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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
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
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 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
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.
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.