene Dryers depend on the same low-pressure regeneration system as the Acetylene
Converters, etc. To avoid over-pressure of the regeneration system during normal dryer
operation, secure isolation is achieved using blinds. Before the regeneration system can be safety
commissioned to regenerate a dryer, the dryer must be depressured and isolated (blinded from
the high pressure ethylene). Strict adherence to isolation/blinding procedure is necessary to avoid
severe over pressure of the regeneration system.
The Ethylene Fractionator operates at about 215 PSIG with an overhead temperature of -32 °F.
The largest hazard in the Ethylene Fractionator system is a flammable vapor cloud due to a leak
from the large volatile liquid inventory. To address this hazard, the Ethylene Fractionator Reflux
Pumps are provided with suction side remote isolation to protect against a major seal failure.
2.2.12 Depropanizer, MAPD Converter, and C3 Fractionator
The Depropanizer Tower is a conventional distillation tower that separates the deethanizer
bottoms stream into a C3 overhead and a C4+ bottoms stream. It operates at design bottoms
conditions of 78 PSIG and 161 F. The principal process hazard is loss of containment, which
could produce a large flammable vapor cloud. The tower contains a large inventory of C4s in its
sump and a significant amount of liquid C3s in its distillate drum. To limit the size of a potential
release, remotely-operated isolation valves are provided in the tower’s bottoms line and in the
suction line of its distillate pump.
The Depropanizer’s overhead stream is pumped to the MAPD Converter, which selectively
hydrogenates the methylacetylene (MA) and propadiene (PD) to propylene at up to 376 PSIG and
127 F. It is a liquid-phase down-flow reactor with a large liquid recycle, which serves to control the
reaction. The principal process hazard is a runaway reaction, which can be initiated by a number
of abnormal conditions. The control is a SIS that shuts down the flow of both fresh liquid feed and
hydrogen to the reactor on high bed or outlet temperature. Loss of containment is another
significant process hazard. The reactor system’s liquefied gas inventory is large; a leak could
produce a large flammable vapor cloud. To limit the size of a release from a seal failure, the
reactor’s recycle pump is provided with a remotely-operated suction isolation valve.
The Hydrogen Stripper Tower removes hydrogen gas dissolved in the MAPD Converter’s product
stream. It presents no unusual process hazards.
Degassed bottoms from the Hydrogen Stripper Tower are fed to the Propylene Fractionator, which
separates propylene from propane at design overhead conditions of 55 PSIG and 21 F. The
Fractionator is integrated with the Propylene Refrigeration Compressor in an open-loop heat-
pump arrangement. The largest hazard in the Propylene Fractionator system is a flammable
vapor cloud due to a leak from the large liquefied gas inventory. To address this hazard, the
tower’s bottoms pumps are provided with suction side remote isolation to protect against a major
seal failure.

A small fraction of the MAPD present in the MAPD Converter feed is left un-reacted and passes
downstream. Under certain circumstances, it is possible for these compounds to accumulate in
the Propylene Fractionator. At high concentrations, they are dangerously unstable. The tower’s
temperature profile will not reveal such an accumulation. Instead, on-line analyzers monitor the
concentration of MAPD above tray 167, and in the tower’s overhead and bottoms streams.
2.2.13 Debutanizer and C4 Hydrogenation
The Debutanizer Tower recovers C4s overhead and sends a C5+ stream bottoms to the
Aromatics Recovery Unit (commonly called the Pygas plant). It is a conventional distillation tower
operating at design bottoms conditions of 61 PSIG and 214 F. The principal process hazard is
loss of containment, which could lead to either a pool fire or flammable vapor cloud. Since the
Debutanizer Tower contains a large hydrocarbon inventory, remotely-operated isolation valves are
provided in both its bottoms line and the suction line of its distillate pump.
Normally, the Debutanizer’s overhead stream is sent to C4 Processing Unit to recover the
butadiene and upgrade the butenes to salable products. If this outlet is not available, the
overhead is recycled to the cracking furnaces by way of the C4 Hydrogenation Reactor. This
reactor selectively hydrogenates butadiene to butene, to prevent excessive coking in the furnace
tubes. It is a trickling bed reactor with a large liquid recycle stream, operating at up to 320 PSIG
and 219 F. The principal process hazard is a runaway reaction. This is controlled by a SIS that
stops the flow of both fresh C4 feed and hydrogen to the reactor on excessively high bed or outlet
temperature. The bottom of the reactor contains a significant liquid hydrocarbon inventory. A
remotely-operated isolation valve is provided to limit the size of the spill in the event of a seal
failure at the recycle pump.
2.2.14 Ethylene and Propylene Refrigeration
The ethylene refrigeration system operates at pressures from near ambient to ca. 400 PSIG with
temperatures ranging from above ambient to as low as -150 F. The refrigeration system contains
a large inventory of liquid ethylene. The greatest hazard is a flammable vapor cloud due to a
major leak of vapor or flashing liquid. To minimize this hazard due to failure of Ethylene
Refrigerant Compressor seals, remote isolation valves are provided at the three suction inlets and
at the compressor discharge. To facilitate rapid isolation, multiple combustible gas monitors are
provided in the area to detect seal leaks.
To protect the compressor from mechanical damage due to liquid carryover, the suction drums
are provided with high-high level switches which initiate compressor shutdown. To ensure a high
degree of reliability and avoid spurious trips, each suction drum utilizes three switches with two-
out-of-three voting. To provide protection from excessive discharge temperature, a compressor
trip is also initiated upon detection of high-high temperature at the compressor discharge. Three
upscale burn-out thermocouples with two-out-of-three voting are provided. The compressor and
steam turbine driver are also provided with additional protective instrumentation against
mechanical damage. This includes minimum flow bypass/anti-surge controls, and machine
shutdown on over-speed, excessive vibration, excessive axial shaft displacement, seal trouble, or
loss of lube oil.
The propylene refrigeration system operates at pressures from near ambient to ca. 265 PSIG with
temperatures ranging from above ambient to as low as -40 F. The refrigeration system contains a
large inventory of liquid propylene. The greatest hazard is a flammable vapor cloud due to a major
leak of vapor or flashing liquid. To minimize this hazard due to failure of the Propylene Refrigerant
Compressor seals, remote isolation valves are provided at the three suction inlets and the two
discharge outlets. To facilitate rapid isolation, multiple combustible gas monitors are provided in
the area to detect seal leaks.

The Propylene Refrigerant Compressor is protected against abnormal process conditions by shut-
down trips similar to those on the ethylene machine. It is further protected from mechanical
damage by minimum flow bypass/anti-surge controls, and shutdowns on over-speed, excessive
vibration, excessive axial shaft displacement, seal trouble, or loss of lube oil.
Parts of both refrigeration systems operate at low temperatures. Equipment in these areas is built
of impact-tested carbon steel or stainless steel, as necessary, to prevent brittle failure. See
Section 2.2.1.1 for additional discussion of cold service hazards and safeguards.
2.3 Aromatics Recovery Plant (Pygas)
2.3.1 General
The common hazard in the Aromatics Recovery Plant (Pygas) is the presence of a known human
carcinogen, benzene, in concentrations from ca. 20 to 100 wt %. This hazard is controlled by de-
sign practices and operating procedures that prevent personnel exposure to the process streams.
2.3.2 Hydrogenation Section
The pygas feed to the Aromatics Recovery Plant undergoes two hydrogenation steps to destroy
diolefins, olefins, sulfur compounds, and nitrogen compounds. The first stage hydrogenation
reactor is a liquid-phase, trickling-bed design. It selectively converts dienes and olefinic aromatics
at moderate conditions – up to ca. 360 PSIG and 260 F. The principal hazard is a runaway
reaction. Normally the extent of the reaction is controlled by maintaining a large liquid recycle
flow, which controls both the temperature and reactant concentration in the feed. Since hot spots
can lead to a runaway, temperatures are monitored at a total of thirty locations in the catalyst bed.
On sensing high-high temperature at two locations, a SIS stops flow of pygas feed and hydrogen
to the reactor, and the flow of steam to the feed heater. A pushbutton function associated with
this SIS allows the operator to depressure the reactor to the flare in the event of fire or an
uncontrollable leak.
The Depentanizer Tower removes a C5 fraction from the product of the first stage in order to
reduce the volume of feed handled by the downstream equipment. It is a conventional distillation
tower operating at design bottoms conditions of 78 PSIG and 336 F. It presents no unusual
process hazards.
The Second Stage Hydrogenation Reactor is a gas-phase, down-flow design. It completes the
conversion of olefins, sulfur compounds, and nitrogen compounds at conditions up to ca. 380
PSIG and ca. 670 F. The principal hazard is a runaway reaction, which is controlled by a SIS
essentially similar to that protecting the first stage reactor. The Second Stage Reactor operates at
relatively severe conditions with respect to high-temperature hydrogen attack (HTHA); to prevent
this type of damage, it is made of Type 321 stainless. See Section 2.2.8 of this report for
additional discussion.
The Second Stage Recycle Gas Compressor is a multi-stage centrifugal unit. Loss of
containment is the major hazard; a seal failure here could produce a flammable vapor cloud. This
hazard is mitigated by remote isolation valves on the suction and discharge which allow rapid
block-in of the machine. H2S and benzene monitors are provided in the area to provide prompt
indication of a leak. Additional instrumentation protects the compressor from mechanical damage.
Compressor trip is initiated on high-high level in the suction knock-drum, and on low-low
discharge flow. In addition, the compressor is provided with other protection per normal vendor
practice. This instrumentation includes minimum flow bypass/anti-surge controls and interlocks
that shut the machine down on high shaft speed, excessive vibration, excessive shaft
displacement, and loss of seal or lube oil.

The Stabilizer Tower removes dissolved H2S, NH3, and other light ends from the hydrogenated
pygas stream before it is fed to the aromatics recovery section proper. It is a conventional
distillation tower operating at design bottoms conditions of 75 PSIG and 335 F. Loss of
containment is the principal hazard.
High H2S concentrations (on the order of 1 wt%) in the Second Stage Hydrogenation recycle gas
and the Stabilizer Tower make loss of containment in this area a particularly serious personnel
hazard. H2S monitors are located at the most likely leak points. Warning lights are actuated in
the field when H2S is detected to warn personnel to evacuate.
2.3.3 Predistillation
The Predistillation Tower is a conventional distillation tower that separates the fully hydrogenated,
degassed pygas stream into a benzene fraction, a toluene fraction, and a C8+ gasoline fraction.
Its design bottoms conditions are 13 PSIG and 338 F; it contains a large volume of hydrocarbons.
The principal hazard is loss of containment. To limit the volume of a release due to a seal failure,
the tower’s bottoms, distillate, and side-stream pumps are all provided with remotely-operated
suction isolation valves.
2.3.4 Extractive Distillation
The Extractive Distillation section consists of the Extractive Distillation Tower and the Stripper
Tower. The unique feature of this section is the presence of N-formyl morpholine (NFM). This
solvent selectively lowers the boiling points of benzene and toluene, which allows them to be
separated by distillation from the C6-C8 non-aromatics with which they are mixed. NFM presents
no unusual physical or health hazards. It is chemically stable; while combustible, it is less a fire
hazard than the other compounds present in this section of the plant. Normal operating conditions
heat NFM above its flash point of 257F, but not above its normal boiling point of 470F. The NFPA
hazard codes for this chemical are Health – 1; Fire – 1; Reactivity – 0.
Ignoring the presence of the extraction solvent, the Extractive Distillation Tower is a conventional
distillation tower with a large hydrocarbon inventory. Its design bottoms conditions are 16 PSIG
and 350 F. The principal hazard is loss of containment. To limit the volume of a release due to a
seal failure, the tower’s bottoms and distillate pumps are provided with remotely-operated suction
isolation valves.
The Stripper Tower is a conventional vacuum distillation tower that recovers benzene and toluene
from the circulating NFM. Its hydrocarbon inventory is large. The principal hazards are pump
seal failures and vacuum leaks. The former could lead to a pool fire or vapor cloud; the latter to
an explosive gas mixture in the tower. The seal failures are mitigated by remotely-actuated
isolation valves on the suction side of the tower’s bottoms and distillate pumps. The hazard of air
ingress is mitigated by segregating the Stripper Tower’s vent gas stream. It flows to the Thermal
Oxidizer in a dedicated header, which is protected from back-flashing by a pair of detonation
arresters fitted with high-temperature alarms.
2.3.5 Benzene/Toluene Splitter Tower
The B/T Splitter Tower is a conventional distillation tower. Its design bottoms conditions are 10
PSIG and 266 F; it contains a significant volume of hydrocarbons. The principal hazard
associated with this tower is loss of containment. Since the tower is filled with high-purity benzene
and toluene, loss of containment here presents a particular IH concern in addition to the usual
risks of
a vapor cloud or pool fire. To limit the volume of a release due to a seal failure, both the bottoms
and distillate pumps at the B/T Splitter are provided with remotely-operated suction isolation
valves.

2.4 BTP Flare System

The BTP Flare System contains two subheaders, the Dry (Cold) Flare Header and the Wet Flare
Header. The Dry Flare Header is used to collect process fluids that may flash and auto-
refrigerate when let down to header pressure. The Wet Flare Header collects all process fluids
that may contain water. Separating these two fluid types prevents relief devices and the flare
headers from being plugged with ice. Each subheader has a knock-out drum at its downstream
end; flare gases flow from these drums through a common Main Flare Header to the Flare Knock-
out Drum and the Flare Water Seal Drum. The flare gas continues from the Seal Drum to one of
two flares. The Base Load Flare is designed to efficiently combust the small normal flare gas
stream. The much larger Ground Flare is used when upset conditions require high flaring rates,
or when the Base Load Flare is not available. The burners for both flares are at grade.
Since the burners of the Ground Flare are at grade, pilot failure may be the most significant
process hazard associated with BTP’s flare system. While such a failure is remotely unlikely, in
principle it could create a cloud of unburned flammables near grade. BTP’s design incorporates
many safeguards to make the flare pilots as reliable as possible. Pilot gas is supplied by two
independent natural gas pipelines; the pilot gas lines connect to their sources upstream of the
block valves that isolate all of BTP’s other natural gas users from these pipelines. The pilot gas
system at the Ground Flare has redundant let-down regulators and parallel distribution lines. Most
of the flare runners have multiple pilots. Where this is the case, the pilots are fed from different
pilot gas regulators. The pilots are automatically re-lit by a common flame-front generator when
their temperature sensors indicate loss of flame. Each pilot has dual temperature sensors; they
are retractable for on-line replacement. Pilot failures and igniter trouble will alarm in the DCS.
The Base Load Flare is also at grade, but its pilot system is not as reliable as the Ground Flare’s.
While the Base Load Flare is the normal disposition for flare gas, it is designed to use the Ground
Flare as a back-up. If pilot failure or low pilot gas pressure are detected at the Base Load Flare, a
SIS automatically diverts flare gas to the Ground Flare.
Another significant hazard associated with the flare system is the creation of a combustible gas
mixture in the flare header and its subsequent deflagration. Multiple safeguards have been
adopted to prevent this. A water seal drum protects BTP’s flare headers from back flashing
initiated at the Ground Flare or Base Load Flare. Continuous fuel gas purges are maintained on
all sections of the flare header to prevent infiltration of air into them from the flare burners.
Continuous nitrogen purges are maintained at the Ground Flare to prevent air infiltration into any
idle runners. Timed ‘de-staging’ purges with nitrogen are used to clear the Ground Flare’s
runners of combustible gas as they are idled. However, back-burning in Runner F may have
contributed to the extensive damage there in 2005. The cause of the damage was never
conclusively explained. See AIM report 0126-UTIL-05-0055. The Base Load Flare has a nitrogen
purge system similar to Ground Flare’s. It provides both continuous and de-staging purges. All
flare headers are normally run at positive pressure to prevent air being sucked into them from the
flare tips, or directly into the headers through leaks.
The BTP flare header is further protected from back flashing, and from vacuum, by a SIS
designed to dump large volumes of fuel gas and natural gas into the system on a low-low
pressure signal. Despite these precautions, back flashing precipitated by Hurricane Rita
apparently damaged D-8505X in September 2005. Loss of multiple utilities due to the storm
caused/contributed to this incident. See AIM report 0126-UTIL-05-0202.
The Main Flare Header’s pressure is actively controlled by a PLC that opens and shuts valves to
alter the number of flare burners in operation. It is extremely unlikely, but the possibility exists that
all these valves could fail shut, leaving no outlet for the flare gas. The safeguard is a set of
buckling pin relief valves in the flare gas distribution manifold at the Ground Flare. They bypass
the block valves in most of the Ground Flare’s runners, providing fail-safe paths by which flare gas

can reach the flare’s burners. Since the Base Load Flare is not a fail-safe disposition for flare
gas, its distribution manifold has no such relief valves.
The possibility of water ice forming in the flare system due to the flashing of liquefied gases is
mentioned above. Here is a more complete list of the safeguards installed to prevent this:
 Separate flare headers to collect ‘cold/dry’ and ‘wet’ streams.

 A vaporizer to drive low-temperature liquefied gases out of the Cold Flare Knock-out
Drum.
 A SIS that dumps the water in the Flare Water Seal Drum on low-low temperature, to
prevent its freezing.
The Dry Flare Header and Dry Flare Knock-out Drum are designed to handle cryogenic fluids
directly. The Main Flare Header also can be chilled to very low temperatures by a large Cold
Section flaring event. To prevent brittle fracture, the Dry Header and its drum are built entirely of
stainless steel. The Main Header is built of stainless for 950 ft. downstream of the Dry Header’s
connection to it, to prevent brittle failure and provide warming by the ambient air. The
downstream portion of the flare system (i.e., the Flare Knock-out Drum, Flare Water Seal Drum,
flares and connected piping) is either impact-tested or conventional carbon steel. The transition
from stainless to carbon steels is 50-100 ft. upstream of the Flare Knock-out Drum. The pipe wall
temperature there is monitored in the DCS, but there is no interlock to protect the carbon steel
equipment from being chilled below design temperature. Should this occur, the only remedy is to
stop flaring as soon as possible, and allow the equipment to return to normal temperature. Refer
to Section 2.2.1.1 for more discussion of low-temperature service.
The discharge of liquid from the burners is another hazard common to many types of flares. The
three liquid knock-out drums and the seal drum act as safeguards against such an event. Despite
these control measures, several burner tips on X-8501’s Row H discharged a combustible liquid
during an episode of heavy flaring in late August, 2006.

3.0 Process Specific Hazards – C4 Complex
3.1 Butadiene Extraction Unit (BEU)
3.1.1 General
Butadiene is useful because it is chemically reactive. Unfortunately, it also readily reacts to form
several dangerous or undesirable compounds -- butadiene peroxides, ‘popcorn’ polymer, and an
amorphous polymer usually referred to as poly-butadiene rubber.
Butadiene and oxygen readily react to form butadiene peroxide. The peroxide is denser than
butadiene, and only slightly soluble in it. It will tend to collect in stagnant areas and react to form
higher molecular weight peroxides. Concentrated, the peroxides are chemically and thermally
unstable, and shock sensitive; they can decompose violently. C4 controls peroxide formation by
carefully excluding oxygen from the process and using t-butyl catechol (TBC), an oxygen and free
radical scavenger. The plant is also designed to minimize stagnant areas where peroxides might
accumulate.
Butadiene ‘popcorn’ polymer varies in appearance, but in any form, its growth in a confined space
can exert enough force to rupture equipment. It is most likely to grow in the presence of
butadiene vapor, or a liquid with a high (>85%) butadiene concentration. Seeds of popcorn
polymer are initiated by free oxygen, peroxides or other sources of oxygen. Water and rust are
also believed capable of producing popcorn seeds. Once formed, a seed is self-propagating;
internal stresses create new free radical sites for monomer to react with. The material can be
self-heating, and can ignite on exposure to air, but is not explosively unstable.
Popcorn formation is controlled by excluding oxygen to prevent seed formation and using TBC to
suppress the propagation of the polymer. Untreated metal surfaces can contribute to popcorn
formation; they are passivated with hot NaNO2 solution to prevent this. Sodium nitrite (NaNO2) is
continually added to the N-methyl pyrrolidone (NMP) solvent to circulate this oxygen scavenger
through the process.
Butadiene also reacts to form a rubbery polymer. The reaction is accelerated by peroxides and
increased temperature. The rubber is relatively harmless; it can plug equipment and piping, but it
cannot rupture metal parts. It is not unstable or pyrophoric. Rubber formation is controlled by
excluding oxygen, using inhibitors to control peroxides, and limiting peak process temperatures.
Butadiene also spontaneously dimerizes. There is no known countermeasure for the

phenomenon, but it is essentially harmless, except to the extent that the dimer may react further
to slowly form polymer. The dimer product, vinylcyclohexene, is malodorous but is not a notable
fire or personnel hazard.
3.1.2 Prefractionator Tower
The Prefractionator Tower is provided to separate C3 components, primarily methylacetylene,

from the mixed C4 feed. Aside from the common concerns regarding overpressure of a distillation
column system, there is the added concern of concentrating methylacetylene to the point where it
becomes unstable. In general, methylacetylene in mixtures with butadiene is stable to about 80
mole percent. Refer to the BASF safety manual for more information. Under normal operation, the
methylacetylene concentration in the overhead is 25 mole percent.
Although it is unlikely, at near total reflux conditions, coincident with lower than normal cooling
water temperatures, it is possible to concentrate methylacetylene to 80 mole percent. A SIS is
provided to vent the net overhead of the Prefractionator to flare based on low-low temperature in
the tower overhead (an indication of high C3 concentration). If the vent to flare is

equal to the normal net overhead flow, it is impossible to concentrate the methylacetylene. Since
the set point of this interlock is higher than the lowest ambient temperature, a start-up bypass will
be required for this interlock.
The Prefractionator, associated overhead condenser, reflux drum, and reboiler tube side are
protected from overpressure by pressure relief valves located on the Prefractionator overhead
line. Potential causes of overpressure include loss of overhead condensing/reflux, excessive
reboiler heat input, and external fire exposure.
Since the Prefractionator relief is part of the flare mitigation system, a SIS shutdown is initiated by
high-high pressure in the overhead line, or by global cooling water or power failure. This interlock
prevents overpressure by isolating the heating mediums to the reboilers.
The three Prefractionator Reboilers have individual isolation valves on the process (tube) side to
allow removal from service for maintenance. These valves are locked open to prevent
overpressure from a blocked outlet when the heating medium is in service. Administrative
procedures are required to prevent these valves from being unlocked and closed before the
heating medium has been safely isolated, by locking a block valve closed. For the reboiler that
uses solvent as heating medium, tube rupture is also a potential cause of overpressure. Since the
valve to the column is locked open, administrative procedures must be employed so that both the
solvent inlet and outlet are isolated, by locking block valves closed, before the process side block
valve is unlocked and closed. Due to the large volume of the Prefractionator, a tube rupture will
not cause overpressure as long as the process side block valve is open. Pressure relief valves
are provided at the reboiler outlets for protection from overpressure due to external fire exposure.
Pressure relief valves on the shell side of the reboilers provide overpressure protection for
external fire exposure. The shell sides of the reboilers are designed for pump shutoff pressure.
Block valves are provided to isolate individual shells of the overhead condenser for maintenance.
The process side inlet and outlet valves are locked open to provide a path for relief of the
overhead drum due to external fire. Administrative procedures are required to ensure that at least
one set of block valves on the condensers is always open. The valves on the outlet of the cooling
water side of the condensers are locked open. Administrative procedures are required to ensure
blocking and cooling of the process side, before the cooling water outlet valves can be unlocked
and closed. This is to prevent overpressure due to thermal expansion of the cooling water.
Loss of level due to cessation of feed or level control failure can result in loss of suction to the
Prefractionator Reflux Pumps. DCS interlocks shut them down on low-low level to protect them
from running dry. Separate DCS interlocks shut the pumps down on high-high temperature.
3.1.3 Feed Vaporization System
The feed vaporization system provides the vapor feed to the extractive distillation system. The
Feed Vaporization Drum is open to the extractive distillation system, i.e. there are no block valves
between the Vaporization Drum and the Main Wash Tower.
The Feed Vaporization Drum and the extractive distillation system are protected by relief valves in
the drum’s overhead line. These relief valves protect the system from loss of cooling water to the
Main Washer and Afterwasher Condensers, excessive heat input from the Feed Evaporators, and
external fire.
Since the feed vaporizer relief is part of the flare mitigation system, a SIS shutdown is initiated by
high-high pressure in the overhead line, or by global cooling water or power failure. This interlock
prevents overpressure by stopping the flow of heating media to the reboilers, and the flow of the
Prefractionator bottoms. In addition, a DCS interlock is provided to stop the feed to the
Prefractionator to avoid overfilling it.

The three Feed Evaporators have individual isolation valves on the process (tube) side to allow
removal from service for maintenance. These valves are locked open to prevent overpressure
from a blocked outlet when the heating medium is in service. Administrative procedures are
required to prevent these valves from being unlocked and closed before the heating medium has
been safely isolated by locking a block valve closed. Tube rupture is also a potential cause of
overpressure. Since the valve to the drum is locked open, administrative procedures must be
employed so that both the solvent inlet and outlet are isolated, by locking block valves closed,
before the process side block valve is unlocked and closed. Due to the large volume of the drum,
and the extractive distillation system, a tube rupture will not cause overpressure as long as the
process side block valve is open. Pressure relief valves are provided at the reboiler outlets for
protection from overpressure due to external fire exposure. Pressure relief valves on the shell side
of the Evaporators provide overpressure protection for external fire exposure. The shell sides of
the Evaporators are designed for pump shutoff pressure.
3.1.4 Main Washer System and Solvent Cooler
The Main Washer system includes the Main Washer Column with its condenser, accumulator,
raffinate pumps, and bottoms pumps. As previously described, the main washer column,
condenser and accumulator are protected by the relief valves on the overhead of the Feed
Vaporizer Drum. Since the individual Main Washer Condensers have block valves for
maintenance, the shell sides of these exchangers have relief valves for external fire case. The
valves on the outlet of the cooling water side of the condensers are locked open. Administrative
procedures are required to ensure blocking and draining of the process side, before the cooling
water outlet valves can be unlocked and closed. This is to prevent overpressure due to thermal
expansion of the cooling water.
A relief valve is provided on the main washer accumulator for the fire case since the accumulator
can be isolated from the tower.
Loss of accumulator drum level due to cessation of feed or level control failure can result in loss
of suction to the Raffinate Reflux Pumps. To avoid potential pump damage, a pump trip is
activated on low-low level via a SIS.
Failure of mechanical seals of the Raffinate Pumps can result in a vapor cloud. Since the liquid
inventory in the drum exceeds 10,000 pounds of light hydrocarbons, a remotely operated suction
isolation valve is provided. To be effective, pump isolation must be carried out promptly upon
detection of a seal leak. A combustible gas monitor has been provided in the vicinity of these
pumps for this purpose. To protect the pumps from damage due to loss of suction when the
isolation valve is closed, pump trip is activated from the DCS upon detection of valve closure via a
position switch.
Failure of mechanical seals of the Main Washer Pumps can result in a vapor cloud. Since the
liquid inventory in the drum exceeds 10,000 pounds of light hydrocarbons, a remotely operated
suction isolation valve is provided. To be effective, pump isolation must be carried out promptly
upon detection of a seal leak. Combustible gas monitors have been provided in the vicinity of
these pumps for this purpose. To protect the pumps from damage due to loss of suction when
the isolation valve is closed, pump trip is activated from the DCS upon detection of valve closure
via a position switch. In addition, minimum flow protection for the Main Washer Pumps is
provided by a low-low flow shutdown via a DCS interlock.
The Solvent Cooler consists of two parallel sets of two exchangers. Each set of two exchangers
can be blocked in; as discussed above, administrative procedures are required to prevent
overpressure due to thermal expansion. The four exchangers share a common solvent side relief
valve and a common cooling water side relief valve. The exchangers are designed for pump
shutoff pressure.

3.1.5 Rectifier Column System
The rectifier column system consists of the Rectifier Column, its bottoms pumps, the Solvent Heat
Exchanger, the Degasser Feed Pumps, and the Solvent Heater.
As previously described, the Rectifier Column is protected by the relief valves on the overhead of
the feed vaporizer drum.
Failure of mechanical seals of the Rectifier Bottoms Pumps or the Degasser Feed Pumps can
result in a potential vapor cloud. Since the liquid inventories in the sump exceed 10,000 pounds
of light hydrocarbons, remotely operated suction isolation valves are provided on the pump
suction to each pump. To be effective, pump isolation must be carried out promptly upon
detection of a seal leak. Combustible gas monitors have been provided in the vicinity of these
pumps for this purpose. To protect the pumps from damage due to loss of suction when the
isolation valve is closed, a pump trip is activated from the DCS upon detection of valve closure via
a position switch. Minimum flow protection for the Rectifier Bottoms Pumps is provided by a DCS
interlock that trips them on low-low discharge flow. The Degasser Feed Pumps are protected
against minimum flow by a similar DCS interlock.
The Solvent Heat Exchanger consists of two sets of three shells. Each set of three shells can be
isolated for maintenance. Both sides of the heat exchangers are designed for pump shutoff. Relief
valves are provided on the tube side for fire case, and for thermal expansion. Relief valves are
provided on the shell side for fire case.
The Solvent Heater tube side is designed for pump shutoff pressure. A relief valve is provided on
the tube side for thermal expansion and for fire case. A relief valve is provided on the shell side
for fire case and for tube rupture case.
3.1.6 Afterwasher Column System
The Afterwasher Column system includes the Afterwasher Column with its condenser,
accumulator, Crude Butadiene Pumps, and bottoms pumps. As previously described, the
Afterwasher Column, condenser and accumulator are protected by the relief valves on the
overhead of the feed vaporizer drum. Valves on the cooling water side of the condensers are
locked open. Administrative procedures are required to ensure blocking and cooling of the
process side, before the cooling water outlet valves can be unlocked and closed. This is to
prevent overpressure due to thermal expansion of the cooling water.
A relief valve is provided on the Afterwasher overhead line to the accumulator for fire case, since
the accumulator can be isolated from the relief valves on the feed vaporizer drum via the pressure
control valve. This relief valve also protects the Afterwasher for fire case relief because when the
liquid holdup in the Afterwasher packing "dumps" to the column sump, the path back to the feed
vaporizer relief valves is blocked. To accommodate this case, the control valve on the overhead of
the Afterwasher must have a mechanical minimum (open position) stop so that a path exists for
the fire relief load from the Afterwasher.
Loss of accumulator drum level due to cessation of feed or level control failure can result in loss
of suction to the Crude Butadiene Pumps. DCS interlocks shut them down on low-low level to
protect them from running dry. Separate DCS interlocks shut the pumps down on high-high
temperature.
Loss of Afterwasher sump level due to cessation of feed or level control failure can result in loss
of suction to the Afterwasher Bottoms Pumps. DCS interlocks shut them down on low-low level to
protect them from running dry. Separate DCS interlocks shut the pumps down on high-high
temperature.

3.1.7 Degasser System
The Degasser system consists of the Degasser Column, Degasser Column Reboiler and
condensate pot, bottoms pumps, the Cooling Column, Cooling Column Bottoms Pumps, and the
Water and Solvent Cooler.
Relief valves are provided on the overhead line of the Degasser to protect the Degasser, Cooling
Column, Degasser Column Reboiler (tube side), and the Acetylene Washer system. The major
cases are blocked outlet (loss of compressor) and fire case.
Since the Degasser relief is part of the flare mitigation system, a SIS shutdown is initiated by high-
high pressure in the overhead line, or by global cooling water or power failure. This interlock
prevents overpressure by isolating the heating medium to the reboilers and solvent heater, as well
as stopping the Degasser feed to prevent flashing of the feed. The set pressure of this shutdown
is much lower than the design pressure of the equipment to prevent simultaneous high pressure
and high vinyl acetylene concentrations. This is discussed further in the section describing the
acetylene washer system.
The two Degasser Column Reboilers have individual isolation valves on the process (tube) side to
allow removal from service for maintenance. The tube outlet valves are locked open to prevent
heating has been safely isolated by locking a block valve closed. Tube rupture is also a potential
cause of overpressure. Since the valve to the column is locked open, administrative procedures
must be employed so that both the steam inlet and outlet are isolated, by locking block valves
closed, before the process side block valve is unlocked and closed. Tube rupture case is
considered in the relief valves on the Degasser Overhead. Pressure relief valves are provided at
the reboiler outlets for protection from overpressure due to external fire exposure. Pressure relief
valves on the shell side of the reboilers provide overpressure protection for external fire exposure.
The condensate pot also has a relief valve for protection for external fire exposure.
Loss of Degasser sump level due to cessation of feed or level control failure can result in loss of
suction to the Degasser Bottoms Pumps. To prevent damage, these pumps are tripped on low-
low level by DCS interlocks. Additional DCS interlocks trip the pumps on low discharge flow. A
remotely-operated suction isolation valve is provided here to limit the release in the event of a seal
failure. DCS interlocks shut down the pumps when the valve closes.
Loss of Cooling Column sump level due to cessation of feed or level control failure can result in
loss of suction to the Cooling Column Bottoms Pumps. To prevent damage, these pumps are
tripped on low-low level by DCS interlocks. Additional DCS interlocks trip the pumps on low
discharge flow.
The Water and Solvent Cooler shell side is designed for pump shutoff pressure. A relief valve is
provided on the shell side for fire case. The valve on the outlet of the cooling water side of the
cooler is locked open. Administrative procedures are required to ensure blocking and cooling of
the process side, before the cooling water outlet valves can be unlocked and closed. This is to
prevent overpressure due to thermal expansion of the cooling water.
3.1.8 Recycle Gas Compressor
The Recycle Gas Compressor compresses the degassed hydrocarbons from the degasser
system to the extractive distillation system. The major source of overpressure is a blocked outlet
case. Relief valves are provided on the discharge of the compressor for blocked outlet. The
suction side of the compressor is protected by the relief valves on the degasser overhead.

Back flow is prevented by the check valve in the discharge line and by closing a valve in the
discharge line in case of compressor trip. Based on the design pressure of the suction system,
back flow is not an overpressure case for the suction equipment. Capability is provided to block in
and depressure the compressor to flare in case there is a seal leak in the compressor.
A number of SIS’s protect the compressor from mechanical damage. Their functions include
protecting the machine from excessive temperature and pressure, surge, and failures in the lube
oil and dry gas seal systems.
3.1.9 Acetylene Washer
The Acetylene Washer system includes the Acetylene Washer, its condenser, the separator,
reflux pumps and slops pumps. As described previously, this equipment is protected from
overpressure by the relief valves on the Degasser overhead.
The primary safety concern in this area is the potential for high concentrations of C4-acetylenes,
which could result in an exothermic decomposition. The C4-acetylenes are removed from the
process in the Degasser side-draw stream, which consists mostly of water and NMP; the
acetylenes concentration is about 20 wt%, well within the stable range. In the Acetylene Washer
the C4-acetylenes remain diluted with water and below the stability limit. The C4-acetylene
overhead vapor from the Acetylene Washer is diluted further with raffinate vapor from the Main
Wash Column. This is to ensure that the hydrocarbon stream leaving the Acetylene Washer
Condenser remains diluted after the water is condensed from it. As long as the process is
operating, and the Main Wash Column is pressurized, raffinate vapor will be available for dilution.
A SIS trip is provided to block the outlet from the Acetylene Washer Condenser if the ratio of
dilution raffinate flow to hydrocarbon flow from the Acetylene Washer Condenser is too low. This
stops the acetylene side draw flow from the Degasser Column, stopping the removal of
acetylenes from the system. The acetylene concentration will gradually build up in the compressor
loop, and if the dilution raffinate cannot be established, the plant must be shut down. Analyzers
are provided at the outlet of the Acetylene Washer Condenser, and at the outlet of the
compressor to monitor the C4-acetylenes concentration. The normal C4-acetylenes
concentration is about 25 mole%. The trip system will be set up to prevent the concentration from
exceeding 30 mole%. The high-high pressure trip, and the relief valve set pressures should be set
low enough (i.e. 40 psig) to ensure that dilution raffinate can always flow from the Main Wash
Column to the Acetylene Washer Condenser. This will prevent high pressure in the system as a
cause for loss of dilution raffinate.
3.1.10 C4-Acetylene Condenser and TBC Removal Column
This system includes the Acetylene condenser, accumulator, and pumps along with the tert-butyl
catechol (TBC) removal column, reboiler and pumps.
The Acetylene Condenser, accumulator and pumps have two functions. They are used to
condense the C4-acetylenes from the Degasser side-draw, and to condense the TBC Column
overhead. The condenser system is protected against overpressure from the Degasser Column
and the TBC Column by relief valves at those towers. A relief valve is provided for external fire
exposure on the accumulator, and tube rupture in the condenser. Relief valves are provided on
the refrigerant side of the acetylene condenser for vaporization of refrigerant in a blocked in
situation.
Relief valves are provided for the C4-Acetylene Pumps to protect from overpressure due to
thermal expansion. These pumps are further protected against mechanical damage by DCS
interlocks that shut them down on low-low suction level and high-high pump temperature.
The TBC Column and its reboilers are protected by a relief valve for blocked outlet and fire
exposure. The reboilers have relief valves on the tube side for thermal expansion and fire

exposure, and on the shell side for fire exposure and tube rupture. To date, the TBC Column has
not operated as designed; feed flows through it without separation. A project is planned to provide
a slipstream of heavies to allow the reboilers to work properly. The current state of the column
does not affect its safety concept.
3.1.11 Crude Butadiene Cooler and Coalescer
These two items have been removed from service. The coalescer was intended to reduce salt
consumption in the butadiene product dryers; it worked well. The cooler, however, caused
flooding and repeated upsets in the Butadiene Column by sub-cooling its feed excessively. The
original Lummus design concept is presented below for reference.
The Crude Butadiene Cooler shell side and Crude Butadiene Coalescer are designed for pump
shutoff pressure. A relief valve is provided on the shell side for fire case. The valve on the outlet of
the cooling water side of the cooler is locked open. Administrative procedures are required to
ensure blocking and draining of the process side, before the cooling water outlet valve can be
unlocked and closed. This is to prevent overpressure due to thermal expansion of the cooling
water. [The cooling water piping will be sized to relieve the tube side of the cooler in the event of
fire.]
3.1.12 Butadiene Column System
This system includes the Butadiene Column, condenser, accumulator, reboiler, overhead pumps,
and product pumps.
The Butadiene Column, associated overhead condenser, reflux drum, and reboiler tube side are
protected from overpressure by safety valves located in the overhead line. Potential causes of
overpressure include loss of overhead condensing/reflux, excessive reboiler heat input, and
external fire. Since the Butadiene Column relief is part of the flare mitigation system, a SIS
shutdown is initiated by high-high pressure in the overhead line, or by global cooling water or
power failure. This interlock prevents overpressure by isolating the heating medium to the
reboilers.
The four Butadiene Column Reboilers have individual isolation valves on the process (tube) side
to allow removal from service for maintenance. These valves are locked open to prevent
heating has been safely isolated by locking a block valve closed. Tube rupture is also a potential
cause of overpressure. Since the valve to the column is locked open, administrative procedures
must be employed so that both the solvent inlet and outlet are isolated, by locking block valves
closed, before the process side block valve is unlocked and closed. Due to the large volume of
the Butadiene Column, a tube rupture will not cause overpressure as long as the process side
block valve is open. Pressure relief valves are provided at the reboiler outlets for protection from
overpressure due to external fire exposure. Pressure relief valves on the shell side of the reboilers
provide overpressure protection for external fire exposure.
The valves on the inlet of the cooling water side of the condensers are locked open.
Administrative procedures are required to ensure blocking and cooling of the process side, before
the cooling water outlet valves can be unlocked and closed. This is to prevent overpressure due to
thermal expansion of the cooling water.
Loss of drum level due to cessation of feed or level control failure can result in loss of suction to
the Butadiene Column Reflux Pumps. To avoid potential pump damage, the pumps are tripped on
low-low level by individual DCS interlocks. Separate DCS interlocks shut the pumps down on
high-high pump temperature. The Butadiene Product Pumps are protected by similar level and
temperature trips.

3.1.13 Solvent Regenerators
This system includes two identical NMP Solvent Regenerators. Each Solvent Regenerator is a
semi-continuous vacuum still, consisting of a drum with an agitator and external steam coil. Dirty
solvent is fed to the Regenerator on flow control. NMP is recovered as a vapor, while high-boiling
impurities (NMP residue) collect in the Regenerator. As the residue concentration rises, the
Regenerator’s temperature rises and NMP boil-up drops. Feed is periodically stopped to improve
through-put by draining the accumulated residue.
A relief valve protects the Solvent Regenerator from overpressure due to the nitrogen pressure
regulator failing open, external fire exposure, and from overfilling. The Regenerator cannot be
overpressured from heat input from the steam jacket, since NMP will not boil at the relieving
pressure.
A major safety concern for this system is overconcentration of nitrites. At high concentrations, the
nitrites can decompose. This exothermic reaction can cause the remaining solvent to boil off.
Without solvent present, the residue can detonate. This could occur during the process of boiling
off excess solvent prior to emptying the residue from the Regenerator. To prevent
overconcentration of nitrites, a SIS is provided to shut off the steam based on high-high
temperature in the vessel. In addition, a second SIS is provided to dump a fixed quantity of cold
solvent into the tank based on high-high-high temperature.
NMP residue is periodically drained from the Regenerator to a truck. DCS interlocks are used to
prevent flashing of the residue and air ingress during this operation. These interlocks prevent the
residue drain valve from being opened until the Regenerator is at or above atmospheric pressure,
the temperature is below 200 deg F, the block valve in the nitrogen line is open, and the block
valve in the line to the vacuum system is closed.
A relief valve on the Regenerator’s heating jacket protects it from overpressure due to fire
exposure.
3.1.14 Regenerated Solvent Recovery System
This system includes the Regenerated Solvent Condenser, Receiver and Pumps. Its operation is
supported by the Steam Ejector package, Ejector Seal Tank and Ejector Water Pumps.
A relief valve is provided on the Regenerated Solvent Receiver to prevent overpressure of the
receiver and condenser from external fire, fail open of the nitrogen valve, or overfilling via the
start-up line.
the Regenerated Solvent Pumps. To avoid potential pump damage, a pump trip is activated on
low-low level by a DCS interlock.
The valve on the outlet of the cooling water side of the Solvent Condenser is locked open.
Administrative procedures are required to ensure blocking and cooling of the process side, before
the cooling water outlet valves can be unlocked and closed. This is to prevent overpressure due to
thermal expansion of the cooling water.
A relief valve is provided on the Ejector Seal Tank to prevent overpressure from external fire, fail
open of the nitrogen valve, loss of cooling in the ejector condenser, or blocked outlet.

the Ejector Water Pumps. To avoid potential pump damage, a pump trip is activated on low-low
level by a DCS interlock.
The valve on the outlet of the cooling water side of the Steam Ejector’s outlet condenser is locked
open. Administrative procedures are required to ensure blocking and cooling of the process side,
before the cooling water outlet valves can be unlocked and closed. This is to prevent
overpressure due to thermal expansion of the cooling water.
3.1.15 Tert-Butyl Catechol (TBC) Injection System
Tert-butyl catechol (TBC) is used to inhibit the polymerization of butadiene. It is not a fire hazard.
The pure material is solid at room temperature; it is used in aqueous solution in Port Arthur. TBC
is a skin irritant, but not a serious personnel hazard.
This system includes a bulk storage tank, the Inhibitor Drum, and the Injection Drum. An air-
driven diaphragm pump transfers batches of TBC solution from the tank to the Inhibitor Drum.
These batches are periodically transferred to the Injection Drum by gravity flow. TBC flows
continuously from the Injection Drum into the process under nitrogen pressure.
The Inhibitor Drum and Injection Drum are provided with relief valves to protect them from the
relevant overpressure contingencies. These include fire exposure and nitrogen overpressure.
(The nitrogen supply pressure is much higher than the drums’ rated pressures.)
A release of TBC solution could result from a leak or from backflow from the drums to the bulk
storage tank, but this is not a significant hazard. A release of process fluid resulting from
backflow into the TBC injection system could be of greater concern. However, the Atmospheric
Relief Screening Study for the Port Arthur Site (PA-Atm Relief Rep_Feb09.doc) assigned such an
event to Risk Class ‘E’ due to its low probability.
3.1.16 Solvent Inhibitor System
The solvent inhibitor is aqueous sodium nitrite (NaNO2), an oxygen scavenger used to suppress
the formation of peroxides and polymers in the butadiene plant. This material is non-flammable,
and only a moderate personnel hazard.
This system includes the Solvent Inhibitor Vessel, its agitator and pump. An air-driven diaphragm
pump transfers batches of inhibitor from bulk shipping containers to the Inhibitor Vessel. A
diaphragm pump meters the inhibitor into the circulating NMP solvent.
The Inhibitor Vessel has a relief valve to protect it from the relevant overpressure contingencies,
which include fire exposure and nitrogen overpressure.
A release of solvent inhibitor could result from a leak or from backflow from the Inhibitor Vessel to
the bulk containers, but this is not a significant hazard. A release of process fluid resulting from
backflow into the solvent inhibitor system could be of greater concern. However, the Atmospheric
Relief Screening Study for the Port Arthur Site (PA-Atm Relief Rep_Feb09.doc) assigned such an
event to Risk Class ‘E’ due to its low probability.
3.1.17 Antifoam System
A silicone oil is used to control foaming in the butadiene process. The material is metered directly
from bulk shipping containers into the circulating NMP solvent by a set of diaphragm pumps. The
oil is used in small volumes; it is not a significant fire or personnel hazard.

A spill of silicone oil is not a significant hazard. A release of process fluid resulting from backflow
into the antifoam system could be of greater concern. However, the Atmospheric Relief
Screening Study for the Port Arthur Site (PA-Atm Relief Rep_Feb09.doc) assigned such an event
to Risk Class ‘F’ due to its low probability.
3.1.18 Butadiene Drain Drum and NMP Slop Vessel
The Butadiene Drain Drum and NMP Slop Vessel are used for clearing equipment. They collect
fluids from the plant’s Solvent Drain Header. The header is protected against overpressure by a
locked-open valve and a three-way valve. These valves guarantee that the header is always open
to one drum or the other. The Drain Drum is protected from overpressure by a PSV sized for the
relevant contingencies. The Slop Vessel vents to the flare through a locked-open vent line. The
vent line is sized to protect the drum from overpressure due to fire exposure.
3.1.19 Solvent Surge Tank
The Solvent Surge Tank provides temporary storage for the NMP solvent. A relief valve protects
it from overpressure due to the nitrogen valve failing open, normal tank out breathing, overfilling
and external fire exposure.
Backflow through the Solvent Surge Tank Pump is prevented by a check valve on the pump
discharge, and a block valve that trips closed when the pump is off.
Vacuum protection is provided by a DCS interlock that supplies nitrogen to the tank from the
nitrogen header. A SIS shuts the tank’s NMP solvent feed valve to protect it from high-high
pressure. The same valve is tripped shut by a DCS interlock to protect the tank from overfilling.
A dike is provided to contain any spills from the tank.
3.1.20 Raffinate Chilling and Coalescing
This system includes the Raffinate Chiller, Interchanger, and Coalescer.
A relief valve is provided on the Raffinate Coalescer to protect it, the Interchanger, and the tube
side of the Chiller from overpressure due to external fire exposure. A relief valve is provided on
the shell side of the raffinate chiller to protect it from overpressure due to external fire exposure.
Blocked in refrigerant is not a relief case since overpressure cannot be attained by heating the
propylene to the normal process side operating temperature. The coalescer and heat exchangers
are design for pump shutoff pressure.
3.1.21 Bisulfite Wash System
The Bisulfite Wash System removes oxygenated impurities from a mixed feed stream consisting
of Raffinate I and other byproducts from the Butadiene Plant. This treatment extends the life of
the Selop and InAlk catalysts. The liquid hydrocarbon stream is contacted twice with aqueous
sodium bisulfite, an oxygen scavenger which reacts with the ketones, alcohols, and other
impurities. A Totall water wash removes any salts from the hydrocarbon stream. Each contacting
stage consists of a static mixer, reagent circulation pumps, and a settling drum.
The bisulfite treatment takes place at ambient temperature and 90-150 PSIG to keep the
hydrocarbons from flashing. There is no danger of a runaway reaction. The principal process
hazards are loss of containment of the C4 hydrocarbons and loss of aqueous phase in the 2nd and
3rd Stage Settling Drums. Loss of the aqueous phase will result in liquid C4 hydrocarbons being
sent to BTP’s Spent Caustic Treating system or Wastewater Treating area, respectively. Two
safeguards are used to prevent flow of hydrocarbon to BTP:

 Remotely-operated isolation valves at the bottom outlet of the 2nd and 3rd Stage Settling
Drums close on low-low level in the drums.
 A separate valve in the wastewater line from each stage of process shuts when an
analyzer in that line senses low conductivity, meaning hydrocarbon is present.
The most likely cause of loss of containment is a pump seal failure in the 2nd or 3rd stage. The
remote isolation valves under the 2nd and 3rd Stage Settling Drums can be shut to limit the spill
volume. A hydrocarbon spill from the 1st Stage Bisulfite Circulation Pump is unlikely, because the
1st Stage Settling Drum has internal baffles and does not run flooded.
Sodium bisulfite is delivered as a 40% wt aqueous solution. It is non-flammable, but dangerous

on contact. Work procedures that prevent personnel exposure are enforced.
3.1.22 Tank Farm
The C4 Tank Farm consists of a refrigerated API tank and four storage spheres. The Butadiene
(BD) Product Tank holds up to 80 kbbls of product butadiene; its normal operating conditions are
~ 1 PSIG and 24 F. The spheres, in aggregate, hold up to 85 kbbls of crude butadiene, off-spec
butadiene, and raffinate streams. They operate at stream vapor pressure (up to ~ 60 PSIG) and
ambient temperature. Obviously, the primary process hazard is loss of containment and its
consequences. A pool fire might be possible at the tank, but a loss of containment in the tank
farm is most likely to produce a large flammable gas cloud.
To limit the volume of a spill, a remotely-operated isolation valve is provided in the pump suction
line at all five vessels. For additional protection, all the bottom connections on each sphere
contain an excess-flow cut-off valve. Combustible gas detectors at each vessel sound alarms in
the control house to warn of leaks.
An extensive fire water deluge system protects the spheres, nearby equipment, and portions of
nearby pipe racks from fire damage. The BD Product Tank is protected by fire water monitors
and a permanent header for delivering fire-fighting foam.
The BD Product Tank and the Product Blending (Off-spec) Sphere contain pure, or nearly pure,
butadiene. After fire, the biggest hazard posed by butadiene product storage may be vessel
overpressure due to the plugging of relief devices with butadiene polymer. Polymer formation is
particularly likely on surfaces exposed to stagnant butadiene vapor, so all relief device inlet lines
are continuously sprayed with liquid butadiene to keep them clean. As an additional precaution,
the entire upper portions of these vessels are also sprayed. (Refer Section 3.1.1 and the
references in Section 4.1 for more on butadiene reactions.)
Due to its size and low (2.0 PSIG) design pressure, the BD Product Tank requires additional
safeguards against loss of containment. It is built with a double wall and floor; the outer shell is
designed to completely contain any material leaking through the inner shell. The annular space
between the shells is inerted with a continuous nitrogen purge; the escaping nitrogen is
continuously monitored for combustible gases. Since the potential consequences of over-
pressuring this tank are so severe, its pressure/vacuum relief valve has an on-line spare. Excess
vacuum is an equally serious hazard, so the primary vacuum breaker is a SIS that floods the tank
with nitrogen on low pressure. The mechanical vacuum breaker is intended as a back-up device
only, as its operation will introduce oxygen into the tank.
The BD Product Tank is a cold-storage vessel that depends on a mechanical refrigeration unit for
its normal operation. Loss of mechanical refrigeration is a likely event, but the tank is well-
protected against it by its dual pressure relief valves and by the insulation between its inner and
outer shells.

3.2 Indirect Alkylation Unit (InAlk)
3.2.1 General
This plant uses the UOP Indirect Alkylation (InAlk) process to convert isobutene and 1-butene into
a high octane gasoline blending component. The principal source of these butenes is the
Raffinate I byproduct from the Butadiene Extraction Unit.
3.2.2 Feed Dryer System
InAlk’s solid phosphoric acid (SPA) polymerization catalyst is very sensitive to moisture; the feed’s
water content must be reduced to ppm levels for it to perform properly. The InAlk Feed Dryer
System consists of two molecular sieve beds and their associated regeneration equipment.
Drying is done in down-flow mode with the bed flooded at 335 PSIG and ambient temperature.
No special hazards exist in normal operation; there is no threat of a runaway reaction, and the
liquid hydrocarbon inventory is relatively small. No special safeguards are provided.
The Feed Dryer’s regeneration system produces a superheated C4 vapor stream to remove water
from a saturated mol sieve bed, which is subsequently cooled with a liquid C4 stream. The
process is largely automated, and the regeneration equipment is all rated for the same pressure
as the Feed Dryers. This subsystem has a relatively small flammables inventory, and presents no
unusual process hazards. No special safeguards are provided.
3.2.3 C4 Selective Hydrogenation Unit (Selop I)
Selop I selectively hydrogenates any butadiene or acetylenes present in the InAlk feed stream at
conditions up to 245 PSIG and 205F. In particular, butadiene must be reduced below 1500 ppm
to control fouling in the polymerization and hydrotreating reactors. Raffinate I is mixed with a
liquid recycle stream and hydrogen before being fed to the Selop I Reactor, a trickling-bed unit.
Reactor effluent flows to the Selop I Separator Drum, where a small excess of hydrogen is
disengaged from the liquid. Part of the liquid product is pumped forward to InAlk’s Polymerization
Reactors; the balanced is recycled to the Selop I Reactor by a separate pump. The reaction is
exothermic; control depends largely on the recycle stream and the recycle cooler that removes the
reaction heat.
The Selop I Reactor is provided with a SIS designed to prevent the principal process hazard, a
runaway reaction. Its principal action is to shut off C4 liquid and hydrogen feed to the reactor on
high-high bed or outlet temperature. It also opens a pressure control valve on the reactor’s outlet
to drain the reactor into the Selop I Separator Drum.
Selop I contains a significant volume of flammable gas and a moderately large volume of liquid
C4s. Loss of containment is a potentially serious hazard; the most likely cause is a seal failure at
the Selop I Reactor Recycle Pump or the Selop I Product Pump. To limit the volume of such a
release, remotely-operated isolation valves are provided in these pumps’ suction lines.
3.2.4 Polymerization Reactors
The mixed C4 stream from the Selop I Separator Drum is combined with an iso-octane (Alkylate)
recycle stream from the Product Stripper and is fed to the Polymerization (Poly) Reactors. The
recycle flow is varied to moderate the reaction temperature. In the Poly Reactors, isobutene
dimerizes and isobutene and 1-butene react to form a highly branched iso-octene. The reactor
product is fed to the Debutanizer Tower.
The Poly Reactors operate flooded, in upflow mode; they contain a large inventory of liquid
hydrocarbons. To limit the extent of a spill, they are provided with remote isolation valves at both
the inlet and outlet. Outlet design conditions for the main reactors are 492 PSIG and up to 340 F.

The polymerization reaction is exothermic and produces a significant temperature rise. Control of
the reaction depends on the inert Alkylate recycle. A SIS shuts down fresh feed to the
Polymerization Reactors on loss of this recycle.
3.2.5 Debutanizer Tower
The Debutanizer Tower, operating at design bottoms conditions of 108 PSIG and 387F, separates
the poly reactor product into three streams. The tower overhead stream, rich in isobutane, is
pumped to Total or co-cracked, depending on economics. The side stream is a 2-butene rich
stream which is cooled and sent to the Raffinate II Sphere prior to being fed to the Olefins
Conversion Unit (OCU). The tower bottoms stream is the iso-octene product from the
polymerization reactors that is fed to the Hydrotreater Reactor.
The Debutanizer contains a significant vapor inventory and a large liquid hydrocarbon inventory.
The principal process hazard in this area is loss of containment, which could result in a flammable
vapor cloud or a pool fire. A pump seal failure is the most likely cause of a release; as a
safeguard, remote isolation valves are provided in the suction line of Debutanizer Bottoms Pump,
the Raffinate II Pump, and the Debutanizer Overhead Pump.
The Debutanizer Reboiler is heated by 600 PSIG steam. To reduce the relief requirement for the
Debutanizer’s PSVs, a SIS stops steam flow to the reboiler on high-high overhead pressure in the
tower.
3.2.6 Hydrotreater Reactor
The Debutanizer bottoms are fed to the Hydrotreater Reactor after being combined with a recycle
iso-octane stream, recycle hydrogen, and make up hydrogen. The recycle flow is varied to
moderate the reaction temperature. In the Hydrotreater Reactor, the iso-octene product is
saturated to form the iso-octane product. The discharge of the reactor then feeds the product
separator drum.
The Hydrotreater Reactor operates at design conditions of up to 360 PSIG and 478 F. Its
vapor/gas feed flows downward through the reactor’s three beds; slipstreams of liquid debutanizer
bottoms trickle down through the lower two beds. DMDS is used to moderate catalyst activity as
needed. The reactor and associated equipment are built of SA387 steel to prevent high-
temperature hydrogen attack (HTHA). See Section 2.2.8 of this report for additional discussion.
The principal process hazard in this section is a runaway reaction. The safeguard is a SIS. On
high-high signals from any two of the reactor’s twelve temperature probes, it stops hydrogen and
liquid feed to the reactor and depressures it. The same SIS also stops fresh feed to the Poly
Reactors.
3.2.7 Product Separator Drum and Recycle Gas Compressor
Iso-octane from the Hydrotreater Reactor is de-gassed in the Product Separator Drum at design
conditions of 310 PSIG and 210 F. Unreacted hydrogen flows to the Recycle Gas Compressor,
which recycles it to the Hydrotreater Reactor. The iso-octane product flows to the Product
Stripper Tower under system pressure.
There are no reactive hazards in this section. It does contain a significant inventory of highly
flammable gas, and a fairly large inventory of combustible liquid. A principal process hazard is
loss of containment, which could lead to either a flammable gas cloud or a pool fire.
The InAlk Recycle Gas Compressor is a two-stage centrifugal unit. The principal process hazard
is a seal failure, which will likely create a flammable vapor cloud. A combustible gas monitor is
provided near the compressor to provide prompt warning of a leak. Additional instrumentation
protects the compressor from mechanical damage. A SIS shuts down the machine on high-high

liquid level in the Product Separator Drum. The compressor is also provided with other protection
per normal vendor practice. Such instrumentation typically includes minimum flow bypass/anti-
surge controls and interlocks that shut the machine down on high shaft speed, excessive
vibration, excessive shaft displacement, and loss of seal or lube oil.
The recycle gas contains a potentially lethal concentration of H2S. Appropriate administrative
controls are enforced to prevent personnel exposure. In addition, an ambient-air H2S monitor
near the Recycle Gas Compressor alarms in the control room.
3.2.8 Product Stripper Tower
The Product Stripper Tower removes the remaining light ends, typically hydrogen, H2S, and C4s,
from the de-gassed iso-octane product. Its design bottoms conditions are 122 PSIG and 397 F.
The non-condensable light ends are sent to the Charge Gas Compressor within the Cold Section.
The Stripper Tower is designed to operate on total reflux, but in the case where there is a build up
of C4’s in the system, these are purged to the iso-octane (alkylate) bottoms product. Part of this
bottoms stream is recycled within the InAlk plant, as described above.
This is a conventional stripping tower; it contains a moderate vapor inventory but a large inventory
of liquid Alkylate product. Operating temperature is fairly high. The principal process hazard is
loss of containment due to a pump seal failure, which could result in either a flammable gas cloud
or a pool fire. To mitigate the risk of a pump seal failure, remote isolation valves are provided on
the suction side of the tower’s bottoms and overhead pumps.
The Product Stripper Reboiler is heated by 600 PSIG steam. To reduce the relief requirement for
the Product Stripper’s PSVs, a SIS stops steam flow to the reboiler on high-high overhead
pressure in the tower.
A significant concentration of H2S exists in the Stripper’s overhead vapor. Appropriate

administrative controls are enforced to prevent personnel exposure.
3.3 Olefins Conversion Unit (OCU)
3.3.1 General
The Olefins Conversion Unit (OCU) reacts ethylene and 2-butene over a tungsten catalyst to
produce propylene. Under favorable market conditions, this upgrades the ethylene and butene to
propylene value.
Many of the process streams at OCU contain ethylene and propylene, refrigerants that can
produce very low temperatures on flashing. To protect equipment from low-temperature
embrittlement, special procedures are followed for filling and clearing.
3.3.2 C4 Selective Hydrogenation Unit (Selop II)
OCU feeds Raffinate II, the side stream from InAlk’s Debutanizer Tower. Despite having been
treated in Selop I, this stream must be treated again to further reduce the butadiene content to
below 50 ppm. This is necessary to protect OCU’s reactors from fouling. Raffinate II and
hydrogen are mixed, preheated, and fed to the bottom of the Selop II Reactor, a liquid-filled,
upflow unit. Since the amount of material being reacted is relatively small, there is no recycle
quench stream. The reactor effluent normally flows to a storage sphere; there is no effluent
disengaging drum.
The Selop II Reactor is provided with a SIS designed to prevent the principal process hazard, a
runaway reaction. It shuts off C4 liquid and hydrogen feed to the reactor on high-high bed or

outlet temperature.
Selop II contains flammable gas and a moderately large volume of liquid C4s. Loss of
containment is a potentially serious hazard; a likely cause is a seal failure at the unit’s Raffinate II
Booster Pump. To limit the volume of such a release, a remotely-operated isolation valve is
provided in the pump’s suction line. The Selop II Reactor can also be blocked in using remotely-
operated valves.
3.3.3 Feed Treatment
Fresh Raffinate II and recycled butenes from the Recovery Section of the plant are mixed in the
C4 Surge Drum. Ethylene is then mixed into the C4s by a static mixer; process pressure is
maintained above 500 PSIG to keep the ethylene dissolved. The resulting C2/C4 liquid mixture
flows upward through the DP Reactor Feed Treaters. The Treaters contain beds of alumina that
adsorb impurities that would poison the catalyst in the Disproportionation (DP) Reactors
downstream. The adsorption is not strongly exothermic, so there is no need for a SIS to stop an
incipient runaway.
There are three Feed Treaters, two in service at any one time, the other on standby or being
regenerated. Parts of the regeneration gas system are low pressure; to prevent them being
overpressured a number of safeguards are provided. The isolation valves used during the regen
process are triple offset butterfly valves designed to work as double block and bleed
arrangements. To limit the possibility of error, the regen sequence is automated. Finally, a SIS is
provided to prevent overpressuring the regeneration system. It prevents the regen gas isolation
valves from being opened before the reactor pressure has been lowered to a safe level.
The ethylene/butene ratio in the feed must be controlled in a certain range for good results.
Ethylene is fed in excess; if this excess drops, production of propylene will suffer. However, if the
concentration of ethylene in the feed rises too high, it may decompose in the DP Reactor. To
prevent this, a SIS is provided that shuts down ethylene feed flow on sensing a high-high ratio of
ethylene to C4 feed flow.
3.3.4 Feed Preheat System for the Diproportionation (DP) Reactors
The Feed Preheat System consists of an exchanger in which the cold C2/C4 feed stream is
heated and vaporized by hot vapor effluent from the DP Reactor. The vaporized feed is then
superheated in the DP Reactor Feed Heater, a natural-draft fired heater.
Fire and explosion at the Reactor Feed Heater are two principal process hazards in this system.
Loss of containment due to overheating or abnormal conditions is another. To prevent them, a
group of SIS’s shuts the heater down on the following abnormal conditions:
 Low-low feed flow to any individual coil pass

 High-high process fluid outlet temperature
 Low-low total C4 flow to the heater
 High-high pressure at the coil outlet
 High-high heater stack gas outlet temperature
 High-high and low-low burner fuel gas pressure
 High-high and low-low pilot gas pressure
The SIS’s take the following major actions when they trip the heater:
 Close the main fuel gas block valves

 Close the heater coil inlet and outlet isolation valves
 Depressure the heater coils by opening the flare vent valves

 Stop the C4 and ethylene pumps

 Open the stack damper
In addition, a DCS interlock purges the heater’s coils with nitrogen when they are isolated.
To minimize the possibility that it will ignite a flammable vapor cloud, the Reactor Feed Heater is
located near the C4 Flare structure, as far as possible from process equipment. The
Regeneration Heater and C4’s utility boiler are also located there, for the same reason.
The heater is also provided with standard burner management controls; these include two flame
sensors, a fire eye and a flame rod. Both must sense loss of flame for a shutdown to occur.
Appropriate purging, lighting, and operating procedures are enforced in order to prevent an
explosion in the firebox. Permanent purge steam supply connections are provided on the firebox
for purging and for extinguishing a fire, should one occur.
3.3.5 Disproportionation (DP) Reactors and Regeneration System
OCU has two Disproportionation (DP) Reactors; normally, one is in service, the other on standby
or in regeneration. Superheated feed vapor flows downward through a DP Reactor at design
conditions up to 437 PSIG and 700 F. Both isomerization and disproportionation occur; the
reactions are at most only slightly exothermic. There is no danger of a runaway reaction, provided
the ethylene concentration in the feed is not too high. While loss of containment would result in a
flammable vapor cloud or a jet fire, there is no likely failure point, such as a shaft seal, in the
system.
A DP Reactor must be regenerated after about a month’s service to burn off coke. After the
fouled reactor is isolated, it is purged and heated to decoking temperature with nitrogen.
Compressed air is added to the nitrogen stream for the decoking step. After another nitrogen
purge, hydrogen is added to reduce and reactivate the catalyst. These treatments are performed
at low pressures (12-45 PSIG) and elevated temperatures (500-1020 F). The regeneration gas is
heated by the Regeneration Heater, a forced-draft fired heater. Safety Instrumented Functions
are used to positively isolate the reactor being regenerated. The decoking offgas is vented to
atmosphere to keep oxygen out of the flare system.
The process hazards at the Regeneration Heater are the same as those at the Reactor Feed
Heater, and the safeguards provided are essentially similar.
Excessive temperatures are unlikely when the DP Reactor is on line, but they could easily occur
during decoking. To prevent such excursions, a SIS monitors the bed temperature at sixteen
locations. On a high-high signal from any two of them, it shuts down the air flow to the
Regeneration Heater’s coils, and the Heater’s main fuel gas supply.
3.3.6 Recovery Section
The Recovery Section consists of two conventional distillation towers. The DP Reactor product is
fed to the Deethylenizer, which recovers ethylene for recycle at design overhead conditions of
353 PSIG and -1.6 F. The tower’s bottoms stream (design 223 F) flows to the Depropylenizer.
This tower produces pure propylene at design overhead conditions of 256 PSIG and 113 F. It
also produces a butenes side stream for recycle, and a bottoms stream (Raffinate III). The
Depropylenizer has a hot gas bypass arrangement instead of conventional overhead condensers,
but this is not a process safety concern.
The principal process hazard is loss of containment. Both towers contain large inventories of light
hydrocarbons. Given the normal operating temperatures, a leak in this area is unlikely to result in
a pool fire, but a large flammable vapor cloud is very possible. All the pumps in the Recovery
Section are provided with remotely-operated suction isolation valves, to limit the volume released

in the event of a seal failure. Each tower is protected by an overhead PSV, and by a SIS that
shuts down steam flow to its reboiler in the event of high-high overhead pressure, power failure, or
condenser coolant failure. The SIS reduces the PSV relief requirement.
3.4 C4 Flare Systems

C4 has two separate flare systems of its own, the High Pressure (HP) Header and the Low
Pressure (LP) Header. Each includes a primary and secondary knock-out drum, a water seal,
and an elevated flare burner. The LP Header serves a few other vessels, but its principal purpose
is to provide a low-pressure relief path for the BD Product Storage Tank, which is rated for only
2.0 PSIG. Vent streams from OCU and various chillers using propylene refrigerant can produce
low temperatures; they are segregated in an extension of BTP’s Dry Flare Header. The HP
Header serves the balance of C4’s flare gas sources.
Pilot failure is not as serious a safety issue at C4 as it is at BTP. C4’s two flare stacks rise 375 ft.
above grade. Unburned gas released at this elevation can be assumed to disperse before it finds
a source of ignition. Nonetheless, C4’s flare pilots are designed for high reliability, for the sake of
minimizing air emissions. C4’s flare tips have three pilots each. Each pilot has a dual retractable
temperature sensor. The pilots are automatically re-lit by integral spark igniters when the sensors
indicate loss of flame. Each flare tip has a common flame-front generator at grade to back up the
spark igniters. The flame-front system is manual.
The HP Flare’s pilot sensors have been damaged and cannot be replaced. One of the LP Flare’s
pilot sensors is out of service. Operations is currently (late 2009) using remote cameras to prove
flame on both flare tips. Better mountings will be installed at the next maintenance turnaround to
make the temperature sensors more maintainable.
Both C4 flare systems are protected from air infiltration and back flashing by standard safeguards:
 A water seal at the base of the flare stack. If the seal is lost, a back-up supply of seal
water, maintained in a separate chamber in the stack, can be dumped to quickly restore
it. Steam spargers are provided in each chamber to prevent the water from freezing. In
addition, a DCS control loop will dump the water in the seal chamber on low temperature
to prevent blocking the relief path with ice. Another DCS loop prevents water from being
added to the seal if the flare gas rate is too high; this condition is sensed indirectly as a
high pressure in the stack above the water seal.
 The header system is continually purged with fuel gas. The purge volume is chosen to
provide a minimum flare gas velocity at the flare burner that will prevent air infiltration
there. A velocity seal at the flare burner reduces the purge volume required.
 The water seal and fuel gas purges maintain the flare header at positive pressure,
preventing air infiltration upstream of the seal. A SIS at the primary knock-out drum will
prevent vacuum conditions in the header by dumping large volumes of fuel or natural gas
into it on a low-low pressure signal.
Liquid discharge from the flare tips should be prevented by the primary and secondary knock-out
drums mentioned above.

4.0 References
4.1 Port Arthur Documents
The Port Arthur Safety Concept consists largely of material collected from the earlier process
design documents listed below. Some of these documents have been copied into the Safety
Concept largely verbatim.
1) “NAFTA Region Olefins Complex – Scope of Work, Sect. 8, Health and Process Safety,” by
ABB Lummus Global, Inc. Rev. 1, dated May 13, 1988. 22 pp.
2) “NROC Project Aromatics Recovery Plant for ABB Lummus Global Inc. -- Basic Engineering
Package,” by Krupp UDHE, dated October 10, 1998. Volume 1 of 5.
3) “Butadiene Extraction Unit – Process Safety Design Considerations,” by ABB Lummus Global,
Inc. Rev. 0, undated. 21 pp.
4) “NROC Safety Systems,” by Johnathan Weatherly, BASF Corp. 2004? 46 pp.
5) “Supervisory Operating Manuals” for various Port Arthur processes. ABB Lummus Global,
various dates.
6) “Process Training Workbooks” for various Port Arthur processes, by TTS, Inc. Various dates.
7) HAZOP review reports in PHAWorks format. Available on the Port Arthur server.
8) BTP and C4 operating procedures. Available on the Port Arthur web site.
9) NROC Supervisory Operating Manual, ABB Lummus Global.
4.2 Olefins Process Safety References

1) Proceedings of the Ethylene Producers’ Conferences, AIChE. Available at
http://epc.omnibooksonline.com/demo.asp
The conferences are annual and usually include a section of papers dealing with process safety
issues in olefins plants. Many of them deal with specific incidents. A few of the more general
papers on the subject include:
2) “An Overview of Olefin Unit Accidents and Safety Lessons Learned” by J.A. Reid. EPC 1999,
Article 65F.
3) “Loss Prevention in a Modern Ethylene Plant” by John Olivo. EPC 1993, Article 15C.
4) “Butadiene Product Stewardship Guidance Manual,” American Chemistry Council, dated March
10, 2002. 72 pp.
4.3 General Process Safety References and Resources

1) Lees’ Loss Prevention in the Process Industries, 3rd ed’n., Elsevier. Available at
www.knovel.com
2) Plant Safety Progress (serial), AIChE.
3) Loss Prevention in the Process Industries (serial).
4) BASF’s NAFTA Information Center, Wyandotte, MI.
5) BASF AG’s SIRiUS data bases. Available on the intranet.

5.0 Block Flow Diagrams
5.1 Ethylene Plant (BTP)

5.2 C4 Complex



PA Site Process Safety Concept

Încărcat de

Informații document

Descriere originală:

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

PA Site Process Safety Concept

Încărcat de

Drepturi de autor:

Formate disponibile

Port Arthur Safety Concept Rev.

PORT ARTHUR SITE

Eric Christman - Petrochemicals Technology Manager

Document Revision Change Table

PA Site Process Safety Concept.doc 1 of 49

PA Site Process Safety Concept.doc 2 of 49

1.0 General Hazards

1.1 Preventing Fires and Explosions

1.1.1 Preventing Leaks and Spills

1.2 Chemical Hazards

2.0 Process Specific Hazards -- BTP

2.1 Hot Section

2.1.1 Feed Preparation

2.2 Cold Section

2.2.1 General Cold Section Hazards

PA Site Process Safety Concept.doc 3 of 49

2.3 Aromatics Recovery Plant (Pygas)

2.4 BTP Flare System

3.0 Process Specific Hazards – C4 Complex

3.1 Butadiene Extraction Unit (BEU)

3.2 Indirect Alkylation Unit (InAlk)

PA Site Process Safety Concept.doc 4 of 49

3.3 Olefins Conversion Unit (OCU)

3.4 C4 Flare Systems

5.0 Block Flow Diagrams

PA Site Process Safety Concept.doc 5 of 49

1.0 General Process Hazards

1.1 Preventing Fires and Explosions

 Preventing leaks and spills.

1.1.1 Preventing Leaks and Spills

1.1.1.1 General Design and Maintenance Practices

Pressure Vessels and Relief

Instruments and Controls

PA Site Process Safety Concept.doc 6 of 49

 Welded piping is used wherever possible to minimize leak points.

1.1.1.2 Pressure Relief

PA Site Process Safety Concept.doc 7 of 49

1.1.1.3 Emergency Isolation

1.1.2 Excluding Air from Process Equipment

 Equipment is properly inerted, or other measures are taken to prevent a flammable

1.1.3 Eliminating Uncontrolled Ignition Sources

PA Site Process Safety Concept.doc 8 of 49

1.1.3.1 Electrostatic energy sources

 All conducting equipment must be properly grounded and/or bonded.

1.1.3.2 Transitory ignition sources

1.2 Chemical Hazards

PA Site Process Safety Concept.doc 9 of 49

1.2.2 Highly Toxic Chemicals

1.2.3 Pyrophoric Materials

 Maintain a nitrogen purge on the filter between steam-out and opening.

PA Site Process Safety Concept.doc 10 of 49

PA Site Process Safety Concept.doc 11 of 49

2.0 Process Specific Hazards -- BTP

2.1 Hot Section

2.1.1 Feed Preparation

2.1.2 Pyrolysis Section (Heaters 0100-1000)

 Low or no flow rate in selected coils.

PA Site Process Safety Concept.doc 12 of 49

 Multiple quench oil pumps will be provided.

PA Site Process Safety Concept.doc 13 of 49

 Prior to light-off fuel gas is isolated via redundant isolation/block valves.

PA Site Process Safety Concept.doc 14 of 49

2.1.3 Gas Fractionation