Sampling and Analysis in light of the PHMSA/DOT Final Rule

Transcription

1 Sampling and Analysis in light of the PHMSA/DOT Final Rule COQA Meeting, New Orleans, LA Kesavalu M. Bagawandoss Ph.D., J.D. October 22,

2 Disclaimer The information contained in this presentation is intended solely for broad informational purposes. Intertek makes no representation regarding, and assumes no responsibility or liability for, the accuracy or completeness of, or any errors or omissions in, any information contained herein. In addition, the views expressed are based on an overview of current practices which are subject to change over time and geographic location. It is not the intention to provide, and you may not rely on this presentation as providing, a complete or comprehensive analysis of the situations encountered in actual field conditions, for which you should refer to applicable methodologies, rules and regulations. This presentation does not constitute an offer or invitation to purchase or subscribe to our services. 2

3 Outline of Presentation Introduction PHMSA/DOT Final Rule 49 CFR Federal Register Explanations of Final Rule Classification Tests Study Tests Conducted Initial Boiling Point ASTM D86 options Why RP 3000? Alternate Test Method for IBP GPA 2177 M IBP using GPA 2177 M - IBP Calculator Comparison of D86 vs GPA 2177 M Comparison of D7900 vs GPA 2177 M Summary 3

4 Introduction Classification of Crude Oil offered in Rail Transportation (Class 3 Flammable Liquids) Flash Point ASTM D56 etc. Initial Boiling Point ASTM D86 API RP 3000 DOT Final Rule Codified in 49 CFR Sampling and testing program for unrefined petroleum-based products 4

5 49 CFR Sampling and testing program for unrefined petroleum-based products. (a) General. Unrefined petroleum-based products offered for transportation must be properly classed and described as prescribed in , in accordance with a sampling and testing program, which specifies at a minimum: (1) A frequency of sampling and testing that accounts for any appreciable variability of the material (e.g., history, temperature, method of extraction [including chemical use], location of extraction, time of year, length of time between shipments); (2) Sampling prior to the initial offering of the material for transportation and when changes that may affect the properties of the material occur (i.e., mixing of the material from multiple sources, or further processing and then subsequent transportation); (3) Sampling methods that ensure a representative sample of the entire mixture, as offered, is collected; 5

6 49 CFR (4) Testing methods that enable classification of the material under the HMR; (5) Quality control measures for sample frequencies; (6) Duplicate sampling methods or equivalent measures for quality assurance; (7) Criteria for modifying the sampling and testing program; and (8) Testing or other appropriate methods used to identify properties of the mixture relevant to packaging requirements (e.g., compatibility with packaging, identifying specific gravity for filling packages). 6

7 49 CFR (b) Certification. Each person who offers a hazardous material for transportation shall certify, as prescribed by of this subchapter, that the material is offered for transportation in accordance with this subchapter, including the requirements prescribed by paragraph (a) of this section. (c) Documentation, retention, review, and dissemination of program. The sampling and testing program must be documented in writing (i.e. hardcopy or electronic file thereof) and must be retained for as long as the sampling and testing program remains in effect, or a minimum of one year. The sampling and testing program must be reviewed at least annually and revised and/or updated as necessary to reflect changed circumstances. The most recent version of the sampling and testing program must be available to the employees who are responsible for implementing it. When the sampling and testing program is updated or revised, all employees responsible for implementing it must be notified, and the most recent version must be made available. 7

8 49 CFR (d) Access by DOT to program documentation. Each person required to develop and implement a sampling and testing program must maintain a copy of the sampling and testing program documentation (or an electronic file thereof) that is accessible at, or through, its principal place of business, and must make the documentation available upon request at a reasonable time and location to an authorized official of the Department of Transportation. [80 FR 26746, May 8, 2015] 8

9 Federal Register Explanations of Final Rule 80 FR 26746, May 8, 2015 We are not incorporating API RP 3000 by reference. However, shippers may still use API RP 3000 as a voluntary way to comply with the newly adopted sampling requirements. It should be noted that all of the testing provisions of API RP 3000 do not align with the requirements in the HMR. As the testing provisions were not proposed to be modified, shippers must continue to use the testing methods for classification of flammable liquids outlined in and flammable gases in It should be noted that PHMSA may consider the adoption of the non-codified testing provisions of API RP 3000 in a future rulemaking. Ref: Federal Register /Vol. 80, No. 89 / Friday, May 8, 2015 /Rules and Regulations 9

10 Federal Register Explanations of Final Rule 80 FR 26746, May 8, 2015 Finally, we are not adopting API RP 3000 as a requirement at this time. As indicated in the NPRM, we did not contemplate or propose adopting API RP 3000 in the NPRM, as it had not yet been finalized. Furthermore, the boiling point test specified in the API RP 3000 does not align with the requirements currently authorized in the HMR. Shippers must continue to use the testing methods for classification of flammable liquids outlined in and flammable gases in However, API RP 3000 is otherwise consistent with the sampling program requirements in paragraph (a)(1) (6) and may be used to satisfy these adopted sampling provisions. Furthermore, voluntary use of API RP 3000 provides guidance for compliance with these provisions, but still allows flexibility for meeting requirements through other methods. Ref: Federal Register / Vol. 80, No. 89 / Friday, May 8, 2015 / Rules and Regulations. 10

11 Classification Tests Packing Group Assignment Criteria Ref: API RP 3000, First Edition, September

12 Study Tests Conducted API RP sec alternate methods GPA 2177 M D7900 Determination of IBP using D7169 IBP Calculator (Envantage software) Comparison method ASTM D

13 Initial Boiling Point ASTM D86 options 4 options in sample handling for IBP Option 1 is the most viable option for IBP Options 2-4 will lead to higher IBP Could alter packing group assignment Due to method setup light ends could be lost no matter which option is utilized 13

14 Initial Boiling Point ASTM D86 options Ref: ASTM D

15 Why RP 3000? RP 3000 option in section to determine IBP utilizing an alternate method - GPA 2177 M Samples collected in FPC s or Closed systems Samples introduced into the instruments without loss of light ends single phase liquid Un-weathered IBP and not weathered sample IBP s as determined by ASTM D86 15

16 Alternate Test Method for IBP GPA 2177 M Samples are introduced into GC utilizing FPC s or Water Filled Cylinders Back pressure is applied during sample introduction into GC GC TCD/FID with back flush valves Samples introduced as single phase C1 - C6 data (wt. %) collected for IBP determination as stated in RP 3000 section IBP is evaluated at 0.5 wt. % recovery point 16

17 Alternate Test Method for IBP GPA 2177 M 17

18 IBP using GPA 2177 M GC calibrated using certified standards Calibration check is performed each day C1 - C6 data collected for IBP determination as stated in RP 3000 section IBP is evaluated based on 0.5 wt. % recovery point Data is subjected to the IBP calculator IBP curve is generated and IBP determined 18

19 IBP Calculator Developed by Envantage Automated to process data from file directory Manual input Data output 19

20 Example Data - Standard 20

21 Example Data - Standard 21

22 Comparison of D86 vs GPA 2177 M Samples collected in FPC s GC analyses (GPA 2177 M) IBP determinations by ASTM D86 using group 1 criteria Dramatic differences in IBP!!! 22

23 IBP Comparison - D86 vs GPA 2177 M Sample ASTM_D86 API ISM GPA 2177 M F 42.7 (-)44F F 46.0 (-)127F F 41.2 (-)44F F 42.3 (-)44F F 41.8 (-)44F F 43.9 (-)44F F 41.7 (-)44F F 43.1 (-)44F F 41.9 (-)44F F 42.3 (-)44F 23

24 Comparison of D7900 vs GPA 2177 M Samples collected in FPC s for GPA 2177 M GC analyses (GPA 2177 M) For D7900 analysis Samples collected in Boston Round bottles - samples chilled Followed by ASTM D7900 analysis IBP determinations 24

25 Comparison of D7900 vs GPA 2177 M D7900 vs GPA 2177 M comaprison data - IBP Sample ASTM_D7900 ISM GPA 2177 M Doss 100 (-)44 F (-)44 F Doss 200 (-)44 F (-)44 F Doss 300 (-)44 F (-)44F Doss 400 (-)44 F (-)44 F Doss 500 (-)44 F (-)44 F Doss 600 (-)44 F (-)44 F Doss 700 (-)44 F (-)44 F 25

26 Comparison of D7900 vs GPA 2177 M 3 Comparison of D7900 vs GPA 2177 M 2.5 Wt. % D7900 GPA2177 M Doss 100 Doss 200 Doss 300 Doss 400 Doss Doss 600 Doss Methane Ethane Propane Butane Pentane Hexane 26

27 Comparison of D7900 vs GPA 2177 M 3 Comparison of D7900 vs GPA 2177 M 2.5 W e i g h t % D7900 GPA 2177 M Sample Doss 100 Doss 200 Doss 300 Doss 400 Doss 500 Doss 600 Doss Methane Ethane Propane Butane Pentane Hexane 27

28 Summary Sampling and Analysis plans must be established as outlined in 49 CFR IBP determinations made from collection of samples in Boston Round Bottles must follow Group 1 criteria outlined in ASTM D86-12 IBP determinations by GPA 2177 M compared to ASTM D86 are significant IBP can be determined utilizing D7900 (samples must be preserved) 28

29 Summary DO NOT CONFUSE VAPOR PRESSURE measurements with the above tests still need FPC s or Closed Systems for Sample Collection 29

30 References 1. ASTM D GPA GPA ASTM D ASTM D Classifying and Loading of Crude Oil into Rail Tank Cars, ANSI/API Recommended Practice 3000, First Edition, September Federal Register / Vol. 80, No. 89 / Friday, May 8, 2015 / Rules and Regulations &rgn=div5#se _

31 Contact Information Kesavalu M. Bagawandoss Ph.D., J.D Acknowledgements: Thanks to our Bismarck, ND Laboratory Staff for providing Data for this Presentation. 31