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# Richard Lambert, Eli Lilly Michael Foster, Eli Lilly

#  

# The Emission Monitoring System in this paper was installed at the Eli Lilly Tippecanoe Laboratory Facility from 2005 until 2010  

# Evonic DeGussa purchased the Tippecanoe Laboratory site in 2010  

# This paper will focus ONLY **on the operation from 2005 to 2010 while under the ownership**  **of Eli Lilly** 1/6/2013 RH Lambert 3

#  

# Key Points to Remember  

# Background  

# Regulatory  

# Multi - Metals CEMS Technology  

# X - Ray Fluorescence Technology  

# “Doped Tape” for elemental and ionic metals (Hg)  

# Quantitative Aerosol Generator

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#  

# Quality Assurance  

# Accuracy Test using a Quantitative Aerosol Generator  

# Experience using Multi - Metals CEMS  

# Used in lieu of M29 for most recent Performance Test  

# Used to gather information on specific waste lots  

# Used at Coal Fire Boiler for Hg study  

# The Good, the bad, and ugly

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# Lilly successfully installed, certified, and operated a Multi - Metals

Emission Monitoring System on a Rotary Kiln Incinerator  

# The benefit of using a multi - metals CEMS was in conjunction to using a total particulate and HCL CEMS  

# The Regulatory piece was significant and required negotiation with EPA technical branch and the Sate of Indiana  

# The Quantitative Aerosol Generator was essential for development, certification and on - going QA  

# The choice of X - Ray Fluorescence as the analytical technique was not an accident  

# The sample interface design was integral to success  

# Development of compliance software and interfacing the instrument to a site control system takes time and patience 1/6/2013 RH Lambert 6

#  

# Requires a proven analytical technique

 

# Use of solutions become problematic  

# Requires a proven sample interface  

# Providing a representative sample to the analyzer is experience based  

# Requires a proven standard generator for comparison of analytical results  

# Real time information is necessary to fully understand the system

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#  

# Tippecanoe Labs Rotary Kiln hazardous waste incinerator (T149 Kiln)  

# T149 kiln capacity is 50 mm BTU/hour  

# T149 Kiln was permitted as a NEW incinerator under the interim HWC MACT Standards  

# There is a site Title V permit

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# The T149 Kiln used 3 continuous emission monitoring systems (CEMS) to demonstrate compliance with specific HWC MACT emission standards  

# Ecochem TM 

# multi - component CEMS  

# Sigrist TM 

# total particulate CEMS  

# Xact **TM** 

# multi **- metals CEMS**  

# These three CEMS allow compliance with **respective HWC MACT emission limits in lieu**

**of specific operating limits**

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#  

# Alternative Monitoring Petition required

 

# Approved by OAQPS (EPA) in 2006  

# Title V permit approved in early 2007  

# Major modification  

# Required prior to using the metals CEMS for compliance with the HWC MACT metals emission standards  

# This was a three year exercise with EPA and the State of Indiana

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### Cooper Environmental Services 12 

# ~700 **lpm QAG**  **Spike**

**CES Xact MM CEMS**

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#  

# Quantitated 26 metals every 15 minutes  

# Averaging time was 12 hour rolling average updated every hour  

# Compliance was based upon the HWC MACT Metals  

# High Volatile (Hg)  

# 45 ug/dscm @7% O 2  

# Semi - Volatile (Pb + Cd)  

# 120 ug/dscm @7% O 2  

# Low Volatile (Be + As + Cr)  

# 97 ug/dscm @7% O 2 

###  Be has a default value of 2 ug/dscm for each sample added to the LVM category 1/6/2013 RH Lambert 14

#  

# Precision: Stability check with each sample

 

# Pd rod  

# Accuracy: Zero and upscale drift check daily for MACT metal classes  

# High volatile (Hg)  

# Semi volatile (Cd, Pb)  

# Low volatile (Cr)  

# Sample Flow Check daily

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#  

# Quarterly Audits

 

# Thin film calibration audit (MACT Metals)  

# Sample Volume Audit  

# Annual Audit  

# Thin film calibration audit (MACT Metals)  

# Sample Volume Audit  

# Linearity Test with QAG  

# Four levels for each MACT metal

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#  

# QAG provides quantitative metal aerosols at selected concentrations over the expected measurement range  

# 0 to 10,000 ug theoretical range  

# Method 301 validated as NIST traceable for Heavy Metals

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### Cooper Environmental Services 19 

# Dry **ing Chamber Bubblers**  **Pump Reserv**  **oir Balance**  **Nebulizer Droplet**  **Size Control**  **Focused Tr**  **ansport**

### Cooper Environmental Services 20

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### Cooper Environmental Services 22

#  

# Provide metal aerosols at a minimum of three levels and zero for MACT metals  

# Use QAG to quantitatively spike metals  

# 5 MACT metals simultaneously spiked  

# Minimum of nine data points per spiking level  

# Spike through the emission limit for all metals  

# Establish Quantitative Range of “system”  

# Regression analysis

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# Regression Analysis  

# Plot Xact CEMS response versus quantitatively spiked metal concentration  

# Slope represents accuracy  

# 0.85 – 1.15  

# Correlation Coefficient represents precision  

# < 0.90  

# Intercept must be < 20% of applicable emission standard for each metal

1/6/2013 RH Lambert 24**Plo tte**  **d Line ar**  **R eg**  **ressi on for**  **H g:**  **0- 1500**  y = 0.7491x + 6.7424 R 2 = 0.9986 0 500 1000 1500

0 500 1000 1500 2000

**Re fe**  **ren ce**  **u g/**  **ds cm**  **( QA**  **G) X** **a c** **t u** **g /** **d s** **c m**  **Pl otte**  **d Line ar**  **R eg**  **ressi on**  **for P**  **b: 0-**  **2300** y = 0.7588x + 13.157 R 2 = 0.9949
0 500 1000 1500 2000 2500

0 1000 2000 3000

**Re fe**  **ren ce**  **u g/ds**  **cm (**  **QA G)** **X a** **c t** **u g** **/ d** **s c** **m**

**Plot te**  **d Line**  **ar R** 

**eg ressi**  **on for**  **As :**  **0- 2300**  y = 0.769x + 13.482 R 2 = 0.9965 0 500 1000 1500 2000

0 400 800 1200 1600 2000 2400 2800

**Re fe**  **ren ce**  **ug/ds cm**  **( QA**  **G) X** **a c** **t u** **g /** **d s** **c m**  **Plot te**  **d Li**  **ne ar**  **R eg**  **ressi on**  **for Cd:**  **0- 2300**  y = 0.8139x + 5.1694 R 2 = 0.9966 0 500 1000 1500 2000

0 500 1000 1500 2000 2500

**Re fe**  **ren ce**  **u g/**  **ds cm**  **( QA**  **G) X** **a c** **t u** **g /** **d s** **c m** 



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### Pl **otte d**  **Li ne**  **ar R**  **eg ressi**  **on for**  **C r:**  **0- 850**  y = 0.8277x - 1.1648 R 2 

### = 0.9977 0 200 400 600 800

0 200 400 600 800 1000

**Re fe**  **ren ce**  **u g/**  **ds cm**  **( QA**  **G) X** **a c** **t u** **g /** **d s** **c m** 



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### 1/6/2013 RH Lambert 29 **Me ta**  **l: C**  **r Da**  **te (s**  **) Da**  **ta C**  **ol le**  **cte d:**  **8/ 05/**  **10 -**  **8-06-10 Nu**  **mb er**  **o f**  **Ru ns**  **C ol**  **le cte**  **d: 36**  **Re gre**  **ssi on**  **Cri te**  **ri a**  **Re gre**  **ssi on** 

**Cr it**  **er ia**  **L imit**  **s Re**  **gre ssi**  **on Re**  **su lt**  **s Pa**  **ss/ Fa**  **il** Slo pe 0. 85 - 1. 15 0. 9747 **Pa ss**  Int erc ept <1 9. 4 3. 7603 **Pa ss**  R 2 NA 0. 996 NA Correlat io n Coef fi ci ent ( r) >0 .9 0 1. 00 **Pa ss** 

**Me ta**  **l: A**  **s Da**  **te (s**  **) Da**  **ta C**  **ol le**  **cte d:**  **8/ 05/**  **10 -**  **8-06-10 Nu**  **mb er**  **o f**  **Ru ns**  **C ol**  **le cte**  **d: 36**  **Re gre**  **ssi on**  **Cri te**  **ri a**  **Re gre**  **ssi on** 

**Cr it**  **er ia**  **L imit**  **s Re**  **gre ssi**  **on Re**  **su lt**  **s Pa**  **ss/ Fa**  **il** Slo pe 0. 85 - 1. 15 1. 061 **Pa ss**  Int erc ept <1 9. 4 1. 62 **Pa ss**  R 2 NA 0. 995 NA Correlat io n Coef fi ci ent ( r) >0 .9 0 1. 00 **Pa ss**  **Cl ic**  **k fo**  **r Ch**  **rom iu**  **m R egressi**  **on**

**Cl ic**  **k fo**  **r Arseni**  **c Reg**  **ressi on** 

y = 0 . 9747 x + 3 . 7603 R 2 = 0 . 996 0 50 100 150 200

0. 00 50. 00 100. 00 150. 00 200 . 00**X a** **c t** **C o** **n c** **e n** **t r** **a t** **i o** **n (** **μ g** **/ d** **s c** **m )** 

**Reference Co**  **ncentrati on**  **(μ g/**  **dscm )**  

### Pl **ot ted**  **Li near** 

**R egr**  **essi on**  **fo r C**  **hromi um** 

y = 1 . 0611 x + 1 . 6166 R 2 = 0 . 995 0 50 100 150 200 250

0 50 100 150 200**X a** **c t** **C o** **n c** **e n** **t r** **a t** **i o** **n (** **μ g** **/ d** **s c** **m )** 

**Reference Co**  **ncentrati on**  **(μ g/**  **ds cm**  **)** 

### Pl **ot te**  **d Li**  **near Re**  **gressi on**  **fo r Ars**  **eni c** 

#  

# Used as reference method during performance test of the T149 incinerator  

# Total particulate and HCL  

# Used to profile coal fired boiler for:  

# Hg emissions during different firing rates  

# Profiling different lots of coal  

# Understanding impact of carbon injection on Hg removal  

# Efficiency
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#  

# Development of “WSIS” sheets for various lots of solid waste  

# Characterizes solid waste drums into categories based upon contents and emissions profiled by CEMS (metals, PM, HCL)  

# Used to understand best operating conditions for efficiency (energy reduction)  

# PM and HCL as well

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#  

# Metals CEMS installed and operated on - line since 2005  

# Clean Air Act Technology Award Winner  

# Largest hurdle to reach steady operation was the interfacing to the site control system as well as the compliance software in the site control system  

# Required deconvolution work for some overlapping energy lines  

# Lab development brought analysis to the 90% level 1/6/2013 RH Lambert 32

#  

# The paper (doped) used to collect the aerosol and particulate costs approximately $20,000 annually  

# The detector tube life is 12 – 18 months  

# Very few issues with mechanical parts of system  

# Things do wear out and part of our experience was documenting this for a preventative maintenance plan Maintenance support agreement with Cooper Environmental Services was necessary and prudent 1/6/2013 RH Lambert 33

#  

# The unit does not enjoy lightening strikes  

# The unit is not hydrophobic  

# The Xact multi - metals CEMS has evolved since the 2004 unit was build  

# Better detection limits  

# Component upgrades from Lilly experience  

# Flows now mostly reducing orifice  

# Controller for unit now PLC based  

# XRF components and software different with better control and flexible software  

# Unit operates well but requires attention from trained personel 1/6/2013 RH Lambert 34

##  

# Dr. John Cooper and staff, Cooper Environmental Services LLC  

# Mike Foster, Corporate Environmental Affairs, Eli Lilly  

# Sherman Wright, Tippecanoe Laboratory Incineration Operations, Evonik Degussa  

# Jason Marlin, Operations, Eli Lilly

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