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.

This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author@).Contents of the paper,
as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author@). The material, as presented, does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publicationreview by Editorial Committees of the Society
of Petroleum Engineers.Permissionto copy is restricted to an abstract of not more than300 words. Illustrations may not be copied. The abstract should contain conspicuousacknowledgment
of where and by whom the paper is presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836 U S A . Telex, 730989 SPEDAL.

Abstract Among the most popular is the use of Triethylene Glycol

(TEG) as the desiccant. By contacting the gas with TEG,
Glycol dehydration units utilized in natural gas service have water vapor is absorbed and removed, yielding dehydrated
been identified as potential sources of aromatic hydrocarbon gas for pipeline sale.
emissions into the atmosphere. Depending upon the
concentration of aromatic content in the natural gas, large TEG, in addition to having good water absorption
amounts of aromatics may be concentrated in the still characteristics, has a high affinity for aromatic
overhead water vapor vent. Federal and state regulations hydrocarbons. When dehydrating natural gas containing
have targeted glycol dehydration units for emission control aromatic compounds, TEG will readily absorb the aromatics
on these carcinogenic compounds. In the near future, some along with the water vapor. This phenomenon tends to
states will levy annual fees to operators who exceed concentrate the aromatic compounds in the "rich" glycol
maximum daily discharge limits. stream. The "lean" TEG is regenerated with heat by
vaporizing the water and hydrocarbons out of the "rich"
Conoco has developed and applied for a patent on a novel TEG.
addition to the standard glycol dehydration unit that
eliminates the emission of almost all of the aromatics and In a standard glycol dehydration unit (GDU), the still
other hydrocarbons. Hydrocarbons, that are normally overhead vapors are vented to the atmosphere. The vented
vented with the water vapor, are recovered as a condensate stream, which is primarily water, contains varying amounts
product or as regenerator fuel. of hydrocarbons. These contaminants include free gas
passing through the system and small amounts of heavier
A prototype of the Aromatic Recovery Unit (ARU) was paraffinic and aromatic hydrocarbons. In many systems,
successfully placed in operation in November 1990, along some of the vapors are condensed in the still vent line
with a new 30 MMSCFD glycol dehydration unit. Two through natural cooling. The condensate that reaches the
additional units are now built and in operation. ground contributes toward contamination of the soil and
groundwater.
This paper describes the design and Conoco's experience
with the prototype Aromatic Recovery Unit. The main aromatic hydrocarbons found in natural gas are
the B-T-E-X components. They are:
Background
Comrmnent Chemical Formula
Most natural gas sale contracts limit water content of the gas Benzene c, I-&
to 7.0 pounds or less per million standard cubic feet of gas Toluene GH,
(1 MMSCF). To achieve these low water contents, Ethyl Benzene C* H10
producers use various means of dehydrating the gas. 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 The GDU, along with the ARU, was put into service in
emissions. Some of these units emit up to 3 to 4 tons of B- November 1990 and has been in continuous operation ever
T-E-X per year per standard million cubic feet of daily gas since. The system is currently processing approximately 18
production while others emit considerably less. The main to 20 MMSCFD and meets the 7 pounds of water
factor that dictates aromatic emissions is the original specification. In general, operation of the ARU has been
aromatic concentrations in the gas, i.e., the higher the trouble free, with no apparent impact on normal GDU
concentrations, the higher the emissions. TEG circulation operations.
rate and regenerator efficiency also affect emissions, but to
a lesser degree. Process Description

Recognizing the potential problem associated with glycol Figure 1 illustrates the flow of glycol through the
dehydration units, Conoco, along with other companies, combination GDU-ARU. Rich TEG, loaded with absorbed
investigated ways to reduce or eliminateB-T-E-X emissions. water, some free gas, hydrocarbon liquids and aromatic
In early 1990, Conoco's Production Technology Group hydrocarbons, leaves the base of the GDU contact tower (1)
located in Houston, Texas, developed an Aromatic Recovery and flows through a solids filter and then through the power
Unit (ARU) that can be incorporated into a new GDU side of a dual action glycol pump (2-R). Exiting the pump,
design or added to existing units. The ARU was designed the low pressure stream flows to the top of the regenerator
to eliminate all aromatic hydrocarbons emissions. In still where it acts as the cooling medium for a reflux
addition, the ARU effectively eliminates all other condenser located in the top of the still (3). The flow then
hydrocarbon emissions from the glycol regenerator still continues to a heat exchanger (4) where additional heat
overhead vapor system. It does so by condensation through helps break out solution gas prior to the rich glycol entering
ambient cooling, phase separation, and combustion of the a flash separator (5).
remaining vapors.
The flash separator is a three-phase unit that is an essential
A prototype unit was incorporated into a new GDU installed part of the process. It serves to minimize the amount of
at Conoco's North Maurice Central Battery, located non-condensible vapors that would be liberated from the
southwest of Lafayette, Louisiana. The GDU was designed ARU condensate separator and must be incinerated in the
to dehydrate a maximum of 30 MMSCF of natural gas per reboiler firebox. The flashed gas, separated in the vessel
day down to pipeline specifications of 7 pounds of water per (6), is recovered and used as fuel gas for the regenerator.
MMSCF (million cubic feet) of gas. An analysis of the Separated hydrocarbon liquids are trapped in an internal
North Maurice sales gas is shown below: "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. 3

oil bucket and over a weir into the rich glycol section (8). (10) and is cooled in richllean glycol heat exchangers (4)
and (9). It is collected in the atmospheric surge tank (16).
Many GDU's have the three-phase flash separator described From the surge tank, the lean glycol is pumped by the gas-
in the above paragraph to recover hydrocarbon liquids and powered glycol pump (2-L), further cooled in the gaslglycol
vapor from the rich glycol. However, this separator is not heat exchanger (17), and injected into the contact tower
effective in removing aromatic hydrocarbon from the rich (18). In the contactor, lean glycol dehydrates the wet inlet
glycol due to the high solubility of these compounds in gas by counter current contact and absorption.
TEG. Consequently, most of the B-T-E-X dissolved in the
rich TEG will eventually end up in the glycol regenerator. Test Results
Leaving the flash separator, rich TEG will continue its flow
toward the regenerator section. The solution first passes The prototype unit at North Maurice has been subjected to
through another set of heat exchangers (9) and then into the a significant amount of testing. Among the tests was the
vertical still of the regenerator (10). mass balance technique used to determine amounts of
aromatic and total hydrocarbons recovered from the "rich"
The regenerator, operating at a temperature normally glycol.
between 360" and 400"F, vaporizes the water and aromatic
hydrocarbons in the TEG. These vapors migrate up the still Two different samples of "rich" glycol and one sample of
and through the reflux condenser (3). Normally these "lean" glycol were collected and analyzed. The first sample
vapors would then continue to flow unimpeded into the of "richn glycol was taken immediately downstream of the
atmosphere. In the ARU, the vapors are further cooled and glycol pump and the second "rich" sample was taken
partially liquified in a "condenser" (11). This condenser downstream of the flash separator. The "lean" sample was
can either be an electric powered fin-fan unit or a G-fin taken at the glycol pump discharge, upstream of the
exchanger (similar to the gadglycol exchanger) that uses gaslglycol exchanger and the contact tower. Analyses of the
cool, dried gas from the contactor as the cooling medium. two "rich" samples are shown below:

At atmospheric pressure, water condenses at 212°F Partial Analysis of "Rich" Glycol Samples
(100°C). The normal boiling temperatures of the main
aromatic hydrocarbons are: Glycol Pumv Flash Separator

Comnent Normal Boiling Point Benzene 4,430 mgll 4,000 mg/l

OF
- -OC Toluene 2,920 mgll 2,880 mgll
Ethyl Benzene 400 mgll 776 mgll
Benzene 176" 80" Xylene 1.320 mgll 2.470 me11
Toluene 231" 111"
Ethyl Benzene 277" 136" Subtotal 9,070 mgll
Xylenes 281"-292" 138"-144" B-T-E-X-

The condensed water and aromatic hydrocarbon stream, Total Petroleum 12,500 mg/l
along with some non-condensible vapors flow to a small Hydrocarbons
three-phase separator (12) that operates at or slightly below
atmospheric pressure. The hydrocarbon liquids, composed There has been some concern that samples of the "rich"
primarily of aromatics, are pumped to a hydrocarbon glycol taken directly downstream of a glycol pump do not
treating vessel (13). Water is pumped to the salt water give a true representation of the aromatic hydrocarbon
disposal system (14). Any remaining noncondensible content of the glycol. The close comparison shown above
vapors are piped back to the glycol reboiler where they are indicates that interference of the gas phase may not be a
incinerated in the firebox. The vapors are introduced into problem since the aromatic compounds are predominantly in
the firebox via a separate burner (15). The natural draft the liquid phase. An accurate determination of the B-T-E-X
effect created by the hot gas rising in the flue stack provides concentration can be achieved as long as the sample is
the slight vacuum to pull the vapors into the firebox. representative of the flowing liquid stream.

The flow of the regenerated TEG or "lean glycol" is Analysis of the correspondinglean glycol (to the rich glycol)
unchanged from that of a standard unit. The hot TEG, is given below:
stripped of its water and hydrocarbons, exits the reboiler
 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 With the GDU processing gas at a daily rate of 18.5
Hydrocarbons MMSCF, three stack tests were performed with the ARU in
operation and three tests with the ARU bypassed. Test
Calculations of the annual throughput of total and aromatic results showed that there is no statistical difference in total
hydrocarbons were based on the analyses shown above, emissions with the ARU in operation and when the unit was
using the "rich" glycol sample taken downstream of the bypassed. The results of the tests taken over a two day
flash separator. The measured glycol circulation rate of period are shown in Table 1.
1.53 gallons per minute was utilized in the calculations.
The results are: 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 Because hydrocarbon condensate captured in the flash
Difference) x (Glycol Pump Rate in GPM) separator is recovered before entering the reboiler, the
possibility of "coking" and "hot spots" is reduced,
Based on the B-T-E-X components only, the relative thereby improving the life of the reboiler firetube.
amounts of the aromatic hydrocarbons in the samples were:
The ARU also improves the glycol regeneration process by
Benzene 39.7% inducing a slight vacuum to the reboiler system. If all of
Toluene 28.3 % the still overhead vapors are condensed in the condenser, the
Ethyl Benzene 7.7 % liquid falling into the condensate separator would pull a
Xylene 24.3 96 significant vacuum behind it. The magnitude of the vacuum
is dictated by the difference in elevation between the
Gas was flowing through the GDU at a daily rate of 18 condenser and separator. Even without total condensation,
MMSCF when samples were taken. Based on the mass the vacuum created by the natural draft in the firetube would
balance, this unit would have emitted 1.85 tons of aromatic overcome the frictional losses through the condenser and
hydrocarbons per year per million cubic feet of gas had it piping, and still induce a measured .5" IE,O vacuum in the
not been for the ARU. With the ARU, the emission is reboiler.
virtually zero, and the hydrocarbons are recovered as a
salable product (stock tank oil) or fuel for the GDU It is important to have little to no back pressure on the
regenerator. 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. 5

atmospheric pressures. It has been reported that some for regenerator fuel or compressed for sales. It is estimated
companies experienced rupture of the reboiler shell that $11,100 per year in revenue and savings is realized by
when other extraction methods were attempted that utilizing the recovered gas (estimate based on gas heating
placed back pressure on the regenerator. Conoco value of 1200 BTUISCF, Gas Value - $1.30/MMBTU and
initially experienced back pressure problems in the Net Revenue Interest of 75%).
prototype unit before it was determined that a plugged
mistextractor was left in the refurbished, condensate Six barrels of hydrocarbon liquids are recovered by the
separator. Removal of the demister eliminated the ARU each day. Approximately one barrel of hydrocarbons
problem. are captured in the flash separator, and five barrels of
mostly aromatics is recovered in the condensate separator.
2. Additional back pressure above atmospheric pressure in At $20 per barrel, these liquids would generate $32,850 per
the reboiler raises the temperature required to year of additional net revenue.
regenerate TEG to the desired purity. Approximately
374°F (190°C) is needed to achieve 99% pure TEG at The benefits, from savings in emission fines, fuel gas, and
atmospheric pressure. Any back pressure would result product sales, that are attributable to the ARU total $45,300
in lower quality TEG at the same temperature. Raising per year. Based on the unit cost of $30,000, payout on the
the working temperature would compensate for the investment is only 8 months. The rate of return, for the
higher pressures, but pushes the TEG towards its primarily environmental preservation project, is equally
degradation temperature of approximately 420°F. favorable.

Economics

The additional cost for equipping a 30 MMSCFD GDU with Conoco originally set out to develop an aromatic
a fully automated ARU is approximately $30,000 (1992 hydrocarbon emission control system for Glycol
prices). Because of the potential dangers of emitting Dehydrators. We succeeded in this primary objective, and
aromatic hydrocarbons, the expenses could be considered a in addition, were able to eliminate all hydrocarbon
cost of prudent operations. However, there are direct emissions from the glycol regenerator still overhead. The
benefits that help repay the investment. In some cases, an system is cost effective, easy to operate, adds no back
attractive rate of return may be achieved. The sources of pressure to the reboiler and recovers all the hydrocarbons in
pay back are from the elimination of fine payments for the form of fuel gas or salable products.
excessive emissions and from the recovery of fuel gas and
hydrocarbon liquids. Acknowledgements

The State of Louisiana assesses an annual fee of $100 per The authors would l i e to acknowledge the North Maurice
ton for each ton of Benzene emitted into the atmosphere in Field Operations Team in providing data and assistance for
excess of 260 pounds per year. Fees are also assessed for this report. We want to also recognize the efforts of the
emissions of Toluene, Ethyl Benzene and Xylene if initial project engineer, Stephen M. Dorcheus, and his
emissions of any of these components exceeds ten tons per supervisor, Glenn D. Schaaf, in their pioneering efforts with
year. Other states will probably follow Louisiana's lead. the installation of the first ARU.
The ARU will eliminate payment of the annual fees and the
inherent liability of environmental discharges. References

The North Maurice GDU, producing 13.2 tons of Benzene 1. State of Louisiana - DEQ Internal Report 9/17/90 T.L
per year, would be assessed an annual fee of $1,300 without Starrett - "Status Report on the Glycol Dehydrator
an ARU. At the rated 30 MMSCFD capacity, the GDU, Survey"
without an ARU would be assessed a fee of $2,525 for
excessive Benzene, Toluene and Xylene. 2. Summation of Tabulations of BTEX Emission Data
from 17 Lafayette Division GDUs and 16 New Orleans
On an average day, an estimated 26 MSCF of gas passes Division GDUs operated by Conoco Inc.
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
 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