Summary of HRS sampling and analysis in HyCoRA. HyCoRA OEM workshop Trondheim, Thor Anders Aarhaug, SINTEF Materials and Chemistry

Transcription

1 Summary of HRS sampling and analysis in HyCoRA HyCoRA OEM workshop Trondheim, Thor Anders Aarhaug, SINTEF Materials and Chemistry

2 SINTEF sampling background SINTEF subcontracted Smart Chemistry for HRS QC in HRS in Norway Rented sampling instrumentation from SC (ASTM D ) 2

3 HyCoRA sampling strategies Commercial instrumentation available at SoP Linde: Qualitizer 70 MPa gas sampler HYDAC: 70 MPa particulate sampler In-line strategy making use of FCEV as sink Instruments purchased by SINTEF 3

4 Gas sampling adapter Linde 'Qualitizer' No IrDA (limit of 60 MPa) Manual override of HRS safety not required 4

5 Gas sampling adapter Manual purge at 6 Mpa with UHP H 2 before first time use (to remove air) Hose kept slightly pressurized by check valves Depressurization by bleed valve Purge procecure by abortion of refuelling sequence and depressurization possible Internal volume not significant compared with the L sample. SINTEF has not purged instrument between samples. No indication of impurity carry over has been observed in analytical results 5

6 Sample cylinders 10L Aluminium (SS valve) Spectraseal canisters Cylinder lining requirement Feedback from VSL, NPL and Linde (HyQ project) Different types of linings Spectraseal (Linde) Sulfinert Silonite 6

7 Particulate sampler HYDAC PSA MPa sampling No IrDA Series connection with gas sampler 7

8 Particulate sampler Depressurized by bleed valve 0.2 and 5 µm filters available "Clean room" required for filter change 8

9 Combined sampling Sampling adapter in series for the use of only one FCEV 1st sampling campaign: gas only 2nd sampling campaign: gas downstream particulate sampler 3rd sampling campaign: gas upstream particulate sampler 9

10 Sampling issues not addressed Sampling cylinder purging requirements Sampling adapter purging requirements No indication of carry over observed Stability of samples in (lined) cylinders Sample tranference to other (smaller) cylinders Used with shipping to US (Smart Chemistry) HRS back to back sampling Impact of serial sampling Gas upstream particulates Particulates upstream gas 10

11 Sampling stragegy downsides Some critic for the use of FCEV as sink Need 1 (2) empty FCEV Depressurization to air depreciated Use of HRS safety vent HYDAC redesign available 11

12 Strategy for analysis SoP: only Smart Chemistry available for analysis with full compliance with ISO (SAE J2719) Shipping cost high Time from sampling to analysis at least two weeks For the third sampling capaign: 10 samples sent to Smart Chemistry 5 samples sent to NPL 5 samples sent to Protea 12

13 Additional analysis Long path FTIR analysis by SINTEF Cryo focusing GC-MS analysis by VTT and SINTEF Stability of HCHO and HCOOH in H 2 matrix evaluated HyCoRA has taken part in two round robin tests Typically 1 ppm mol level for stability Analysis by NPL and SYFT Analysis of 3x SC2 samples for organohalides 13

14 Smart Chemistry Analytical methods ASTM Analytical technique Pre concentration THC (C1) WK34574 GC-MS Cryo/TD/Cryo He D1946 GC-TCD N 2, Ar, O 2, H 2 O D7649 GC-MS CO 2 D7649 GC-MS CO D1946 GC-PDHID Cryo HCHO D GC-MS Cryo/TD/Cryo HCOOH D GC-ELCD Cryo/TD/Cryo NH 3 D GC-ELCD Cryo/TD/Cryo HCl, HBr, Cl 2 D GC-ELCD Cryo/TD/Cryo TS D7652 GC-SCD Cryo/TD/Cryo C-X D GC-MS Cryo/TD/Cryo 14

15 Results from 1st sampling campaign ID Tol HY-1 HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 Feed WE SMR SMR/BIO SMR/BIO WE CA WE WE Storage C C L L C C C C On-site Y N N N Y N N N H 2 O 5 < 1 < 1 < 1 < 1 < < 1 < 1 THC (C1) O He 300 < 10 < 10 < < 10 < 10 < 10 < 10 N 2 + Ar CO 2 2 < 0.2 < 0.2 < 0.2 < < 0.2 < 0.2 CO HCHO 0.01 < < < < < < < < CHOOH 0.2 < < < < < < < < NH < < < < < < < < TS TX FI (%)

16 Results from the 2nd campaign ppm mol HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 LOD Tol Commissioned Fuel Index H2O THC (C1) O He N2 & Ar N Ar CO CO TS HCHO HCOOH NH TH <

17 HRS QC time trends HRS Gothenburg from "bad to good" > 2017 HRS Porsgrunn N 2 improvement Porsgrunn Chlor-alkali Fuel Index (%) N CO Ar THC Ethane, Buthane, N-butane CH H2O < O2 < CO TH <

18 Particulates Big difference upstream vs downstream collection Independent sampling (2x FCEV) until further clarification Upstream Downstream 18

19 Halogenates ISO revision Need to remove "total halogenates" OK Exemplified by HCl and R-X (CEN TC 268) Cl-ion basis justification? Cl 2 -> HCl OK but CH 2 Cl 2? Presence and stability of C 4 Cl 4 F 6 19

20 Conclusions Hydrogen fuel quality generally good Few violations observed since 2012 Significant impurity levels observed for N 2, He O 2, CO 2, H 2 O, THC C 4 Cl 4 F 6 Impurities does not correlate with H 2 feedstock No correlation between commissioning date and fuel quality found Maintenance schedule probably important 20

21 Old slide separator Extra slides 21

22 HRS locations SC1 22

23 HRS locations SC2 Sample Location Storage Feedstock Technology Operator Bottle pressure Commissioning HY-2 Hamburg Compressed SMR Air Products Shell 125 bar 2013 HY-3 Berlin Liquid SMR Linde Total 125 bar 2015 HY-4 Berlin Liquid SMR Linde Total 125 bar 2015 HY-5 Munich CCH2 SMR Linde Total 125 bar 2015 HY-6 Geiselwind Liquid SMR Linde Total 125 bar 2015 HY-7 Kolding Compressed WE H2 Logic H2 Logic 125 bar 2016 HY-8 Århus Compressed WE H2 Logic H2 Logic 125 bar 2016 HY-9 Køge Compressed WE H2 Logic H2 Logic 125 bar 2016 HY-10 Gothenburg Compressed WE Woikoski Vätgas SWE 125 bar 2015 HY-12 Århus Compressed WE H2 Logic H2 Logic 125 bar

24 Strategy Samples must be collected at the nozzle at representative pressure and velocity Combined sampling of gas and particulates Focus in impurities sourcing from HRS: newly commissioned HRS Previous campaign: impact of feedstock on fuel quality Analysis of all impurity constituents; compliance with ISO :2012 and SAE J2719 No analytical capabilities in EU Smart Chemistry, Sacramento CA 24

25 Results: overview ppm mol HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 LOD Tol Commissioned Fuel Index H2O THC (C1) O He N2 & Ar N Ar CO CO TS HCHO HCOOH NH TH <

26 Results: fuel index Fuel Index (%) HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 26

27 Results: inerts N2 He Ar Inerts (ppm mol) Tol Fuel index, He Tol N2 + Ar HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 27

28 Results: other constituents O2 H2O CO2 THC 25 Constituent concentration (ppm mol) HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 28

29 Results: total sulfur H2S COS CS2 TBM THT Sulfur constituent concentration (ppm mol) HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 29

30 Results: total halogenates C4Cl4F6 CH2Cl Constituent concentration (ppm mol) HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 30

31 Results: particulates 1 mg/kg tolerance limit 95 % Single sided confidence Particulate concentration (mg kg -1 ) HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 31

32 Results: particulates Filter Total Stainless steel Ni-P Other metals Oxides Organic particles Organic residues HY-2 medium HY-3 low HY-4 medium HY-5 low HY-6 medium HY-7 low HY-8 low HY-9 low HY-10 low HY-12 high µm PTFE filter penetration 32

33 Acknowledgement Fuel QA activity part of the FCH-JU funded project HyCoRA: Hydrogen Contaminant Risk Assessment Grant agreement no: Project duration Apr 2014 March 2017

34 Uncertainty of analysis RSD HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 Fuel Index H2O 9.8 THC (C1) O He N2 & Ar N Ar CO2 8.7 CO TS HCHO HCOOH NH3 TH 34

35 Results: Organic consituents Acetone EtOH Propane Octene Decene ppm CH4 Constituent concentration (ppm mol) HY-2 HY-3 HY-4 HY-5 HY-6 HY-7 HY-8 HY-9 HY-10 HY-12 35

36 Analytical methods 36