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Spe 26588 MS PDF
Spe 26588 MS PDF
SPE 26588
This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper,
as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect
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791
2 API Tank Vapor Project SPE 26588
emissions for regulatory reporting. In July 1992, Conoco • Breathing Loss - vapors that are generated when
presented the idea of using process simulation techniques the tank is heated and cooled during the course of
to estimate tank emissions to API's Clean Air Issues Work a day, and liquid hydrocarbon vaporization due to
Group. With the help of Chevron, Mobil, Shell and others, the stripping effects of air. Typically, the
the basic concept was refined and the scope of work for a temperature in a tank will increase during the day
joint industry project was prepared for API funding. Upon due to radiation heat gain. The energy imparted to
execution of the agreement between API and Conoco (with the saturated liquid will cause more vaporization
Conoco as the prime contractor for the project) in June and emissions. The hotter gas in the air space will
1993, work on the project began in earnest. expand in volume and is also vented into the
atmosphere. During the night, the tank will cool
The ultimate goal of the project is to develop and gain due to conductive and radiation heat losses. The
regulatory acceptance for a simplified correlation similar to cooler liquid will reabsorb some of the tank vapor
AP-42. But before development of a correlation can be while the remaining vapors contract. Air is sucked
attempted, a data base on the aromaticity of oil (as a into the tank, resulting in a new set of equilibrium
function of its macro properties, i.e. API gravity, molecular conditions.
weight, etc.) and the associated HAP emissions must first
be generated. little data is currently available for this
purpose. After refinement and validation, process Difficulties with Direct Measurements
simulation will be used to generate a statistically large data
base to search for trends and empirical correlations. The most rigorous way of determining tank emissions is to
Although it is our intention to develop a simplified meter the actual flow, sample the stream and analyze the
correlation for general use, such a correlation may not sample compositionally through Gas Chromatography Mass
exist. If that turned out to be the case, we would have to Spectrography (GCMS) techniques. Unfortunately,
settle on the more costly process simulation method to accurate metering and quality sampling and analysis are
estimate HAP and VOC emissions. costly to perform and impractical for every location. The
minimum cost of a meter system suitable for the
application is about $30,000, while a sampling event may
Nature of Field Tank Emissions require another $30,000 for field technicians and laboratory
analyses.
Many operators have attempted to meter and sample vapor
emissions directly. However the high cost and erratic Not only are field tests costly, many operators have
results derived from field measurements have discouraged discovered to their dismay, the data obtained are practically
further development of this method. The poor results can unusable due to inconsistency in the measurements.
be directly attributed to the nature of the tank system. Accurate tank vapor flow measurements are difficult to
achieve due to the low system pressure and often erratic
Air emissions (VOC and HAP) from field storage tanks can rates. Since vapor rate and composition are influenced by
be classified in 3 categories: ever changing conditions, i.e. temperature, pressoure, fluid
surges, tank level, air ingress, etc., repeatability of "snap
• Flashing Loss - vapors that are generated when the shot" field measurements is poor due to the' inherent
pressure of the saturated oil or water is reduced nature of the system. Even if the instantaneous samples
from that of the low pressure separator to the and measurements were .judged to be valid, the
storage tank. This source of emission is typically uncertainties introduced by extrapolating the time
the largest of the three. The rate and composition dependent data to annual emissions make the results
of flash vapors are dictated primarily by the questionable. To accurately determine tank emissions
temperature, pressure and composition of the through field measurements, continuous meters and
incoming fluid. samplers can be utilized to account for system fluctuations.
However due to the expense and practicality of long term
• Working Loss - vapors that are displaced from the continuous measurements, along with the huge number of
tank during the fill cycle. Although the emission tanks that must be monitored, the industry has ruled out
rate is essentially the volumetric equivalent of the direct measurements as a viable option for tank emissions
incoming liquid (after the flash), the composition of inventory.
the vapor is highly dependent on timing in the
system's fill and drain cycles. For example, the
vapors emitted immediately after the tank is Advantages of Computer Process Simulation
emptied will have a greater concentration of air
(mostly nitrogen and oxygen) than when the tank Advances in equations-of-state and simple-to-use
is deep into the fill cycle. This is due to air ingress computer-based process simulators have provided a low
when liquid is pumped out of the tank. cost alternative to accurately estimate tank vapors.
Process simulation is not a cure-all. It still requires basic
792
SPE 26588 M. S. CHOI 3
knowledge of the tank battery configuration and a limited sold through the tank system could be obtained from oil
number of measured data as input. It does however allow accounting and used as the basis for emissions
the use of less expensive and easier to acquire data as calculations. In addition. the product price is often
input. while calculating the more difficult to obtain adjusted by the RVP (Reid Vapor Pressure). API gravity or
parameters. Unlike field measurements. a computer model assay value of the oil. All three parameters are used to
can be quickly and easily setup and modified to reflect characterize the volatility or stability of the oil. The
differences in location and operating conditions. The stability of the oil could change significantly from one
procedure being refined and validated in the API project season to the next, especially if the facility produces a light
(fully explained in later sections) can be implemented for oil and experiences extreme seasonal temperature
about $500 per tank (or system of tanks in parallel variations. For these facilities. the most accurate results
operation). With timely cooperation from operating are achieved with simulations performed on a seasonal or
personnel and laboratory. cycle time on an emissions monthly basis (if the data are available). and summed to
estimate can be limited to less than one week. derive the annual emissions.
__
.. .. .. _--_ .. -.. _-----_ .. _.. _-~-_._ .. - -_.-_ .. -.,'""';
.5 oz/in 2 vacuum to 4-8 oz/in 2 pressure. Tank temperature
! and heat gain or loss are highly dependent on the
i temperature of the incoming fluid and ambient temperature.
ori Rot..
ori 0--. Amount of vaporization due to air stripping is a function of
1\1'"
SeplrDt.or Oi I R--....... ~Vltlf
the frequency and rate of oil removal (pump-out). Since
CcnpoaI't.IQf"I '!"y none of the dynamic parameters affecting vaporization of
the oil while in the tank are recorded (as normal practice).
~~~.
C;1 .. C2.. G3,I-04.. N-C"1 .. ! 011 Tart:::
793
4 API Tank Vapor Project SPE 26588
• Fractional distillation to approximate the components "in the "live" stock tank oil (product of the
"weathering" effects which are responsible for the adiabatic flash) are vaporized so that the resultant oil will
working and breathing emissions. match one of the characterizations (RVP, gravity or assay
value) available for the product oil. The stabilizer operation
An adiabatic flash (pressure reduction without a gain or loss not only establishes the liquid composition that will match
of energy) is the process by which flash vapors are the product oil characterization, but also the relative
generated. When the saturated low-pressure separator oil amount and composition of the vapor that is in equilibrium
is throttled across the liquid level control valve, certain with the oil. By working backward from the product oil
gaseous components of the oil will come out of solution. characterization and rate, the amount of air ingress, heating
The phenomenon can be accurately simulated by an and cooling cycle, etc. that the oil is subjected to in the
adiabatic flash operation on the computer. Once the tank are eliminated from the calculations.
composition and conditions (temperature and pressure) of
the separator oil are known, the amount and composition The components removed from the oil to achieve the
of flash gas liberated can be accurately determined. In the stabilization (stabilizer gas) are the constituents of the
same unit operation, the relative amount and composition working and breathing vapors. Therefore, total emissions
of the "live" stock tank oil (oil that is in equilibrium with the from the tank are the sum of the flash and stabilizer gases.
flash gas) can also be generated. Since annual or monthly rather than instantaneous
emissions are of interest, a steady-state simulation model
Calculating the instantaneous working and breathing vapor may be used and accumulation in the tank may be ignored.
compositions and rates are impossible with the limited
information available on the dynamics of the system.
However, those vapors can be estimated by material Process Simulation Methodology
balance techniques around the system. Since the material
that enters the tank (separator oil) must exit either as vapor
emissions or product oil, the vapors may be determined by
difference. The steady state material balance equation may
be expressed as:
794
SPE 26588 M. S. CHOI 5
Hg PLlllP
795
6 API Tank Vapor Project SPE 26588
2) Adequate amount of the sample is introduced into apparatus. This, of-course is not quite true. There is flash
the apparatus to raise the system pressure to gas in the apparatus in addition to the liquid. The
approximately 8 psia. The sample is kept above its simplifying assumption is that the mass of the gas is
bubble point pressure by mercury displacement negligible relative to the liquid. Quantity of flash gas is not
until it is flashed in the apparatus. measured directly. Instead it is calculated from the ideal
gas la,!" based on the measured parameters, temperature
3) After the system has reached equilibrium, the and pressure, and the gas volume estimated by difference
entire apparatus containing the flashed sample (gas from the liquid volume. Accuracy in these measurements
and liquid) is once again weighted. has a large impact on the extremely small molar quantity of
gas in the system.
4) The flash gas is analyzed by standard GCMS (gas
chromatography mass spectrography). method.
Validation with HAP contents in Product Oil
5) The stabilized oil is analyzed by standard GCMS
method. Although representative tank vapor samples are impossible
to obtain, good product oil samples can be achieved
6) The stabilized oil weight is estimated by system relatively easy. Therefore in addition to the laboratory
weight (determined in step 3) minus the evacuated validation discussed above, a number of product oil
weight (step 1). samples will be collected along with the separator liquid
samples. The constituents of the product oil will be
7) Molecular weight of the stabilized oil is estimated determined by laboratory analysis, with special emphasis
through freezing point depression techniques. Oil on the HAP concentrations. The HAP concentrations in the
density is calculated from the oil composition product oil calculated by process simulation will be checked
(determined in step 5). against the laboratory-derived concentrations. The two
independently obtained results should be reasonably close
8) Volume of oil in the apparatus is calculated by in value (within the uncertainties of the laboratory
dividing the weight of the oil in the apparatus (step analytical techniques). This material balance method will
6) by oil density (step 7). be used as an indirect means of validating our vapor
emissions estimated by process simulation.
9) Volume of gas in the apparatus is equal to the
known system volume minus the oil volume (step
8). Need for Simplified Correlations
10) Quantity (moles) of gas in the apparatus is Although process simulation appears to be the answer for
estimated by the ideal gas law, i.e. N = PV IRT. field storage tank emissions inventories, the estimated cost
of $500 per tank system is still relatively high. Given the
Through the above procedure, the relative quantities of gas tens of thousands of tanks the E&P industry has in service,
and oil (gas-to-oil ratio), and gas compositions are the total cost of a process simulation-based inventory
determined. Those are the same information provided by effort would be substantial. In addition, emissions
process simulation and used in calculating HAP and VOC inventories are typically compiled by operating personnel
emissions. The only difference is that the laboratory who have little working knowledge of process simulation.
procedure yields a stabilized oil at a fixed set of conditions The cost of training these personnel to run the computer
(approximately 70°F and 8 psia). Process simulation is model would increase the cost even further.
expected to stabilize the oil to the characterization that is
available on the product oil. For validation purposes, the Therefore the ultimate goal of the project is to develop a
simulation will be setup to stabilize the oil to the laboratory simplified, empirical correlation or correlations (similar to
test temperature and pressure. The emissions based on AP-42) suitable for general application. By using a
both laboratory and simulated results will be calculated and statistically large data base derived from process
compared for discrepancies. An example ofthe comparison simulations, emissions trends could become apparent as a
may be found in attachment 4. function of easily obtainable field data such as: stock tank
oil and separator gas specific gravities and rates, ASTM D-
The validation procedure described above is judged to be a 86 distillation results, oil molecular weight, low pressure
practical method to simulate the flashing and weathering separator pressure and temperature, etc.
effects that take place in a tank and to obtain quantitative
data on the resultant streams. Like most complex
operations faced by E&P, it is not perfect. The Problems with Developing a Correlation
acceptability of the way some of the data are treated is
disputable. For example, it is assumed that the system Oil and natural gas are not pure compounds, and as such,
weight minus empty weight is the mass of the liquid in the their volatility and equilibrium compositions depend on the
796
SPE 26588 M. S. CHOI 7
constituents in the original reservoir fluid and process The representative at the facility will collect 2 separator oil
conditions. Since the CAAA through the HAPs samples according to the sampling instructions. Only 1
classification has targeted the aromatic hydrocarbons and sample will normally be analyzed. The second sample is a
n-hexane for more stringent treatment, these constituents backup and will be used in the event the integrity of the
in oil must be fully quantified. first sample is of suspect. The samples will be shipped
back to Core Lab with the information on sample tags
Conventional characterizations such as specific gravity, recorded. If the annual production through the tank system
vapor pressure, GOR and water cut do not provide any and oil characterization is available at the site, the
indication of the amount of HAPs in the produced fluid or information may be submitted along with the samples. If
in the oil. Without knowing the concentrations of HAPs in not, arrangements may be made to forward the information
the system, determining emissions from storage tanks is from another office.
impossible. There is no theoretical basis for predicting
HAPs content in reservoir fluid. Actual compositional The separator oil sample will be analyzed by GCMS
analyses are required to establish the presence of HAPs. methods and its constituents quantified compositionally.
For these reasons, simplified correlation(s) based on readily The analysis, along with the separator information will be
available parameters to estimate emission rates of the use in the process simulation. From the results of the
components of interest may not be possible. simulation and the annual oil production, the annual
emissions will be calculated. The emissions data and any
However, the industry's knowledge of oil aromaticity is other pertinent information will be submitted to the
very limited. When an adequate data base covering a range company for its use, and become a part of the data base
of process conditions and reservoir fluids is developed, from which, hopefully a correlation will be developed.
correlatable trends against easily measured parameters may
become apparent. This effort will have to be purely
empirical. Conoco believes process simulation is the most Project Cost & Schedule
cost effective method to generate the data base necessary
to develop the correlation(s). The API tank vapor project is estimated to cost $250,000
to complete. The total does not include QAfOC or other
special expenses that may be imposed by EPA or other
Data Base Generation regulatory agencies. Conoco is the prime contractor
responsible for implementing the project. Work began in
To achieve the goal of developing a simplified correlation earnest in June 1993 when the agreement between API
(similar to AP-42) for general application, a large data base and Conoco was executed. The effort is expected to take
on aromaticity of oil and relationship to HAP emissions is 24 months with project completion schedule for mid 1995.
needed. Since there is no theoretical bases for prediction, Due to recent changes in EPA's CAAA implementation time
the effort must be achieved through empirical means. A table, the industry may need the estimation method ready
data base using samples from 200 tank batteries will be for general use prior to 1995. In that case, the project
generated by the API project. These 200 sites will be schedule may be accelerated.
selected from a list of facilities nominated by the
participating companies with the highest potential of HAP
and VOC emissions. Conclusion
The project will delivered to a responsible person at the Process simulation appears to be the best candidate for a
facility: cost-effective method of estimating field storage tank HAP
and VOC emissions. Preliminary review and testing yield
• Pressure cylinders (2) for the separator oil samples. consistent and reasonable results. The API tank vapor
project was created to refine and validate the method, gain
• Sample tags to record facility name, separator regulatory acceptance for the method as the industry
operating temperature and pressure, and any usual standard for emission inventory calculations, and if
separator configuration that may have an effect on possible, develop an even lower-cost method in the form of
the tank operation. a simplified correlation.
• Sampling instructions. At the completion of the API tank vapor project, the
industry will have:
• Sample return shipping instructions.
• Secured a cost-effective HAP and VOC emissions
• Standard Material Safety Data Sheet (MSDS) for estimation method based on process simulation
pressurized oil. techniques to calculate emission inventories.
797
8 API Tank Vapor Project SPE 26588
Nomenclature
Acknowledgements
Reference
798