Pilot-Plant Performance Testing to SupportD l t f EPA HCl CEMSDevelopmentofanEPAHClCEMSPerformance SpecificationJeff RyanUS EPAOffi f R h d D l t–Office ofResearchandDevelopmentandPeter KariherARCADIS US IncARCADISUS,IncOffice of Research and DevelopmentNational Risk Management Research Laboratory.37th Stationary Source Sampling & Analysis for Air Pollutants ConferenceMarch 26, 2013Hilton Head, SCBackground•OAQPS is developing a new PerformanceSpecification(PS-18)for HCl CEMS to support(ppemissions monitoring in the Portland Cement MACTand Electric Utility MATS rulesD t di CEM t f d•Data regardingCEMs measurementperformance andquality to inform decision making is a component ofthe development process•ORD is conducting research to support data needs•Independent, industry-driven research/demonstrationt ti l t ki ltesting alsotaking place1M Thi t C idManyThingstoConsider ...HCl emissions monitoring is a new requirement with its•HClemissionsmonitoringisanewrequirementwithitsown challenges–Multiple technologies are available with many fundamentaldifferences and technical issues–Movement towards a performance based Performance Specificationthat is inclusive of these technologies–Low level regulatory emission limits present technical challenges•HCl CEMS•Reference Methods (RMs)ReferenceMethods(RMs)–Quality and availability of Reference Gas Standards–Practicality of associated procedures2EPA Research and Support Objectives•Establish data supporting finalization of PS•Evaluate commercial HCl CEMS (extractive only) as perD ft PS d t ll d d t ti i iDraftPSunder controlledandrepresentative emissionenvironments–Stackgas compositionp–HCl emission levels•Demonstrate suitability of candidate RMsD t t t t d lit f il bl G St d d•Demonstrate status andquality ofavailableGasStandards•Provide environment for vendors to optimize their CEMS3Participating HCl CEMS4 Commerciallyavailable extractive technologies in•4Commercially-available,extractivetechnologiesinTest Program–2 Gas Filter Correlation(GFC))–1 FTIR–1 Cavity Ring-Down (CRD)–No TDLAS cross stack system•Span ranges:05–-ppm–0-10ppm?Over span measurement capabilities (≤100 ppm)–Overspanmeasurementcapabilities(100ppm)4PS-18 Elements and ORD Testing Focus•Interference TestsInterferenceTests•Limit of Detection (LOD) Tests•7-DayDrift•Linearity•RATAs•Dynamic Spiking5Test Facility•ORD’sMulti-PollutantCombustionResearchFacility–4M Btu/h down-fired combustor firing coaland/or NG–Multiple pollution control configurationspossible•SCR,ESP,FF,Wet Scrubber–Duct injection of gases to controlemission profiles and combinations•HCl, SO2, NOx, CH4, CO, NH3, H2O, CH2O–All CEMS and RM measurements fromsame basic location6Reference Methods•Method 26A (MATS only)P i dt i–Pairedtrains–Static spiking?•Methods 320/321(ASTM D6348-12 too)–Looking at 3 different high resolution FTIR analyzers–Focus on DLs, measurement quality and RM performance atvery lowHCllevelsverylow–Point of reference for HCl Gas Standards7Testing Status•Still in early stages of testing due to extended facilitymaintenance•All HCl CEMSs and RM FTIRs installed–Vendors recentlyreturned for final optimizationp•Testing to date has focused on:–FTIR RM measurement capabilities and performanceE l ti HCl G St d d–EvaluatingHClGasStandards–Preliminary interference tests–Preliminary LOD tests–Reference Method performance–All while firing on NG with HCl injection•Target HCl stack concentrations 0.2–2ppm8Testing ...•We’re only now just getting started–Mostly proof-of-concept at this time–“Learning and practicing”•Working primarily with NG and pure gas injections–Some coals butHClconcentrations too highSomecoals,butconcentrationstoohigh•We’ve still managed to try a few things ...9Interference Testing ...•What gases and concentrations to test?•How practical is performing the test?1.2•How do individual vs. combined gases compare?0.81

p pm) p pm SO2

m SO2 pm CH4

a ldehyde0 40.6

C l Concentration ( p ~700 p

~80 pp ~800 p

~750 ppm ~20 ppm Form a0.20.4

H C100 9:00:1 ... 9:07:5 ... 9:15:3 ... 9:23:0 ... 9:30:3 ... 9:38:0 ... 9:45:4 ... 9:53:2 ... 10:00: ... 10:08: ... 10:15: ... 10:23: ... 10:31: ... 10:38: ... 10:46: ... 10:53: ... 11:01: ... 11:08: ... 11:16: ... 11:24: ... 11:31: ... 11:39: ... 11:46: ... 11:54: ... 12:02: ... 12:10: ... 12:18: ... 12:26: ... 12:34: ... 12:42: ... 12:50: ... 12:58: ... 1:06:1 ... 1:13:5 ... 1:21:2 ... 1:28:5 ... 1:36:3 ... 1:44:0 ... 1:51:4 ... 1:59:0 ...160Reference FTIR with HCl and Formaldehyde1401001206080

e ntration (ppmv)HCl4060

Conc eFormaldehydeHCL at 3.9 ppmv02005010015020025030011-20050100150200250300Time (minutes)120HCl CEMS Response to Formaldehyde10080

p mv)4060

C oncentration (p p20

HCl010:04:48 AM 11:16:48 AM 12:28:48 PM1:40:48 PM 2:52:48 PM 4:04:48 PM12-20Time (HH:MM:SS)LOD Testing•How well does the approach work?•What concentration(s) should be used?H d thi h t th ?Reference FTIR HCl CEMS "A"HCl CEMS "B" HCl CEMS "C"0.5 ppm Point avg 0.61 0.57 0.78 0.70std 0.03 0.02 0.01 0.07•Howdoesthis approachcompareto others?LOD 0.08 0.05 0.04 0.222 ppm Point avg 2.00 1.99 2.61 1.95std 0.04 0.01 0.04 0.05LOD 0.12 0.04 0.12 0.160.2 ppm Pointavg 0.19 0.19 0.41 0.35std 0.02 0.01 0.04 0.07LOD 0.06 0.04 0.13 0.21SystemConfigASTMMDC1 ASTMMDC2 ASTMMDC3 EPAM320MAU EPAM320FMU*REPAOCULN2‐16 0.14 0.14 0.15 0.25 0.27 0.2713Method 26A -How low can you go?CalPoints Area Calculated Agreement y=mx+b•Analyticalug/mL Counts ug/mL % m= 35.417470.20 6.81088 0.19‐3.74%b=‐7.8701E‐031.00 36.57592 1.033.29%y=area5 00178 899465 051 03%x=amount.178.89946..10.00 353.41158 9.98‐0.21%MDL=0.03ug/mL15.00 529.28789 14.94‐0.37%Liquid Total Total Total•In-stack ExampleTarget Functional Sample SampleSampleSampleSampleSampleSampleSampleConc. Dilution Conc. Volume Mass Rate Time Volume Volume ConcConcug/ml Factor ug/ml mL mg cfm min ft3 m3 mg/m3ppm0.20 1 0.2 275.0 0.06 0.75 30 22.5 0.637 0.0860.0614FTIR-How low can you go?2.5DyanmicSpikingonNaturalGas1 5211.5

n centrationHCl(ppm)SF6(ppm)0.5

Co n0 50 1 1:30:49 AM 1 1:36:50 AM 1 1:42:50 AM 1 1:48:52 AM 1 1:54:52 AM 1 2:00:53 PM 1 2:06:54 PM 1 2:12:54 PM 1 2:18:55 PM 1 2:24:56 PM 1 2:30:56 PM 1 2:36:57 PM 1 2:42:58 PM 1 2:48:59 PM 1 2:55:00 PM 1:01:00 PM 1:07:01 PM 1:13:02 PM 1:19:03 PM 1:25:03 PM 1:31:04 PM 1:37:05 PM 1:43:06 PM 1:49:06 PM 1:55:07 PM 2:01:08 PM 2:07:08 PM 2:13:09 PM 2:19:10 PM 2:25:11 PM 2:31:12 PM 2:37:12 PM 2:43:13 PM 2:49:14 PM 2:55:15 PM 3:01:15 PM 3:07:16 PM 3:13:17 PM 3:19:17 PM 3:25:18 PM 3:31:19 PM15‐0.5 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1Reference Method AgreementM321/ASTM M-26A AbsoluteTarget FTIR HCl HCl Avg Differenceppmppmv/ wetppmv/ wetppmv/ wet0.20.19 0.270.080.50.59 0.580.012.01.98 2.010.02163Let’s Put it All Together ...2.5M321/ASTM M-26ATarget FTIR HCl HCl Avg HCl CEMS "A" HCl CEMS "B" HCl CEMS "C"ppm ppmv / wet ppmv / wet ppmv / wet ppmv / wet ppmv / wet0.20.190.270.19 0.41 0.350.50.590.580.57 0.78 0.702 01 982 011 992 611 952

(ppm)2.01.982.011.992.611.951.5

HCl ConcentrationReference FTIRHCl CEMS "A"HCl CEMS "B"0.51HCl CEMS "C"0 : 09 : 39 : 18 : 57 : 27 : 09 : 36 : 10 : 45 : 24 : 54 : 33 : 14 : 42 : 21 : 00 : 30 : 09 : 47 : 24 : 54 : 33 : 03 : 42 : 21 : 58 : 30 : 09 : 39 : 18 : 48 : 18 : 05 : 36 : 15 : 45 : 24 : 54 : 33 : 14 : 42 : 21 : 51 : 30 : 09 : 39

9:00 : 9:07 : 9:15 : 9:22 : 9:30 : 9:38 : 9:45 : 9:53 : 10:00 : 10:08 : 10:15 : 10:23 : 10:31 : 10:38 : 10:46 : 10:54 : 11:01 : 11:09 : 11:15 : 11:23 : 11:30 : 11:38 : 11:46 : 11:53 : 12:01 : 12:08 : 12:16 : 12:24 : 12:31 : 12:39 : 12:46 : 12:54 : 13:02 : 13:09 : 13:17 : 13:24 : 13:32 : 13:39 : 13:47 : 13:55 : 14:02 : 14:10 : 14:17 : 14:25 : 14:33 : 14:40 :Time17Gas StandardsGas Standards are needed as part of PS and ongoing•GasStandardsareneededaspartofPSandon-Quality Assurance operations•Conventional compressedgases(dry),evaporativeg ( y), p(wet), and humidification of dry gases being considered•NIST traceable gas standards do not yet exist(but are in the worksreally!)(butareintheworks–really!)•Reference Gas quality at low concentrations andpracticalityof use a focus of our effortsy18Gas Standard TestingC dG•ompressedGases:–Ordered ~20 HCl cylinders (concentrationsranging from ~2-100 ppm) from Airgas andAirgas FTIRTag Value Measured Agreementppmppm %Linde last Summer–Initial measurements 10-50% low, most ~20%–After 6 months - some stable, some notpppp1.84 1.850.3%4.60 4.53-1.6%9.28 9.441.7%47.55 46.85-1.5%–Good news ...100.7 95.67-5.0%•Hovacal:W h i ithTarget Hovacal FTIRC t tiCl ltdM dA t–Wehave many years experience withthe Hovacal–Much faster response and equilibrationConcentrationCalculatedMeasuredAgreementHCl ppm HCl ppm HCl ppm %0.5 0.57 0.57-0.4%1.0 1.15 1.182.4%2.0 2.24 2.365.3%5 05 505 825 8%–We believe it to be accurate, but ...•Bottom line is that it is critical to our researchth th li bl f5.05.505.825.8%10.0 10.73 11.628.3%19thatwehave a reliable reference gasNIST Status•Actively developing their capabilities to provide traceabilityPrepared m ltiple ref gas c linders (812ppm)–Preparedmultiplerefgascylinders(8-–Cylinders concentrations established and confirmed•Electrochemical titration (U= 0.5%)•IC confirmation–Now establishing their RGM naming system (Tiger Optics CRDS)–Expect to be able to provide RGMs with U≤2%•Future plans–Expect to be able to name RGM cylinders for gas vendors in the nextseveral monthsseveralmonths–Prepare and study low level (~2 ppm) ref gas cylinders–Inter-laboratory comparison study with VSL this Summer20Gas Vendor Status•Multiple gas vendors now providing low level (<10 ppm) HClgas standardsgasstandards–Targeting 1-2 ppm gases•Veryaware of recent discrepancies and are workingto resolvepgthose issues•Improving/establishing their certification system instrumentationE i i t bilit•Examining stability•Discussing guidance for cylinder use•Anxious to send RGM cylinders to NISTAnxioustosendRGMcylinderstoNIST21What We’ve Learned So Far ...I t f i t t id ti•Interferences are animportantconsideration–Spectral and chemical•Candidate Reference Methods are suitable for low levelsCandidateReferenceMethodsaresuitableforlowlevels•HCl Gas Standards are a challenge–Need accurate and reliable point of reference/traceability – soon!–Dry gases have transport concerns–Practicality of the wet, evaporative systems•There’much work left to dosmuchworklefttodo...22Future Plans ...FuturePlans...•Expect to be testing through end of CY13F ll i l t PS18 ( lti l ti )•FullyimplementPS-18(multipletimes)–Conduct more comprehensive Interference Tests–Conduct more comprehensive LOD Tests–RATAs on spiked NG and low HCl coal–Consider practical alternativesWork onHClCEMS Dynamic Spiking•WorkonCEMSDynamicSpiking–levels, techniques, during RM measurements•Continue to facilitate the establishment of NIST Traceability•Support regulatory data needs23Questions...24