PNNL 25077rev2

PNNL-25077
Prepared for the U.S. Department of Energy

Under Contract DE-AC05-76RL01830
Hydrotreater/Distillation
Column Hazard Analysis
Report
Rev. 2
April 2016
Hydrotreater/Distillation Column Hazard Analysis Report
Revision Effective Date Description of Change

Number
0 11/2012 Initial issue.
1 12/14/2015 Update to reflect changes in procedures; clarification of HTDC
processes; clarification of controls; BLEVE and PVB
calculations updated.
2 4/8/2016 Update to remove pressure interlocks as critical controls (see
HTDC-2016-023 and HTDC-2016-026); clarification that
attached drawings are subject to change.
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Executive Summary
This project Hazard and Risk Analysis Report contains the results of several hazard analyses and
risk assessments. An initial assessment was conducted in 2012, which included a multi-step
approach ranging from design reviews to a formal What-If hazard analysis. A second What-If
hazard analysis was completed during February 2013 to evaluate the operation of the
hydrotreater/distillation column processes to be installed in a process enclosure within the Process
Development Laboratory West (PDL-West) facility located on the PNNL campus. The
qualitative analysis included participation of project and operations personnel and applicable
subject matter experts. The analysis identified potential hazardous scenarios, each based on an
initiating event coupled with a postulated upset condition. The unmitigated consequences of each
hazardous scenario were generally characterized as a process upset; the exposure of personnel to
steam, vapors or hazardous material; a spray or spill of hazardous material; the creation of a
flammable atmosphere; or an energetic release from a pressure boundary.
In response to independent review comments received by PNNL from PNSO, two supplemental
hazard analyses were conducted and quantitative risk assessments performed for the Distillation
Column and Hydrotreater units in June 2014 and April 2015, respectively (see Appendices D and
E). As described below, selected hazardous scenarios received increased attention:
For scenarios involving a release of hazardous material or energy, controls were identified
in the What-If analysis table that either prevent the occurrence or mitigate the effects of
the release.
For scenarios with significant consequences that could impact personnel outside the
enclosure, critical controls were identified in the What-If analysis table that either
prevent the occurrence or mitigate the effects of the release.
For events requiring critical controls (highly energetic releases and potential
deflagrations), quantitative analyses were performed to determine the potential magnitude
of the scenario, including the potential to affect the environment outside of the PDL-West
facility.
Only for the conservative unmitigated analysis involving a Boiling Liquid Expanding Vapor
Explosion (BLEVE) of the reactor vessel (R-130) could a significant overpressure (greater than
21 kPa) challenging PDL-West facility structure occur. Calculations determined that there were
no cases in which overpressures were sufficient to result in greater than minor damage (7 kPa) at
any of the normally occupied facilities outside of the PDL-West facility.
The following critical controls prevent these high-energy scenarios from occurring:
Vessel and piping design, including pressure relief valves
Hydrogen utility (supply) design
Reactor and distillation column temperature and pressure controls
Enclosure design and ventilation system
Hydrogen and flammable vapor monitors and selected interlocks
Safe Operating Procedures
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The analysis concludes that with the identified hazard controls in place, the risks posed from
operation of the hydrotreater and distillation columns are adequately mitigated, and these systems
can be operated safely, consistent with PNNL control of other laboratory operations.
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Table of Contents
1.0 INTRODUCTION .....................................................................................................................................1
1.1 PURPOSE ........................................................................................................................................................ 1
1.2 SCOPE ............................................................................................................................................................ 1
2.0 FACILITY AND PROCESS DESCRIPTION ..........................................................................................3
2.1 SITE AND FACILITY LAYOUT.......................................................................................................................... 3
2.2 HYDROTREATER/DISTILLATION COLUMN PROCESSES ................................................................................... 5
2.2.1 Hydrotreater Operations Outline ....................................................................................................... 10
2.2.2 Distillation Operations Outline .......................................................................................................... 11
3.0 HAZARD ASSESSMENT ....................................................................................................................... 13
3.1 HAZARD IDENTIFICATION ............................................................................................................................ 13
3.2 WHAT-IF ANALYSIS ..................................................................................................................................... 16
3.3 ANALYSIS RESULTS ..................................................................................................................................... 17
3.4 EVALUATION OF HIGH HAZARD SCENARIOS ................................................................................................ 65
3.4.1 Boiling Liquid Expanding Vapor Explosion (BLEVE) ....................................................................... 65
3.4.1.1 BLEVE Consequence Methodology ............................................................................................................... 65
3.4.1.2 BLEVE Results ............................................................................................................................................... 68
3.4.2 Pressure Vessel Burst Scenarios ........................................................................................................ 71
3.4.2.1 PVB Consequence Methodology .................................................................................................................... 71
3.4.2.2 PVB Results .................................................................................................................................................... 72
3.4.3 Deflagration Scenarios....................................................................................................................... 73
3.4.3.1 Deflagration Consequence Methodology ........................................................................................................ 74
3.4.3.2 Deflagration Results........................................................................................................................................ 74
3.4.4 Calculation Summary ......................................................................................................................... 76
4.0 HAZARD CONTROLS ........................................................................................................................... 78
4.1 CRITICAL CONTROLS ................................................................................................................................... 78
4.1.1 Vessel and Piping Design ................................................................................................................... 79
4.1.2 Reactor and Distillation Column Temperature Critical Controls ...................................................... 80
4.1.3 Enclosure Design and Ventilation ...................................................................................................... 81
4.1.4 Hydrogen Monitors ............................................................................................................................ 81
4.1.5 Flammable Vapor Monitors ............................................................................................................... 81
4.1.6 Safe Operating Procedures (SOPs) .................................................................................................... 81
4.2 OTHER CONTROLS (NON-CRITICAL) ............................................................................................................ 82
4.2.1 Flame Detectors ................................................................................................................................. 82
4.2.2 Fire Suppression System..................................................................................................................... 82
4.2.3 Temperature and Pressure Controls/Alarms Prompting Operator Response .................................... 82
4.2.4 Check Valves ...................................................................................................................................... 83
4.2.5 Facility Configuration ........................................................................................................................ 83
4.3 SAFETY MANAGEMENT PROGRAMS ............................................................................................................. 83
4.3.1 Worker Safety and Health .................................................................................................................. 83
4.3.2 Fire Protection Program .................................................................................................................... 83
4.3.3 Training and Qualification ................................................................................................................. 84
4.3.4 Maintenance and Testing Program .................................................................................................... 84
4.3.4.1 Initial Testing .................................................................................................................................................. 84
4.3.4.2 Maintenance .................................................................................................................................................... 85
5.0 CONCLUSION ........................................................................................................................................ 86

6.0 REFERENCES .............................................................................................................................................. 87
Appendix A : Attendees .................................................................................................................................................................. 88
Appendix B : Key Design Information Reviewed ........................................................................................................................... 90
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Appendix C : November 2012 Hydrotreater / Distillation Column Project Hazard and Risk Analysis Report ............................... 93
Appendix D : Supplemental Hazard Analysis and Risk Assessment Distillation Column .............................................................. 95
Appendix E : Supplemental Hazard Analysis and Risk Assessment - Hydrotreater ......................................................................... 97
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1.0 Introduction
The hydrotreater/distillation column project consists of catalytic hydrotreatment (hydrotreater)

and distillation processes to produce a range of desired petroleum products from fast pyrolysis
bio-oil feedstock. The hydrotreater and distillation processes are being installed in a portion of
the Process Development Laboratory West (PDL-West) facility located on the PNNL Campus.
1.1 Purpose
As part of the PNNL Integrated Safety Management process, the hazards associated with
performing work within PNNL-managed facilities are identified and appropriate controls applied.
The hazards associated with the hydrotreater/distillation column processes have been reviewed
during design review meetings as part of the overall design process. In addition, facilitated
hazard analysis sessions and quantitative risk assessments were performed. The purpose of this
report is to document the hazards and controls associated with the process-related system
components forming the hydrotreater/distillation column processes contained within the PDL-
West facility and the potential interactions of these hazards with respect to supporting systems
and the facility as evaluated during What-If hazard analysis sessions held in February 2013 and
supplemental hazard analyses and risk assessments performed in 2014 and 2015 (Appendices D
and E).
1.2 Scope
The What-If hazard analysis used for the hydrotreater/distillation column project is consistent
with the methodology found in the American Institute of Chemical Engineers (AIChE) Guidelines
for Hazard Evaluation Procedures With Worked Examples, 2nd Edition [AIChE, 1992], and in
Chemical Process Hazards Analysis [DOE-HDBK-1100-2004].
The scope of this assessment did not include evaluating those hazards that were considered
normal and incidental to the operation of the PDL-West facility unless those hazards were judged
to have the potential to challenge the safe operation of the hydrotreater/distillation column
processes. These incidental hazards are adequately addressed through the Integrated Operations
System (IOPS) and existing PNNL work controls.
Examination of the spectrum of potential upset conditions that could expose members of the
public, onsite workers, facility workers, and the environment to hazardous materials and
conditions is incorporated into this report. The hazard evaluation postulated scenarios involving
both single-point/event failures and common-cause initiators. The upset conditions with the
potential to result in highly energetic releases or potential deflagrations were evaluated using
quantitative analysis to determine the potential magnitude of the scenario, including the potential
to affect the environment outside of the PDL-West facility.
Section 2, Facility and Process Description, provides a brief description of the design and
information to enable an understanding of the hazards associated with the hydrotreater/distillation
column processes.
Section 3, Hazard Assessment, provides a summary of the What-If methodology used, description
of the hazardous scenarios considered, and the results of the analysis.
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Section 4, Hazard Controls, describes the critical controls for the high consequence hazards and
PNNL Safety Management Programs which support performing work safely. The critical
controls are those required to prevent or mitigate significant consequences associated with the
hydrotreater and distillation column process hazards. Other non-critical controls were included to
further reduce hazardous event frequencies.
Appendices A and B contain the meeting participant information and design information
reviewed during the hazards analysis meetings. The design documents in Appendix B are
historical and subject to change. See the Hydrotreater/Distillation Column SharePoint site for
current design documents.
Appendix C contains the November 2012 Hydrotreater / Distillation Column Project Hazard and
Risk Analysis Report which described a number of appropriate controls that were, or are being,
put in place to ensure the safe operation of the hydrotreater and distillation processes. The 2012
report will be retained as a static part of this hazard analysis; it will not be revised.
Appendices D and E contains the July 2014 and April 2015 Supplemental Hazard Analysis and
Risk Assessment for the Distillation Column and Hydrotreater units. These reports were
generated in response to independent review comments received by PNNL from the U.S.
Department of Energy Pacific Northwest Site Office (PNSO) with regard to the
Hydrotreater/Distillation Column Hazard Analysis Report issued in April 2013.
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2.0 Facility and Process Description
2.1 Site and Facility Layout
The hydrotreater/distillation column processes will be conducted in the PDL-West high bay work
area in a dedicated process enclosure. The PDL-West building is located on the PNNL site in
north Richland as shown in Figure 2-1.
Approximate distances from the hydrotreater/distillation column process enclosure to key

landmarks are shown in Table 2-1.
Table 2-1. Distance from PDL-West to Surrounding Landmarks

Distance from Process Enclosure
Landmark Direction
feet meters
Process Development Laboratory East* East 116 35
5th Street South 120 37
Innovation Boulevard West 140 43
Chemical Engineering Laboratory East 175 53
Technical Support Warehouse North 290 88
4th Street South 420 128
Research Technology Laboratory South East 730 222
George Washington Way East 790 241
Atmospheric Measurement Laboratory Northwest 825 251
Inhalation Laboratory Northeast 880 268
KinderCare West-Southwest 1120 341
*Nearest normally occupied Facility outside PDL-West, endpoint for the evaluation of impacts in
Section 3.4.
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Figure 2-1. Location of PDL-West (PDLW)
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2.2 Hydrotreater/Distillation Column Processes
The hydrotreater/distillation column project consists of catalytic hydrotreatment (hydrotreater)

and distillation processes to produce a range of desired petroleum products derived from fast
pyrolysis bio-oil feedstock. Figure 2-2 depicts the process flow diagram for the hydrotreater and
distillation processes. The planned operation duration and frequency are 1 week (five, 24-hour
continuous operation days per month). The hydrotreater/distillation systems are located in a
dedicated enclosure as shown in Figure 2-3. Figure 2-4 shows the major hydrotreater process
equipment; Figure 2-5 shows the major distillation process equipment.
Hydrogen is supplied to the hydrotreater by a high pressure compressor, storage bottles (or tube
trailer), and a distribution system. This system will also supply hydrogen to other research
projects located near PDL-West. High and low pressure nitrogen will be supplied via a
distribution system that is dedicated to the hydrotreater/distillation processes.
During hydrotreatment, deoxygenation of bio-oil takes place to produce hydrocarbon products

that are similar to gasoline, diesel and jet fuel blendstock. Hydrotreatment is accomplished by
adding hydrogen as feed along with the bio-oil in the presence of a catalyst. The process is
typically operated at temperatures up to approximately 400C and pressures up to approximately
135 atm. Distillation is then used to obtain the specific gasoline, diesel and jet fuel cuts from the
hydrotreated product.
The hydrotreater consists of a down-flow trickle, fixed bed reactor with gas and liquid feed
systems, liquid/gas product separation and recovery, and an instrumentation/control system. The
system is designed for a 2.5 liter per hour bio-oil feed capacity at 400C and 135 atm with
hydrogen feed at 5 m3/h. In addition, the distillation column will be used to fractionate the
hydrocarbon product into gasoline, diesel, jet fuel, and cycle oil products. The distillation column
can be, but is not planned to be, operated concurrent with the hydrotreater and is designed with a
throughput of 7.515 liters of feed per hour. Both the hydrotreater and the distillation column are
skid mounted with power distribution systems, transformers, outlets, wiring, panels, cooling,
heating, control, and other ancillary process systems.
To support the hazards analysis, the key process steps for the hydrotreater/distillation operations
were outlined and reviewed for in Section 2.2.1 and 2.2.2.
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Figure 2-2. Hydrotreater/Distillation Process Flow Diagram
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Figure 2-3. Location of Hydrotreater/Distillation Enclosure within PDL-West

(from CTI-12-631)
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Figure 2-4. Hydrotreater Process Major Components
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Figure 2-5. Distillation Process Major Components
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2.2.1 Hydrotreater Operations Outline

Prestart Operations
1) Install reactor
2) Chain out inter-skid area prior to working on upper head.
3) Load catalyst
4) Seal reactor
5) Pre-op valve position check for entire system
6) Connect bio-oil tank
7) Pressure check system
8) Put valves to flow positions
9) Transfer bio-oil to feed tank
Startup/Sulfiding
1) Clear area of all maintenance work and equipment not compatible with Class 1 Div 2
environment
2) Initiate purge of electrical cabinets and furnace.
3) Put sulfiding tank in place
4) Direct product valves to slop tank
5) Fill pumps with sulfiding solution
6) Pressurize reactor to operating pressure
7) Flow hydrogen at sulfiding flowrate and verify offgas handling system flow
8) Bring reactor to sulfiding temperature
9) Begin sulfiding flow
10) Ramp temperature through sulfiding procedure
11) Block out and remove sulfiding tank
Bio-oil feeding
1) Adjust hydrogen flow and temperature to operating conditions
2) Fill pumps with bio-oil from feed tank
3) Start bio-oil supply drum recirculation/take-up loop
4) Direct product valves to L/L separator and A or B product tanks
5) Start bio-oil feed at ~30% of target flowrate
6) Allow system to equilibrate
7) Gradually bring reactor to target flowrate
Operation
1) Monitor feed and product levels
2) When product drums are at 85 to 90% full, switch to other product tanks
3) Download water vessel to product container
4) Download oil vessel to product container or transfer to still skid feed tank
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Transfer to still feed tank

1) Pad oil product container
2) Depad still feed tank
3) Connect transfer line
4) Open transfer valves
5) When empty, close transfer valves
6) Pad still tank
7) Depad product container
8) Remove transfer line
Shutdown
1) Stop oil feed and turn off reactor heaters.
2) Continue product vessel monitoring per operation section
3) Empty pumps back to bio-oil feed tank
4) Reduce gas flow once product collection has diminished
5) Allow reactor to cool
Flush
1) Reactor should be around 150C or lower for this procedure
2) Load acetone into pumps via transfer tank
3) Direct product valves to slop tank
4) Inject acetone into reactor
5) Shut down feed system and allow reactor to cool below 100C
6) Halt gas flow and depressurize reactor
7) Flush with N2
8) Verify that all systems are off
Refit
1) Depressurize and verify zero energy state on all hydrotreater subsystems
2) Chain out inter-skid area prior to working on upper head
3) Open upper reactor head.
4) Remove catalyst
2.2.2 Distillation Operations Outline

Prestart Operations
1) Seal process tanks
2) Pre-op valve position check for entire system
3) Pressure check system (purge and pad all subsystems)
4) Transfer feed to tank via hydrotreater skid or transfer tank using tank pads
5) Alternately, feed can be loaded into one of the bottoms product tanks and padded over
6) Put valves to flow positions, including bottoms and distillate product tanks
7) Prime feed pump and turn to auto control
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Startup
1) Clear area of all maintenance work and equipment not compatible with Class 1 Div 2
environment
2) Initiate purge of electrical cabinets and furnace
3) Turn on coolant to HX and to bottoms pump
4) Turn on nitrogen purge to heatup setpoint and set system backpressure
5) Engage feed pump and set backpressure loop
6) Fill still bottom to submerge heater elements via feed control badger and/or bypass.
7) Turn on still heater and external jacket heater
8) As liquid level drops in still, set feed badger to maintain liquid height in still
Reflux
1) Observe reflux in sight glass via level sensor
2) Once distillate reaches 8 inches, engage reflux pump (P-183) and set backpressure loop
3) Prime reflux pump
4) Set reflux badger to target kg/hr
5) Set product badger to target liquid level in sight glass
6) Reduce nitrogen flow to target setpoint and adjust system backpressure
Full operation
1) Set feed rate badger to target feed rate
2) Turn on and prime bottoms level control pump to target setpoint
3) Monitor liquid level on bottoms and distillate tanks, and switch to alternate tank when full
4) Monitor feed tank level
Shutdown
1) Turn off still heater and jacket.
2) Halt feed pump and set feed badger to zero
3) Close reflux badger.
4) Set reflux level control to zero to drain reflux glass into distillate product
5) Turn off reflux pump after low level indicator
6) Set bottoms level control to zero
7) Turn off bottoms level pump after low level indictor
8) Turn on nitrogen sweep to low level
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3.0 HAZARD ASSESSMENT
A series of facilitated hazards analysis sessions were conducted in February 2013. These hazard
analysis sessions built upon the previous hazards analysis documented in the November 2012
Hydrotreater / Distillation Column Project Hazard and Risk Analysis Report. The scope of the
February assessment was focused on the operations and hazards associated with the process-
related system components forming the hydrotreater/distillation column processes located within
the PDL-West facility and the potential interactions of these hazards with respect to supporting
systems and the facility. The PNNL team assembled for the hazards analysis sessions included
Engineering (F&O and Project); R&D operations and engineering; Fire Protection; Pressure
Systems; Environmental, Safety and Health; and hazard and safety analysts. PNSO observers
also attended. Appendix A lists the attendees at the hazards analysis sessions. (Note: not all
attendees listed were present for the entire duration; however, a core team representing design,
operations, fire protection, pressure systems, and hazard and safety analysis was always present.)
The following sections provide a brief description of hazard evaluations performed and results of
the evaluations.
3.1 Hazard Identification
The first step of the hazard analysis process was to identify the form, quantities, and
characteristics of hazards, including chemicals associated with the major process components
(Hazard Identification). This allowed the screening of hazards considered as normal laboratory
practices or activities incidental to the operation of the facility to be addressed through IOPS and
existing PNNL work controls. For the hydrotreater/distillation column processes, significant
hazards requiring further evaluation via the hazards analysis process included high pressure
processes and the presence of flammable and combustible liquids and gases. Table 3-1 identifies
the product of the hazard identification process.
Regulatory provisions of 40 CFR 355, 29 CFR 1910.119, and 40 CFR 68 provide guidance
relative to screening chemical hazards based on quantities and the potential consequences they
represent to workers and the public. As shown in Table 3-2, these threshold values are many
times greater in magnitude than those of the process chemicals and products common to the
hydrotreater/distillation column processes.
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Table 3-1. Hydrotreater Hazard Identification Checklist
Component Inventory Vessel Operating

Volume Pressure
Liter (1) psig
Supply Drum Bio-Oil 55 gal Atm
V-120 Bio-Oil (filtered) 72 10
V-125 Di-tert-butyl disulfide / 20 10
Acetone
R-130 Treated Bio-Oil 26 2100
Hydrogen
V-140/LG-142 Treated Bio-Oil 6 2100
Hydrogen
LG-147 Treated Bio-Oil 4 (2) Atm
V-160A/B Treated Bio-Oil 20 10
V-161A/B Process Water 20 10
V-162 Slop Bio-oil 38(3) 10
V-163 Process Water 38(3) 10
V-180 Treated Bio-Oil 140(4) 10
Light Product (recycle)
Bottoms Product (recycle)
V-184 Treated Bio-Oil 16(4) 15
Light Product (recycle)
Bottoms Product (recycle)
V-191 Light Distillates (e.g. 72 10
(V-193) naphtha, gasoline, jet)
V-192 Bottoms Product (e.g., 72 10
(V-194) diesel, cycle oil)
1/4"-T035-316 High Pressure (3000 psi) - 2500
Hydrogen
1/4"-T035-316 Low Pressure (100 psi) - 100
1/2-T035-316 Nitrogen
1/4"-T035-316 High Pressure (3000 psi) - 2500
Nitrogen
(1) From CTI 12-631, unless otherwise noted.
(2) Project Drawing-782-4-140
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Table 3-2. Comparison of Chemicals to Screening Thresholds
Material 40 CFR 355 29 CFR 1910.119 40 CFR 68

Bio-Oil Not Listed Not Listed Not Listed
Treated Bio-Oil(a) Not Listed Not Listed Not Listed
Light Distillate Not Listed 10,000 lbs Not Listed
-naphtha (flammable
-gasoline liquids)
-jet fuel
Bottoms Product Not Listed Not Listed Not Listed
-diesel (combustible
-cycle oil liquids)
Nitrogen Not Listed Not Listed Not Listed
(Compressed Gas)
Hydrogen (Gas) Not Listed 10,000 lbs 10,000 lbs
(flammable gas) (flammable
gas)
Acetone Not Listed Not Listed Not Listed
Di-tert-butyl Not Listed Not Listed Not Listed
disulfide
Hydrogen 100/500 lbs (c) 1500 lbs 10,000 lbs
(b)
Sulfide
(a) Assumed to be bio-diesel, http://www.apexoil.com/msdsbio.pdf
(b) Byproduct of hydrotreatment and sulfiding process
(c) Reportable quantity/planning threshold quantity
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3.2 What-If Analysis
The What-If analysis technique is a structured brainstorming method of determining potential

undesired events (what things can go wrong). The answers to these what-if questions form the
basis for making judgments regarding the acceptability of the controls that prevent or mitigate
hazardous conditions and determining a recommended course of action for events requiring
further consideration. The What-If concept encourages the team to think of potential upsets or
deviations based on initiating questions generally beginning with What if.
As noted in Section 3.0, facilitated hazards analysis sessions were held in February 2013
following incorporation of design changes resulting from review comments and actions from the
hazards analysis documented in the November 2012 Hydrotreater / Distillation Column Project
Hazard and Risk Analysis Report. The What-If sessions were held in two blocks of time; a four-
day session covering the hydrotreater process and supporting systems followed by a two-day
session to cover the distillation column process and interface with PDL-West facility systems.
Involvement by the participants was outstanding, particularly the operations team which had
recently returned from the Factory Acceptance Testing held at the vendors facilities.
The What-If analysis was structured around the process steps of hydrotreater and distillation
operations as outlined in Sections 2.1.1 and 2.1.2. The scope of the hazards analysis focused on
the process systems and potential for adverse interactions to the process from upsets in the
supporting utilities. For the hydrotreater and distillation column processes, a selected operator
presented the key process steps in his/her area of expertise followed by a series of What-If
questions posed for each step. The What-If team leveraged the operators recent test experience
to gain insight on the operation of the systems under postulated off-normal or upset conditions.
The process and utility drawings reviewed included redline drawings from the factory acceptance
test, as appropriate, to reflect the most current state of the design and are identified in Appendix
B, Key Design Information Reviewed. 1
As part of the What-If analysis, a qualitative likelihood was assigned to all unmitigated hazardous
scenarios. This reflected the teams estimation regarding the likelihood of an initiating event
coupled with a postulated upset condition, absent of the preventive or mitigative effects of hazard
controls (i.e., unmitigated). The basis for the likelihood of a given hazardous scenario was the
number and types of operational failures needed to result in the identified potential upset
condition (Table 3-3).
Each hazardous scenario was further defined by qualitative evaluations of the potential
unmitigated consequences such as: process upset; exposure of personnel to steam, vapors or
asphyxiant; spray or spill of flammable material; creation of a flammable atmosphere; or
energetic release events from a vessel pressure boundary (boiling liquid expanding vapor
explosion [BLEVE] or pressure vessel burst [PVB]). It was clarified that the unmitigated
consequences identified during the analysis were not sure to occur even under the failures
postulated; rather the consequences identified represent the bounding case outcomes in most
instances, rather than a less significant expected outcome.
1
These design documents are historical and subject to change. See the Hydrotreater/Distillation Column SharePoint
site for current design documents.
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Table 3-3. Likelihoods Used for the Hydrotreater/Distillation Column What-If Analysis
Likelihood Qualitative Evaluation Criteria
Likely Failure of a single process control, failure of active

components or support systems (e.g., power), or
administrative steps
Unlikely Conditions involving failure of two or more of the above,
mechanical failures of active systems (e.g., pump/motor
failures)
Very Multiple failures (more than 2), failures of robust passive
Unlikely systems
Extremely Many concurrent, independent failures
Unlikely
3.3 Analysis Results
The results of the What-If analysis are provided in Table 3-4. For all releases of hazardous
material or energy, controls were identified to prevent the occurrence or mitigate the effects of the
release (Table 3-4). Footnotes have been added to Table 3-4 to provide addendum information
pertinent to the analysis.
Approximately 66 highly energetic releases (33) BLEVE and PVB and (33) potential
deflagrations were identified. For these events, additional analysis was performed (Section 3.3)
to determine the potential magnitude of the impacts from the event to receptor locations within
and outside of the PDL-West building for bounding scenarios of each type. The critical controls
credited to mitigate the likelihood or consequences of these events are identified in the hazard
analysis tables and summarized in Chapter 4.0.
One action affecting control selection was identified during the What-If analysis for scenarios
H.2-17 and H.6-1. This action replaces the T upstream of HV-2009/2006 with HV-2018, a
3 way valve (e.g., Swagelock SS-H83PS8) to provide positive isolation from potential reactor
backpressure during pump flushing operations.
No other control-affecting actions were identified or required to assure adequate protection

against the release of hazardous material or energy during the What-If analysis sessions. In some
cases, the What-If team identified suggestions to improve the design and operational processes.
These suggestions were captured for consideration by project management.
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Table 3-4. What-If Hazards Analysis Results
Hydrotreater Process Step 1. Prestart Operations
1) Install reactor. 2) Chain out inter-skid area prior to working on upper head. 3) Load catalyst. 4) Seal reactor. 5) Pre-op valve position check for entire system. 6) Connect bio-oil tank.
7) Pressure check system. 8) Put valves to flow positions. 9) Transfer bio-oil to feed tank.
Hazard
ID/
Likeli- Hazard Controls
Process What if: Hazardous Scenario Consequences Comments
hood C = Critical Control
Step
H.1- 1 What if we drop or impact Damage reactor Likely Process upset. During Lift Procedure and engineered lift
1 the reactor? thermocouple from sulfiding or operating steps. points on vessel.
dropping reactor or running Pressure Test Procedure on
it into object results in loss (also see heater/thermocouple startup.
of thermocouple events in subsequent process Instrument test Procedure
functionality steps) Interlocks on thermocouple.
H.1- What if we impact another Damage to furnace or Likely Short circuit of heater leads to Lift Procedure and engineered lift
2 1 piece of equipment or furnace door due to impact high temperature in reactor points on vessel.
piping? (for instance reactor vessel) during sulfiding operations Heater circuits are fused
results in short circuit of and potential energetic event (protection against short circuit)
heater or damage to furnace due to pressure boundary Pressure indication (alarm) on
door and it might not shut failure. (see subsequent events furnace Z purge.
properly. e.g., H.2-3, H.2-20)
Loss of purge operations,

during sulfiding or operating
steps, leads to potential
ignitions of flammable gases
in reactor furnace- requires
concurrent failure in pressure
boundary. (see subsequent
events e.g., H.2-3)
H.1- 3 What if you improperly Failure to properly prepare Likely Process upset during sulfiding Pressure Test Procedure.
3 load the column? the column before adding or operating steps. High Pressure Nitrogen Supply
catalyst. (Forgetting the set @ 3000 psi.
screen would result in the Plugging the reactor flow path High Pressure Nitrogen System
catalyst running down exit and/or plug filter (F-4019) set @ 2500 psi.
hole and plugging up the 90 downstream of separator with
degree bend.) pressurization of the reactor.
Page 18 of 98
Hazard
ID/
Step
H.1- 3 What if you use the wrong Failure to select the right Likely Process upset during sulfiding Startup operating procedure Pyrophoric catalysts are not
4 catalyst? catalyst (matched to or operating steps. gradual start up. currently proposed.
sulfiding agent and bio-oil, Pre-testing/qualification
operating conditions). Potential plugging of the (benchtop) of new catalyst-
reactor flowpath (due to heavy sulfiding combinations for use
oils) with pressurization of the with bio-oils.
reactor. If left for long period
potential complete blockage
See H.4-6
H.1- 3 What if you introduce Introduction of wrong Unlikely Process upset during sulfiding Startup operating procedure
5 wrong material? catalyst results in failure to or operating steps. gradual start up.
produce quality product. Pressure monitoring.
Potential plugging of the
reactor flowpath (due to heavy
oils) with pressurization of the
See H.4-6
H.1- 3 What if you dont put Failure to add sufficient Likely Process upset during sulfiding Startup operating procedure Cannot overfill with catalyst
6 enough catalyst into catalyst results in failure to or operating steps. gradual start up. and still close reactor head.
reactor? produce quality product. Procedural- Keep track of volume
Potential plugging of the of catalyst added.
reactor flowpath (due to heavy Pressure monitoring.
oils) with pressurization of the
See H.4-6
H.1- 4 What if there is failure to Failure to properly re- Likely Exposure of personnel. Assembly Procedures.
7 properly reassemble assemble reactor Pressure Test Procedure.
reactor components (e.g., forget to Release of nitrogen into Low pressure alarms.
seals/flanges/piping install VCR nickel gaskets). enclosure during pressure
connections? testing.
Page 19 of 98
Hazard
ID/
Step
H.1- 4 What if there is failure to Failure to properly re- Unlikely Flammable atmosphere, Pressure Test Procedure. C High pressure spray of (jet
8 properly reassemble assemble reactor during subsequent operations. (detection of no pressure on flame) of combustible liquid
reactor seals, flanges, components (e.g., forget to system components) and potential creation of
piping connections? install VCR nickel gaskets) Leak of hydrogen/bio-oil or Hydrogen monitors on skid and C flammable atmosphere may
results in subsequent leak at sulfiding agent /steam into in enclosure. be mitigated by steam.
operating temperature and enclosure. Enclosure Design Class 1 C
pressure. Division 2.
Enclosure Ventilation System. C
Flammable vapor monitor on C
skid.
Low pressure alarm - R-130.
H1- 5 What if valve is left open? Failure to close valve (vent Likely Process Upset. Fail pressure Valve lineup procedure.
9 valve) results in inability to test (vent valve) release of
pressurize system nitrogen into vent system. Pressure Test Procedure.
H.1- 5 What if valve is left open? Failure to close valve (drain Very Exposure of personnel. Valve lineup procedure.
10 valve) resulting in nitrogen Unlikely Creation of oxygen deficient Pressure Test Procedure.
released into enclosure atmosphere with personnel Enclosure Ventilation System -
present. operable when system is
pressurized.
H.1- 5 What if valve is left open? Failure to close process Likely Energetic event - over Valve lineup procedure. Relief valves have been
11 valve results in pressurization of low pressure Pressure Relief valves on low C sized for this scenario.
pressurization portions of system (LG-147/Vent line). pressure system components.
system not designed for This would require two
high pressure. valves to be misaligned.
H.1- 5 What if fail to pressure Inadequate pressure check, Unlikely Flammable atmosphere, Pressure Test Procedure. C High pressure spray of (jet
12 check part of system due combined with pre-existing during subsequent operations (detection of no pressure on flame) of combustible liquid
to valve misalignment? leak or failure to re- Release of hydrogen/bio-oil or system components) and potential creation of
assemble properly results in sulfiding agent/steam into Hydrogen monitors on skid and C flammable atmosphere may
leak at operating enclosure. in enclosure. be mitigated by steam.
temperature and pressure. Enclosure Design Class 1 C
Division 2.
Flammable vapor monitor on C
skid.
Low pressure alarm - R-130.
Page 20 of 98
Hazard
ID/
Step
H.1- 6 What if failed to connect Failure to connect return Likely Spray/Spill. Procedural check.
13 return line to drum? line to feed drum results in Spill of Bio-Oil into Secondary containment on the
release of Bio-oil. enclosure. Cleanup. drum.
H.1- 7 What if fail to do the Failure to perform pressure Likely Flammable atmosphere, Hydrogen monitors on skid and C
14 pressure test? check, combined with pre- during subsequent operations. in enclosure.
existing leak or failure to re- Leak of hydrogen/bio-oil or Enclosure Design Class 1 C
assemble properly results in sulfiding agent /steam into Division 2.
leak at operating enclosure. Enclosure Ventilation System. C
temperature and pressure. Flammable vapor monitor on C
High pressure spray of (jet skid.
flame) of combustible liquid Low pressure alarm - R-130.
and potential creation of
flammable atmosphere
mitigated by steam.
H.1- 7 What if too high pressure Over pressurization of low Unlikely Energetic event - over- Pressure regulation of the low
15 for low pressure system? pressure system pressurization of low pressure pressure nitrogen supply to 100
components due to system (>100 psi) psi.
excessive nitrogen pressure Pressure regulation of the low
pressure nitrogen system pressure
to 10 psi.
Low pressure component PRVs C
set at 100 psi.
Pressure Test Procedure.
H.1- 7 What if too high pressure Over pressurization of high Unlikely Energetic event - over- Pressure regulation of the high
16 for high pressure system? pressure system pressurization of high pressure pressure nitrogen supply to 3000
components due to system (>3000 psi) psi.
excessive nitrogen pressure. Pressure regulation of high
set at 2500 psi.
High pressure component PRVs C
set at 3000 psi.
High pressure vessel and C
component design pressure
3000 psi.
High pressure alarms.
High pressure interlocks.
Page 21 of 98
Hazard
ID/
Step
H.1- 7 What if you inadvertently Failure to use correct gas Unlikely Flammable atmosphere. Pressure Test Procedure. C
17 use Hydrogen instead of for pressure check Hydrogen buildup and Valve and line labeling.
nitrogen for leak check? (combined with pre-existing deflagration in Enclosure Hydrogen monitor on skid and in C
leak or failure to re- enclosure.
assemble properly) results Enclosure Ventilation System C
in potential flammable operable prior to pressurizing the
atmosphere in the enclosure system
with a piece of equipment
not qualified for the
hydrogen atmosphere.
H.1- What if you inadvertently Failure to use correct gas Likely Energetic event - Deflagration Pressure Test Procedure. C Lack of ignition source
18 7 use Hydrogen instead of for pressure check results in in reactor column. Valves and Line labeling. unless we are reusing the
nitrogen for leak check? Hydrogen/Air atmosphere catalyst. If we are reusing
in the reactor system, column, it is kept at
potential ignition of pressure. There is no
flammable atmosphere in oxygen.
the system at a transition
point .
H.1- 8 What if there is failure to Failure to correctly align Likely Energetic event during Design of R-130/V-140 and C
19 line up properly for system for operations after subsequent operations. component pressure 3000 psi
operations? pressure test results in Deadhead within system with MAWP.
blocked flow within the potential failure of pressure R-130/V-140 PRVs set at 3000 C
system up to liquid boundary due to high pressure psi.
separator. in V-140 and reactor. Pressure regulation of the
hydrogen supply to 3000 psi.
Pressure regulation of hydrogen
system pressure set at 2500 psi.
High pressure alarm in R-130.
High-high pressure interlock in
R-130
H.1- 8 What if an already closed Inadvertent opening of Unlikely Exposure to personnel. Procedural Step.
20 valve is inadvertently (drain/manual transfer) Potential for nitrogen release Drains are double valved, valved
opened? valve results in venting to into enclosure or vent. and capped, or valve and quick
enclosure or header disconnect.
Page 22 of 98
Hazard
ID/
Step
H.1- 8 What if failure to reopen a Failure to open vent Likely Energetic event. Deadhead Procedural Step.
21 valve on the low pressure isolation valve in low within system, during PRVs on low pressure vessels. C
tanks? pressure system results in subsequent operations. High
blocked flow within the pressure in vessels.
system during sulfiding or
operations.
H.1- 9 What if we transfer bio-oil Transfer of bio-oil to V-120 Likely Spray or spill. Release of bio- Pump can only achieve maximum System designed for
22 too fast or at too high of at greater than expected oil into enclosure (also see supplied air pressure. maximum flow from pump
pressure? pressure or flow results in l H.1.24). Air system pressure set at at maximum air supply
system breach nominally 100 psi (normal pressure.
Filter breakthrough. (See operating pressure is 80 psi).
H.1.27). Filters are rated at 250psi.
V-120 rated at 135psi. PRV set
at 70. 3/4 inch stainless steel
transfer line is rated at >3000psi.
H.1- 9 What if there is transfer Failure to stop transfer Likely Spray or spill. Overfill V-120 V-120 level indicator.
23 too much bio-oil (over results in over fill of V-120. resulting in release of bio-oil V-120 high-high level interlocks.
fill)? into the vent system. - Interlock to pump (automatic
mode).
- Procedure, manual transfer
mode.
H.1- 9 What if there is a leak in Leak in transfer line results Likely Spray or spill. Release of bio- Filtered oil (feed line) SS This portion is not pressure
24 the bio-oil line? in spill /spray to enclosure. oil into enclosure. tubing. checked every time.
Secondary containment provided
by enclosure.
H.1- 9 What if the filters Plug? Potential plug leading to Likely Spray or spill. Release of bio- Round sanitary clamp. Filter is
25 high pressure in transfer oil into enclosure (also see open at both ends. Use second
line from drum to V-120. H.1.24). filter. The bypass allows you to
go to second filter. These will be
Filter breakthrough (See changed every week.
H.1.27).
H.1- 9 What if air gets in the Air in reactor Likely Process Upset. Unable to Low level control in V-120 and Filters would most likely
26 system? Is bio-oil foam a pump. interlocks associated with it. break up foam.
hazard? ISCO pump shutoff due to
insufficient liquid refill.
Page 23 of 98
Hazard
ID/
Step
H.1- 9 What if you don't filter? Filter by-passed or breeched Likely Process Upset. R-130 is Procedural control on use of
27 results in unfiltered bio-oil designed to handle solids so bypass.
to V-120, results in the no direct hazard to process.
potential plugging of the
plugging the ISCO injector
or slow plugging of catalyst ISCO ejector plugging would ISCO Pump high pressure set
bed during subsequent lead to loss feed (Process point (process controlled).
operations. upset) a pump is design for ISCO Pump firmware maximum
full pressure. pressure of 3750psi.
ISCO Pump shear pin at 4500 psi.
For potential plug in R-130

See H.4-6
H.1- 9 What if there is a failure Failure of V-120 results in Very Spray or spill/Exposure of Design V-120 135 psi MAWP.
28 in the pressure boundary leak of bio-oil to the Unlikely personnel.
(V-120)? enclosure. Bio-Oil on Floor also release
of nitrogen to enclosure
nitrogen.
Hydrotreater Process Step 2. Startup/Sulfiding

1) Clear area of all maintenance work and equipment not compatible with Class 1 Div 2 environment. 2) Initiate purge of electrical cabinets and furnace. 3) Put sulfiding tank in place. 4)
Direct product valves to slop tank. 5) Fill pumps with sulfiding solution. 6) Pressurize reactor to operating pressure. 7) Flow hydrogen at sulfiding flowrate and verify offgas handling
system flow. 8) Bring reactor to sulfiding temperature. 9) Begin sulfiding flow. 10) Ramp temperature through sulfiding procedure. 11) Block out and remove sulfiding tank.
Hazard ID/
Process Step Likeli- Hazard Controls
What if: Hazardous Scenario Consequences Comments
H.2-1 1 What if you leave non- Presence of non-Class 1 Likely Flammable atmosphere. Pressure Test Procedure.
Class 1 Div 2 Division 2 equipment Potential ignition of a Enclosure Ventilation System. C
equipment in presents a potential for a flammable vapor given leak Hydrogen monitors on skid and C
environment subsequent ignition sufficient to result in a in enclosure.
source, given a like in the flammable atmosphere. Flammable vapor monitor on C
process boundary skid.
Page 24 of 98
Hazard ID/
Process Step What if: Hazardous Scenario Consequences Comments
H.2-2 1 What if non Class 1 Introduction of non-Class Likely Flammable atmosphere. Pressure Test Procedure.
Div 2 equipment is 1 Division 2 equipment Potential ignition of a Enclosure Ventilation System C
brought into the presents a potential for a flammable vapor given leak Hydrogen monitors on skid and C
enclosure during subsequent ignition sufficient to result in a in enclosure.
operations. source, given a like in the flammable atmosphere. Limit access to trained operators.
process boundary Procedural steps in place during
operations. Limit what you can
take into the enclosure during the
operation [use of anti-sparking
tools].
H.2-3 2 What if there is failure Failure to initiate purge Likely Flammable atmosphere. Procedural step initiate purge
to initiate purge of results in the potential for Potential ignition of a Pressure monitoring and alarms
electrical cabinets and a flammable atmosphere, flammable vapor given leak on cabinets and furnace
furnace? given a leak in the process sufficient to result in a enclosure.
boundary, to reach flammable atmosphere. Enclosure Ventilation System C
ignition sources within the Hydrogen monitors on skid and C
cabinets. in enclosure.
Flammable vapor monitors on C
skids.
H.2-4 3 What if the sulfiding Failure to connect V-125 Likely Process upset. Failure to Procedural step
tank is not put in to process results in not activate catalyst.
place? adding sulfiding agent to
the catalyst.
H.2-5 3 What if it is other than Failure to correctly put Likely Process upset. Failure to Procedural step
sulfiding agent? sulfiding agent in V-125 activate catalyst.
results in the failure to
activate the catalyst.
H.2-6 4 What if the product Failure to align valves Likely Process upset. Sulfiding Procedural step
valves are not aligned properly results in solution directed into the
to slop tank? misdirection of sulfiding product tank instead of slop
solutions. tank.
Page 25 of 98
Hazard ID/
H.2-7 5 What if there is too Failure to set low pressure Likely Energetic event - failure of V- Pressure regulation of the low
much pressure to V- nitrogen pad pressure 125 vessel pressure boundary. pressure nitrogen supply to 100
125 from nitrogen correctly results in psi.
pad? overpressurizing V-125 Flammable atmosphere. Pressure regulation of the low
with up to 100 psi of Spill of combustible liquid and pressure nitrogen system pressure
nitrogen. potential creation of flammable to 10 psi.
atmosphere. Design V-125 155 psi MAWP C
V-125 PRV set at 100 psi. C
H.2-8 5 What if there is failure Failure to connect vent Likely Spill of sulfiding solution to Procedural step. Connect the
to connect vent line V- line to header results in the enclosure. vent line prior to the nitrogen and
125 to rupture disk? venting of V-125 contents outlet.
to enclosure on system
overpressure/failure of
rupture disk and release of
sulfiding solution
/nitrogen to enclosure
atmosphere.
H.2-9 6 What if there is failure Failure to pressurize the Unlikely See other pressure boundary Low pressure alarms, procedural
to verify pressure and reactor with nitrogen prior scenarios. steps.
there is low pressure? to starting flow of
hydrogen results in In no leak, the hydrogen would
undetected leak or pressurize the reactor on
unintended flow path. system startup.
H.2- 6 What if there is over Failure to set hydrogen Unlikely Energetic event - over- Design of R-130/V-140 and C
10 pressurize the system? pressure correctly results pressurization of R-130/V-140 component pressure 3000 psi
in filling reactor with piping pressure boundary MAWP.
3000 psi hydrogen. R-130/V-140 PRVs set at 3000 C
psi.
Pressure regulation of the
hydrogen supply to 3000 psi.
Pressure regulation of hydrogen
system pressure set at 2500 psi.
High pressure alarm in R-130.
High-high pressure interlock in
R-130
Page 26 of 98
Hazard ID/
Procedural step for pressure set
point.
Procedural step to verify the off
gas flow
H.2- 8 What if the furnace Furnace controller fails Likely None identified. Limited by design of heater such The heatup rate is less than
11 controller fails high high resulting in too fast that the worst case is that you 5 degrees C per minute.
resulting in too fast heatup with potential heat up in allowable range.
heatup? impact to catalyst.
H.2- 8 What if the catalyst is Failure to stop heating the Likely Process upset to the catalyst. Procedural step to monitor
12 heated above desired reactor at desired temperature.
sulfiding temperature? temperature results in start
of sulfiding with catalyst
at higher than desired
temperature.
H.2- 8 What if there is failure Failure to heat the reactor Likely Process upset to the catalyst. Procedural step to monitor
13 to heat system up to to desired sulfiding temperature.
desired sulfiding temperature results in start
temperature? of sulfiding too early with
reactor at lower than
desired temperature.
H.2- 9 What if flow rate of Failure to properly Likely Process upset to the catalyst. Process monitoring. Flow rate is limited by the
14 sulfide is wrong? transfer (flowrate) of the pump to 400 ml / min. which
sulfiding solutions results would only last 2.5 minutes
in incomplete activation of
catalyst.
H.2- 9 What if valve HV - Failure to open HV-2006 Likely Spray or Spill. High pressure Transfer Line (tubing) is rated at
15 2006 is closed? results in deadheading the spray of sulfiding solution. 4800 psi.
flow with over- Pressure Indicator PI-2011
pressurization of the ISCO Pump high pressure set
transfer line (pump point (process controlled).
pressure 4500 psi) ISCO Pump firmware maximum
resulting in leak. pressure of 3750psi.
ISCO Pump shear pin at 4500 psi
H.2- 9 What if there is a Failure in the pressure Very Spray or leak of sulfiding Pressure Test Procedure.
16 failure in the pressure boundary results in spray Unlikely solution to the enclosure Design of V-125 and transfer line
boundary? or leak of sulfiding components.
solution to the enclosure.
Page 27 of 98
Hazard ID/
H.2- 9 What if the drain valve Failure to Close HV-2009 Unlikely Spray or leak of sulfiding HV-2018 Action: Replace T
17 HV-2009 is open? results in spray or leak of solution to the enclosure upstream HV-2009 with 3-way
sulfiding solution to the Valve.
enclosure
Procedural check that drain valve
is closed and plugged.
H.2- 10 What if the furnace Failure of the furnace Likely Process upset. H2S evolution Limited by design of heater such
18 controller fails high controller (high) resulting at higher than expected rate. that the worst case is that you
resulting in too fast in too fast heatup to heat up in allowable range.
heatup. reactor during sulfiding.
H2S monitor on vent stack.
H.2- 10 What if the catalyst is Failure of the furnace Likely Process upset to the catalyst. Procedural step to monitor
19 heated above 400C controller (high) resulting temperature.
in sulfiding with reactor at
higher than desired
temperature (400C).
H.2- 10 What if the reactor is Failure of the furnace Likely Energetic event- failure of Software prevents operator from
20 heated over 450C? controller (high) resulting reactor pressure boundary changing settings above
in failure of reactor maximum set point of 425C.
pressure boundary There is an internal thermocouple
(>450C). interlocked to furnace control.
Cascade furnace control
R-130 High High temperature. C
Design of R-130, 3000 psi C
MAWP at 537C (shell).
H.2- 10 What if operator fails Start sulfiding too early Likely Process upset to the catalyst. Procedural step to monitor
21 to heat system up to with reactor not at desired temperature.
400C? temperature.
H.2- 11 What if there is failure Failure to isolate the Likely Spray or Spill. Pressurized Procedural step. Disconnect vent
22 to isolate the sulfiding sulfide tank (V-125) spray of sulfiding solution. last. Quick disconnects are
tank before you results in opening Potential for oxygen deficient closed on both sides except for
disconnect it? disconnects on tank while atmosphere. vessel vent. Pressure boundary
pressurized results in controls between V-125 and
release of sulfiidng reactor.
solution via venting back
into enclosure.
Page 28 of 98
Hazard ID/
H.2- What if there is a Failure in pressure Spray or Spill. Spray or leak of Design of V-125.
23 failure in the pressure boundary (V-125) results sulfiding solution to the
boundary (V-125)? in release of sulfiding enclosure
solution (or acetone-
cleanout) and nitrogen to Potential for oxygen deficient
the enclosure atmosphere.
H.2- What if there is a Failure in the Low Exposure of Personnel. ~10-15 Design of Low Pressure Nitrogen
24 failure in the pressure Pressure Nitrogen psi release of nitrogen to Piping.
boundary (nitrogen)? Pressure boundary. enclosure, potential for oxygen
deficient atmosphere. Loss of
ability to transfer.
H.2- What if there is too Failure to set Low Exposure of Personnel Piping System design pressure is
25 much pressure Pressure Nitrogen Supply Potential for oxygen deficient 2500 psi.
(nitrogen)? regulator results in over atmosphere PCV-2001 sets pressure to ~10
pressurization of system psi.
and release of nitrogen to Overpressure relief on Supply
the enclosure. system provided by PCV-2030
(15 psi) vented to offgas vent
header.
Overpressure vented (V-120, V-
125) through LP relief header.
H.2- What if there is too Failure to correctly set Very Spray or Spill. Spray or leak of Vessel Design V-120, 135 psi.
26 much pressure low pressure nitrogen Unlikely sulfiding solution to the Vessel Design V-125, 155 psi.
(nitrogen)? (PCV-2001) results in enclosure Pressure regulation of the low
over-pressurization of V- pressure nitrogen supply to 100
120 /125 Potential for oxygen deficient psi.
atmosphere. Pressure regulation of the low
to 10 psi.
Overpressure relief on Supply
system provided by PCV-2030
(15 psi) vented to offgas vent
header.
Overpressure vented (V-120, V-
125) through LP relief header.
Overpressure vented through LP
relief header.
Page 29 of 98
Hydrotreater Process Step 3. Bio-oil feeding

1) Adjust hydrogen flow and temperature to operating conditions. 2) Fill pumps with bio-oil from feed tank. 3) Start bio-oil supply drum recirculation/take-up loop. 4) Direct product
valves to L/L separator and A or B product tanks. 5) Start bio-oil feed at ~30% of target flowrate. 6) Allow system to equilibrate. 7) Gradually bring reactor to target flowrate.
Hazard ID/
Process Likeli- Hazard Controls
Step hood C = Critical Control
H.3- 3 What if there is failure Failure to initiate flow of Likely Process impact on loss of feed. Low level Interlock V-120.
1 to initiate bio-oil supply bio-oil from feed drum ISCO pump will shutoff due to
from feed drum? results inV-120 will insufficient liquid refill.
empty during the process.
Nitrogen to the ISCO
pump.
H.3- 4 What if there is failure Failure to realign valves Likely Spray or Spill. Possibility to Tank is designed for full flow Volume of V-162 could
2 to realign valves to L/L results in bypass of LG- overfill the V-162 tank and from V-140 (LV-4003). contain overflow for up to
separator and product 147 (liquid-liquid overflow V-162 into vent Procedural check in place. 19 hours.
tanks? separator) with direct header, which could plug the PSV 4016 set pressure at 70psi.
transfer to the V-162 vent and/or low pressure
(slop tank). nitrogen feed.
H.3- 4 What if there is failure Failure to align 3 way Likely Spray or Spill. Potential to LG-147 visual indication during
3 to align 3 way valve to valve to product tanks overflow to product gas header operator rounds.
product tanks? results in deadhead on and plug (V-153 or WTM-152). Product scales on V-160 and V-
Deadhead line and overfill of LG- 161.
147. Local indication on wet WTM-
152 test meter.
Relief valves on product gas
header at 10 psi.
Relief Valve on LG-147 feed line
at 70 psi.
H.3- 4 What if you align to a Operator aligns to a Likely Spray or Spill. Overfill tank LG-147 visual indication during
4 product tank that is full product tank with potential overflow to operator rounds.
already full? resulting in overfill the product gas header line and plug Product scales on V-160 and V-
product tank. (V-153 or WTM-152). 161.
Local indication on wet WTM-
152 test meter.
header at 10 psi.
Relief Valves on V-160A/B and
V-161A/B set at 70 psi.
at 70 psi.
Page 30 of 98
Hydrotreater Process Step 3. Bio-oil feeding
1) Adjust hydrogen flow and temperature to operating conditions. 2) Fill pumps with bio-oil from feed tank. 3) Start bio-oil supply drum recirculation/take-up loop. 4) Direct product
valves to L/L separator and A or B product tanks. 5) Start bio-oil feed at ~30% of target flowrate. 6) Allow system to equilibrate. 7) Gradually bring reactor to target flowrate.
Hazard ID/
H.3- 4 What if there is failure Pressurize the product Likely Spray or Spill. Pressurize tank LG-147 visual indication during You always go to A tank for
5 to open vent line on tank. with potential overflow to Low operator rounds. primary and switch to B
correct product tank? Pressure relief header Product scales on V-160 and V- tank temporarily.
161.
Local indication on wet WTM-
152 test meter.
header at 10 psi.
Relief Valves on V-160A/B and
V-161A/B set at 70 psi.
at 70 psi.
H.3- 5 What if the Bio-oil feed Excessive feed rate of Likely Energetic event- failure of R- Procedural step. There is Operator Response to
6 rate is started at more bio-oil results in potential 130 pressure boundary. temperature and feedback to the audible alarm should be to
than desired? excessive exothermic operator. turn off the bio-oil and/or
reaction in catalyst bed R-130 High High temperature. C the hydrogen.
with failure of reactor Audible alarms on internal
pressure boundary due to thermocouples.
excessive temperature.
Page 31 of 98
Hydrotreater Process Step 4. Operation
1) Monitor feed and product levels. 2) When product drums are at 85 to 90% full, switch to other product tanks. 3) Download water vessel to product container. 4) Download oil vessel to
product container or transfer to still skid feed tank.
Hazard ID/
H.4-1 1 What if the ISCO Failure in ISCO pumping Unlikely Energetic event- PSE2005 @ 100 psi sized for C
pump freezes (open results in liquid backflow Pressurization of V-120 backflow.
valves). from reactor. (Check
valves are assumed to leak Check Valve (CK-2007)
and upstream vessels
subject to hydrogen
backflow).
H.4-2 1 What if the pumps run Failure in pumping control Likely Process Upset. Local Limited to 1 liter due to design of Flow rate is limited by the
in phase? Will they (synchronized) results in temperature increase slight pumps. System would slow pump to 400 ml / min.
cause problems? exothermic reaction. pressure increase. down and not get as much. It which would only last 2.5
would not refill and shut off. minutes
[If combined with a plug - See hazard controls for the

refer to H.4-7] Refer to H.4-7 exothermic event H.4-7
H.4-3 1 What if the pumps run Failure in pumping control Likely Process Upset. Pressurization Limited to 1 liter due to design of
in phase? Will they (synchronized) results in of system due to plugging by pumps. Design of the system for
cause problems? excessive flow of bio-oil high viscosity product. full pressure to receive on this
to Flood the catalyst bed scenario.
with bio-oil.
H.4-4 1 What if there is a leak Seal on piston and/or Likely Spray or Spill. Release of Bio- There is a catch under the seal Flow rate is limited by the
in the ISCO pump? pump leak results in oil to the enclosure. and it would run down a tube into pump to 400 ml / min.
release of Bio-oil to the a small bottle or built in which would only last 2.5
enclosure.. secondary container. For large minutes
leak pumps would run out of
phase and shut down.
H.4-5 1 What if there is a leak Seal on piston and pump Unlikely Spray or Spill. Release of Bio- There is a catch under the seal
in the ISCO pump? leak with backflow of oil and hydrogen to the and it would run down a tube into
hydrogen through check enclosure. a small bottle or built in
valves. secondary container. For large
leak pumps would run out of
phase and shut down. Ventilation
of enclosure, hydrogen monitors
on skid and enclosure..
Page 32 of 98
Hazard ID/
H.4-6 1 What if there is There is a plug in the Likely Energetic event failure of R-130 Design pressure 3000 psi C
excessive pressure in system and we continue to Reactor Pressure relief valve set at 3000 C
the reactor? pump (normal operation), psi.
challenging the pressure ISCO Pump high pressure set
boundary of the system. point (process controlled). ISCO
Pump firmware maximum
pressure of 3750psi.
Pressure set point on hydrogen
system (3000 psi).
High-High pressure interlock at
2700 psi.
Process control alarms for high
pressure.
H.4-7 1 What if there is an Exothermic reaction in Unlikely Energetic event failure of R-130 Design pressure 3000 psi C Operator Response to
excessive exothermic reactor column combined Reactor Pressure relief valve set at 3000 C audible alarm should be to
reaction resulting in with a plug, results in psi. turn off the bio-oil feed
the pressure increase? challenging the pressure Pressure set point on hydrogen and/or the hydrogen.
boundary of the system. system (3000 psi).
High-High pressure interlock at
2700 psi.
ISCO Pump high pressure set
point (process controlled).
ISCO Pump firmware maximum
pressure
Procedural step. There is
temperature and feedback to the
operator. Audible alarms on
internal thermocouples.
Page 33 of 98
Hazard ID/
H.4-8 What if there is a Material failure (e.g. Unlikely Flammable atmosphere. R-130 Design C
failure in the reactor design flaw, undetected High pressure release to Routine internal inspection
vessel? flaw) or leak at the flange enclosure (steam, hydrogen, vessel.
connection at head or hydrocarbons) Pressure Test Procedure. C
connections or a failure at Operating within design
the weld results in a spray parameters-overpressure over-
leak temperature alarms and controls.
Enclosure Design Class 1 Div C
2. C
Hydrogen monitors on skid and
in enclosure. C
Flammable vapor monitor on
skid.
Expanded metal screen and
acrylic shield on walkway on
north side of flange. Graylock
around flange would generally
stop direct steam impingement.
H.4-9 What if there is a Material failure (e.g. Very Energetic event - failure of R-130 Design C
failure in the reactor design flaw, undetected Unlikely Reactor Routine internal inspection
vessel. flaw) results in vessel.
catastrophic failure of the Pressure Test Procedure. C
vessel Operating within design
parameters - overpressure over
temperature alarms and controls.
Page 34 of 98
Hazard ID/
H.4- What if there is flame Catastrophic failure of the Extremely Energetic event - failure of Design of hydrogen pipe system. C
10 impingement due to reactor vessel due to flame Unlikely Reactor Excess flow valve on hydrogen C
hydrogen leak. impingement from a supply.
hydrogen fire (hydrogen Flame detection inside enclosure.
line break) results in loss Hydrogen monitor on skid and
of pressure integrity. enclosure.
Fire suppression system in
enclosure.
Reactor column shielded by
furnace enclosure which would
limit exposure and rapid
temperature rise to heat up the
vessel.
Operator response and emergency
stop.
H.4- What if there is a Catastrophic failure of the Extremely Energetic event - failure of Design of Product Tank (V-160 C Event may be incredible
11 flame impingement reactor due to Flame Unlikely Reactor A/B). based on lack of quantity or
due to a flammable impingement from a Pressure Test Procedure. C heat energy from a pool fire.
liquid fire? flammable liquid fire Distillation skid has separate
results in loss of pressure containment from the Size of product tank. V-
integrity. hydrotreater skid. 160A/B is 19 liters. This is
Enclosure Design Class 1 Div 2 a days worth of running
Flammable vapor monitor on skid production at 1-2 liter/hr (38
Flame detection inside enclosure. liters total volume of both
Fire suppression system in product tanks).
enclosure
Reactor column is shielded by
furnace enclosure which would
limit exposure and rapid
temperature rise to heat up the
vessel.
stop.
Page 35 of 98
Hazard ID/
H.4- What if we lose Loss of hydrogen pressure Likely Process upset. Loss of L/L mass flow alarm and an System not set to shut down
12 hydrogen flow to the results in process upset (no product quality. interlock to shut off hydrogen and or trip. It would keep
reactor? reaction) and pressure the ISCO pump. running for a while due to
decrease over time. There is also a low mass flow low usage
alarm.
If continued filling of the Overpressurization. See Procedural monitoring of system.
reactor with bio-oil energetic Reactor
occurred, the potential for overpressure events.
subsequent plugging- once
you plug the reactor you
could over pressurize
this would require a long
time.
H.4- What if you lose Loss of heat input Likely Process upset. Loss of Sufficient time for Operator
13 heaters? resulting in incomplete product quality. response.
reaction. Process indicators.
If continued filling of the Overpressurization. See

reactor with bio-oil energetic Reactor
occurred there is the overpressure events.
potential for subsequent
plugging- once you plug
the reactor you could over
pressurize this would
require a long time.
H.4- What if you misalign Operator moves the Likely Process upset. Loss of Administrative controls.
14 thermo couples to thermocouple tree out of product quality Indicator on shell would indicate
zone? alignment with the reactor over temperature condition on
heating zone resulting in one zone. On large temperature
unstable furnace control. differential between the center
and the shell controller would
ramp heater output down.
Page 36 of 98
Hazard ID/
H.4- What if the thermowell Failure of thermowell Unlikely Flammable atmosphere. Preventative maintenance and .Release is directed away
15 fails? pressure boundary results Steam, flammable vapor, inspection. Routine internal from personnel.
in spray leak hydrogen, potential liquid leak inspection vessel.
to the enclosure. Design of R-130 (including C Thermowell pressure
thermowell). boundary is a robust system
Pressure Test Procedure. C but was qualitatively judged
Operating within design to be more susceptible to
parameters - overpressure over- leaks than the Reactor
temperature alarms and controls. Vessel.
Enclosure Design Class 1 Div 2.
Enclosure Ventilation System.
in enclosure.
skid.
Thermo-well is replaceable.
H.4- What if we have high Blockage of flow path (F- Likely Process Upset. Partial Design of High pressure
16 pressure associated 143 or F-4019) results in blockage of flow and components.
with this portion of the high pressure in separator. pressurization of reactor. Pressure Relief Valve PSV-4002
separator? set at 3000 psi.
Overfill of V-140 could divert Level control on V-140. Pressure
the liquid to the gas system indicators and alarms.
causing it to plug also. Pressurization controls from
reactor.
H.4- What if we have high Blockage of flow path (F- Unlikely Total blockage of flow, Design V-140 3000 psi MAWP C
17 pressure associated 143 or F-4019) results in pressurization of system (back Pressure Relief Valve PSV-4002 C
with this portion of the high pressure in separator. to reactor). set at 3000 psi.
separator? Level control on V-140. Pressure
indicators and alarms.
Overpressurization controls from
reactor.
H.4- What if we have Material failure (e.g. Very Energetic event failure in V- Design of V-140/LG-142 C
18 failure of system design flaw, undetected Unlikely 140/LG-142 pressure Level control on V-140.
boundary V-140/LG- flaw) results in failure of boundary. Pressure indicators and alarms.
142? V-140 pressure integrity. Pressure Test Procedure. C
Page 37 of 98
Hazard ID/
H.4- What if we have Material failure (e.g. Unlikely Flammable atmosphere. Robust design for glass C
19 failure of LG-142? design flaw, undetected Release steam, and flammable components.
flaw) results in failure of vapors, treated bio-oil to Pressure indicators and alarms.
LG-142 pressure integrity enclosure. Bound by line Pressure Test Procedure. C
shear.
H.4- What if we have Material failure (e.g. Unlikely Flammable atmosphere. Design high pressure C
20 failure of high pressure design flaw, undetected Release steam, hydrogen and components.
piping (leak/ spray)? flaw) or leak at a flange flammable vapors, treated bio- Pressure Test Procedure. C
Gasket failure, swagelock oil to enclosure. Operating within design
leak results in a spray leak. parameters
in enclosure.
Flammable vapor monitor skid.
H.4- What if there is a low LIT-4003 fails low Likely Process upset. Partial Operator response to the low low
21 failure in LIT-4003? resulting in closing LV- blockage of flow and alarm on the level indicator LIT-
4003 which stops the pressurization of reactor. 4003. Visual inspection of LG-
aqueous flow and 142.
increases the liquid level
in V-140. Overfill of V-140 could divert Pressure indicators and alarms.
the liquid to the gas system Pressurization controls from
causing it to plug also. reactor.
H.4- What if higher than Failure of LV-4003(full Likely Energetic event - failure of PSV-4016 set at 70psi. C
22 expected pressure open) or failure/opening of pressure boundary (LG-147) LG-147 designed at 100 psig C
downstream of the bypass line results in and release of bio-oil to MAWP.
LV4003? over pressurization of LG- enclosure. LG-147 vented to product gas
147 or low pressure header.
components downstream PSV-5001 in product gas vent
header downstream of LG-147 is
set at 10psi.
Page 38 of 98
Hazard ID/
H.4- What if higher than Failure of PCV-4007 (full Likely Flammable atmosphere. The badger valve (PV-4005)
23 expected pressure open) or failure/opening of Release of hydrogen or would try to control the pressure.
downstream the bypass line results in flammable vapors to enclosure PSV-5001 set at 10psi.
PCV4007? over pressurization of but although most likely Vent system flow path design
product off gas header and would vent through stack or (1/2 or greater SS Tubing.
failure of downstream back pressure through vented Low alarm at PIT-4005 and PIT-
2 vessels and pressure relief to 3001.
components due to high
velocity flow (Impact to LP Relief Header. Design of vent system.
Wet Test Meter). Enclosure Design Class 1 Div 2 C
Ultimately drop reactor Enclosure Ventilation System. C
pressure.
H.4- What if high pressure Fail open PV4005 or open Likely High pressure at WTM-152. PSV-5001 set at 10psi. Vent
24 downstream PV-4005? bypass results in 100 psig system flow path design (1/2 or
pressure (PCV-4007) greater SS Tubing).
downstream.
H.4- What if V-153 is Failure to drain V-153 Likely Process upset. Liquid to the Sight Glass SG-153 normally
25 blocked? results in high liquid level. WTM152. empty. Drain valve HV-5001
manually opened to remove the
liquid in V-153.
H.4- What if there is a leak Failure at a connection or Likely Flammable atmosphere. Design of vent system.
26 in the low pressure the WTM seal results in Potential creation of Procedural step calibration of
vent system? release of hydrogen or flammable atmosphere. WTM.
flammable vapor to Enclosure Design Class 1 Div 2 C
enclosure. Enclosure Ventilation System.
Hydrogen monitors on skid and C
in enclosure.
skid.
enclosure.
Containment pan on skid and by
the enclosure.
2
In particular, PI-4008 had a minimum burst pressure of ~ 2200 psig; it has been replaced with a gage that has a minimum burst pressures in excess of 3000 psig.
Page 39 of 98
Hazard ID/
H.4- What if you dont Failure to switch from full Likely Spray or Spill. Overfill of LG- Level indication V-160A.
27 switch tanks when tank results in overfilling 147 Could divert the liquid to H/H alarm. Weight indication set
they are full? tank with the potential to the gas system causing it to at H (12 kg) and H/H interlock
backup to LG-147 or into plug also. (14kg) to ISCO pump. Trips LV-
the product gas header line Partial blockage of flow and 4003 to close.
and plug (V-153 or WTM- pressurization of reactor.
152).
H.4- What if there is a leak Failure of connection or Unlikely Flammable atmosphere. Pressure Test Procedure. C
28 in product bio-oil open drain valve on V-160 Spill of combustible liquid Design V-160A/B and piping.
system downstream of A/B results in release of (treated Bio-oil) and potential Drains are double valved, valved
LG-147. hydro-treated bio-oil to creation of flammable and capped, or valve and quick
containment and/or to atmosphere. disconnect.
enclosure. 19 liters Enclosure Design Class 1 C
maximum material spill Division 2
from completely full Enclosure Ventilation System. C
vessel V-160A/B. Flammable vapor monitor on
skid.
enclosure.
the enclosure.
Page 40 of 98
Hazard ID/
H.4- What if high pressure Failure in low pressure Likely Energetic event failure of V- Design of V-160A/B 155 psi. C
29 V-160A/B? nitrogen system results in 160A/B pressure boundary. V-160A/B PRV set at 70 psi. C
high pressure in V-160A/B Pressure regulation of the low
and failure of pressure Spill/Spray of combustible pressure nitrogen supply to 100
boundary release treated liquid (treated bio-oil) and psi.
bio-oil and nitrogen to potential creation of Pressure regulation of the low
enclosure. flammable atmosphere. pressure nitrogen system pressure
to 10 psi.
Creation of oxygen deficient Enclosure Design Class 1
atmosphere. Division 2
skid.
enclosure.
the enclosure.
H.4- What if there is a Failure to close or Likely Process Upset loss of product. Valve lineup procedure. Tank V-
30 bypass of LG-147? inadvertent opening of 162 is 38 liters. System designed
HV-4022 results in to 180 psi but open to
directing aqueous and atmosphere. Weight of product
treated bio-oil into the tank vessels would indicate lack of
V-162. filling.
Visual inspection (low level) of
LG-147.
H.4- What if there is a leak Failure of connection or Unlikely Spray or Spill. Spill of water Pressure Test Procedure. Spill of product is mostly
31 in product water open drain valve on V- to containment and/or to Design V-161A/B and piping. water.
system downstream of 161A/B results in release enclosure. Drains are double valved, valved
LG-147? of product water to and capped, or valve and quick
containment and/or to disconnect.
enclosure. 19 liters Containment pan on skid and by
maximum material spill the enclosure.
from completely full
vessel V-161A/B.
Page 41 of 98
Hazard ID/
H.4- What if high pressure Failure in low pressure Likely Energetic event failure of V- Design of V-161A/B 155 psi. C
31 in V-161A/B? nitrogen system results in 161A/B pressure boundary. V-161A/B PRV set at 70 psi. C
high pressure in V-161A/B Pressure regulation of the low
and failure of pressure pressure nitrogen supply to 100
boundary releases water Creation of oxygen deficient psi.
and nitrogen to enclosure. atmosphere. Pressure regulation of the low
to 10 psi.
H.4- What if there is a Failure to connect properly Likely Spray or Spill. Spill of water Design of quick disconnects
32 failure to connect connect transfer line from to enclosure. closed unless properly engaged.
properly connect V-161A/B to transport
transfer line to vessel results in spill of
transport vessel? water
H.4- What if there is a Failure to properly connect Likely Personnel Exposure. Creation Design of quick disconnects
33 failure to connect transport vessel ventline to of oxygen deficient closed unless properly engaged.
properly connect low pressure relief header atmosphere.
transport vessel results in venting of
ventline? nitrogen to enclosure
Page 42 of 98
Hydrotreater Process Step 5. Transfer to still feed tank
1) Pad oil product container. 2) Depad still feed tank. 3) Connect transfer line. 4) Open transfer valves. 5) When empty, close transfer valves. 6) Pad still tank. 7) Depad product
container. 8) Remove transfer line.
Hazard ID/
Step What if: Hazardous Scenario Consequences Comments
H.5- What if there is failure Operator fails to depad V- Likely Process upset. No transfer. Weight indication on V-160A.
1 to depad V-180? 180 prior to starting Nominal pressure is the same in Level indicator on V-180.
transfer from V-160A/B both systems. High-High level alarm on V-
results in inability to 160A.
transfer due to high Procedural step.
pressure in V-180 (nominal
pressure is the same in both
systems).
H.5- What if there is failure Failure to properly connect Likely Flammable atmosphere. Design of quick disconnects C Bounds line failures.
2 to properly connect the transfer line to V-180 Spill/Spray of combustible (closed unless properly engaged).
transfer lines from results in spill or spray of liquid (treated bio-oil) and Enclosure Design Class 1 Div 2. C
160A to V-180? hydro-treated bio-oil to the potential creation of flammable Enclosure Ventilation.
enclosure. atmosphere. Containment for both skids and
enclosure.
Flammable vapor monitoring on
hydrotreater skid.
enclosure.
H.5- What if there is failure Operator applies pad to V- Likely Creation of oxygen deficient Design of quick disconnects
3 to close the transfer 180 without closing the atmosphere. (closed unless properly engaged).
valves and restore the three valves (HV-8017 & Enclosure Design Class 1
pad to V-180? HV- 6028 & HV 6016) Division 2.
results in nitrogen flows Enclosure Ventilation.
backflow until pressure Procedure.
equalizes or release of
nitrogen enclosure via
disconnect on transfer line.
Page 43 of 98
Hydrotreater Process Step 6. Shutdown

1) Stop oil feed and turn off reactor heaters. 2) Continue product vessel monitoring per operation section. 3) Empty pumps back to bio-oil feed tank. 4) Reduce gas flow once product
collection has diminished. 5) Allow reactor to cool.
Hazard ID/
H.6- 3 What if there is failure Operator opens HV2009 Likely Flammable atmosphere. HV-2018 Action: Replace T C
1 to isolate the reactor without closing HV2006 Release of steam, hydrogen, upstream HV-2009 with 3-way
from the feed pumps? resulting in backflow of flammable gas, bio-oil into Valve.
steam/hydrogen, enclosure with personnel in the Check Valve (CK-2007)
flammable vapors, bio-oil area. Procedural step.
into enclosure.
Hydrotreater Process Step 7. Flush

1) Reactor should be around 150C or lower for this procedure. 2) Load acetone into pumps via transfer tank. 3) Direct product valves to slop tank. 4) Inject acetone into reactor. 5) Shut
down feed system and allow reactor to cool below 100C. 6) Halt gas flow and depressurize reactor. 7) Flush with Nitrogen. 8) Verify that all systems are off.
Hazard
ID/
Step
H.7- What if the reactor is Operator initiates flush prior Likely Process upset, inefficient Procedural step
1 greater than desired to cooling below desired cleaning Design of R-130 pressure is 3000 C
temperature? temperature results in psi MAWP.
failure to adequately clean Energetic Event. R-130 PRV set at 3000 psi. C
catalyst/reactor. Potential plug of reactor and High-High pressure interlock at
energetic failure due to 2700 psi.
overpressure (continued ISCO Pump high pressure set
pumping of acetone). point (process controlled).
ISCO Pump firmware maximum
pressure.
H.7- What if we don't align Failure to properly align Likely Process upset. Loss of product Procedural step
2 product valves to slop valves results in due to mixing of acetone
tank? misdirection of acetone solution with product.
solutions to the product tank
instead of slop tank.
Page 44 of 98
Hazard
ID/
Step
H.7- What if other than Operator error results in Likely Process upset. Coke the catalyst H2S monitor on vent stack.
3 acetone in V-125? filling V-125 with sulfiding and potentially evolve higher Procedural step.
solution instead of acetone. than expected H2S.
H.7- What if too much Failure to correctly set (or Likely Energetic event - failure of V- Pressure limit on the low pressure
4 pressure to V-125 failure of pressure control 125 pressure boundary. system.
from nitrogen pad? valve) low pressure nitrogen Pressure set point, pressure
pressure results in Flammable atmosphere. control for system,
overpressurize V-125 with Spill of flammable liquid and Design of V-125 155 psi MAWP C
> 10 psi up to 100 psi of potential creation of flammable V-125 PRV set at 100 C
nitrogen resulting in failure atmosphere with personnel Enclosure Design Class 1 Div 2.
of pressure boundary and present. Enclosure Ventilation System.
release of acetone /nitrogen Flammable vapor monitoring on
to enclosure. Creation of an oxygen deficient skid.
environment. Fire suppression system in
enclosure.
H.7- What if there is failure Failure to connect vent line Likely Flammable atmosphere. Procedural step. Connect the
5 to connect vent line to header results in venting Spill of flammable liquid and vent line prior to the nitrogen and
V-125 to rupture disk? of V-125 contents to potential creation of flammable outlet.
enclosure on system atmosphere with personnel Flammable vapor monitoring on
overpressure/failure of present. skid.
rupture disk and release of Fire suppression system in
acetone /nitrogen to Creation of an oxygen deficient enclosure.
enclosure. environment. Enclosure Design Class 1 Div 2. C
Enclosure Ventilation System C
H.7- What if flow rate of Set pump flow rate too Likely Process upset. Potential to Process monitoring. Same Flow rate is limited by the
6 acetone is too high? high. overwhelm liquid to gas controls as Plugging and pump to 400 ml / min.
separator V-140 resulting in overfilling V-140. which would only last 2.5
over flow to the product gas minutes
system and out to the vent
system.
Page 45 of 98
Hazard
ID/
Step
H.7- What if valve HV - Deadhead the flow. Likely Flammable atmosphere. Transfer Line (tubing) is rated at C
7 2006 is closed? Line pressure goes to 4500psi 4800 psi.
resulting in a spray/leak of Pressure Indicator PI-2011
acetone creating a flame or ISCO Pump high pressure set
flammable atmosphere in point (process controlled).
enclosure. ISCO Pump firmware maximum
H.7- What if there is a Failure in V-125 or piping Very Flammable atmosphere. Pressure Test Procedure (prior to C
8 failure in the pressure system pressure boundary Unlikely Spill/Spray of flammable liquid operations).
boundary? results in spray/spill of and potential creation of Design of V-125. C
acetone. flammable atmosphere Enclosure Design Class 1 Div 2.
Enclosure Ventilation
H.7- What if the drain Failure to close drain valve Unlikely Flammable atmosphere. Procedural check that drain valve
9 valve HV-2009 is after pumping feed back to Spill/Spray of flammable liquid is closed. C
open? V-120 results in loss of and potential creation of Enclosure Design Class 1 Div 2. C
acetone solution. flammable atmosphere. Enclosure Ventilation.
Containment for skid.
H.7- What if temperature Heaters turn on raising the Unlikely Process upset. Potential loss of Procedural controls. Bench Scale testing.
10 increases during temperature or exothermic catalyst. Design of R-130 (temperature).
Cleaning > 350C? reaction between catalyst Temperature alarms.
acetone and hydrogen
results in temperature
increase during cleaning.
H.7- What if gas flow Hydrogen flow stopped too Likely Process upset. Potential loss of Procedural Control.
11 stopped to early early (reactor above 100C) catalyst.
(Reactor above results in loss of cooling to
100C)? catalyst.
Hydrotreater Process Step 8. Refit

1) Depressurize and verify zero energy state on all hydrotreater subsystems. 2) Chain out inter-skid area prior to working on upper head. 3) Open upper reactor head
4) Remove catalyst.
Page 46 of 98
Hazard ID/
H.8- What if fail to Operator fails to Likely Personnel exposure. Release of Procedural. Pressure indicator on
1 depressurize before depressurize reactor vessel Nitrogen to the enclosure. reactor.
breaking into the prior to breeching pressure Enclosure Ventilation System.
system? boundary resulting in Potential personnel exposure to Flammable vapor monitor and
release of nitrogen. high pressure nitrogen. hydrogen monitor on skid would
detect significant flammable
vapor /hydrogen release.
H.8- What if fail to purge Operator fails to perform Likely Flammable atmosphere. Procedural. Nitrogen flush peformed
2 with nitrogen before nitrogen purge after Release of hydrogen gas - Enclosure Ventilation System. prior to disassembly.
breaking into the acetone flush resulting in Creation of flammable Flammable vapor monitor on (possibly between step 6
system? release of environment with personnel skid. and 7 of flush)
hydrogen/acetone vapors present. Hydrogen monitor on skid and in
to the enclosure enclosure
H.8- What if fail to purge Operator fails to purge and Unlikely Flammable atmosphere. Pressure indicator on reactor. .
3 and depressurize before depressurize reactor vessel Spray of hydrogen gas - Procedural. Verify zero energy- C Nitrogen flush peformed
breaking into the prior to breeching pressure Creation of flammable procedural step and hold point. prior to disassembly.
system? boundary resulting in environment with personnel This defines transition to non (possibly between step 6
release of high pressure present. Class I/Div 2. and 7 of flush)
hydrogen/acetone vapors Enclosure Ventilation System.
to the enclosure Potential personnel exposure to Flammable vapor monitor on
high pressure hydrogen and skid.
acetone vapors. Hydrogen monitor on skid and in
enclosure.
Page 47 of 98
Distillation Process Step 1. Prestart Operations

1) Seal process tanks. 2) Pre-op valve position check for entire system. 3) Pressure check system (purge and pad all subsystems). 4) Transfer feed to tank via hydrotreater skid or transfer
tank using tank pads. 5) Alternately, feed can be loaded into one of the bottoms product tanks and padded over. 6) Put valves to flow positions, including bottoms and distillate product
tanks. 7) Prime feed pump and turn to auto control.
Hazard
ID/
Step
D.1- What if you fail to Failure to re-assemble or failure Likely Creation of oxygen deficient Pressure Test Procedure.
1 properly in seals/flanges/piping atmosphere with personnel Enclosure Ventilation System
reassemble seals / connections results in loss of present. operable when system is
flanges / piping pressure boundary integrity and pressurized.
connections? release of low pressure nitrogen Design of pressure vessels and
into enclosure. components.
Pressure indication on the
distillation column.
D.1- What if valve is Failure to close vent valve prior Likely Process Upset. Vent to vent Valve lineup procedure.
2 left open? to starting pressure check. header Pressure Test Procedure.
Pressure indication throughout
system.
D.1- What if valve is Failure to close valve (drain Very Personnel exposure. Creation of Valve lineup procedure.
3 left open? valve) resulting in nitrogen Unlikely oxygen deficient atmosphere Pressure Test Procedure.
released into enclosure. with personnel present. Ventilation system operable when
(see HV-8007/8, system is pressurized.
etc.) Potential for small (residual Drains are double valved, valved
amounts) flammable liquid and capped, or valve and quick
accumulation. disconnect.
D.1- What if failed to Inadequate pressure check, Unlikely Spray or Spill. Release of treated Valve lineup procedures.
4 pressure check combined with pre-existing leak bio-oil/ intermediate product Pressure Test Procedure -pressure
part of system due results in leak at operating vapors/ nitrogen into enclosure. indicators on individual tanks and
to valve temperature and pressure, (subsequent operation) sub-systems.
misalignment? releases of treated bio-oil/ Flammable vapor monitor on skid.
intermediate product vapors/ Enclosure Design Class 1
nitrogen into enclosure. Division 2.
D.1- What if fail to do Failure to perform pressure Unlikely Spray or Spill. Release of Pressure Test Procedure.(detection
5 the pressure test? check, combined with pre- processed bio-oil intermediate of no pressure)
existing leak results in leak at product vapors/ nitrogen into Flammable vapor monitor on skid.
operating temperature and enclosure. Enclosure Design Class 1
pressure, releases of treated bio- (subsequent operation) Division 2.
oil/ intermediate product vapors/ Enclosure Ventilation System.
nitrogen into enclosure.
Page 48 of 98
Hazard
ID/
Step
D.1- What if too high Failure in supply (Nitrogen Unlikely Energetic event - failure of low Pressure regulation of the low
6 pressure for low Tank) regulator results in over pressure system (>100 psi) pressure nitrogen supply to 100 psi.
pressure system? pressurization of low pressure Pressure regulation of the low
system components due to pressure nitrogen system pressure
excessive nitrogen pressure. to 10 psi.
Pressure regulator to offgas vent
header (PCV-9008) set at 15 psig.
Design of low pressure components C
Low pressure component PRVs set C
at 100 psig.
Pressure Test Procedure (verify
pressure).
D.1- What if too high Failure in PCV-9006 results in Unlikely Energetic event - failure of low Pressure regulation of the supply to
7 pressure for low pressurization of low pressure pressure system (~100 psi) 100 psig.
pressure system? system components due to Design of Pressure vessel and C
excessive nitrogen pressure. System components MAWP 135
except for the still (V-184, MAWP
70 psig).
Distillation skid pressure C
components PRVs set at 70 psig.
D.1- What if you Failure to use correct gas for Very Flammable atmosphere. Hydrogen monitors on skids and C
8 inadvertently use pressure check (combined with Unlikely Deflagration in Enclosure enclosure.
Hydrogen instead pre-existing leak or failure to re- Enclosure Ventilation System. C
of nitrogen for assemble properly) results in Procedures Test Procedure. C
leak check? Potential flammable atmosphere Valve and line labeling.
in the enclosure with a piece of Different gases have different bottle
(Requires equipment not qualified for the fitting.
connection of hydrogen atmosphere.
Low Pressure
Nitrogen Supply
to Hydrogen
bottle?)
D.1- What if hydrogen Failure to isolate V-160 from Very Process Upset. Hydrogen Valve line on transfer.
9 is introduced to skid before transfer, combined Unlikely released to vent system (normal See process hydrotreater process
distillation system with upset condition that operations). controls.
Page 49 of 98
Hazard
ID/
Step
from introduces process gas (requires

hydrotreater? multiple conditions).
D.1- What if we Transfer of product at greater Unlikely Flammable atmosphere. Pressure Limited to Low pressure System designed for
10 transfer product than expected pressure or flow Spray or spill of flammable Nitrogen pressure. maximum flow from
too fast or at too results in system breach and liquid and vapors V-180 rated at 135psi MAWP. C pump at maximum air
high of pressure? release of treated bio-oil/ Design 1/2 inch stainless steel C supply pressure.
intermediate products (recycle transfer line
from V-191-194) into enclosure V-180 PRV set at 70. C
D.1- What if we Failure to stop transfer results in Unlikely Spray or Spill. Overfill V-180 Level indicator on V-180 and H/H Would require 6 or 7
11 transfer too much over fill of V-180. resulting in release of bio-oil into alarm. transfers.
bio-oil (over fill)? Requires multiple transfers from the vent system. V-180 sized at 140 liters
V-160A/B
D.1- What if there is a Leak in transfer line from Likely Spray or Spill. Release of treated Pressure boundary design.
12 leak in the bio-oil Hydrotreater results in spill bio-oil into enclosure. Secondary containment provided
line? /spray to enclosure. by enclosure.
D.1- What if air gets in Air in V-180 during manual Likely Energetic event - Air in system Pressure Test Procedure with C
13 the system? cleaning of vessel. results in potential deflagration in nitrogen purge.
V-180, if not purged.) P-181 will not pump gas.
D.1- What if we failed Failure to correctly align system Likely Deadhead within system. High Valve Lineup Procedure.
14 to line up properly for operations after pressure test pressure in distillation column or Multiple PRVs (PRV on vessels, C
for operations? results in blocked flow within piping. PRV on pump),
the system distillation column. Multiple process control alarms on
(can HV- high level, high pressure.
9025/HV-9021
block flow?)
D.1- What if we Inadvertent opening of Unlikely Potential for nitrogen release into Procedures in place. Majority is
15 inadvertently (drain/manual transfer) valve enclosure or vent. double- valved or pathways to
open an already results in venting to enclosure or enclosure are valved and capped.
closed valve? header
Page 50 of 98
Distillation Process 2. Startup
1) Clear area of all maintenance work and equipment not compatible with Class 1 Div 2 environment. 2) Initiate purge of electrical cabinets and furnace. 3) Turn on coolant to HX and
pump bottoms. 4) Turn on nitrogen purge to heatup setpoint and set system backpressure. 5) Engage feed pump and set backpressure loop. 6) Fill still bottom to submerge heater
elements via feed control badger and/or bypass. 7) Turn on still heater and external jacket heater 8) As liquid level drops in still, set feed badger to maintain liquid height in still
Hazard ID/
D.2-1 1 What if you leave Potential for flammable Unlikely Flammable atmosphere. Procedure steps.
non-Class 1 Div 2 atmosphere to reach ignition Potential ignition of a flammable Pressure Test Procedure. C
equipment in sources. vapor given leak sufficient to Enclosure Ventilation System. C
environment? result in a flammable Alarms for flammable vapors on
atmosphere. skid.
D.2-2 1 What if you bring in Potential for flammable Unlikely Flammable atmosphere. Procedure steps.
non-Class 1 Div 2 atmosphere to reach ignition Potential ignition of a flammable Pressure Test Procedure. C
equipment into the sources. vapor given leak sufficient to Enclosure Ventilation System. C
enclosure during result in a flammable Alarms for flammable vapors on
operations? atmosphere. skid.
Limit access to trained operators.
Procedural steps in place during
operations.
D.2-3 2 What if you fail to Potential for flammable Unlikely Flammable atmosphere. Enclosure Design Class 1 Div 2,
initiate purge of atmosphere to reach ignition Potential ignition of a flammable Pressure monitoring and alarm on
electrical? sources. vapor given leak sufficient to cabinets (Z-purge).
result in a flammable System design C
atmosphere. Pressure Test Procedure. C
Flammable vapor monitor on skid. C
D.2-4 3 What if you fail to Loss of cooling to HE-185. Likely Spray or Spill. Vent lighter Flow monitor, temperature alarm
start coolant flow? components to vent header from on Chilled Water system. Manual
V-186. Potential to fill vent flow indicator FIC-8001 (would
header with liquid (which would not see at computer). PRVs,
go to stack) and plug system, pressure indication, pressure
leading to back pressure on the alarms on distillation column.
distillation column. Steam in the
water jacket.
D.2-5 What if you fail to Loss of tempered water to P- Likely Spray or Spill Failure of pump Temperature, local flow indication
start coolant flow? 182. seals and leak of heavy on tempered water. Secondary
components to secondary containment.
containment.
D.2-6 What if P-182 is Set temperature control on Likely Process upset. Inability to pump Temperature and flow indication.
over-cooled? tempered water too low. from bottom of column. Pressure on the line from the
Increase level in distillation. pump. Level indication on
Potential failure of pump. columns and product tanks.
Page 51 of 98
Hazard ID/
Temperature indication on product

tanks. Temperature indication,
alarm, interlock to Chiller system
on L/L.
D.2-7 4 What if too much Overpressurize V-184/V-186 Unlikely Energetic event - failure of V- Pressure limit on the low pressure
pressure to from with greater than 100 psi of 184/V-186 pressure boundary. system.
nitrogen purge? nitrogen and blocked vent Pressure set point, pressure control
header. for system.
Design of V-184/V-186. C
PRV on V-184 set at 70 psi. C
Pressure indication on vent header.
D.2-8 4 What if too little Failure op open/close HV- Likely Process upset. Incomplete Procedural steps. Local flow May be a desired normal
pressure to from 8008. Run out of nitrogen. purge. indication. operational scenario
nitrogen purge?
D.2-9 4 What if there is a Failure in nitrogen line. Unlikely Personnel Exposure. Nitrogen LP Nitrogen piping inside
failure in the release to enclosure. Potential Enclosure is Stainless Steel, ASME
pressure boundary backflow of flammable vapors B-31.3. Flammable vapor
(nitrogen)? from system. Loss of ability to detection on skid. Enclosure
transfer. ventilation.
Possible process upset.
Incomplete purge.
D.2- 5 What if back Set back pressure within Likely Process upset. Eventual increase Pressure and temperature
10 pressure too high? distillation column too high of temperatures in top of indication in distillation column.
(e.g., max of V-182). distillation column. H/H pressure alarm on column.
Temperature alarm.
D.2- 5 What if back See no nitrogen flow.
11 pressure too low?
D.2- 6 What if fill distill Failure to stop pumping. Likely Process upset. Overfill to Level indication and alarm on V-
12 too high? distillate product tanks. 184, V-186. Visual indication in V-
Overflow to vent header. 186. Pressure indicator PI-8023.
D.2- 6 What if fill distill Failure to submerge heaters. Likely Process upset. Damage heater Temperature indication on heater
13 too low? elements with excessive heat. JE-N-8028. H/H trips to zero %
output on heater element. Safety
H/H trips power to heater.
Level indication in column.
Page 52 of 98
Hazard ID/
D.2- What if no still Failure to turn on still heater. Likely Process upset. No heat-up. Temperature indication on column
14 heater? and still.
D.2- What if no jacket Failure to turn on jacket heater. Likely Process upset. Longer than Temperature indication on column
15 heater? expected heat-up rate. and still.
D.2- What if still heater Loss of still heater control. Likely Process upset. Faster than Thermocouple on still heater.
16 too high? expected boil-off of product. Level indication in column. Output
Potential uncovering of heater flow indication.
and damage to heater (see
above). Process upset.
D.2- What if jacket Loss of jacket heater control Likely Energetic Event. Potential Temperature indication on heater
17 heater too high? results in over-heating. failure of pressure boundary due JE-N-8023.
to excessive temperature. High-High Temperature on V-184. C
Faster than expected boil-off of

product (see above).
D.2- 8 What if feed rate is Feed rate set too high. Likely Process upset. Potential eventual Procedural step on start-up of
18 too high? overfill into vent system. reflux. Level indication and alarm
on V-184, V-186.
Visual indication in V-186.
Pressure indicator PI-8023High-
High provides alarm and shuts off
pump.
D.2- 8 What if feed rate is Feed rate set too Likely See loss of still heater control.
19 too low?
Distillation Process Step 3. Reflux

1) Observe reflux in sight glass via level sensor. 2) Once distillate reaches 8 inches, engage reflux pump (P-183) and set backpressure loop. 3) Prime reflux pump. 4) Set reflux badger to
target kg/hr. 5) Set product badger to target liquid level in sight glass. 6) Reduce nitrogen flow to target setpoint and adjust system backpressure.
Hazard
ID/
Step
D.3-1 1 What if reflux level too Failure to start reflux Likely Process upset. Overfill to Procedural step. Level indication and
high? pump. distillate product tanks. alarm on V-186. Visual indication in
Page 53 of 98
Distillation Process Step 3. Reflux
1) Observe reflux in sight glass via level sensor. 2) Once distillate reaches 8 inches, engage reflux pump (P-183) and set backpressure loop. 3) Prime reflux pump. 4) Set reflux badger to
target kg/hr. 5) Set product badger to target liquid level in sight glass. 6) Reduce nitrogen flow to target setpoint and adjust system backpressure.
Hazard
ID/
Step
Overflow to vent header. V-186. Pressure indicator PI-8023.

D.3-2 1 What if reflux level too Start reflux pump when Likely Process upset. Low level alarm. L/L interlock to
low? level is too low. stop P-183.
D.3-3 2 What if we fail to set Set reflux back pressure Likely Process upset. Build up in V-186 High-High level for LIT-8028 (95%)
reflux back pressure too low. and overflow. to manual 100% output.
(PCV-8024) correctly?
D.3-4 2 What if we fail to set Set reflux back pressure Likely Process upset. More or less than Procedural step. Level indication and
reflux back pressure too high. expected product to distillation. alarm on V-186. Visual indication in
(PCV-8024) correctly? V-186. Pressure indicator PI-8023.
D.3-5 4 What if fail to set reflux See D.3-1 and D.3-2.
badger to target rate?
D.3-6 5 What if fail to set See D.3-1 and D.3-2.
product (bottoms)
badger to target rate?
D.3-7 6 What if we fail to set See D.3-3 and D.3-4.
feed pressure correctly?
Distillation Process Step 4. Operation

1) Set feed rate badger to target feed rate. 2) Turn on and prime bottoms level control pump to target setpoint. 3) Monitor liquid level on bottoms and distillate tanks, and switch to
alternate tank when full. 4) Monitor feed tank level.
Hazard ID/
D.4-1 1 What if we fail to set FV-8014 fails or set Likely Process upset Recycle back to L/L alarms on V-184. Temperature
feed rate (FV-8014) closed. V-180. Drive still to low level. interlocks that shut down still
correctly? heaters. Temperature interlock for
jacket heater. User set flow alarm
on FIC-8014.
D.4-2 1 What if pump (P-181) Pump P-181 fails or Unlikely Process upset Drive still to low L/L alarms on V-184. Temperature
fails to pump? shutdown. level. interlocks that shut down still
heaters. Temperature interlock for
jacket heater. User set flow alarm
Page 54 of 98
Hazard ID/
on FIC-8014 pump indication if loss

of electrical power to the pump.
D.4-3 1 What if we have There is a plug in the Likely Energetic event - failure of V-184 V-184 Design pressure C Bottoms pump P-182
excessive pressure in system and we continue to V-184 PRV set at 70 psi. C would try to maintain
the Distillation pump (normal operation), Pressure relief and control on pump. level in V-184
Column? challenging the pressure Pump high pressure set point.
boundary of the system.
D.4-4 3 What if there is a Catastrophic failure of the Very Energetic event - failure of V-184 V-184 Design pressure C
failure in the vessel. Unlikely Pressure Test Procedure. C
Distillation Column? Operating within design parameters
- overpressure over temperature
alarms and controls.
D.4-5 3 What if there is a flame Catastrophic failure of the Extremely Energetic event - failure of V-184 Design of distillation skid C
impingement due to a vessel. Unlikely components pressure components.
flammable liquid fire? Enclosure Design Class 1 Div 2. C
Flame detection inside enclosure.
Flammable vapor monitor on skid.
enclosure.
stop.
D.4-6 3 What if you lose Loss of power to heaters or Likely Process upset (see previous loss
heaters? heaters fail. of heater hazards)
D.4-7 3 What if there is a leak Failure at a connection to Very Flammable atmosphere. Design of vent system.
in the low pressure vent common vent line and Unlikely Flammable atmosphere. Enclosure Ventilation System. C
system? release of flammable Flammable vapors in enclosure. Enclosure Design Class 1 Div 2.
liquids/vapor to enclosure. Flammable vapor monitor skid.
D.4-8 3 What if you dont Overfill a product tank. Likely Process upset. Backup to vent Level indication, H/H and L/H level
switch tanks when they Backup to into vent header. alarm. Product tanks are sized for a
are full? header. run.
D.4-9 3 What if there is a leak Failure of connection. Likely Flammable atmosphere. Pressure test Procedure. C
downstream of Open drain. Flammable vapors or liquid in Design of distillation skid C
Distillation? Spill of flammable enclosure. components.
liquid/vapors) to Enclosure Ventilation System. C
containment and/or to Enclosure Design Class 1 Div 2.
Page 55 of 98
Hazard ID/
enclosure. Flammable vapor monitor skid.

Containment pan on skid that could
capture the spill.
D.4- 3 What if bypass valve is Bypass valve is opened or Likely Process upset. Higher than Flow indication.
10 open? fails. expected flow rate in distillation Other controls for higher than
column expected flow (see startup controls)
D.4- 3 What if there is a Failure in pressure Very Flammable atmosphere. Pressure Test Procedure. C
11 failure in the pressure boundary results in release Unlikely Fire or flammable atmosphere in Design of distillation skid C
boundary? of flammable liquid/vapors enclosure. components.
Flammable vapor monitor on skid.
D.4- 3 What if there is a Failure of water jacket Very Process upset. Steam, water Pressure Test Procedure.
12 failure in the pressure pressure boundary, leak Unlikely vapor into system. Design of distillation skid
boundary? into distillation system. components.
Eventual leak of product back Low level indication on Chiller
into the chilled water reservoir system.
outside enclosure. Flow monitor, temperature alarm on
Chilled Water system. Manual flow
indicator FIC-8001 (would not see
at computer).
D.4- 3 Over pressure of V-191 Failure in supply (Nitrogen Unlikely Energetic event - failure of low Pressure regulation of the supply to
13 thru V-194 due to low Tank) regulator results in pressure system (>100 psi) 100 psig.
pressure nitrogen? over pressurization of V- Pressure regulation (PCV-9006) set
191 V-194 due to at 10 psig regulates downstream
excessive nitrogen system pressure)
pressure. Pressure regulator to offgas vent
header (PCV-9008) set at 15 psig.
Low pressure component PRVs set C
at 100 psig.
Design of Low pressure C
components.
Pressure Test Procedure. C
Page 56 of 98
Distillation Process Step 5. Shutdown

1) Turn off still heater and jacket. 2) Halt feed pump and set feed badger to zero. 3) Close reflux badger. 4) Set reflux level control to zero to drain reflux glass into distillate product. 5)
5) Turn off reflux pump after low level indicator. 6) Set bottoms level control to zero. 7)Turn off bottoms level pump after low level indictor. 8) Turn on nitrogen sweep to low level.
Hazard ID/
D.5-1 1 What if you fail to off Shut down pumps before Likely (see boil off of columns)
heater and jacket before the heaters are shutdown.
stopping flow?
D.5-2 What if you run out of (see boil off of column)
product?
D.5-3 2 What if you fail to stop (see overfill of column or loss of
flow? heaters)
D.5-4 3 What if you fail to close Failure to close FV-8027. Likely Process upset. Loss of some
reflux badger? product.
D.5-5 3 What if you close Close FV-8027 too early. Likely Process upset. Minor impact on
reflux badger too early? product quality.
D.5-6 4 What if you close Failure to set reflux level Likely Process upset. Loss of some
depressurize reflux? control to zero. product
D.5-7 4 What if you open Drain too early. Likely Flammable atmosphere. Enclosure Ventilation System. C
bypass to drain reflux Potential spill of flammable Enclosure Design Class 1 Div 2. C
(while pressurized)? liquids to enclosure Flammable vapor monitor skid.
Containment pan on skid that could
capture the spill.
D.5-8 What if you fail to Failure to properly connect Likely Flammable atmosphere. Enclosure Ventilation System.
correctly align during to Apache tank. Spills of flammable liquid into Enclosure Design Class 1 Div 2.
unloading? enclosure
D.5-9 What if you over fill Overfill product to vent Likely
Apache tank? header.
Utilities: Process Ventilation, Enclosure Ventilation, Compressed Air, Hydrogen, Nitrogen, Power,
Hazard ID/
U-1 What if loss (blockage) Overflow of flammable Very Spray or spill. (see overflow scenarios)
of process vent header? liquids into vent header. Unlikely Flammable liquid accumulation in
stack in unoccupied area vapors
Would require continued would dissipate out the stack.
operations for extended
Page 57 of 98
Hazard ID/
period of time.
U-2 What if loss (blockage) Loss of vent header. Process upset. Pressurize low (See earlier (system specific) block
of process vent header? pressure side WTM-152, V-153, flow events).
LG-147, LG-142, V-140 and
reactor and all associated piping.
U-3 What if ventilation Failure of stack due to high Very Blockage of vent flow due to Exhaust flow switch initiates
flowpath is lost? wind. Unlikely collapsed or bent stack. Scenario A on loss of flow.
Loss of ventilation. Potential loss
of flow or back flow into vent
header. Blockage of exhaust gas
flow and potential creation of
flammable environment in
enclosure and vent stack.
U-4 What if ventilation Failure of stack due to high Very Process upset. No immediate Design of Stack.
flowpath is lost? wind. Unlikely release.
Break of stack at ground level.
Vent of effluent at ground level.
Potential loss of ventilation fan.
U-5 What if ventilation is Failure of ventilation fan. Likely Potential flammable Loss of ventilation fan trips process
lost? concentrations of hydrogen or controls.
vapors in stack. Vapors would
dissipate out the stack.
U-6 What if loss of Enclosure ventilation is Likely Loss of environmental control in Loss of ventilation shuts off the
Enclosure Ventilation? lost. enclosure. hydrogen flow, the heaters and the
pumps via shutdown scenario A.
U-7 What if relief header Relief header is blocked by Unlikely Inadequate pressure relief. Administrative controls to check
flow is lost? bird/bees nests. relief header.
Design of system includes bird
Mud daubers screens, double release path at top.
commonly plug drain at Design pressure of knockout pot is
382 (100 psi) 12 psi.
U-8 What if relief header Activation of pressure Likely Flammable atmosphere. Design of knockout pot and lines. C Auto-ignition would
flow is activated? relief Potential flammable atmosphere require high
in relief header and knockout pot. temperature.
U-9 What if there is a pool Leak of flammable liquid Unlikely Energetic Event. Design of Product Tank (V-160 C
Fire in Enclosure accumulation in enclosure, Potential impingement on vessels, A/B).
secondary containment and lines, or structure. Pressure Test Procedure.
subsequent pool fire. Structural failures and Distillation skid has separate
impingement could lead to line or containment from the hydrotreater
Page 58 of 98
Hazard ID/
vessel ruptures. skid.

Enclosure Design Class 1 Div 2
Flammable vapor monitor on skid
Fire suppression system in enclosure
Reactor column is shielded by
furnace enclosure which would limit
exposure and rapid temperature rise
to heat up the vessel.
stop.
U-10 What if there is an Line leak of hydrogen Unlikely Energetic Event. Potential Design of hydrogen pipe system. C
impingement (jet) fire supply or pressurized impingement on vessels, lines, or Excess flow valve on hydrogen C
(hydrogen or flammable liquid line. structure. supply.
pressurized flammable Structural failures and Flame detection inside enclosure.
liquid line) in impingement could lead to line or Hydrogen monitor on skid and
Enclosure? vessel ruptures. enclosure.
enclosure.
Reactor column shielded by furnace
enclosure which would limit
exposure and rapid temperature rise
to heat up the vessel.
stop.
U-11 What if there is a fire in Loss of function of various Very (The scenarios identified for other Vessel protection, pressure relief. Two power cabinets.
electrical power components (pumps, Unlikely hazards, including the bounding Enclosure Design. Design of Two separate
cabinets inside valves, control systems). scenario of vessel over electrical cabinets. All cables in instrument cabinets.
enclosure? Potential multiple spurious pressurization.) conduit.
actions.
U-12 What if the water mist Inadvertent actuation Unlikely Process upset. No immediate Column design.
system actuates? results in water mist during release. Spraying water on hot The mist system is a low volume
operation. systems, leading to loss of system.
pressure boundary due to thermal Top of vessels are not insulated and
stress (e.g., reactor and distillation could be at 160 C.
columns). Columns are not constrained.
U-13 What if the water mist Inadvertent actuation Unlikely Process upset. No immediate Cabinets are sealed and purged.
system actuates? results in water mist during release. Shorting in electrical
Page 59 of 98
Hazard ID/
operation. cabinets.
U-14 What if Fire in Fire department quenches Process upset. No immediate Notification of fire department
enclosure? vessel. release. Spraying water on hot would only occur with initiation of
systems, leading to loss of Scenario C.
pressure boundary due to thermal
stress (e.g., reactor and distillation
columns). Note: Standard
response to vessels in fire
including liquid gases is to spray
water and move to safe distance.
U-15 What if Fire in PDL- Fire outside enclosure Likely Process upset. No immediate Fire alarm system activation initiates
West? initiates evacuation. release. Evacuation of PDL-West Scenario A.
resulting in unattended operation
of the system.
U-16 What if process control Loss of process control due Unlikely. Process upset. No immediate PLC design such that all control
is lost? to PLC failure. release. PLC fails to goes to their failed states (fail safe)
indeterminate state. as controlled by skid.
PLC is protected by UPS.
U-17 What If you lose power Short term loss of power. Likely Process upset. No immediate Process monitoring and control on Back pressure
and you are in the (Seconds- expected release. VFD on exhaust fan goes UPS and still available. Loss of regulator allows
middle of the run? monthly). offline on a fault but hydrotreater ventilation shuts off the hydrogen reactor to lose
system does not recognize it. flow, the heaters and the pumps via pressure slowly.
shutdown scenario A. Process can
start on resumption of ventilation
flow.
U-18 What if longer term Longer term loss of power Likely Process upset. No immediate Process monitoring on UPS and still
loss of power and you (minutes expected a few release. Loss of exhaust fan and available. E-Stop maintained. Loss
are in the middle of the times a year). compressed air. Loss of MAU. of ventilation shuts off the hydrogen
run? Loss of normal power lighting. flow, the heaters and the pumps via
shutdown scenario A. Alarm on Z
purge. Reactor pressure maintained
in stable condition with slow decay.
U-19 What if longer term Extended power outage (> Likely Process upset. No immediate Procedures to initiate shut-down.
loss of power and you than UPS capacity). release. Forced Shutdown. Loss Loss of fire system UPS battery
are in the middle of the of process monitoring and control. would result in opening XV-4020.
Page 60 of 98
Hazard ID/
run? Loss of exhaust fan and

compressed air. Loss of MAU.
Loss of normal power lighting.
U-20 If there is loss Loss of air compressor. Likely Process upset. No immediate Enclosure ventilation is maintained.
instrument air, what Failure in the compressed release. Pneumatic hydrogen and E-Stop functionality is maintained.
happens from system air delivery system. nitrogen valves close, badger Alarm on z-purge.
overall? valves close. The ISCO pump Alarm notification on loss of
valves would close. Loss of Z hydrogen. Reactor pressure
purge. boundary is stable. Distillation
pressure boundary is stable.
U-21 What if there is loss of Loss of cooling to V-140 Likely Process upset. Condensation leads Switch over to tempered water. See
the chilled water? results in excessive vapors to potential plug of off gas controls for loss of off-gas
and steam carryover to off system. scenarios.
gas system.
U-22 What if there is loss of Loss of cooling to V-140 Likely Process upset. Blow-down of Switch over to tempered water.
the chilled water? results in steam generation steam into the chilled water Procedural control over restart of
in the water jacket around system Z-172. system. (Check integrity of hoses)
V-140.
U-23 What if there is loss of Tempered water loss. Likely Process upset. Overheating of P- Procedural steps.
the tempered water? Results in difficulty in 182.
pumping bio-oil and heavy
products.
U-24 What if there is a Failure in the hydrogen Very Flammable atmosphere -PDL. It is one piece of tubing (`~17 feet)
hydrogen line leak line. Unlikely Release of hydrogen to PDL. rated at maximum pressure.
outside the enclosure? Loss of hydrogen to reactor. Located in a tray sitting in a tube
holder supported across the length.
It is at 13 foot elevation, in a tray,
protected from edge of building.
Excess flow valve on hydrogen
supply (catastrophic break).
Makeup air unit for enclosure.

Passive PDL roof vents.
U-25 What if there is a Failure in the hydrogen Very Flammable atmosphere. Design Hydrogen pipe system. C
hydrogen line leak in line. Unlikely Excess flow valve on hydrogen C
the enclosure? Process impacts same as loss of supply (catastrophic break).
hydrogen flow to reactor. Enclosure Design Class 1 Division
2.
Page 61 of 98
Hazard ID/
Enclosure Ventilation System

Hydrogen monitors on skid and in
enclosure.
enclosure.
U-26 What if hydrogen Addressed previously.
pressure goes down? -
How to regulate
U-27 What if temperature too Loss of HVAC Likely Process upset. Potential failure of Initiation of shutdown sequence Personnel will get
high in the hi-bay? conditioning high PLC or instrumentation in based on personnel comfort too hot before
temperature. enclosure. temperature. electronics fail
U-28 What if temperature too Loss of HVAC Likely Process upset. Potential impact in Initiation of shutdown sequence
low in hi-bay? conditioning low PDL-West, freezing due to based on personnel comfort
temperature. continued operation of Enclosure temperature.
exhaust air.
Lose ability to operate water mist
system.
U-29 What if you have a Addressed previously. Unlikely Personnel Exposure. Potential Enclosure Ventilation System.
nitrogen leak into oxygen deficient atmosphere.
enclosure?
U-30 What if nitrogen leaks Personnel Exposure Potential
into PDL-West? oxygen deficient atmosphere in
PDL-West.
U-31 What if operational Impact from Crane or load. Likely Flammable atmosphere. Operational restriction on crane use.
upset from other PDL- Rupture of process lines or utility
West operations? (See lines leading to release of
hazardous scenario.) flammable gases. Impact to
enclosure, exhaust ducts.
U-32 What if operational Spill or leak in PDL-West Likely Flammable atmosphere. Flammable vapor monitor.
upset from other PDL- results in introduction of Flammable or hazardous vapors Enclosure Design Class 1 Div 2.
West operations? (See flammable or hazardous in Enclosure. MCA alarm, 20 minute bypass timer
hazardous scenario.) vapors to Enclosure. until Scenario A is initiated (unless
operator bypasses).
U-33 What if operational Intake vehicle exhaust into Likely Personnel Exposure/Process Administrative Control of vehicles Intakes are at ground
upset from other PDL- ventilation system. upset. Impact to operations staff in vicinity of building intakes (e.g., level.
West operations? (See in PDL West and within Do not park and idle)
Page 62 of 98
Hazard ID/
hazardous scenario.) Enclosure.

Inadvertent actuation of
flammable vapor detection system
U-34 What if operational Hot work in PDL-West Likely Process upset. Inadvertent flame Hot Work Administrative Control.
upset from other PDL- results inadvertent flame detection, actuation of mist
West operations? (See detection, actuation of mist system during operation (see
hazardous scenario.) system. above)
U-35 What if operational Future chemical fume hood Likely Flammable atmosphere. Exhaust flow operation.
upset from other PDL- operations and tie-in. Release of flammable, hazardous Administrative control of fume
West operations? (See vapors into exhaust system. hood.
hazardous scenario.) Includes chemicals like Ensure future Tie-ins occur
acetone, sulfide agents downstream of the Enclosure
Page 63 of 98
Page 64 of 98
3.4 Evaluation of High Hazard Scenarios
Accident scenarios perceived as having high unmitigated consequences (energetic events with impacts
outside the hydrotreater enclosure) were identified for further evaluation of the consequence and
adequacy of controls. The following classes of scenarios were identified as being highly energetic and
having high consequences and are further evaluated herein:
1. Boiling Liquid Expanding Vapor Explosion (BLEVE)
2. Pressure Vessel Bursts (PVB)
3. Flammable Vapor/Hydrogen leaks leading to deflagrations in the process enclosure (FA)
3.4.1 Boiling Liquid Expanding Vapor Explosion (BLEVE)

The hazard analysis identified hazard scenarios potentially resulting in BLEVEs in the hydrotreater
reactor and distillation column and in several process vessels.
Of these events, consequences for the hydrotreater reactor (R-130) and distillation column (V-184) are
further presented here. These components pose the highest consequences based on heat input, pressure
and volume of material.
For the other pressurized process vessels, the possibility of a BLEVE is very remote as there were no
identified internal heat inputs which would raise the temperature of the liquid above boiling and the
vessels are insulated which would serve to protect them against the consequences of a BLEVE
associated with an external fire. BLEVEs are not associated with atmospherically vented vessels unless
a mechanism is identified that also results in a complete blockage of the ventilation pathway for the
vessel.
3.4.1.1 BLEVE Consequence Methodology

A Boiling Liquid Expanding Vapor Explosion (BLEVE) is the result of the sudden catastrophic failure
of a pressurized vessel containing liquid above its atmospheric boiling point. A BLEVE requires that
the loss of containment be sudden and significant in size. Partial failures leading to two-phase jet
releases would not be called a BLEVE since it does not represent a sudden loss of containment (CCPS,
2010). Depending on whether the liquid in the vessel is flammable or non-flammable, a BLEVE may
include the following effects:
blast effects (pressure wave due to the rapid vaporization of the liquid)
missile impacts (fragment and debris throw)
fireball (thermal hazards)

For analyzing BLEVEs, the process outlined in CCPS, 2010 was followed. Since the distillation column
V-184 vessel is comprised of two sections of differing size and wall thickness, the process outlined in
CCPS, 2000 was used to calculate the missile fragment range.
Page 65 of 98
Blast Effects: It was conservatively assumed that the blast effects are based on the work done during an
isentropic expansion process and that the energy is based on the combined energy from the liquid and
vapor. The explosion energy can be written as:
Explosion Energy, Eex= 2eexm

Where:
2 = a multiplier for ground effects.
eex = work done, u1-u2, the change in internal energy from state 1 (just before the failure)
to state 2 (atmospheric) for both the fluid (f) and gas (g).
m = mass of fluid released; the volume of fluid/specific volume V1/v1.
u1(f,g) = internal energy of the (fluid, gas) at the initial conditions. These values can be
obtained directly from NIST thermodynamic data.
u2(f,g) = internal energy of the (fluid, gas) in the expanded state, adjusting for the flashing
fraction.
Where:
u2f = (1-Xf)*u2f +Xf*u2g
u2g = Xg*u2f+ (1-Xg)*u2g
Xf = (s1f- s2f)/ (s2g s2f)
Xg = (s2g- s1f)/ (s2g s2f)
Energy available Per the CCPS, 2010 methodology assuming ductile failure, the energy available is
Eex,a = 0.4* Eex. Recent work by Casal and Salla present BLEVE overpressure estimations based on
superheat and state the energy available is ~ 14% (assumed to be 15%) of the superheat energy
calculated by the isentropic process. Therefore; a range based on the above correlations is provided for
each of the BLEVE overpressure calculations.
The scaled standoff distance, of the receptor is then determined by:
= R*[p0/ Eex,a]1/3
Where:
R= distance to receptor
p0 = atmospheric pressure
The scaled pressure s and impulse s at the receptor location are then estimated - Figures 7.6 and 7.8 of
CCPS, 2010 and the final side-on pressure (PS) and impulse (IS) are calculated:
PS =kp*s* p0
IS =ki* s* p02/3*Eex,a1/3/a0
Where:
a0 = speed of sound in ambient air
k(p,i) scaling factor for cylindrical vessels, from Lees, 2012 - Table 17.54
Scaled dist. < 0.3 < 3.5 > 3.5 Scaled dist. < 0.3 < 1.6 > 1.6
kP 4 1.6 1.4 kI 4 1.6 1.4
Page 66 of 98
Missile impacts (Hydrotreater): For missiles or rocketing fragments from a bursting vessel, CCPS,
2010 provides a simplified approach (Baum) to estimate the maximum likely range for fragments, Rfrag.
This approach is judged to be very conservative with respect to the potential for fragment travel for
hydrotreater components:
1) The approach is derived from open field events (impacts of fragments with the enclosure and
PDL-West building would significantly reduce the distance travelled),
2) The approach ignores drag associated with the fragments, and
3) The approach was derived for thin-walled vessels where the energy potential to weight ratio is
much larger than that for the hydrotreater/distillation column components.
From CCPS, 2010 the maximum likely range for of the fragments, Rfrag, meters is estimated by:
For vessels < 5 m3 the maximum likely range Rfrag= 90*m0.333
Where:
m = mass of the liquid and vapor in the vessel at the time of failure, kg
Missile impacts (Distillation Column): For missiles or rocketing fragments from the Distillation
Column, a different approach was used to estimate the maximum likely range for fragments, Rfrag. This
approach was used to account for the two different sections of the vessel with varying wall thickness.
This approach is judged to be very conservative with respect to the potential for fragment travel for
distillation column components:
1) The approach is derived from open field events (impacts of fragments with the enclosure and
PDL-West building would significantly reduce the distance travelled) and
2) The approach ignores drag associated with the fragments.
From CCPS, 2000 the interpolated likely range for of the fragments, Rfrag, meters is estimated by:
Rfrag = ( * mfrag)/(0 * CD *AD)
Where:
= scaled maximal range (dimensionless)
mfrag = mass of the fragment, lb
0 = density of air, lbm/ft3
CD = drag coefficient for fragment; for sphere = 0.47
AD = fragment surface area, ft2
g = acceleration due to gravity, length/time2
Where:
= 0CDADu2/(mfrag*g)
mfrag = mvessel/nfrag
AD = Avessel/nfrag
Page 67 of 98
Thermal Hazards: Thermal hazards, including radiation impacts, would be limited as the hazard
scenarios are enclosed within the process enclosure and PDL-West building versus an open field. As
such the (maximum) fireball size and duration are calculated as a measure of the potential severity of the
event with respect to close (engulfed) distances.
CCPS, 2010 provides an estimate of the fireball diameter, Dc and duration, tc based on mass of fuel, mf
in the vessel.
Dc = 5.8*mf(1/3)
tc = 0.45* mf(1/3) for mf <30,000 kg
Where:
mf = mass of the fuel in the fireball, kg
3.4.1.2 BLEVE Results
Hydrotreater Reactor (R-130)
For the hydrotreater reactor, R-130, it is assumed the pressure in the vessel is at the PRV set point
3000 psig. This is a reasonably conservative assumption as this is a significantly higher pressure than
the operating pressure (~2000 psig) and there were no events identified which would cause rapid
significant pressure increases. It was conservatively assumed that the reactor contained only water and
catalyst, and that the 13 liters of water volume contained 6.5 liters of liquid (water), as normally only
minimal liquid is expected in the reactor and the remainder of the vapor space is steam. Accounting for
hydrogen and bio-oil within the reactor would lower their potential energy due to the thermodynamic
properties compared to water.
Input Assumptions:
Pressure State 1 3000 psig 20.6 MPa
Temperature State 1 368 C, saturation temperature
Pressure State 2 14 psi 0.1 MPa
Temperature State 2 99.6 C, saturation temperature
Volume of Reactor 26 liters 0.026 m3
Free volume (assume 50% filled with catalyst) 13 liters 0.013 m3
Volume of Liquid (assume 50% of free volume) 6.5 liters 0.0065 m3
Speed of sound in air, a0 340 m/s
Page 68 of 98
Thermodynamic properties -Water; http://webbook.nist.gov/chemistry/fluid/

Specific Internal Entropy Sound
Temperature Pressure Cv Cp
Volume, v Energy, u S Spd. Phase
(C) (MPa) (J/g*K) (J/g*K)
(m3/kg) (kJ/kg) (J/g*K) (m/s)
99.606 0.1 0.0010432 417.4 1.3028 3.7702 4.2152 1543.5 liquid
99.606 0.1 1.6939 2505.6 7.3588 1.5548 2.0784 471.99 vapor
368.22 20.6 0.0021291 1817.5 4.067 3.6749 31.326 383.96 liquid

368.22 20.6 0.005359 2261.5 4.8629 4.4004 65.397 373.25 vapor
Using the input assumptions and thermodynamic data provided:
The positive side-on overpressure (Ps) and positive side-on impulse (Is) at the following receptor
locations are:
Actual Receptor 3 7 10 30 35
Distance, meters
scaled distance , m 1.6-1.2 3.8 - 2.7 5.4 3.9 16.3 - 11.7 19 - 13.7
Ps, kPa 45 - 70 12- 28 8 -12 2-3 1.4 2.5
IS, Pa-s 0.09 - 0.16 0.03 - 0.06 0.02 0.03 <0.01 0.01 <0.01
The maximum likely range of fragments calculated using the CCPS, 2010 method was determined to be
~ 145 meters. As noted in Section 3.4.1.1 this distance is judged to be a very conservative estimate.
Thermal hazards were not assessed as the evaluation assumed the vessel was filled with water (liquid
and vapor) to maximize the pressure and fragment impacts. Thermal hazards would be constrained by
the PDL-West building and would be expected to be minimal given the steam (inerting and heat
absorption) and limited quantity of flammable material. Thermal hazards are addressed in the following
discussion for the distillation column and in Section 3.4.2 PVB for the reactor (assuming only hydrogen)
in the vapor space.
Distillation Column (V-184)
For the Distillation Column, V-184, it is assumed the pressure in the vessel is at the PRV set point of
70 psig. This is a reasonably conservative assumption as this is a significantly higher pressure than the
typical operating pressure (atmospheric to 15 psig) and there were no events identified which would
cause rapid significant pressure increases. V-184 consists of two pipe sections of differing wall
thickness; the smaller wall thickness (0.203 inches) was used in calculations as a conservative estimate.
Due to the differing size of the sections, it was assumed that two fragments would result in the event of a
BLEVE. It was conservatively assumed that the distillation column was filled ~70% (11 liters) with
octane and the remaining vapor space (5.3 liters) consisting of saturated octane vapors. Accounting for
treated bio-oil or heavy distillates within the distillation column would lower the potential energy of the
process due to their thermodynamic properties compared to octane.
Page 69 of 98
Input Assumptions:
Temperature State 1 193 C saturation temperature
Temperature State 2 126 C saturation temperature
Volume of V-184 16.3 liters 0.0163 m3
Volume of Liquid, octane, 70% 11 liters 0.011 m3
Equivalent spherical diameter 0.3145 m
Vessel failure pressure 70 psig 482.63 kPa abs
Vessel liquid fill fraction 0.675
Vessel wall thickness 0.203 in 0.52 cm
Vessel wall density 7800 kg/m3
Temperature 193C 466.15 K
Ambient pressure 101.325 kPa abs
Drag coefficient of fragment 0.47
Lift to drag ratio: 0
Thermodynamic properties -Octane; http://webbook.nist.gov/chemistry/fluid/

Specific Internal Entropy Sound
Temperature Pressure Cv Cp
Volume, Energy, u S Spd. Phase
(C) (MPa) (J/g*K) (J/g*K)
v (m3/kg) (kJ/kg) (J/g*K) (m/s)
125.51 0.101 0.0016331 -0.47239 -0.00076975 2.1864 2.6481 772.03 liquid
125.51 0.101 0.27138 274.56 0.75746 2.0434 2.1426 164.49 vapor
192.93 0.48253 0.0018453 188.72 0.43715 2.4468 2.9968 525.54 liquid

192.93 0.48253 0.058767 409.58 0.96994 2.3665 2.5465 156.9 vapor
locations are:
Actual Receptor 3 7 10 30 35
Distance, meters
scaled distance , m 3.6 2.6 8.5 6.1 12 8.7 36 - 26 42 -30
Ps, kPa 13 - 29 4.3 - 7 3-4 <1.3 1.4 <1.3
IS, Pa-s 0.017 - 0.04 0.007 - 0.01 0.005 - 0.009 <0.004 <0.004
The interpolated likely range of fragments calculated using the CCPS, 2000 method was determined to
be ~ 84 meters. As noted in Section 3.4.1.1 this distance is judged to be a very conservative estimate.
Page 70 of 98
The maximum fireball size was determined to be 10.6 meters with a duration of 0.8 seconds, not
accounting for confinement provided by the enclosure or building.
3.4.2 Pressure Vessel Burst Scenarios
The hazard analysis identified scenarios as resulting in pressure vessel bursts (PVBs) in the Reactor and
Distillation Columns and Process Vessels.
Of these events, consequences for the Hydrotreater Reactor (R-130) and Distillation Feed Tank (V-180)
are further presented here. These vessels are pose the highest consequences based on pressure and
vessel volume.
3.4.2.1 PVB Consequence Methodology
Similar to a BLEVE, a PVB accident is the result of the sudden catastrophic failure of a pressurized
vessel containing gas. Depending on whether the gas in the vessel is flammable of non-flammable a
PVB may include the following effects:
blast effects (pressure wave due to the rapid expansion of the gas)
missile impacts (fragment and debris throw)
fireball (thermal hazards)
CCPS, 2010 notes PVBs usually do not result in ignition; therefore, thermal hazards are only addressed
for the R-130 reactor under the assumption that the vessel free volume (headspace) is completely filled
with hydrogen.
For analyzing PVBs, the Brode constant volume energy addition methodology, which provides an upper
limit of the energy released, according to CCPS, 2010, was followed.
Blast Effects: The explosion energy can be written as:
Explosion Energy, Eex,Br = (p1-p0)V1/(1 -1)

Where:
1 = ratio of constant pressure to constant volume of specific heat of the gas in the vessel
p0 = ambient (atmospheric) pressure to constant volume of specific heat of the gas in the vessel
p1 = pressure in the vessel prior to burst
V1 = Volume of vessel (gas)
Energy available assuming ductile failure Eex,a = 0.4* Eex,Br
The scaled standoff distance, of the receptor is then estimated:
= R[p0/ Eex,a]1/3
Where:
R= distance to receptor
p0 = atmospheric pressure
Page 71 of 98
The scaled pressure s and impulse s at the receptor location are then determined - Figures 7.6 and 7.8
of CCPS, 2010 and the final side-on pressure (PS) and impulse (IS) are calculated:
PS =kp*s* p0
IS =ki* s* p02/3*Eex,a1/3/a0
Where:
a0 = speed of sound in ambient air
k(p,i) scaling factor for cylindrical vessels, Lees, 2012, Table 17.54
Scaled dist. < 0.3 < 3.5 > 3.5 Scaled dist. < 0.3 < 1.6 > 1.6
kP 4 1.6 1.4 kI 4 1.6 1.4
Missile impacts (rocketing fragments): For missiles or rocketing fragments from a bursting vessel, the
same approach as discussed for BLEVEs was used.
Thermal Hazards: For thermal hazards from a bursting vessel, the same approach as discussed for
BLEVEs was used.
3.4.2.2 PVB Results
For the hydrotreater reactor, R-130, it is assumed the pressure in the vessel is at the PRV set point 3000
psig. This is a reasonably conservative assumption as this is a significantly higher pressure than the
typical operating pressure (~2000 psig) and there were no events identified which would cause rapid
significant pressure increases resulting in a common cause failure of the pressure relief valve. It was
conservatively assumed that the reactor contained only hydrogen and catalyst.
Input Assumptions:
Volume of Reactor 26 liters 0.026 m3
Free volume (assume 50% filled with catalyst) 13 liters 0.013 m3
Volume of hydrogen 13 liters 0.013 m3
3
Specific Volume 0.13651 m /kg
1 1.41
locations are:
Page 72 of 98
Actual Receptor Distance, 3 7 10 30 35

meters
scaled distance , m 1.7 4.1 5.8 17 23
Ps, kPa 46 11 7 1.7 <1.4
IS, Pa-s 0.08 0.02 0.015 0.005 <0.005
The maximum likely range of fragments calculated using the CCPS, 2010 method was determined to be
~ 41 meters. As noted in Section 3.4.1.1 this distance is judged to be a very conservative estimate.
The maximum fireball size was determined to be 2.6 meters with a duration of 0.2 seconds.
Distillation Feed Tank (V-180)
For the Distillation Feed Tank, V-180, it is assumed the pressure in the vessel is at the PRV set point of
70 psig. This is a reasonably conservative assumption as this is a significantly higher pressure than the
typical operating pressure (atmospheric to 15 psig) and there were no events identified which would
cause rapid significant pressure increases resulting in a common cause failure of the pressure relief
valve. It was conservatively assumed that the vessel contained only nitrogen.
Input Assumptions:
Volume of vessel 140 liters 0.140 m3
Specific Volume (20C) 0.18107 m3/kg
1 1.4
locations are:

meters
scaled distance , m 2.95 6.88 9.83 29.48 34.40
Ps, kPa 20.3 5.5 3.7 <1.42 <1.42
IS, Pa-s 0.02 0.008 0.005 <0.0004 <0.0004
The maximum likely range of fragments was determined to be ~83 meters. As noted in Section 3.4.1.1
this distance is judged to be a very conservative estimate.
3.4.3 Deflagration Scenarios

The hazard analysis identified scenarios as resulting in flammable gas/vapors being released to the
enclosure from the hydrogen system and process vessels and piping.
Of these events, consequences from a rupture of the hydrogen supply piping within the hydrotreater
enclosure was analyzed as a bounding case. The consequences for a large release of hydrogen gas
Page 73 of 98
(assumed not to be a PVB or BLEVE) from the hydrotreater reactor was also analyzed to provide a
bounding case for the release of vapors from process vessels and piping.
3.4.3.1 Deflagration Consequence Methodology

Potential ignition of flammable vapors within the enclosure were modeled using the TNT Equivalency
Method as evaluated in the Physical Sciences Facility Fire Hazards Analysis Report, following the
approach presented in Analytical Approach for Gas Explosions for DOE Nuclear and Non-Nuclear
Facilities (Louie and Restrepo).
The TNT approach provides a proportional relationship between the total quantity of flammable material
released (whether or not it is within the flammability limits or at the stoichiometric concentration) to an
equivalent weight of TNT. This weight of TNT, WTNT, is then used to determine a scaled distance, R,
from which predicted overpressure can used determined using the peak side-on overpressure curve
appropriate for the surface TNT equivalence method:
WTNT = g(Wg*Hg /HTNT )
Where:
g = TNT equivalence factor or yield factor (dimensionless)
Wg = weight of the combustible gas (kg)
Hg = combustion energy of the combustible gas (J/kg)
HTNT = TNT blast energy (J/kg)
The scaled distance, R is then calculated by:
R = R/W1/3 TNT
Where:
R = distance to receptor
For TNT equivalency methods, the side-on pressure can then be taken directly from the appropriate
overpressure curve.
3.4.3.2 Deflagration Results
Hydrogen Supply Line Rupture
For the hydrogen supply line rupture, it was assumed the quantity of hydrogen released equated to the
volume of the hydrotreater enclosure.
Input Assumptions and thermodynamic data:

Volume of hydrogen in the enclosure 285 m3
Density of Hydrogen at 20C 0.083191 kg/ m3
Weight of Hydrogen 23.7 kg
TNT equivalence factor g 0.2 from (Louie and Restrepo)
Combustion energy, Hg 4.6E+06 J/kg
TNT blast energy, HTNT 1.42E+06 J/kg
Page 74 of 98
From the TNT equivalence method:

WTNT = g*(Wg*Hg /HTNT )
= 1.5E-01 kg
The positive side-on overpressure (Ps) at the following receptor locations was then determined based on
the scaled distance (Louie and Restrepo):

meters
scaled distance , m 5.6 13 19 56 65
Ps, bar 0.40 0.15 0.07 0.02 0.014
Ps, kPa 40 15 7 2 1.4
For the hydrotreater reactor, R-130, it is assumed the mass in the vessel was based on the vessel free
volume and the pressure at the pressure relief valve setpoint of 3000 psig with a temperature of 368 C
as was evaluated in the BLEVE case. This is a conservative assumption with respect to normal
operating pressure (~2000 psig). To account for hydrogen within the supply line, the weight of
hydrogen released was doubled.
Page 75 of 98
Input Assumptions and thermodynamic data:

Volume of hydrogen is Vessel 0.013 m3
Specific volume of Hydrogen v1 0.13651 m3/kg
Weight of Hydrogen (V/v1) 0.095231 kg
TNT equivalence factor g 0.2 from (Louie and Restrepo)
Combustion energy, Hg 4.6E+06 J/kg
TNT blast energy, HTNT 1.42E+06 J/kg
From the TNT equivalence method:

WTNT = g(Wg*Hg /HTNT )
= 1.23E-03 kg
The positive side-on overpressure (Ps) at the following receptor locations was then determined based on
the scaled distance (Louie and Restrepo):
Actual Receptor Distance, 3 7 10

meters
scaled distance , m 28 65 93
Ps, bar .025 0.01 < 0.01
Ps, kPa 2.5 1 <1
3.4.4 Calculation Summary
Comparing the calculated overpressures from the above conservative analyses to the damage estimates
of Table 3-5 shows that a failure of the hydrotreater/distillation column enclosure would result in the
event of a BLEVE, PVB, or explosion of hydrogen within the enclosure. However, only for a BLEVE
of the reactor (R-130) could significant overpressures (greater than 21 kPa) be developed which would
challenge the PDL-West building structure itself. There were no cases in which overpressures sufficient
to result in greater than minor damage (7 kPa) reached at the nearest analyzed location (PDL-East).
For missile generation, the CCPS, 2010 methodology conservatively estimates missile ranges out to
~145 meters for the hydrotreater. As noted, this ignores several physical properties associated with the
event. DOE-TIC 11268, Figure 6.17 identifies that the 90th percentile fragment range as being less than
~24 meters (80 feet) for an energy level of 2.2E+07 joules (1.6E+07 foot-pounds) which is more than 10
times greater than calculated energy available for the R-130 BLEVE limiting case.
For all events analyzed, the robust design of the hydrotreater/distillation column systems make the
overpressure and missile generation events very low likelihood scenarios.
Page 76 of 98
Table 3-5. Damage Estimates for Common Structures Based on Overpressure

Pressure
kPa psig Damage
2.07 0.3 Safe distance (probability 0.95 of no serious damage below this
value); projectile limit; some damage to house ceilings; 10%
window glass broken.
3.4-6.9 0.5 - 1 Large and small windows usually shattered; occasional damage to
window frames.
13.8 - 20.7 2-3 Concrete or cinder block walls, not reinforced, shattered
20.7(1) - 27.7 3-4 Frameless, self-framing steel panel building demolished; rupture of
oil storage tanks
34.5 5 Wooden utility poles snapped; tall hydraulic press (40,000 lb) in
building slightly damaged
34.5 - 48.2 5-7 Nearly complete destruction of houses
68.9 10 Probable total destruction of buildings; heavy machine tools
(7000 lb) moved and badly damaged; very heavy machine tools
(12000 lb) survive
AIChE/CCPS, Guidelines for Chemical Process Quantitative Risk Analysis, New York: AIChE, 2000
(1) Assumed threshold for serious damage from Lees 2012.
Table 17.28- Typical Values of Failure Pressures in Building Structures
Failure Pressure (kN/m2) [kPa]
Windows (normal) 3-4.6
Windows (strained) 1, or even 0.2
Chipboard (19mm) 7
Brick wall (114mm) Survived at 23, destroyed at 35
Brick wall (228mm) Survived at70, destroyed at 105
It has been suggested by Buckland (1980) that the explosion pressure should not
exceed 21 kN/m2 if the building is to avoid serious damage.
Page 77 of 98
4.0 HAZARD CONTROLS
4.1 Critical Controls
This section describes the attributes of the critical controls (Table 4-1) specifically identified in the
hazard analysis as mitigating against the higher consequence hazards associated with the
hydrotreater/distillation column process as addressed in Section 3.4.
Table 4-1 Critical Hazard Controls

Hazard Control Event Type Hazard ID
Vessel Design per ASME Section VIII BLEVE H.4-6; H.4-7; H.4-9; H.7-1; H.2-10; H.4-11;
and ASME B341.3 H.4-18; H.1-19; H.2-20; D.2-7; D.4-3;
D.4-4; D.4-5; U-9
PVB H.1-16; H.2-7; H.4-17; H.4-18; H.4-22;
H.4-29; H.4-31; H.7-4; D.1-6; D.1-7;
D.4-13
FA H.4-8; H.4-15; H.4-20; H.7-8; D.1-10;
D.2-3; D.4-11; D.4-9;
Relief Valve Sizing and Flowpath BLEVE H.1-19; H.2-10; H.4-6; H.4-7; H.7-1;D.2-7;
Design D.4-3;
PVB H.1-11; H.1-15; H.1-16; H.1-21; H.2-7;
H.2-10; H.4-1; H.4-17; H.4-22; H.4-29;
H.4-31; H.7-4; D.1-6; D.1-7; D.1-14;
D.4-13
FA D.1-10; U-8
Piping Design per B31.3 and NFPA 55 FA H.5-2; H.6-1; H.7-7; D.1-10
Hydrogen Piping and Excess Flow BLEVE H.4-10; U-10
Valve Design per IFC FA U-25
Reactor and Distillation Column High- BLEVE H.2-20; H.3-6; D.2-17
High Temperature Interlock
Enclosure Design as Class 1 Division 2 BLEVE D.4-5
environment FA H.1-8; H.1-12; H.1-14; H.4-23; H.4-26;
H.4-28; H.4-8; H.5-2; H.7-5; H.7-9; D.5-7
Enclosure Ventilation System Design FA H.1-8; H.1-12; H.1-14; H.1-17; H.2-1;
H.2-2; H.2-3; H.4-23;H.4-28; H.4-8; H.7-5;
H.7-9; D.1-8; D.2-1; D.2-2; D.2-3; D.4-7;
D.4-9; D.5-7
Hydrogen Monitor FA H.1-8; H.1-12; H.1-14; H.1-17; H.2-1;
H.2-2; H.2-3; H.4-8; H.4-26; D.1-8
Flammable Vapor Monitor FA H.1-8; H.1-12; H.1-14; H.2-1; H.2-3; H.4-8;
D.2-3
Pressure Test Procedure BLEVE H.4-9; H.4-11; D.4-4
PVB H.4-18; D.4-13
FA H.1-8; H.1-12; H.1-17; H.1-18; H.4-8;
H.4-15; H.4-20; H.4-28; H.7-8; D.1-8;
D.1-13; D.2-1; D.2-2; D.2-3; D.4-9; D.4-11
Page 78 of 98
4.1.1 Vessel and Piping Design

The robust design of vessels, components, and piping (tubing) ensures the pressure integrity of the
process boundary for normal operations and upset conditions.
Vessel Design: The R-130 reactor vessel and V-184 distillation column are designed, fabricated,
welded, inspected, and tested in accordance with ASME B31.3 and augmented consistent with the
ASME Boiler and Pressure Vessel Code (ASME B&PV Code), Section VIII.
All vessels with a diameter greater than 6 inches and a design pressure greater than 15 psi are designed,
fabricated, welded, inspected, and tested in accordance with the ASME B&PV Code, Section VIII.
Relief Valve Sizing: All relief valves and pressure relief flowpaths are sized for the worst-case flow
rates, including any backflow from high to low pressure areas, per API 521. This includes the addition
of vessel insulation on vessels where required to support flow rates (CTI 12-631).
PSE-2005 upstream of Check Valve CK-2012 protects against backflow through P-121A/B from the
reactor.
Piping Design: All pressure piping is designed, installed (approved fittings, quick disconnects,
appropriate support distances, etc.), and leak tested in accordance with ASME B31.3 and NFPA 55. The
new valve, HV-2018, upstream of HV-2009 provides positive pressure boundary from the reactor R-130
when draining bio-oil/acetone from the P-121A/B pumps during the shutdown flushing modes.
Hydrogen Utility (supplied) Design: All hydrogen piping is installed in accordance with the
International Fire Code (IFC), which includes an appropriately sized excess flow control valve.
Maximum hydrogen pressure limited by compressor (3000 psi) and protected by pressure relief valve.
Page 79 of 98
Table 4-2 Vessel and Piping Design Summary

Component Vessel Design Vessel Design Pressure Relief Insulation (1)
Pressure (1)(2) Temperature (3) Setpoint
psig C Psig (1)
V-120 135 148 70 Yes
V-125 155 148 100 No
R-130 3000 426 (heads) 3000 No
537 (shell)
V-140 3000 454 3000 No
LG-142 3000
LG-147 100 148 Atm(4) NR
V-160A/B 155 148 70 Yes
V-161A/B 155 148 70 Yes
V-162 180 (4) 148 Atm(5) NR
V-163 180 (4) 148 Atm(5) NR
V-180 135 148 70 Yes
V-184 100 (5) 454 70 Yes
V-191 & 135 148 70 Yes
V-193
V-192 & 135 148 70 Yes
V-194
1/4"-T035-316 5100 (6) -
3/8"-T049-316 4800 (6)
1/2-T049-316 3700 (6) -
(1) From CTI 12-631, unless otherwise noted.
(2) Maximum Allowable Working Pressure
(3) From Project Drawings: 782-4-100 through 782-4-190
(4) Note: additional pressure relief provided by PSV-4016 upstream DWG-782-4-140
(5) From Project Drawing: 782-4-160
(6) Swagelock Tubing Data (R10) accessed at
http://www.swagelok.com/downloads/WebCatalogs/EN/MS-01-107.PDF
4.1.2 Reactor and Distillation Column Temperature Critical Controls

The high-high temperature interlock (500 C) for each of the eight zones of the R-130 vessel removes
power to its respective heater. This eliminates the source of external heat to that zone and provides
adequate margin below the vessel (shell) design temperature of 537C (Table 4-2).
The high-high temperature interlocks (425 C) remove power to the V-184 distillation column reboiler
and bottom section heaters to provide adequate margin below the vessel design temperature of 454C
(Table 4-2).
The ten (10) critical temperature controls (eight associated with R-130 and two associated with V-184)
use safety circuitry, independent of the control circuitry, to fulfill their shutdown functions {within the
HTDC documentation (e.g., P&IDs, Cause and Effect Diagram), TAHH-xxxxA denotes a control
circuit; TAHH-xxxxB denotes a safety circuit}. These safety and control circuits utilize independent
Page 80 of 98
thermocouples and PLCs to ensure safety system response is not compromised by failure of a control
system. These temperature critical controls (designated as P3 in the Supplemental HARs) receive
their own credit in the quantitative risk assessment (see Appendices D and E).
4.1.3 Enclosure Design and Ventilation

The enclosure design and ventilation system reduce the potential for deflagrations resulting from the
release of flammable vapors from the hydrotreater/distillation process pressure boundary.
Enclosure Design Class1 Division 2: All exposed electrical in the enclosure is Class 1 Division 2
(explosion proof) or contained in air purged cabinet (Z-Purge) to prevent the introduction of flammable
vapors/gases. This minimizes the potential for an ignition source.
Enclosure Ventilation System: The enclosure is normally ventilated at 6 air changes per hour, which is
consistent with standard laboratory flow rates at PNNL. The ventilation is well mixed due to the inlet
being toward the bottom of the enclosure and the outlet near the top. This minimum ventilation rate
meets the requirements of NFPA 55 and the IFC and reduces the concentration of flammable vapors to
below lower flammability limits. Loss of enclosure ventilation shuts off the hydrogen supply and
initiates Shutdown Scenario A (heaters, pumps, and hydrogen shutoff) from the hydrotreater/distillation
column process controller (see Appendix B, Key Design Information Reviewed, Interlock Matrices).
4.1.4 Hydrogen Monitors

There are three hydrogen monitors; one is installed high on the reactor skid and two are installed near
the ceiling in the enclosure. The ceiling detectors alarm at 10% of the LEL resulting in a fire alarm
control panel (FACP) supervisory alarm, and alarm at 25% of the LEL which results in an FACP
supervisory alarm, isolates the hydrogen supply, and initiates Shutdown Scenario A. The reactor skid
detector is interlocked to isolate the hydrogen supply at 25% of the LEL and also initiates Shutdown
Scenario A.
4.1.5 Flammable Vapor Monitors

Flammable vapor monitors (one H2S and two combustible gas detectors) are installed on the reactor and
distillation skids. The H2S detector alarms at 5 ppm resulting in an FACP supervisory alarm, and alarms
at 40 ppm which results in an FACP supervisory alarm and initiates Shutdown Scenario B. The two
combustible gas detectors alarm at 10% of the LEL and at 25% of the LEL initiate Shutdown
Scenario A.
4.1.6 Safe Operating Procedures (SOPs)

The system will be operated via approved procedures. Per the SOPs:
Trained operators: Each shift will have two operators (experienced with similar equipment) trained
per the approved operating procedures. The system will not operate unattended.
Pressure testing: Prior to the initiation of each run, the system is leak checked with nitrogen to
ensure any re-assembly or cycling does not create a leak.
System shutdown: This will ensure the system has been placed in a non-Class I/Div 2 status.
Page 81 of 98
4.2 Other Controls (Non-Critical)
This section describes the attributes of the other non-critical controls (Table 4-3) identified as providing
significant benefit in further reducing the event frequency for higher consequence hazards associated
with the hydrotreater/distillation column process as addressed in Section 3.4.
Table 4-3. Other Non-Critical Controls.

Hazard Control Event Type Hazard ID
Flame Detectors BLEVE D.4-5; H.4-10; H.4-11; U-9; U-10; U-25
Fire Suppression System BLEVE D.4-5; H.4-10; H.4-11; U-9; U-10; U-25
Temperature and Pressure BLEVE D.4-3; H.1-1; H.1-2; H.1-5; H.1-6; H.1-19;
Controls/Alarms Prompting Operator H.2-10; H.2-15; H.2-20; H.3-6; H.4-2; H.4-
Response 6; H.4-7; H.7-1; H.7-7
PVB H.4-17; H.4-27; U-1; U-7
Check Valves PVB H.4-1
Facility Configuration FA U-24; U-30
4.2.1 Flame Detectors

There are two flame detectors located in the enclosure; activation of either results in the following:
FACP alarm,
Isolation of the hydrogen supply,
Shutdown of the enclosure exhaust ventilation,
Activation of the water mist system,
Deactivation of power to the enclosure (after 5 second delay),
Opening the reactor purge (vent) valve (after 60 second delay), and
Initiation of Shutdown Scenario C.
4.2.2 Fire Suppression System
There are both sidewall wet-pipe sprinklers and a mist system located in the enclosure. The mist system
is activated when the flame detector is activated.
4.2.3 Temperature and Pressure Controls/Alarms Prompting Operator Response

There are numerous high temperature and pressure alarm and control set points that provide the operator
an opportunity to identify and correct an off-normal occurrence and to prevent/mitigate potential
problems; many of these instruments will automatically control the system to limit potential problems in
the unlikely event that prompt operator action is not taken. The high-high pressure interlocks (2700
psig) for the R-130 reactor vessel and the V-140 HP separator stop the flow of hydrogen and nitrogen
and feed of bio-oil into the reactor. This eliminates the sources of pressure input and limits any
exothermic reaction once the hydrogen is consumed thus protecting the pressure boundary of the reactor.
These temperature and pressure alarms and controls would further reduce the frequency of a hazardous
event.
Page 82 of 98
4.2.4 Check Valves

Check valves are in place throughout the hydrotreater system to protect against backflow.
4.2.5 Facility Configuration
The configuration of the facility housing the hydrotreater and distillation column skids will aid in ventilation of
the system. PDL-West facility is equipped with a passive ventilation system. In the event of loss of enclosure
ventilation, the large size of the PDL-West facility and passive ventilation system would further reduce the
frequency of hazardous event scenarios.
4.3 Safety Management Programs

In addition to the critical controls described above, institutional Safety Management Programs (SMPs)
are integrated into the PNNL requirements management infrastructure and delivered to staff members
through the How Do I? (HDI) work flows and work controls. HDI deploys the Laboratory-level
requirements and procedures to PNNL staff. SMPs that are directly related to the
Hydrotreater/Distillation project are identified below.
4.3.1 Worker Safety and Health

The Worker Safety and Health programs include the Chemical Hygiene Program, Hazard
Communication Program, Hazard Assessment Program, Chemical Management System, and Integrated
Safety Management System. Specific standards and procedures related to the operations of the
hydrotreater/distillation project (Working with Chemicals, Compressed Gases, Pressure and Vacuum
Systems, etc.) are provided in HDI, and implemented through Integrated Operations System (IOPS), and
other implementing procedures.
IOPS helps managers and staff to identify and mitigate operational risks of experimental work in PNNL-
operated workspaces. The processes involve identifying and managing risks and hazards associated
with activities performed in each IOPS workspace, continually assessing ongoing or changing work
risks, and controlling access so that only trained and authorized people are working in the workspace.
The IOPS tool delivers automated processes to support implementation of the IOPS program workflows
that IOPS Administrators, Cognizant Space Managers, workers, and others use to achieve a safe
workplace and efficient operations. The processes are designed to support the following:
Configuration of IOPS buildings
Establishing and maintaining IOPS workspaces
Providing tailored controls
Authorizing activities
Performing work and monitoring work for changes.
4.3.2 Fire Protection Program

PNNL has established and maintains a Fire Protection Program that implements the applicable
requirements of DOE O 420.1B, Facility Safety. This SMP applies to DOE facilities operated by PNNL
Page 83 of 98
including the PDL-West facility. The program affords a level of protection by providing the following
services:
Management of combustible materials and flammable liquids and gases
A permit process for hot work
Proper workspace housekeeping; facility and equipment modification design reviews and approvals;
and periodic facility inspections and assessments
Engineered features that minimize the potential for fire and the propagation of fires, including:
Facility fire walls and barriers
Fire detection and alarm systems
Automatic suppression systems including the mist suppression system within the enclosure
Portable fire extinguishers
Emergency services (e.g., fire, medical) for PDL-West are provided by the City of Richland
Implementation of applicable NFPA 101 requirements
Inspection and maintenance of fire alarm, detection, and suppression systems
Outages and impairments impacting fire protection systems are controlled and tracked through
formal, documented systems to minimize the fire risks while systems are out of service.
The fire protection program is intended to ensure an available means of egress for personnel during a
fire, minimize damage to property, and minimize the potential for DOE programs to suffer unacceptable
delays or effects as a result of fire.
4.3.3 Training and Qualification

The training and qualification function establishes Laboratory-wide policies and standards and maintains
a system for training delivery and documentation. Training and qualification requirements are
implemented to ensure that personnel responsible for facility operations, process operations, vehicle
operation, maintenance, and technical support are trained and qualified, as applicable, to accomplish
their safety-related responsibilities. Line management makes sure that personnel are trained to work
safely, effectively, and in accordance with DOE requirements and PNNL policies. PNNL training
requirements and standards provide a uniform method for identifying, performing, and documenting the
required indoctrination and training of PNNL staff.
4.3.4 Maintenance and Testing Program

This section discusses initial (startup) testing and maintenance programs for the PDL-West facility,
including the Hydrotreater/Distillation Column project.
4.3.4.1 Initial Testing

PNNL facility design procedures require testing to verify proper operation of equipment and systems
prior to their installation or return to service following facility modifications. Documents that
implement installation and post-modification testing are developed based on operational and equipment
functional requirements. Documents implementing installation, modifications, and associated tests
Page 84 of 98
(plans, permits, procedures, etc.) are prepared and peer reviewed by technical disciplines and line-
management, as appropriate.
4.3.4.2 Maintenance
The PNNL facility operations function establishes a maintenance program that implements applicable
maintenance requirements, including equipment vendor specifications and recommendations; and
applicable national, state, local, and DOE codes and standards. PNNL facility procedures require testing
to verify proper operation of specific safety equipment and systems (e.g., ventilation, cranes/hoists, fire
alarm/detection/suppression) prior to returning them to service following preventive/corrective
maintenance activities. Documents based on operational requirements; equipment functions;
manufacture recommendations; operational restrictions; and/or applicable national, state, local, and
DOE codes and standards implementing preventive/corrective maintenance actions and post-
maintenance testing are prepared and peer reviewed by technical disciplines and line management, as
appropriate.
Page 85 of 98
5.0 CONCLUSION
Two What-If hazard analyses were performed by PNNL to support the Hydrotreater/Distillation Process
operation. These hazard analyses postulated off-normal or upset conditions including the release of the
hazardous material or energy. For all events involving the release of material or energy, the hazard
analyses identified the hazard controls which would prevent or mitigate the release. For high-energy
events which could breach the hydrotreater and distillation column enclosure, the analyses were
supplemented by calculations documenting the potential magnitude of the bounding case unmitigated
consequences. The critical controls which are relied on to prevent the occurrence of these events are
identified (see Table 4-1). Additional hazard controls identified for these events provide defense-in-
depth by reducing either the potential for or consequences of the postulated events (See Table 3-4,
What-If Hazards Analysis Results). In addition, two supplemental hazard analyses were conducted and
quantitative risk assessments performed for the Distillation Column and Hydrotreater units (see
Appendices D and E).
With the identified hazard controls applied and operations performed within the envelope of the PNNL
Safety Management Programs, the risks posed from operation of the hydrotreater and distillation
columns are adequately mitigated, and these systems can be operated safely, consistent with PNNL
control of other laboratory operations.
Page 86 of 98
6.0 REFERENCES
AIChE, 1992, Guidelines for Hazard Evaluation Procedures With Worked Examples, 2nd Edition,
American Institute of Chemical Engineers, New York.
Casal, Joaquim and Salla, Josep, Using Superheating energy for a quick estimation of overpressures in
BLEVEs and similar explosions, Journal of Hazardous Materials, A137, 2006 pp. 1321-1327
CCPS, 2000, Center for Chemical Process Safety, Guidelines for Chemical Process Quantitative Risk
Analysis, American Institute of Chemical Engineers, New York.
CCPS, 2010, Center for Chemical Process Safety, Guidelines for Vapor Cloud Explosion, Pressure
Vessel Burst, BLEVE and Flash Fire Hazards, American Institute of Chemical Engineers, New York
DOE-HDBK-1100-2004, Chemical Process Hazards Analysis, U.S. DOE
DOE/TIC-11268, A Manual for the Prediction of Blast and Fragment Loadings on Structures, Change
1, 15 August 1981, U.S. DOE Albuquerque Operations Office
CTI 12-631, Rev 2, Pressure Relief Vent Header and KO Vessel Sizing for PNNL Hydrotreater Facility,
January 2013, Centaurus Technology Inc. Simpsonsville KY 40067
Lees Loss Prevention in the Process Industries. (Fourth Edition) Elsevier 2012,
DOI: http://dx.doi.org/10.1016/B978-0-12-397189-0.00017-3
Louie, David L.Y. and Restrepo, Louis F., Analytical Approach for Gas Explosions for DOE Nuclear
and Non-Nuclear Facilities.
Page 87 of 98
Appendix A: Attendees
Page 88 of 98
Attendees
Name Affiliation Role

Brawn David PNNL Building Engineer
Brooks Shirley PNNL Hazards Analysis
Carlson Jeff PNSO
Clark Pat PNNL Facilities and Operations
Coles Garril PNNL Hazards Analysis
Cuello Rob PNNL Operations
Dotson Paul PNNL Facility PM
Edwards Dan PNNL ES&H
Elliot Doug PNNL CBPDG
Elliot Mike PNNL
Evans Brad PNNL Nuclear Safety and Facility Authorization
Hart Todd PNNL Hydrotreater Project Operator
Hastings David PNSO
Lowry Pete PNNL Hazards Analysis
McGaughy Renee PNNL WS&H
McMullin Ken PNNL Building Manager
Minister Andrew PNNL Fire Protection
Neuenschwander Gary PNNL Hydrotreater Project Operator
Olarte Mariefel V PNNL Hydrotreater Project Operator
Orth Rick PNNL Line Manager
Paulsen Sam PNNL Pressure Safety
Rohrig David PNNL ES&H - Pressure Safety
Rotness L.J. PNNL Hydrotreater Project Operator
Sauve Gerald PNSO
Short Steve PNNL Hazards Analysis
Stephens Vicki PNNL Operations
Wagner Dan PNNL Building Engineer
Wyatt David PNNL WS&H Fire Protection
Xuan Vic PNSO
Zacher Alan PNNL Hydrotreater Project-PM
Note: Personnel who attended 1 or more meetings.
Page 89 of 98
Appendix B: Key Design Information Reviewed
Page 90 of 98
Design Information Reviewed
HYDROTREATER/DISTILLATION SYSTEM Calculations
CTI 12-631, Rev 2, Pressure Relief Vent Header and KO Vessel Sizing for PNNL Hydrotreater Facility
HYDROTREATER/DISTILLATION SYSTEM Drawings 3

PNNL HYDROTREATER DISTILLATION PROCESS SKETCH
hydro_process.pdf
782-4-100 PNNL BIO-OIL HYDROTREATER BIO-OIL BATCH FILTRATION

Zeton Redlines.pdf
782-4-110 PNNL BIO-OIL HYDROTREATER GAS FEED
782-4-120 PNNL BIO-OIL HYDROTREATER LIQUID FEED
782-4-130 PNNL BIO-OIL HYDROTREATER REACTOR
782-4-140 PNNL BIO-OIL HYDROTREATER GAS/OIL/WATER SEPARATION
782-4-150 PNNL BIO-OIL HYDROTREATER PRODUCT GAS MEASUREMENT
782-4-160 PNNL BIO-OIL HYDROTREATER LIQUID PRODUCT COLLECTION
782-4-170 PNNL BIO-OIL HYDROTREATER WATER RECIRCULATION
782-4-180 PNNL BIO-OIL DISTILLATION COLUMN
782-4-190 PNNL BIO-OIL DISTILLATION COLUMN CUT COLLECTION
ENCLOSURE/FACILITY Drawings3
A2.0 PNNL HYDROTREATER ENCLOSURE DESIGN PDLW FLOOR PLAN
A2.0_PLDW_FLOOR
_PLAN[2].pdf
A3.1 PNNL HYDROTREATER ENCLOSURE DESIGN Exterior Elevations PLAN

A3.1_Hydrotreater -
Enclosure.pdf
M2.0 PNNL HYDROTREATER ENCLOSURE - Enclosure P&ID
M2.0 Enclosure
P&ID.pdf
M2.1 Enclosure
P&ID.pdf
M2.3 Enclosure
P&ID.pdf
3
These drawings are historical documents and subject to change. See the Hydrotreater/Distillation Column SharePoint site
for current drawings.
Page 91 of 98
INTERLOCK MATRICES 4
Cause/Effect Matrix
Cause and Effect
Rev 2_24Jan_2013_P
FACP Hydrotreater Logic

3030
Logic-Hydotreater-R2
4
These documents are historical and subject to change. See the Hydrotreater/Distillation Column SharePoint Site for current
versions.
Page 92 of 98
Appendix C: November 2012 Hydrotreater / Distillation Column Project

Hazard and Risk Analysis Report
Page 93 of 98
November 2012 Hydrotreater / Distillation Column Project Hazard and Risk Analysis Report
Hydrotreater HA Nov
2012.pdf
Page 94 of 98
Appendix D: Supplemental Hazard Analysis and Risk

Assessment Distillation Column
Page 95 of 98
Supplemental Hazard Analysis and Risk Assessment Distillation Column
Supplemental HAR -
Distillation Column
Page 96 of 98
Appendix E: Supplemental Hazard Analysis and Risk

Assessment - Hydrotreater
Page 97 of 98
Supplemental Hazard Analysis and Risk Assessment - Hydrotreater
Supplemental HAR -
Hydrotreater
Page 98 of 98
Page 99 of 98

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5.0 CONCLUSION ........................................................................................................................................ 86

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The hydrotreater/distillation column project consists of catalytic hydrotreatment (hydrotreater)

2.0 Facility and Process Description

2.1 Site and Facility Layout

Approximate distances from the hydrotreater/distillation column process enclosure to key

Table 2-1. Distance from PDL-West to Surrounding Landmarks

Figure 2-1. Location of PDL-West (PDLW)

2.2 Hydrotreater/Distillation Column Processes

The hydrotreater/distillation column project consists of catalytic hydrotreatment (hydrotreater)

During hydrotreatment, deoxygenation of bio-oil takes place to produce hydrocarbon products

Figure 2-2. Hydrotreater/Distillation Process Flow Diagram

Figure 2-3. Location of Hydrotreater/Distillation Enclosure within PDL-West

Figure 2-4. Hydrotreater Process Major Components

Figure 2-5. Distillation Process Major Components

2.2.1 Hydrotreater Operations Outline

Transfer to still feed tank

2.2.2 Distillation Operations Outline

3.0 HAZARD ASSESSMENT

3.1 Hazard Identification

Table 3-1. Hydrotreater Hazard Identification Checklist

Component Inventory Vessel Operating

Table 3-2. Comparison of Chemicals to Screening Thresholds

Material 40 CFR 355 29 CFR 1910.119 40 CFR 68

3.2 What-If Analysis

The What-If analysis technique is a structured brainstorming method of determining potential

Likelihood Qualitative Evaluation Criteria

Likely Failure of a single process control, failure of active

3.3 Analysis Results

No other control-affecting actions were identified or required to assure adequate protection

Loss of purge operations,

For potential plug in R-130

Hydrotreater Process Step 2. Startup/Sulfiding

Hydrotreater Process Step 3. Bio-oil feeding

[If combined with a plug - See hazard controls for the

If continued filling of the Overpressurization. See

Hydrotreater Process Step 6. Shutdown

Hydrotreater Process Step 7. Flush

Hydrotreater Process Step 8. Refit

Distillation Process Step 1. Prestart Operations

from introduces process gas (requires

Temperature indication on product

Level indication in column.

Faster than expected boil-off of

Distillation Process Step 3. Reflux

Overflow to vent header. V-186. Pressure indicator PI-8023.

Distillation Process Step 4. Operation

on FIC-8014 pump indication if loss

enclosure. Flammable vapor monitor skid.

Distillation Process Step 5. Shutdown

vessel ruptures. skid.

run? Loss of exhaust fan and

Makeup air unit for enclosure.

Enclosure Ventilation System