SAND2016-4455PE

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Crude Oil Characterization

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Research Study
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Committee for a Study of Domestic Transportation of
space Petroleum, Natural Gas, and Ethanol
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May 12, 2016

Presented by
Anay Luketa, Ph.D.
Fire Science and Technology Department
Sandia National Laboratories

Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin
Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000. SAND NO. 2011-XXXXP

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 Outline

 Problem Statement and Objectives

 Project Governance and Workflow
 Overview of Task 2 – Task 3 Testing
 Potential Hazards from a Crude Oil Rail Car Breach
 Project Management Contacts and Publications

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Technical Objectives

PROBLEM STATEMENT

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 Problem Statement
Casselton, ND, Dec 30, 2013
 Crude transport by rail poses
risks recognized by US and
Canadian regulators
 Hazards have been realized
in a number of high-profile
train derailments leading to oil NTSB (2014). "Preliminary Report Railroad
spills, environmental DCA14MR004."

contamination, fire, property

damage, and fatalities
 Open debate on whether the
types of crude (tight oil vs.
conventional production) have
significant bearing on severity TSBC (2014). "Runaway and Main-Track Derailment
of transportation accidents Montreal, Maine & Atlantic Railway Freight Train
Lac-Megantic, Quebec 06 July 2013." R13D0054.4
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 DOE/DOT Project Objectives
 Determine what combinations of sample capture and analysis
methods are suitable for characterizing selected physical properties
of volatile crudes
 Evaluate selected physical properties of crude oils (tight vs.
conventional production) that are moved within rail transport
environment that may have some bearing on flammability risks
 Measure combustion properties (flame dimensions, surface
emissive power) of selected crude oils (tight vs. conventional) in
controlled burn scenarios that have bearing on hazard determination
 Compare combustion properties to existing published data on other
flammable liquids, including methanol, ethanol, jet fuel, hexane
 Evaluate if selected tight oils exhibit measurably different
combustion properties from conventional crudes and the reference
fluids tested previously 5

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PROJECT GOVERNANCE

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 Project Governance
Crude Oil Research Coordination Steering Committee

US Department US Department
Transport
of of
Canada
Energy Transportation
Direct $ Direct $ In-kind sampling,
analysis, data transfer.

Sandia
Technical Lead Lab National
Laboratories

UND Energy &

Allen Energy Environmental
GRAM, Inc.
Services, Inc. Research
Center

Crude Oil Analytical Technical Services

Service Companies
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 Overall Project Workflow
Phase I Phase II Phase III

Problem Definition Phase Experimental Phase Implementation Phase

Completed Current/future SNL future work scope All stakeholders

• Task 1: Analyze existing

data
• Task 2: Sampling and
Sampling analytical method • Utilize knowledge
Literature and evaluation gained during prior
Survey Analysis • Task 3: Combustion
phases to inform
Plan experiments and modeling
• Task 4: Crude decisions on:
characterization, tight vs.  Industry best practices
conventional  Standards
• Task 5: Railcar combustion  Regulations
testing and modeling
Peer • Task 6: Comprehensive oil
characterization
review
Peer
review

Public outreach
API: American Petroleum Institute ASTM: ASTM International Standards
COQA: Crude Oil Quality Association Phase III
GPA: Gas Processors Association
CCQTA: Canadian Crude Quality Technical Association SPR: Strategic Petroleum Reserve

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 Overall Project Workflow
Phase I Phase II Phase III

Problem Definition Phase Experimental Phase Implementation Phase

Completed Current/future SNL future work scope All stakeholders

• Task 1: Analyze existing

data
• Task 2: Sampling and
Sampling Current Scope
Completed
Literature and
analytical method
evaluation
• Utilize knowledge
gained during prior
Survey Analysis • Task 3: Combustion
phases to inform
Plan experiments and modeling
• Task 4: Crude Possible Future
decisions on :
 Industry best practices
characterization, tight vs.

Implementation
Standards
conventional
• Task 5: Railcar combustion  Regulations
testing and modeling
Peer Possible
• Future Work
Task 6: Comprehensive oil
characterization
review
Peer
review

Public outreach
API: American Petroleum Institute ASTM: ASTM International Standards
COQA: Crude Oil Quality Association Phase III
GPA: Gas Processors Association
CCQTA: Canadian Crude Quality Technical Association SPR: Strategic Petroleum Reserve

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High-Level Project Schedule, Phase II

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Crude Oil Property and Combustion Tests

TESTING OVERVIEW

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 Task 2 Overview
 Compare sample capture and analysis methods for two
selected North American crude oils
 Prefer upstream production or tank terminals handling tight oils

 Sandia National Laboratories and Transport Canada will

administer parallel tests using a variety of sample capture
and analysis methods
 Critical review of open vs. closed capture and applicability
for use on minimally stabilized oils for measuring:
 Crude vapor pressure VPCRx(T) at selected V/L and temperatures
 Pressurized GC light ends concentration
 Unpressurized GC DHA and simulated distillation
 Unpressurized physical property measurements MW, SG, viscosity
 IBP based on 0.5 wt% determination
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 Task 2 Test Matrix

• Test matrix will be performed on two minimally stabilized North

American crudes
• Objective is to compare multiple methods on a homogeneous
sample
• Note: Oil variability across production regions or supply chain
is addressed in Task 4, not Task 2
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 Task 3 Overview
 Subject four selected North American crudes to basic
property and controlled burn testing
 Span a range from tight oils (Bakken, Eagle Ford) with
high visibility, to baseline light sweet (WTI, LLS), to
specially-stabilized crude from the Strategic Petroleum
Reserve
 Compare results against existing hydrocarbon liquid
combustion test data

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 Task 3 Combustion Tests
Pool fire
• Surface emissive
power (SEP)
• Heat flux to engulfed
objects
• Flame height
• Fuel consumption rate
Fireball
• Surface emissive power
(SEP)
• Heat flux to nearby objects
• Fireball diameter
• Fireball duration
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 Task 4 Sampling and Analysis of
Tight and Conventional Oils

 Develop a comprehensive data set that characterizes

multiple crude oil types
− Illustrate differences in crude oil properties and composition
− Support combustion property modeling efforts
− Enable prioritization of future crude characterization based on
geography, environmental conditions, well life, and supply chain.
 Acquire samples using methods developed in Task 2
 Conduct comprehensive crude oil analysis
– Volatility (VPCRx, light ends including inert gases, flashpoint)
– Detailed hydrocarbon analysis (assay)
– API, molecular weight, specific heat, conductivity, viscosity, metals,
cold flow properties

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Combustion related events

POTENTIAL HAZARDS
FROM A CRUDE OIL RAIL CAR
BREACH
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 Overview of Potential Hazards
Tank rupture
BLEVE non-BLEVE

Immediate Delayed
• Fireball ignition ignition
• High speed
projectiles
• Overpressures Pool fire Flare

Vapor cloud Flash

explosion fire

Deflagration Detonation
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 Boiling Liquid Expanding Vapor Explosion
 Commonly accepted definition for BLEVE:
‘an explosion resulting from the failure of a vessel containing a liquid at a
temperature significantly above its boiling point at normal atmospheric
pressure’. (Center for Chemical Process Safety, 1994) Note the word
‘explosion’ refers to a mechanical explosion.

 Initiated by pool fire impinging on a tank increasing its temperature and

pressure causing tank to rupture. Liquid in superheated state and hence
large energy released in the form of a rapid phase change expansion.

 Tank will fragment into pieces forming projectiles that travel at high
speeds and can be thrown large distances (~1 km). These provide the
greatest range of hazard impact.

 Shock waves from BLEVE can lead to damaging overpressures but will
not be the dominant hazard at far distances.

 Simultaneously the liquid/vapors are ignited to form a spherical partially

pre-mixed flame termed a fireball.
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 Fireballs

 Fireball length and time scales are

correlated with mass of fuel involved.
 Correlations are of the form L = aMb
 L can represent diameter, height
(center to ground), or duration
 a and b are empirical constants
 M is mass of fuel
 Surface emissive power ranges
between about 100 – 400 kW/m2 based
on experiment.

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 Behavior of Pool Fires

 Pool fires are burning liquids

classified as as low-momentum,
highly buoyant diffusion flames.
 Behavior changes with size and
shape of pool (e.g. level of
turbulence, soot production, burn
rate, and flame height).
 Wind and surrounding geometry can
significantly affect the behavior.
 Water can also affect behavior.

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 Dispersion of Vapors

 If not immediately ignited after a spill, vapors can

propagate freely in the open or into confined or semi-
confine areas such as nearby infrastructure.
 If vapors reach an ignition source, a flash fire or
explosion can occur depending on level of confinement
of the vapors and number of obstacles.
 Flash fire is the burning of a vapor cloud without
damaging overpressures.
 Explosions do result in damaging overpressures and can
be classified as either a deflagration or detonation.

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 Chemical Explosions
 Deflagration: Reaction front moves at a speed less than
the speed of sound and typically produces overpressures on
the order of 0.1 bar.
 Detonation: Reaction front moves at a speed greater than
the speed of sound (~2000 – 3000 m/s) and produces
overpressures of up to around 20 bars.
 Deflagration-to-Detonation Transition (DDT):
Deflagration transitioning to a detonation. Unconfined vapor
cloud detonation is difficult to achieve without a high-
explosive.
 DDT can occur when a combustible fuel-air mixture is
confined or semi-confined (presence of buildings, obstacles,
etc.) 23

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How are combustion events related to
flammability classification?

 Flammability classification is useful for operational

handling.
 In crash scenarios, however, the most probable
outcome will be the production of very high energy
sources to cause ignition, far exceeding any
hydrocarbon flammability classification threshold.
 Ignition potential is influenced by several factors.

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 Ignition

 Ignition is a function of chemical kinetics, heat and mass

transfer.
 Too much heat loss will not allow sustained burning.
 Insufficient mixing of fuel and oxidant will not allow
sustained burning.
 Difficulty with prediction lies in knowledge of detailed
chemical reactions, as well as solving the fundamental
equations that span all of the time and length scales
necessary to capture the chemical kinetics, heat and
mass transfer.

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 Flammability
No single parameter defines the degree of flammability,
but some relevant parameters include:
 Flashpoint - Temperature that results in a vapor
concentration corresponding to the lower flammability
limit. (principle index of flammability)
 Flammability limits – range of vapor concentration in
air that will support combustion termed lower
flammability limit (LFL) and upper flammability limit (UFL)
 Auto-ignition temperature – minimum temperature at
which a fuel-air flammable mixture spontaneously
ignites.
 Minimum ignition energy – minimum energy required
to ignite a flammable fuel-air mixture
 Burning velocity – Velocity at which a gaseous fuel-air 26
mixture issuing fromUnclassified
a burner burns
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 Flammability

 A fuel is considered more flammable with a

− lower flashpoint
− wider range of flammability limits
− lower auto-ignition temperature
− lower minimum ignition energy
− higher maximum burning velocity

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PROJECT CONTACTS AND
PUBLICATIONS

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 Project Sponsor Contacts

U.S. Department of Energy

Evan Frye
Office of Fossil Energy, Office of Oil & Natural Gas
evan.frye@hq.doe.gov, 202-586-3827

U.S. Department of Transportation

Joseph Nicklous
Office of Hazardous Materials Safety
Pipeline and Hazardous Materials Safety Administration
joseph.nicklous@dot.gov, 202-366-4545

Transport Canada
Barbara Di Bacco
Transport Dangerous Goods Directorate
barbara.dibacco@tc.gc.ca, 613-990-5883
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 Sandia Project Contacts
Sandia technical leads
David Lord
Principal Investigator
Geotechnology & Engineering Department
dllord@sandia.gov, 505-284-2712

Anay Luketa
Fire Science and Technology Department
aluketa@sandia.gov, 505-284-8280

Sandia geosciences program manager

Erik Webb
Senior Manager
Geoscience Research & Applications
ekwebb@sandia.gov, 505-844-9179

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 Project Publications

 Lord, D., A. Luketa, C. Wocken, S. Schlasner, R. Allen

and D. Rudeen (2015). "Literature Survey of Crude
Properties Relevant to Handling and Fire Safety in
Transport." Unlimited Release SAND2015-1823. Sandia
National Laboratories, Albuquerque, NM 87185.
 SNL (2015). "Crude Oil Characteristics Sampling,
Analysis and Experiment (SAE) Plan." Office of Fossil
Energy. U.S. Department of Energy,
http://energy.gov/fe/articles/crude-oil-characteristics-
research. 9-Jul-2015.

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QUESTIONS?

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