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# TEST PROTOCOL FOR THE DETERMINATION

OF DEST R UCTION EFFICIENCY OF PRESSURE

ASSISTED AND STEAM

- ASSISTED FLARE BURNERS

This test activity is undertaken by The Dow Chemical Company in support of an application to the TCEQ for an Alternate Means of
Control

.



# Oct 1 , 20 13

PREPARED BY

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## Contents

INTRODUCTION

................................ ................................ ................................ ...... 3

PURPOSE

................................ ................................ ................................ ................ 4

FUEL COMPOSITION FOR P RESSURE

- ASSISTED BURNER TESTS

.................. 5

FUEL COMPOSITION FOR STEAM

- ASSISTED BURNER TESTS

......................... 6

TESTING METHODOLOGY

................................ ................................ ..................... 7

1.1 Division of Labor

................................ ................................ .......................... 7

1.2 Fuel Gas and Steam Flow Measurement

................................ ..................... 7

1.3 Description of Sample Gas Extraction Method

................................ ............. 8

1.4 Passive Fourier Transform Infrared S pectroscopy (PFTIR) Measurement

.. 8

1.5 Testing Duration and Replicates

................................ ................................ .. 9

1.6 Flue Gas Sampling and Analysis

................................ ................................ . 9

1.6.1 CO Emissions Analyzer

................................ ................................ ....... 10

1.6.2 CO 2 

### Emissions Analyzer

................................ ................................ ..... 10

1.6.3 Total Unburned Hydrocarbon Emissions Analyzer

.............................. 10

1.6.4 Oxygen Analyzer

................................ ................................ ................. 10

1.6.5 NOx Emissions Analyzer

................................ ................................ ..... 10

1.6.6 Propylene Emissions Analyzer

................................ ............................ 11

1.7 Fuel Gas Sampling and Analysis

................................ ............................... 11

1.8 Data Acquisition Systems

................................ ................................ .......... 11
A) John Zink Data Acquisition System

................................ ........................ 11
B) CleanAir Engineering and TRC Data Acquisition System

....................... 12

1.9 General Conduct of Test

................................ ................................ ............ 12

QUALITY ASSURANCE AND QUALITY CONTROL ACTIVITIES

.......................... 14

CALCULATIONS OF DESTRUCTION REMOVAL EFFICIENCY AND COMBUSTION EFFICIENCY

................................ ................................ ................. 15

FINAL REPORT CONTENTS

................................ ................................ ................. 16

APPENDIX A

– PFTIR OPERATION AND CALIBRATION

................................ ..... 17

APPENDIX B

– TEST ARRANGEMENT FOR PRESSURE ASSISTED BURNER

. 25

APPENDIX C

– PROPOSED FUEL COMPOSITION

................................ .............. 26

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# INTRODUCTION

High destruction efficiency of flared gases is very desirable. This level of flare performance requires good mixing of gas and ambient air. The traditional means of drawing air into the gas and promoting mixing is a steam

- assisted flare burner. Air from a blower or fan is also used as a source
of air for combustion and the energy for mixing. There are, however, flare systems that have significant static energy in the gases. By converting this static energy (gas pressure) into kinetic energy (velocity) it is possible to educt air into the gas a chieving a high level of mixing. T hese flares are often referred to as high

- pressure flares or pressure

- assisted flares. Pressure

- assisted flare burners described above have been in use in Texas for more than 30 years.

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# PURPOSE

The purpose of these tests is to determine the destruction removal efficiencies of pressure assisted
and steam

- assisted flare burners that will be used for the disposal of hydrocarbon emissions from a DOW Chemical facilit y located in Texas

. The tests will be conducted under conditions representative of the expected normal operating conditions. The data will be used to define the air quality impact of such flaring operations.

Using equipment, gases and procedures agreed by all parties involved, emission m easurements will
be made t o determine concentrations of carbon dioxide (CO 2 ), carbon monoxide (CO)

, oxygen (O 2 ),
total hydrocarbons ( T HC)

, propylene, and NOx

. A ddition al data that will be logged includes: process conditions ( fuel flow s , fuel pressure , etc .) and meteorological measurements.

Previous studies conducted in the 1980’s

, and more recently, indicate that pressure assisted flare designs are capable of achieving high destruction efficiencies with very high exit velocities for various hydrocarbons. The ultimate purpose of the study is to provide TCEQ with sufficient data to
demonstrate that pressure assisted flare tips can a chieve a minimum destruction efficiency that meets or exceeds the minimum destruction efficiency for steam assisted or air assisted flares operating within the ve locity restrictions contained in 40 CFR 60.18 & 40 CFR 63.11

.

A small portion of the burners associated with this system will be steam

- assisted burners. This burner type will also be investigated to determine the operating envelope for good destruction efficiency.

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# FUEL COMPOSITION FOR PRESSURE

- ASSISTED BURNER

TESTS

A total of seven tests will be performed with four fuel compositions . The fuel composition for each test will consist of the following:

Test # P 1 H : 100% P ropylene

. B urner fuel pressure to be max imum operating pressure.

Test # P 1L : 100% Propylene

. B urner fuel pressure to be minimum operating pressure.

Test # P 2 H: Mixture of propylene and nitrogen. B urner fuel pressure to be max imum

operating pressure. Initial run of this test will vary the proportion of nitrogen to propylene to determine minimum heating value for stability. Once the minimum heating value for stability is determined, the first emissions test run will commence. Replicate runs of test P 2H and all runs of test P 2L will use the same heating value.

Test # P 2L : Mixture of propylene and nitrogen

. Proportion of nitrogen to propylene

determined from test P 2H. B urner fuel pressure to be minimum operating

pressure

.

Test # P 3 H : Mixture of 50% propylene / 50% natural gas by volume diluted with nitrogen

.

B urner fuel pressure to be max imum operating pressure. Initial run of this test will vary the proportion of nitrogen to hydrocarbon to determine minimum heating value for stability. Once the m inimum heating value for stability is determined, the first emissions test run will commence. Replicate
runs of test P 3H and all runs of test P 3L will use the same heating value.

Test # P 3 L : Mixture of 50% propylene / 50% natural gas by volume diluted wit h nitrogen

.

Proportion of nitrogen to hydrocarbon determined from test P 3H. B urner fuel pressure to be minimum operating pressure

.

Test # P 4 : Mixture of 90% hydrogen / 10% natural gas by volume. B urner fuel pressure

to be max imum operating pressure

. This test is to prove flame stability. No emissions data will be taken and no replicates conducted for this test. Expected run time for this test is less than 5 minutes.

Note that standard conditions are defined as 6 8 °F and 14.696 psia pressure.

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# FUEL COMPOSITION FOR STEAM

- ASSISTED BURNER TESTS

A total of six tests will be performed. The fuel composition for each test will consist of the following:

Test # S 1 : Mixture of propylene/nitrogen at or slightly above critical pressure to

produce sonic exit velocity. Steam to be at design flow rate. Proportion of propylene to nitrogen will be adjusted to the minimum heating value which produces a stable flame. This test would allow operation of the SKEC burners at maximum pressure as long as the heat content of the relief gases was
above the determined minimum.

Test # S2 : Same fuel composition and flow rate determined in test S 1. Steam to be shut

off. This test will show that steam is not needed for high destruction efficiency or smokeless operation when the exit velocity is sufficient ly high

.

Note: Tests S1 & S2 are designed to show that this type of burner can operate as a

pressure assisted burner with or without steam and meet emissions requirements.

Test # S3 : Steam flow rate set to the cooling r ate (minimum steam rate). Fuel to be

propylene / nitrogen mixture of 300 btu/scf LHV. Fuel flow to initially be at a
low rate. The fuel flow rate will be slowly increased until the flame becomes unstable, at which point the flow rate will be slightly reduced.

Test # S4 : Steam flow rate set to the cooling rate (minimum steam rate). Fuel to be

propylene / nitrogen mixture of 700 btu/scf LHV. Fuel flow to initially be at a
low rate. The fuel flow rate will be slowly incr eased until the flame becomes unstable, at which point the flow rate will be slightly reduced.

Test # S5 : Steam flow rate set to produce 10 psig steam pressure at the burner. Fuel to

be propylene / nitrogen mixture of 300 btu/scf LHV. Fuel flow to initia lly be
at a low rate. The fuel flow rate will be slowly increased until the flame becomes unstable, at which point the flow rate will be slightly reduced. If 300 btu/scf LHV cannot be made stable with this steam rate, a higher LHV composition will be use d.

Test # S6 : Steam flow rate set to produce 10 psig steam pressure at the burner. Fuel to

be propylene / nitrogen mixture with an LHV of test S5 + 400. Fuel flow to initially be at a low rate. The fuel flow rate will be slowly increased until the flame becomes unstable, at which point the flow rate will be slightly reduced.

Note that standard conditions are defined as 68°F and 14.696 psia pressure.

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# TESTING METHODOLOGY

1.1 Division of Labor

The John Zink Company will be responsible for overall conduct of the testing. JZ will be directly responsible for supply and metering of fuel gases, logging of process conditions (fuel flow, fuel pressure, etc.), logging of meteorological data, supply of test burners, generation of
fi nal report, video recording, and sub

- contracting to third parties.

TRC ( a gas analysis compan y ) will be responsible for supply, calibration, and operation of all gas sampling and analysis equipment as well as supply of all calibration gases

. TRC will calculate the flare destruction efficiency and combustion efficiency at the conclusion of each test point and will supply JZ a writ ten formal test report that documents the fi ndings of the testing program.

CleanAir Engineering will be responsible for supply, calibration, and operation of the PFTIR emissions measurement device. CleanAir Engineering will calculate the flare combustion efficiency at the conclusion of each test point and will supply JZ a written formal test report
that documents the resul ts of their measurements.

Other contractors that will b e employed include ; crane rental services

, liquid nitrogen storage and vaporization services , and hydrogen delivery services

.



## 1.2 Fuel Gas and Steam Flow Measurement

All testing will be performed at the John Zink R&D Test Facility located in Tulsa, Oklahoma. The John Zink R&D Test Facility has liquid, commercial grade, propylene, nitrogen and Tulsa natural gas (TNG) available on site. The Test Facility is equipped with a water bath vaporizer capable of vaporizing approximat ely 20,000 lb/hr of propylene.

The John Zink R&D Test Facility has nitrogen available at low flow rates. In order to meet the nitrogen supply demand required for testing, supplemental liquid nitrogen storage and vaporization capabil ity wil l be brought on site.

The John Zink R&D Test Facility has hydrogen available at low flow rates. In order to meet the hydrogen supply demand required for testing, supplemental hydrogen wil l be brought on site via transport. The meter run used for nitrogen will be re

- tasked for hydrogen for test P 4

.

The flow rate of each fuel component will be measured separately using an orifice metering system designed in accordance to ANSI standards. The orifice plate and orifice flange s will be certified to meet all applicable procedures and specifications. All fuel measurements are fully compensated for pressure and temperature. The propylene meter run uses differential pressure, static pressure, and temperature transmitters to provi de the data acquisition system with sufficient information to calculate flow rate. The nitrogen /hydrogen and natural gas meter runs employ fully compensated mass flow meters which internally calculate the flow rate and outputs the mass flow.

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Sample s of t he fuel mixture flowing to the flare will be collected from a point near the burner in order to confirm the composition and heating value of the waste gas stream. A minimum
of two samples during each test run will be analyzed per EPA Method 18. A sample will be collected at the start and end of each test point. Additional samples will be taken if time
allows.

The temperature and pressure of the fuel gas will also be measured at a location just upstream of the test burner . These measurements will be use d as a check to insure that the flow rate through the metering system properly corresponds t o these readings.

Steam flow will be measured via an ultrasonic flow meter fully compensated for pressure and temperature. Steam pressure and temperature will be measured at a location very near the
burner.



## 1.3 Description of Sample Gas Extraction Method

The sample gas extraction apparatus designed and employed for the TCEQ 2010 Flare Study will be used for this test campaign. (See Figure 1) The apparatus consists of an inlet cone, a sample preparation section, a sample extraction section, and eductor. The inlet face of the
cone is 20” di ameter tapered to a 12” outlet. Around the perimeter of the cone, 120° apart, are three exposed junction thermocouples for sensing the temperature of the plume. The
12” cone outlet is connected to a 90 degree elbow in which mixing tabs have been installe d. The mixing tabs ensure the plume sample that is pulled through the extraction apparatus is well mixed and homogeneous. The outlet of the elbow is connected to the inlet of the sample preparation section. The sample preparation section is a 9.5’ long 12” pipe with a
Vortab flow conditioner located in the first 3 feet. The Vortab flow conditioner will also assist in mixing the gases as well as conditioning the flow profile. At the exit of the sample preparation section is the extraction section. The sampling section is 1.5 feet long and consists of a pitot tube for measurement of the flue gas velocity in the apparatus, an exposed junction temperature element, and a flue gas extraction probe. The flare flue gas sample that will be analyzed for emissio ns composition will be obtained from this location. Downstream of the sampling section 7.5 feet is the end of the sample gas extraction apparatus where the eductor is attached. The eductor uses compressed air to induce flow through the apparatus.
The sa mple gas extraction apparatus is designed with lifting lugs to allow it to be positioned with a crane; it is also designed with guide chains that will allow it to be positioned from grade in order to prevent the apparatus from swinging.



## 1.4 Passive Fourier Tr ansform Infrared Spectroscopy (PFTIR)

Measurement

A single PFTIR instrument will be used during all tests. PFTIR data will be collected simultaneously with the extractive data. Appendix A details the PFTIR methodology.

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- 0001 9 Figure 1 Sample Gas Extraction Apparatus



## 1.5 Testing Duration and Replicates

Tests P 1

- P 3 H/L will be run for 20 minutes with three replicates. Consequently

, the total run
time for each of these tests is 1 hour. Replicates will be separated by the other 5 tests in this

matrix

. Test P 4 is unique in that only a small percentage of the fuel gas is a hydrocarbon; consequently determination of DRE is problematic. Test P 4 is to demonstrate stability and it is expected that this test run will take less than 5 minutes. No replicates will be run for test

P 4.

Tests S1 to S6 will be run for 20 minutes once process conditions have been determined and stabilized. No replicates will be run for tests S1 to S6.



## 1.6 Flue Gas Sampling and Analysis

A representative exhaust sample of the flare emissions will be collected through the sample gas extraction apparatus that will be positioned over the exhaust plume of the flare. The sampling apparatus cone will be positioned outside the visible flame. The position of the
inlet will be adjusted so that the average temperature readings of the three inlet thermocouples are between 700° and 300°F. Effort will be made to ensure the temperature of the gas e s entering the extraction apparatus does not e xceed 800°F. 800°F is chosen
because it is below the auto

- ignition temperature of Methane (1076°F), Propylene (856°F),
and Ca r bon Monoxide (1128°F). Ensuring that the gases entering the gas extraction apparatus do not exceed 800°F gives confidence that the combustion process has ceased prio r to the sample being extracted.

The extracted sample will be pulled through a heated sample line and into a mobile laboratory for analysis. A portion of the sample gas will be analyzed on a wet basis (total hydrocarbons and GC analysis of propylene ) to avoid condensation of the hydrocarbons prior to measurement. The remainder of the sample will be dried and sent to the CO, O 2 , CO 2 and

NOx analytical instruments.

The moisture content of the plume will be calculated using a combination of Equations 19

- 13
and 19

- 34 of EPA Method 19. The total hydrocarbon concentration will then be converted

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from a wet basis to a dry basis, and then the concentration on a dry basis w ill be used in the
remainder of the emission calculations.

The sampling and analysis procedures to be used during these tests will conform in principle
with those outlined in the Code of Federal Regulations , Title 40, Part 60, Appendix 1, Methods 3A, 10

, 25A

, 7E , and 18 . Mass emissions rates will be determined by the stoichiometric calculation techniques of EPA Method 19; see section titled “Calculation of Destruction Removal Efficiency” of this document for detail s . A discussion of the continuous analyz ers used for this type of testing is presented below.



## 1.6.1 CO Emissions Analyzer

CO concentrations will be determined in accordance with procedures set forth in
EPA Method 10. A continuous non

- dispersive infrared (NDIR) analyzer will be used.
The NDIR analyzer is equipped with a gas correlation filter that removes any
interference from CO 2 or other combustion products; this eliminates the need for ascarite traps and the associated correction factors.



## 1.6.2 CO 2 

## Emissions Analyzer

The CO 2 concentration measure ments will be made in accordance with the procedures of EPA Method 3A. An infrared absorption CO 2 analyzer will be utilized
for these test s

.



## 1.6.3 Total Unburned Hydrocarbon Emissions Analyzer

EPA Method 25A will be utilized to determine concentrations of total hydrocarbons. Calibrated on a methane basis, the analyzer will utilize a flame ionization detector to determine THC. The analyzer is equipped with an adjustable heated oven, containing a heated pump and a burner. A small flame, inside the oven, is elevated and sustained by regulated flows of air and hydrogen. The burner jet acts as an electrode and is connected to the negative side of a precision power supply. An additional electrode, known as the “collector,” is connected to a high impedance, low noise electronic amplifier. The two electrodes establish an electrostatic field. When a gaseous sample is introduced to the burner, it is ionized in the flame. The charged particles (ions) migrate to their respective electrodes creating a small current between the electrodes. A precision electrometer amplifier is used to measure this current. The current is directly proportional to the hydrocarbon content of the sample.



## 1.6.4 Oxygen Analyzer

T he O 2 concentration measurements will be made in accordance with the procedures of EPA Method 3A. A paramagnetic cell O 2 analyzer will be utilized for
these tests.



## 1.6.5 NOx Emissions Analyzer

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- 0001 11 EPA Method 7E will be used to determine concentrations of NOx (via chemiluminescence)

. Within the ch e miluminescence analyzer, the gaseous sample is routed through an NO 2 to NO converter. In the presence of ozone, the chemiluminescence reaction yields excited NO 2 , oxygen, and a photon (NO + O 3 → NO 2 + O 2 + photon). The transition to this state produces light intensity proportional to the mass flow rate of NO 2 into the reaction chamber. The light is measured by means of a photomultiplier tube and associated amplification
electronics. NOx mass emission r ates will be calculated as if all the NOx was in the
form of NO 2 . This approach corresponds to EPA’s convention; however, it tends to overestimate the actual NOx mass emission rates since the majority of NOx is in the form of NO which has less mass per un it volume than NO 2 .



## 1.6.6 Propylene Emissions Analyzer

The concentrations of propylene, methane, ethane, propane, and butane will be
measured in a ccordance with the procedures of EPA Method 18 . A gas chromatograph will be used for these measurements

.



## 1.7 Fuel Gas Sampling and Analysis

The fuel gas will be analyzed via a gas chromatograph to validate the measured fuel flows. The analysis will be made in accordance with the procedures of EPA Method

18.



## 1.8 Data Acquisition Systems

All acquisition systems will be synchronized at the beginning of each test day to a master
clock which auto

- synchronizes to the government generated time signals every evening.



## A) John Zink Data Acquisition System

The John Zink data acquisition system logs d ata once per second. It is stored in a CSV format file which can be read by spreadsheet programs. All of the data logged will be visible real time in the flare test facility control room. The following information will be logged to this file:

 Date

– Mo nth/Day/Year

 Time

– Hour:Minute:Second AM/PM

 Comment

– Comment entered by operator to help sort data.

 Nitrogen or Hydrogen Flow Rate

– lb/hr

 Natural Gas Flow Rate

– lb/hr

 Propylene Differential Pressure Across Orifice

– “H2O

 Propylene Static Pressure

– psig

 Propylene Temperature

– °F

 Propylene Flow Rate

– lb/hr

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- 0001 12  Calculated Total Fuel Flow to Flare

– lb/hr

 Calculated Lower Heating Value of Fuel to Flare

– BTU/SCF

 Fuel Pressure at Burner

– psig

 Mixed Fuel Temperature

- °F

 Steam Flow Rate

– lb/hr

 Steam Pressure Near Burner

– psig

 Steam Temperature Near Burner

– °F

 Temperature of Gases Entering Sample Collector (qty 3)

- °F

 Calculated Average Temperature of Gases

- °F

 Temperature of Gases at Sample Extraction Point

- °F

 Differential Pressure Across Sample Collector Pitot

– “H2O

 Static Pressure at Sample Collector Pitot

– “H2O

 Calculated Flow Through Sample Collector

- SCFH

 Ambient Temperature

- °F

 Barometric Pressure

– psia

 Wind Speed

– mph

 Wind Direction

– 0 = North, 90 = East, 180 = South, 270 = West

 Relative Humidity

- %



## B) CleanAir Engineering and TRC Data Acquisition System

One minute averages will be logged for the continuous monitors (O2, CO, CO2,
NOx, and THC). The results of GC analysis will be logged internally to the GC. Barometric pressure, dry bulb temperature, and wet bulb temperature will be hand logged at the beginning of each test. PFTIR data will be logged in 1 minute

averages.



## 1.9 General Conduct of Tes t

Two sets of tests will be conducted, tests of a pressure assisted burner and tests of a steam
assisted burner. A single burner will be used for each pressure assisted emissions test

. A single burner will be used for each steam assisted emissions test. The test burner s will either be project burner s or burner s that are geometrically identical to project burner s (same basic burner casting with the same size/number of ports). During testing, o nce the main flame is
established on a burner, the pilot will be turned off for the emissions sampling portion of the

test

.

When all fuel flow conditions are stable, the sample gas collection apparatus will be positioned, by a crane, at a location above the visible flare flame . Prior to positioning the sample collector , all initial calibrations and other quality assurance activities will be complete. Samples of flare exhaust gas will be extracted from the sample collector and delivered through heat trace d lines into the mobile laboratory. The sample gas will be conditioned, if

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- 0001 13 necessary, (dried for the CO, O 2 , NOx and CO 2 analyzer s ) and delivered to each analyzer at the appropriate flow rate. When the analyzers respond to the exhaust gas and stabilize, a test run will be started. The data logger will record the concentrations from each analyzer over the test run period in one minute averages

. At the beginning and end of each test run , a GC analysis of the incoming fuel will be performed. During the test period, GC analysis of the flue gas will occur periodi cally. Also, du ring the course of the 20 minute run time, an average bag sample of the flue gas will be extracted into two bags with one bag as primary and the second bag as a back

- up. The primary bag sample will be analyzed at the conclusion of the

test run via GC.

An additional, non

- emissions, test will also be conducted. This additional test will consist of

nine or more burners spaced the same distance as the project burners. This test will be conducted with 100% propylene. This test will demonstrate the cross

- lighting of the burners as well as pr ovide the length of the flame.

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# QUALITY ASSURANCE AND QUALITY CONTROL ACTIVITIES

All instruments supplied and utilized by JZ will undergo calibration and span checks prior to testing. These calibration and span checks will validate the accuracy of the instruments as well as the proper logging of the data. All analytical instruments will be calibrated per their respective methods during the course of the test

After the testing has been completed, the collection hood will be positioned in clean air (air not effected by flare emissions) and a sample of ambient air will be analyzed to determine the ambient
contribution to result s collected during the testing.

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# CALCULATIONS OF DESTRUCTION REMOVAL EFFICIENCY

AND COMBUSTION EFFICIENCY

The calculation of flare destruction removal efficiency (D R E) will be determined using the calculation techniques from 40 CFR 60, Appendix A, EPA Reference Method 19. Knowing the composition of the fuel, a fuel specific “F factor” (scf of combustion products / MMBtu of fuel burned) can be determined by the equations shown in Section 12.3.2.1 of EPA Reference Method 19. The “F factor” is used to calculate the mass emission rate of the exhaust hydrocarbons as sampled from the gas collection apparatus. Both O 2 and CO 2 concentrations will be used to
calculate dilution ratios resulting in the calculation of two D R Es . Using the total hydrocarbon

measurement , equations 19

- 4 and 19

- 8 of Method 19 can be used to calculate the mass of
unburned hydrocarbons on a pounds per mi llion BTU fired basis

. M ultiplying these number s by the
heat release of the hydrocarbon flowing to the flare will yield the pounds per hour of unburned hydrocarbons exiting the flare flame. Knowing the mass flow rate of hydrocarbon sent to the flare
and the mass of unburned hydrocarbon exiting the flame, the destruction efficiency can be
determined as follows: [ ]

The advantage of using this method is that all of the flare exhaust does not have to be captured. If the exhaust plume is diluted by ambient air (hydrocarbon concentrations biased low), the increased

O 2 or decreased CO 2 in the exhaust sample will correct this bias by means of the dilution ratio component of the respective equation s

.

These same calculations will be repeated but instead of using the total hydrocarbon measurement, the propylene, propane, and butane measurem ents from the GC will be added and the sum used to determine destruction efficiency. [ ]

The combustion efficiency of the flare will also be calculated using the following equation : [ ]

Where CO 2 , CO, and THC d are the volume fractions of the components on a dry basis.

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# FINAL REPORT CONTENTS

After the testing program is complete, all operational data is organized and labeled, all the testing results are reviewed and corrected for QA/QC activities, a formal test report will be prepared that documents the findings of the testing program. The te st report will include the following items:

A) Introduction : A discussion of what was tested, why it was tested, and the goal of this project

.

B) Summary of Results : 1) Discussion of results 2) Discrepancies or problems that arose during tests 3) Tabular summaries containing the following:

a. Date, Test ID
b. Ambient Conditions

c. Process Data (fuel flows, burner pressure, etc.)
d. Calculated Process Values (fuel LHV, fuel exit velocity, etc.)

e. Propylene DRE (using THC & GC data and O2 as tracer)
f. Propylene DRE (using THC & GC da ta and CO2 as tracer)

g. Propylene DRE (using GC data and O2 as tracer)
h. Propylene DRE (using GC data and CO2 as tracer)

i. Combustion Efficiency

C) Test Protocol : A copy of this document.

D) Appendices : 1) CleanAir Engineering and TRC report s which will include:

a. Calculations Used in the Analysis
b. Detailed Results

c. Analytical Techniques
d. Quality Assurance Activities

e. Supporting Data 2) JZ Data Log Index 3) Calculations used by JZ 4) JZ Quality Control Documents

a. Calibration Records
b. Gas Analysis Records

Electronic copies of the JZ data logs will be supplied with the report.

Note: The final report will be non

- confidential and can be placed into the public domain.

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# APPENDIX A

– PFTIR OPERATION AND CALIBRATION

PFTIR Operation

Passive Fo u rier T ransform Infrared (PFTIR) a n alysis operates on the p r inciple of spectral analy s is of ther m al radi a tion e m itted by hot gase s

.

In nor m al absorption spectroscopy, light is passed through a region containing gas to be analyzed a n d the transmitted li gh t is spread out into a spe c trum using an in terfero m eter (FTIR) or a spectro m eter. In this spectru m , the presence of specific co m pounds can be
deter m ined from the patterns of light absorbed while the co mp ound ’ s concentrations can be m easured from the intensity of the patt e rns. T he low energy of infrared light is absorbed my m olecular species cau s i ng them to vibrate and rotate fa s t er. Because each molecule consists of a unique structure of bound ato m s, the patterns of infrared wavelengths (IR colors) absorbed by a m olecule are als o u n i q ue. These molecular “finger prints” are u s ed in the i n frared analysis of gases.

To m onitor flares, standard absorption infrared spectroscopy could be used. However it is difficult to pass an in f

rared light beam through an elevated flare plu m e and th en

c apture the trans m ission. Fortunately, a passive approach is possible. Passive m eans that no “active” infrared light source is u s ed. I n stead, the hot gases of the flare are t h e infrared so u rce. The spectro m eter is a recei v er only. This approach is possi ble because
the infrared radiation e m itted by hot gases h a s t h e sa m e patterns or fingerprints as their absorption spectrum does. Consequently, obse r ving a flare with an infrared instru m ent allows for identification and quantification of species through e m ission spectroscopy just as absor

p ti o n spectr o sc o py can. However, there is one m ain difference: the signature arising from a hot gas is propo r tional to the gases concentration AND to its

te m perature. To do e m ission or ra d i a n ce m easure m ents therefore, the t emperat u re m u st be deduced in addition to the gas concentrations.

When a PFTIR is used as an e m ission m onitor it is calibrated in absolute radiance units. This calibrates the output voltage of the instru m e nt to the r e ceived power per unit area of

source, per unit solid angle of observation, and per unit wavelength or wave nu m ber (watt s /c m 2 

### /steradian/wavenu m ber). This calibration uses a black body source. A Blackbody is an object that is perfectly abs o rbing throughout the infrared. If a body is perfectly a b sorbing, t h e Planck ra d i ation law gi v es the power e m itted by this body, when
hot. This law states that the e m ission of a blackbody at a given absolute te mperature ( T )

, and wave number ( ̃ ) , is given by:



## ( ̃ ) ̃

̃ 

### (1)

Here h is Planck’s constant, c the speed of light, and k Boltz m ann’s constant. This function looks like that shown in Figure A

- 1 at a te mperature of 200 °C. As the

te m perature rises, the peak of this function m oves toward larger wave numbers (s m aller

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### wavelengt h ) and it increases in inte n sity. For this reason, h o tter o b jects will e m it m ore in the short wavelengths or visible while cooler bodies e m it in the longer w avelengths or the
infrared.

70

60
50

40

30

20

10

0

0 1000 2000 3000 4000 5000

Wavenumbers (cm

- 1)

Figure A

- 1. Planck F u nction Sho w i ng the Radiation Emitted by a Blackbody at 200 °C

If a body is not “black” or tot a lly absorbing, the ene r gy it emits is just the Planck function
ti m es the body’s absor p tion. For example, if the body is 50% absorbing it will e m it 50%
of the Planck function.

Gases have highly variable absorption with wav e length. It is in fact t h is vari a tion th a t produces the absorption patterns t h at allow f or t h eir identi f

i c a tion in the i nf

rared. If t h e
trans m ission of a gas is given by τ ( ̃

, T) then [1

- τ( ̃

, T) ] is the a m ount of absorption.
The radi a ti o n the gas e m its a t te m perature T is then given by:

N ( ̃

  ) = [1

- τ  ̃ ,T)] * N bb 

### ( ̃ ,T) (2)

For flare m easure m ents, it is this signal that is being detected from the hot gases above
the co m bustion zone.

However, there are also other contributions to the signal an analyzer “sees.” As shown in Figure A

- 2, the background (typically the s ky) has so m e e m i ssion, also defined by equation (2) that when trans m itted t h rough the pl u m e and the intervening at m osphere is seen by the analyzer. T he plu m e e m issions trans m itted through this sa m e a t m ospheric path provides the signal of intere s t . The int e rve n ing at m osphere itself has so m e e m ission, which is also seen by the analyzer. T he total radiant s i gnal received then consists of:

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R a diance F l are

Radiance

Atmosphe r ic

Trans m is s ion
& R a di a n c e



### Figure A

- 2 Contributions to the m easured flare radiance that must be accounted for.

The total radiant signal received then consists of:

(3)

In Equation (3) the argu m ents ̃ ,T have been dropped for clarity and the individual ter m s

are:

N

t otal 

### = tot a l radia n ce N bkg 

### = background sky radiance



## τ flr 

### = flare trans m issivity



## τ atm 

### = at m ospheric tra ns m issivity
N flr 

### = flare radiance
N atm 

### = at m o s pheric radiance
N f 

### = radiance of the FTIR instru m ent itself

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The actual m easur e m ents perfor m ed by the PFTIR consist of the f ollowi n g:

M flr 

### = The m easured plu m e radiance given by equation (3)

M b 

### = The m easured background radiance taken by m oving the PFTIR off the flare

to m onitor the sky background. This is given by

M n 

### = A m e asure m ent m ade looking at the calibration source (see below) with a

c old (liquid nitro g en) e m itter in place of t h e nor m al (black body)

M b b 

### = A m e asure m ent m ade looking at the calibration source with a

com m ercial black body e m itter in the so u rce



## τ atm 

### = Measured at m ospheric p ath trans m ission

,

Based on these m easure m ents Equation (3) can be rearranged to give the plu m e
trans m ission as:

( )

( ) 

### (4)

In this equation, the superscript on the Planck f unction radiance ( N BB 

### ) de n otes t h at t h is is
the Planck f

unction co mputed at the te m perature of the flare. C is a calibration

m easur e m ent m ade with a black body calibration source. The cali b ration source is a
tel e scope i d enti c al to t h at of the PFTIR but with the capa b ility of using various radiation
sources. F o r C the ra d i a tion sou r ce is a com m ercial b l ack b o dy e m itter. C then bec o m es the Planck f

unction for the te mperature of the black body divided by the m easured
radiance from the calibration source. This f actor converts the FTIR voltages to radiance units and it is given by:

( ) 

### (5)

The m easured black bo d y radia n ce ( M bb 

### ) has the cold source m easur e m ent ( M n 

### )
subtracted to cancel e m i ssions from the i n tervening air and/or the PFTIR instru m ent its e l f

.

A t m ospheric trans m ission 

## τ atm 

### is also m easured using the c a lib r ation so u rce. In this case the black body is replaced by a standard infrared source and the m easure m ent is m ade at a path length roughly equal to that of the s l ant

- path from the PFTIR to the flare.
A t m ospheric trans m ission is then given by:

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M IR 

### is the m easured s i g n al from the cali b ration source using the IR source and M
n 

### is t h e

m easured cold source as defined earl i er. The only term not defined is I 0



### . This is t h e s o

called synthetic background. It is frequently used in open

- path FTIR m e a sure m ents to convert a measured spectrum to trans m ission. It represents the shape of the spectrum that
the PFTIR would m easure if no gases were pre s ent. It can be synthesized from t he ( M IR 

### – M n 

### ) m easure m ent by doing a m athe m atical fit to points in the spectrum known to be free
of m olecular absor p tions. An e x a m ple is given in Figure A

- 3. In this Figure, the bottom plot is the m easured spectrum ( h ere a relatively clean spectrum done in the laborator y ),
the m i ddle plot t h e points c hosen for fitting, and the top pl o t the m athe m atical f it to the

c h osen points. The top plot is the I o 

### s p ectru m

.

Figure A

- 3

, a n e x a mple of synthetic I o 

### generation from a m e asured spectru m

.

W ith equations (5) and (6), equation (4) then contains only m easured or computed ter m s. However, to co mpute the Planck function at the te mperature of the flare ( ) the flare
gas te m perature m ust be known. Fortunately, this can be m easured using features in the

PFTIR data itself. One convenient feature is the CO band near 2150 c m - 1



### .

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Figure A

- 4 shows this band at two di f f erent t e mperatures. The upper plot is at a m bient

te m perature (300 K) and the bottom plot is at 550 K. The eff e ct of increasing

te m perature is to ex p and the band s h i f ting the pe a k position aw ay f rom band cent e r while increasing the stren g th of the weaker li n es farther from band center. This is a

sen s iti v e function of te mperature, so the shape of t h e band essentially m easures temperature.

0

. 0 3 5 C O 5 0 p p m 3 0 0 K 7 6 0 T o r r 1 m e t e r p a th

0

. 0 3 0

0

. 0 2 5

A b 0

. 0 2 0

s

0

. 0 1 5

0

. 0 1 0

0

. 0 0 5

- 0

. 000

0

. 0 1 6 C O 5 0 p p m 5 5 0 K 7 6 0 T o r r 1 m e t e r p a th

0

. 0 1 4

0

. 0 1 2

0

. 0 1 0 Ab

s 0

. 0 0 8

0

. 0 0 6

0

. 0 0 4

0

. 0 0 2

0

. 0 0 0 

### Figure A

- 4. Structure of the Fundam e ntal CO Band at 300K (top) and 550K (bottom) Sho w i ng Alte r ation of Band Shape with Temperature

The CO lines arise (in e m ission) from a transition of the m o l ecule from a higher
vibration/rotation state to a lower one. The transitions are dictated by quantum

m echanics. However, the inte n sities of the individual lines are st r ongly influenced by the

nu m ber of molecules in the initial state available to m ake the transition. Th is “population”
of the initial sta t es is dictated by the Boltz m a nn distribution which is given by:

( 7)

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### Here N J ” 

### is the nu m

ber of m olecules in the initi a l rot a tion a l state de fi ned by the rotational quantum number J”. N 0 

### is the tot a l nu m ber of m olecul e s availa b le, E” the energy o f the
i nitial st a te, k Boltz m ann’s constant, T the absolute te m perature, and Q a “partition s u m .” The partiti o n sum is just the sum of t he exponential term over all pos s ible energy levels. If the log of the m easured inten s ity o f the CO lines is pl o tted again s t the initial s tate energy,

t h e plot is li n ear and its slope is proportional to

W here h is Planck’s c o nstant and c the speed of light. Te mperat u re can therefore be
deter m ined by m easuring the slo p e of the plot. A n exa mple of this process is shown in Figure A

- 5. In this case the te mperature was 22 5  C and the group of li n es to the left in Figure A

- 4 were used. These are d e fined as the R

- branch li n es of th e CO band.

- 36

0 50 100 150 200 250 300 350 400 450 500

- 3 6.5 T = 22 3 .5 C

y = - 5.518 9 09E

- 03x

- 3.596 9 06E + 01

R 2 = 9 .9618 1 6E

- 01

- 37

- 3 7.5

- 38

- 3 8.5

- 39



### E"

Figure A

- 5, a plot of the CO line intensities versus initial state energy for determination of gas temperature.

Given te m p erature, all ter m s in Equation ( 4 ) can be deter m ined. Equation (4) represents
the trans m ission spectrum, just as would be observed if an active FTIR were used and an IR beam propagated through the plu m e. As a result, the sa m e algorith m s used in nor m al spectr o sco p y can be used to anal y ze this trans m ission spectr um . As in nor m al absorption spectroscopy, the trans m issio n is exponential in gas concentration. That is trans m i ssion is given by:

( ) 

### (8)

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W here K (υ ) is the absor p tion coefficient for the s p ectral line, c the gas c o ncentration, and l the p a th l e ngth in t h e g as. E ff ectively K (υ ) is the referen c e stand a rd in the FTIR for the gas being m onitored. Taking the negative l og of this equation gives what is called
Absorbance. That i s : ( ) ( ) (9)

A bsorbance is li n ear in c oncent r ation ti m es path length and the absorbance spectrum is analyzed u sing standard Classical Least Square s procedures to get the individual gas
concentrati o ns in the s p ectru m . To co mpute combustion efficiency, t h e c o ncentratio n s of CO, CO2, and Total Hydrocarbon (THC) are used to co m pute:

[ ] [ ] [ ] [ ] [ ]



### The re m aining ter m , [ soot ] , is the c o ncent r ation of any soot present. If it is present at any signi f ica n t c oncent r atio n , it w ill be s een in t h e IR spectra as an attenuation of the si g nal
with characteri s tic spectral s hapes d riven by particle s ize d i stribution. It is not believed
that so o t will be a s ignificant issue in m ost w ell r un f lares but if it is p res e nt

, proced u r e s can be developed to treat it.

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# APPENDIX B

– TEST ARRANGEMENT FOR PRESSURE ASSISTED BURNER

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# APPENDIX C

– PROPOSED FUEL COMPOSITION

The purpose of this section is to discuss the selected test fuel compositions.

The predicted compositions that will be sent to PDH

- 1 flare are shown in Table 1 below:

Table 1, PDH

- 1 Multi

- Point Ground Flare Steams (weight %) Compound Normal Net Gas RXPRD N2 Purge Mix Maintenance
Nitrogen

- - - 73.80

- - Carbon Dioxide

- - - 1.10

- - Hydrogen 2.11 64.46 4.200

- 17.73 2.11
Methane 1.92 31.46 2.600 23.30 8.38 1.92
Ethane 10.27 2.94 2.900 1.20 2.28 10.27 Ethylene 0.39 0.35 0.200

- 0.10 0.39 Propylene 27.85 0.45 28.900

- 33.33 27.85 Propane 57.32 0.33 61.100 0.40 36.88 57.32

Butene 0.05

- 0.000

- 0.33 0.05

Butane 0.05

- 0.100

- 1.00 0.05

Pentane

- - 0.000 0.14 0.00 0.00

Benzene 0.04

- 0.000 0.19 0.00 0.04

The propose d test gases for the flare efficiency tests are propylene and mixtures of propylene / nitrogen
and propylene / nitrogen / natural gas

. Although propane is a major component in some of the cases from
Table 1 , the John Zink Co. flare test facility is equipped with a single vaporizer and only one fuel requiring vaporization can be run at a time. Previous flare testing [1] has shown that propylene is more
difficult to completely combust than propan e thus propylene was selected.

A major component in the “Net Gas” case is hydrogen. Given the difficulty of flowing significant quantities of hydrogen at the JZ flare test facility for any length of time, a short term test is proposed to
validate the sta bility of the pressure assisted flare burner with a fuel containing a large proportion of hydrogen. Tests conducted by CMA [ 2 ] the EPA and EER [ 3 ] and the EPA and DuPont [ 4 ] clearly demonstrate that the burning efficiency of a flare is directly related to flame stability. If a predominately hydrogen fuel is stable in a pressure assisted flare burner at sonic velocity, the research indicates the destruction efficiency will be high.

REFERENCES

[1] Marathon Petroleum Company LP, “Performance Test of a St eam

- Assisted Elevated Flare with

Passive FTIR

– Detroit, Final Report”, November 23, 2010.

[2] Engineering Science, “A Report on a Flare Efficiency Study, ” Volume 1 for Chemical Manufacturers Association, March 1983.

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[3] Pohl, J. H., and Soelberg, N.R., “Evaluation of the Efficiency of Industrial Flares: H2S Gas Mixtures and Pilot Assisted Flares,” Energy and Environmental Research Corporation, EPA Contract No. 68

- 02

- 3661, September 1986

.

[4] Energy and Environmental Research Corporation, “Hydrogen Flare Equivalency Demonstration

– Final Report”, October 14, 1997