An Analysis of BTEX Emissions from Amine Sweetening

and Glycol Dehydration Facilities

Jay Collie
and
Michael Hlavinka
Bryan Research & Engineering, Inc.
Bryan, TX

and

Amy Ashworth
Amoco Exploration and Production
Houston, TX

175
 ABSTRACT
The amount of BTEX components emitted from gas processing facilities has
become a significant environmentalconcern. Recently, amine sweetening units have
received the same environmentalscrutiny as glycol units with regard to BTEX emissions.
This paper compares the BTEX emissions from amine sweetening and glycol dehydration
facilities as well as the methods available to minimize BTEX pickup in these systems.
Reducing solvent circulation rates in both the amine and glycol units and minimizing the
lean amine temperature were found to be the most effective ways of limiting overall
BTEX emissions. Changing solvent type can also reduce emissions, but the effect on
treated gas quality must be considered as well. In the cases investigated approximately
25% of the overall BTEX emissions came from the amine units, while the remaining 75%
came from the glycol system.

176
Introduction and Background
In 1990 several new regulatory programs were established under the Clean Air
Act Amendments that changed the way gas processors viewed their plants. Several
aromatic compounds including benzene, toluene, ethylbenzene and xylene, collectively
known as BTEX, were included on a list of 189 hazardous air pollutants (HAP). The
limits placed on these compounds are 25 tons per year (tpy) of total BTEX and no more
than 10 tpy of any individual compound 1'2. Previously, producers had known that some
level of BTEX existed in a number of natural gas streams, but they had not bothered to
test for these components. Special procedures were necessary, and the amounts in
question were typically on a part per million basis. 3
The industry has given increased attention to these compounds, and in mid-1990
the Gas Processors Association (GPA) and American Petroleum Institute (API) got
involved with the issue. In the late 1980's, GPA and API had jointly funded a research
project to investigate the solubility of light hydrocarbons in water and in desiccant
systems. Due to the new regulations, the project focus was shifted to evaluating the
solubility of the BTEX compounds in triethylene glycol (TEG) solutions instead. The
results from this work were published in GPA Research Report RR-131.4
Additional information was gathered by the API Glycol Reboiler Emissions
Measurement Work Group who collected field data on BTEX emissions from ten
operating plants in Oklahoma, Louisiana and Texas. The information was then provided
to several companies for the purpose of developing computer models to estimate the
BTEX emissions from glycol unit regenerators. 3 Bryan Research & Engineering
included information from both the GPA and API research along with plant data in the
process simulator PROSIM ®'5. Results from PROSIM have been evaluated against data
taken from the operating plants and found to compare favorably as shown by Hlavinka, et
al 6,7.

Since these early studies were initiated, research projects in the area have been
increasing. Radian Corporation has performed several studies in conjunction with GPA
and the Gas Research Institute (GRI). Much of the research involves developing simple,
yet accurate analytical methods to measure the BTEX content of vent gas streams. These

177
 methods include direct measurement and indirect measurement by rich/lean glycol
material balance(LRGCC 1993) 8.

Recently, BTEX emissions from amine treating units have also been targeted, and
consequently attention is being given to reducing these emissions as well 9. GRI has also
sponsored research in this area, and results from some of this work were presented at the
1995 GRI Glycol Dehydrator/Gas Processing Air Toxics Conference in Denver ~°. A
more in depth report was published in early 1996 j~ Bryan Research & Engineering used
this data to incorporate the BTEX components into its amine process simulator,
TSWEET ®'~2. Comparison of TSWEET predictions to operating data by Morrow and
Lunsford 9 has shown good results.

This paper examines the influences of various plant operating parameters for both
amine sweetening and glycol dehydration units on BTEX emissions using TSWEET and
PROSIM. All figures and tables were developed from the results obtained using these
programs.

Integrated Gas Plant Configuration

Figure 1 shows a process flow diagram for a typical gas processing facility
containing an amine treating unit for H2S and/or CO2 removal and a glycol dehydration
unit for water removal. If the raw gas contains appreciable amounts of H2S, a sulfur plant
or other sulfur reduction method is used to treat the overheads from the rich amine
stripper. This treating normally destroys any BTEX or other hydrocarbons. However, if
little or no H2S is present, this gas may be vented directly to the atmosphere, and BTEX
emissions may be of concern. Limiting the BTEX entering a sulfur plant is also
advantageous since these compounds can hurt overall sulfur recovery m4'15.

178
 [ ] Glycol Pump

Vent

Lean/Rich
Fuel
Gas Exchanger
t,,,==,,,i¸
--,--,,N
Glycol
Glycol
Contactor
Stripper

----,,4
Glycol
Boost
Pump

Amine
Amine Amine Storage
Cooler Pump Tank To Sulfur
Plant or Vent

f ~ Flash
Gas Exchan~
Lean/Rich
.~

Amine
Feed Stripper
Gas

~ J

Figure 1 - Integrated Gas Processing Plant

179
Amine Plant Operation
An amine unit operates by contacting an alkanolamine solution with the sour gas
(or liquid) feed countercurrently in an absorber column. H2S and CO2 in the feed are
absorbed by the amine in the solution, and the sweetened gas exits the top of the column.
Rich amine exits the bottom of the column and is sent through a regeneration system to
remove the acid gases and dissolved hydrocarbons, including BTEX. The lean solution is
then recirculated to the top of the absorber to continue the cycle. The sweetened gas
exiting the absorber is saturated by water from its contact with the amine and must be
dehydrated before being processed further or sent to a pipeline. The overheads from the
amine regenerator column are sent to a sulfur recovery unit or vented to the atmosphere
depending on the sulfur content.

Operating Parameters

Several operating parameters directly affect the amount of BTEX absorbed in an

amine unit. These factors include the inlet BTEX composition, contactor operating
pressure, amine circulation rate, solvent type and lean solvent temperature. Table 1 shows
the process conditions used to investigate the effects of some of these parameters on
BTEX pickup. Figures 2 and 3 show the BTEX emission rates predicted by T S W E E T for
MEA, DEA and M D E A as functions of circulation rate and lean solvent temperature.

180
 TABLE 1 Amine Unit Base Case
Parameters

Inlet Gas

Temperature Pressure Flowrate

F psia MMSCFD
90 1000 50

Component Composition Component Composition

Mol % Mol %
H20 0.10 IC4 0.40
N2 0.50 C4 0.50
CO2 7.00 IC5 0.20
C1 84.45 C5 0.15
C2 4.60 C6 0.21
C3 1.70 C7+ 0.15

Component Benzene Toluene Ethylbenzene O-Xylene

ppm 200 170 10 90

Process Equipment

Contactor Flash L/R Stripper Pump Cooler

Exchanger
7 ideal stages 75 psia 200 F 10 ideal stages 1000 psia 120 F
6 ft. diameter rich outlet 28 psia ovhd.
3 in. weir temperature 120 F cond. temp.
1.0 lb steam/gal
sol.

Amine Strengths

Amine MEA DEA MDEA

Wt. % 20 30 50

Note: A circulation rate of 600 gpm amine is used unless otherwise

noted.

181
 8O
:: L. 60
.2 ~
m m 40 DFA

w
~ 20

300 500 700 900

ISS MDFJ,

Lean solvent circulation

gpm

F i g u r e 2 - B T E X Emissions vs. L e a n A m i n e Circulation

60

:: ~ 50
DEA
m m 40
.... MEA
w ~ 30 ~ MDEA
20 ; I i

90 i00 II0 120 130 140

Lean solvent temp.

F

F i g u r e 3 - B T E X E m i s s i o n s vs. L e a n A m i n e T e m p e r a t u r e

A. Amine Circulation Rate

Figure 2 illustrates the dependence of BTEX emissions in an amine unit on the
lean solvent circulation rate. As the circulation increases, so do the BTEX emissions.
The BTEX emissions equate to approximately 2-6% of BTEX in the inlet gas. While
minimizing the circulation rate in any amine unit makes sense from an economic
standpoint, it is crucial to limiting the amount of BTEX absorbed.

182
B. Lean Solvent Temperature
Figure 3 shows that the amount of BTEX emissions in amine systems decreases
with an increase in lean solvent temperatures. However, increasing the lean solvent
temperature also decreases the pickup of H2S and results in higher circulation rates and/or
higher reboiler duties to make specification. CO2 pickup will also decrease in M E A and
DEA; although, it may actually increase under certain conditions using MDEA. Figure 4
also shows that the amount of water in the sweetened gas increases dramatically with
increased lean solvent temperature, and thus results in a larger load on the downstream
glycol system, which would in turn increase its BTEX emissions.

125

i00

M~
_m 5O MD~
25 I I I I

90 i00 Ii0 120 130 140

Lean solvent temp.

F

Figure 4 - Water in Sweetened Gas vs. Lean Amine Temperature

C. Amine Type
As seen on both Figures 2 and 3, M D E A absorbs the lowest amount of BTEX,
and M E A has only slightly increased emissions over DEA for the same circulation rates
and at the same lean solvent temperatures. Although this would suggest that M D E A
should always be used over the other two amines from an emissions standpoint, the CO2
and H2S specification in the sweet gas must also be taken into account. At lower
pressures M D E A may be unable to achieve a very low specification for either
component 16.

183
Glycol Plant Operation
Once the saturated sweetened gas leaves the amine unit, it must be dehydrated,
typically with a glycol system, before further processing can take place. The operation of
a glycol unit is very similar to that of an amine unit. In a standard glycol unit the wet gas
is contacted countercurrently with lean glycol in an absorber column. Water in the gas is
absorbed into the glycol, and the dry gas exits the top of the column. Rich glycol exits
the bottom of the column and is sent through a regeneration system to remove the excess
water. Any dissolved hydrocarbons, including BTEX, leave the system as vent gas in the
regenerator or as flash gas. The regenerated glycol is then cooled and recycled back to
the top of the absorber column.

Operating Parameters
The effect of operating parameters on BTEX emissions from glycol dehydration
facilities has been comprehensively presented earlier 7. However, for convenience and
development of the current scenario, a brief analysis is provided here.
Again, the same parameters that affect BTEX absorption in amine units also apply
to glycol units. Lean solvent circulation rate and lean solvent temperature are potential
process variables in determining BTEX pickup. One other factor to consider is the
stripper pressure which has a large effect on the lean glycol water content. Table 2 shows
the process conditions used to investigate the effect of these parameters on BTEX
emissions from glycol units. It should be noted that the cases investigated have been
simplified to show the effects of a single variable on BTEX emissions. The dehydrated
gas in each case may not necessarily pass pipeline specifications.

184
 TABLE 2 Glycol Unit Base Case Parameters

Inlet Gas

Temperature Pressure Flowrate

F psia MMSCFD
120 1000 47

Component Composition Component Composition

Mol % Mol %
H20 0.22 IC4 0.43
N2 0.41 C4 0.53
CO2 1.86 IC5 0.21
CI 89.54 C5 0.16
C2 4.69 C6 0.22
C3 1.61 C7+ 0.16

Component Benzene Toluene Ethylbenzene O-Xylene

ppm 215 180 100 95

Process Equipment

Contactor Flash L/R Stripper Pump Cooler

Exchanger
2 ideal stages 75 psia 300 F (TEG) 4 ideal stages 1000 psia 120 F
250 F (DEG) 14.7 psia ovhd.
rich outlet 0.2 reflux ratio
temperature 400 F (TEG), 320 F (DEG)
reboiler temperature

Note: A glycol circulation rate of 4 gal./lb. H 2 0 is used unless otherwise noted.

185
A. Lean Solvent Circulation Rate
As with the amine systems, BTEX emissions from a glycol unit are strongly
dependent upon the circulation rate. Figure 5 shows that BTEX pickup increases almost
linearly with an increase in circulation rate. However, Figure 6 shows that there is very
little benefit in circulating more than four gallons of solvent per pound of water in the
inlet gas. Again, from an economic point of view and to limit BTEX emissions,
minimization of solvent circulation is crucial.

400
350
300
0

.... DEG
"~ 200
TEG
~ O 150 lid t¢, f f

IO0
5O
I I ~ I I I [

O 1 2 3 4 5 6 7 8

Lean solvent circulation

gal/ib H20

Figure 5 - B T E X Emissions vs. Lean Glycol Circulation

 25

2O

io
• m l l l l l m l l

.... DEG
,T E G

I I I I I I I

0 1 2 3 4 5 6 7 8

Lean solvent circulation

gal/Ib H20

Figure 6 - Residual Water Content vs. Lean Glycol Circulation

B. Lean Solvent Temperature

As shown in Figure 7, the lean glycol temperature has very little effect on the
BTEX emissions from a dehydration unit. This notable difference from BTEX
absorption in amine units is due to the relatively large gas to glycol mass ratio,
approximately 13:1 in the cases presented here. As a result, the rich glycol temperature is
primarily a function of the inlet gas temperature. In an amine unit the gas to amine mass
ratio is typically much lower, approximately 1:3 in the cases presented here, and the
treated gas temperature is normally within a few degrees of the lean amine temperature.
Figure 8 shows that the water content of the treated gas is only weakly related to lean
glycol temperature as well.

187
 250
In 230
c
O
210
c
O
, m
190 .... DEG
.E 170 TEG
E
tu 150 l I I I

I00 Ii0 120 130 140 150

Lean solvent temp.
F

Figure 7 - B T E X Emissions vs. Lean Glycol T e m p e r a t u r e

20

• is

i0
0 .... DEG
TEG

I I I I

i00 ii0 120 130 140 150

Lean solvent temp.
F

Figure 8 - Residual Water Content vs. L e a n Glycol T e m p e r a t u r e

C. Stripper Pressure
Another process parameter that can have affect the BTEX emissions from a glycol
unit is the stripper pressure. As seen in Figure 9, the higher the stripper pressure, the
lower the overall B T E X emissions. This is due to a change in the equilibrium
composition in the stripper, and the effect is more noticeable with DEG than with TEG.

188
However, increasing the stripper pressure also increases the water in the lean solvent and
may mean that the water specification cannot be met in the treated gas without using
stripping gas. Thus the potential decrease in BTEX emissions at higher stripper pressures
may be outweighed by the pipeline requirements. Figure 10 illustrates this limitation.

&.
225

200
0

175
0 . . . . DEG
QQ

._¢ 150 elm

D Q
TEG
E
125 I l l

10 20 30
Stripper pressure
psia

Figure 9 - BTEX Emissions vs. Glycol Stripper Pressure

30
o
¢ II,

20
¢ •
O
.... DEG
TEG

0 i I , r

I0 20 30
Stripper pressure
psia

Figure 10 - Residual Water Content vs. Glycol Stripper Pressure

189
D. Glycol Type
T w o facts are clear based on all of the preceding figures:
1. There are fewer BTEX emissions from a given DEG unit than a comparable T E G unit
at the same operating conditions.
2. D E G units cannot treat a wet gas to the same level as a T E G unit at the same
circulation rate.

The solvent choice for a given situation must consider both of these factors. If the
treated gas water specification is sufficiently low, DEG may be unable to accomplish the
job and may be ruled out regardless of the emissions benefits.

M i n i m i z a t i o n of T o t a l Emissions
In an integrated plant with both amine and glycol units, the ultimate goal is to
limit total BTEX emissions. By comparing Figures 2 and 3 with Figures 5, 7 and 9, it is
clear that the bulk of the BTEX is emitted from the glycol units. In our examples,
approximately 25 % of the overall emissions are from the amine units, although the
amine circulation rate is roughly sixty times the glycol circulation rate. This extreme
difference is primarily due to the fact that the amine solutions are 85-90% water on a
molar basis, whereas the glycols contain only 10-20 % water, and all o f the B T E X
c o m p o u n d s are much more soluble in glycol than in water. Therefore, it should be
evident that glycol circulation rate is the most important variable that has been discussed
thus far. However, the other process parameters should not be overlooked.

The following is a list of strategies that should be followed to limit B T E X emissions from
an integrated gas plant:

1) Minimize the lean amine circulation rate. BTEX emissions are directly proportional
to the circulation rate.
2) Minimize the lean amine temperature. This parameter has a significant effect on the
amount of water fed to the glycol unit, and thus the amount of glycol that must be
circulated to achieve a residual water specification.

190
3) Minimize the lean glycol circulation rate. As stated earlier, BTEX pickup in the
absorber is strongly dependent on circulation rate, and circulation rates greater than 3-
4 gallons per pound of water result in little decrease in outlet water content 7.

The choice of amine solvent must be weighed against items 1 and 2 above, as well as
the treating requirements. At similar circulation rates, using MEA instead of DEA or
M D E A reduces the amount of water in the sweetened gas. However, BTEX emissions
from an M D E A unit and the associated glycol system under the same conditions are
considerably lower. The choice of dehydration solvent in a glycol system must be
weighed against treating requirements also. If a DEG system can achieve the required
water removal, then it should be used instead of TEG to limit BTEX emissions.
From the discussion above, it is clear that a number of factors need to be examined
when designing a grass-roots gas processing facility. The amine unit must meet the
required sweet gas specification, but the potential environmental consequences (i.e.
BTEX emissions) should also be considered. Lean amine temperature, lean solvent
circulation rate and solvent selection all factor into the final operation of the plant.
Similar parameters need to be addressed in the design of the glycol dehydration system,
and in which BTEX emissions are even more important. Given the number of
parameters that need to be addressed, a thorough parametric study should be performed to
maximize operating efficiency while minimizing BTEX and other emissions.

Other Options to Consider

Once all of the strategies on the previous list have been investigated and
optimized, the overall BTEX emissions may still be above the maximum limits. If such
is the case, there are additional processing options that may be investigated. BTEX
condensers are used to condense the aromatics from the vent gas from glycol
strippers 17'18'19. As discussed by Morrow and Lunsford, carbon beds may be used to
adsorb the BTEX components in amine unit vent gas, or the vent gas may be incinerated.
There are also BTEX stripper designs that use stripping gas to remove BTEX from the
rich amine and glycol solutions prior to regeneration 9. The byproduct gas is burned as
plant fuel.

191
Conclusions
Due to growing environmental concerns, limiting the total BTEX emissions from
gas processing plants is of primary importance. Glycol units have been under scrutiny
for some time; however, amine units have recently been targeted as well. In the cases
discussed earlier, approximately 25% of the overall emissions came from the amine units
while 75% came from the glycol dehydration unit. Reducing circulation rates in both
amine and glycol units and minimizing the lean amine temperature are the best ways to
achieve this goal. The choice of solvent can also affect the BTEX emissions. However,
treated gas specifications must be taken into account since changing operating parameters
to decrease BTEX emissions can also decrease unit performance. A thorough parametric
study is recommended to limit BTEX emissions while maintaining treated gas quality.

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192
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193