I Society d Petroleum Engineers 1

SPE 24828
Control of Aromatic Emissions From Glycol Dehydrators
M.S. Choi, C.D. Spisak, and J.A. Dodd Jr., Conoco Inc.
SPE Members

Copyright 1992, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the 67th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers held in Washington, DC, October 4-7, 1992.

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Abstract Among the most popular is the use of Triethylene Glycol

Glycol dehydration units utilized in natural gas service have
been identified as potential sources of aromatic hydrocarbon
emissions into the atmosphere. Depending upon the
concentration of aromatic content in the natural gas, large
amounts of aromatics may be concentrated in the still
overhead water vapor vent. Federal and state regulations
have targeted glycol dehydration units for emission control
on these carcinogenic compounds. In the near future, some
states will levy annual fees to operators who exceed
maximum daily discharge limits.
Conoco has developed and applied for a patent on a novel
addition to the standard glycol dehydration unit that
eliminates the emission of almost all of the aromatics and
other hydrocarbons. Hydrocarbons, that are normally
vented with the water vapor, are recovered as a condensate
product or as regenerator fuel.
A prototype of the Aromatic Recovery Unit (ARU) was
successfully placed in operation in November 1990, along
with a new 30 MMSCFD glycol dehydration unit. Two
additional units are now built and in operation.
This paper describes the design and Conoco's experience
with the prototype Aromatic Recovery Unit.
Background
Most natural gas sale contracts limit water content of the gas
to 7.0 pounds or less per million standard cubic feet of gas
(1 MMSCF). To achieve these low water contents,
producers use various means of dehydrating the gas.
(TEG) as the desiccant. By contacting the gas with TEG,
water vapor is absorbed and removed, yielding dehydrated
gas for pipeline sale.
TEG, in addition to having good water absorption
characteristics, has a high affinity for aromatic
hydrocarbons. When dehydrating natural gas containing
aromatic compounds, TEG will readily absorb the aromatics
along with the water vapor. This phenomenon tends to
concentrate the aromatic compounds in the "rich" glycol
stream. The "lean" TEG is regenerated with heat by
vaporizing the water and hydrocarbons out of the "rich"
TEG.
In a standard glycol dehydration unit (GDU), the still
overhead vapors are vented to the atmosphere. The vented
stream, which is primarily water, contains varying amounts
of hydrocarbons. These contaminants include free gas
passing through the system and small amounts of heavier
paraffinic and aromatic hydrocarbons. In many systems,
some of the vapors are condensed in the still vent line
through natural cooling. The condensate that reaches the
ground contributes toward contamination of the soil and
groundwater.
The main aromatic hydrocarbons found in natural gas are
the B-T-E-X components. They are:
Comrmnent Chemical Formula
Benzene c, I-&
Toluene GH,
Ethyl Benzene C* H10
Xylenes CL3 Hlo
 CONTROL OF AROMATIC EMISSIONS
FROM GLYCOL DEHYDRATORS SPE 24828

The B-T-E-X compounds are listed among the 189 Component Analysis
Hazardous Air Pollutants to be regulated under the amended North Maurice Sales Gas
Federal Clean Air Act of 1990. A recent survey, conducted
by the State of Louisiana1 using data from 191 GDU7s Comvonent Mole Percent
which use TEG, indicated that an average 0.93 tons of B-T- Carbon Dioxide 2.06 %
E-X were emitted each year for each million standard cubic Nitrogen 0.18%
feet per day of gas processed. Methane 84.47%
Ethane 6.49%
Conoco data2 from 33 onshore and offshore GDTJ's Propane 3.51%
indicates a little higher average of 1.09 tons of B-T-E-X Iso-Butane 1.26%
emitted per year per million standard cubic feet of daily N-Butane 0.95%
production. Breakdown of the B-T-E-X in the two surveys Iso-Pentane 0.36 %
are: N-Pentane 0.25 %
Hexanes Plus 0.47%
Comuonent State of Louisiana Conoco Units
Remarks:
Benzene 35 % 31% 1. Specific Gravity @ 60°F (Air = 1.00) - 0.699
Toluene 36 % 41 % 2. BTUICubic Foot @ 60°F and 15.025 psia
Ethyl Benzene 5% 4% Dry - 1207.2 Wet - 1186.6
Xylenes 24 % 24% 3. I-&S Content - 2 ppm

The average figures obscure the wide range in the
emissions. Some of these units emit up to 3 to 4 tons of B-
T-E-X per year per standard million cubic feet of daily gas
production while others emit considerably less. The main
factor that dictates aromatic emissions is the original
aromatic concentrations in the gas, i.e., the higher the
concentrations, the higher the emissions. TEG circulation
rate and regenerator efficiency also affect emissions, but to
a lesser degree.
The GDU, along with the ARU, was put into service in
November 1990 and has been in continuous operation ever
since. The system is currently processing approximately 18
to 20 MMSCFD and meets the 7 pounds of water
specification. In general, operation of the ARU has been
trouble free, with no apparent impact on normal GDU
operations.
Process Description

Recognizing the potential problem associated with glycol
dehydration units, Conoco, along with other companies,
investigated ways to reduce or eliminateB-T-E-X emissions.
In early 1990, Conoco's Production Technology Group
located in Houston, Texas, developed an Aromatic Recovery
Unit (ARU) that can be incorporated into a new GDU
design or added to existing units. The ARU was designed
to eliminate all aromatic hydrocarbons emissions. In
addition, the ARU effectively eliminates all other
hydrocarbon emissions from the glycol regenerator still
overhead vapor system. It does so by condensation through
ambient cooling, phase separation, and combustion of the
remaining vapors.
A prototype unit was incorporated into a new GDU installed
at Conoco's North Maurice Central Battery, located
southwest of Lafayette, Louisiana. The GDU was designed
to dehydrate a maximum of 30 MMSCF of natural gas per
day down to pipeline specifications of 7 pounds of water per
MMSCF (million cubic feet) of gas. An analysis of the
North Maurice sales gas is shown below:
Figure 1 illustrates the flow of glycol through the
combination GDU-ARU. Rich TEG, loaded with absorbed
water, some free gas, hydrocarbon liquids and aromatic
hydrocarbons, leaves the base of the GDU contact tower (1)
and flows through a solids filter and then through the power
side of a dual action glycol pump (2-R). Exiting the pump,
the low pressure stream flows to the top of the regenerator
still where it acts as the cooling medium for a reflux
condenser located in the top of the still (3). The flow then
continues to a heat exchanger (4) where additional heat
helps break out solution gas prior to the rich glycol entering
a flash separator (5).
The flash separator is a three-phase unit that is an essential
part of the process. It serves to minimize the amount of
non-condensible vapors that would be liberated from the
ARU condensate separator and must be incinerated in the
reboiler firebox. The flashed gas, separated in the vessel
(6), is recovered and used as fuel gas for the regenerator.
Separated hydrocarbon liquids are trapped in an internal
"oil" bucket and piped (7) to an oil treating vessel for
recovery as stock tank oil. The rich glycol flows under the
SPE 24828 M.S. CHOI, C.D. SPISAK, J.A. DODD JR.
oil bucket and over a weir into the rich glycol section (8).
Many GDU's have the three-phase flash separator described
in the above paragraph to recover hydrocarbon liquids and
vapor from the rich glycol. However, this separator is not
effective in removing aromatic hydrocarbon from the rich
glycol due to the high solubility of these compounds in
TEG. Consequently, most of the B-T-E-X dissolved in the
rich TEG will eventually end up in the glycol regenerator.
Leaving the flash separator, rich TEG will continue its flow
toward the regenerator section. The solution first passes
through another set of heat exchangers (9) and then into the
vertical still of the regenerator (10).
The regenerator, operating at a temperature normally
between 360" and 400"F, vaporizes the water and aromatic
hydrocarbons in the TEG. These vapors migrate up the still
and through the reflux condenser (3). Normally these
vapors would then continue to flow unimpeded into the
atmosphere. In the ARU, the vapors are further cooled and
partially liquified in a "condenser" (11). This condenser
can either be an electric powered fin-fan unit or a G-fin
exchanger (similar to the gadglycol exchanger) that uses
cool, dried gas from the contactor as the cooling medium.
At atmospheric pressure, water condenses at 212°F
(100°C). The normal boiling temperatures of the main
aromatic hydrocarbons are:
Comnent Normal Boiling Point
OF
- -OC
Benzene 176" 80"
Toluene 231" 111"
Ethyl Benzene 277" 136"
Xylenes 281"-292" 138"-144"
The condensed water and aromatic hydrocarbon stream,
along with some non-condensible vapors flow to a small
three-phase separator (12) that operates at or slightly below
atmospheric pressure. The hydrocarbon liquids, composed
primarily of aromatics, are pumped to a hydrocarbon
treating vessel (13). Water is pumped to the salt water
disposal system (14). Any remaining noncondensible
vapors are piped back to the glycol reboiler where they are
incinerated in the firebox. The vapors are introduced into
the firebox via a separate burner (15). The natural draft
effect created by the hot gas rising in the flue stack provides
the slight vacuum to pull the vapors into the firebox.
The flow of the regenerated TEG or "lean glycol" is
unchanged from that of a standard unit. The hot TEG,
stripped of its water and hydrocarbons, exits the reboiler
3
(10) and is cooled in richllean glycol heat exchangers (4)
and (9). It is collected in the atmospheric surge tank (16).
From the surge tank, the lean glycol is pumped by the gas-
powered glycol pump (2-L), further cooled in the gaslglycol
heat exchanger (17), and injected into the contact tower
(18). In the contactor, lean glycol dehydrates the wet inlet
gas by counter current contact and absorption.
Test Results
The prototype unit at North Maurice has been subjected to
a significant amount of testing. Among the tests was the
mass balance technique used to determine amounts of
aromatic and total hydrocarbons recovered from the "rich"
glycol.
Two different samples of "rich" glycol and one sample of
"lean" glycol were collected and analyzed. The first sample
of "richn glycol was taken immediately downstream of the
glycol pump and the second "rich" sample was taken
downstream of the flash separator. The "lean" sample was
taken at the glycol pump discharge, upstream of the
gaslglycol exchanger and the contact tower. Analyses of the
two "rich" samples are shown below:
Partial Analysis of "Rich" Glycol Samples
Glycol Pumv Flash Separator
Benzene 4,430 mgll 4,000 mg/l
Toluene 2,920 mgll 2,880 mgll
Ethyl Benzene 400 mgll 776 mgll
Xylene 1.320 mgll 2.470 me11
Subtotal 9,070 mgll
B-T-E-X-
Total Petroleum 12,500 mg/l
Hydrocarbons
There has been some concern that samples of the "rich"
glycol taken directly downstream of a glycol pump do not
give a true representation of the aromatic hydrocarbon
content of the glycol. The close comparison shown above
indicates that interference of the gas phase may not be a
problem since the aromatic compounds are predominantly in
the liquid phase. An accurate determination of the B-T-E-X
concentration can be achieved as long as the sample is
representative of the flowing liquid stream.
Analysis of the correspondinglean glycol (to the rich glycol)
is given below:
 CONTROL OF AROMATIC EMISSIONS
FROM GLYCOL DEHYDRATORS SPE 24828

Partial Analysis of "Lean" Glycol Sample Reboiler Stock Test

Benzene 64 mgll A series of tests were performed in September 1991 on the

Toluene 67 mgll emissions from the reboiler exhaust stack of the prototype
Ethyl Benzene 14 mgll unit's GDU. These tests were performed to determine
Xylenes 55 mgll whether injection of the non-condensible vapors from the
ARU would create a significant difference in the aromatic
Subtotal B-T-E-X 200 mgll hydrocarbon emissions from the stack.

Total Petroleum 630 mgll
Hydrocarbons
Calculations of the annual throughput of total and aromatic
hydrocarbons were based on the analyses shown above,
using the "rich" glycol sample taken downstream of the
flash separator. The measured glycol circulation rate of
1.53 gallons per minute was utilized in the calculations.
The results are:
With the GDU processing gas at a daily rate of 18.5
MMSCF, three stack tests were performed with the ARU in
operation and three tests with the ARU bypassed. Test
results showed that there is no statistical difference in total
emissions with the ARU in operation and when the unit was
bypassed. The results of the tests taken over a two day
period are shown in Table 1.
Features of the ARU

Difference Amounts Cavtured* The emission of potentially hazardous aromatic

hydrocarbons is eliminated.
Benzene 3,936 mgll 13.20 Tonslyear
Toluene 2,813 mgll 9.44 Tonslyear All fuel needed by the glycol regenerator is provided
Ethyl Benzene 762 mgll 2.56 Tonslyear by vapors recovered in the two separators ("flash" and
Xylene 2,415 m d l 8.10 Tonslvear "condensate" separators). Pipeline gas that would have
been normally used for fuel is now sold.
Subtotal 9,926 mgll 33.30 Tonslyear
B-T-E-X Vaporized heavier hydrocarbons, including both
paraffinic and aromatic compounds, which are
Total Petroleum 13,770 mgll 46.20 Tonslyear normally emitted into the atmosphere are condensed,
Hydrocarbons recovered and sold.

*Formula: Tons per year = (2.193 x lo3) (Component
Difference) x (Glycol Pump Rate in GPM)
Based on the B-T-E-X components only, the relative
amounts of the aromatic hydrocarbons in the samples were:
Benzene 39.7%
Toluene 28.3 %
Ethyl Benzene 7.7 %
Xylene 24.3 96
Gas was flowing through the GDU at a daily rate of 18
MMSCF when samples were taken. Based on the mass
balance, this unit would have emitted 1.85 tons of aromatic
hydrocarbons per year per million cubic feet of gas had it
not been for the ARU. With the ARU, the emission is
virtually zero, and the hydrocarbons are recovered as a
salable product (stock tank oil) or fuel for the GDU
regenerator.
Because hydrocarbon condensate captured in the flash
separator is recovered before entering the reboiler, the
possibility of "coking" and "hot spots" is reduced,
thereby improving the life of the reboiler firetube.
The ARU also improves the glycol regeneration process by
inducing a slight vacuum to the reboiler system. If all of
the still overhead vapors are condensed in the condenser, the
liquid falling into the condensate separator would pull a
significant vacuum behind it. The magnitude of the vacuum
is dictated by the difference in elevation between the
condenser and separator. Even without total condensation,
the vacuum created by the natural draft in the firetube would
overcome the frictional losses through the condenser and
piping, and still induce a measured .5" IE,O vacuum in the
reboiler.
It is important to have little to no back pressure on the
regenerator for two reasons:

1. GDU regenerator vessels are built to operate at nearly

SPE 24828 M.S. CHOI, C.D. SPISAK, J.A. DODD JR.
atmospheric pressures. It has been reported that some
companies experienced rupture of the reboiler shell
when other extraction methods were attempted that
placed back pressure on the regenerator. Conoco
initially experienced back pressure problems in the
prototype unit before it was determined that a plugged
mistextractor was left in the refurbished, condensate
separator. Removal of the demister eliminated the
problem.
2. Additional back pressure above atmospheric pressure in
the reboiler raises the temperature required to
regenerate TEG to the desired purity. Approximately
374°F (190°C) is needed to achieve 99% pure TEG at
atmospheric pressure. Any back pressure would result
in lower quality TEG at the same temperature. Raising
the working temperature would compensate for the
higher pressures, but pushes the TEG towards its
degradation temperature of approximately 420°F.
Economics
The additional cost for equipping a 30 MMSCFD GDU with
a fully automated ARU is approximately $30,000 (1992
prices). Because of the potential dangers of emitting
aromatic hydrocarbons, the expenses could be considered a
cost of prudent operations. However, there are direct
benefits that help repay the investment. In some cases, an
attractive rate of return may be achieved. The sources of
pay back are from the elimination of fine payments for
excessive emissions and from the recovery of fuel gas and
hydrocarbon liquids.
The State of Louisiana assesses an annual fee of $100 per
ton for each ton of Benzene emitted into the atmosphere in
excess of 260 pounds per year. Fees are also assessed for
emissions of Toluene, Ethyl Benzene and Xylene if
emissions of any of these components exceeds ten tons per
year. Other states will probably follow Louisiana's lead.
The ARU will eliminate payment of the annual fees and the
inherent liability of environmental discharges.
The North Maurice GDU, producing 13.2 tons of Benzene
per year, would be assessed an annual fee of $1,300 without
an ARU. At the rated 30 MMSCFD capacity, the GDU,
without an ARU would be assessed a fee of $2,525 for
excessive Benzene, Toluene and Xylene.
On an average day, an estimated 26 MSCF of gas passes
through the regenerator section of the dehydration unit. In
the past this gas would have been vented into the
atmosphere along with the steam and aromatic
hydrocarbons. With the ARU, the gas is captured and used
659
5
for regenerator fuel or compressed for sales. It is estimated
that $11,100 per year in revenue and savings is realized by
utilizing the recovered gas (estimate based on gas heating
value of 1200 BTUISCF, Gas Value - $1.30/MMBTU and
Net Revenue Interest of 75%).
Six barrels of hydrocarbon liquids are recovered by the
ARU each day. Approximately one barrel of hydrocarbons
are captured in the flash separator, and five barrels of
mostly aromatics is recovered in the condensate separator.
At $20 per barrel, these liquids would generate $32,850 per
year of additional net revenue.
The benefits, from savings in emission fines, fuel gas, and
product sales, that are attributable to the ARU total $45,300
per year. Based on the unit cost of $30,000, payout on the
investment is only 8 months. The rate of return, for the
primarily environmental preservation project, is equally
favorable.
Conoco originally set out to develop an aromatic
hydrocarbon emission control system for Glycol
Dehydrators. We succeeded in this primary objective, and
in addition, were able to eliminate all hydrocarbon
emissions from the glycol regenerator still overhead. The
system is cost effective, easy to operate, adds no back
pressure to the reboiler and recovers all the hydrocarbons in
the form of fuel gas or salable products.
Acknowledgements
The authors would l i e to acknowledge the North Maurice
Field Operations Team in providing data and assistance for
this report. We want to also recognize the efforts of the
initial project engineer, Stephen M. Dorcheus, and his
supervisor, Glenn D. Schaaf, in their pioneering efforts with
the installation of the first ARU.
References
1. State of Louisiana - DEQ Internal Report 9/17/90 T.L
Starrett - "Status Report on the Glycol Dehydrator
Survey"
2. Summation of Tabulations of BTEX Emission Data
from 17 Lafayette Division GDUs and 16 New Orleans
Division GDUs operated by Conoco Inc.
 CONTROL OF AROMATIC EMISSIONS
FROM GLYCOL DEHYDRATORS SPE 24828

Table 1
-
Unburned Aromatic Hydrocarbon Emissions Pounds per Hour
Reboiler Stack Testing - DeClouet No. 1 GDU - September 1991
ARU in Operation ARU Bypassed
Component Run 1 Run2 Run3 Avg. Run 1 Run2 Run3 Avg.
Benzene .012 .012 .012 .012 .021 .013 .012 .017
Toluene .003 .014 .007 .008 .014 .012 .019 .015
Ethyl Benzene .004 .002 .001 .002 .001 .001 .001 .001
Xylenes .007 .005 .003 .005 .001 .003 .002 .002
Average Totals - Pounds per Hour
Equivalent Tons per Year

Figure 1
Glycol Dehydration Unit equipped with Aromatic Hydrocarbon Recovery Process

GLYCOL DEHYDRATOR
WITH
AROMATIC RECOVERY
UNIT (ARQ

FIB