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SPE 52730

Glycol Used for Natural Gas Dehydration: Evaluation of Subsurface Transport and
Fate Issues
J.A. Sorensen, S.B. Hawthorne, J.R. Gallagher, Energy & Environmental Research Center, and J.A. Harju, Gas Research
Institute

Copyright 1999, Society of Petroleum Engineers Inc.


cosolvents, 3) very little research has been performed regard-
This paper was prepared for presentation at the 1999 SPE/EPA Exploration and Production ing the biodegradability of gas industry glycols and their asso-
Environmental Conference held in Austin, Texas, 28 February–3 March 1999.
ciated wastes under environmentally relevant conditions, and
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 4) regulatory scrutiny of glycols has increased in recent years
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 any
(1).
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at Generally, adequate data exist to confirm the presence of
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper glycols and at least some of their biodegradation products and
for commercial purposes without the written consent of the Society of Petroleum Engineers is other associated contaminants in soils, sediments, and
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous acknowledg- groundwater at the sites in question. However, analytical and
ment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box
833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435. other difficulties have typically prevented the nature and extent
of glycol-related contamination from being delineated in detail
Abstract at individual sites. At the same time, limited work has been
Triethylene glycol (TEG), diethylene glycol (DEG), and ethyl- done on the behavior of the chemical species in question in the
ene glycol (EG) are commonly used to dehydrate the natural subsurface, and, therefore, little is known about their subsur-
gas stream. These compounds may be introduced into the sub- face transport and fate. Air emissions from glycol-based gas
surface environment as a result of spills, leaks, mechanical dehydration units have been regulated under the Clean Air Act
failures, and past disposal practices. The toxicity of the dehy- for a number of years, but the U. S. Environmental Protection
dration glycols at concentrations typically found in the subsur- Agency (EPA) has recently added ethylene glycol (EG) to its
face in the vicinity of a dehydration unit is generally consid- list of contaminants to be considered for regulation under the
ered to be low. However, the miscibility of the glycols sug- Safe Drinking Water Act. This places the natural gas industry
gests that they may act as cosolvents for other more toxic, less in the difficult position of having to effectively address a con-
soluble, organic compounds such as polycyclic aromatic hy- tamination issue that is neither well defined nor well under-
drocarbons (PAHs), thereby increasing the subsurface mobility stood.
of those compounds. In 1998, a series of laboratory-based The research described in this paper has focused on subsur-
research activities was initiated to determine 1) the nature of face transport and fate issues related to triethylene glycol
cocontaminants that may be associated with the gas dehydra- (TEG), diethylene glycol (DEG) and EG. TEG and DEG were
tion process, particularly spent glycols, 2) the biodegradability selected for examination because they are used in a vast ma-
of the dehyradation glycols under environmentally relevant jority of gas dehydration units, and EG was chosen because it
conditions in soils from three different gas-producing regions is currently under regulatory scrutiny as a drinking water pol-
of North America, and 3) the potential effect of the dehydra- lutant.
tion glycols on the subsurface mobility of PAHs in the same The intention of this research is to provide the natural gas
three North American soils. industry with data and insights that will enable it to 1) signifi-
cantly improve the assessment of subsurface glycol-related
Introduction contamination at sites where it is known or suspected to occur
Examination of the literature on gas industry wastes indicated and 2) make soundly based decisions concerning the remedia-
that wastes associated with glycols from gas dehydration op- tion of that contamination.
erations may be of some environmental concern. These re-
views concluded that 1) past disposal practices have resulted Background
in the release of glycol-related wastes into the subsurface envi- Water in natural gas can cause serious operational problems in
ronment, 2) their physicochemical properties suggest that gly- both the transmission and processing of the gas. The natural
cols may be readily transported in the subsurface and act as gas industry has found that dehydration ensures smooth opera-
tion of gas transmission lines, prevents formation of gas hy-
2 J.A. SORENSEN, S.B. HAWTHORNE, J.R. GALLAGHER, J.A. HARJU SPE 52730

drates, and reduces corrosion. The most common dehydration glycol solution is then sent through a series of heat exchangers
process used in the gas industry is the glycol absorp- and filters, after which water is either distilled or stripped from
tion/stripping process. While the actual number of operating the glycol solution in a regenerator (3). Rising steam in the
glycol units is unknown, it is estimated that as many as 40,000 regenerator strips the water vapor from the rich glycol solu-
units exist in the United States and about 100,000 exist world- tion, and the glycol, carried by the rising vapor, is condensed
wide (2); however, it is the authors’ belief that the actual num- in the reflux section and washed back into the reboiler. The
ber is significantly higher than that. In the United States, 90% regenerated, lean (dry) glycol is then cooled and returned to
to 95% of the units process less than 10 million standard cubic the absorber (6). Fresh glycol solution that may be added to a
feet per day (mmscfd) of natural gas (2). No estimates were dehydrator for makeup or changeover operations is referred to
available on the total number of glycol dehydration units oper- in this paper as “raw” glycol. As such, the raw glycol dis-
ating in Canada, but they are very commonly used in Canadian cussed later in this paper has not been exposed to a natural gas
gas fields. The total volume of natural gas dehydrated in stream.
North America each year is approximately 17–18 trillion cubic
feet (tcf) (3). While no figures were available on percentage Research Program Approach
of gas dehydrated by glycol dehydrators, a literature search The approach of this research program is to use a systematic
and discussions with gas industry personnel indicate that a series of laboratory-based research activities that are focused
large majority of the dehydration is done using glycol-based on the subsurface transport and fate of glycol-related wastes to
units. determine the potential environmental hazards that those
EG, TEG, DEG, tetraethylene glycol (TREG), and blends of wastes may pose. The research activities can be grouped into
these glycol solutions have all been used in natural gas stream two areas: 1) characterization of glycol-related dehydration
dehydration processes for decades. Around 1950, TEG be- wastes for cocontaminant organics and 2) determination of the
came the most commonly used glycol because its higher boil- biodegradability of TEG under conditions that are relevant to
ing point provided better water removal without its being the subsurface environment. In order to generate widely ap-
thermally decomposed (4). EG and TREG are used in some plicable data, the biodegradation experiments were performed
specialized cases; however, TEG remains the most commonly on three distinctly different soils that were obtained from three
used glycol in natural gas dehydration processes. It has been gas-producing areas of North America (New Mexico, Louisi-
estimated that TEG is used in approximately 95% of glycol ana, and Alberta).
dehydration units (3). The objectives of this research are to characterize the
In terms of chemistry, glycols are aliphatic organic com- chemical nature of spent TEG and EG from natural gas dehy-
pounds and are members of a group of chemicals referred to as dration units and to directly investigate the natural attenuation
the dihydric alcohols (diols). This group has the general for- processes that control the fate of TEG and DEG. The ultimate
mula CnH2n(OH)2 and is characterized by the presence of two goal is to provide the natural gas industry with presently un-
hydroxyl (OH−) functional groups linked to methylene (CH2) available data and insights that will enable glycol-related con-
subunits. Ethylene glycols have the general formula tamination to be more effectively addressed where it is known
HO(C2H4O)nH, where n can be 1 (monoethylene), 2 (dieth- or suspected to occur in the subsurface.
ylene), 3 (triethylene), or 4 (tetraethylene). Table 1 provides
some general physical and chemical properties of glycols Waste Characterization
commonly used by the gas industry. The primary objective of the characterization activities was to
Physically, glycols are similar to water in that they are clear, determine the gross chemical characteristics, identities, and
colorless, odorless liquids. However, compared to water, the relative amounts of organic cocontaminants in spent glycols
glycols have a greater specific gravity and viscosity at all tem- and glycol-related dehydration wastes. Glycols and glycol-
peratures, a higher boiling point, and a lower freezing point. related wastes derived from dehydration units that use TEG
Glycols are completely water-soluble and can also act as sol- and EG were characterized qualitatively and semiquantita-
vents for some organic compounds, including most aromatic tively. Particular focus was on species of high toxicological
compounds (5). and regulatory interest (e.g., benzene). This information will
The absorption/stripping dehydration process in which the ultimately be used to estimate the potential for facilitated
glycols are used begins by scrubbing compressed wet inlet gas transport, to design experiments to determine the effect of co-
to remove liquid and solid impurities. This is followed by contaminants on glycol transport, and (more likely) to deter-
sending the scrubbed gas countercurrently through a liquid mine the effect of glycols on the transport of organic cocon-
glycol absorber. The lean (dry) glycol absorbs the water from taminants. Since the vast majority of regulated organics are in
the wet gas stream, and the dried gas leaves the absorber for the volatile and semivolatile range, the primary emphasis was
further processing or transport. The rich glycol exits the bot- on these compounds.
tom of the absorber and, on some units, is sent through a gas- Spent glycol solutions and other glycol-related dehydration
driven or electric pump to a flash tank, where much of the ab- wastes that are derived from TEG-, DEG-, and EG-utilizing
sorbed natural gas is separated from the glycol solution. The dehydration units were collected for use in experimental ac-
SPE 52730 GLYCOL USED FOR NATURAL GAS DEHYDRATION: EVALUATION OF SUBSURFACE TRANSPORT AND FATE ISSUES 3

tivities. Approximately 29 samples of rich, lean, and raw gly- Results of Characterization Activities
col solution were collected from 12 dehydration units from A total of 29 samples was collected from 12 glycol-based de-
eight gas-processing facilities in different gas-producing parts hydration units at nine different gas-conditioning facilities and
of North America (Louisiana, Texas, New Mexico, Oklahoma, analyzed as described above. All samples were composed pri-
and Alberta, Canada). Samples were collected from a variety marily of either TEG or EG, depending on what was used at
of dehydration units in order to examine the heterogeneity the sampled dehydrator. Glycol concentrations ranged from
between wastes that may be caused by different gas composi- 54.2% to 92.1%. Table 2 qualitatively describes the relative
tions, feed rates, and/or the use of various additives. Collection abundance of organic cocontaminants (BTEX, PAH, and al-
of samples was conducted by EERC personnel to ensure the kanes) in samples from eight of the gas-processing facilities.
consistency of sampling methods. Gas company personnel Table 3 quantitatively describes the content of organic cocon-
familiar with the operation of each dehydration unit were taminants from three of the gas-processing facilities. As ex-
asked to fill out a questionnaire on the operating characteris- pected, raw TEG and EG samples were typically observed to
tics of the sampled unit and the nature of the natural gas stream be generally clean, although a sample from one site did contain
itself. moderate levels of organic cocontaminants (toluene, benzene,
and naphthalene). Also as expected, rich glycol solutions typi-
Characterization of Cocontaminant Organics in cally included high concentrations of BTEX with smaller, but
Glycol Wastes potentially significant, concentrations of PAHs and alkanes.
The general experimental plan for determining the character of The presence and abundance of organic cocontaminants in
cocontaminant organics in the glycol samples was as follows: lean glycol solutions was found to vary widely from facility to
1. Samples of raw, rich, and lean TEG and EG were ana- facility, with relative concentrations ranging from low to high.
lyzed for gross characteristics, including elemental analyses In fact, at some facilities it was difficult to differentiate be-
(C, H, O, N, and S) and total organic carbon (TOC). tween lean and rich samples based on the analytical results
2. Initial characterization of volatile and semivolatile co- alone. Figures 1–4 show GC chromatographs selected to il-
contaminant organics was performed on all samples. These lustrate organic characteristics “typical” of raw, rich, and lean
initial characterizations were performed to categorize the glycol solutions. Other notable observations that resulted from
overall chromatographic behavior of the volatile and semi- the characterization activities include the lack of significant
volatile organics (following methylene chloride extraction). levels of chlorine- and bromine-containing organics and the
Difficulty in extracting many volatile and semivolatile organic presence of significant organosulfur compounds in the rich EG
pollutants of interest from glycol wastes was expected using sample from Alberta. The organosulfur compounds in the
conventional (e.g., methylene chloride) approaches. There- Alberta sample are not surprising, considering that the raw
fore, the ability of the extraction methods was evaluated by natural gas stream at that particular facility may contain up to
determining the recovery of appropriate deuterated spikes 25% H2S. Further, there is little or no use of chlorinated sol-
(e.g., labeled BTEX [benzene, toluene, ethylbenzene, and xy- vents in natural gas processing.
lenes] compounds and several PAHs [polycyclic aromatic hy-
drocarbons]) from representative glycol wastes. In addition, Evaluation of Glycol Biodegradability
an innovative extraction method, solid-phase microextraction A number of attenuation mechanisms can affect the transport
(SPME), was evaluated for its ability to provide class-selective and fate of organic compounds in the environment, but bio-
removal of nonpolar organics (e.g., BTEX, PAHs) from glycol logical metabolism is often the most important of these
wastes. mechanisms. Therefore, in order to understand the ultimate
fate of organic compounds in the environment and the factors
3. Identification of organic cocontaminants was performed
that control the biological processes, biodegradation studies
using organic solvent extracts (and SPME extracts) that were
are required. Biodegradation is typically composed of three
characterized using gas chromatography–mass spectroscopy
phases: acclimation of the microbial population to a particular
(GC–MS) and gas chromatography–atomic emission detection
compound, logarithmic metabolism, and a plateau period.
(GC–AED). GC–AED allows selective detection of individual
Physical factors that can affect biodegradation include tem-
elements in individual organics. Elements monitored in this
perature, pH, moisture content, contaminant concentrations,
study included C, H, N, S, and selected halogens. Semiquant-
size of the biodegrading microbial population, the availability
itative determinations of significant (either in quantity or be-
of oxygen or other nutrients, and other intrinsic factors specific
cause of regulatory or toxicological interest) organic cocon-
to the soil and to the contaminant. A determination of the
taminants were performed using appropriate combinations of
factors that control the biodegradation of TEG under environ-
GC–MS, GC–AED, and GC–flame ionization detection (FID).
mentally relevant conditions is critical for assessing remedial
These studies also included quantitative determinations of the
options and predicting the ultimate environmental fate of these
original glycols (whether TEG or EG).
compounds.
The biologically based experimental activities described
below were designed and performed to meet several objec-
4 J.A. SORENSEN, S.B. HAWTHORNE, J.R. GALLAGHER, J.A. HARJU SPE 52730

tives. The primary goals for the investigations of TEG and for microbial growth. The reason for this possible growth in-
DEG biodegradability are 1) to determine the biodegradation hibition is not known, but may be a toxic effect. Support for
parameters for TEG and DEG and 2) to evaluate the impact of the theory that TEG may have a toxic effect on the Louisiana
such key variables as soil/sediment type, contaminant concen- and New Mexico sediments is given by Bringmann and Kühn
trations, and oxygen availability on biodegradation. The ob- (8), who found that TEG showed a growth inhibition toxicity
jective of the planned experiments was to provide information threshold for Pseudomonas putida at 320 mg/L. The inhibi-
on the natural ability of the three selected soils to degrade tion of growth and TEG metabolism in the Louisiana sediment
TEG and DEG. The general experimental plan follows. at the 200-mg/kg dose may be due to the lower pH of this
Biodegradation testing was conducted to evaluate the length sediment (see Table 3) or because this sediment has been
of the acclimation phase, the rate constant for biodegradation, shown in other experiments to have low microbial activity.
and the extent of biodegradation for TEG and DEG in soils Aerobic biodegradation of DEG at a low dose is shown in
collected from natural gas-producing regions of New Mexico, Figure 7. At this 200-mg/kg dose, the Alberta soil showed a
Louisiana, and Alberta, Canada. Characterization data for lag of 5.6 days, and a maximum rate of degradation of 1.6 mg
these soils are presented in Table 4. Biodegradation was carbon dioxide evolved per 100 gdw per day. The New Mex-
evaluated by respirometric methods following those of Bartha ico soil showed a similar lag period, 6.1 days, but the rate was
and Pramer (7), which measure evolved carbon dioxide, about one-half of that seen with the Alberta soil (0.9 mg
thereby indicating mineralization of the subject compound. All CO2/100 gdw-d). Biodegradation of DEG in the Louisiana
experiments were conducted in soils at 25°C, 60% of the soil was much slower, demonstrating a lag period of about 20
moisture-holding capacity, with static incubation in the dark. days, and a maximum rate of 0.5 mg CO2/100 gdw-d. The
TEG and DEG concentrations of 200 and 1000 mg/kg were extent of biodegradation seen in all three soils is similar,
chosen to represent environmentally significant values. Bio- ranging from 78% to 89% of theoretical possible. It is inter-
degradation kinetics with respect to oxygen were evaluated to esting to compare the patterns of carbon dioxide evolution
demonstrate the rates that may be obtained in unsaturated and noted in these three soils. For the Alberta soil, the curve is a
saturated soils and in anaerobic environments. The data from classical hyperbolic function (exponential increase, gradually
this work will demonstrate the biodegradation kinetics in natu- shifting to a plateau) with a lag period. In the New Mexico
ral, unamended environments. soil, the curve shows a minor exponential increase, but quickly
shifts to an arithmetic increase, gradually flattening to a pla-
Results of Aerobic Biodegradation of TEG and DEG teau. In the Louisiana soil, the carbon dioxide evolution pat-
Figures 5 and 6 show cumulative CO2 evolution from the min- tern shows a very gradual increase and does not attain a pla-
eralization of TEG under aerobic conditions over the course of teau.
the experimental period (62 days) at concentrations of 200 and Overall biodegradation of DEG at the higher dose of
1000 mg/kg, respectively. These data, summarized in Table 5, 1000 mg/kg was similar to that at the low dose, with the ex-
show relative lag times, biodegradation rates, and extent of ception that the extent of biodegradation was lower and quite
mineralization for TEG in the three soils at 25°C. The data different among the three soils, as shown in Figure 8. As with
indicate that TEG was biodegraded from 23.6% to 99.6% of the low dose, the Alberta soil shows a classic hyperbolic func-
the theoretical possible in the sediments after a lag period tion with a lag period. The lag period was 5.4 days, with a
ranging from 2 to 13 days. Only rarely is the extent of biodeg- maximum rate of 3.1 mg CO2/100 gdw-d, and the extent of
radation, based on evolved carbon dioxide, observed to be biodegradation was 51% of theoretical possible. Biodegrada-
100%. This is because of the incorporation of carbon into tion in the New Mexico soil showed a lag period of 4.7 days
biomass. The amount of CO2 incorporated into biomass is a and a maximum rate of 1.3 mg CO2/100 gdw-d, and the extent
function of the types and amounts of biomass present at the of biodegradation was 25.6% of theoretical possible. The
start, the organic compound, and the conditions (pH, electron Louisiana soil showed the poorest biodegradation of DEG,
acceptor, etc.). The fastest biodegradation rates were observed with a lag period of almost 40 days, a maximum rate of 0.9
in the Alberta sediment at both the low dose (200 mg/kg) and mg CO2/100 gdw-d, and the extent of mineralization was
the high dose (1000 mg/kg). Biodegradation of TEG in the 19.3% of theoretical possible.
New Mexico sediment was similar to that in Alberta sediment
in rate and extent and length of the lag period at the low dose, Results of Anaerobic Biodegradation of TEG
but was only poorly biodegraded at the higher dose. Biodeg- Figure 9 shows cumulative CO2 evolution from the minerali-
radation of TEG in the Louisiana sediment was poor for both zation of TEG under anaerobic conditions over the course of
the low and the high dose. Moreover, biodegradation of TEG the experimental period (165 days) at a concentration of
in Louisiana sediment at both doses and in the New Mexico 1000 mg/kg. These data, summarized in Table 6, show rela-
sediment at the high dose showed a simple arithmetic increase tive lag times, biodegradation rates, and extent of biodegrada-
in carbon dioxide, rather than the hyperbolic increase normally tion for TEG in the three soils at 25°C. TEG was biodegraded
associated with microbial metabolism. This arithmetic rather under anaerobic conditions in the Alberta sediment after a lag
than hyperbolic metabolism suggests that TEG is not allowing period of 13.6 days. The extent of biodegradation seen in the
SPE 52730 GLYCOL USED FOR NATURAL GAS DEHYDRATION: EVALUATION OF SUBSURFACE TRANSPORT AND FATE ISSUES 5

Alberta sediment (64.4% of theoretical possible) suggests that References


during the 165-day period, the TEG was essentially completely 1. Sorensen, J.A., Fraley, R.H., Gallagher, J.R., and Schmit, C.R.,
metabolized. The rate of TEG biodegradation in Alberta sedi- “Background Report on Subsurface Environmental Issues
ment was 27% of that found at the same dose under aerobic Relating to Natural Gas Sweetening and Dehydration
conditions. Biodegradation of TEG in the Louisiana and New Operations,” report for Gas Research Institute Contract GRI-
95/0143 (1996).
Mexico sediments was much slower than for Alberta. Calcu- 2. Grizzle, P.L., “Glycol Mass-Balance Method Scores High for
lated lag periods for Louisiana and New Mexico are low, but Estimating BTEX, VOC Emissions,” Oil and Gas Journal, 70,
kinetics appear to be arithmetic, again suggesting inhibition of 61 (1993).
growth in these sediments. 3. Thompson, P.A., Cunningham, J.A., and Berry, C.A., “PC
Experiments to evaluate the biodegradation of DEG under Program Estimated BTEX, VOC Emissions, Glycol-Reboiler
anaerobic conditions were initiated at the EERC in October, Emissions Conclusion,” Oil and Gas Journal, 41, 36 (1993).
1998. The experimental activities were not complete, and 4. Pearce, R.L., “Fundamentals of Gas Dehydration with Glycol
therefore no data were available at the time of publication. Solutions and Glycol Analysis Dehydrator Problem Solving,”
presented at the Gas Conditioning Conference, University of
Oklahoma (1982), 58 p.
Implications 5. Dow Chemical Company, “Latest Material Safety Data Sheets
The results of the characterization investigations have demon- and/or Sales Specs from the Dow Chemical Company,”
strated that a range of organic cocontaminants (e.g., BTEX, Midland, Michigan (1993).
PAHs, alkanes, and other process-related organic cocontami- 6. Ballard, D., “The Fundamentals of Glycol Dehydration,”
nants) is associated with glycols used for natural gas dehydra- Coastal Chemical Co., American Institute of Chemical
tion, particularly “rich” glycols. This suggests that at gas in- Engineers, New Orleans, Louisiana (1986).
dustry sites where rich or lean dehydrator glycols are known to 7. Bartha, R., and Pramer, D., “Features of a Flask and Methods
have been released to the subsurface environment, such co- for Measuring the Persistence and Biological Effects of
contaminants could also be present. The association of these Pesticides in Soils,” Soil Science, 10, 68–70 (1965).
8. Bringmann, G. and Kühn, R., “Comparison of the Toxicity
organic cocontaminants with the glycols may be problematic
Thresholds of Water Pollutants to Bacteria, Algae and Protozoa
from two angles. First, the presence of cocontaminants could in the Cell Multiplication Test,” Water Research 14, 231–241
affect the rate and/or extent of glycol biodegradation, thereby (1980).
complicating remediation efforts. Second, the glycols in water
could act as a cosolvent and greatly increase the transport of
the organic cocontaminants (or any other organic compounds
that the glycols might happen to come into contact with) be-
yond what would normally be predicted. Future investigations
of the subsurface environmental effects of dehydration glycols
will be designed to determine the effect of glycols on the
transport of organic cocontaminants.
Another lesson that stands out from the results of the re-
search is that site-specific variables need to be considered
when assessing glycol-related contamination in the subsurface.
For instance, the results of the biodegradability evaluations,
which consistently show biodegradation to be inhibited in the
Louisiana soil, suggest that soil type may be an important fac-
tor in predicting the ultimate fate of TEG and DEG in the sub-
surface environment. The characteristics of the raw gas stream,
which are typically very site-specific, can also have a tremen-
dous effect on the nature of the organic cocontaminants in a
rich glycol, as evidenced by the organosulfur compounds pres-
ent in the samples from the sour gas fields of Alberta.

Acknowledgements
The authors wish to thank Marc Kurz of the EERC for his ef-
forts in obtaining the glycol samples and Lori Gunderson for
her assistance in preparing this paper. The authors also want to
thank the many gas-processing plant managers who provided
the samples that made this research possible.
6 J.A. SORENSEN, S.B. HAWTHORNE, J.R. GALLAGHER, J.A. HARJU SPE 52730

Table 1. General physical and chemical properties for selected glycols.1


EG DEG TEG TREG
Molecular Weight 62.1 106.1 150.2 194.2
Boiling Point 387.3/197.4 473.8/245.5 550.0/287.8 618.1/325.6
@760 mm Hg,
°F/°C
Freezing Point, 7.9/13.4 16.4/8.7 19.0/7.2 15.1/9.4
°F/°C
Flash Point, °F/°C 247/119 281/138 325/163 400/204
Specific Grav- 1.110 1.111 1.120 1.123
ity@ 25°C
Vapor Pressure, <0.1 <0.01 <0.01 <0.01
mm Hg @ 25°C
Aqueous Solubil- Completely Completely Completely Completely
ity miscible miscible miscible miscible
Color Clear, color- Clear, color- Clear, color- Clear, col-
less less less orless
1
Dow Chemical Company, 1992.

Table 2. BTEX, etc., in glycol samples, L = Low, M = Moderate,


and H = High concentrations.
Rich Lean Raw
Site 1 TEG L L L
Site 2 TEG H, H1 H M
EG (amine heater) L
Site 3 TEG H, H1 H L
EG (amine heater) L
Site 4 TEG H L L
Site 5 TEG M M M
Drip L
Site 6 EG H L L
Site 7 TEG H M L
Site 8 TEG H M L
1
Two Samples analyzed.
SPE 52730 GLYCOL USED FOR NATURAL GAS DEHYDRATION: EVALUATION OF SUBSURFACE TRANSPORT AND FATE ISSUES 7

Table 3. BTEX, etc., in glycol samples, 1998.


Site Benzene Toluene Ethylbenzene m-,p-xylene o-xylene Napthalene
4 – Rich 150 260 34 190 63 <0.1
4 – Lean 0.9 0.3 <0.1 <0.1 <0.1 <0.1
6 – Rich 480 250 7.5 64 27 <0.1
6 – Lean 7.9 5.0 0.6 2.3 2.3 <0.1
8 – Rich 100 160 21 80 32 28
8 – Lean 4.6 2.3 0.6 1.6 0.8 15
1
Concentration in µg/g.

Table 4. Base sediment characterization.


Alberta Louisiana New Mexico North Dakota
Parameter Sediment Sediment Sediment Sediment
Sand (0.074 to 2 mm), % 25 15 39 NA1
Silt (0.005 to 0.074 mm), % 33 55 35 NA
Clay (<0.005 mm), % 42 31 26 NA
Total Organic Carbon, % 2.0 0.7 0.3 5.6
Carbonate, % 4.7 0.2 1.6 0.9
Cation Exchange Capacity,
milliequivalents/100 g 25.0 10.8 12.5 37.5
pH 7.6 5.2 7.7 7.2
1
Not available.

Table 5. Biodegradation parameters for TEG in the three soils at 25°C, 60% of the
moisture-holding capacity, with static incubation in the dark for 62 days under aerobic
conditions.
Alberta Louisiana New Mexico

Dose, mg/kg 200 1000 200 1000 200 1000


Lag Period, d 3.7 4.4 13.1 1.9 2.4 13.1

Maximum Rate,1 2.56 5.81 0.42 0.67 2.03 0.75


mg CO2 /100g-d ±0.36 ±0.29 ±0.02 ±0.03 ±0.15 ±0.02
Theoretical Degra- 99.6 71.5 53.2 23.6 93.3 31.5
dation, %
R2 for Regression 0.981 0.990 0.990 0.984 0.994 0.990
1
Plus or minus the standard error.
8 J.A. SORENSEN, S.B. HAWTHORNE, J.R. GALLAGHER, J.A. HARJU SPE 52730

Table 6. Biodegradation parameters for TEG in the three soils at 25°C, 60% of the
moisture-holding capacity, with static incubation in the dark for 165 days under
anaerobic conditions.

Alberta Louisiana New Mexico

Lag Period, days 13.6 2.7 1.0


Maximum Rate, 1 1.59 0.20 0.60
mg CO2 /100g-d ±0.06 ±0.01 ±0.03
Theoretical Degra- 64.4 8.1 32.3
dation, %
R2 for Regression 0.991 0.983 0.982
1
Plus or minus the standard error.
SPE 52730 GLYCOL USED FOR NATURAL GAS DEHYDRATION: EVALUATION OF SUBSURFACE TRANSPORT AND FATE ISSUES 9

Fig. 1—Gas chromatogram of rich glycol from Site 2.

Fig. 2—Gas chromatogram of lean glycol from Site 8.


10 J.A. SORENSEN, S.B. HAWTHORNE, J.R. GALLAGHER, J.A. HARJU SPE 52730

Fig. 3—Gas chromatogram of rich glycol from Site 6.

Fig. 4—Gas chromatogram of raw glycol from Site 3.


SPE 52730 GLYCOL USED FOR NATURAL GAS DEHYDRATION: EVALUATION OF SUBSURFACE TRANSPORT AND FATE ISSUES 11

Fig. 5—Cumulative net carbon dioxide evolution for TEG at doses of 200 mg/kg under aerobic conditions.

Fig. 6—Cumulative net carbon dioxide evolution for TEG at doses of 1000 mg/kg under aerobic conditions.
12 J.A. SORENSEN, S.B. HAWTHORNE, J.R. GALLAGHER, J.A. HARJU SPE 52730

Fig. 7—Cumulative net carbon dioxide evolution for DEG at doses of 200 mg/kg under aerobic conditions.

Fig. 8—Cumulative net carbon dioxide evolution for DEG at doses of 1000 mg/kg under aerobic conditions.
SPE 52730 GLYCOL USED FOR NATURAL GAS DEHYDRATION: EVALUATION OF SUBSURFACE TRANSPORT AND FATE ISSUES 13

Fig. 9—Cumulative net carbon dioxide evolution for TEG at doses of 1000 mg/kg under anaerobic conditions.

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