DATA FOR DESIGN OF VAPOR RECOVERY UNITS FOR CRUDE OIL STOCK TANK EMISSIONS

Final Report EPA/IPEC Award Number R-82-7015-010 Subcontract 14-2-1201270-94844 R.E Babcock, P.I. J. M. Plaza, Graduate Assistant

Department of Chemical Engineering College of Engineering University of Arkansas-Fayetteville

February 6, 2004

ABSTRACT According to EPAs Natural Gas STAR program there are about 573000 crude oil storage tanks in the United States. These tanks are used to keep crude oil after being extracted from production wells. During loading and storage, lighter hydrocarbons dissolved in the feedstock separate from the oil and are often vented into the atmosphere. The composition of these vapors varies, but the largest component is methane followed by ethane, propane, and butane classified as Vapor Organic Compounds (VOC). Other heavier compounds that may be present are benzene, ethyl benzene and xylene (BTEX). These emissions provide a nuisance because of smell and in rare cases, even in the absence of hydrogen sulfide, actually create an identifiable health hazard. The June 17, 1999 regulations issued by EPA call for control systems to reduce emissions by 95% on stock tanks containing API gravity oil greater than 40" and having a gas-oil ratio (GOR) greater than 1750 SCF/STB (Standard Cubic Feet/ Stock Tank Barrel). One way to comply with these regulations and obtain economic savings is to install vapor recovery units (VRU) on oil storage tanks. These simple units can capture 95% of the emissions from stock tanks, which can be disposed for sale or use as fuel on site. However, feasibility of these units requires close design tolerances. EPA and API have developed models to estimate emissions, especially for regulation compliance. These are based on flash vaporization calculations. Yet, it has been established that in less volatile crude oils (API<40) model predictions tend to be overestimated. It is believed that solubility is the controlling mechanism for some of these heavier oil sites. This work presents an approach to emissions based on temperature driven gas solubility and weather conditions. The model uses the Scatchard Hildebrand solubility equation combined with the Prausnitz/Shair fugacity chart for fugacities of gases well above their critical temperature. The only stock tank oil parameters required are an ASTM D-86 boiling point distribution curve and API gravity. The specific details of the model are presented and discussed as well as the results of field-testing of the model in Oklahoma and Arkansas.

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TABLE OF CONTENTS 1. INTRODUCTION .................................................................................................. 1 2. PROPOSED MODEL............................................................................................. 1 2.1. Solubility Parameter Calculations........................................................................... 1 2.2. Molecular Weight Models ...................................................................................... 3 2.2.2. Heat of Vaporization........................................................................................... 4 2.3. Weather Conditions .............................................................................................. 10 2.4. Heating Degree Day.............................................................................................. 10 2.5. Temperature-Humidity-Sun-Wind Index (THSW Index) .................................... 11 3. MODEL CALCULATIONS................................................................................. 11 4. PROJECT EXECUTION...................................................................................... 14 4.1. Sample Recollection and Laboratory Analysis..................................................... 14 4.1.1. Liquid Samples ................................................................................................. 14 4.1.2. Gas Samples...................................................................................................... 15 4.2. Site Visits. ............................................................................................................. 18 4.2.1. Site 1: Exxon-Vastar #1 .................................................................................... 19 4.2.2. Site 2: Marathon Oil-Will Rogers International Airport battery. ..................... 20 4.2.3. Site 3: ENOGEX Wellston Stabilizer Facility............................................... 20 4.2.4. Site 4: Timmins #1............................................................................................ 20 5. RESULTS ............................................................................................................. 21 6. CONCLUSIONS................................................................................................... 23 7. RECOMMENDATIONS...................................................................................... 24 8. REFERENCES ..................................................................................................... 25 9. APPENDIX A: CRUDE OIL CHARACTERIZATION RESULTS.................... 27 9.1. ASTM D86 Results............................................................................................... 27 9.2. API gravity results. ............................................................................................... 53 10. APPENDIX B: SITE VISIT RESULTS ............................................................... 54 10.1. Site 1: Exxon-Vastar #1 .................................................................................... 54 10.1.1. February Visit. .................................................................................................. 54 10.1.2. July Visit. .......................................................................................................... 54 10.2. Site 2: Marathon Oil-Will Rogers International Airport battery ...................... 56 10.2.1. March Visit. ...................................................................................................... 56 10.2.2. July Visit. .......................................................................................................... 58 10.3. Site 3: ENOGEX Wellston Stabilizer Facility............................................... 60 10.3.1. April Visit. ........................................................................................................ 60 10.4. Site 4: Timmins #1............................................................................................ 62 10.4.1. August Visit ...................................................................................................... 62 11. APPENDIX C: GAS CHROMATOGRAPHY RESULTS. ................................. 64

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1. INTRODUCTION This document presents the methodology employed and results obtained during the execution of the project Data for the Design of Vapor Recovery Units for Crude Oil Stock Tank Emissions. Included are the correlations used to estimate the solubility of light compounds (C1-C6) in crude oil using the ASTM D86 distillation curve and the API gravity. Field collected data for the four sites visited is presented as well as results from analytical laboratory analysis of field samples. In addition, recommendations for future work are presented. 2. PROPOSED MODEL This project proposes a model to approximate the yearly VOC emissions of crude oil storage tanks based on the variations in solubility due to changes in temperature and pressure between ambient tank conditions. The model has been developed for standard fixed roof crude oil stock tanks (API 202) for sites with medium to heavy crude oil. Emissions were assumed to be composed of only methane, ethane, propane, ibutane, n-butane, i-pentane, n-pentane. The following concepts and equations are the basis for the proposed model. They were used to define the different parameters that were taken into account in the prediction of tank emissions. 2.1. Solubility Parameter Calculations Solubility parameters were calculated using the Scatchard-Hildebrand equation (10) taking into account the considerations presented by Prausnitz and Shair (10, 13, 14) for gases far from their critical point in a mixed solvent:

 v L fG Oil X i = L exp i i R T f i

)
2

= the Hildebrand solubility parameter. fG = the fugacity of the gaseous solute at the initial state. fiL =the fugacity of the solute (hypothetical) as a pure liquid at the defined temperature. Xi = solubility of gas i expressed as mole fraction in the solvent Subscript i refers to component i. In this equation the liquid fugacity and volume of the solute are hypothetical values taking into account the fact that some vapor components are well above the critical point. These fugacity values were obtained from the classical figure and table presented by Prausnitz and Shair in (10), (13), and (14) for methane and ethane. In the case of C3-C5 compounds the following set of equations were used (7): log 0 = log (0 ) + log (1)

log (0 ) = A0 +
log (1)

A1 + A2Tr + A3Tr2 + A4Tr3 + A5 + A6Tr + A7Tr2 Pr + ( A8 + A9Tr )Pr2 log Pr Tr 1.22060 = 4.23893 + 8.65808Tr 3.15224Tr3 0.025(Pr 0.6 ) Tr

Table 1 presents the values used for the Ai constants:

Constant

A0
5.75748

A1
-3.01761

A2
-4.98500

A3
2.02299

A4
0

A5
0.08427

A6
0.26667

A7
-0.31138

A8
-0.02655

A9
0.02883

Value

Table 1: Constants presented by Chao et al in (7) The crude oil solubility parameter

Oil

was calculated in two ways. First

using a volume fraction weighted average as follows:

= i i
i =1

Here the solubility parameter i for volume fractions at 20%, 60% and bottoms of the ASTM D86 curve were calculated and multiplied by the fraction value (i.). The second procedure to calculate the solubility parameter used the bulk properties of the crude oil In both approaches the solubility parameter was determined using the energy of vaporization and the molar volume of the fraction or bulk sample

i =

U i vi

vap

The energy of vaporization Uivap is equal to Hivap-PV. At low pressures it is possible to assume ideality of the vapor in equilibrium with the liquid (10) so PV was replaced with RT thus the final expression for solubility parameter is:

i =

H i

vap

RT
L

vi

Where T is the temperature at which the value of solubility is being estimated. The molar volume was calculated using the following expression:

vi =
L

Mwi

2.2. Molecular Weight Models In order to calculate the molecular weight of petroleum mixtures it is common to use pseudo component correlations. Thus, various mathematical relationships have been developed to predict pseudo component molecular weights. (16) These correlations are normally based on boiling point, specific gravity data, viscosity, and UOP K factor. For the project calculations a method presented in (2) was used as described below. 2.2.1. Molecular weight calculations according to API Technical Data Book Procedure 2B2.1 3

This method is presented in the Procedure 2B2.1 of the API Technical Data Book (2). It has been selected due to its simplicity for performing computer calculations. The expression for this method is as follows:
MW = 20.486[exp (1.165 E 4Tb 7.78712 SG + 1.1582 E 3 Tb SG )]Tb1.26007 SG 4.98308

Where: MW= molecular weight of the fraction Tb=is the mean average boiling point of the petroleum fraction (oR) SG=Specific gravity of the cut. 2.2.2. Heat of Vaporization. As observed in the Scatchard-Hildebrand equation, the heat of vaporization is another factor necessary to determine the solubility parameter of the oil fractions. This variable was calculated using API Technical Data Procedure 7B.4.7 also documented in (2) which can be used to estimate liquid and gas enthalpies for petroleum fractions. The method divides calculations according to two regions. The first region includes reduced temperatures less or equal to 0.8 and reduced pressures less or equal to 1.0, the equation for the liquid enthalpy is:
H L = A1 (T 259.7 ) + A2 T 2 259.7 2 + A3 T 3 259.7 3

Where: HL is the enthalpy of the liquid petroleum in BTU per pound. 1149.82 46.535 K A1 = 10 3 1171.26 + 23.722 + 24.907 SG ) K + SG 13.817 A2 = 10 6 (1.0 + 0.82463K ) 56.086 SG

 2.3653 A3 = 10 9 (1.0 + 0.82463K ) 9.6757 SG K SG T 3 is the Watson Characterization factor equal to K = b SG is the specific gravity 60F/60F
1

T is the chosen temperature. The reduced pressure and temperature were calculated using the pseudo critical pressure and temperature (Ppc and Tpc) as follows

Pr =

P Ppc

Tr =

T T pc

The formulas used to calculate the two pseudo critical properties will be presented later in this text. The values of enthalpy for the vapor phase of the first region and for the liquid and vapor phases of the second region (Pr >1 and Tr > 0.8) are calculated using the following:
H = H L + B1 (T 0.8T pc ) + B2 T 2 0.64 T pc + B3 T 3 0.512 T pc ~ o ~ H RT pc H + 4.507 + 5.266 MW RT pc
# 2

Where: H HL# is the enthalpy of the petroleum fraction in BTU per pound. is the liquid enthalpy at a reduced temperature of 0.8 calculated by the equation for region 1.

248.46 B1 = 10 3 356.44 + 29.72 K + B4 301.42 SG 253.87 B2 = 10 6 146.24 + (77.62 2.772 K )K B4 301.42 SG

B3 = 10 9 ( 56.487 2.95 B4 )

12.8 10.0 4 B4 = K 1.0 1.0 K (SG 0.885)(SG 0.70 ) 10 for 10.0<K<12.8 with 0.70<SG<0.885 B4=0 for all other cases. MW is the molecular weight in lb/lbmol R is the gas constant, 1.986 BTU/lbmol oR

( )

~o ~ H H is the dimensionless pressure effect on enthalpy obtained from RT pc procedure 7B3.2 in (2). It may be disregarded if Pr <0.01

is the acentric factor. The following paragraphs present the remaining terms necessary to evaluate the enthalpy of vaporization from the previous equations. 2.2.3. Pseudo critical Pressure and Temperature The pseudo critical temperature and pressure were calculated using the specific gravity of the fraction and the mean average boiling point (Procedures 4D3.1 and 4D4.1) in (2). The equations are as follows:

T pc = 10.6443 exp 5.1747 10 4 Tb 0.54444 SG + 3.5995 10 4 Tb SG T 0.81067 S 0.53691 Ppc = 6.0162 10 6 exp 4.725 10 3 Tb 4.8014 SG + 3.1939 10 3 Tb SG Tb0.4844 SG 4.0846
Where: Tpc is the pseudo critical temperature of the petroleum fraction (oR) Ppc is the pseudo critical pressure of the petroleum fraction (psia) Tb is the mean average boiling point (oR) SG is the specific gravity.

( (

))

( (

))

2.2.4. The Acentric Factor The acentric factor of the fraction is defined as (2):

= log Pr* 1.000

Where: Pr* is the reduced vapor pressure P*/Ppc P* is the vapor pressure at 0.7*Tpc To estimate the vapor pressure procedure 5A.1.19 from (2) was used. This method uses a correction for boiling point temperatures of hydrocarbons with a Watson K factor different than 12. The equations are:
log P * = 3000.538 X 6.761560 43 X 0.987672

for X>0.0022

log P * =

2663.129 X 5.994296 95.76 X 0.972546 2770.085 X 6.412631 36 X 0.989679

for 0.0013X0.0022

log P * =

for X<0.0013

Where:

P* is the vapor pressure (mm Hg)

Tb' 0.0002867 Tb' X = T 748.1 0.2145 Tb'

Where: Tb is the normal boiling point corrected to K=12 (oR) T is the absolute temperature (oR) A trial and error is necessary for the K=12 correction. The following set of equations are used: T = Tb Tb' = 2.5 f (K 12 ) log Tb is the normal boiling point (oR) f is a correction factor. For all sub atmospheric vapor pressures and for all substances having normal boiling points greater than 400 F. f = 1. For substances having normal boiling points less than 200 F, f= 0. For super atmospheric vapor pressures of substances having normal boiling points between 200 F and 400 F, f is evaluated by: P* 760

f =

Tb 659.7 200

2.2.5. Pressure Effect on enthalpy term

~o ~ H H The dimensionless pressure effect on enthalpy was RT pc obtained from procedure 7B3.2 in (2). The equation used was:

~ o ~ ~ o ~ (0 ) H H H H = + (h ) RT RT pc pc Where:

~ o ~ ( h ) ~ o ~ (0 ) H H H H RT pc RT pc

~o ~ H H is the dimensionless effect of pressure on enthalpy of RT pc the fluid of interest.

~ o ~ (0 ) H H is the effect of pressure on enthalpy for the simple RT pc fluid. ~ o ~ (h ) H H is the effect of pressure on enthalpy for the heavy RT pc reference fluid (n-octane).

is the acentric factor calculated for the fraction. (h) is the acentric factor of the heavy reference fluid = 0.3978 The effect of pressure on enthalpy for the simple and heavy fluid is calculated by the following equation:
~ o ~ (i ) H (i ) b2 + 2b3 / Tr + 3b4 / Tr2 c 2 3c3 / Tr2 d2 H 1 3 = Tr + + z E 2 5 RT T V 2 5 T V T V pc r r r r r r

Where:
E= c4 2Tr3 +1 +1+ Vr2 exp V 2 r

The superscript (i) will be (0) when the equation is applied to the simple fluid and (h) when it is applied to the heavy reference one. Tr is the reduced temperature T/Tpc T is the desired temperature (oR) The rest of the unknowns were obtained from equations and values found in Procedure 6B1.8 (2). The main equation to be used from this procedure is:

z (i ) =
Where:

PrVr c B C D = 1+ + 2 + 5 + 3 4 2 Tr Vr Vr Vr Tr Vr

+ V 2 exp V 2 r r

The superscript (i) is (0) when the equation is applied to the simple fluid and (h) when it is applied to the heavy reference one.
Vr = PpcV RT pc

V is the molar volume (ft3/lbmol) for the simple or heavy model according to which z is being calculated. R is the gas constant (10.731 psia ft3/lbmol oR)

B = b1

b2 b3 b4 Tr Tr2 Tr3
c 2 c3 + Tr Tr 3

C = c1

D = d1 +

d2 Tr

The rest of the constants are listed in the following table for the simple and heavy reference fluids.

Table 2: Constants from procedure 6B1.8 (2) Heavy Constant Simple Fluid Reference Fluid 0.1181193 0.2026579 b1 0.265728 0.331511 b2 0.154790 0.027655 b3 0.030323 0.203488 b4 0.0236744 0.0313385 c1 0.0186984 0.0503618 c2 0.0 0.016901 c3 0.042724 0.041577 c4 4 0.155488 0.48736 d1 x 10 4 0.623689 0.0740336 d2 x 10 0.65392 1.226 0.060167 0.03754 2.3. Weather Conditions Emissions from crude oil stock tanks are affected by the weather conditions at the site.(15) The model takes into account the differences between the crude oil feed temperature and pressure and the stock tank oil temperature and pressure. In order to include this variable in the model, two indicators are proposed for analysis: the heating degree-day and the THSW (Temperature-Humidity-Sun-Wind) index. 2.4. Heating Degree Day The heating degree-day concept has been proposed as an indicator of the amount of time the temperature of a geological area is above a certain pre-established threshold temperature. It has been used by ecologists to measure or predict the effect of temperature on biological processes, such as plant growth, and used by engineers as an index of heating fuel requirements. The latter application defines the heating degree day as the difference between the mean of the high and low temperatures for one day minus 65 F, which is normally the temperature limit for a building to require heating to maintain an inside temperature of 70 F.

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The ecological definition is more complex and approximates better the behavior of ambient temperature through out a normal day. The calculations are based on the area under the diurnal temperature curve and between the predefined thresholds (9). The most commonly used methods are linear; they are identified, in order of mathematical complexity as: single triangle, double triangle, single sine, double sine and Hubers. 2.5. Temperature-Humidity-Sun-Wind Index (THSW Index) The THSW index uses humidity and temperature to calculate apparent temperature. It also includes the heating effects of solar radiation and the cooling effects of wind on the perception of temperature (8). A set of equations (17) has been developed to describe sultriness given the ambient temperature, humidity, wind and extra radiation (direct and indirect insolation; terrestrial and sky radiation). A table with an apparent temperature scale is also available and applicable in most populated areas of North America (17). However this index employs different values and correlations that are pertinent to humans, a modification would be required in order to make it applicable to stock tanks for the model of interest here. 3. MODEL CALCULATIONS. The fundamental hypothesis of this project is that vapor emission rates from stock tanks can be estimated with greater precision than currently exist in literature by characterizing the gas solubility of the crude sales oil using parameters commonly available or easily obtained for lease sites (API gravity and boiling point distribution curve) and then estimating the rate of individual component vapor emissions released from the oil as a function of ambient conditions, and residence time in the tank. Inherent in this hypothesis are the following assumptions: Based on results from (15), vapor emissions are only considered to be VOC (mainly C1-C5) since HAPs are assumed to be only 1.3% at the most.

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The crude oil enters the stock tank saturated with the VOCs listed above at its heater/treater temperature and pressure. If free gas is present in the feed it must be accounted for outside the model.

The oil characterization parameters mentioned previously are capable of determining the Hildebrand solubility parameter specific to the oil in question, which in turn adequately represents the solubility of the VOCs in the crude oil as a function of temperature and pressure.

The temperature history of the crude oil in the stock tank can be correlated with the climatic conditions obtained from nominal National U. S. Weather data for the general region of the lease sites. (5)

Gas solubility of the dead oil decreases with temperature so if the oil enters the stock tank at some temperature and then begins to cool off on a cold winter day, no gas will be released except volumetric displacement due to oil production entering the tank. Based on these assumptions the following system of equations composes the solubility model proposed:
V = Q Rsin RsO dt + N B RSO max RSO min Q j RS j + Q * 5.62 * t
0 j =1 t

Where: V is the amount of cumulative vent flow in SCF (over a defined time period, t). Q is the oil production rate during the time period (in Bbl); h such events Qj is the amount of oil removed from the tank during a jth unloading event (in bbl) NB is the number of barrels present in the tank at time zero. Rs is the sum of the solubility of the supercritical gases measured in SCF/Bbl 5.62 SCF/Bbl The subscripts refer to the following conditions: sO atmospheric pressure and tank temperature sin heater/treater conditions. sO-max, sO-min maximum and minimum values during the accounting period.

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sj unloading conditions during the j time. (Atmospheric pressure and Tj temperature) The first term represents the emissions generated due to change in solubility of the oil entering the tank during the accounting period because of varying tank conditions. The second term describes the emissions produced during the observation period due to the impact of fluctuations in tank temperature upon the crude oil initially in the tank at time zero (breathing losses). The following term is the sum of the gas that leaves the tank as soluble gas in the sales oil. The last term is the working displacement term due to displacement as oil comes in. For year round calculations the second term of this equation is assumed small compared to the other two so it will normally be omitted from the model calculations. Furthermore, using weather conditions the gas solubility will be averaged for the accounting period so the final model equation will be

V = Q Rsin RsO t Q j Rs j + Q * 5.62 * t

j =1

Where: Rsin , RsO are average gas solubilities for the accounting period. t is the length of the accounting period. As presented before, solubilities (Rs) for each compound in the emissions in crude oil was estimated using regular solution theory following the established work of Prausnitz and Shair (10),(13),(14) including the necessary modifications for which:

oil Rsi = 132.86 Mw oil

Here

P f L pure

L exp vi i R T

Rsi is the solubility of one of the vent gas components in Scf / bbl. oil is the density for the stored crude oil in kg/m3. Mwoil is the molecular weight of the crude oil P is pressure of the crude oil (bar)

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fpureL is the fugacity of the solute (hypothetical) as a pure liquid at the defined temperature (bar) vL is the hypothetical molar liquid volume of the solute. (cm3/gmol) is the solubility parameter of the gaseous solute (J) is the solubility parameter for the crude oil at the established temperature (J) R is the universal gas constant T is absolute temperature. 132.86 is a unit conversion constant.(SCF/BBl) The fugacity parameter of the gas at the initial state fG was considered to be equal to the product of the gas fraction and the total pressure of the system. For each compound in the gas the solubility was calculated independently. The final equation for each component then becomes:

oil Rsi = 132.86 Mw oil

P f L pure

L exp vi i R T

The total solubility was then obtained by adding the values of Rsi calculated for each of the C1-C5 compounds mentioned previously. 4. PROJECT EXECUTION. 4.1. Sample Collection and Laboratory Analysis. 4.1.1. Liquid Samples Crude oil liquid samples were collected twice during each site visit: at the beginning and end of the data recollection period. For this purpose a Boston bottle mounted on a brass cage was introduced in the tank through the thief hatch. A sample was collected at approximately the middle of the liquid level present in the tank at the time of collection. These samples were sealed, transported and then stored in the bottles until analysis occurred in the lab. Samples were analyzed using standard ASTM D-86 simulated distillation to obtain the boiling point curve (3) and a hydrometer was used for measuring the API gravity of each combined (4).

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API gravity measurements for the combined sample were performed using one of three hydrometers acquired, depending on the interval of measurement desired. Available hydrometers had the following ranges: 10 to 40, 30 to 50 and 45 to 90 API. For the ASTM D-86 distillations a PRECISION distillation apparatus was acquired using 125 ml flasks with taper joint neck according to the method and a pair of 7C and 8C ASTM E1 thermometers. Thermometer Condenser water line

Distillation Flask

Graduated Cylinder (Distillate recollection)

Figure 1: ASTM D86 Simulated Distillation Apparatus

Weight of the distillate was measured during the first ASTM D86 distillations to try to estimate the density of the volume percentage cuts of the method by using the difference in volume and weights of each cut. However, this idea was discarded because results were inconsistent. (see Appendix A) Cumulative samples at 20%, 60% and final cut volume were taken for density measurement using a pycnometer. These data was used to emulate the components of the crude oil to be introduced in the model calculations. (Appendix B) 4.1.2. Gas Samples Gas samples were collected using 6-liter TO-14 canisters and a Veriflo SC423XL flow controller metering valve. The system was connected to the vent pipe of the tank and flow was regulated by the metering valve to fill the canister

15

in approximately six hours. Some instantaneous grab sample of vent gas were also collected. (Figure 2)
Quick-change connection Vacuum gauge Vent gas
P

Crude Oil inlet TO-14 Canister

Dry gas meter Flow controller

Figure 2: Crude oil stock tanks gas sampling set up

Previous to each site visit TO-14 canisters were evacuated to approximately -26 in.Hg in the laboratory. Once in the field they were connected to a segment of pipe added to the vent pipe through the flow controlling system. The dry gas meter was installed at the end of this pipe segment. Gas samples were analyzed using gas chromatography to determine the composition of the emissions collected. The method for analysis was based on GPA 2261. The method was initially implemented for the analysis of air, methane, ethane, propane and butane by using pure gas standards of the first three components and a 10% in helium standard for the butane. Analysis of additional components was accomplished by utilizing a natural gas standard with a fixed composition (Table 3).

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Component Nitrogen Carbon Dioxide Helium Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane

Mole Faction % 5.01 0.999 0.501 70.44 9.01 6.00 3.02 3.00 1.01 1.01

Table 3: Composition calibration standard for GC analysis.

Carrier Gas line Vacuum Pump

PI

Sampling loops (30l)

10 port switching valve Gas sample canister

TCD inlet

FID inlet

Figure 3: Set up for Gas Chromatography analysis

To draw the sample for analysis, a vacuum of 100 mmHg was pulled on two 30l sampling loops hooked up to a 10 port-sampling valve. The sample canister was connected to the valve and once the vacuum pressure in the system was reached the sample was allowed to enter the loops. Later it was injected into

17

two columns in the GC. One was a 2-meter x 1/16 stainless steel packed column with mesh 80/100 Carboxen 1004 packing connected to the TCD and dedicated to the analysis of permanent gases (air in this case). The second column was a 15 ft. x 0.04 in stainless steel column with a 25% SP-2100 phase and 80/100 mesh Chromosorb PAW packing, used for analysis of the hydrocarbons present by using the FID.(See Figure 3) The established operating conditions for the method are presented in Table 4 Variable Injection loop Pressure Injection Temperature Detector Temperature Initial Temperature Initial time Temperature ramp rate Final Temperature Final Time Carrier gas Carrier gas flow TCD Carrier gas flow FID Value 350 mmHg 230 oC 230 oC 35 oC 2 min. 24 oC / min. 225 oC 3 min. Helium 0.096 ml/s 0.093 ml/s

Table 4: Gas Chromatography Analysis conditions. Calibration runs were performed by connecting the standard cylinder instead of the sample canister to the sampling valves. For air the sampling valves were left open at the inlet and the vacuum pump was started so that the loops filled with ambient air. 4.2. Site Visits. During execution of the project 6 field site visits were made at locations in Oklahoma and Arkansas. During each site visit the following variables were monitored:

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Temperature of the oil: measured from a sample taken from the middle of the tank or in some cases using a thermocouple so located connected to a wireless transmitter that sent the signal to the recording weather station.

Heater/Treater temperature and pressure. Level of oil in the tank. This variable served as a measurement of the amount of feed oil that had entered the tank. It was monitored using a gauge tape.

Temperature of the tank wall. To monitor this variable a thermometer was taped on the side of the tank. Vent gas flow: quantified using a dry gas meter connected to the vent line of the stock tank. Ambient weather Conditions. Weather variables were obtained from a Davis Instruments wireless portable weather station. The main variables monitored were wind speed and direction, ambient temperature, humidity and solar radiation, although temperature was the most pertinent parameter

4.2.1. Site 1: Exxon-Vastar #1 This site is located in South Arkansas situated approximately 45 minutes southeast of El Dorado, AR. operated by Shuler Drilling Co. The well was put online about one year ago with production averaging around 30 BPD. The lease setup is relatively simple with one well, a heater/treater with no heat input and a 30 psia pressure swing flash to the stock tank. The thief hatches were set to hold a backpressure of 2 oz. Two visits were made to this site one in March and a second in mid July. During both visits oil flow was halted due to well operation problems, which in turn obviously affected the collected data. Additionally, it was not possible to completely isolate the tank under analysis. The thief hatch had sealing problems and the tank was connected to a second oil stock tank, a brine tank in addition to a return line to the wellhead for fuel to the pump jack engine. Data collected from these visits are presented in Appendix C

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4.2.2. Site 2: Marathon Oil-Will Rogers International Airport battery. Located near Oklahoma City, Marathon Oil is the operator; it is located just off site of the Will Rogers International Airport It is set-up with 26 wells online (some operating and some shut-in) pumping into five stock tanks. Dual heater/treaters are inline as well as a vacuum vapor recovery unit drawing vapor from a surge tank between the heater/treaters and the stock tanks. Thief hatches were set to hold 2 oz backpressure and the vent gas fluctuated widely apparently due to well head operating conditions. This site was visited twice during the project. The first site visit was conducted at the end of March. During this visit the vapor recovery unit was not online because of insufficient gas flow to maintain its operation (the unit shuts off if the unit creates vacuum pressure at the suction point at the surge tank.). Even with the VRU operating this lease site was characterized by noticeable vent gas flow fluctuations. The second visit was scheduled in mid July. During this visit the VRU unit was kept online most of the time. Again gas flow during the monitoring period was characterized by large flow surges. (See Appendix C) 4.2.3. Site 3: ENOGEX Wellston Stabilizer Facility. This site is located off the Wellston exit of Interstate HY 44. It consists of upstream processing of condensate gas yielding a high gravity (60 to 90 API) oil, feeding three stock tanks with production of 600-700 BPD. This site was monitored at the beginning of April. (See Appendix C) 4.2.4. Site 4: Timmins #1 This site is also operated by Shuler Drilling Co. and is located near Strong, Arkansas, in the vicinity of Site 1. This site was monitored in mid August. It is a simple set up consisting of one oil well connected to a single heater/treater with two storage tanks and three brine tanks.

20

During this visit difficulties in isolating the system were encountered. An uncapped recycle gas line was discovered midway through the site visit. As a result of this, very small gas flow readings were observed. (see Appendix C). However, results from lab analysis show this to be a promising site. API gravity was around 330 and gas composition shows high content of methane. 5. RESULTS The results obtained for the analysis of each of the samples from the field are presented in this section. Data from site 1 reflect the wellhead problems that were faced during field visits.(high air content due to either low or non existent oil feed flow). Sites 2 and 3 demonstrate higher concentrations of C3+ hydrocarbons. Site 4 has the highest concentration of methane of all studied sites. Component Air Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane C6+ Site 1 90.5-83.1 3.4-0.8 0.9-0.3 0.5-0.1 2.2-1.0 1.1-0.5 2.4-1.3 2.2-1.3 6.0-4.7 Site 2 66.4-20.0 14.8-3.6 19.6-9.8 26.7-14.3 3.6-2.0 11.3-6.0 2.1-1.1 2.8-1.4 2.0-0.6 25.5-21.1* Site 3 30.7-12.6 23.1-18.5 6.3-4.1 12.2-6.3 24.7-18.0* Site 4 63.6-50.7 41.1-33.0 1.9-1.1 0.3-0.1 1.1-0.6 1.1-0.5 0.8-0.3 0.8-0.3 2.2-0.4

* Site 3 data only available using initial pure component GC calibration

Table 5: Data results for GC analysis. For sample-by-sample data see AppendixC Results from the ASTM D86 distillation analysis show little variation in the characteristics of the oil for a given site. (See Table 6 and Appendix A) Deviation of

21

results in most cuts are below 10% between visits and even smaller between samples taken during a given site visit. The API gravity analysis deviations are less than 5% between samples of a given site (Table 7) Temperature (C.) Volume% IPB 5 10 15 20 30 40 50 60 70 80 85 90 95 FBP Site 1 63.3 79.34 96.44 107.22 118.23 144.29 174.76 207.83 242.39 279.72 322.57 350.13 373.27 383.13 383.13 368.4 Site 2 45.25 64.03 94.92 115.4 135.0 177.5 227.1 281.7 329.6 352.5 362.9 367.4 368.4 Site 3 29 29.7 36.8 39.4 42 46.4 51.5 57.1 63.3 71.0 81.4 87 94 111.7 111.7 363.34 Site 4 76 99.82 138.26 171.48 199.56 257.96 301.74 332.42 349.12 357.58 362.18 363.34

Table 6: Average results for the ASTM D86 Analysis. (Site 4 were averaged between the initial and final sample.

Cut %

Site 1

Site 2

Site 3 94.4 86.8 70.6 81.5

Site 4 62.5 41.8 33.1 33

75.2 69.4 20 57.6 44.0 60 41.8 33.2 Bottoms Whole 52 38.9 sample Table 7: Average results for API gravity tests.

22

An emission model pre-run with simulated site conditions was carried out for each site. For this pre run heater/treater conditions were set at temperature of 90oF and a pressure of 35 psi. Tank temperature was defined at 100 F with atmospheric pressure (14.7 psi.). An inlet flow of 34.41 Bbl/hr was used. Results are presented in Table 8. These calculations demonstrate the possibility of calculating solubilities using only API gravity and the D86 curve using both approaches: whole sample as a single cut and three distillation cuts for a weighted average. However, field monitoring verification is incomplete. Site 1 Liquid Fractions Whole sample 2700 2780 Site 2 2640 2690 Site 3 4620 4530 Site 4 2250 2350

Table 8: Model calculated solubilities. Results in SCF/Bbl of solubility difference between heater/treater and tank conditions. 6. CONCLUSIONS It was demonstrated that a model can be developed that yields vent gas estimates by summing individual vent gas component solubility changes in the sales oil characterized by API gravity and boiling point distribution curves. Data collected from visits to sites 1-3 serve as guiding point for future trips. It was possible to observe that Site 1 and especially Site 3 present values well above the applicability of the proposed model because of high API gravity. The system layout in site 2 is too complex making difficult the analysis of the operation. However, Site 4 seems promising for future study since it has a simple layout with one heater/treater unit and a two-tank battery for oil recollection. Also, oil characteristics in this site are within the model range.(See Table 7). consideration. An additional site in central Oklahoma is under

23

There were no noticeable variations in oil characterization at any of the sites during the monitoring period in that API gravity and the boiling point distributions of the ASTM D86 curve showed very little variation between samples of a given lease oil. Field data gathered relating ambient weather conditions and tank temperature behavior is inconclusive. Work is being directed towards determining the best way to correlate this variable in the field with the national weather reports and the model calculations. A final model will include all this variables as proposed in order to yield an estimate of yearly vent gas emissions for each field site. 7. RECOMMENDATIONS Results obtained from the project although not conclusive, demonstrate the importance and potential of the model. However it is necessary to modify some aspects and field verification protocol This can be done by the following actions: There is a need to schedule longer site monitoring periods. A month long period is recommended for future studies since it will give a more representative set of data for each season. Continuous gas flow readings are required due to the considerable fluctuations of this variable on site during monitoring periods. A thermal dispersion meter with a continuous wheel chart recorder is the suggested option for flow monitoring. It creates very low backpressure and may record fluctuating flow rates continuously. It is necessary to carefully isolate the tank under analysis leaving only one inlet for oil feed and two outlets for vent gas and sales oil. This will assure accurate representation of vent gas flow data. Comparison with other simulators is recommended, especially the Vasquez and Briggs model and the E&P Tanks software because of their widespread use in the industry for both regulatory purposes and VRU design purposes.

24

8. REFERENCES (1) Allen, J.C Modified Sine Wave Method for Calculating Degree Days Environmental Entomology. 5(3) pp. 388-396 (1976)

(2) API Technical Data Book. American Petroleum Institute, Washington D.C. 5th ed. (1992). (3) (4) ASTM D86 00,Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure, August, 2000. ASTM D 1298 Standard Practice for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method, May 1990

(5) Babcock R. Data for the Design of Vapor Recovery Units for Crude Oil Stock Tank Emissions. IPEC Project document. Department of Chemical Engineering University of Arkansas-Fayetteville. (2002) (6) Baskerville, G.L. Emin, P. Rapid estimation of heat accumulation from maximum and minimum temperatures, Ecology, 50(3) pp. 514-517 (1969) (7) Chao K.C, Seader J.D. A general correlation of Vapor-Liquid Equilibria in Hydrocarbon Mixtures AICHE Journal Vol.7 No.4, pp. 598-605 (1961) (8) Console Manual. Davis Vantage Pro-Weather Station. Davis Instruments (2001)

(9) Degree Days and Phenology Models. University of California. Statewide Integrated Pest Management Program. (Revised September 13, 2002) http://www.ipm.ucdavis.edu/WEATHER/ddconcepts.html (10) Hildebrand J.H. Prausnitz J.M. and Scott R.L. Regular and Related Solutions. The solubility of gases, liquids and solids. Van Nostrand Reinhold Co. (1970) (11) Moretti E., Reduce VOC and HAP emissions,Chem. Eng. Progress,98 (6), pp 30-40 (June 2002) (12) Peress J., Estimate Storage Tank Emissions, Chem. Eng. Progress, 97 (8), pp. 44-45 (Aug. 2001) (13) Prausnitz J.M. and Shair F.H. A Thermodynamic Correlation of Gas Solubilities. A.I.Ch.E Journal , 7, pp 682-687 (1961)

25

(14) Prausnitz J.M. Lichtenthaler R. N. and Gomes de Azevedo E. Molecular Thermodynamics of Fluid-Phase Equilibria. 3rd Ed. Prentice Hall. (1999) (15) Radian International LLC, Evaluation of a Petroleum Production Tank Emission Model American Petroleum Institute Publication Number 4662, Washington, D. C., 1997. (16) Schneider D. Select the Right Hydrocarbon Molecular Weight Correlation Chem Eng Progress pp.40-44. (December 1998) (17) Steadman, R.G. The Assessment of Sultriness, Part II: Effects of Wind, Extra Radiation and Barometric Pressure on Apparent Temperature Journal of Applied Meteorology. (July 1979) (18) Twu, C.H. An Internally Consistent Correlation for Predicting the Critical Properties and Molecular weights of Petroleum and Coal Tar Liquids, Fluid Phase Equilibria,16, pp. 137-150 (1984) (19) U.S Environmental Protection Agency, Emission Factor Documentation for AP-42, Section 7.1, Organic Liquid Storage Tanks. Final Report US EPA , Office of Air Quality Planning and Standards, Emission Factor and Inventory Group (Sept. 1997) found at http://www.epa.gov/ttn/chief/ap42 (20) Vasquez, M., Beggs H.D. Correlations for Fluid Physical Property Prediction. Journal of Petroleum Technology. pp.968-970 (1980)

26

9. APPENDIX A: CRUDE OIL CHARACTERIZATION RESULTS 9.1. ASTM D86 Results. The following pages present the results obtained for the ASTM D86 Distillation analysis.

27

D86 DISTILLATION CURVE Site 1-March Visit-Sample 1 (First Test)

400 350 300 Temperature (C) 250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 Volume Percentage

28

D86 DISTILLATION CURVE Site 1-March Visit- Sample 1 (Second test)

400 350 300 Temperature (.C) 250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 Volume Percentage

29

D86 DISTILLATION CURVE Site 1-March Visit- Sample 1 (Second Test)

1.8 1.6 1.4 Density (g/ml) 1.2 1 0.8 0.6 0.4 0.2 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Percentage

30

D86 DISTILLATION CURVE Site 1- July Visit-Sample1 (First Test)

400 350 300

T em p eratu re (C)

250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 Volume Percentage

31

D86 DISTILLATION CURVE Site 1 - July Visit- Sample 1 (Second Test)

450 400 350
Temperature (C)

300 250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Percentage

32

D86 DISTILLATION CURVE Site 2- April Visit-Sample1 (First Test)

400 350 300

Temperature (C)

250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Percentage

33

D86 DISTILLATION CURVE Site 2- April Visit-Sample 1 (First Test)

0.95 0.9 0.85

Density (g/m l)

0.8 0.75 0.7 0.65 0.6 0.55 0.5 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Percentage

34

D86 DISTILLATION CURVE Site 2 - April Visit - Sample 1 (Second Test)

400 350 300 Temperature (C) 250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Pe rce ntage

35

D86 DISTILLATION CURVE Site 2 - April Visit - Sample 1 (Second Test)

1 0.95 0.9 0.85
Density (g/m l)

0.8 0.75 0.7 0.65 0.6 0.55 0.5 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Pe rce ntage

36

400 350 300

D86 DISTILLATION CURVE Site 2- April Visit- Sample 2 (First Test)

T em p eratu re (C )

250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Percentage

37

D86 DISTILLATION CURVE Site2- April Visit- Sample 2 (Second Test)

0.95 0.9 0.85 Density (g/ml) 0.8 0.75 0.7 0.65 0.6 0.55 0.5 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Pe rce ntage

38

400 350 300 Temperature (C) 250 200 150 100 50 0 0 5

D86 DISTILLATION CURVE Site 2 - July Visit - Sample 1 (First Test)

10

15

20

30

40

50

60

70

80

85

90

Volume Percentage

39

D86 DISTILLATION CURVE Site 2- July Visit- Sample1 (Second Test)

400 350 300 Temperature (C) 250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 Volume Percentage

40

D86 DISTILLATION CURVE Site 2- July Visit - Sample 2 (First Test)

400 350 300 Temperature (C) 250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 Volume Percentage

41

D86 DISTILLATION CURVE Site 2-July Visit - Sample 2 (Second Test)

400 350 300
Temperature (C)

250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 Volume Percentage

42

D86 DISTILLATION CURVE Site 3 - April Visit - Sample 1 (First Test)

160 140 120 Temperature (C) 100 80 60 40 20 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Percentage

43

D86 DISTILLATION CURVE Site 3 - April Visit - Sample 1 (First Test

0.8 0.75 0.7 0.65 0.6 0.55 0.5 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Pe rce ntage

Density (g/ml)

44

140 120 100 Temperature (C) 80 60 40 20 0 0 5

D86 DISTILLATION CURVE Site 3 - April Visit- Sample 1 (Second Test)

10

15

20

30

40

50

60

70

80

85

90

95

Volume Percentage

45

D86 DISTILLATION CURVE Site 3 - April Visit - Sample 1 (Second Test)

1.3 1.2 1.1

Density (g/ml)

1 0.9 0.8 0.7 0.6 0.5 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Pe rce ntage

46

160 140 120 Temperature (C) 100 80 60 40 20 0 0 5

D86 DISTILLATION CURVE Site 3 - April Visit -Sample 2 (First Test)

10

15

20

30

40

50

60

70

80

85

90

95

Volume Percentage

47

D86 DISTILLATION CURVE Site 3 - April Visit -Sample 2 (First Test)

1 0.9 0.8 0.7 Density (g/ml) 0.6 0.5 0.4 0.3 0.2 0.1 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Pe rce ntage

48

D86 DISTILLATION CURVE Site 3 - April Visit - Sample 1 (Second Test)

160 140 120

Temperature (C)

100 80 60 40 20 0 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Percentage

49

D86 DISTILLATION CURVE Site 3 - April Visit - Sample 1 (Second Test)

0.8 0.75 0.7 0.65 0.6 0.55 0.5 0 5 10 15 20 30 40 50 60 70 80 85 90 95 Volume Pe rce ntage

Density (g/ml)

50

400 350 300 Temperature (C) 250 200 150 100 50 0 0

D86 DISTILLATION CURVE Site 4 - August Visit - Sample 1 (First Test)

10

15

20

30

40

50

60

70

80

85

90

Volume Percentage

51

D86 DISTILLATION CURVE Site 4 - August Visit - Sample1 (Second Test)

400 350 300 Temperature (C) 250 200 150 100 50 0 0 5 10 15 20 30 40 50 60 70 80 85 90 Volume Percentage

52

9.2. API gravity results. Distillation Volume Cut 20% 73.9 74.0 77.7 69.4 69.2 70.0 69.2 93.9 94.8 62.5 60% 56.7 56.5 59.7 44.4 43.3 44.4 43.9 87.7 86.1 41.8 Bottoms 42.1 39.2 44.2 33.0 33.9 33.8 32.1 72.5 68.7 33.1 Whole sample measurement 52.0 52.0 52.0 38 39 39.3 39.3 81.0 82.0 33.0

Site

Month

Sample 1

March 1 July 2 1 1 April 2 2 1 July 2 1 3 April 2 4 August 1

53

10. APPENDIX B: SITE VISIT RESULTS Presented in this section is the data collected during monitoring of the different sites under study. 10.1. Site 1: Exxon-Vastar #1 10.1.1. February Visit.
Temperatures (oC) Day Time Oil 10:00 AM 11:00 AM 2:00 PM 5:00 PM 9:00 AM 1:00 PM 2:00 PM Tank wall 15 11 11 10.5 6 9 8 11 7.5 6.5 4 8.5 10 11.5 8 7 4.5 10 11.5 21.1 21.1 20.0 15.6 16.7 17.2 Ambient Heater /Treater Gas Flow (sfcm) 0.0 0.0 0.0 0.0 0 1.3 1.3 Pressure Heater /Treater (psi) 34 33 34 5.0 6 14 18 Tank Oil Level (ft) 9.25 9.17 9.67 9.71 9.68 9.83 9.75

10.1.2. July Visit.

Pressure Heater /Treater (psi) 30 29 29 29 29 29 29 29 Tank Oil Level (ft) 10.83 10.42 10.42 10.42 10.42 10.42 10.42 10.42

Day

Time 10:00AM 11:00AM

Gas Flow (SCF) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

1:30PM 2:30 PM 6:37PM 9:00AM

10:55PM 1:20PM

54

Temperature (C)
10 15 20 25 30 35 40 45 50

Time

Temperature Profiles Site 1- July Visit

55

10:00 10:30 11:00 11:30 12:00 12:30 1:00 1:30 2:00 2:30 3:00 3:30 4:00 4:30 5:00 5:30 6:00 6:30 7:00 7:30 8:00 8:30 9:00 9:30 10:00 10:30 11:00 11:30 12:00 12:30 1:00 1:30 2:00 2:30 3:00 3:30 4:00 4:30 5:00 5:30 6:00 6:30 7:00 7:30 8:00 8:30 9:00 9:30 10:00 10:30 11:00 11:30 12:00 12:30 1:00 1:30

AM AM AM AM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM PM PM PM PM

Toil Tamb T wall T heater

10.2.

Site 2: Marathon Oil-Will Rogers International Airport battery

10.2.1. March Visit.

Pressure Heater /Treater (psi) 27 25 25 23 25.5 22.5 22.0 26.0 24 21.5 20.5 21.0 21.0 24.0 22.5 26.0 24.5 25.0 Tank Oil Level (ft) 5.82 N.A 4.92 4.00 N.A N.A 2.94 2.92 N.A N.A N.A 6.67 6.85 7.21 7.38 N.A N.A N.A

Day

Time 9:45AM 10:45AM 11:45AM 12:45PM

Gas Flow (SCF) 0 380 427.3 122.0 346.7 471.9 429.9 76.1 507.7 133.2 221.0 325.4 357.8 383.2 418.0 286.0 446 427.7

1:45PM 2:45PM 3:45PM 4:45PM 5:45PM 9:30PM 7:45AM 8:45AM 9:45AM

10:45PM 11:45PM 12.:45PM 2:15PM 10:45PM

56

Temperature (C)
10 20 30 40 50 60 0

Time

Temperature Profile Site 2- March visit

57

9:45 10:45 11:45 12:45 1:45 2:45 3:45 4:45 5:45 6:45 7:45 8:45 9:45 10:45 11:45 12:45 1:45 2:45 3:45 4:45 5:45 6:45 7:45 8:45 9:45 10:45 11:45 12:45 1:45 2:45 3:45 4:45 5:45 6:45 7:45 8:45 9:45 10:45

AM AM AM PM PM PM PM PM PM PM PM PM PM PM PM AM AM AM AM AM AM AM AM AM AM AM AM PM PM PM PM PM PM PM PM PM PM PM

T oil

Tamb.

T heater

10.2.2. July Visit.

Day Time 8:45AM 9:45AM 1 10:45AM 12:45PM 2:30PM 6:30PM 7:00AM 8:00AM 2 9:00AM 10:00AM 11:00AM 12:00PM Gas Flow (SCF) 0 150 140 730 430 1100 2850 200 120 160 50 170 Pressure Heater /Treater (psi) 23 22.5 23 25.5 24.5 25.5 24.0 25.6 25.0 25.0 26.5 26.0 Tank Oil Level (ft) 6.00 5.08 4.67 3.42 3.58 4.27 6.25 6.25 6.08 5.42 5.00 4.16

58

Temperature (C) 10 20 30 40 50 60 0

Time

Temperature Profiles Site 2 -July visit

59

8:45 9:15 9:45 10:15 10:45 11:15 11:45 12:15 12:45 1:15 1:45 2:15 2:45 3:15 3:45 4:15 4:45 5:15 5:45 6:15 6:45 7:15 7:45 8:15 8:45 9:15 9:45 10:15 10:45 11:15 11:45 12:15 12:45 1:15 1:45 2:15 2:45 3:15 3:45 4:15 4:45 5:15 5:45 6:15 6:45 7:15 7:45 8:15 8:45 9:15 9:45 10:15 10:45 11:15 11:45

AM AM AM AM AM AM AM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM

T oil

T wall

Tamb.

T heater

10.3.

Site 3: ENOGEX Wellston Stabilizer Facility.

10.3.1. April Visit.

Day Time 8:45AM 9:45AM 10:45AM 11:45AM 1 12:45PM 1:45PM 2:45PM 3:45PM 4:30PM 8:45AM 9:45AM 11:00AM 11:50AM 2 12:30PM 2:30PM 3:30PM 4:30PM 6:00PM 6:30 Gas Flow (SCF) 0 230 330 340 390 310 370 300 320 4140 160 200 160 150 490 210 260 180 90 Tank Oil Level (ft) 2.17 2.67 2.67 2.67 4.33 N.A N.A N.A N.A N.A N.A N.A N.A N.A N.A N.A N.A N.A N.A

*Tank level data is limited due to difficulties to gauge the tank

60

Temperature (C) 10 15 20 25 30 0 5

Time

Temperature Profiles Site-3 April visit

61

8:45 9:30 10:15 11:00 11:45 12:30 1:15 2:00 2:45 3:30 4:15 5:00 5:45 6:30 7:15 8:00 8:45 9:30 10:15 11:00 11:45 12:30 1:15 2:00 2:45 3:30 4:15 5:00 5:45 6:30 7:15 8:00 8:45 9:30 10:15 11:00 11:45 12:30 1:15 2:00 2:45 3:30 4:15 5:00 5:45 6:30

AM AM AM AM AM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM PM PM PM PM PM PM PM PM PM

T oil

T wall

Tamb.

10.4.

Site 4: Timmins #1.

10.4.1. August Visit

Day 1

Time 5:42 PM 7:49 AM

Gas Flow (SCF) 0.00 0.30 0.00 0.00 0.45 1.55

Pressure Heater /Treater (psi) 38 40 38 37 43 42

Tank Oil Level (ft) 7.05 7.65 7.88 8.15 8.82 8.91

1:09 PM 7:45 PM

8:40AM 12:52PM

62

Temperature (C) 10 15 20 25 30 35 40 0 5

Time

Temperature Profiles Site 4 August visit

63

5:45 6:30 7:15 8:00 8:45 9:30 10:15 11:00 11:45 12:30 1:15 2:00 2:45 3:30 4:15 5:00 5:45 6:30 7:15 8:00 8:45 9:30 10:15 11:00 11:45 12:30 1:15 2:00 2:45 3:30 4:15 5:00 5:45 6:30 7:15 8:00 8:45 9:30 10:15 11:00 11:45 12:30 1:15 2:00 2:45 3:30 4:15 5:00 5:45 6:30 7:15 9:00 9:45 10:30 11:15 12:00 12:45

PM PM PM PM PM PM PM PM PM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM AM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM PM AM AM AM AM AM AM AM AM AM AM AM AM AM AM PM PM

T oil

T wall

Tamb.

T heater

11. APPENDIX C: GAS CHROMATOGRAPHY RESULTS. Mol Percentages

Site Month No Air Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane C6+ Remarks

1 1 July 2 3 1 March 2 2 July 1 2 3 1 3 March 2 3 1 4 August 2 3

90.5 87.0 83.1 23.2 66.4 57.7 20.0 30.2 12.6 30.7 20.5 50.7 61.3 63.6

0.8 3.4 1.8 9.1 3.6 6.2 13.3 14.8 23.1 18.5 22.9 41.1 34.1 33.0

0.3 0.6 0.9 19.6 9.8 10.2 18.4 16.1 6.3 4.1 4.4 1.9 1.5 1.1

0.1 0.2 0.5 26.7 14.3 15.0 26.6 20.7 12.2 6.3 6.3 0.3 0.2 0.1 1.1 0.8 0.6 2.0 3.6 2.8 1.0 2.2

0.3 0.5 1.1 10.9 5.8 6.0 11.3 8.7 24.7 18.0 20.4 1.1 0.8 0.5 0.8 0.5 0.3 1.1 2.1 1.7 1.3 2.4

8.0 1.3 2.2 10.48 4.7 6.0 Instantaneous Sample

1.4 2.8 2.3 21.1 22.4 25.5 0.8 0.4 0.3

0.6 2.0 1.7 VRU on

2.2 0.4 0.4

Instantaneous Sample

64

65