SRI/USEPA-GHG-QAP-20 September 2003 Environmental Technology Verification Report Engineered Concepts, LLC Quantum Leap Dehydrator Greenhouse Gas Technology Center Southern Research Institute oEPA Under a Cooperative Agreement With U.S. Environmental Protection Agency ------- EPA REVIEW NOTICE This report has been peer and administratively reviewed by the U.S. Environmental Protection Agency, and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. ------- ETV Joint Verification Statement TECHNOLOGY TYPE: Emissions Control of Criteria Pollutants, Hazardous Pollutants, and Greenhouse Gases APPLICATION: Natural Gas Dehydration TECHNOLOGY NAME: Quantum Leap Dehydrator COMPANY: Engineered Concepts, LLC ADDRESS: 1909 E. 20th St., Farmington, NM 87401 E-MAIL: gasstripDer@netscape.net The U.S. Environmental Protection Agency (EPA) has created the Environmental Technology Verification (ETV) program to facilitate the deployment of innovative or improved environmental technologies through performance verification and information dissemination. The ETV program goal is to further environmental protection by accelerating the acceptance and use of improved and cost-effective technologies. ETV seeks to achieve this by providing high-quality, peer-reviewed performance data to those involved in the purchase, design, distribution, financing, permitting, and use of environmental technologies. ETV works in partnership with recognized standards and testing organizations, stakeholder groups composed of buyers, vendor organizations, and permitters, and with the full participation of individual technology developers. The program evaluates technology performance by developing test plans that are responsive to stakeholders" needs, conducting field or laboratory tests, collecting and analyzing data, and preparing peer-reviewed reports. All evaluations are conducted in accordance with rigorous quality assurance protocols. This ensures that the resulting data are of known quality and that the results are defensible. Southern Research Institute operates the Greenhouse Gas Technology Center (GHG Center), one of six ETV Centers, in cooperation with EPA's National Risk Management Research Laboratory. The GHG Center has recently evaluated the performance of the Quantum Leap Dehydrator (QLD), manufactured by S-l ------- Engineered Concepts, LLC, of Farmington, NM. This Verification Statement provides a QLD verification test summary. TECHNOLOGY DESCRIPTION Background Natural gas often contains excess water vapor at the wellhead which must be removed to avoid pipeline corrosion and solid hydrate formation. Glycol dehydration is the most widely used natural gas dehumidification process. Triethylene glycol (TEG) typically absorbs water from natural gas in a contactor vessel. The TEG absorbs water from the natural gas, but also absorbs methane (CH4), volatile organic compounds (VOCs), and hazardous air pollutants (HAPs). Gas-assisted or electric pumps circulate the TEG through a distillation column for regeneration and back to the contactor vessel. Distillation removes the absorbed water and HAPs from the TEG to the still column vent as vapor. Conventional dehydrator still columns often emit this vapor directly to the atmosphere. Natural gas dehydration is the third largest CH4 emission source in the natural gas production industry. Glycol dehydrators also cause over 80 percent of the industry's annual HAP and VOC emissions. OLD Technology Information supplied by Engineered Concepts, LLC provided the basis for this discussion. GHG Center personnel verified the function and operation of major system components during the test campaign. The QLD is an integrated system which collects the water and hydrocarbons present in the glycol reboiler vent stream and separates condensable and non-condensable fluids. The two primary condensable products are: (1) wastewater, which can be disposed of with treatment and (2) hydrocarbon condensate, which is a saleable product. The reboiler burner combusts the uncondensable vapors as the system's primarily fuel. The QLD uses condensation and combustion to reduce both HAP and CH4 emissions. The QLD uses a series of heat exchangers, condensers, separators, and electric pumps to recover and use distillation column vapors. First, a liquid removal vacuum separator condenses and collects still column vent water and HAPs vapors under vacuum. The separator partitions the vapor stream into three products: (1) wastewater, (2) condensate, and (3) uncondensed hydrocarbon vapors. The separator discharges the wastewater and condensates into product holding tanks through pneumatically-operated level controllers. Negative gage pressure, created by glycol flow through an eductor (which provides additional scrubbing), transfers hydrocarbon vapors to the emissions separator. The emissions separator further separates liquid products from uncondensable hydrocarbon vapors and glycol. It transfers liquid products back to the vacuum separator while the reboiler burner combusts the hydrocarbon vapors. The burner operates continuously and throttles the heat output in response to still column heat demand. Burner performance is the primary indicator of whether the QLD can combust the widely varying amounts and quality of fuel gas recovered by the system. The burner system can also accept makeup natural gas if the still column demands additional heat. An electric pump circulates approximately four gallons per minute (gpm) of TEG through the natural gas contactor vessel. A separate pump circulates about 72 gpm within the QLD condensation/separation system. Electric pumps, in contrast to the widely used gas-assisted pumps, further reduce CH4 emissions and losses. Primary QLD air emission sources include: (1) the reboiler burner exhaust, (2) HAPs dissolved in the recovered wastewater, and (3) pressure-relief vents (PRVs). The QLD fabricator and field installers certified the equipment as leak-free, so this verification did not quantify fugitive emissions. S-2 ------- VERIFICATION DESCRIPTION The GHG Center executed the QLD performance verification test at the Kerr-McGee Gathering Station in Brighton, CO. The test campaign proceeded under requirements set forth in the Test and Quality Assurance Plan - Engineered Concepts. LLC Quantum Leap Dehydration (SRI/USEPA-GHG-QAP-20), June, 2002 (Test Plan). The system was designed to dehydrate approximately 28 million standard cubic feet per day (mmscfd) of natural gas. Testing commenced in April 2003, approximately one month after completion of system start-up activities. Tests consisted of a seven-day operational performance monitoring period followed by one day of environmental performance testing. The system operated normally during testing, and the GHG Center evaluated the verification parameters listed below: Operational Performance Sales Gas Moisture Content: The field site requires that dry natural gas exiting the QLD process contain less than seven lb water/mmscf. An inline moisture analyzer continuously monitored and recorded sales gas moisture readings at one-minute intervals. Sales Gas Production Rate: The QLD must allow uninterrupted natural gas dehydration and maintain a continuous natural gas flow. An inline integral orifice meter continuously monitored the natural gas flow rate. Data were logged in one-minute intervals. Glycol Circulation Rate: Facilities affected by the 40 CFR Part 63 standard (Subpart HH) regulations must continuously monitor TEG circulation rates. An ultrasonic meter, installed on the regenerated lean glycol line, recorded one-minute average circulation rates. Makeup Natural Gas Flow Rate: A separate meter continuously monitored reboiler burner makeup natural gas. The one-minute average readings characterized any additional fuel required by the QLD. Environmental Performance Reboiler Stack Emission Rates: Emissions tests determined concentration in parts per million volume, dry (ppmvd) and emission rates in pound per hour (lb/h) for the following air pollutants: nitrogen oxide (NOx), carbon monoxide (CO), VOCs, HAPs (benzene, toluene, ethylbenzene, xylene, and hexane), and greenhouse gases (C02 and CH4). Three test runs were conducted, each lasting approximately 90 minutes. All testing conformed to U.S. EPA Title 40 CFR 60 Appendix A Reference Method procedures. HAP Destruction Efficiency: Dehydration facilities subject to MACT must reduce HAP emissions by 95 percent. The tests verified HAP destruction efficiency as a measure of emissions reduced by the QLD. HAP destruction efficiency is the HAPs entering the system (absorbed in rich and lean glycol streams) minus the HAPs emitted from the system (discharged and vented to atmosphere from stack, PRVs, and wastewater) divided by the HAPs entering the system. HAPs dissolved in the condensate product stream are not an emission source because the site uses this product as feedstock for other processes. The regulation defines this as "controlled" or "sequestered" emissions. Wastewater and Condensate Production Rate: HAP destruction efficiency determination required volumetric measurement of wastewater and condensate production rates. Independent GHG Center QA personnel conducted a technical systems audit during testing to ensure that field activities complied with the Test Plan. The Center's QA Manager implemented a data quality audit S-3 ------- of at least ten percent of the data to ensure that data reduction and reporting accurately represented actual results. The field team leader conducted performance evaluation audits to ensure that the measurement system produced reliable data. In addition to these quality assurance audits, EPA QA personnel conducted a quality assurance review of the Verification Report and a quality systems audit of the GHG Center's Quality Management Plan. PERFORMANCE VERIFICATION Operational Performance One-minute readings provided daily average flow rates and moisture content over the seven-day performance evaluation period. The 75th percentile interval of these readings defined normal operating conditions. • The QLD natural gas dehydration process met the test site's 7.00 lb/mmscf moisture content requirement. Daily average values ranged between 0.89 and 1.28 lb/mmscf. • The QLD enabled continuous sales gas flow, with daily average flow rates ranging between 26.8 and 29.3 mmscfd. • Daily average glycol circulation rates through the absorption and regeneration process ranged between 3.00 and 3.77 gpm. • The verification test demonstrated that the QLD required little to no makeup natural gas. The normal range of the makeup natural gas flow rate was 0.00 to 1.76 scfh, which is well below the 166 scfh design capacity. The volume and fuel quality of the uncondensed hydrocarbon vapors was generally sufficient to maintain optimum burner control. Environmental Performance • Average NOx concentration for the three test runs was 65.1 ppmvd during normal operations. This equates to a mass emission rate of 0.0817 lb/h. • Emissions of CO and VOCs were low during all three test runs, averaging 0.6 ppmvd (0.0005 lb/h) and 0.6 ppmvd (0.0003 lb/h), respectively. • Stack emissions of all HAP constituents were below the sensitivity of the sampling system. The detection limit was 0.1 ppmvd, which meets the specifications of the Title 40 CFR 60 Appendix A reference methods. The hourly average stack HAP emission rate is verified to be less than 0.0016 lb/h. • Methane concentrations were not detected during any of the test periods The detection limit was 0.1 ppmvd, which meets the specifications of the Title 40 CFR 60 Appendix A reference methods. C02 concentrations averaged about 9.3 percent of the stack gas volume, equating to a mass emission rate of 111 lb/h. • PRVs did not operate at any time during the entire test campaign, nor are releases anticipated during normal operations. Therefore, no expected emissions were assigned to PRV operation. S-4 ------- REBOILER STACK EMISSIONS NOx CO voc ppmvd lb/h ppmvd lb/h ppmvd lb/h Run 1 67.8 0.0873 0.3 0.0003 0.4 0.0002 Run 2 66.0 0.0817 1.0 0.0007 0.8 0.0004 Run 3 61.6 0.0761 0.6 0.0004 0.5 0.0002 Avg. 65.1 0.0817 0.6 0.0005 0.6 0.0003 HAP CH, co2 ppmvd lb/h ppmvd lb/h ppmvd lb/h Run 1 <0.6 <0.0016 <0.1 <0.00004 9.5 117 Run 2 <0.6 <0.0016 <0.1 <0.00004 9.2 109 Run 3 <0.6 <0.0015 <0.1 <0.00004 9.1 108 Avg. <0.6 <0.0016 <0.1 <0.00004 9.3 111 • HAPs entering the QLD were 9.09 lb/h. Maximum HAPs leaving the system in the reboiler exhaust and wastewater were 0.0016 and 0.0220 lb/h, respectively. The HAP destruction efficiency is greater than 99.74 ± 0.01 percent. • Wastewater production rate was approximately 0.106 gallons per minute or 6.36 gallons per hour. • Saleable condensate product recovery rate was approximately 0.048 gallons per minute or 2.88 gallons per hour. Signed by: Hugh W. McKinnon, 9-2003 Hugh W. McKinnon, M.D., M.P.H. Director National Risk Management Research Laboratory Office of Research and Development Signed by: Stephen D. Piccot, 9-2003 Stephen D. Piccot Director Greenhouse Gas Technology Center Southern Research Institute Notice: GHG Center verifications are based on an evaluation of technology performance under specific, predetermined criteria and the appropriate quality assurance procedures. The EPA and Southern Research Institute make no expressed or implied warranties as to the performance of the technology and do not certify that a technology will always operate at the levels verified. The end user is solely responsible for complying with any and all applicable Federal, State, and Local requirements. Mention of commercial product names does not imply endorsement or recommendation. S-5 ------- This page intentionally left blank. S-6 ------- SRI/USEPA-GHG-QAP-20 September, 2003 Greenhouse Gas Technology Center A U.S. EPA Sponsored Environmental Technology Verification ( ElV ) Organization Environmental Technology Verification Report Engineered Concepts, LLC Quantum Leap Dehydrator Prepared by: Greenhouse Gas Technology Center Southern Research Institute PO Box 13825 Research Triangle Park, NC 27709 USA Telephone: 919/806-3456 Reviewed by: Engineered Concepts, LLC [SI Kerr McGee Gathering, LLC S Selected Members of GHG Center Stakeholder Panel [SI U.S. EPA Office of Research and Development QA Team S \Z\ indicates comments are integrated into Verification Report ------- TABLE OF CONTENTS Page Appendices iii List of Figures iii List of Tables iii Distribution List iv 1.0 INTRODUCTION 1-1 1.1. BACKGROUND 1-1 1.2. QLD TECHNOLOGY DESCRIPTION 1-2 1.3. TEST FACILITY DESCRIPTION AND QLD MODIFICATIONS 1-6 1.4. PERFORMANCE VERIFICATION OVERVIEW 1-10 1.4.1. Performance Verification Parameters 1-10 1.4.2. Measurement Approach 1-11 1.4.2.1. Sales Gas Moisture Content 1-14 1.4.2.2. Sales Gas Production Rate 1-14 1.4.2.3. Glycol Circulation Rate 1-14 1.4.2.4. Makeup Natural Gas Flow Rate 1-15 1.4.2.5. Reboiler Stack Emission Rates 1-15 1.4.2.6. HAP Destruction Efficiency 1-16 1.4.2.7. Additional Supporting Measurement Details 1-16 1.4.2.7.1 Glycol Flow 1-16 1.4.2.7.2 Lean Glycol Sample Condition 1-16 1.4.2.7.3 Lab Analysis 1-17 1.4.2.7.4 Wastewater Discharge Rate 1-17 1.4.2.7.5 HAPs Emitted from Pressure-Relief Vents 1-18 1.4.2.7.6 HAPs Entering in Makeup Natural Gas 1-18 2.0 VERIFICATION RESULTS 2-1 2.1. OVERVIEW 2-1 2.2. OPERATIONAL PERFORMANCE 2-2 2.3. ENVIRONMENTAL PERFORMANCE 2-3 2.3.1. Reboiler Stack Emissions Performance 2-5 2.3.2. HAP Destruction Efficiency 2-6 2.3.2.1. HAP Inputs from Glycol Streams 2-7 2.3.2.2. HAP Outputs in Reboiler Exhaust Stream 2-9 2.3.2.3. HAP Outputs in Wastewater Production Stream 2-10 2.3.2.4. HAP Outputs in Condensate Production Stream 2-12 3.0 DATA QUALITY ASSESSMENT 3-1 3.1. DATA QUALITY OBJECTIVES 3-1 3.2. DQO AND DQI RECONCILIATION 3-4 3.2.1. Sales Gas Flow Rate and Moisture Content 3-7 3.2.2. Glycol Circulation Rate 3-7 3.2.3. Makeup Natural Gas Flow Rate 3-8 3.2.4. Reboiler Stack Emissions 3-9 3.2.4.1. NO, and TIIC 3-9 3.2.4.2. CO, CO and ()• 3-9 3.2.4.3. HAPs 3-9 3.2.4.4. Moisture Measurement 3-10 3.2.4.5. Emission Rate Measurement Error 3-10 ii ------- 3.2.5. HAP Destruction Efficiency 3-10 3.2.5.1. Liquid Analysis Data Quality 3-11 4.0 TECHNICAL AND PERFORMANCE DATA SUPPLIED BY ENGINEERED CONCEPTS, LLC 4-1 5.0 REFERENCES 5-1 APPENDICES Page Appendix A Rich Glycol Flow Rates A-l Appendix B Emissions Testing QA/QC Results B-l Appendix B-l Summary of Daily Reference Method Calibration Error Determinations B-2 Appendix B-2 Summary of Reference Method System Bias and Drift Checks B-3 Appendix B-3 Summary of GC/FID Calibration Results B-4 Appendix C Liquid Analysis QA/QC Results C-l Appendix C-l Rich Glycol—Duplicate and Spike Analysis Results C-2 Appendix C-2 Lean Glycol—Duplicate and Spike Analysis Results C-3 Appendix C-3 Wastewater—Duplicate and Spike Analysis Results C-4 Appendix C-4 Condensate—Spike Analysis Results C-5 Appendix C-5 Rich and Lean Glycol Moisture Content—Duplicate Analysis Results C-6 Appendix D Pre-Test Makeup Natural Gas Analysis Data D-l Appendix D-l Pre-Test Makeup Natural Gas Analysis D-2 LIST OF FIGURES Page Figure 1-1 Generic Natural Gas Dehydration Process 1-3 Figure 1-2 QLD Natural Gas Dehydration Technology 1-5 Figure 1-3 QLD at Kerr-McGee Gathering Station 1-7 Figure 1-4 QLD Interior 1-8 Figure 1-5 Measurement System Schematic 1-13 Figure 2-1 Operational Parameters Measured During Verification Test Period 2-4 Figure 2-2 Fuel Gas Flow Rates Measured During the Verification Test Period 2-4 LIST OF TABLES Page Table 1-1 Test Site Design and Operating Conditions 1-9 Table 1-2 Verification Test Matrix 1-12 Table 1-3 Emissions Testing Methods Summary 1-15 Table 2-1 Pre-Test Operational Data and Establishment of Normal Operating Conditions 2-2 in ------- Table 2-2 Verification Test Period Operational Data Summary 2-3 Table 2-3 Additional Process Operating Data for Verification Test Periods 2-5 Table 2-4 Reboiler Stack Emissions Summary 2-5 Table 2-5 HAP Destruction Efficiency 2-6 Table 2-6 HAP Inputs From Glycol Streams 2-8 Table 2-7 Reboiler Exhaust Stream HAPs Output 2-10 Table 2-8 Pre-Test Wastewater Discharge Rate Determinations 2-10 Table 2-9 Wastewater Production Rate During Verification Testing 2-11 Table 2-10 HAP Outputs in Wastewater Production Stream 2-12 Table 2-11 Run-Specific Condensate Production Rate 2-13 Table 2-12 HAP Outputs in Condensate Production Stream 2-14 Table 3-1 Verification Parameter Data Quality Objectives 3-1 Table 3-2 Data Quality Indicator Goals and Results 3-2 Table 3-3 Calibration Results and QC Checks 3-5 Table 3-4 Comparison Between Length-of-Stain Moisture Content and Analyzer Reading 3-7 Table 3-5 Destruction Efficiency Error Determinations 3-12 Table 3-6 Maximum Percent Difference in Duplicate Injection Results 3-12 Table 3-7 Benzene Audit Results 3-13 iv ------- LIST OF ABBREVIATIONS AND ACRONYMS acfh actual cubic feet per hour ARL atmospheric rich/lean method bcfy billion cubic feet per year BTEX benzene, toluene, ethylbenzene, xylenes CAR corrective action report dscfh dry standard cubic feet per hour dscfm dry standard cubic feet per minute ECL Engineered Concepts, LLC EPA Environmental Protection Agency EPA-ORD Environmental Protection Agency-Office of Research and Development ETV Environmental Technology Verification fps feet per second ft feet (foot) gal gallon(s) gal/in. gallons per inch GC gas chromatograph GC/FID gas chromatograph with flame ionization detector gPm gallons per minute GRI Gas Research Institute (became the Gas Technology Institute) GTI Gas Technology Institute HAP hazardous air pollutant hp horsepower in. inches lb pound lb/h pounds per hour lb/mmscf pounds per million cubic feet LDL lower detection limit m meters mm millimeters MACT maximum achievable control technology MDL method detection limit mBtu thousand British thermal units mBtu/h thousand British thermal units per hour ml milliliter mg milligram mmscfd million standard cubic feet per day mmscfh million standard cubic feet per hour mscf thousand standard cubic feet mscfd thousand standard cubic feet per day MW molecular weight ng nanogram NIST National Institute of Standards and Technology ppm parts per million pmvd parts per million by volume, dry psia pounds per square inch, absolute psig pounds per square inch, gage PRV pressure-relief vent (or valve) QA quality assurance QA/QC quality assurance / quality control v ------- LIST OF ABBREVIATIONS AND ACRONYMS, CONTINUED QLD Quantum Leap Dehydrator QMP Quality Management Plan scfgal standard cubic feet per gallon scfh standard cubic feet per hour SRI Southern Research Institute TEG triethylene glycol VOC volatile organic compound w.g. water glass or water head pressure °F degrees Fahrenheit ig microgram ig/ml micrograms per milliliter il microliter VI ------- DISTRIBUTION LIST Engineered Concepts, LLC Rodney Heath Kerr-McGee Gathering, LLC Paul Morehead Robert Smith U.S. EPA-Office of Research and Development David Kirchgessner Shirley Wasson Southern Research Institute (GHG Center) Stephen Piccot Mark Meech Robert Richards Ashley Williamson Technical Peer Revieweres Curtis Rueter-Wind River Environmental James M. Evans, Consultant Vll ------- This page intentionally left blank. Vlll ------- 1.0 INTRODUCTION 1.1. BACKGROUND The U.S. Environmental Protection Agency's Office of Research and Development (EPA-ORD) is charged with facilitating the deployment of improved and innovative environmental technologies. EPA- ORD operates the Environmental Technology Verification program (ETV) to achieve this end. ETV's mission is to further environmental protection by accelerating these technologies acceptance and use. To realize its mission, ETV independently verifies technology performance and disseminates the results to a wide variety of public, industry, regulatory, and private stakeholders. Congress funds ETV in response to the belief that there are many viable environmental technologies that are not being used for the lack of credible third-party performance data. With performance data developed under ETV, technology buyers, financiers, and permitters will be better equipped to make informed decisions regarding environmental technology purchase and use. EPA's partner organization, Southern Research Institute (SRI) operates the Greenhouse Gas Technology Center (GHG Center) which is one of six ETV organizations. The GHG Center verifies the performance of promising greenhouse gas mitigation and monitoring technologies by developing verification protocols, conducting field tests, collecting and interpreting field and other data, obtaining independent peer review input, and reporting findings. Externally reviewed "Test and Quality Assurance Plans" (test plans) and well-established quality assurance (QA) protocols regulate the GHG Center's verification activities. Volunteer stakeholder groups guide the GHG Center. These stakeholders advise on specific technologies most appropriate for testing, help distribute results, and review test plans and "Environmental Technology Verification Reports" (reports). National and international environmental policy, technology, and regulatory experts participate in the GHG Center's Executive Stakeholder Group. The group includes industry trade organizations, environmental technology finance groups, governmental organizations, and other interested parties. Industry-specific stakeholders also peer-review key GHG Center publications and guide verification test strategies in those areas related to their expertise. The GHG Center's Oil and Gas Stakeholder Group has identified a need for independent third-party methane (CH4) and carbon dioxide (C02) emission reduction technology verification. Natural gas dehydration is a significant source of these two greenhouse gases and other pollutants. This report documents the performance of a new dehydration technology that reduces greenhouse gases, hazardous air pollutant (HAP), and volatile organic compound (VOC) emissions. Approximately 252,000 natural gas production wells currently operate in the U.S. The natural gas often contains excess water vapor which can cause corrosion and form solid gas hydrates inside pipelines. The natural gas production and transportation sectors consequently invest considerable resources to remove water from natural gas. Glycol dehydration is the process where dry triethylene glycol (TEG) absorbs water vapor by directly contacting the sales gas. It is the most widely used natural gas dehumidification process. TEG primarily absorbs water, but it also absorbs CH4, VOCs, and HAPs from the gas. Dehydrators re-dry the TEG (usually in at least one reboiler per dehydrator), often emitting both the absorbed water and air pollutants directly to the atmosphere. 1-1 ------- EPA estimates that the more than 38,000 active glycol dehydrators in the U.S. collectively emit about 18.6 billion cubic feet per year (bcfy) of CH4 [1], Natural gas glycol dehydration is the third largest CH4 emission source within the production sector, creating 17 percent of this sector's total greenhouse gas emissions [2], Glycol dehydrators are also responsible for 85 and 81 percent of the production sector's HAP and VOC emissions, respectively [3,4], The EPA promulgated final maximum achievable control technology (MACT) standards on June 17, 1999, which require that glycol dehydrator owners or operators reduce HAP emissions by 95 percent [5], The MACT standard requires affected facilities install control devices to recover or destroy pollutants in the dehydration vent stream. Engineered Concepts, LLC (ECL), located in Farmington, NM, has developed a patented gas dehydration technology known as the Quantum Leap Dehydrator (QLD) to meet this goal. The QLD is an integrated system which collects all the water and hydrocarbons present in the glycol reboiler vent stream. It condenses and collects most hydrocarbons into a salable product; water is collected for disposal; and the uncondensed hydrocarbon balance is routed to the reboiler burner for combustion. The end result of the QLD process is the reduction of both HAP and CH4 emissions. ECL requested that the GHG Center perform an independent QLD performance verification at a natural gas gathering station operated by Kerr-McGee Gathering, LLC. This report presents the results obtained during the recently concluded performance verification test. The Test and Quality Assurance Plan— Engineered Concepts, LLC Quantum Leap Dehydrator [6] provided the verification test design, measurement and quality assurance/quality control (QA/QC) procedures. It is available for download from the GHG Center's web site (www.sri-rtp.com) or the ETV Program web site (www.epa.gov/etv). ECL, SRI, selected stakeholders, and EPA-ORD have reviewed the test plan and report as evidenced by the signature pages at the front of both documents. They satisfy the pertinent GHG Center Quality Management Plan (QMP) requirements. The following paragraphs describe the QLD technology and the as-built system at the Kerr-McGee site. The remaining subsections define the verification parameters and briefly describe the test methods used to quantify these parameters. Section 2.0 presents the verification test results and Section 3.0 assesses data quality. Circumstances required departures from the Test Plan in some cases and Corrective Action Reports (CARs) were prepared to describe such modifications. The appropriate sections below discuss any deviations. Section 4.0 was submitted by ECL and presents additional QLD system information, its performance at the test site, and other facts the manufacturer deems significant to the reader. The GHG Center has not independently verified information contained in Section 4.0. 1.2. QLD TECHNOLOGY DESCRIPTION Comparison between conventional natural gas dehydrators and the QLD is an effective way to understand the latter's operating principles. Figure 1-1 shows the schematic of a generic dehydrator. The wet natural gas enters a two-phase separator which divides liquid hydrocarbons from the gas stream. Pipelines route the liquid products to a condensate storage tank for sale and the wet gas to an absorber. Lean TEG (which contains little water) directly contacts the wet gas and absorbs the water vapor. Dry natural gas exits the absorber column as pipeline-quality gas, ready for sale. 1-2 ------- Wet Natural Gas From - Compressors Gas/Liquid Separator Lean „ Glycol r Dry Natural Gas to Sales Liquid Hydrocarbons to Tank Still Vent(H>0,CH4, C02 HAPs, VOCs) t Still Column Burner Exhaust (CH^ CO, C02, HAPs, NOx, VOCs) Reboiler 14 I _ Burner Fuel Natural Gas Surge Tank Tnnnrs Rich Glycol J Rich Glycol/Natural Gas Mixture ' Regeneration Process GasAssjsted Glycol Cjrculation Pump \ High-Pressure Natural Gas Gas Liquid Products Rich Glycol Lean Glycol Figure 1-1. Generic Natural Gas Dehydration Process The rich (wet) glycol exiting the absorber contains the constituents which the TEG easily absorbs or dissolves. These are mainly water, CH4, VOCs, and HAPs. The primary HAPs, as defined in the MACT regulations [5], include benzene, ethylbenzene, toluene, and xylene (collectively referred to as BTEX) and n-hexane. These five pollutants are estimated to represent about 99 percent of HAP emissions from glycol dehydrator vents. A regeneration reboiler removes the absorbed constituents, resulting in a lean glycol mixture that is suitable for reuse in the absorber. The regeneration process is the primary emission source. It consists of a glycol circulation pump, a reboiler still, and a variety of heat exchangers (Figure 1-1). The circulation pump moves the glycol throughout the system. Conventional dehydrators may employ either of two different types of circulation pumps: electric-powered and gas-assisted. Gas-assisted pumps are the most common type because many dehydration facilities are located in remote sites where electricity is not readily available. Gas-assisted pumps use energy from externally supplied high-pressure natural gas to pressurize the glycol. Since CH4 is the primary constituent in natural gas, CH4 emissions are substantially higher when the glycol/natural gas mixture passes through the reboiler. Conventional dehydrators may include a reduced-pressure flash tank (not shown) prior to the reboiler. A flash tank allows dissolved methane to escape and be re-routed to other processes. This prevents its being emitted from the still column. 1-3 ------- The reboiler strips the absorbed water (and HAPs) out of the glycol and into the still column. The regenerated lean glycol exits the reboiler and enters a surge tank. The pump then conveys it to a glycol/gas heat exchanger and back to the absorber. This heat exchanger reduces the lean glycol temperature prior to the lean glycol entering the absorber tower. This reduces hydrocarbon condensation within the absorber [7], The still column vent conveys the stripped water vapor, CH4, HAPs, C02 and VOCs away from the process. Most conventional dehydrators emit this overhead gas/vapor stream directly to the atmosphere. The still vent stream contains water vapor (90 percent), trace C02, HAPs, CH4, VOCs, and other components absorbed from the natural gas. Two common still vent emission control methods are combustion and condensation. Combustion devices typically include flares and thermal oxidizers. The Kerr-McGee test site initially controlled still vent emissions with enclosed flares, but the site was unable to continuously operate them because the vapor stream's heat content varied widely. Condensers include water knockout systems and other separation systems that produce condensate product for sale. These devices vent non-condensable gases to the atmosphere or burn them in a flare, thermal oxidizers, or the reboiler. An additional emissions control measure used at some sites is to separate lighter hydrocarbons (such as CH4) from the rich glycol in flash tank separators prior to the still column. The QLD also employs both condensation and combustion to control still vent emissions. Its implementation of controlled condensation and partial vacuum-phase separation produces: 1) a saleable product, 2) wastewater that does not require significant cleaning, and 3) very little air pollution. The most significant result is that the reboiler burns uncondensed hydrocarbons, significantly reducing fuel input requirements and emissions. Figure 1-2 depicts the primary design features. Process modifications to this system, as compared to the majority of conventional dehydrators, are: • Replacement of gas-assisted pump with electric pump (reduces CH4 losses and emissions); • Recovery and use of still vent emissions (eliminates direct release of CH4, HAPs, and VOCs); and • Reboiler burner re-design (reduces natural gas fuel input and emissions). Major QLD components are: • Glycol Circulation Pump An electric pump circulates the glycol through the absorber at about 4 gallons per minute (gpm). This feature is intended to save a significant amount of high-pressure natural gas over a gas-assisted pump. The Gas Technology Institute (formerly the Gas Research Institute) estimates that pump gas losses account for as much as three standard cubic feet natural gas per gallon (scfgal) of glycol circulated. Over 20 thousand standard cubic feet per day (mscfd) natural gas or $14,600 per year (based on a gas price of $2.00 per mscf) would be saved by switching to an electric pump at the host site. Note that this analysis is conservative because recent natural gas prices have risen to $5.45/Mcf and more in some areas. An additional benefit is that CH4 and BTEX, normally present in increased quantities when a gas-assisted pump is used, will not be vented from the still column. • Effluent Condenser The effluent condenser is a fin-and-tube heat exchanger that reduces the vapor stream temperature from the still vent to about 120 degrees Fahrenheit (°F) to enable product 1-4 ------- separation. It uses the rich glycol, circulated from the emissions separator, as the coolant media. The cooled overhead vapor stream is brought into the liquid removal vacuum separator. Quantum Leap Dehydrator System absorption/regeneration) Rich Glycol Circulation (67to72gpm Hydrocarbon Vapors or Burner Exhaust Figure 1-2. QLD Natural Gas Dehydration Technology Liquid Removal Vacuum Separator (vacuum separator) Internal baffles and weirs in this vessel condense and partition the vapor stream from the still vent into three phases: (1) wastewater, (2) condensate, and (3) uncondensed hydrocarbon vapors. The condensed hydrocarbons and wastewater collect in the appropriate chamber and are periodically discharged into storage tanks for sale and disposal. An eductor system creates a partial vacuum to remove uncondensable hydrocarbons and the remaining water vapor to the emissions separator. Glycol Condenser A forced-draft, air-cooled heat exchanger cools the rich glycol exiting the still column reflux coil and the overhead condenser. Ambient air reduces the glycol temperature to between 150 and 110 °F. A pipeline conveys condensed liquids, rich glycol, and noncondensable gas to the emissions separator. Emissions Separator The emissions separator operates in three phases to separate rich glycol, liquid hydrocarbons, and gaseous hydrocarbon streams. 1-5 ------- Control valves and piping split the rich glycol exiting the emissions separator. The first stream, about 4 gpm, originates from the bottom of the separator. This is precisely equal to the amount of lean glycol pumped into the absorber. A 72-gpm pump pressurizes the second rich glycol stream for use as a working fluid throughout the QLD. The effluent condenser uses about 10 gpm for still vent- stream cooling. The remainder provides cool glycol to other heat exchangers, compresses the recovered uncondensed hydrocarbons for use at the burner, and powers the eductor system which, in turn, creates the required partial vacuum at the vacuum separator. Separate piping conveys condensed hydrocarbons to the vacuum separator which collects them as described above. The uncondensed hydrocarbons exit the emissions separator at about 20 pounds per square inch, gage (psig), and serve as fuel gas for the reboiler burner. • Water Exhauster The water exhauster removes any remaining water and condensable hydrocarbons from the lean glycol. Section 4.0 discusses some of its benefits. • Still Column The still column collects the entrained gases, water, and hydrocarbon vapors from the rich glycol as it flows through the reboiler. The resulting hot lean glycol exits the still column and reboiler through a glycol/glycol heat exchanger. • Reboiler The QLD incorporates a re-designed conventional U-shaped firetube reboiler. The QLD burner is unlike many commercial burners, in that it contains air injectors which allow effective combustion with wide ranges in operating pressure and water vapor content. The burner operates continuously and throttles the heat output in response to reboiler heat demand, in contrast with many conventional burners which cycle off and on to meet changing demand. The burner can accept up to 30 percent of capacity, or 166 standard cubic feet per hour (scfh) of supplemental natural gas if needed. ECL and the test facility installed certain modifications after the initial shakedown period because of site- specific natural gas conditions. Consequently, the as-tested unit differed from the original design. The following subsection includes a brief discussion. Air emission sources include the reboiler burner exhaust, vacuum separator and fuel accumulator vessel PRVs, HAPs dissolved in the recovered wastewater, and fugitive emissions (which were subsequently found to be negligible). The QLD uses recovered hydrocarbon vapors as its primary fuel source, so VOC and HAP emissions may be present in the burner exhaust. There may also be NOx, CO, C02, and unburned CH4 emissions. The wastewater stream could contain dissolved HAPs which could be emitted to the atmosphere through evaporation. Wastewater condensation occurs under partial vacuum so there should be no HAP and CH4 flash-loss emissions. 1.3. TEST FACILITY DESCRIPTION AND QLD MODIFICATIONS The Kerr-McGee Gathering Facility, located 14 miles northwest of Brighton, CO, processes about 26 million standard cubic feet per day (mmscfd) of natural gas through the QLD. Kerr-McGee installed the QLD technology after excess moisture content in the still vent caused persistent problems with thermal oxidizers. Figures 1-3 and 1-4 show the as-built system at the site. 1-6 ------- Effluent Housing For Pumps, Separators, etc. Reboiler Stack Reboiler Figure 1-3. QLD at Kerr-McGee Gathering Station 1-7 ------- Reboiler Glycol Circulation Pump Liquid Removal Vacuum Separator Wastewater Discharge Line Figure 1-4. QLD Interior ln-ground storage tanks collect and store the wastewater from the QLD and other processes at atmospheric pressure. Fixed-roof tanks receive the condensate. Contractors periodically transfer the stored wastewater and condensate into tank trucks for transport and disposal or sale. Table 1-1 summarizes the test site's key design and operating parameters. These parameters formed the basis for the test plan's verification strategy. 1-8 ------- Table 1-1. Test Site Design and Operating Conditions 1. Natural gas production rate 26 mmscfd (at 14.7 psia, 60 °F) 2. Sales gas moisture content < 7 lb water / mmscf natural gas 3. Circulation rates for electric pumps • Glycol for absorption and regeneration • Glycol for condensation and eductor power 5 gpm, 5-hp motor 72 gpm, 5-hp motor 4. Glycol/Glycol Heat Exchanger • Duty • Shell operating conditions (lean glycol) • Tube operating conditions (rich glycol) 325 mBtu atmospheric pressure @ 400 °F 30 psig @ 300 °F 5. Reboiler Still • Duty • Operating Conditions 600 mBtu/h 0 to 2 in. water column (vacuum) 6. Reboiler Burner • Total heat input required • Fuel gas from the emissions separator • Makeup natural gas • Stack dimensions 1.2 mmBtu/h ~ 233 to 388 scfh (70 to 80% volume), specific gravity = -0.75, LHV = -1410 Btu/ft3 - 0 to 166 scfh (0 to 30% volume), specific gravity = -0.65, LHV = -950 Btu/ft3 10-in. diameter, 20-ft high 7. Glycol Condenser - Glycol/Air Heat Exchanger • Duty • Rich glycol operating conditions 225 mBtu/h 30 psig@ 150 °F 8. Emissions Separator • Dimensions • Operating Pressure 30-in. diameter, 6'-6" high 15 psig 9. Vacuum Separator • Dimensions • Operating Pressure • Water discharge rate • Condensate discharge rate 20 in. diameter, 5'-6" high 0 to 5 in. w.g. vacuum Every 1.5-in. change in liquid level - 1.89 gal Every 1.5-in. change in liquid level - 1.89 gal 10. Effluent Condenser - Vapor/Glycol Heat Exchanger • Duty • Tube operating conditions (still vapors) • Shell operating conditions (rich glycol) 100 mBtu/h 0 to 5 in. w.c. vacuum @ 212 °F 30 psig® 110 °F Operators discovered that the burner (and reboiler) was not operating at consistent temperature after the QLD system was installed at the host site. The recovered fuel gas heating value sometimes exceeded that which could be efficiently burned. The system would upset and remain out of balance for extended periods because the burner was unable to burn all the gas. Consequently, the recovered fuel gas pressure would begin to increase such that the eductor was unable to pull an adequate vacuum. The vacuum separator pressure would rise and break the required -5" water glass (w.g.) partial vacuum. The entire system operation would destabilize. ECL installed three improvements to prevent this pressure buildup and to enable proper burner control: 1-9 ------- Pressure-Relief Valve: ECL installed a pressure-relief valve (PRV) in the vacuum separator to open it to atmosphere when the recovered fuel gas pressure reached 30 psig. The PRV would close when the recovered fuel gas pressure dropped below 30 psig. This PRV is a safety device. The system utilizes this feature only during initial system start-up. The vent remains closed during normal operations. Fuel Accumulator Vessel: ECL installed a 430-gallon accumulator vessel to dampen the effects of large swings in fuel gas volumes entering the reboiler burner. The accumulator vessel increased the fuel gas system's reserve volume during high recovery periods. This allows a relatively constant volume of fuel gas to be fed to the burner. A pressure-activated valve would open to atmospheric conditions if the gas pressure in the vessel exceeded 28 psig. This operation could produce air emissions, but this PRV is also a safety device which would actuate only under abnormal conditions. Water-Injection System: ECL installed a compressed air-driven pump to inject a portion of the vacuum separator's recovered wastewater back into the reboiler. This would increase the reboiler load when necessary, enabling the burner to demand more fuel. Fuel gas pressure and effluent condenser temperature control this pump. The effluent condenser temperature is a key control point because very hot vapors result in inefficient hydrocarbon condensation. The pump operates when the fuel gas pressure is 20 psig or more and the overhead temperature is 120 °F or less. The pump automatically shuts down when the fuel pressure falls below 20 psig or the overhead temperature is greater than 120 °F. ECL specified the water pump with reserve capacity sufficient to handle all reasonably expected gas compositions at the test facility. 1.4. PERFORMANCE VERIFICATION OVERVIEW 1.4.1. Performance Verification Parameters The GHG Center developed the QLD verification approach to provide credible performance data of interest to potential industry users and environmental regulators. Verification parameters consist of: Operational Performance Parameters: • sales gas moisture content and production rate • glycol circulation rate • makeup natural gas fuel flow rate Environmental Performance Parameters: • reboiler stack emission rates • HAP destruction efficiency The natural gas moisture content leaving the system is the QLD's primary performance indicator. This stream must not exceed 7 lb water / mmscf (lb/mmscf) gas. Verification tests, therefore, included direct natural gas moisture content and sales gas production rate measurements. Process glycol circulation rate is another key QLD performance indicator. Over-circulation requires more pump energy, more makeup natural gas consumed to operate the reboiler, or more pollutants to be absorbed and eventually emitted to the atmosphere. Facilities subject to the 40 CFR Part 63 standard [5] 1-10 ------- (which includes the host site) must monitor glycol circulation rates to minimize such impacts. The GHG Center used an ultrasonic flow meter to verify lean glycol circulation rates during the verification tests. The GHG Center also monitored the makeup natural gas flow rate fed to the reboiler. Makeup-gas data is useful information to technology users for estimation of possible QLD fuel savings. Operational performance monitoring occurred after the completion of QLD start-up and shakedown and ECL subsequently announced the system to be functioning normally. These steps ensured the collection of representative data. The GHG Center monitored all operational parameters as one-minute averages for seven days. Section 2.2 reports the daily and overall production averages found during the monitoring period. Environmental performance parameters quantified the reboiler exhaust stack criteria pollutant, greenhouse gases, and HAPs emission rates. Three 90-minute (nominal) emissions test runs verified all environmental parameters over a one-day test period while the system was operating at "normal conditions". The seven days of operational data prior to testing formed the basis for establishing normal operating conditions. The test plan specified the normal operating range as the rates represented by 75 percent of the individual one-minute operational data entries. The GHG Center also verified HAP destruction efficiency to determine the QLD's ability to recover or destroy HAPs taken up from the sales gas by the glycol. 1.4.2. Measurement Approach Table 1-2 summarizes the text matrix. It identifies the required measurements and type of data collected. Figure 1-5 illustrates the measurement system and provides numbered locations for each measurement. The following subsection provides a measurement strategy overview for each verification parameter. The test plan provides detailed background discussions and procedures. 1-11 ------- Table 1-2. Verification Test Matrix Verification Parameter Location Descriptionb Units Method/ Instrument Sampling Intervals3 Sales Gas Moisture 1 Sales gas moisture content lb H20 / mmscf gas Electrolytic moisture transmitter 1-min averages, reported as daily averages and run averages Content and Production Rate Sales gas flow rate mmscfd Integral orifice meter 1-min averages, reported as daily averages and run averages Glycol Circulation Rate 2 Lean glycol flow rate gpm Ultrasonic flow meter 1-min averages, reported as daily averages and run averages Makeup Natural Makeup natural gas flow rate scfh Turbine flow meter 1-min averages reported as daily averages and run averages Gas Fuel Flow Rate 7 BTEX concentration in makeup natural gas ppm Sample collection by GHG Center, analysis by independent laboratory 3 gas samples collected per test run (if preliminary samples indicate BTEX > 10,000 ppm) Reboiler Stack Emission Rates 4 C02, NOx, CO, CH4, THC, and HAP concentration & emission rates ppm and lb/h Varies, see Table 1-3 three test runs (90 minutes each), reported as average for each test run Lean glycol flow rate gpm Turbine flow meter 1-min averages, reported as average for each test run 2 HAP concentration in lean glycol ig/mL Sample collection by GHG Center, analysis by independent laboratory 4 liquid samples per test run, reported as average for each test run 3 Rich glycol flow rate gpm Lean glycol flow rate corrected for water and hydrocarbon content 1-min averages, reported as average for each test run HAP concentration in rich glycol ig/mL Sample collection by GHG Center, analysis by independent laboratory 4 liquid samples per test run, reported as average for each test run HAP Destruction Efficiency 5 Wastewater flow rate gpm Prior to testing, determine discharge rate per "dump" and per inch of sight glass level change. Record times and number of each discharge dump occurring during test run Each time discharge dump occurs HAP concentration in wastewater ig/mL Sample collection by GHG Center, analysis by independent laboratory 4 liquid samples per test run, reported as average for each run 6C Condensate flow rate gpm Record condensate sight glass height before and after each dump. Use wastewater discharge rate in gal/in. to calculate condensate discharge rate in gal/dump Each time discharge occurs HAP concentration in condensate product stream ig/mL Sample collection by GHG Center, analysis by independent laboratory 4 liquid samples per test run, reported as average for each run (continued) 1-12 ------- Table 1-2. Verification Test Matrix (Concluded) Verification Parameter Location Descriptionb Units Method/ Instrument Sampling Intervals3 HAP Destruction Efficiency 8 Vacuum separator vent gas flow rate scfin Assigned as 0 because vent was capped throughout testing HAP concentration in vacuum separator vent gas ig/mL 9 Accumulator vessel vent gas flow rate scfin Dry gas meter, slack tube manometer, and thermocouple meter Assigned as 0 because dry gas volume counter did not change throughout testing HAP concentration in accumulator vent gas ig/mL Sample collection by GHG Center, analysis by independent laboratory a For destruction efficiency, a test run corresponds to the 90-minute stack rim. b HAPs are the sum of BTEX and n-Hexane. c HAPs dissolved in the condensate product are reported for information purposes. They are not used to determine HAP destruction efficiency. See section 1.4.2.6 I y Filter ,JMaterJxhauster^ 1 )i I i J . . «*£_X X I ¦5— S 1 Glvcol/Glvcol Heat • Rich Glycol Circulation (for condensation/separation) Lean Glycol Hydrocarbon Vapors or Burner Exhaust Glvcol/Glvcol Heat Equalizing Line J System Boundary Figure 1-5. Measurement System Schematic 1-13 ------- 1.4.2.1. Sales Gas Moisture Content The host site continuously monitors sales gas moisture as a part of normal operations (Location 1, Figure 1-5). The GHG Center used the one-minute average moisture data to measure the QLD's operational performance. Test personnel obtained the data files from the host site's central computer. The host site had replaced the MEECO moisture sensor (as described in the test plan) with a new Panametrics brand sensor. The Panametrics meter provided the same performance: moisture measurement range of 0 to 20 lb/mmscf, lower detection limit (LDL) of 0.2 lbs/mmscf, and a rated accuracy of ± 5 percent of reading. Panametrics calibrated the meter with National Institute of Standards and Technology (NIST) - traceable instruments prior to installation. 1.4.2.2. Sales Gas Production Rate The host site uses an Emerson MVS205 Multi-Variable Sensor orifice meter to document sales gas production. The GHG Center used the meter's one-minute average sales gas production data to measure the QLD's operational performance. Test personnel obtained the data files from the host site's central computer. The sales gas meter contains a 4.00-inch orifice plate and is temperature and pressure compensated to 60 °F, 14.7 psia (gas industry standard conditions). Its operating range is 0 to 2 mmscfh with a rated accuracy of ± 1 percent of reading. Site personnel calibrated the flow meter with NIST-traceable reference standards prior to testing. 1.4.2.3. Glycol Circulation Rate The GHG Center initially planned to use the site's Halliburton MC-II EXP turbine meter to measure glycol circulation rate (Location 2, Figure 1-5). However, a performance comparison with the GHG Center's ultrasonic meter (Controlotron 1010EP1) revealed a large discrepancy (greater than two percent allowed in the Test Plan). The site investigated potential turbine meter problems while the GHG Center and ECL evaluated the glycol pump's theoretical capacity. The consensus was that the ultrasonic meter reported flow rates that were within the expected range for this pump. Consequently, the GHG Center used ultrasonic meter for the verification test. Section 3.0 and associated Corrective Action Reports (CARs) document these findings. The ultrasonic meter is a digitally integrated flow-metering system that consists of a portable computer and ultrasonic fluid flow transmitters. The meter determines fluid velocity by measuring ultrasonic pulse transit times between the transducers. A precision-mounting jig secures the transducers to the pipe at a known distance apart. The operator enters the fluid composition (100 percent TEG for this test), pipe diameter, material, wall thickness, and expected sonic velocity into the meter's computer. The flow meter determines the sonic velocity based on the known distance between the transducers under zero-flow conditions with the pipe full of fluid. It multiplies the fluid velocity by the internal area of the pipe, and reports one-minute average volumetric flow rate during operation. The flow meter's overall rated accuracy is ± 1.0 percent of reading and can be used on pipe sizes ranging from 0.25 to 360 inches in diameter with fluid flow rates ranging from zero to 60 feet per second (fps). 1-14 ------- 1.4.2.4. Makeup Natural Gas Flow Rate The QLD reboiler burner can accept up to 166 scfh makeup natural gas as supplemental fuel. A Halliburton MC-II EXP turbine meter installed on the one-inch (inside diameter) gas line upstream of the reboiler (Location 7, Figure 1-5) measured makeup gas flow. The site's central computer collects the one-minute average data and test personnel obtained the data files from the host site. The Halliburton flow analyzer is a turbine meter and integral signal display and transmitter with a linear flow range sufficient to measure gas flows should the reboiler operate on makeup gas only (0 to 600 scfh). The manufacturer used a piston-type volume prover to calibrate the meter. It is temperature and pressure compensated, and provided mass flow output accurate to ± 1.0 percent at standard conditions. 1.4.2.5. Reboiler Stack Emission Rates Cubix Corporation, an independent stack testing contractor located in Austin, TX, performed reboiler stack emissions testing to determine concentrations and emission rates for the following air pollutants: CO, THCs, GHGs (C02, NOx, and CH4), BTEX, and total HAPs (BTEX plus n-hexane). Cubix conducted three 90-minute (nominal duration) test runs for each parameter while the system was operating at normal conditions. All the test procedures are well-documented Title 40 CFR 60 Appendix A reference methods. Table 1-3 summarizes reference methods performed for emissions testing supporting this verification. The test plan provides a detailed discussion of the test methods and QA/QC requirements. Emission rates reported in Section 2.0 are in terms of parts per million by volume dry (ppmvd). These values, correlated with the stack volumetric flow rates in dry standard cubic feet per minute (dscfm), yield pound per hour (lb/h) emission rates for NOx, CO, CH4, VOC, hexane, BTEX, and HAPs. VOC emissions are the sum of all organic compounds minus methane and ethane emissions according to Colorado Department of Public Health and Environment regulations. HAP emissions at this facility are the sum of hexane and BTEX emissions. Table 1-3. Emissions Testing Methods Summary Measurement Variable U.S. EPA Reference Method Analyzer Type Instrument Range NOx 7E TEI Model 42C (chemiluminescence) 0 to 100 ppm CO 10 TEI Model 48C (NDIR) 0 to 100 ppm THC 25A JUM Model VE-7 (FID) 0 to 100 ppm o2 3A CAI Model 200 (Paramagnetic) 0 to 25% o o 3A CAI Model 200 (NDIR) 0 to 20% ch4 18 Hewlett Packard 5890a (GC/FID) 0 to 100 ppm BTEX3, n-Hexane 18 Hewlett Packard 5890a (GC/FID) 0 to 100 ppm Exhaust gas volumetric flow rate 1A and 2C (modified) Differential Pressure 9,000 to 11,000 scfh Moisture 4 Gravimetric Oto 100% a Includes separate benzene, toluene, ethylbenzene, and xylene quantification 1-15 ------- 1.4.2.6. HAP Destruction Efficiency Section 2.6 of the Test Plan discusses HAP destruction efficiency, the required measurements, and the calculations in detail. Destruction efficiency is the net HAPs entering the system boundary (from the glycol) minus that leaving the system from emissions sources divided by the net HAPs entering the system. Testers determined the HAPs inputs via the Atmospheric Rich/Lean Method for Determining Glycol Dehydrator Emissions (ARL) [8], HAP emission sources at this site are: fugitive leaks, the reboiler burner exhaust stack, wastewater, and PRVs. The GHG Center determined that fugitive leaks are negligible because the fabricator certified the system to be leak-tight. This certification was documented, signed, and provided to the GHG Center. The burner stack may emit unburned HAPs to the atmosphere and HAPs dissolved in the wastewater can be released during disposal. HAPs dissolved in the condensate stream are deemed to be "controlled" or "sequestered" and not considered an emission. This is consistent with 40 CFR Part 63 and is documented in the Test Plan. 1.4.2.7. Additional Supporting Measurement Details The following sections discuss verification test events and conditions beyond those presented in the test plan. 1.4.2.7.1 Glycol Flow Direct flow measurement of the rich glycol stream is difficult due to the presence of multi-pollutant, multi-phase (liquid, vapor) products. Therefore, the natural gas industry, EPA, and the Gas Technology Institute (GTI) normally assign the process circulation rate (measured on the lean glycol stream) as the rich glycol flow rate. This causes a negative bias (approximately 4 percent during this verification) in the reported rich glycol flow rate because of the rich glycol's higher water and hydrocarbon content. This bias is minimized by modifying the ARL method by correcting the lean glycol flow rate to yield the true rich glycol flow rate. The procedure required rich and lean glycol analyses for density, water content, and total hydrocarbon content. Analysts then applied these data to produce the correction. Appendix A describes the approach. 1.4.2.7.2 Lean Glycol Sample Condition The lean glycol temperature was about 210 °F. The sample tubing passed through an ice water bath during sampling. This allowed the samples to cool before entering the sample vials. The rich glycol samples did not require cooling because the rich glycol temperature was close to the absorber temperature (approximately 90 to 100 °F). The rich glycol samples were extremely foamy. The foam developed as dissolved gas escaped when the glycol was exposed to atmospheric conditions during sampling. This is equivalent to sampling a conventional glycol dehydrator with no flash tank. The ARL method warns that volatile components in the glycol can be unavoidably lost during sampling under these conditions. Such losses would result in understatement of glycol hydrocarbon concentrations. Section 2.3.2 provides further discussion of this phenomena and its possible effects on the verification results. 1-16 ------- 1.4.2.7.3 Lab Analysis Enthalpy Analytical of Durham, NC, analyzed the glycol samples for HAPs and moisture via gas chromatography/flame ionization detector (GC/FID) and Karl Fischer titration, respectively. The laboratory used a Hewlett-Packard 5890 Series II GC (with FID) and a hydrogen carrier gas. The capillary columns were Restek 20 meter (m) x 0.18 millimeter (mm) Rtx-1. The method detection limit (MDL) was as low as 6.0 micrograms per milliliter (i g/ml) depending on the required dilutions. 1.4.2.7.4 Wastewater Discharge Rate The GHG Center quantified the volume of nine wastewater discharges before the verification by capturing each discharge in a tared bucket, noting the bucket's full weight, and measuring the temperature. Center personnel also logged the changes in liquid level by reading an engineer's scale attached to the liquid sight glass on the vacuum separator. The water weight divided by the density at the recorded temperature yields the gallons per dump for each discharge. The sight glass level change divided by the gallons per dump yields gallons per inch of movement on the sight glass. Section 2.0 presents the results as 3.057 gal/dump or 1.283 gallons per inch (gal/in.) with a maximum variation of 1.2 percent. GHG Center personnel logged the time of each wastewater dump during all test runs during the verification. The measured discharge rate (3.057 gal/dump) divided by the elapsed time between two successive discharges yielded the wastewater flow rate (gpm). For example, discharge number 323 occurred at 14:03 and discharge number 324 occurred at 14:31 (28 minutes later). The first test run started at 14:03, so, during the first minute, the system produced 3.057/28 or 0.109 gpm. The field team leader collected wastewater samples from the petcocks located on the vacuum separator vessel instead of from the discharge traps described in the Test Plan (Location 5, Figure 1-5). His observation during an initial site visit was that the vacuum separator vessel had separate tapped and plugged ports available for liquid (wastewater and hydrocarbon) sampling. Discharge trap installation would have required extensive pipeline modifications. The GHG Center consequently determined that installation of petcocks directly into the separator vessel was the best sampling method. An April 4, 2003 CAR documented this determination. The field team leader opened the vacuum separator manual vent valve to break the vacuum during each sampling event. This allowed the samples to be collected. The open valve caused a momentary process upset and the QLD system began to pressurize. The vacuum separator pressure quickly re-stabilized to desired negative gage pressure after closing the sample valve. These upsets also caused perturbations in stack gas emission concentration. Test personnel observed this problem during the verification test runs. The GHG Center determined that the perturbations would not significantly affect the overall verification results because stack gas concentrations quickly returned to normal when the valve was closed. Also, installing the discharge traps at that point would have introduced significant delays into the test campaign. The stack test verification results therefore do not include the time periods corresponding to the liquid sampling disturbances. Section 3.0 describes the technique the GHG Center analysts used to identify these invalid time periods. The laboratory analyzed the wastewater samples by the purge-and-trap method. All dilutions were six- fold, or one milliliter (ml) of sample plus 5 ml of MeOH solvent. The analyst used a Restek 60 m x 0.32 mm Rtx-1 capillary column. Other equipment and procedures were as described above for the glycol sample analysis. 1-17 ------- The laboratory employed the same analysis procedures described earlier for the glycol samples except that all dilutions were 1001 to 1, or 10 microliters (il) of sample added to 10 ml solvent. 1.4.2.7.5 HAPs Emitted from Pressure-Relief Vents The automatic PRVs at the accumulator vessel and the vacuum separator were potential intermittent (non- continuous) emission points. The PRV would open to atmosphere if the accumulator vessel gas pressure exceeded 28 psig. The vacuum separator PRV opens and emits gases to atmosphere only when gas pressures in the QLD system reach a level high enough to upset the overall system function. GHG Center personnel observed that this happened only during initial system start-up and shake-down activities. The vent remains closed during all normal operations once the pressure stabilizes. The GHG Center developed measurement techniques for quantifying HAP emissions from both sources (Locations 8 and 9, Figure 1-5). ECL had stabilized the system such that high-pressure conditions no longer occurred during normal operations. Neither of the PRVs opened during the verification test. The GHG Center verified that the resulting HAP emission rate was zero lb/h. Internal CARs contain complete documentation on the PRVs. 1.4.2.7.6 HAPs Entering in Makeup Natural Gas The GHG Center determined BTEX in the makeup natural gas to assess the possible effects on the total HAP inputs to the system boundary. Additional samples would be collected during verification testing if preliminary testing indicated BTEX levels in the natural gas were greater than 10,000 ppm. The field team leader collected three makeup natural gas samples prior to the verification tests. Appendix D presents the results and they indicate that BTEX entering the system from the makeup gas is negligible. Additional sampling during the verification test runs was not required. 1.4.2.7.7 Miscellaneous Considerations HAP destruction efficiency does not require the condensate product HAP mass flow rate. It is, however, useful data with which to complete an entire QLD system mass balance. The condensate production rate may also be useful to readers interested understanding the recovery potential of the saleable product. This report, therefore, presents condensate production rate (gpm) and HAPs (lb/h) within the condensate stream. The flow rate determination requires the gallons per inch approach described above for the wastewater flow rate determination. Observation of condensate sight-glass level changes by field personnel quantified the condensate production rate. The GHG Center did not directly quantify the discharges because of its hazardous properties, especially when handled in open containers. The vacuum separator vessel collects both the wastewater and condensate, separated by a weir and bulkhead system. The cylindrical vessel's diameter is constant throughout. This means that a one-inch level change in both sections of the vessel correspond to the same liquid volume. A one-inch level change in the condensate product's sight glass corresponds to the same volume as measured by a one-inch level change in the wastewater sight glass, or 1.283 gal/in. as described above. 1-18 ------- 2.0 VERIFICATION RESULTS 2.1. OVERVIEW Installation and start-up activities for the QLD system occurred in Winter of 2002. ECL then installed the fuel accumulator vessel, the water injection pump, and the vacuum separator and fuel accumulator PRVs in response to the conditions described in Section 1.2. ECL pronounced the system to be functioning properly in late March 2003. The GHG Center initiated verification testing in April 2003. GHG Center personnel did not perform leak tests (soap screening) because the system fabricator performed industry-standard system pressure tests during and after final assembly. The fabricator performed air- and hydrostatic-pressure tests. Air testing consisted of using 125 psig compressed air to pressurize the pipe spools or assemblies. Operators then applied soap solution or submerged the assembly in water, noted any bubbling, and performed repairs as needed. Hydrostatic testing consisted of having operators fill the vessel or assembly with water and then pressurize it, watching for any leakage. The fabricator's certification listed no significant leaks. Physical wear, settlement, and vibration likely did not cause new leaks by the time the verification tests occurred because this was new equipment used in a new application. Although ECL performed repairs and modifications after the site installed the QLD, they also performed the appropriate leak checks prior to restarting the unit. The GHG Center, therefore, assigned the fugitive leak rate as negligible. Operational performance testing occurred between April 23 and 29, 2003. The GHG Center acquired seven days of continuous sales gas moisture, sales gas flow, make-up gas flow, and glycol circulation rate data during this period. The QLD consistently met or exceeded specifications as summarized below: • The moisture content of dry natural gas was well below the 7.00 lb/mmscf limit required by the operator throughout the entire monitoring period. Actual daily average values ranged between 0.89 and 1.28 lb/mmscf. • The QLD enabled continuous operation of the sales gas stream, with daily average flow rates ranging between 26.8 and 29.3 mmscfd. • The QLD system burned all uncondensable hydrocarbon vapors without venting them to the atmosphere. The system accomplished this with little or no makeup natural gas. Makeup natural gas flow rate was between 0.00 and 1.76 scfh, well below the 166 scfh initially expected. • The daily average glycol circulation rate varied between 3.00 and 3.77 gpm. Environmental performance testing occurred on April 30, 2003, after completion of operational tests on the previous day. The GHG Center representatives met with the ECL and Kerr-McGee representatives prior to emissions testing to verify that the seven-day operational test period had yielded results typical of normal plant operations. Each of the three test runs acquired between 70 to 85 minutes of stack emissions data, summarized as follows: • Overall average emission rates for NOx, CO, and VOC from the reboiler stack were 0.0817, 0.0005, and 0.0003 lb/h, respectively. • HAP concentrations in the reboiler stack were non-detectable. Maximum HAPs leaving the system in the reboiler exhaust and wastewater were 0.0016 and 0.0220 lb/h, respectively. 2-1 ------- • PRVs did not operate at any time during the entire test campaign, nor are releases anticipated during normal operations. Therefore, no expected emissions were assigned to PRV operation. • HAP destruction efficiency was greater than 99.74 ± 0.01 percent. • Average wastewater and condensate production rates were 6.36 and 2.88 gph, respectively. The following subsections present the verification test data for each parameter. 2.2. OPERATIONAL PERFORMANCE Table 2-1 summarizes daily performance data for the four primary operational performance parameters. The results are representative of 85 to 100 percent of one-minute data recorded in a 24-hour period except for the first test day (April 23). The table shows that the values for all key operational parameters are relatively consistent from day-to-day. This supports the conclusion that the QLD operations are stable. Table 2-1. Pre-Test Operational Data and Establishment of Normal Operating Conditions" Date Hours Of Valid Data Sales Gas Moisture Content' Sales Gas Flow Rate' Makeup Natural Gas Flow Rate' Glycol Circulation Rate (lb H20/mmscf) (mmscfd) (scfh) (gpm) Range Average Range Average Range Average Range Average 4/23/03 15.05 0.80 to 1.69 1.02 28.67 to 31.39 29.31 0.11 to 345.98 16.32 1.55 to 6.04 3.63 4/24/03 24.00 0.79 to 1.03 0.89 26.18 to 32.02 28.63 0.00 to 220.19 1.22 1.47 to 4.00 3.30 4/25/03 20.73 0.91 to 1.44 1.12 26.09 to 29.96 28.38 0.00 to 190.44 0.63 0.00c to 4.71 3.00 4/26/03 24.00 0.73 to 1.99 1.28 26.13 to 29.97 28.15 0.00 to 317.04 1.68 0.64 to 5.34 3.21 4/27/03 23.95 0.95 to 1.69 1.27 25.69 to 28.83 26.88 0.00 to 3.92 0.83 1.79 to 4.23 3.67 4/28/03 24.00 0.85 to 1.76 1.24 23.13 to 29.96 26.81 0.00 to 706.33 5.41 1.68 to 4.61 3.68 4/29/03 24.00 0.89 to 1.64 1.18 25.20 to 29.96 27.38 0.00 to 3.61 0.83 1.87 to 4.43 3.77 Overall Average 1.14 27.9 3.85 3.47 Normal Operating Conditions1 0.89 to 1.50 26.54 to 29.26 0.00 to 1.76 3.14 to 3.93 s Normal operating condition is defined as the range represented by 75 percent of individual one-minute measurement values b Source-Kerr-McGeeoperations. c The flow meter reported zero during certain times on this date because of aeration in the pipeline. When the onerator added makeut) TEG to the svstem. The aeration ceased and the flowmeter resumed normal onerations. The overall daily average sales gas moisture content was 1.14 lb/mmscf. The highest level recorded was 1.99 lb/mmscf which is well below the site's 7.00 lb/mmscf requirement. The normal operating range for this parameter (based on 75 percent of the one-minute data) is from 0.89 to 1.50 lb/mmscf. The sales gas flow rate varied little throughout the test period. The overall average daily production rate was 27.9 mmscfd. The normal range for this parameter is from 26.5 to 29.3 mmscfd. The glycol recirculation rate, measured on the lean side, averaged about 3.47 gpm. The circulation rate remained between 3 and 4 gpm during the majority of the monitoring period. Rates higher than 5 gpm were recorded for one hour on April 23 and about two minutes on April 26. The elevated rates are not typical, since they occurred for an extremely short period of time. The normal operating range for the glycol recirculation rate is between 3.14 and 3.93 gpm. ECL expected the reboiler to consume up to 166 scfh of makeup natural gas (about 30 percent of burner capacity) in the initial design phase. Recovered hydrocarbon vapors would supply the remaining fuel 2-2 ------- requirement. Table 2-1 shows that the reboiler burner actually consumed significantly less makeup gas. This amounts to a significant fuel savings for the site operator and demonstrates complete use of waste gas that would normally be vented. The overall average makeup natural gas flow rate was 3.85 scfh. However, the normal operating range was well below this average (0.00 to 1.76 scfh). The data show some higher intermittent gas flow rates, but these generally lasted for less than 15 minutes in a 24-hour period. The verification data demonstrated that the QLD system is capable of recovering and using high- Btu, wet hydrocarbon vapors as a primary process fuel. 2.3. ENVIRONMENTAL PERFORMANCE Environmental performance verification tests took place on April 30, 2003. The Test Plan required three 90-minute test runs to verify reboiler stack emissions performance and HAPs destruction efficiency. The GHG Center, however, deemed some data as invalid because wastewater and condensate sampling events disrupted the QLD process. Valid data varied between 70 and 85 minutes per test run. Section 3.0 discusses the invalidated data. Table 2-2 shows test run times and duration. The table also summarizes average sales gas moisture content, average sales gas flow rate, average makeup natural gas flow rate, and the average glycol circulation rate. Figures 2-1 and 2-2 are operational data time series plots which correspond to the test runs. The data demonstrate that verification tests occurred while the system was operating at normal conditions. The average values observed during each test run are representative of the normal operating range established in the pre-test evaluation (see Table 2-1). Table 2-2 . Verification Test Period Operational Data Summary Run Times Run Duration3 Average Sales Gas Moisture Content Average Sales Gas Flow Rate Average Makeup Natural Gas Flow Rate Average Lean Glycol Flow Rate Start Stop (mins) (lb H20/mmsct) (mmscfd) (scfh) (gpm) Run 1 14:30 16:23 85 1.25 28.49 0.48 3.77 Run 2 17:01 18:30 70 1.36 28.45 0.84 3.60 Run 3 18:57 20:27 72 1.16 28.53 2.77 3.89 Overall Average 1.25 28.49 1.37 3.75 3 Excludes times corresponding to invalid data 2-3 ------- 1.6 31 |—Moisture Content Gas Flow Rate | Figure 2-1. Operational Parameters Measured During Verification Test Period 0 * 24 rCMP)^lfl(DSCOO)OrCN(Otlfl(DSCOO)OrCM(0^lfl(DKCOO)OrCN|P)^lfl c>itq^tq^tqcoiOrcoiOrcoiorcoqn^qn^qc>iM;qfOiOrniOr cocoQrooidddT-T-T-CNifNifNicococo^^ihuriihfflfflffiNNNcococoaiaiaid Time (Hrs) Time (Hrs) 7 Run 1 ^ ~ Figure 2-2. Fuel Gas Flow Rates Measured During the Verification Test Period 2-4 ------- GHG Center personnel also monitored several key process variables although they were not required in the Test Plan. They were: absorber operating temperature and pressure, still column vapor exit temperature, and emissions separator operating temperature. They were measured and reported to provide the capability of comparing this system to other systems. Test personnel logged these data from instruments permanently installed at the site. Table 2-3 summarizes the data. Table 2-3. Additional Process Operating Data for Verification Test Periods Verification Test Run No. Absorber Still Column Vapor Exit Temperature Emissions Separator Temperature Temperature Pressure (°F) (psig) (°F) (°F) Run 1 98- 130a 1010 106 - 129 114.95 - 115.71 Run 2 102 - 105 1010 94 - 120 111.37 - 114.58 Run 3 90-94 1010 110 - 128 103.94 - 106.90 3 This 130°F reading is suspect. It occurred only once, and all other readings were 105°F or less. The following subsections present reboiler stack emissions and HAP destruction efficiency results. 2.3.1. Reboiler Stack Emissions Performance All test runs conformed to the applicable reference method procedures (see Table 1-3). The reference method results are in terms of parts per million by volume, dry (ppmvd), corrected for moisture content. C02 emissions are in volume percent. These values, correlated with stack gas flow rates, yield lb/h emission rates as follows: where: Q *MIV * C „ E pi Eqn. 1 385.15 * 106 Eib/h = emission rate (lb/h) Qstd = stack gas volumetric flow rate (dscfh) MW = pollutant molecular weight, pounds per pound mole (lb/lbmol) Cpoii = pollutant concentration (ppmvd) 385.15 = standard cubic feet per pound mole (scf/lb.mol) -v6 10 = parts per million All pollutant and gas emissions were relatively consistent between the three test runs. Table 2-4 summarizes the run average NOx, CO, VOC, CH4, C02 and HAP concentrations, emission rates and the overall average emissions from the reboiler stack. Table 2^4. Reboiler Stack Emissions Summary Verf. Test Run No. Exhaust o2 Stack Gas V elocity Stack Flow Rate NOx Emissions CO Emissions VOC Emissions ch4 Emissions co2 Emissions Total HAP Emissions % ft/sec dscfh ppmvd lb/h ppmvd lb/h ppmvd lb/h ppmvd lb/h % lb/h ppmvd lb/h Run 1 6.4 23.64 10,793 67.8 0.0873 0.3 0.0003 0.4 0.0002 <0.1 < 0.00004 9.5 117 <0.6 <0.0016 Run 2 6.7 23.72 10,369 66.0 0.0817 1.0 0.0007 0.8 0.0004 <0.1 < 0.00004 9.2 108 <0.6 <0.0016 Run 3 6.8 24.27 10,359 61.6 0.0761 0.6 0.0004 0.5 0.0002 <0.1 < 0.00004 9.1 107 <0.6 <0.0015 Avg. | 6.6| 23.87| 10,507| 65.l| 0.0817| 0.6| 0.0005| 0.6| 0.0003| < 0.l| <0.00004| 9.3| lll| <0.6 | < 0.0016 2-5 ------- Average N0X emissions were 65.1 ppmvd and 0.0817 lb/h. Emissions of CO and VOCs were very low during all three test runs, averaging 0.6 ppmvd (0.0005 lb/h) and 0.6 ppmvd (0.0003 lb/h), respectively. A continuously extracted stack gas sample, periodically injected into a gas chromatograph, provided the material for organic (CH4, HAPs) concentration determinations. Test personnel performed six injections, each about 15 minutes apart, during each test run. The analyst determined that each HAP constituent was consistently below the instrument's detection limit (< 0.1 ppmvd). This equates to an average hourly emission rate of < 0.0016 lb/h which is well below the site's permit requirement. All methane results were also below the GC/FID's detection limit (< 0.1 ppmvd). C02 concentrations averaged 9.3 percent, corresponding to an average 111 lb/h emission rate. Test personnel conducted all sampling system QA/QC checks in accordance with test plan specifications. These included analyzer linearity tests, sampling system bias and drift checks, interference tests, and use of audit gases. Section 3 discusses the QA/QC check results. 2.3.2. HAP Destruction Efficiency Table 2-5 summarizes HAP destruction efficiency for each test run and the overall average. Note that the test plan specified that ARL glycol sample analyses data correlated with the glycol flow rate form the basis for the quantity of HAPs entering the system. This means that an average of 9.09 lb/h net HAPs entering the system with less than 0.0236 lb/h leaving it results in a destruction efficiency exceeding 99.74 ± 0.01 percent. Section 3.2.5 discusses the accuracy derivation for this determination. Table 2-5. HAP Destruction El flciency Verification Test Run No. HAPrich HAPiean net HAPjn HAPwastewater I l \Ps|ack 11 \ I\ ented HAPemitted HAP DE lb/h lb/h lb/h lb/h lb/h lb/h lb/h % Run 1 9.83 0.33 9.50 0.0209 <0.0016 0.00 0.0226 99.76 Run 2 8.37 0.37 8.00 0.0220 <0.0016 0.00 0.0236 99.70 Run 3 10.19 0.40 9.79 0.0232 <0.0015 0.00 0.0245 99.75 Average 9.46 0.37 9.09 0.0220 0.0016 0.00 0.0236 99.74 90% Confidence Interval 1.62 0.06 1.62 0.0020 0.00015 0.002 0.01 The overall HAP average mass rate in the condensate product stream was 16.41 lb/h. This means that net HAPs entering the system (as determined by the ARL method) were consistently less than the summed HAPs in the two effluent (stack gas and wastewater) and one product (condensate) streams. The glycol streams failed to account for approximately 7.34 lb/h of the total mass exiting the system. The GHG Center targeted the rich glycol samples as the primary location where HAP mass loss could have occurred after ruling out potential flow measurement problems or bias. The field team leader withdrew rich glycol at absorber pressure (1010 psig) into a sampling vial at atmospheric pressure during each sampling event. The rich glycol foamed instantly as it entered the vial. The foam was not allowed to overflow the vial, it was capped immediately, and stored on ice according to the ARL procedure. The reader should note that these procedures directly correspond to the ARL sampling instructions for glycol dehydrators without flash tank gas separators. The method's Figure A-l [9] specifies, in the absence of a flash tank, a sampling location between the charcoal filter and the reboiler. Section A.4.4 indicates that rich glycol from that sampling location "generally sprays from the sample line as a foamy aerosol" which is consistent with the field conditions. 2-6 ------- Test personnel did, however, deviate from the ARL method in one respect. As documented in a GHG Center corrective action report (CAR), field personnel did not employ an iced cooling coil for the rich glycol samples because the rich glycol was at absorber temperature, or about 90 to 100 °F throughout the test runs. Section A.4.2 of the ARL method requires that the sample pass through an iced cooling coil, but "cooling the glycol sample is not necessary if the temperature of the glycol is less than 70 °F" [9], It is possible that this temperature discrepancy may have negatively biased the rich glycol HAPs concentrations. The HAPs may have volatilized and escaped while the foamy glycol filled the sampling vials. The GHG Center cannot conclusively state whether this was the primary cause. GRI studies have found that the ARL method does negatively bias VOC, but not necessarily BTEX results [8,10], This possible negative bias could cause a negative effect on the reported HAPs destruction efficiency. Table 2-5 shows that the destruction efficiency, based on average HAP inputs of 9.46 lb/h (as quantified by the ARL method) is 99.74 percent. If the HAP inputs are assumed to be at least equal to the sum of the wastewater, stack gas, and condensate HAPs (average 16.41 lb/h), the resulting destruction efficiency is 99.86 percent. The GHG Center therefore concludes that the QLD emits very little HAPs and that overall destruction efficiency is 99.74 percent (or more) in either scenario. 2.3.2.1. HAP Inputs from Glycol Streams Table 2-6 summarizes the average glycol flow rates for the three test runs as measured with the ultrasonic flow meter. The lean glycol flow rates were between 3.77 and 3.92 gpm. The corrected rich glycol flow rates were between 3.77 and 4.05 gpm. The added water content and hydrocarbons increased rich glycol flow rate by about 4 percent. 2-7 ------- Table 2-6. HAP Inputs From Glycol Streams Run 1 Concentration, CLean (Ig/mL) V Lean HAPlean Lean 1 Sample 1 Sample 2 Sample 2a Sample 3 Average Ig/mL lb/gal gpm lb/h n-Hexane 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.769 0.01 Benzene 69.4 54.0 68.2 59.1 62.66 0.0005229 3.769 0.12 Toluene 89.6 66.5 87.6 69.4 78.26 0.0006531 3.769 0.15 Ethylbenzene 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.769 0.01 p-Xylene 16.6 15.6 14.8 19.9 16.73 0.0001396 3.769 0.03 o-Xylene 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.769 0.01 Total HAP 193.58 154.14 188.63 166.28 175.66 0.0014659 3.769 0.33 Concentration, Crm, (Ig/mL) VRjch HAPRich Difference net HAPin Rich 1 Sample 1 Sample 2 Sample 2a Sample 3 Average Ig/mL lb/gal gpm lb/h lb/h n-Hexane 140.13 107.27 144.50 137.00 132.22 0.0011034 3.916 0.26 0.25 Benzene 1660.5 1424.8 1704.8 1394.5 1546.13 0.0129031 3.916 3.03 2.91 Toluene 2744.7 2393.9 2843.6 2293.2 2568.85 0.0214381 3.916 5.04 4.89 Ethylbenzene 58.98 51.47 62.31 48.01 55.19 0.0004606 3.916 0.11 0.10 p-Xylene 614.6 545.7 647.7 511.2 579.80 0.0048386 3.916 1.14 1.11 o-Xylene 137.67 120.91 144.49 113.18 129.06 0.0010771 3.916 0.25 0.24 Total HAP 5356.52 4644.02 5547.40 4497.10 5011.26 0.0418210 3.916 9.83 9.50 Run 2 Concentration, CLean (Ig/mL) V Lean HAPlean Lean 2 Sample 1 Sample 2 Sample 2a Sample 3 Average Ig/mL lb/gal gpm lb/h n-Hexane 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.604 0.01 Benzene 82.5 74.4 68.6 75.5 75.25 0.0006280 3.604 0.14 T oluene 102.5 94.5 86.6 92.8 94.11 0.0007853 3.604 0.17 Ethylbenzene 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.604 0.01 p-Xylene 20.6 16.1 24.8 14.3 18.96 0.0001582 3.604 0.03 o-Xylene 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.604 0.01 Total HAP 223.66 202.98 197.99 200.64 206.32 0.0017218 3.604 0.37 Concentration, Crm, (Ig/mL) VRjch HAPRich Difference net HAPin Rich 2 Sample 1 Sample 2 Sample 2a Sample 3 Average Ig/mL lb/gal gpm lb/h lb/h n-Hexane 135.27 122.23 119.66 134.68 127.96 0.0010679 3.772 0.24 0.23 Benzene 1476.1 1461.7 1332.5 1467.7 1434.50 0.0119715 3.772 2.71 2.57 Toluene 2197.3 2355.2 2133.1 2275.6 2240.32 0.0186964 3.772 4.23 4.06 Ethylbenzene 44.96 47.96 42.70 43.75 44.84 0.0003742 3.772 0.08 0.07 p-Xylene 474.4 508.0 458.7 470.2 477.84 0.0039878 3.772 0.90 0.87 o-Xylene 106.65 112.41 100.60 103.05 105.68 0.0008819 3.772 0.20 0.19 Total HAP 4434.72 4607.53 4187.29 4495.03 4431.14 0.0369797 3.772 8.37 8.00 Run 3 Concentration, CLean (Ig/mL) V Lean HAPlean Lean 3 Sample 1 Sample 2 Sample 2a Sample 3 Average ig/ml lb/gal gpm lb/h n-Hexane 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.887 0.01 Benzene 74.3 74.3 71.6 86.0 76.57 0.0006390 3.887 0.15 Toluene 91.1 88.7 86.5 105.6 92.98 0.0007760 3.887 0.18 Ethylbenzene 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.887 0.01 p-Xylene 17.1 21.6 16.5 18.4 18.41 0.0001536 3.887 0.04 o-Xylene 6.00 ND 6.00 ND 6.00 ND 6.00 ND 6.00 0.0000501 3.887 0.01 Total HAP 200.51 202.67 192.57 228.09 205.96 0.0017188 3.887 0.40 (continued) 2-8 ------- Table 2-6. HAP Inputs From Glycol Streams (concluded) Rich 3 Concentration. Cnm dsi/ml,) VRjch HAPRich Difference net HAPin Sample 1 Sample 2 Sample 2a Sample 3 Average Ig/mL lb/gal gpm lb/h lb/h n-Hexane 144.62 128.69 144.76 135.22 138.32 0.0011544 4.047 0.28 0.27 Benzene 1652.1 1566.6 1576.0 1592.6 1596.84 0.0133263 4.047 3.24 3.09 Toluene 2609.8 2517.0 2529.8 2665.7 2580.59 0.0215361 4.047 5.23 5.05 Ethylbenzene 50.25 51.93 51.89 53.51 51.90 0.0004331 4.047 0.11 0.09 p-Xylene 524.0 542.0 544.3 550.5 540.19 0.0045081 4.047 1.09 1.06 o-Xylene 115.01 121.90 121.59 120.08 119.64 0.0009985 4.047 0.24 0.23 Total HAP 5095.74 4928.21 4968.39 5117.57 5027.48 0.0419563 4.047 10.19 9.79 Overall Avg Sample 1 Sample 2 Sample 2a Sample 3 Average Avg. Flow Rate Avg. Mass Rate Difference net HAPin ig/mL ig/mL ig/mL ig/mL ig/mL lb/gal gpm lb/h lb/h Lean - Total HAP 205.92 186.60 193.06 198.33 195.98 0.0016355 3.753 0.37 Rich - Total HAP 4962.33 4726.59 4901.03 4703.23 4823.29 0.0402523 3.912 9.46 9.09 ND Non-detect or analytical result below the minimum detection limit (MDL) Viean Lean glycol flow rate, gpm Vrich Rich glycol flow rate, gpm Table 2-6 also summarizes the GC/FID results. The table shows that four lean and four rich samples were collected during each test run. The field team leader collected samples 2 and 2a sequentially and all other samples were collected about 20 minutes apart. The lean glycol HAPs mass rate is smaller than the rich stream. This demonstrates that the QLD glycol regeneration process is indeed removing a significant mass of HAPs through condensation and combustion. The overall average HAP concentration in rich and lean glycol streams was 4823.29 ig/mL and 195.98 ig/mL, respectively. The primary HAP species present in both streams are benzene and toluene, followed by p-xylene. Net HAPs entering the QLD system boundary ranged between 8.00 and 9.79 lb/h at a minimum and the overall average is 9.09 ± 1.09 lb/h with a 90 percent confidence interval. 2.3.2.2. HAP Outputs in Reboiler Exhaust Stream Section 2.3.1 shows that HAP concentrations in the reboiler exhaust stream were below the instrument's detection limit. Table 2-7 summarizes the mass emission rate results. Note that the lb/h detection limits vary because the volumetric flow rate varied from run to run. 2-9 ------- Table 2-7. Reboiler Exhaust Stream HAPs Outputs Verification Run No. Concentration, CS|ad; H^Psiadt ppm lb/h Run 1 n-Hexane <0.1 <0.000241 Benzene <0.1 <0.000218 Toluene <0.1 <0.000258 Ethylbenzene <0.1 <0.000297 p-Xylene <0.1 <0.000297 o-Xylene <0.1 <0.000297 Total HAP <0.00161 Run 2 n-Hexane <0.1 <0.000232 Benzene <0.1 <0.000210 Toluene <0.1 <0.000247 Ethylbenzene <0.1 <0.000286 p-Xylene <0.1 <0.000286 o-Xylene <0.1 <0.000286 Total HAP <0.00155 Run 3 n-Hexane <0.1 <0.000232 Benzene <0.1 <0.000210 Toluene <0.1 <0.000247 Ethylbenzene <0.1 <0.000285 p-Xylene <0.1 <0.000285 o-Xylene <0.1 <0.000285 Total HAP <0.00154 Overall Avg. 0.00157 2.3.2.3. HAP Outputs in Wastewater Production Stream Table 2-8 shows the wastewater discharge amounts per dump based on nine dump cycles. Five dumps occurred during Run 1 and 2, and three dumps occurred during Run 3 of the verification test. The field team leader collected these data prior to the test campaign. The data show that the discharge rate was repeatable: 3.057 ± 0.019 gal/dump or 1.283 ± 0.007 gal/in. Test planners expected this consistency because the repeatability of the pneumatically operated controllers were 1/1000 of an inch. The test plan anticipated that, for the size and configuration of the vacuum separator, the discharge repeatability would be better than ±2.0 percent. The actual repeatability was about ±0.6 percent. Table 2-8. Pre-Test Wastewater Discharge Rate Determinations Date Time Time Diff Dump Tare Full Gain Temp Density Discharge Rate Sight Glass Readings Dis- charge Rate Start End Diff min ID lb lb lb degF lb/gal gal/dump gpm in in in gal/in. 4/7/03 12:42 1 2.31 27.93 25.62 91 8.301810 3.0861 13:33 51 2 2.31 27.93 25.62 91 8.301810 3.0861 0.0605 3.4063 1.0000 2.4063 1.2825 14:24 51 3 2.33 27.72 25.39 92 8.300227 3.0590 0.0600 3.3750 1.0000 2.3750 1.2880 15:24 60 4 2.32 27.81 25.49 93 8.298644 3.0716 0.0512 3.3750 1.0000 2.3750 1.2933 16:23 59 5 2.30 27.81 25.51 91 8.301810 3.0728 0.0521 3.4063 1.0000 2.4063 1.2770 4/8/03 10:12 23 2.30 27.32 25.02 101 8.285780 3.0196 3.0000 0.6250 2.3750 1.2714 12:07 115 25 2.29 27.62 25.33 101 8.285780 3.0570 3.0156 0.6250 2.3906 1.2788 12:56 49 26 2.30 27.50 25.20 103 8.282211 3.0427 0.0621 3.0000 0.6406 2.3594 1.2896 15:10 134 29 2.30 27.27 24.97 111 8.267735 3.0202 Average: 3.0572 Average: 1.2829 2-10 ------- Table 2-9 shows the elapsed times between dump cycles for each test run. Table 2-9. Wastewater Production Rate During Verification Testing Time Elaps. Dump Discharge Rate Waste- water Produc- tion Rate Per Dump Elapsed Time Since Dump Fraction of Time Relative to Run Durationb Weighted Wastewater Production Rate0 Run- Specific Average Wastewater Production Rate, Wastewater Date Time Diff Min ID gal/dumpa gpm Min gpm gpm 4/30/03 14:03 323 3.0572 14:31 0:28 28 324 3.0572 0.1092 Run 1 Start: 14:30 1 0.008850 0.0010 15:00 0:29 29 325 3.0572 0.1054 29 0.256637 0.0271 15:39 0:39 39 326 3.0572 0.0784 39 0.345133 0.0271 16:06 0:27 27 327 3.0572 0.1132 27 0.238938 0.0271 16:31 0:25 25 328 3.0572 0.1223 Run 1 Stop: 16:23 17 0.150442 0.0184 0.101 17:09 0:38 38 329 3.0572 0.0805 Run 2 Start: 17:01 8 0.089888 0.0072 17:27 0:18 18 330 3.0572 0.1698 18 0.202247 0.0344 17:52 0:25 25 331 3.0572 0.1223 25 0.280899 0.0344 18:23 0:31 31 332 3.0572 0.0986 31 0.348315 0.0344 18:50 0:27 27 333 3.0572 0.1132 Run 2 Stop: 18:30 7 0.078652 0.0089 0.119 19:28 0:38 38 334 3.0572 0.0805 Run 3 Start: 18:57 31 0.344444 0.0277 19:57 0:29 29 335 3.0572 0.1054 29 0.322222 0.0340 20:25 0:28 28 336 3.0572 0.1092 Run 3 Stop: 20:27 30 0.333333 0.0364 0.098 Overall Average 0.106 a Based on the average discharge rate determined during pre-test evaluation (Table 2-8) b Duration for Run 1 = 113 mins, Rim 2 = 89 mins, and Run 3 = 90 mins c Wastewater production rate multiplied by fraction of time between dumps Wastewater total volume for Runs 1, 2, and 3 was 11.36, 10.61, and 8.83 gallons, respectively. Based on the elapsed times for each test run, the wastewater production rate varied between 0.101 and 0.119 gpm. The overall average production rate was 0.106 gpm. Table 2-10 summarizes the laboratory analysis results for four wastewater samples collected during each test run. Benzene and toluene were the primary HAP constituents. Average concentrations ranged between 368 and 472 ig/mL. Multiplication of these concentrations by the production rates shown in Table 2-9 yields the run-specific mass emission rates. The HAP emission rate for all three test runs was 0.0220 Ml 2-11 ------- Table 2-10. HAPs Outputs in Wastewater Stream Run 1 Concentration, CWastev rater Og/mL) Wastewater Production Rate, ^^Wastewater HAINvatei Sample ID Sample ID Sample ID Sample ID Average 1 2 2a 3 ig/mL lb/gal gpm lb/h n-Hexane 0.801 ND 1.001 ND 1.001 ND 1.001 ND 0.951 0.000008 0.101 0.00005 Benzene 200.489 227.145 313.737 289.688 257.764 0.002151 0.101 0.01298 Toluene 104.976 113.377 175.446 157.164 137.741 0.001150 0.101 0.00693 Ethylbenzene 0.971 J 1.279 J 1.918 J 1.642 J 1.453 0.000012 0.101 0.00007 m- and p-Xylene 8.352 9.058 16.928 15.516 12.463 0.000104 0.101 0.00063 o-Xylene 2.829 J 3.434 J 5.570 5.212 4.261 0.000036 0.101 0.00021 Total HAP 318.417 355.294 514.600 470.223 414.634 0.003460 0.101 0.0209 Run 2 n-Hexane 0.400 ND 1.001 ND 1.464 J 1.001 ND 0.967 0.000008 0.119 0.00006 Benzene 186.603 271.942 146.598 284.810 222.488 0.001857 0.119 0.01328 Toluene 96.426 165.647 78.479 168.820 127.343 0.001063 0.119 0.00760 Ethylbenzene 0.855 J 1.635 J 1.001 ND 1.803 J 1.324 0.000011 0.119 0.00008 m- and p-Xylene 8.629 15.951 7.379 16.304 12.066 0.000101 0.119 0.00072 o-Xylene 2.671 5.173 2.485 J 5.408 3.934 0.000033 0.119 0.00023 Total HAP 295.584 461.350 237.407 478.147 368.122 0.003072 0.119 0.0220 Run 3 n-Hexane 1.001 ND 1.001 ND 1.001 ND 1.001 ND 1.001 0.000008 0.098 0.00005 Benzene 275.285 272.485 291.060 307.250 286.520 0.002391 0.098 0.01407 Toluene 156.729 157.039 165.044 168.717 161.882 0.001351 0.098 0.00795 Ethylbenzene 1.609 J 1.555 J 1.706 J 1.677 J 1.637 0.000014 0.098 0.00008 m- and p-Xylene 15.815 15.510 16.673 16.276 16.068 0.000134 0.098 0.00079 o-Xylene 5.391 5.090 5.367 5.323 5.293 0.000044 0.098 0.00026 Total HAP 455.829 452.680 480.850 500.245 472.401 0.003942 0.098 0.0232 Overall Avg. Total HAP 356.610 423.108 410.952 482.871 418.386 0.003 0.106 0.0220 ND Non-detect or analytical result below the minimum detection limit (MDL) J Analytical result between the MDL and the limit of quantification (LOQ) 2.3.2.4. HAP Outputs in Condensate Production Stream The run-specific condensate production rate determination first requires an estimate of the condensate discharge rate (gal/dump). The gal/in. discharge rate would be identical for both product streams because the liquids collect in a common vessel and the condensate pneumatic level controller is identical to the wastewater level controller. GHG Center personnel recorded the initial and final condensate sight-glass levels before and after each dump cycle. The sight-glass level change (in.) multiplied by the wastewater discharge rate reported in Section 2.3.2.3 (1.283 gal/in.) yielded condensate discharge rate (gal/dump). Table 2-11 summarizes the results for each test run. 2-12 ------- Table 2-11. Run-Specific Condensate Production Rate Date Time Time Ref Elaps Ref Dump Ref Condensate Sight-Glass Reading Waste water Discharge Rate3 Condensate Discharge Rateb Condensate Production Rate Elapsed Time Since Dump Fraction of Time Relative to Run Duration0 Weighted Condensate Production Rated Run-Specific Average Condensate Production Rate, v Start End Diff Diff Min ID in. in. in. gal/in. gal/dump gpm Min gpm gpm 4/30/03 13:50 200 2.6250 0.3438 2.2813 1.2829 2.9267 14:45 0:55 55 201 2.5625 0.2500 2.3125 1.2829 2.9668 0.0539 Run 1 Start: 14:30 15 0.1327 0.0072 15:46 1:01 61 202 2.5938 0.1875 2.4063 1.2829 3.0871 0.0506 61 0.5398 0.0273 16:44 0:58 58 203 2.5938 0.3438 2.2500 1.2829 2.8866 0.0498 Run 1 Stop: 16:23 37 0.3274 0.0163 0.051 17:25 0:41 41 204 2.5938 0.1875 2.4063 1.2829 3.0871 0.0753 Run 2 Start: 17:01 24 0.2697 0.0203 18:41 1:16 76 205 2.5938 1.1875 1.4063 1.2829 1.8041 0.0237 Run 2 Stop: 18:30 65 0.7303 0.0173 0.038 19:19 0:38 38 206 2.5938 0.3438 2.2500 1.2829 2.8866 0.0760 Run 3 Start: 18:57 22 0.2444 0.0186 20:17 0:58 58 207 2.5938 0.3125 2.2813 1.2829 2.9267 0.0505 Run 3 Stop: 20:27 68 0.7556 0.0381 0.057 Overall Average 0.048 a Based on the average discharge rate determined during pre-test evaluation (Table 2-9). b Estimated by multiplying wastewater discharge rate by level change in sight glass reading. c Duration for Run 1 = 113 minutes, Run 2 = 89 minutes, and Run 3 = 90 minutes. d Wastewater production rate multiplied by fraction of time between dumps. 2-13 ------- Two to three complete condensate dumps occurred during each test run. The overall average condensate production rate was 0.048 gpm. The condensate recovery rate was about half as much as the wastewater production rate. Table 2-12 summarizes the laboratory analysis results for four condensate samples collected during each test run. Similar to the wastewater stream, benzene, toluene, and p-xylene were the primary HAP constituents in each condensate sample. Average HAP concentrations ranged between 637,339 and 714,412 ig/ml. Multiplication of these concentrations by the production rates shown in Table 2-11 resulted in run-specific mass emission rates. The overall average HAP production rate from the condensate product stream was 16.41 lb/h. Table 2-12. HAP Outputs in Condensate Production Stream Run 1 Concentration, CWater (ig/mL) Condensate Production Rate, Condensate HAP Condensate Sample ID Sample ID Sample ID Sample ID Average 1 2 2a 3 ig/mL lb/gal gpm lb/h n-Hexane 10,107 8,776 10,370 9,589 9711 0.08 0.051 0.25 Benzene 212,553 176,446 222,001 208,710 204928 1.71 0.051 5.21 Toluene 383,335 315,392 407,011 381,067 371701 3.10 0.051 9.45 Ethylbenzene 8,033 6,589 8,663 8,129 7854 0.07 0.051 0.20 m- and p- Xylene 84,897 69,741 90,867 85,705 82803 0.69 0.051 2.11 o-Xylene 18,307 15,027 19,666 18,573 17893 0.15 0.051 0.45 Total HAP 717,233 591,971 758,578 711,773 694,889 5.80 0.051 17.67 Run 2 n-Hexane 9,790 10,707 9,514 9,259 9817 0.08 0.038 0.19 Benzene 206,344 225,489 200,974 197,164 207493 1.73 0.038 3.91 Toluene 379,359 415,395 370,220 363,980 382238 3.19 0.038 7.20 Ethylbenzene 8,192 9,157 8,315 8,191 8464 0.07 0.038 0.16 m- and p- Xylene 86,724 95,446 83,958 82,771 87225 0.73 0.038 1.64 o-Xylene 18,847 20,866 18,683 18,302 19175 0.16 0.038 0.36 Total HAP 709,256 777,061 691,665 679,667 714,412 5.96 0.038 13.47 Run 3 n-Hexane 9,170 9,052 9,336 7,536 8773 0.07 0.057 0.25 Benzene 191,505 190,064 196,546 162,279 185098 1.54 0.057 5.25 Toluene 351,340 350,878 361,019 298,660 340474 2.84 0.057 9.67 Ethylbenzene 7,987 7,976 8,272 6,700 7734 0.06 0.057 0.22 m- and p- Xylene 80,639 80,386 82,471 68,505 78000 0.65 0.057 2.21 o-Xylene 17,838 17,814 18,260 15,124 17259 0.14 0.057 0.49 Total HAP 658,479 656,169 675,904 558,803 637,339 5.32 0.057 18.09 Overall Avg. Total HAP I 694,9891 I 675,0671 I 708,7161 I 650,0811 I 682,2131 5.69| 0.0481 16.41 2-14 ------- 3.0 DATA QUALITY ASSESSMENT 3.1. DATA QUALITY OBJECTIVES The test plan specified methodologies, instruments, and QA/QC requirements which would ensure that the final results have known data quality. The test plan's stipulations lead to specific data quality objectives (DQOs) for each verification parameter. Each measurement that contributes to a verification parameter determination has stated data quality indicators (DQIs) which, if met, ensure achievement of the applicable DQO. The establishment of DQOs begins with the determination of each verification parameter's desired confidence level. Test planners then identify the expected values of all contributing measurements and determine the tolerable error level. Table 3-1 summarizes the test plan's specified DQOs for each verification parameter. The table also shows those achieved during the test campaign. Table 3-1. Verification Parameter Data Quality Objectives Verification Parameter Allowable Measurement Error a Achieved Sales Gas Flow Rate Moisture Content ± 1% ± 2 °C dewpoint ±0.13% ± 1 °C dewpoint Glycol Circulation Rate ± 1% ± 0.4% Makeup Natural Gas Makeup Natural Gas Flow Rate ± 1% ±0.8% BTEX Content ±5% n/ac Reboiler Exhaust Stack Emissions Concentration (ppm or%) NOx ± 2% of FS or 2 ppm 2.0 ppm CO ± 2% of FS or 2 ppm 1.2 ppm o2 ± 2% of FS or 0.5% 0.2% co2 ± 2% of FS or 0.5% 0.4% THC ± 5%o of FS or 5 ppm 2.0 ppm CH4 ± 5%o of FS or 5 ppm 0.1 ppm HAPs ± 5%o of FS or 5 ppm 0.6 ppm Emission Rate (lb/h)b NOx ± 0.0088 lb/h 0.0048 lb/h CO ± 0.0053 lb/h 0.0009 lb/h co2 ± 16.2 lb/h 7.5 lb/h THC ±0.0031 lb/h 0.0009 lb/h CH4 ±0.00019 lb/h 0.000003 lb/h HAPs ±0.018 lb/h 0.0001 lb/h HAP Destruction Efficiency ± 0.5% ±0.01% a Full scale (FS) during testing was 0 -100 ppm. for NOx, CO, THC, CH4, and FlAPs Full scale during testing was 0 - 25% for 02 and C02 b Stated as 7% of the emission rate when the concentration is at 100% of analyzer span and stack flow is 10,507 dscfh. c Not available. Please refer to Section 3.2.3. Analysts most often state the DQIs in terms of measurement accuracy, precision, and completeness. Table 3-2 specifies each DQI goal and those achieved during testing. 3-1 ------- Table 3-2. Data Quality Indicator Goals and Results Measurement Variable Instrument Type / Manufacturer Instrument Range (FS)a Accuracy Completeness Goal" Actual0 How Verified / Determined Goal Actual Sales Gas Flow Rate Emerson Model MVS205 Orifice Meter 0 to 2 mmscfh ± 1% reading ±0.13% reading Field calibration with NIST- traceable reference standards 90% of 1-min average readings Opr. Testing: 93% Env. Testing: 84% Moisture Content MEECO (test plan) Panametrics (installed) 0 to 20 lb/mmscf ± 2 °C Dewpoint ± 1 °C Dewpoint Calibration with NIST- traceable reference standard Opr. Testing: 93% Env. Testing: 84% Glycol Circulation Rate Flow Rate Controlotron Ultrasonic Flow Meter Pipe diameter: 0.25 to 360 inch Flow velocity: 0 to 60 fps ± 1% reading ± 0.4% reading Calibration with NIST- traceable reference standard Opr. Testing: 85% Env. Testing: 84% Makeup Natural Gas Fuel Flow Rate Flaliburton MC-II EXP turbine meter 0 to 1,500 scfh ± 1% reading ± 0.8% reading Calibration with NIST- traceable reference standard Opr. Testing: 93% Env. Testing: 84% BTEX Content GC/FID HP Model 5890 or Equivalent 0 to 10,000 ppm % Diff. in 3 Pt. Calibration < 5% n/ad Calibration with certified standards Pre-test: 2 samples 2 samples Exhaust Stack Emissions NOx Concen. Chemiluminescent/ TEI Model 42C 0 to 100 ppmv ± 2% FS or ± 2 ppmv < 2.0% FS or ± 2.0 ppmv c Calculated following EPA reference method calibrations (Before and after each test run) three valid 90 minute runs (90- percent completeness) Run 1: 85 mins Run 2: 70 mins Run 3: 72 mins CO Concen. NDIR / TEI Model 48C 0 to 100 ppmv ± 2% FS or ± 2 ppmv < 1.2% FS or ± 1.2 ppmv c THC Concen. FID / JUM Model VE-7 0 to 100 ppmv ± 5% FS or ± 5 ppmv < 2.0% FS or ± 2.0 ppmv c CO2 Concen. NDIR / CAI Model 200 0 to 25% ± 2% FS or ±0.5% < 1.7% FS or ± 0.4% c O2 Concen. NDIR / CAI Model 200 0 to 25% ± 2% FS or ±0.5% < 0.9% FS or ± 0.2% c CFLt Concen. GC/dual FID, HP Model 5890a 0 to 100 ppmv ± 5% FS or ± 5 ppmv ±0.1 ppmvf HAP Concen. ±0.6 ppmv1'8 FhO Content NA 0 to 100% ± 5% reading ± 5% reading NIST-traceable equipment calibrations (pitot, thermocouple, gas meter, and balance) Stack Gas Flow Rate Pitot and thermocouple NA ± 5% reading ± 5% reading (continued) 3-2 ------- Table 3-2. Data Quality Indicator Goals and Results (concluded) Measurement Variable Instrument Type / Manufacturer Instrument Range (FS)a Accuracy Completeness Goal" Actual0 How Verified / Determined Goal Actual HAPs in Liquid Streams Wastewater Discharge Rate NA NA Repeatability of ± 1% between dump cycles ±0.6% Manual collection and weighing of wastewater produced during a discharge dump Minimum of 3 dump captures in pre-weighed container 9 dump cycles captured HAPs in rich glycol, lean glycol, wastewater, and condensate GC/FID 0 to 1000 ppm, nominal < 5% diff. in 3 pt. calibration < 5% diff in cal. error Minimum of 3 pt. calibration with certified standard. 3 samples per test run 4 samples per test run < 5% Maximum diff in duplicate injections rich glycol: 2.9%c lean glycol: 4.5%)c wastewater: 9.8%o c'e Duplicate sampling and analysis on at least one rich, lean, and wastewater sample. s FS: full scale b In the Test Plan, FS for NOx, CO, and THC was 0-100 ppm, and 0-50 ppm for CH4 and HAPs. For 02 and C02, FS was 0 - 25%. During the test, FS for all compounds except CH4 and HAPs was same as those defined in the Test Plan. For CH4 and HAPs, FS was changed to 0 -100 ppm. The accuracy goals listed here represent the FS of instruments used during testing. c Actual values shown represent the maximum system error observed throughout the test periods. See the discussion in Section 3.2.3 e The laboratory prepared and injected one duplicate sample aliquot, unlike the duplicate injections for the GC/FID analyses. Goal for this duplicate analysis was ± 10%. f Cubix calibrated the GC/FID at low, medium, and high levels. Since stack gas concentrations were non-detectable, error at the low level calibration is the assigned error. See Appendix B-3. 8 Represents compounded average error for all HAPs at low reference concentration. 3-3 ------- 3.2. DQO AND DQI RECONCILIATION Data completeness goals are summarized in Table 3-2. "Completeness" is defined as the number or percent of valid determinations actually made relative to those specified in the Test Plan. The goal for operational parameters was at least 90 percent valid data during each 24-hour segment of the 7-day monitoring period or during each test run. Nearly all one-minute data collected during 5 of the 7 days were valid. The remaining two days included 15.05 hours and 20.73 hours of one-minute data (Table 2-1). On average, 93 percent of the one-minute measurements data were valid and the GHG Center used those data to report operational performance results. The field team leader discovered during the first environmental performance test run that sampling events at the vacuum separator caused process upsets. The reboiler stack CO (and other gas) concentrations would rise or drop abruptly when the manual vent valve was opened to break the vessel's vacuum. The GHG Center invalidated data where CO concentration was greater than 90 percent of the average initial value for two consecutive data points and until the concentration reached 90 percent of a stable final value following the event. Test personnel observed that the primary upset indicators were CO concentration step changes. The step changes were clear and well-defined during all but one sampling event. Other stack gas concentrations changed unpredictably during sampling events with known CO step changes. It was impossible to tell during the one sampling event with no CO step change whether other gas concentration changes were due to the sampling event or normal variability. Exclusive use of the CO step changes as a criterion may have left invalid data in the set. The GHG Center therefore invalidated the data collected during this sampling event. Cubix performed no gas chromatograph injections during this period. The actual run durations were 85, 70, and 72 minutes for runs 1, 2, and 3, respectively, after analysts removed invalid data. The tests, therefore, did not meet completeness goals for Runs 2 and 3. The GHG Center believes that this does not affect the overall verification results because: • Environmental performance results were extremely consistent from run to run, and • Most regulatory instrumental analyzer test runs must acquire, at most, 60 minutes of valid data. This means that the test data are adequate for regulatory purposes. It should also be noted that the test plan specified 90-minute test runs to accommodate the time required for the sampling events. The Test Plan specified three liquid samples to be collected from each liquid stream per run. Table 3-2 shows that the field team leader collected four valid samples. This met the completeness goals. Table 3-3 shows the planned and achieved accuracy goals. Instrument calibrations (by the manufacturer or performed in the field) or reasonableness checks form the basis for the achieved accuracies. Table 3-3 identifies the QA/QC checks performed during the tests and how these results contribute to DQI reconciliation. The following subsection discusses each instrument's accuracy results and the effect on the corresponding DQO. 3-4 ------- Version 1.2-August 13, 2003 DRAFT Do not cite, quote, use, or distribute without written permission from GHG Center Table 3-3. Calibration Results and QC Checks Parameter QA/QC Check When Performed/ Frequency Expected or Allowable Result Maximum Results Measured3 Sales Gas Flow Rate Field calibration by manufacturer Beginning of test Differential pressure: 6 point cal. Static pressure: 4 point cal. Temperature: 1 point cal. Results should be less than 1% of NIST traceable reference values Diff. pressure (10 pt. cal): ± 0.12% Static pressure (4 pt. cal): ± 0.12% Temperature (1 pt. cal): ± 0.01% Avg. flow rate error: +0.13%g Factory calibration by manufacturer Most recently available records ± 2 °C dewpoint of NIST- traceable calibration standard ± 1 °C dewpoint Moisture Content Field check - adjust sampling rate into moisture meter Beginning of test Moisture reading at 50% and 200% of normal sampling rate should be 0.5 and 2 times the reading at normal rate Not performed; documented in CAR Reasonableness check - compare with manually collected gas sample 2 samples per day of testing ±21% of lab results 400% or 2.21 lb/mmscf Glycol Circulation Rate Lean Glycol Flow Rate Reasonableness check - compare with ultrasonic meter Beginning of test ± 2% of NIST-traceable ultrasonic meter reading For Run 1, avg. rate for site meter = 5.14 gpm, and avg. rate for ultrasonic meter =3.82 gpm. Avg. percent difference = 34.6%. GHG Center used ultrasonic meter during testing. Factory calibration by manufacturer (Controlotron) Beginning of test ± 1% of NIST-traceable calibration standard ± 0.4% Makeup Natural Gas Flow Rate Factory calibration by manufacturer Beginning of test ± 1% of NIST-traceable calibration standard ± 0.8% BTEX Content Calibration of GC/FID with gas standards Prior to analysis ± 5% of reference value n/a. See discussion in Section 3.2.3 Duplicate analysis Each sample ± 5% difference Not Performed Reboiler Stack Emissions NOx N02 converter efficiency Once before testing begins 98% efficiency or greater 99.2% NOx, CO, co2, o2 Analyzer calibration error test Daily before testing ± 2% of analyzer span or less NOx: 0.9% of span or 0.9 ppmvd CO: 1.9% of span or 1.9 ppmvd CO,: 0.96% of span or 0.24% 02: 1.12% of span or 0.28% System bias tests Before and after each test run ± 5% of analyzer span or less NOx: 2.0% of span or 2.0 ppmvd CO: 1.2% of span or 1.2 ppmvd C02: 1.7% of span or 0.4% 02: 0.9% of span or 0.2% Calibration drift test After each test ± 3% of analyzer span or less NOx: 0.5% of span or 0.5 ppmvd CO: 1.5% of span or 1.5 ppmvd C02: 0.6% of span or 0.2% 02: 0.9% of span or 0.2% THC System bias tests Before and after each test run ± 5% of analyzer span or less 2.0% of span or 2.0 ppmvd System calibration drift test After each test ± 3% of analyzer span or less 0.7% of span or 0.7 ppmvd (continued) 3-5 ------- Table 3-3. Calibrations and QC Checks (concluded) Parameter QA/QC Check When Performed/ Frequency Expected or Allowable Result Maximum Results Measured3 Duplicate analysis Each sample ± 5% difference NA° ch4 GC/FID calibration Prior to analysis of 6 samples per run ± 5 ppm or less 0.1 ppmvc Duplicate analysis Each sample ± 5% difference NA° HAP Content GC/FID calibration Prior to analysis of 6 samples per run ± 5 ppm or less 0.6 ppmvc,d Stack Gas Flow Rate Thermocouple calibration Once after testing ± 1.5% of average stack temp, recorded during final test run 0.22% Liquid Measurements Wastewater Discharge Rate Determine wastewater discharge rate for 3 dumps (i.e., collect liquid in tared container and monitor sight glass level change per dump cycle). Beginning of test ± 2% difference in discharge rate (gal/dump and gal/in.) For 9 dump cycles, 95% confidence interval was ± 0.6% of mean discharge rate Calibration of GC/FID with gas standards by certified laboratory Prior to analysis ± 5% of reference value Pre- and post-test calibration error < 5% of reference value Duplicate injection Each sample ± 5% difference Rich glycol: 2.9%e Lean glycol: 4.5%e Condensate: 2.0%e HAP Content Duplicate analysis One sample ± 5% difference Rich glycol: 2.3% e Lean glycol: 45.1% e'f Wastewater: 9.8%) e,f Condensate: not performedf 3 benzene audit samples Prior to analysis ± 5% of certified concentration For audit concen. in range of: Rich glycol Results: -10.1 %of Lean glycol and wastewater results: -6.5%of Condensate results: 4.2%) Comparison with internal standard 3 liquid samples ± 5% of spike levels Rich glycol: 8.0%o e,t Lean glycol: 7.4%o e'f Wastewater: 22%o e'f Condensate: 9%o e,f a See Appendix B and C for individual test run results. b Not Applicable. Cubix performed on-line sampling for CH4, BTEX, and n-hexane. This eliminated the need for duplicate grab (bag) samples. Instead, Cubix conducted six individual sample injections during each test run. c Cubix calibrated the GC/FID at low, medium, and high levels. Since the measured stack gas concentration was non detectable, error at the low level is the assigned error. See Appendix B for results for each compound. d Represents compounded average error for all HAP species at low reference concentration. e Represents maximum value observed for a HAP compound. See Appendix C for results for each compound. f See Section 3.2.5.1 for discussion. g The host facility (not the manufacturer) performed the most recent calibration with NIST-traceable instruments. Total flow rate error is quoted from the calibration certificate. 3-6 ------- 3.2.1. Sales Gas Flow Rate and Moisture Content The DQO and DQI goal for sales gas flow rate was + 1 percent. The DQI for sales gas moisture was ±2 °C dewpoint. Kerr McGee calibrated sales gas flow meter with NIST-traceable analyzers on March 12, 2003. Analysts employed ten differential-pressure, four static-pressure, and a single-point temperature standard. Table 3- 3 shows that the calibration checks were below the target levels. The calibration certificate states that overall flow meter error was ±0.13 percent. The moisture analyzer manufacturer subjected the instrument to a 14-point NIST-traceable calibration on December 14, 2001. The Test Plan Table 3-2 specifies this instrument must be accurate to "± 5 percent of reading". The manufacturer states this specification is incorrect. The instrument specification should be "± 2 °C dewpoint". All calibration results were less than ± 1 °C dewpoint. The Test Plan specified a reasonableness check to be performed on the moisture analyzer. The field team leader collected two sales gas samples and determined the moisture content length-of-stain ("Draeger" brand) tubes. The results were as follows: Table 3-4. Comparison Between Length-of-Stain Moisture Content and Analvzer Reading Draeger Tube Result Analyzer Reading Difference Time mg/mL lb/mmscf lb/mmscf % lb/mmscf 15:32 0.05 3.12 1.26 248 1.86 19:58 0.10 6.24 1.13 552 2.56 Average 0.08 4.68 1.20 400 2.21 It is evident that this reasonableness check is not a valid cross-check of the instrument's performance. This is understandable because Draeger specifies that the method standard deviation for mid-range readings (i.e., 0.5 mg/L) is ± 15 to 20 percent of reading. The method detection limit is 0.05 mg/L and, at small concentrations, the percentage errors can become very large. 3.2.2. Glycol Circulation Rate The test plan specified a maximum glycol circulation rate error of 1.0 percent. A reasonableness check indicated that the site's flow meter output did not agree with the ultrasonic flow meter within the 2 percent specified in the Test Plan. The site average lean glycol flow rate for a one-hour comparison test was 5.14 gpm while the GHG Center's flow meter reported 3.83 gpm (a difference of 34.6 percent). The GHG Center calculated the pump's theoretical flow capacity at 4.13 gpm based on the manufacturer's specifications and assuming a 95 percent efficiency. This agrees very closely with the actual instantaneous ultrasonic flow meter measurements taken during steady-state operations. The ultrasonic flow meter is therefore the source of the reported glycol circulation rates. The manufacturer calibrated the GHG Center's ultrasonic flow meter on October 11, 2002. Lab personnel subjected the instrument to a four-point NIST-traceable calibration using 1.9-inch carbon steel pipe. The calibration range varied between 10.3 and 50.6 gpm. The error at 10.3 gpm, which is closest to the flow rates observed during testing, was 0.4 percent of reading. This value is assigned as the error achieved, which satisfies the 1 percent goal. 3-7 ------- 3.2.3. Makeup Natural Gas Flow Rate The Test Plan specified a 5-point calibration of the makeup natural gas meter to be within ± 1 percent. The manufacturer's calibration certificate dated February 7, 2002, shows that-at from 20 to 100 percent of the meter's design capacity of 1500 actual cubic feet per hour (acfh)-maximum error was ±0.8 percent. The field team leader collected three makeup natural gas samples to determine if significant BTEX was entering the system through that gas stream. This could bias the HAP destruction efficiency results. Empact Analytical Systems, Inc. (Empact), performed the extended natural gas analysis. The Test Plan specified that the lab would calibrate the GC/FID prior to each sample analysis, perform duplicate injections, and analyze each sample "in duplicates to determine total measurement error" (Section 3.4). Empact personnel have stated that the analysts did not perform these steps as described. This lab employed the ASTM D6730 method for detailed hydrocarbon analysis. The method requires two GC machines: (1) the primary for major gas constituents (including non-hydrocarbons) and (2) the secondary for the selected HAPs. Analysts checked the primary GC with a certified standard daily. The high heating value response must be within 1.0 percent of the standard. They then compared the two systems' response to the pentane in the samples. Identical response implies that the two systems were responding similarly. Analysts then entered the method's published reference factors for the selected HAP components to the secondary machine. The secondary GC was not directly challenged with certified standards. The laboratory's procedure did not conform to the Test Plan, so the GHG Center is unable to determine if the laboratory met the + 5.0 accuracy goal. This accuracy was to have been shown by duplicate injections of a certified standard, which the laboratory did not perform. In addition, the laboratory records for the primary GC's certified standard challenge, the pentane cross-responses, and how they relate to overall accuracy are not available. These omissions, however, have minimal effect on the HAPs destruction efficiency because of the low makeup natural gas flow rates observed during the test runs. The Test Plan specified that makeup natural gas BTEX could significantly impact HAPs destruction efficiently only if concentrations exceeded 10,000 ppm. The laboratory results in Appendix D show that makeup gas BTEX as 310 ppm or less for all three samples. Even if BTEX had equaled 10,000 ppm, total BTEX entering the burner would have been very low as shown by the following calculations: • BTEX mass per volume per ppm (assuming equal proportions of all constituents) = 3.90 mg/m3 per ppm [11], or 2.435 x 10-7 lb/ft3 per ppm; • Total BTEX at 10,000 ppm = 2.44 x 10-3 lb/ft3; • BTEX inputs to the burner, at 1.37 scfh (the average makeup natural gas flow rate) = 3.34 x 10"3 lb/h. It is highly unlikely that this 3.34 x 10"3 lb/h of BTEX would have been unaffected as it passed through the combustion zone. The non-detectable BTEX concentrations in the stack support this conclusion. If all the BTEX had passed through and up the stack intact, the total HAPs escaping from the system would have been (Table 2-5): • 0.02 lb/h from the wastewater, • 0.0013 lb/h in the stack gas, and • 0.0034 lb/h in the makeup natural gas passed through the combustion zone to the stack. 3-8 ------- In this case, destruction efficiency would have been 0.0247/9.09, or 99.73 percent, as compared to the 99.74 percent reported in Section 2.3.2. This analysis, then, indicates that the QA/QC discrepancies described here do not significantly affect the test results. 3.2.4. Reboiler Stack Emissions EPA reference method requirements form the basis for the DQOs specified in the test plan. Each method specifies sampling and calibration procedures and data quality checks. This ensures collection of run- specific instrument and sampling system drift and accuracy data throughout the emissions tests. The data quality indicator goals required to meet the DQOs consisted of an assessment of sampling system error (bias) and drift for NOx and THC, bias and drift for CO, C02, and 02, and GC/FID calibration for HAPs. The following subsections discuss the achieved goals as presented in Tables 3-2 and 3-3. Appendix B summarizes all calibration, linearity, bias, and drift results. 3.2.4.1. NOx and THC Test personnel performed NOx and THC sampling system calibration error tests prior to each test run. All calibrations employed EPA Protocol No. 1 calibration gases. The four NOx and THC calibration gases were zero, 25, 45, and 85 to 90 percent of span. Table 3-2 shows that the system calibration error goal for NOx was ± 2.0 ppm. The maximum actual measured error was precisely this value. The maximum system error was ±2.0 ppm for THC which is less than the ± 5.0 ppm goal. Test operators established the NOx analyzer's linearity at the beginning of the test day. Its span was 0 to 100 ppm. The results shown in Appendix B indicate excellent instrument linearity with calibration errors of 0.94 percent of span or less. System response to the zero and mid-level calibration gases provided a measure of drift and bias at the end of each test run. The maximum sampling system drift was 0.51 ppm for NOx and 0.67 ppm for THC, which were both below the method's maximum allowable drift. Testers also performed a NOx converter efficiency test as described in Section 3.5 of the test plan. The converter efficiency was 99.2 percent, which exceeds the 98-percent goal specified in Table 3-3. 3.2.4.2. CO, C02 and 02 CO, C02, and 02 drift and bias checks were similar to those described for NOx and THC. Maximum drift was 1.5 percent of span for CO, 0.6 percent of span for C02, and 0.9 percent of span and 02. All test runs, therefore, met the drift and bias goals. 3.2.4.3. HAPs The test plan specified EPA Method 18 for determining stack gas organic concentrations. Test operators injected calibration gas standards into the GC to establish a concentration standard curve prior to sample analysis. The operator repeated the injections until the average of all desired compounds from three separate injections agreed to within 5.0 percent of the certified value. Appendix B summarizes the results. The acceptance criterion was met for all compounds. 3-9 ------- The analysts injected the mid-range standard to quantify instrument drift at the completion of each test. The analyst would repeat the calibration process used for the average of the two calibration curves to determine concentrations if he observed a variance larger than 5.0 percent. Appendix B shows that no variance was more than 5.0 percent. Method 18 also specifies a recovery study. The analyst checked the entire sampling system with a mid- level calibration gas. Repeated injections were analyzed until the area counts of the desired compounds from three separate injections agreed to within 5 percent of their average. The difference between the average response from the gas injected through the probe and injected directly must be less than 10 percent. All recoveries conformed to this specification (Appendix B). 3.2.4.4. Moisture Measurement Cubix calibrated the dry gas meter used for moisture testing prior to field use in accordance with EPA methodology. Testers also conducted a post-test calibration check with a primary standard bell prover. The pre- and post-test calibrations differed by less than 5.0 percent as required by the reference method. 3.2.4.5. Emission Rate Measurement Error The test plan's DQO for mass emission rate was ± 7.0 percent for all pollutants. The basis for this is the allowable concentration measurement errors compounded with the ± 5.0 percent stack flow rate error. The test plan based each pollutant's concentration error on that analyzer's full-scale reading. The test plan also describes how each analyzer error contributes to the overall emission rate error. An example follows: Assume the stack flow rate is 10,507 dry standard cubic feet per hour (dscfh) and the NOx concentration is equal to the analyzer's 100 ppm span. Pollutant mass flow rate is the concentration multiplied by the exhaust stack flow rate (Eqn. 1, Section 2.3.1). The corresponding NOx emission rate is 0.125 lb/h. Seven percent of this is 0.0088 lb/h, so the NOx lb/h determination must be accurate to ± 0.0088 lb/h to meet this DQO. Table 3.1 summarizes the planned and achieved emission rate DQOs for all the pollutants. The stack flow measurement methods specify pre- and post-test thermocouple calibrations at the average stack gas temperature, as referenced to a NIST-traceable thermometer. The thermocouple and reference thermometer readings must be within 1.5 percent of each other to be acceptable. This temperature measurement error, combined with the Type-S pitot calibration, stack gas moisture measurement, and composition uncertainties yield an overall ±5.0 percent (of reading) volumetric flow rate measurement error [12], The highest NOx, CO, THC, and HAP measurement errors were 2.0 ppm, 1.2 ppm, 2.0 ppm, and 0.6 ppm, respectively. Propagation of these errors with the 5.0 percent stack flow rate error results in an emission rate error to be 0.0048 lb/h or less in all cases. Table 3-1 shows that the tests met DQOs for all criteria and hazardous pollutants. 3.2.5. HAP Destruction Efficiency The test plan specified that HAP destruction efficiency measurement error must be less than 0.5 percent. The plan also describes how actual error achieved requires propagation of multiplicative and additive concentration and flow rate measurement errors. 3-10 ------- The achieved error for each measurement (summarized in Table 3-5) yields an overall destruction efficiency error of 0.01 percent absolute percentage units. The absolute error is relatively small because the total error for HAPemitted and HAPm are very small, or ± 0.173 ± 0.0003 lb/h, respectively. These tests, therefore, met the DQO for HAP destruction efficiency. 3.2.5.1. Liquid Analysis Data Quality The laboratory developed pre- and post-test calibration curves for each HAP constituent using a minimum of three calibration standards. The lab analyzed all calibration levels in duplicate with required agreement within 5.0 percent of the mean of the two injections. Calibration levels bracketed the concentrations of the lean glycol, rich glycol, wastewater, and condensate samples. Lab personnel performed duplicate sample injections. The concentration report is the average of the two injections. Table 3-6 summarizes the highest percent difference observed for lean glycol, rich glycol, and condensate samples. The percent difference for all samples was less than 5 percent, which met the specified goal. 3-11 ------- Table 3-5. Destruction Efficiency Error Determination Measurement Avg. Result Measurement Error Source / Comment Relative (%) Absolute" HAPsin Lean Glycol Stream Flow Rate Mean gpm 3.753 ±0.4 ±0.015 Accuracy of ultrasonic flow meter Concentration Cllean lb/gal 0.002 ±25.25 ± 0.0004 Weighted average lean glycol concentration error for all HAP constituents Mass Emission Rate HAPiem lb/h 0.368 ±25.25 ±0.093 Error propagation for multiplication function HAPsin Rich Glycol Stream Flow Rate Vrich gpm 3.912 ±0.9 ±0.035 Error for lean glycol flow rate plus 0.5% error assigned to other measurements (e.g., water content, density) Concentration C||L|| lb/gal 0.040 ± 1.25 ±0.001 Weighted average rich glycol concentration error for all HAP constituents Mass Emission Rate HAPrich lb/h 9.462 ± 1.54 ±0.145 Error propagation for multiplication function HAPta lb/h 9.094 ± 1.90% ±0.173 Error propagation for subtraction function HAPsin Wastewater Flow Rate ^Wastewater gpm 0.106 ±0.6 ±0.0006 Assigned as the 95%-confidence interval of wastewater discharge rate Concentration p ^Wastewater lb/gal 0.003 ±0.99 ±0.0000 Weighted average concentration error for all HAP constituents in wastewater Mass Emission Rate HAPwastew ater lb/h 0.022 ± 1.16 ±0.0003 Error propagation for multiplication function HAPsin Condensate3 Flow Rate ^Condensate gpm 0.048 ±0.6 ±0.0003 Assigned as the 95%-confidence interval of wastewater discharge rate Concentration ^Condensate lb/gal 5.693 ± 10.00 ±0.569 Weighted average concentration error for all HAP constituents in condensate Mass Emission Rate I IA I\; , 11 ] d:J 1 ] sate lb/h 16.409 ± 10.02 ± 1.643 Error propagation for multiplication function HAPsin Stack Flow Rate Vstack dscfh 10,507 ±5.0 ±525 Assigned as specified in reference method Concentration C stack ppm tMW 57.469 ± 1.07 ±0.613 Weighted average GC calibration error for all HAP constituents in condensate Mass Rate HAP Stack lb/h 0.002 ±5.11 ±0.0001 Error propagation for multiplication function HAP,.,., lb/h 0.023 ± 1.15 ±0.0003 Error propagation for addition function Intermediate Calculation: HAPemitted/HAPin 0.00256 + 2.21 0.0000566 Error propagation for division function HAP Destruction Efficiency | DE % 99.74 ± 0.00567c 0.0000566 Error propagation for subtraction function a Not used to compute destruction efficiency because HAPs contained in the condensate products is assigned to be controlled. b See right-most "Measurement" column for units. c Rounds to + 0.01%. Table 3-6. Maximum Percent Difference in Duplicate Injection Results n-Hexane Benzene Toluene Ethylbenzene m- and p- Xylene o-Xylene Lean Glycol 0.2% 4.5% 4.2% NA 3.6% NA Rich Glycol 2.9% 1.5% 1.4% 1.7% 1.4% 1.3% Condensate 2.0% 1.3% 1.1% 1.1% 1.3% 1.1% 3-12 ------- The laboratory did not perform duplicate injections of the wastewater samples. The analyst prepared and analyzed a duplicate aliquot for the first sample from each test run with required agreement within 10.0 percent for each analyte. The detailed lab report shows that all wastewater purge-and-trap analyses met this criterion. The laboratory also selected one sample from each batch of lean glycol, rich glycol, and wastewater samples for duplicate preparation and analysis. Appendix C presents the results. The percent difference between the rich glycol initial and duplicate preparation concentrations ranged between 1.5 and 2.3 for the six HAP constituents analyzed. The percent difference was much greater (16.6 to 45.1 percent) for the lean glycol sample. The reason for the high error is unclear, but because the lean glycol concentration levels were very small, they do not contribute significantly to the overall lean HAP mass flow rate error. The duplicate analysis results for the wastewater sample were similar to rich glycol sample. The benzene, toluene, and m, p-Xylene results presented in Appendix C-2 show large discrepancies between the duplicate lean glycol sample preparations. The analytical laboratory (Enthalpy Analytical, Durham, NC) attributes this to inhomogeneity in the liquids. Benzene and other HAPs do not necessarily mix uniformly in TEG and the mixtures can stratify easily. The laboratory had observed similar differences for samples taken before the test campaign. These differences also appeared in the rich glycol and wastewater duplicate preparations and analyses in the pretest samples. The matrix spike and recovery results imply that the laboratory properly executed the sample dilutions and other procedures. Analysts spiked a 3.75-ml aliquot of a lean glycol sample and 3.5-ml aliquots of a rich glycol and a condensate sample with known amounts of the target analytes. They then analyzed the spiked samples. Appendix C summarizes the spike amounts and the resulting recovery efficiencies. All spike recovery efficiencies were between 88.1 and 109 percent. The lab prepared a stock solution containing 80 ig/mL of all six wastewater analytes. The analyst added 25 uL of this prepared solution to 2.5 mL of a 1001-fold dilution of sample 1 (Run 1). Appendix C summarizes the results. The recovery efficiencies ranged from 104 to 122 percent. The GHG Center submitted three "blind" audit samples for analysis. Each contained benzene concentrations similar to those expected in the glycol and condensate samples. Table 3-7 summarizes the percent difference between the reported and certified concentrations. The results suggest that the laboratory under-reported benzene in the rich and lean glycol and over-reported it in the condensate. This could have affected the mass balance discussed in Section 2.3.2. Table 3-7. Benzene Audit Results Blind Sample ID Certified Concentration As-Analyzed Concentration Percent Difference ig/mL ig/mL B1090309 200 187 -6.5 B3010280 2,000 1,799 -10.1 B3010279 20,000 20,833 4.2 3-13 ------- This page intentionally left blank. 3-14 ------- 4.0 TECHNICAL AND PERFORMANCE DATA SUPPLIED BY ENGINEERED CONCEPTS, LLC Note: This section provides an opportunity for Engineered Concepts, LLC to provide additional comments concerning the OLD and its features not addressed elsewhere in this report. The GHG Center has not independently verified the statements made in this section. The QLD process can be incorporated by retrofitting dehydrators presently installed in the field or by integrating the process into the design of new dehydrators. Either package will produce a hydrocarbons emissions control system eliminating the need for auxiliary equipment such as an effluent condenser, flare stack, or thermal oxidizer. The QLD process covered by this report utilizes a condensing water exhauster to super-dry the process glycol. This allows high dew point depressions and efficient sales gas dehydration. The condensing water exhauster technology replaced the gas stripping employed for this purpose in the previous reboiler used at this site. Elimination of the gas stripping reduced gas consumption by more than 27 mscfd. Total still column vent emissions from the previous reboiler, including all of the gas used for gas stripping, were collected and routed to a thermal oxidizer. For the QLD process to operate properly, the burner system must be able to throttle over the entire firing range. The QLD system uses specially designed throttling burners first introduced by Olman Heath Company. For new dehydrators incorporating the QLD system, throttling burners will be supplied with the package. On retrofit dehydrators the existing burners may need to be replaced with throttling burners. Because the QLD process collects and compresses the hydrocarbons, these vapors are fed directly into the standard reboiler fuel train with only minor modifications. Alternately, the vapors can also be routed through a low pressure fuel line to other equipment at the site. This is a significant improvement over systems that collect the vapors at or near atmospheric pressure. The host site had electricity available. Where electricity is not available (such as at remote wellhead locations) the QLD system incorporates an electric engine/generator set capable of producing 5 kW of 240/480 VAC power. The engine/generator set is rated for 40,000 hours of continuous service and uses natural gas for fuel. The condensing water exhauster and side stream glycol cooling are able to save approximately $12,500 natural gas annually (based on $2.00 per mscf). This analysis assumes: • TEG concentration of 99.8 percent using Nb=l for a "Stahl" Stripping Column, • 3 scf stripping gas per gallon of TEG circulated (Gas Processors Suppliers Association, Eleventh Edition, 1998, Figure 20-65) The following table illustrates a full analysis of the typical utility consumption and QLD emissions as compared to a conventional dehydration system. 4-1 ------- Conventional Dehydrator QLD Lean TEG circulation rate, gpm (1) 4 4 Reboiler fuel required, Btu per day (1) (11.8 mm) (13.4 mm) Pump used Kimray electric Electric Make-up fuel consumed, Btu per day NHV (1) (2) 0 (6.5 mm) negligible (3) Gas required to power Kimray pump, scfd (4) 32,256 0 0 Excess flash gas NHV, Btu per day (5) (40.1 mm) 0 0 Gas stripping required, scfd (6) 17,280 17,280 0 Gas stripping NHV, Btu per day (19.3 mm) (19.3 mm) 0 Power required for pump, hp 0 3.8 3.8 Power required for circ pump, hp 0 0 6.3 Power required for fan cooler, hp 0 0 10 Total power consumed by motors, hp 0 3.8 20.1 Total energy consumed by motors, Btu / day (7) 0 (0.8 mm) (4.1 mm) Condensate recovered, BPD negligible (8) negligible (8) 2.3 Condensate recovered, Btu per day negligible negligible 11.4 mm Net energy consumed by process, Btu per day (9) (71.2 mm) (31.9 mm) (6.1 mm) Hydrocarbon emissions, lbs per day (10) 3437 1715 negligible (11) (1) Based on assumed reboiler firing efficiency of 50 percent and for design basis of 25 mmscfd at 1000 psig, 120 °F inlet gas temperature and 99.8 percent TEG by weight. Figures are based on BRE Prosim modeling program results. (2) Assumes that gas from flash separator is routed to reboiler burner. Flash gas would include gas used to power Kimray pump (if applicable). (3) QLD required essentially zero makeup fuel from the plant system. (4) Kimray power gas is 5.6 scf per gallon at 1000 psig. (5) Flash gas in excess of that required to fire the reboiler. (6) Stripping gas rate is 3 scf per gallon based on using packed gas stripping column and 99.8 percent wt TEG. (7) For QLD, assume 20.1 total horsepower, 24-hour operation, 2545 Btu per horsepower, and 30 percent efficiency. Total energy usage is: 4.1 mmBtu per day = 20.1 * 24 * 2545 0.3 * 1000000 (8) For modeling purposes only it was assumed that a condenser was installed on still column effluent outlet and a condenser temperature of 120 °F. (9) Summed heat values: Condensate minus the sum of excess flash gas, stripping gas, reboiler fuel, and pump power consumption (10) Still column emissions after condenser plus excess gas from flash separator. Includes all hydrocarbon emissions (BTEX, VOCs, HAPs, methane etc). (11) Miniscule quantities of hydrocarbons were dissolved in the condensed water phase. It is apparent that QLD outperforms a conventional dehydrator based on energy consumption and emissions. The QLD system designers estimated that a conventional dehydrator at this site would require a Kimray PV -type gas-assisted glycol pump. The Kimray Oil and Gas Equipment Controls Catalog, Section G, 4-2 ------- Page 8, states that this pump would use 5.6 scf of gas per gallon of glycol circulated at 1000 psig. At four gallons per minute, total daily usage would be: 32256 scfd = 5.6 * 4 * 60 * 24 Annual gas savings, based on $2.00 per mscf, would be: $23546 = (32256/1000) * 2.00 * 365. This contrasts with the $14,600.00 estimated in Section 1.2. The reader should note that this analysis is conservative because natural gas prices have recently risen to above $5.00/mscf in some areas. 4-3 ------- This page intentionally left blank. 4-4 ------- 5.0 REFERENCES [1] Methane Emissions from the Natural Gas Industry: Volume 2, Technical Report; EPA-6.00/R-96- 080b, U.S. Environmental Protection Agency, National Risk Management Research Laboratory: Research Triangle Park, NC, Jun. 1996. [2] Methane Emissions from the Natural Gas Industry: Volume 1, Executive Summary, EPA-6.00/R-96- 080a, U.S. Environmental Protection Agency, National Risk Management Research Laboratory: Research Triangle Park, NC, Jun. 1996. [3] National Emissions Standards for Hazardous Air Pollutants for Source Categories: Oil and Natural Gas Production and Natural Gas Transmission and Storage—Background Information for Proposed Standards', EPA-453/R-94-079a, U.S. Environmental Protection Agency: Office of Air Quality Planning and Standards, Research Triangle Park, NC, Apr. 1997. [4] Preliminary Assessment of Air Toxic Emissions in the Natural Gas Industry, Phase I, Topical Report, GRI-94/0268, Gas Research Institute: Chicago, IL, 1994. [5] National Emission Standards for Hazardous Air Pollutants for Source Categories, Subpart HH— National Emission Standards for Hazardous Air Pollutants from Oil and Natural Gas Production Facilities', 40 CFR 63, U.S. Environmental Protection Agency: Washington, DC, Jun. 17 1999. [6] Test and Quality Assurance Plan—Engineered Concepts, LLC Quantum Leap Dehydrator, Southern Research Institute GHG Gas Technology Center: Research Triangle Park, NC, Jun. 2002. [7] GRI's Environmental Program in Glycol Dehydration of Natural Gas; www.gastechnologv.org/pub/oldcontent/tech/ets/glydehy/glytop.htm. Gas Technology Institute: Chicago, IL, Mar. 2002. [8] Atmospheric Rich/Lean (ARL) Method for Determining Glycol Dehydrator Emissions; Gas Research Institute: Chicago, IL, Mar. 1995. [9] GRI Topical Report-Glycol Dehydrator Emissions: Sampling and Analytical Methods and Estimation Techniques, Volume 1, Appendix A: Atmospheric Rich/Lean Glycol Method Standard Procedure; Gas Research Institute: Chicago, IL, 1995. [10] Glycol Dehydrator Emissions: Sampling and Analytical Methods and Estimation Techniques; Gas Research Institute: Chicago, IL, 1995. [11] Pocket guide to Chemical Hazards; U.S. Department of Health and Human Services: Washington, DC, 1990. [12] Shigehara, R.T., Todd, W.F., and W.S. Smith. Significance of Errors in Stack Sampling Measurements; presented at the annual meeting of the Air Pollution Control Association: St. Louis, MO, 1970. [13] Skoog, Douglas A., and Donald M. West. Fundamentals of Analytical Chemistry, 4th Edition; CBS College Publishing: Philadelphia, PA, 1982. 5-1 ------- This page intentionally left blank. 5-2 ------- APPENDIX A Appendix A-1. Rich Glycol Flow Rates A-l ------- Appendix A-l Rich Glycol Flow Rates The ARL method involves: • Measurement of chemical concentrations in the lean glycol (lb/gal) • Measurement of chemical concentrations in the rich glycol (lb/gal) • Measurement of the lean glycol volumetric flow rate (gpm) • Calculating the chemical concentration differences (lb/gal) • Multiplying the concentration difference by the lean glycol flow rate to yield the chemical's mass flow rate (lb/min) The calculated mass flow rate for each compound is assigned to be the same in both streams (rich and lean). This approach assumes that mass contribution from water present in the rich glycol is negligible in the overall mass balance. The rich glycol volumetric flow will always be slightly greater than the lean glycol flow because of added water, BTEX, and other hydrocarbons absorbed from the natural gas stream. The reboiler and still column in the QLD system remove the diluents (thereby producing the lean glycol) upstream of the flow measurement device. The ARL method, therefore, slightly under-reports actual mass flow for the chemicals of interest because it assumes that the lean and rich glycol flows are identical. A more accurate approach is to estimate the rich glycol flow rate by correcting for the chemical species present in the rich stream. In fact, the GRI-GLY Calc dehydrator emissions modeling program includes such a correction. The key to implementing this approach is that while the water, BTEX, and hydrocarbon concentrations are different between the rich and lean glycol flows, the stream's TEG mass content does not change (except under process upset conditions). The following glycol stream properties were obtained to quantify the rich glycol flow rate: • Rich and lean glycol density (g/ml) • Rich and lean glycol water content (weight percent) • Rich and lean glycol total hydrocarbons content (ig/ml) This flow rate is used in Equation 3 to more accurately report HAPs entering the QLD system boundary. The following paragraphs discuss the analysis, provide an example, and present the test results. The first step quantified the TEG mass flow rate throughout the system. The lean glycol mass flow rate was: m, =V, p, Eqn. A-l lean lean ~ lean i where: mlean = lean glycol mass flow rate (ig/min) Vkan = lean glycol volumetric flow rate (measured by the Ultrasonic meter), gpm x 3785.41 = (ml/min) plean = lean glycol density (i g/ml) The lean glycol mass flow rate represented the sum of the water, hydrocarbons, and TEG mass flows. The TEG mass flow rate was therefore: A-2 ------- m teg— ™ lean (™H20Jean + ™mCJean ) Eqn. A-2 where: mTEG = TEG mass flow rate (ig/min) ™ mo jean = water mass flow rate in the lean glycol (i g/min) Mwcjean = lolal hydrocarbon mass flow rate in the lean glycol (ig/min) The laboratory reported weight percent water and total hydrocarbon mass per unit volume. These data, combined with the measured lean glycol volumetric flow rate, yield the water and total hydrocarbon mass flow rates as follows: H2O Jean (H 0 ^ n 2 "wt%Jean ioo u V, lean Eqn. A-3 = {mclean)vle, Eqn. A-4 where: h7o> 2^wt%,lean = lean glycol water content (weight percent) mc, = concentration of hydrocarbons in lean glycol (i g/ml) BTEX and hexanes constitute the majority of these hydrocarbons. All test runs showed that their area in the lean glycol sample chromatograms averaged from 58.3 to 72.1 percent of all hydrocarbon peaks recorded. The laboratory did not speciate other hydrocarbons, but they state that the FID response to these hydrocarbons will be linear. Therefore, 176 ig/ml of BTEX and hexanes with an area percent of 62.2 yields total hydrocarbons of 1/0.622 x 176, or 282 ig/ml. Analysts computed the average area percent of the BTEX and hexanes for each test run and applied the concept according to the following equations = ZHAPle, Area %, Eqn. A-5 where: IHAPlean = summation of BTEX and hexanes for each sample, average value for all samples in each run (ig/ml) Area%iean = average BTEX and hexanes area percent for all samples in each TEG mass flow rate is: ™TEG — lean ( H (1 ^ 11 2^wt%Jean YJJCJ f^lean 100 ^^lean lean Eqn. A-6 Rich glycol volumetric flow rate was derived from the following equations: ^ TEG,rich rich TEG,rich Vrichpri, Eqn. A-7 A-3 ------- m. Vrich = —1222 Eqn. A-8 ^ TEG,rich Prich where: cteg, rich = TEG concentration in the rich glycol (proportion) = rich glycol mass flow rate (ig/min) Vrlch = rich glycol volumetric flow rate, ml/min -7- 3785.41 = (gpm) prich = rich glycol density (ig/ml) Rich glycol TEG concentration was: ^ H2^wt%,rich ^ \- t Prich inn Prich rich cteg,rich = Eqn. A-9 Prich where: H20wP/orich = rich glycol water content (weight percent) mcnch = summation of all rich glycol hydrocarbons (i g/ml) rich = rich glycol density (ig/ml) The HHC rich value in equation A-4 was the average of the summed BTEX and hexanes corrected to the area percent hydrocarbons. Substituting Equation A-9 into Equation A-8 yields a rich glycol volumetric flow rate of: Vnch = Hn mTE° Eqn. A-10 ^ ii 2^wt%,rich ^ ^r7/_, Prich |qq Prich ~ rich A-4 ------- The following table provides a sample calculation for Run 1, taken from the field data. Table A-l. Rich Glyco Volumetric Flow Rate Calculation for Run 1 Parameter Units Value ^lean gpm 3.7688 ^'lean ml/min 14266.4 Plean ig/ml 1.125 x 106 H20wt%,lean wt% 0.552 UUP, lean ig/ml 176 Area%iean area% 62.2 mc, lean ig/ml 282 rh TEG ig/min 1.596x 1010 Prich ig/ml 1.119xl06 H20 Mit%rich wt% 3.25 UUP rich ig/ml 5011 Area%nch area% 80.1 mc rich ig/ml 6256 ^'rich gpm 3.916 This example shows that the additional mass of water and hydrocarbons results in the rich glycol flow rate to be about 4 percent higher than the lean glycol flow rate. Table A-2 presents the results for each test run. A-5 ------- Version 1.2-August 13, 2003 DRAFT Do not cite, quote, use, or distribute without written permission from GHG Center Table A-2. Determination of Rich Glycol Flow Rates Runl VLean VLean RllOLean RllOLean H2C>Lean HAPLean HAP HC niTEG RllORich RllORich H2C>Rjch HAPRich HAP HC VRich Area%Lean T OtalLean Area"...,.,-. T otalRich Sample# gpm ml/min SamplelD g/ml ig/ml Sample wt% ig/ml AreaPct ig/ml ig/min Sample g/ml ig/ml Sample wt% ig/ml AreaPct ig/ml gpm ID ID ID la 2001 0.486 194 70.0 1001 3.35 5357 80.0 2 4002 1.125 2002 0.512 154 58.3 3002 1.119 1002 3.31 4644 79.9 2a 2003 0.539 189 58.4 1003 3.05 5547 80.4 3 2021 0.672 166 1021 3.27 4497 Averages 3.7688 14266.4 1.125 1.1250 0.552 176 62.2 282 1.596 1.119 1.1190 3.25 5011 80.1 6256 3.9161 x 10 6 x 10 10 x 10 6 Run 2 VLean VLean RhOLean RhOLean H2C>Lean HAPLean HAP HC niTEG RllORich RllORich H2C>Rjch HAPRich HAP HC VRich Area%Lean T OtalLean Area"...,.,-. T otalRich Sample# gpm ml/min SamplelD g/ml ig/ml Sample wt% ig/ml AreaPct ig/ml ig/min Sample g/ml ig/ml Sample wt% ig/ml AreaPct ig/ml gpm ID ID ID la 2005 0.601 224 61.8 1005 3.38 4435 78.3 2 4006 1.136 2006 0.625 203 57.7 3006 1.12 1006 3.2 4608 79.7 2a 2007 0.626 198 60.7 1007 3.13 4187 81.1 3 2008 0.564 201 62.5 1008 3.12 4495 79.2 Averages 3.6035 13640.8 1.136 1.1360 0.604 206 60.7 340 1.540 1.120 1.1200 3.21 4431 79.6 5569 3.7716 x 10 6 xlO10 x 10 6 Run3 VLean VLean RllOLean RhOLean H2C>Lean HAPLean HAP HC niTEG RllORich RllORich H2C>Rjch HAPRich HAP HC VRich Area%Lean TOtalLean Area"..,,.. TotalRich Sample# gpm ml/min SamplelD g/ml ig/ml Sample wt% ig/ml AreaPct ig/ml ig/min Sample g/ml ig/ml Sample wt% ig/ml AreaPct ig/ml gpm ID ID ID la 2009 0.575 201 61.8 1009 3.11 5096 79.1 2 4010 1.132 2010 0.684 203 58.8 3010 1.122 1010 3.08 4928 78.6 2a 2011 0.564 193 72.1 1011 3.24 4968 79.1 3 2012 0.583 228 59.9 1012 3.11 5118 81.3 Averages 3.8871 14714.1 1.132 1.1320 0.602 206 63.2 326 1.655 1.122 1.1220 3.14 5027 79.5 6322 4.0466 x 10 6 x 10 10 x 10 6 6 ------- APPENDIX B Emissions Testing QA/QC Results Appendix B-l. Summary of Reference Method Calibration Error Determinations B-2 Appendix B-2. Summary of Reference Method System Bias and Drift Checks B-3 Appendix B-3. Summary of GC/FID Calibration Results B-4 B-l ------- Appendix B-l. Summary of Daily Reference Method Calibration Error Determination Range Value Response Difference Calibration Date Gas (ppm for NOx, CO, and THC; % for O2 and CO2) Error (% of Span)* 4/30/03 NOx 100 0.0 0.09 0.09 0.09 (Runs 1 - 3) 25.1 25.19 0.09 0.09 44.6 44.67 0.07 0.07 84.5 85.44 0.94 0.94 CO 100 0.0 0.00 0.00 0.00 24.9 23.27 1.63 1.63 45.3 43.87 1.43 1.43 90.8 88.86 1.94 1.94 co2 25 0.0 0.03 0.03 0.12 11.96 11.72 0.24 0.96 4.00 3.81 0.19 0.76 20.0 19.83 0.17 0.68 o2 25 0.0 0.02 0.02 0.08 11.97 12.12 0.15 0.60 4.00 4.10 0.10 0.40 21.0 21.28 0.28 1.12 Error (% of cal qas)* THC 100 0.0 0.47 0.47 25.5 25.17 0.33 1.29 45.7 44.63 1.07 2.34 89.0 90.3 1.30 1.46 * Allowable calibration error is 2% of span. B-2 ------- Appendix B-2. Summary of Reference Method System Bias and Drift Checks Analyzer Spans: NOx = CO = THC = 100 ppm, C02 = 02 = 25% Initial Run Number Cal 1 2 3 NOxZero System Response (ppm) 0.08 0.59 0.89 0.38 0.09 System Bias (% span) -0.01 0.50 0.80 0.29 Drift (% span) na 0.51 0.30 0.51 NOx Mid (Hi) System Response (ppm) 84.01 83.51 83.44 83.84 85.44 System Bias (% span) -1.43 -1.93 -2.00 -1.60 Drift (% span) na 0.50 0.07 0.40 CO Zero System Response (ppm) 0.00 0.10 0.10 0.00 0.00 System Bias (% span) 0.00 0.10 0.10 0.00 Drift (% span) na 0.10 0.00 0.10 CO Mid System Response (ppm) 43.40 44.90 45.10 45.10 43.87 System Bias (% span) -0.47 1.03 1.23 1.23 Drift (% span) na 1.50 0.20 0.00 C02 Zero System Response (ppm) 0.30 0.20 0.10 0.10 0.03 System Bias (% span) 1.08 0.68 0.28 0.28 Drift (% span) na 0.40 0.40 0.00 C02 Mid System Response (ppm) 11.30 11.45 11.30 11.42 11.72 System Bias (% span) -1.68 -1.08 -1.68 -1.20 Drift (% span) na 0.60 0.60 0.48 02 Zero System Response (ppm) 0.13 0.20 0.25 0.06 0.02 System Bias (% span) 0.44 0.72 0.92 0.16 Drift (% span) na 0.28 0.20 0.76 02 Mid System Response (ppm) 12.22 12.22 12.13 12.04 12.12 System Bias (% span) 0.40 0.40 0.04 -0.32 Drift (% span) na 0.00 0.36 0.36 THC Zero System Response (ppm) 0.00 0.03 0.00 0.00 0.47 System Bias (% span) -0.47 -0.44 -0.47 -0.47 Drift (% span) na 0.03 0.03 0.00 THC Mid System Response (ppm) 46.57 46.60 46.00 45.33 44.63 System Bias (% span) 1.94 1.97 1.37 0.70 Drift (% span) na 0.03 0.60 0.67 Allowable system bias is 5% span, allowable drift is 3% span. B-3 ------- Appendix B-3. Summary of GC/FID Calibration Results pre test low gas max dif- relative absolute ref value inj 1 inj 2 inj 3 avg diff 1 diff 2 diff 3 ference error% error ppm ppm Methane 5.02 549 526 542 539.00 10.00 13.00 3.00 13.00 2.41 0.12 n-Hexane 5.03 3826 3826 4068 3906.67 80.67 80.67 161.33 161.33 4.13 0.21 Benzene 4.9 3984 3984 3736 3901.33 82.67 82.67 165.33 165.33 4.24 0.21 Toluene 4.8 4014 4014 4011 4013.00 1.00 1.00 2.00 2.00 0.05 0.00 Ethylbenzene 4.5 3748 3748 3879 3791.67 43.67 43.67 87.33 87.33 2.30 0.10 o-Xylene 4.8 3558 3558 3507 3541.00 17.00 17.00 34.00 34.00 0.96 0.05 m-Xylene 4.2 3049 3049 3164 3087.33 38.33 38.33 76.67 76.67 2.48 0.10 pre test mid gas ref value inj 1 inj 2 inj 3 avg diff 1 diff 2 diff 3 max dif- repeatability absolute % error ppm ppm ference Methane 50.2 5701 5402 5750 5617.67 83.33 215.67 132.33 215.67 3.84 1.93 n-Hexane 50.4 37102 35023 34126 35417.00 1685.00 394.00 1291.00 1685.00 4.76 2.40 Benzene 50.6 35873 37287 36962 36707.33 834.33 579.67 254.67 834.33 2.27 1.15 Toluene 48.7 39496 43519 41503 41506.00 2010.00 2013.00 3.00 2013.00 4.85 2.36 Ethylbenzene 48.7 41149 43781 41972 42300.67 1151.67 1480.33 328.67 1480.33 3.50 1.70 o-Xylene 42.7 37977 41546 39962 39828.33 1851.33 1717.67 133.67 1851.33 4.65 1.98 m-Xylene 45.3 36631 39616 37117 37788.00 1157.00 1828.00 671.00 1828.00 4.84 2.19 pre test hi gas max dif- repeatability absolute ref value inj 1 inj 2 inj 3 avg diff 1 diff 2 diff 3 % error ppm ppm ference Methane 100 11384 10821 11900 11368.33 15.67 547.33 531.67 547.33 4.81 4.81 n-Hexane 101 67628 70172 73001 70267.00 2639.00 95.00 2734.00 2734.00 3.89 3.93 Benzene 99.1 71325 74034 72208 72522.33 1197.33 1511.67 314.33 1511.67 2.08 2.07 Toluene 99.2 77633 78861 77587 78027.00 394.00 834.00 440.00 834.00 1.07 1.06 Ethylbenzene 99.2 73475 72497 76150 74040.67 565.67 1543.67 2109.33 2109.33 2.85 2.83 o-Xylene 99.2 73166 71481 74490 73045.67 120.33 1564.67 1444.33 1564.67 2.14 2.12 m-Xylene 99.2 71269 68884 71848 70667.00 602.00 1783.00 1181.00 1783.00 2.52 2.50 post test mid gas max dif- repeatability absolute ref value inj 1 inj 2 inj 3 avg diff 1 diff 2 diff 3 % error ppm ppm ference Methane 50.2 5975 5789 5764 5842.67 357.33 171.33 146.33 357.33 6.12 3.07 N-Hexane 50.4 36136 37704 36739 36859.67 719.00 2287.00 1322.00 2287.00 6.20 3.13 Benzene 50.6 38482 38248 38099 38276.33 1774.67 1540.67 1391.67 1774.67 4.64 2.35 Toluene 48.7 42821 43477 42730 43009.33 1315.00 1971.00 1224.00 1971.00 4.58 2.23 Ethylbenzene 48.7 44238 44035 43208 43827.00 1937.33 1734.33 907.33 1937.33 4.42 2.15 o-Xylene 42.7 40512 42657 41642 41603.67 683.67 2828.67 1813.67 2828.67 6.80 2.90 m-Xylene 45.3 39301 39630 38877 39269.33 1513.00 1842.00 1089.00 1842.00 4.69 2.12 Overall stack gas HAPs concentration error is an additive function of the individual HAPs concentration errors. Such errors compound as the square root of the summed individual absolute errors, squared [13], The following table shows the error propagation for stack gas HAPs. Each individual concentration was taken as 0.1 ppm because this was the method's lower detection limit. The relative errors, upon which the absolute errors are based, are taken from the "pre-test low gas" calibrations summarized above. Stack Gas HAPs Error Propagation Chemical Molecular Weight, PPM Mass, Relative Error, Absolute lb/lb.mol ig/m3 Percent Error, ig/m3 Hexane 86.18 0.1 8.618 4.13 0.3559 Benzene 78.00 0.1 7.800 4.24 0.3307 Toluene 92.00 0.1 9.200 0.05 0.0046 Ethylbenzene 106.17 0.1 10.617 2.30 0.2442 p-Xylene 106.17 0.1 10.617 2.48 0.2633 o-Xylene 106.17 0.1 10.617 0.96 0.1019 Compounded Absolute Error = square soot (sum [individual error]2) 0.6127 B-4 ------- APPENDIX C Liquid Analysis QA/QC Results Appendix C-l. Rich Glycol—Duplicate Sample Preparation and Spike Analysis Results C-2 Appendix C-2. Lean Glycol—Duplicate Sample Preparation and Spike Analysis Results C-3 Appendix C-3. Wastewater—Duplicate Sample Preparation and Spike Analysis Results C-4 Appendix C-4. Condensate—Spike Analysis Results C-5 Appendix C-5. Rich and Lean Glycol Moisture Content—Duplicate Analysis Results C-6 C-l ------- Appendix C-l. Rich Glycol-Duplicate Sample Preparation and Spike Analysis Results Duplicate Analysis Spike Analysis Sami )le ID Concentration (na/mL) Sam ale ID Spike Amount Catch Weight - Native Amount Catch Weight - Spiked Sample 0/ /o Recoverv Run No. Sample No. Initial Duplicate % Dif- ference Run No. Sample No. iq iq iq n-Hexane Run 1 2 107 ND 106 ND 1.5 Run 2 1 35.9 78.9 114 98.1 Benzene Run 1 '2 1,425 1,454 2.1 Run 2 1 437 861 1334 108.0 Toluene Run 1 2 2,394 2,443 2 Run 2 1 734 1282 2022 101.0 Ethyl-benz sne Run 1 2 51.5 52.7 2.3 Run 2 1 19.0 26.2 45.1 99.3 m- and p-Xylene Run 1 2 546 558 2.2 Run 2 1 182 277 457 99.1 o-Xylene Run 1 2 121 124 2.3 Run 2 1 38.4 62.2 100 98.5 ND Non-detect or analytical result below the minimum detection limit (MDL) J Analytical result between the MDL and the limit of quantification (LOQ) MDL = 1.00 ug/mL LOQ = 2.00 ug/mL C-2 ------- Appendix C-2. Lean Glycol-Duplicate Sample Preparation and Spike Analysis Results Duplicate Analysis Spike Analvsis Sam Die ID Concentration (ng/mL) Sam ale ID Spike Amount uatcn Weight - Native Amount uatcn Weight - Spiked Sample 0/ /o Recoverv Run No. Sample No. Initial Duplicate % Difl Run No. Sample No. ia ia ia n-Hexane kun 2 '2 8.00 ND 8.00 ND 0.0 Kun '6 3 2GA 0.0 ¦it.t mu Benzene kun 2 2 54.0 8b.4 4t).1 Kun 3 3 DZ4 iuy.u aa. ( Toluene kun 2 2 bb.D W2 4 2.3 Kun 6 6 bl.8 bb.U 11ZU 88.1 Ethyl benzene kun '2 2 b.O J 8.0 0.0 Kun '6 '6 i>8.0 0.0 24.1 Q1Q m- and p- kun 2 2 ID.b lb.4 Ib.b Kun 3 2B.U 11.& 3&.b bZb o-Xylene kun 2 2 b.U J b.U U.U Kun 6 6 I'd. b U.U 24.2 94./ ND Non-detect or analytical result below the minimum detection limit (MDL) J Analytical result between the MDL and the limit of quantification (LOQ) MDL = 1.00 ug/mL LOQ = 2.00 ug/mL C-3 ------- Appendix C-3. Wastewater-Duplicate Sample Preparation and Spike Analysis Results Duplicate Analysis Spike Analysis Sam Die ID Concentrat ion (na/mlJ Spike Amount Catch Weight - Native Amount Catch Weight - Spiked SamDle 0/ /o Recovery Run No. Sample No. Initial Duplicate % Dif- ference ia ia ig n-Hexane Run 1 1 801 ND 803 ND 0 200 0 210 105 Benzene Run 1 1 200,489 198,778 0.9 200 501 745 122 Toluene Run 1 1 104,976 102,520 2.4 200 262 478 108 Ethyl-benzem Run 1 1 971 J 880 ND 9.8 200 2.43 211 104 m- and p-Xyk rie Run 1 1 8,352 8,176 2.1 200 20.9 232 105 o-Xylene Run 1 1 2,829 J 2,679 5.4 200 7.07 215 104 ND Non-detect or analytical result below the minimum detection limit (MDL) J Analytical result between the MDL and the limit of quantification (LOQ) MDL = 2.00 ng LOQ = 8.00 ng C-4 ------- Appendix C-4. Condensate Product-Spike Analysis Results Spike Analysis Sarrmle ID Spike Amount Catch Weight- Native Amount Catch Weight - Spiked Sample % Recovery Run No. Sample No. ¦g ¦g ¦g n-Hexane Run 2 1 35.9 34.2 69.5 98.4 Benzene Run 2 1 437 721 1195 109.0 Toluene Run 2 1 734 1326 2071 102.0 Ethyl-bei izefaen 2 1 19.0 28.6 48.8 106.0 m-and p- XyfciDft 2 1 182 303 487 101.0 o-Xylene Run 2 1 38.4 65.9 105 102.0 MDL = 1.00ug/mL LOQ = 2.0GLig/mL C-5 ------- Appendix C-5. Rich and Lean Glycol Moisture Content-Duplicate Analysis Results RICH GLYCOL % Dif- ference LEAN GLYCOL % Dif- ference Sample ID Moisture Content Moisture Content Run No. Sample No. Initial Duplicate Initial Duplicate Run 1 1 3.380 3.310 -1.05 0.487 0.485 -0.21 2 3.100 3.050 -0.81 0.508 0.516 0.78 2a 3.050 3.050 0.00 0.550 0.531 -1.76 3 3.300 3.250 -0.76 0.681 0.664 -1.26 Run 2 1 3.350 3.400 0.74 0.608 0.595 -1.08 2 3.180 3.220 0.63 0.616 0.634 1.44 2a 3.120 3.140 0.32 0.634 0.619 -1.20 3 3.120 3.120 0.00 0.558 0.570 1.06 Run 3 1 3.100 3.130 0.48 0.566 0.584 1.57 2 3.100 3.060 -0.65 0.692 0.676 -1.17 2a 3.240 3.230 -0.15 0.561 0.567 0.53 3 3.080 3.140 0.96 0.589 0.578 -0.94 -0.02 -0.19 NOTE: % Difference = — xlOO -100 ^ Average (Initial, Duplicate) J C-6 ------- APPENDIX D Pre-Test Makeup Natural Gas Analysis Data D-l ------- Appendix D-l. Pre-Test Makeup Natural Gas Analysis EMPACT ANALYTICAL SYSTEMS, INC 997 US HI WAY 85 BRIGHTON, CO 80603 (303) 637-0150 EXTENDED NATURAL GAS ANALYSIS (*DHA) PROJECT NO. : 0302069 ANALYSIS NO. : 01 COMPANY NAME : SRI ANALYSIS DATE: FEBRUARY 28, 2003 ACCOUNT NO. : P.O. RD307I2 SAMPLE DATE : FEBRUARY 26,2003 PRODUCER : TO: LEASE NO. CYLINDER NO. : 205 NAME/DESCRIP : MAKE-UP GAS #3 @ 13:16 ***FIELD DATA*** SAMPLED BY: RGR AMBIENT TEMP.: SAMPLE PRES. : GRAVITY : SAMPLE TEMP. : COMMENTS GPM@ GPM@ COMPONENT MOLE % MASS % 14.65 14.73 HELIUM 0.016 0.003 ... HYDROGEN 0.000 0.000 ... OXYGEN/ARGON 0.000 0.000 ... NITROGEN 0.386 0.502 ... C02 3.013 6.160 ... METHANE 76.906 57.315 — ETHANE 11.841 16.541 3.1498 3.1670 PROPANE 4.323 8.855 1.1847 1.1911 I-BUTANE 0.816 2.203 0.2655 0.2669 N-BIJTANE 1.422 3.844 0.4461 0.4485 I-PENTANE 0.499 1.672 0.1816 0.1826 N-PENTANE 0.361 1.209 0.1301 0.1308 HEXANES PLUS 0.417 i.696 0.1648 0.1653 TOTALS 100.000 100.000 5.5226 5.5522 BTEX COMPONE> MOL WT% (CALC: GPA STD 2145-94 & TP-17 %14.696 & 60 F) BENZENE 0.019 0.070 BTU % 14.65 14.73 ETHYLBENZENE 0.000 0.000 GROSS DRY REAL : 1222.56 1229.24 TOLUENE 0.007 0.029 GROSS WET REAL : 1201.19 1207.87 XYLENES 0.000 0.001 DENSITY (AIR=1): 0.7454 TOTAL BTEX 0.026 0.100 COMPRESSIBILITY FACTOR 0.99648 *DHA (DETAILED HYDROCARBON ANAL YSIS/NJ1993) ; ASTM D6730 THIS DATA HAS BEEN ACQUIRED THROUGH APPLICATION OF CURRENT STATE-OF-THE-ART AN ALYTICAL TECHNIQUES. THE USE OF THIS INFORMATION IS THE RESPONSIBLE OF THE USER. EMPACT ANALYTICAL SYSTEMS, ASSUMES NO RESPONSIBLITY FOR ACCURACY OF THE REPORTED INFORMATION NOR ANY CONSEQUECES OF ITS APPLICATION. EMPACT ANALYTICAL SYSTEMS, INC 997 US HI WAY 85 BRIGHTON, CO 80603 (303) 637-0150 EXTENDED NATURAL GAS ANALYSIS (*DHA) PROJECT NO. : COMPANY NAME : 0302069 SRI ANALYSIS NO. : ANALYSIS DATE: FEBRUARY 28. 2003 COMPONENT HELIUM HYDROGEN OXYGEN/ARGON 0.016 0.000 0.000 MASS % 0.003 0.000 0.000 GPM 14.65 D-2 ------- Appendix D-l. Pre-Test Makeup Natural Gas Analysis, Cont. NITROGEN 0.386 0.502 ... ... C02 3.013 6.160 ... — METHANE P1 76.906 57.315 — ... ETHANE P2 11.841 16.541 3.1498 3.1670 PROPANE P3 4.323 8.855 1.1847 1.1911 I-BUTANE 14 0.816 2.203 0.2655 0.2669 N-BUTANE P4 1.416 3.823 0.4440 0.4464 2,2 DIMETHYLPROPANE 15 0.006 0.021 0.0021 0.0021 I-PENTANE 15 0.499 1.672 0.1816 0.1826 N-PENTANE P5 0.361 1.209 0.1301 0.1308 2,2 D1METHYLBUTANE 16 0.011 0.042 0.0046 0.0046 CYCLOPENTANE N5 0.014 0.046 0.0041 0.0041 2,3 DIMETHYLBUTANE 16 0.023 0.091 0.0094 0.0094 2 METHYLPENTANE 16 0.091 0.366 0.0376 0.0378 3 METHYLPENTANE 16 0.050 0.199 0.0203 0.0204 N-HEXANE P6 0.092 0.370 0.0376 0.0378 2,2-DIMETHYLPENTAN£ 17 0.002 0.011 0.0009 0.0009 METIIYLCYCLOPENTANE N6 0.033 0.128 0.0117 0.0117 2,4 DIMETHYLPENTANE 17 0.004 0.018 0.0019 0.0019 2,2,3 TRIMETHYI.BUT AN F. 17 0.001 0.003 0.0005 0.0005 BENZENE A6 0.019 0.070 0.0053 0.0053 3,3 DIMETHYLPENTANE 17 0.001 0.004 0.0005 0.0005 CYCLOHEXANE 06 0.022 0.085 0.0075 0.0075 2 METHYLHEXANE 17 0.009 0.042 0.0042 0.0042 2,3 DIMETHYLPENTANE 17 0.003 0.012 0.0014 0.0014 I,I DIMF.THYLCYCLOPENTANE N7 0.002 0.010 0.0008 0.0008 3 METHYLHEXANE 17 0.008 0.035 0.0037 0.0037 LC 3 DIMETHYLCYCLOPENTANE N7 0.002 0.010 0.0008 0.0008 1 ,T 3 DIMETHYLCYCLOPENTANE N7 0.002 0.008 0.0008 0.0008 3 ETHYLPENTANE 17 0.000 0.002 0.0000 0.0000 1 ,T 2 DIMETHYLCYCLOPENTANE N7 0.003 0.012 0.0012 0.0012 N-HEPTANE P7 0.008 0.037 0.0037 0.0037 METHYLCYCLOHEXANE N7 0.010 0.045 0.0040 0.0040 2,2-DlMETHYLHEXANE 18 0.000 0.002 0.0000 0.0000 ETHYLCYCLOPENTANE N7 0.000 0.001 0.0000 0.0000 2,5-DIMETllYLHEXANE 18 0.000 0.001 0.0000 0.0000 2,4-DIMETHYLHEXANE 18 0.000 0.001 0.0000 0.0000 1C,2T,4-TRIMETHYLCYCL0PENTANE N8 o.ooo 0.001 0.0000 0.0000 3,3-DlME 1HYLHEXANE 18 0.000 0.001 0.0000 0.0000 1T,2C,3-TRIMETHYLCYCL0PENTANE N8 0.000 0.001 0.0000 0.0000 TOLUENE A7 0.007 0.029 0.0023 0.0023 2,3-DIMETHYLHEXANE 18 0.000 0.001 0.0000 0.0000 2-MF.THYI.HEPTANE 18 0.000 0.002 0.0000 0.0000 4-ME I'HYLHEP f ANE 18 0.000 0.00 L 0.0000 0.0000 3-METHYLHEPTANE 18 0.000 0.001 0.0000 0.0000 1 C,2T,3-TRIMETH YLCYCLOPENTANE N8 0.000 0.002 0.0000 0.0000 1T.4-DIMETHYLCYCI.OHEXANE N8 0.000 0.001 0.0000 0.0000 1,1-DIMFTHYLCYCLOHEXANE N8 0.000 0.001 0.0000 0.0000 IT,2-DIMFTHYLCYCLOHEXANE N8 0.000 0.001 0.0000 0.0000 N-OCTANE P8 0.000 0.002 0.0000 0.0000 I,3-D1METHYLBENZENE (M-XYLENE) A8 0.000 o'ooi 0.0000 0.0000 TOTALS 100.000 100.000 5.5226 5.5522 EMPACT ANALYTICAL SYSTEMS, INC 997 US HIWAY 85 BRIGHTON, CO 80603 (303) 637-0150 EXTENDED NATURAL GAS ANALYSIS (*DHA) PROJECT NO. : 0302069 COMPANY NAME: SRI ACCOUNT NO. : P.O. RD30712 ANALYSIS NO.: 02 ANALYSIS DATE: FEBRUARY 28,2003 SAMPLE DATE : FEBRUARY 26, 2003 D-3 ------- Appendix D-l. Pre-Test Makeup Natural Gas Analysis, Cont. PRODUCER : TO: LEASE NO. CYLINDER NO. : 265 NAME/DESCRIP : MAKE-UP GAS U\ @ 12:58 ***FIELD DATA *** SAMPLED BY: RGR AMBIENT TEMP.: SAMPLE PRES. : GRAVITY SAMPLE TEMP. : COMMENTS : GPM@ GPM® COMPONENT MOLE % MASS % 14.65 14.73 HELIUM 0.016 0.003 — ... HYDROGEN 0.000 0.000 — ... OXYGEN/ARGON 0.000 0.000 ... NITROGEN 0.376 0.489 ... ... C02 3.024 6.182 ... ... METHANE 76.962 57.345 ... ... ETHANE 11.819 16.508 3.1439 3.1611 PROPANE 4.271 8.749 1.1704 1.1768 l-BUTANE 0.808 2.180 0.2629 0.2643 N-BUTANE 1.405 3.797 0.4408 0.4432 l-PENTANE 0.502 1.681 0.1827 0.1837 N-PENTANE 0.367 1.229 0.1322 0.1329 HEXANES PLUS 0.450 1.837 0.1784 0.1789 TOTALS 100.000 100.000 5.5113 5.5409 (CALC: GP.4 STD 2145-94 & TP-17%14.696 & 60 F) BTU % 14.65 14.73 GROSS DRY REAL : 1222.61 1229.29 GROSS WET REAL: 1201.24 1207.92 DENSITY (AIR=1): 0.7456 COMPRESSIBILITY FACTOR : 0.99651 BTEX COMPONEP MOL: WT% BENZENE 0.019 0.068 ETHYLBENZENE 0.000 0.001 TOLUENE 0.011 0.045 XYLENES 0.001 0.006 TOTAL BTEX 0.031 0.120 *DHA (DETAILED HYDROCARBON ANAL YSIS/NJ1993) ; ASTM D6730 THIS DATA HAS BEEN ACQUIRED THROUGH APPLICATION OF CURRENT STATE-OF-THE-ART ANALYTICAL TECHNIQUES. THE USE OF THIS INFORMA TION IS THE RESPONSIBLITY OF THE USER. EMPACT ANALYTICAL SYSTEMS, ASSUMES NO RESPONSIBLITY FOR ACCURACY OF THE REPORTED INFORMATION NOR ANY CONSEQUECES OF ITS APPLICATION. EMPACT ANALYTICAL SYSTEMS, INC 997 US HI WAY 85 BRIGHTON, CO 80603 (303) 637-0150 EXTENDED NATURAL GAS ANALYSIS (*DHA) PROJECT NO. : 0302069 ANALYSIS NO. : 02 COMPANY NAME : SRI ANALYSIS DATE: FEBRUARY 28, 2003 GPM GPM COMPONENT PIANO # MOLE % MASS % 14.65 14.73 HELIUM 0.016 0.003 HYDROGEN 0.000 0.000 ... OXYGEN/ARGON 0.000 0.000 ... ... NITROGEN 0.376 0.489 ... ... C02 3.024 6.182 ... ... METHANE P1 76.962 57.345 ... ETHANE P2 11.819 16.508 3.1439 3.1611 PROPANE P3 4.271 8.749 1.1704 1.1768 l-BUTANE 14 0.808 2.180 0.2629 0.2643 N-BUTANE P4 1.399 3.776 0.4387 0.4411 2,2 D1METHYLPROPAN E 15 0.006 0.021 0.0021 0.0021 l-PENTANE 15 0.502 1.681 0.1827 0.1837 N-PENTANE P5 0.367 1.229 0.1322 0.1329 2.2 DIMETHYLBUTANE 16 0.011 0.042 0.0046 0.0046 D-4 ------- Appendix D-l. Pre-Test Makeup Natural Gas Analysis, Cont. METHANOL X1 0.003 0.005 0.0004 0.0004 CYCLOPENTANE N5 0.014 0.045 0.0041 0.0041 2,3 DIMETHYLBUTANE 16 0.022 0.090 0.0090 0.0090 2 METHYLPENTANE 16 0.091 0.365 0.0376 0.0378 3 METHYLPENTANE 16 0.050 0.198 0.0203 0.0204 N-HEXANE P6 0.093 0.371 0.0380 0.0382 2,2-DIMETHYLPENTANE 17 0.002 0.011 0.0009 0.0009 METHYLCYCLOPENTANE N6 0.033 0.128 0.0117 0.0117 2,4 DIMETHYLPENTANE 17 0.004 0.019 0.0019 0.0019 2,2,3 TRIMETHYLBUTANF 17 0.001 0.004 0.0005 0.0005 BENZENE A6 0.019 0.068 0.0053 0.0053 3,3 DIMETHYLPENTANE 17 0.001 0.005 0.0005 0.0005 CYCLOHEXANE 06 0.023 0.088 0.0078 0.0078 2 MFTHYLHEXANE 17 0.011 0.050 0.0051 0.0051 2,3 DIMETHYLPENTANE 17 0.003 0.015 0.0014 0.0014 1,1 DIMETHYLCYCLOPENTANE N7 0.002 0.011 0.0008 0.0008 3 METHYLHEXANE 17 0.009 0.044 0.0041 0.0041 l.C 3 DIMETHYLCYCLOPENTANE N7 0.003 0.012 • 0.0012 0.0012 1 ,T 3 DIMETHYLCYCLOPENTANE N7 0.002 0.010 0.0008 0.0008 3 ETHYLPENTANE 17 0.001 0.003 0.0005 0.0005 1,T 2 DIMETHYLCYCLOPENTANE N7 0.003 0.015 0.0012 0.0012 N-HEPTANE P7 0.013 0.059 0.0060 0.0060 1,C 2 DIMETHYLCYCLOPENTANE N7 0.000 0.001 0.0000 0.0000 METIIYLCYCLOIIEXANE N7 0.014 0.066 0.0056 0.0056 2,2-DIMETHYLHEXANE 18 0.001 0.004 0.0005 0.0005 ETHYLCYCLOPENTANE N7 0.000 0.002 0.0000 0.0000 2,5-DIMF.THYLHEXANE 18 0.001 0.003 0.0005 0.0005 2,4-DlMETHYLHEXANE 18 0.001 0.003 0.0005 0.0005 1C,2T,4-TRIMETHYLCYCL0PENTANE N8 0.000 0.002 0.0000 0.0000 3,3-DIMETHYLHEXANE 18 0.000 0.001 0.0000 0.0000 1T,2C,3-TRIMETHYLCYCL0PENTANE N8 0.000 0.001 0.0000 0.0000 TOLUENE A7 0.011 0.045 0.0037 0.0037 2,3-DIMETHYLHEXANE 18 0.000 0.002 0.0000 0,0000 2-METHYLHEPTANE 18 0.001 0.007 0.0005 0.0005 4-METHYLHEPTANE 18 0.001 0.003 0.0005 0.0005 3-METHYLHEPTANE 18 0.001 0.005 0.0005 0.0005 1C,2T,3-TRIMETHYLCYCL0PENTANE N8 0.001 0.005 0.0005 0.0005 1T,4-DIMETHYLCYC1.0HFXANE N8 0.001 0.003 0.0005 0.0005 1,1-DIMETHYLCYCLOHEXANE N8 0.000 0.001 0.0000 0.0000 1T.2-DIMETHYLCYCLOHEXANE N8 0.000 0.002 0.0000 0.0000 N-OCTANE P8 0.002 0.009 0.0010 0.0010 2,3,5-TRIMETHYLHEXANE 19 0.000 0,001 0.0000 0.0000 1,1,4-TRIMETHYLCYCLOHEXANE N9 0.000 0.001 0,0000 0.0000 4,4-DIMETHYLHEPTANE 19 0.000 0.001 0.0000 0.0000 ETHYLCYCLOHEXANE N9 0.000 0.001 0.0000 0.0000 2,5-DIMETHYLHEPTANE 19 0.000 0.001 0.0000 0.0000 ETHYLBENZENE A8 0.000 0.001 0.0000 0.0000 1,3-DIMETHYLBENZENE (M-XYLENE) A8 0.001 0.003 0.0004 0.0004 1,4-DIMETHYLBENZENE (P-XYLENE) A8 0.000 0.002 0.0000 0.0000 1,2-DIMFTHYI,BENZENE (O-XYLENE) A8 0.000 0.001 0.0000 0,0000 N-NONANE P9 0.000 0.002 0.0000 0.0000 TOTALS 100.000 100.000 5.5113 5.5409 EMPACT ANALYTICAL SYSTEMS, INC 997 US HI WAY 85 BRIGHTON, CO 80603 (303) 637-0150 EXTENDED NATURAL GAS ANALYSIS (*DHA) PROJECT NO. : 0302069 ANALYSIS NO. : 03 COMPANY NAME : SRI ANALYSIS DATE: FEBRUARY 28, 2003 ACCOUNT NO. : P.O. RD30712 SAMPLE DATE : FEBRUARY 26, 2003 D-5 ------- Appendix D-l. Pre-Test Makeup Natural Gas Analysis, Cont. PRODUCER : [.EASE NO. : NAME/DESCRIP : * * "FIELD DATA** SAMPLED BY: SAMPLE PRES. : SAMPLE TEMP. : COMMENTS MAKE-UP GAS #2 @ 13:09 TO: CYLINDER NO. : AMBIENT TEMP.: GRAVITY : GPM@ COMPONENT MOLE % MASS % 14.65 14.73 HELIUM 0.022 0.004 HYDROGEN 0.000 0.000 — OXYGEN/ARGON 0.006 0.009 ... NITROGEN 0.388 0.506 C02 3.021 6.182 ... METHANE 76.928 57.378 ... ETHANE 11.842 16.557 3.1500 3.1672 PROPANE 4.300 8.817 1.1784 1.1848 l-BUTANE 0.813 2.196 0.2645 0.2659 N-BUTANE 1.422 3.850 0.4461 0.4485 [-PENTANE 0.499 1.673 0.1816 0.1826 N-PENTANE 0.367 1.230 0.1322 0.1329 HEXANES PLUS 0.392 1.598 0.1543 0.1548 TOTALS 100.000 100.000 5.5071 5.5367 BTEX COMPONE^ mol; WT% (CALC: GPA STD 2145-94 & TP-17 @14. 696 & 60 F) BENZENE 0.017 0.062 BTU @ 14.65 14.73 ETIIYLBENZENE 0.000 0.001 GROSS DRY REAL : 1221.04 1227.71 TOLUENE 0.006 0.025 GROSS WET REAL : 1199.70 1206.37 XYLENES 0.000 0.003 DENSITY (AIR=I): 0.7447 TOTAL BTEX COMPRESSIBILITY FACTOR *DHA (DETAILED HYDROCARBON ANAL YSIS/NJ1993) ; ASTM D6730 THIS DATA HAS BEEN ACQUIRED THROUGH APPLICATION OF CURRENT STATE-OF-THE-ART ANALYTICAL TECHNIQUES. THE USE OF THIS INFORMATION IS THE RESPONSlBLlTY OF THE USER. EMPACTANALYTICAL SYSTEMS, ASSUMES NO RESPONSIBLITY FOR ACCURACY OF THE REPORTED INFORMATION NOR ANY CONSEQUECES OF ITS APPLICA TION. EMPACT ANALYTICAL SYSTEMS, INC 997 US HIWAY 85 BRIGHTON, CO 80603 (303) 637-0150 EXTENDED NATURAL GAS ANALYSIS (*DHA) PROJECT NO. : 0302069 ANALYSIS NO. : 03 COMPANY NAME : SRI ANALYSIS DATE: FEBRUARY 28. 2003 GPM GPM COMPONENT PIANO n MOLE % MASS % 14,65 14.73 HELIUM 0.022 0.004 ... HYDROGEN 0.000 0.000 ... OXYGEN/ARGON 0.006 0.009 — NITROGEN 0.388 0.506 ... ... C02 3.021 6.182 ... METHANE P1 76.928 57.378 ... ... ETHANE P2 11.842 16.557 3.1500 3.1672 PROPANE P3 4.300 8.817 1.1784 1.1848 I-BUTANE 14 0.813 2.196 0.2645 0.2659 N-BUTANE P4 1.416 3.828 0.4440 0.4464 2,2 DIMETHYLPROPANE !5 0.006 0.022 0.0021 0.0021 l-PENTANE 15 0.499 1.673 0.1816 0.1826 N-PENTANE P5 0.367 1.230 0.1322 0.1329 2,2 DIMETHYLBUTANE 16 0.010 0.041 0.0042 0.0042 D-6 ------- Appendix D-l. Pre-Test Makeup Natural Gas Analysis, Cont. METHANOL X1 0.003 0.005 0.0004 0.0004 CYCLOPHNTANE N5 0.012 0.041 0.0035 0.0035 2,3 DIMETHYLBUTANE 16 0.023 0.092 0.0094 0.0094 2 METHYLPENTANE (6 0.089 0.355 0.0367 0.0369 3 METHYLPENTANE 16 0.047 0.190 0.0190 0.0191 N-HEXANE P6 0.087 0.348 0.0356 0.0358 2,2-DIMETHYLPENTANE 17 0.002 0.010 0.0009 0.0009 METHYLCYCLOPENTANE N6 0.030 0.118 0.0106 0.0106 2,4 DIMETHYLPENTANE 17 0.004 0.017 0.0019 0.0019 2,2,3 TRIMETHYLBUTANE 17 0.001 0.003 0.0005 0.0005 BENZENE A6 0.017 0.062 0.0047 0.0047 3,3 DIMETHYLPENTANE 17 0.001 0.004 0.0005 0.0005 CYCLOHEXANE 06 0.019 0.076 0.0065 0.0065 2 METIIYLHEXANE 17 0.008 0.036 0.0037 0.0037 2,3 DIMETHYLPENTANE 17 0.002 0.011 0.0009 0.0009 1,1 DIMETHYLCYCLOPENTANF. N7 0.002 0.008 0.0008 0.0008 3 METHYLHEXANE !7 0.007 0.031 0.0032 0.0032 1,C 3 DIMETHYLCYCLOPENTANE N7 0.002 0.009 0.0008 0.0008 1 ,T 3 DIMETHYLCYCLOPENTANE N7 0.002 0.008 0.0008 0.0008 3 ETHYLPENTANE 17 0.000 0.002 0.0000 0.0000 1,T 2 DIMETHYLCYCLOPENTANE N7 0.002 0.011 0.0008 0.0008 N-HEPTANE P7 0.007 0.032 0.0032 0.0032 1,C 2 DIMETHYLCYCLOPENTANE N7 0.000 0.001 0.0000 0.0000 METHYLCYCLOHEXANE N7 0.008 0.038 0.0032 0.0032 2,2-DIMETIIYLHEXANE 18 0.000 0.002 0.0000 0.0000 ETHYLCYCLOPENTANE N7 0.000 0.001 0.0000 0.0000 2,5-DIMETHYLHEXANE 18 0.000 0.001 0.0000 0.0000 2,4-DtMETHYLHEXANE (8 0.000 0.001 0.0000 0.0000 1C,2T,4-TRIMETHYLCYCL0PENTANE N8 o.ooo 0.001 0.0000 0.0000 IT,2C,3-TRIMETHYLCYCL0PENTANE N8 0.000 0.001 0.0000 0.0000 TOLUENE A7 0.006 0.025 0.0020 0.0020 2-METHYLHEPTANE 18 0.000 0.002 0.0000 0.0000 4-METHYLHFPTANE 18 0.000 0.001 0.0000 0.0000 3-METHYLHEPTANE 18 o.ooo 0.001 0.0000 0.0000 IC,2T,3-TRIME'l'HYLCYCLOPENTANE N8 0.000 0.002 0.0000 0.0000 1T.4-DIMETIIYLCYCLOHEXANE N8 0.000 0.001 0.0000 0.0000 1T,2-DIMETHYLCYCL0IIEXANE N8 0.000 0.001 0.0000 0.0000 N-OCTANE P8 0.001 0.003 0.0005 0.0005 1,1,4-TRIMETHYLCYCI.OHEXANE N9 0.000 0.001 0.0000 0.0000 ETHYLBENZENE AS 0.000 0.001 0.0000 0.0000 1,3-DIMETHYLBENZENE (M-XYLENE) A8 0.000 0.002 0.0000 0.0000 1,4-DIMETHYLBENZENE (P-XYLENE) A8 0.000 0.001 0.0000 0.0000 N-N'ONANE P9 o.ooo 0.001 0.0000 0.0000 5.5367 TOTALS 100.000 100.000 5.5071 D-7 ------- |