Matt Swanson/December 5, 2016/CAI, Inc
• Difference = X – Y
• As Y increases, error in Difference
increases
• When Y is greater than 90% of X,
standard tolerances for error on X and
Y can lead to errors on the Difference
>100%
• Analyzer
• Repeatability
• Noise
• FID Response Factors
• O2 Synergism
• Response Time
• Cutter Efficiency
• Gases
• System Bias
• Source Variability
• Analyzer
• Repeatability
• Noise
• FID Response Factors
• O2 Synergism
• Response Time
• Cutter Efficiency
• Gases
• System Bias (affects all methodologies)
• Source Variability
• Typical HC Levels
•
•
•
•
•
•
•
Methane 500-1,000 ppm
Ethane 1-20 ppm
> C2 Alkanes 0-5 ppm
Alkenes 0-5 ppm
Aldehydes 0-20 ppm
Ketones 0-10 ppm
Alcohols 0-trace ppm
• Typical HC Levels
•
•
•
•
•
•
•
Methane 500-1,000 ppm
Ethane 1-20 ppm
> C2 Alkanes 0-5 ppm
Alkenes 0-5 ppm
Aldehydes 0-20 ppm
Ketones 0-10 ppm
Alcohols 0-trace ppm
• 1065 is a NMHC method, not VOC
• Eliminates System Bias
(8) If any of the xTHC[THC-FID]init values exceed the greatest of the following values,
determine the source of the contamination and take corrective action, such as
purging the system during an additional preconditioning cycle or replacing
contaminated portions:
(i) 2% of the flow-weighted mean concentration expected at the HC (THC or
NMHC) standard.
(ii) 2% of the flow-weighted mean concentration of HC (THC or NMHC) measured
during testing.
(iii) 2 µmol/mol.
(9) If corrective action does not resolve the deficiency, you may request to use
the contaminated system as an alternate procedure under §1065.10
• O2 Synergism
§1065.520 Pre-test verification
procedures and pre-test data collection.
We recommend FID analyzer zero and span gases that
contain approximately the flow-weighted mean
concentration of O2 expected during testing.
§1065.362 Non-stoichiometric raw
exhaust FID O2 interference verification
(14) If the O2 interference is within ±2%, the FID passes the
O2 interference verification
• Repeatability
§1065.550 Gas analyzer range verification and
drift verification
You may not verify the concentration subcomponents (e.g.,
THC and CH4 for NMHC) separately. For example, for NMHC
measurements, perform drift verification on NMHC; do not
verify THC and CH4 separately.
(A) For each test interval of the duty cycle, the difference
between the uncorrected and the corrected brakespecific emission values of the regulated constituent
must be within ±4% of the uncorrected value or the
applicable emissions standard, whichever is greater.
Table 1 of §1065.205, 1% of point or measurement
• Response Factors
§1065.360 FID optimization and verification
RFCH4[THC-FID] is within ±5% of its most recent previously
determined value, the THC FID passes the CH4 response
verification
• Cutter Efficiency
§1065.365 Nonmethane cutter penetration
fractions
PFCH4 >0.85 and a PFC2H6 <0.02
• Analyzer
• Drift (4% of NMHC)
• Repeatability (1%)
• Noise (1%)
• FID Response Factors (5%)
• O2 Synergism (2%)
• Response Time (5 sec)
• Cutter Efficiency (unknown)
• Gases (1%)
• System Bias (2%)
• Source Variability (only for single NMHC unit)
• Cutter Issues
• Calibrate with dry gases
• Measure wet (>20% H2O)
• Required check within 185 days of testing
• Single NMHC analyzer has response time
issues
Single Analyzer
Dual Analyzer
• 40 CFR, Part 53, Subpart B
Day 0
Day 1
Day 2
Day 3
Day 4
Day 5
Day 6
Day 7
Day 8
Day 9
Temp
Voltage
25
115
20
125
20
105
30
125
30
105
20
125
20
105
30
125
30
105
25
115
• 40 CFR, Part 53, Subpart B
Model: 600 HFID H2/He
TEST DAY
DATE
0
5-Sep
1
6-Sep
2
7-Sep
S/N:
600
ANALYZER READING, ppm
3
4
5
8-Sep
9-Sep
10-Sep
Range
3000
Tc=10
6
11-Sep
7
12-Sep
8
13-Sep
600 HFID H2/He
9
14-Sep
P1
603.2325 583.5816 620.0931 589.5753 618.2647 580.5325 615.5992 583.3651 612.7236 604.9347
P2
603.0179 583.7525 620.5893 590.1567 618.4551 580.4444 615.8588 583.5029 612.3652 604.855
P3
602.8039 583.5153 620.7526 590.1162 618.4046 580.6533 616.2677 583.3109 612.6846 604.6644
P4
602.8379 583.3629 620.6087 590.1715 618.2705 580.7083 616.2499 583.3004 612.5682 604.7835
P5
602.9004 583.309 620.3976 589.9504 618.3298 580.927 616.1918 583.304 612.6011 604.7269
P6
602.7421 583.3377 620.6262 589.928 618.3089 580.7071 616.2313 583.3055 612.4635 604.727
P7
2392.32 2315.604 2460.483 2339.221 2451.113 2302.637 2443.88 2312.762 2427.881 2399.297
P8
2394.038 2317.598 2461.656 2338.811 2450.542 2305.745
P9
2393.329 2318.111 2460.792 2339.682 2451.874 2304.083 2442.891 2312.318 2429.421 2399.468
P10
2394.124 2317.551 2462.378 2339.073 2450.534 2305.415 2444.457 2312.006 2428.961 2400.821
P11
2393.706 2316.392 2461.06
P12
2394.19 2317.287 2461.558 2338.975 2450.318
Sn=
2393.618 2317.091 2461.321 2339.13
2445.1
2312.042 2430.271 2400.447
2339.02 2451.858 2303.439 2442.756 2312.017 2428.808 2399.733
2304.7
2444.051 2312.15
2429.67 2400.523
2451.04 2304.336 2443.856 2312.216 2429.169 2400.048
L1
2.7996
1.6666
6.0647
2.7695
3.2551
3.0197
2.9936
2.9532
3.3107
2.5582
L2
Z
S
2.6018
0
2397
2.1979
5.166
2.8965
3.3925
1.0937
3.8237
2.9998
3.4523
2.8928
Cmax
0.0191
0.242
0.9598
6.9247
0.0138
0.327
0.9963
1.1418
0.3759
0.1769
Cmin
-0.0263
0.1892
0.7007
5.8909
-0.0307
0.2773
0.7698
0.9221
0.3283
0.1557
Reading
Number
Time
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
STD. Deviation
S/N:
600 3000 Tc=10
0% of URL
80% of URL
DM
DM
ppm
ppm
Reading
Reading
0.7811
2698.934
0.7789
2700.352
0.7851
2700.361
0.7526
2700.702
0.7384
2700.831
0.7934
2700.774
0.7661
2700.855
0.7404
2701.802
0.7844
2701.485
0.7087
2702.060
0.7452
2701.682
0.7522
2700.634
0.7708
2700.717
0.7482
2700.601
0.7757
2700.660
0.7336
2700.580
0.7458
2700.668
0.7701
2700.498
0.7973
2700.390
0.7835
2700.371
0.7372
2700.351
0.7803
2700.724
0.7242
2700.564
0.7584
2700.255
0.7409
2700.021
S0 =
0.023294 S80 =
0.616080
STD Entire Data
S0 =
Detection Limit
At Zero
% Range
0.021071
0.063 At Span
0.00%
0.552269
1.657
0.06%
• 40 CFR, Part 53, Subpart B
• If using single HFID, limiting factor is
cutter PF factor
• Drift is same for THC and CH4 due to
same detector
• If using dual HFIDs, analyzer
drift/repeatability become factor in
addition to cutter PF
• Hydrate and Oxygenate Cutter
• Limitations if H2O/O2 levels too high/variable
• Remove H2O through cutter
• Sample CH4 on dry basis
• Use different CH4 measurement
• GC, FTIR, NDIR
• Use proper QA/emission calculations
• Tighten existing QA criteria
1.
2.
1065.360 (d)1-10 CH4 Response Factor Determination for FID
C3H8 Span Gas Value (As C1)
CH4 Span Gas Value
3.
Insure Analyzer Flow/Pressure/Temps Ok
4.
5.
6.
Insure FID Analyzer Calibrated using C3H8 to C1 Value
Zero FID Analyzer
Span FID Analyzer with C3H8 Gas Listed in (1) Above
7.
Arithmetic Mean of 30 Seconds of Sampling CH4 Span Gas
8.
Determine CH4 Response Factor by Dividing Step 7. by 2.
1.
2.
3.
4.
5.
6.
1065.365(e) Non-Methane Cutter Penetration Factor Determination
CH4 Span Gas Value
C2H6 Span Gas Value (As C1)
C3H8 Span Gas Value (As C1)
Zero FID In THC Mode
Span FID with C3H8 in THC Mode (As C1)
C3H8 Span Gas in CH4 Mode
7.
C3H8 Penetration Factor by Dividing Step 6. by Step 5.
8.
C2H6 Span Gas in THC Mode
9.
C2H6 Span Gas in CH4 Mode
1065.660(b)(2)(ii) THC, CH4 and NMHC Determination
Input Values Below From Empirical Data
THC INIT THC MODE(as C1)
THC INIT CH4 MODE(as C1)
THC Concentration (as C1)
CH 4 Concentration (as C1)
0
0
1500
1400
Input Response Factor and Penetration Factors Below
RFCH 4 [THC-FID]=
1.05
PF CH4[MHC-FID] =
0.95
PF C2H6[MHC-FID] =
0.02
PF C3H8[MHC-FID] =
0.0000
NHMC (Eq. 1065-660-3)
1500.00
1402.97
26.88
2000.00
2000.00
YES
10. C2H6 Penetration Factor by Dividing Step 9. by Step 8.
THC (Eq.1065-660-1)
CH 4 (Eq. 1065-660-7)
=
=
Zero=
Span=
Mean [30 sec CH4] =
RFCH4[THC-FID]=
14. Check Zero
15. Check C3H8 Span
1.050
2000.00
100.00
2000.00
0.00
100.00
0.00
PF C3H8[MHC-FID] =
0.0000
=
100.00
=
2.00
PF C2H6[MHC-FID] =
0.020
=
100.00
12. CH4 Span Gas in CH4 Mode
=
86.00
PF CH4[MHC-FID] =
0.860
Zero Check =
0.50
Span Check =
100.00
NMHC FID Response & Penetration Factors
Methane Response Factor RFCH4[THC-FID]=
PF CH4[MHC-FID]=
Methane Penetration Factor
Test Result
1.050
0.860
Ethane Penetration Factor
PF C2H6[MHC-FID]=
0.020
Propane Penetration Factor
PF C3H8[MHC-FID]=
0.0000
Pass
Pass
Pass
2100.00
=
=
=
Zero=
Span=
=
11. CH4 Span Gas in THC Mode
13. CH4 Penetration Factor by Dividing Step 24. by Step 23.
YES
0.05
1999.00
Pass
Pass
Pass
Pass
Pass
Pass