Transport Canada Crude Oil Research

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Transport Canada Crude Oil Research Presented to the Canadian Crude Quality Technical Association/ Crude Oil Quality Association March 09, 2016 Tagenine Alladin Safety

1 Transport Canada Crude Oil Research Presented to the Canadian Crude Quality Technical Association/ Crude Oil Quality Association March 09, 2016 Tagenine Alladin Safety Research Transportation of Dangerous Goods Directorate, Transport Canada RDIMS # This presentation is the property of TC and may not be distributed without prior permission.

OUTLINE Completed Crude Oil Work: Crude oil Sampling and Analysis Work Background How and what we sampled Key project findings Recommendations Ongoing Crude Oil Work

2 OUTLINE Completed Crude Oil Work: Crude oil Sampling and Analysis Work Background How and what we sampled Key project findings Recommendations Ongoing Crude Oil Work National Research Council (NRC) Natural Resources Canada (NRCan) US DOT/DOE/TC Crude oil Collaboration 8003 set-up. Photo c/o Alberta Innovates - Technology Futures 2

3 RESEARCH AREAS FOR In , TDG s research projects focused on the following research areas: Jack Rabbit II (large scale toxic gas releases) Crude Oil Dangerous Goods Rail Research Lithium Batteries Research projects were chosen through a selection process in which all TDG branches were consulted internally. All the proposed topics were graded based on their benefits, scope, severity and urgency. 3

4 CRUDE OIL SAMPLING AND ANALYSIS WORK (DEC MAY 2015) 4

5 BACKGROUND: THE PROJECT The Lac-Mégantic derailment on July 6, 2013 and other incidents involving crude oil transported by rail in Canada and the United States have prompted questions regarding the safe transportation of crude oil and highlighted the need to further investigate crude oil properties and behaviour. In response, Transport Canada (TC) undertook a research project to assess the composition and properties of crude oils that are transported by road and rail in Canada. This work aimed to obtain data in support of regulatory and oversight policy decision-making. More research is underway in several areas, while policy options are being developed for consideration on issues which can be addressed in the shorter term. 5

6 BACKGROUND-THE PROJECT Assess properties, behaviour and hazards of crude oil through sampling, testing and analysis of crude oil samples transported across Canada by road and rail. Assess the applicability of current classification requirements under Part 2 of the TDG Regulations. Inform on the most appropriate classification, subsidiary hazards, and packing group (PG) assignments of crude oil. Research performed with Alberta Innovates-Technology Futures (AITF), an Alberta provincial research corporation. Sampling started December 4, 2014 and ended on May 2, Draft report delivered on May 28, 2015, was finalized on August 10, 2015 and made public on December 3,

7 BACKGROUND-THE SAMPLES A total of 68 samples of crude oil destined for transport by rail and/or roadway. Four of the oil producing regions in Canada: British Columbia, Alberta, Saskatchewan and Manitoba. Samples from all major Canadian oil plays in production representing a range of crude oil types from condensate to undiluted bitumen. Two samples of condensate from North Dakota which were being transported within Canada by truck were also collected. 7

8 REGIONAL ALLOCATION OF CRUDE OIL SAMPLES Type of Oil B.C. AB SK MB Condensate Light oil Medium oil Heavy oil N.D. Origin Sweet Sour 2 Sweet Sour Sweet 4 3 Sour 2 Sour, diluted 5 Sweet 3 2 Sour 2 Sour, Diluted 1 No. of Samples % of Total Samples Collected Sweet, Diluted 1 Bitumen, neat Dilbit Synbit Synbit, diluted Synthetic Crude Totals

9 BACKGROUND: TESTS CONDUCTED (CRUDE OIL) Test: Atmospheric sampling No. of Samples Tested Flash Point ( D56, D93 or D3828) 68 IBP ( D86)* C ( D323)* 44 H 2 S in Vapour ( D5705) 68 Water Content ( D4007) C ( D5002) 68 Pressurized Sampling 50 C and V/L 0.2:1 ( D6377) (4:1 for select samples) 60 Gas/Oil Ratio (GOR) and Gas Analysis 60 IBP and Composition ( D7900/D7169 or HPLIS-GC/D7169) 68 Class 2.1 (ISO 10156) 60 *D86 and D323 (RVP) done on only half of the crude oil samples (those with higher light end composition) in order to compare D86 and RVP data with IBP from GC method and VPCRx data, respectively. 9

BACKGROUND - HOW WE SAMPLED Both atmospheric and pressurized sampling methodologies were used. 1L glass bottles were used for tests that did not require pressurized samples (e.g. D86) and for heavy oils that were too viscous to be sampled under pressure.

10 BACKGROUND - HOW WE SAMPLED Both atmospheric and pressurized sampling methodologies were used. 1L glass bottles were used for tests that did not require pressurized samples (e.g. D86) and for heavy oils that were too viscous to be sampled under pressure. Certain tests ( D6377 for VPCRx, HPLIS-GC for composition/ibp and Gas Oil Ratio) could not be performed for the 8 heavy oils were too viscous to be sampled into floating piston cylinders (FPC). The pressurized samples were collected in Proserv Type 5 10k, 700mL FPCs. 10

11 11

12 KEY PROJECT FINDINGS Flash point Compositional Analysis (Gas Chromatography-GC) Gas Oil Ratio H 2 S Initial Boiling Point Vapor Pressure (VPCRx) and Reid Vapor Pressure (RVP) 12

13 KEY FINDINGS: FLASHPOINT The flash point of all light oils, diluted oils, and condensates was <-30.0 o C, except for two light oils which had flash points of o C and o C. Six samples (1 bitumen and 5 heavy oils) had flash points above 60 o C, i.e. would not be classified as a Class 3 flammable liquids under Part 2 of the TDG Regulations. 13

14 KEY FINDINGS: FULL COMPOSITION The chemical composition in mass % up to C24 of each sample was determined by merging two gas chromatography (GC) methods. HPLIS-GC/ D7169: More accurate with light ends retention. D7900/ D7169 : Less accurate with limited light end retention). The light crude oil samples and condensates had the highest amount of C1-C4 and C4 to C8, but the smallest amount in the range of C11 to C24, while the bitumen shows the opposite composition. 14

15 KEY FINDINGS: GAS OIL RATIO (GOR) A measure of the volume of gas produced per volume of oil at standard conditions of temperature and pressure (15.6 o C and atm pressure). GOR is a measure of both the light ends and fixed gases (CO 2, H 2 S, helium, H 2, O 2, N 2 ). These gases are either naturally occurring or introduced through processes. Generally, samples with the highest percentage of light ends will have the highest GORs, such as condensates. Samples with the lowest percentage of light ends will have the lowest GORs, such as synthetic crude and synthetic bitumen. A SK Bakken oil, had the highest GOR, 10.74, and had a high VPCRx of kpa (0.2:1, 50 C) and highest mass percentage of propane (3.7 %). 15

16 KEY FINDINGS: H 2 S TESTING (VAPOR PHASE) Issue Hydrogen sulphide (H 2 S) is a highly toxic gas. Results - Occupational Safety Health (OSH) limit: 20 ppm (or 50 ppm for 10 mins). - Immediately Dangerous to Health of Life (IDHL): 100 ppm. At ppm, death is imminent or immediate. Vapour phase measurements of H 2 S ( D5705) ranged from ppm. 33 of the 68 crude oil samples had values below 100 ppm. 4 samples in the ppm range. 25 samples ranged from 500 to ppm, and one sample at each: , , , , , ppm. Conclusions The levels of H 2 S found in some crude oil samples are significantly higher than the threshold limit value of the OSH standard. In an accident scenario, or during regular transport operations, these high H 2 S crude oils could pose a significant risk to persons handling the DG. While first responders need to be aware of and prepared for the risks, H 2 S usually dissipates rapidly when a container is breached, hence reducing the risk of exposure. 16

17 H 2 S TESTING (VAPOR PHASE, D5705) D 5705 is scoped for the measurement of H 2 S above residual fuel oils, not crude oil. Sampling and testing are done under atmospheric conditions. The test was performed at 60 0 C (except ambient temperature testing for most condensates. Test used has a +/- 25% accuracy rate. The Saskatchewan samples showed the highest average of H 2 S in the vapor phase (around ppm). 17

18 IBP DETERMINATION The IBP of all samples was determined by merged GC analysis. The IBP is the temperature at which 0.5 weight percent of the sample has eluted, as defined in D7169 and API Recommended Practice D86: done only for crude oil samples with a higher proportion of light ends, for comparison purposes. D86 is a distillation performed at atmospheric pressure. The loss of the light ends during sample collection and testing results in an IBP higher than the sample composition would indicate. 18

19 KEY FINDINGS: INITIAL BOILING POINT (IBP) Issue Initial Boiling Point (IBP) differentiates between the three packing groups (PG) of Class 3, Flammable Liquids. Results The PG based on GC merge data ranged from PG I (56 samples) to PG II (3 samples) and PGIII (3 samples). 6 samples did not meet the definition of a Class 3. The IBP determined by D86 was consistently higher than the IBP determined through GC analysis (average T difference: 46.3 o C) when comparing samples that had the highest proportion of light ends. IBP determined by D86 resulted in several crude oil samples being assigned PG II, whereas the GC data for those same samples resulted in PG I assignment (except for one medium crude PG II). Conclusion IBP test ( D86) that is commonly used by industry for the classification of flammable liquids has proven to be unsuitable for IBP testing of crude oil. 19

20 IBP (D86 VS. GC MERGE) Sample Type Average IBP ( o C), D86 Average IBP ( o C), HPLIS-GC/ D7169 Average ( o C) Light Oil Medium Oil 92.8* Diluted Heavy Oil Synthetic Crude Diluted Bitumen Synthetic Bitumen Condensate *not an average, one data point. 20

21 KEY FINDINGS: VAPOR PRESSURE Issue Vapor Pressure (VPCRx): vapor pressure exerted by both the liquid crude oil and the gases contained within, at a specific temperature and vapor/liquid (V/L) ratio. Reid Vapor Pressure (RVP): vapor pressure exerted by the liquid crude oil at a V/L of 4:1 at 37.8 o C. Generally, there is no requirement for vapor pressure in the classification of crude oil as Class 3, Flammable Liquids other than distinguishing them from Class 2, Gases. Results Most VPCRx values at 50 C were above atmospheric pressure (i.e. these crude oils at at 50 C would boil if exposed to the atmosphere). All VPCRx values were above RVP values. A VPCRx test allows for retention of volatile components in the sample, which contribute to the pressure reading; an RVP test allows for loss of volatiles components during sampling and testing. Conclusions Elevated vapour pressures observed in some samples would affect the classification and selection of MOC. One crude oil sample met the vapour pressure threshold for a gas (>300 kpa), which would have required a different MOC. 21

22 VPCRX (D 6377, 50 O C, V/L 0.2:1) Condensates and light oil had the highest average vapor pressure), synthetic crude and synthetic bitumen samples had the lowest average. Hydrocarbons in the range of C1 to C4 have the most significant effect on vapour pressure. The two highest VPCRx data were found in a medium oil (528 kpa) and a light oil (300.8 kpa); only the latter crude oil was representative of what was in transport. Crude Oil Type Average Vapour Pressure 50 o C (kpa), D6377 Minimum Vapour Pressure 50 o C (kpa), D6377 Maximum Vapour Pressure 50 o C (kpa), D6377 Light Oil Medium Oil Diluted Medium Oil* 231 Diluted Heavy Oil Synthetic Crude Diluted Bitumen Synthetic Bitumen* 79 Diluted Synthetic Bitumen* 145 Condensate *Single sample only 22 SD

23 SAMPLES WITH HIGHEST VPCRX, 50 O C, V/L 0.2:1 (527.9 AND KPA) SAMPLING LOCATION 23

24 KEY FINDINGS: REID VAPOR PRESSURE D323 (50 O C, V/L 4:1) All measured VPCRx values (V/L 4:1) were higher than the RVP values for the same samples ( kpa ranging from 6.4 to 19.9). Region Sample Type Vapour Pressure 50 o C (kpa), D6377 Vapour Pressure o C (kpa), D323M (kpa) AB condensate AB condensate AB dilbit AB dilbit AB heavy oil, diluted SK light oil SK light oil AB light oil, sour

25 RECOMMENDATIONS FROM FINAL REPORT Use a sealed, pressurized system for sampling as sampling integrity is key and should be maintained. Use more a accurate method such as the GC merge method (e.g. D8003/D7169) for determining IBP of crude oils containing light ends. Undertake a Phase 2 sampling campaign to assess: seasonality differences, more condensates, dilbit, railbit and Bakken samples from ND, samples of blends from transloading facilities. Conduct further research on the flammability of crude oil. Develop a more appropriate test method for H 2 S vapor phase analysis for crude oil samples under specific headspace volumes and temperatures. Develop test methods to determine the concentration of H 2 S and hydrocarbons in the vapour phase above produced water under transport conditions. 25

26 ONGOING TDG-LED CRUDE OIL WORK NRC-Pool Fire Testing. NRCan- Behaviour of Crude Oil in Container exposed to Fire. 26

27 TANK CARS CARRYING CRUDE OIL IN FIRES NRC Pool Fire Testing Working with NRC to investigate behaviour of tank cars carrying crude oil exposed to fire. Ultimate goal is to develop a high fidelity model to understand this behaviour. This model would then inform existing, faster and simpler models used by industry to estimate survivability of tank cars in fires. NRC completed a literature review in April NRC is currently conducting a series of tests to determine the characteristics of a medium crude fire immersing a tank car analogue. 27

28 TANK CARS CARRYING CRUDE OIL IN FIRES (CONT.) NRC Pool Fire Testing (Cont.) Will also investigate the effect of different substrates (water, ice, earth), height of tank car analogue above fire, and fuel supply (continuous supply to fire vs. static amount). Planning to conduct further tests to investigate characteristics of other crude oil types, condensates, and mixtures (dilbit, railbit, etc.). Future testing would investigate behaviour of pressure relief devices (PRVs) on scaled containers of crude oil in pool fires. 28

29 TANK CARS CARRYING CRUDE OIL IN FIRES Natural Resources Canada (NRCan) Work Working with CanmetENERGY to develop and validate a model of the behaviour of crude oil in a container exposed to a pool fire. Have completed initial modelling of crude with only effects of distillation. Will develop a model including cracking and coking in and perform bench scale validation testing. CanmetMATERIALS has conducted a literature review of the following properties of tank car steels: Performance at elevated temperatures; Fracture toughness; and Corrosion issues with crude oil. 29

30 US DOT/DOE/TC CRUDE OIL COLLABORATION 30

Overall US DOT/DOE Project Workflow Phase I Problem Definition Phase Phase II Experimental

stakeholders Literature Survey Sampling and Analysis Plan Peer review Task 1: Analyze

modeling Task 4: Crude characterization, tight vs.

characterization Utilize knowledge gained during prior phases to inform decisions on:

Institute COQA: Crude Oil Quality Association CCQTA: Canadian Crude Quality Technical

31 Overall US DOT/DOE Project Workflow Phase I Problem Definition Phase Phase II Experimental Phase Phase III Implementation Phase Completed Current/future SNL future work scope All stakeholders Literature Survey Sampling and Analysis Plan Peer review Task 1: Analyze existing data Task 2: Sampling method evaluation Task 3: Combustion experiments and modeling Task 4: Crude characterization, tight vs. conventional Task 5: Railcar combustion testing and modeling Task 6: Comprehensive oil characterization Utilize knowledge gained during prior phases to inform decisions on: Industry best practices Standards Regulations Peer review API: American Petroleum Institute COQA: Crude Oil Quality Association CCQTA: Canadian Crude Quality Technical Association Public outreach : International Standards GPA: Gas Processors Association SPR: Strategic Petroleum Reserve Phase III Lord D et al., SAND PE 31

CRUDE OIL RESEARCH COORDINATION STEERING COMMITTEE US Department of Energy Direct $ US Department of Transportation Direct $ Sandia National Laboratories Transport Canada In-kind

32 CRUDE OIL RESEARCH COORDINATION STEERING COMMITTEE US Department of Energy Direct $ US Department of Transportation Direct $ Sandia National Laboratories Transport Canada In-kind sampling, analysis, data transfer. Allen Energy Services, Inc. UND Energy & Environmental Research Center GRAM, Inc. Crude Oil Analytical Service Companies Lord D et al., SAND PE 32

33 TRANSPORT CANADA S PARTICIPATION Task 1: Provided data from our crude oil sampling and analysis work and will contribute accidents and other dangerous goods data. Task 2: SNL and TC co-developed sampling and analysis plans for the current DOE/DOT study where TC will provide in-kind, parallel analysis and share the data with DOE/DOT/SNL for use in project technical reports. Task 3: SNL gave TC an estimate for FY large-scale combustion tests on selected crude oils of interest to Canadians. TC will re-visit large-scale work with Sandia once some testing on U.S. crude completed. TC s small-scale parallel work with NRC in FY may be used as in-kind. Task 4: TC intends to participate and will provide in-kind, parallel analysis on Canadian oils to ensure that Canadian blends such as railbit, dilbit are included in this phase, with focus on issues that are of more concern to us than the U.S. such as H 2 S. Industry support will be needed. 33

34 Lord D et al., SAND PE 34 TASK 2 TEST MATRIX Property Measurement Sample Technique Standard TVP Composition 1 Composition 2 Composition 3 Avg MW SPR Tight Line Floating Piston Cylinder D6377 & Separator shut-in BPP flash gas D D6377-M GPA2103 M H 2 O displacement GPA D6377-M GPA2103 M Manual Syringe D D6377-M GPA2103 M Boston Round D D6377-M GPA2103 M GOR flash gas GPA D D7169 GPA D D7169 GPA D D7169 GPA D D7169 Separator liquid C30+ D D7169 D D7169 D D7169 D D7169 frz pt dep frz pt dep frz pt dep frz pt dep frz pt dep Relative Density D5002 D5002 D5002 D5002 D5002 Viscosity N/A D7042 D7042 D7042 D7042 Flashpoint N/A D93 or D56 D93 or D56 D93 or D56 D93 or D56 IBP (0.5 wt%) EOS with flash gas Manual Syringe D D N/A N/A N/A N/A N/A N/A N/A N/A Color coding White Red Blue Test Administrator SNL TC Both Test matrix will be run 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. GPA 2103/2177 GPA 2103/2177 GPA 2103/2177 GPA 2103/2177

35 . TASK 2-TC PARALLEL TESTING Work done through a Memorandum of Understanding with AITF. Coordinated sampling with U.S. contractors at two sampling points. Sample Technique Floating Piston Cylinder H 2 O Displacement Manual Piston Cylinder Boston Round Manual Syringe Standard D GPA D D D VPCRx D6377-M D6377-M D6377-M D6377-M D Compositi on 1 GPA 2103 M GPA 2103 M GPA 2103 M GPA 2103 M Compositi on 2 GPA D D7169 GPA D D7169 GPA D D7169 GPA D D7169 Properties Composition 3 D D7169 D D7169 D D7169 D D7169 Gas Phase Analysis GOR GOR GOR GOR Gas Phase Analysis N/A N/A D8009/Dxxx x N/A N/A N/A N/A N/A N/A 35

THANK YOU! For more info contact: barbara.dibacco@tc.gc.

36 THANK YOU! For more info contact: 36

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