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processing costs
A gas treating facility is upgraded to a formulated solvent to achieve reduced
operating costs compared with operations using a commodity amine blend
ROBERT L DOTSON
Dow Oil, Gas & Mining
W
ith the development of exhibits the highest degree of reac-
Acid dissociation constant (pKa) of
new drilling technology pKa (25°C) tion of gas treating amines when
common amines and CO2
and hydraulic fracturing compared to the pKa of aqueous
techniques, global shale gas produc- CO2 of 6.0 at 25°C.2 In comparison,
OH- 13.8
tion has increased significantly over DEA has a pKa of 8.88 and MDEA
Monoethanolamine (MEA) 9.5
the past five years and is projected Diethanolamine (DEA) 8.88 has a pKa of 8.52 at 25°C.
to continue increasing for several Methyldiethanolamine (MDEA) 8.52 In spite of its higher pKa
years. According to the International CO2 (first dissociation) 6.0 compared to MDEA, DEA has
Energy Agency,1 “by 2020 the disadvantages stemming from its
United States becomes a net Table 1 propensity to degrade in the pres-
exporter of natural gas and is almost ence of CO2 and corrode carbon
self-sufficient in energy, in net Amine/CO2 chemistry steel.3 The degradation reactions of
terms, by 2035.” “…as demand The absorption of CO2 from a gas DEA are catalysed by, but do not
increases by 50% to 5 trillion cubic stream uses the solvent’s ability to consume, CO2. Work by Polderman
meters in 2035. Nearly half of the accept a proton, which provides a and Steele,4 Kennard and
increase in production to 2035 is chemical driving force to assist Meisen, 5,6,7,8
Blanc et al,9 and Kim
from unconventional gas, with most solubilisation of the CO2. This and Sartori10 determined the DEA
of this coming from the United propensity for the aqueous CO2 to degradation reaction mechanism
States, Australia, and China…” act as an acid in the subsequent shown in Figure 1.
Increases in shale gas production reaction with an amine takes place According to Kim and Sartori, the
and decreasing energy prices glob- due to the higher dissociation DEA-CO2 degradation reactions
ally will require competitive constant (pKa) of the amine. The are initiated by the direct reaction
exploration and operational larger the difference in pKa of DEA and CO2 forming (HOCH2
expenses among the energy options. between the amine and the CO2, CH2)2NCO2H (DEA-carbamate),
In early 2011, after having plant the more complete the acid/base which condenses to 3-(2-hydrox-
operational issues, poor reliability reaction that will take place. As yethyl) oxazolidone-2 (HEO). The
of gas treating facility equipment Table 1 shows, MEA has the high- HEO then reacts with another mole-
and high operational costs, a US est pKa (9.5 at 25°C) and therefore cule of DEA, releasing a molecule of
gas treating operator met with Dow
Oil, Gas & Mining to discuss
options to reduce operational costs. O OH
Based on the operational perfor- H
mance information provided for N + CO2
N
HO OH HO OH
newly released Ucarsol Shale
DEA DEA-carbamate
Specialty Solvent from Dow, refer-
ence facilities, solvent technical O OH O
performance simulations and no HO
N N
requirement for expensive and O + H2O
HO OH
complicated chemical additives, the HEO
DEA-carbamate
operator decided to offer one unit
that was about to start up as a O HO
HO
demonstration facility. It was one + (HOCH2CH2)2NH
N N OH + CO2
N
HO
of two similar units supplied with O H
sour gas from the same gas pipe- HEO DEA THEED
line and located at the same
facility. Figure 1 Reactions of CO2 catalysed degradation of DEA
09
10
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12
12
01
period, Unit 2 had no major foam-
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20
20
20
l2
ay
ec
g
Ju
Ju
Ja
Au
Fe
ing issues, no shutdowns related to
M
450
400 additives for a 18-month period
prior to the trial averaged ~8000
350
ppmw, with a maximum of 18 000
300
ppmw (see Figure 2). Over 18
250 months, the facilities using MDEA/
200 DEA blend with chemical additives
150 averaged about 3000 ppmw bicine.
100
During the trial, Unit 1, operating
with the MDEA/DEA blend with
50
chemical additives, had bicine
0 concentrations of 3200 and 4000
ppmw (two samples). After upgrad-
11
11
12
12
12
1
20
20
20
20
20
20
ov
ar
p
Ju
Au
Se
M
M
11
11
11
12
01
01
20
20
20
20
20
r2
l2
ec
ct
Ju
Ap
Ju
Fe
Se
O
D
Filter changes, • No filter changes during the trial. • Required two filter changes.
total number
Amine • Required normal amine make-up volume during • Required amine make-up because of two severe foaming events.
make-up, qty the trial.
Chemical additives, • Requires no additives. • Requires continuous addition of corrosion inhibitor and bicine
total dollars (US) “killer” additives.
• Chemical additive cost: $22 752/yr.
Antifoam use • Low antifoam usage due to a low foaming tendency. • Used three times on Unit 1 due to multiple foaming events and
two severe foaming events.
Bicine concentration, • Unit 2 had non-detectable bicine concentration • Unit 1 bicine concentrations were 3200 and 4000 ppmw (two
wt% (<100 ppmv) during the trial and after 18 months of samples).
operation. • The bicine concentration for an 18-month period prior to the trial
• Unit 1, after upgrading from MDEA/DEA blend to averaged 8000 ppmw, with a maximum of 18 000 ppmw.
Ucarsol solvent, has a non-detectable bicine • Over the past 18 months, the MDEA/DEA blend has averaged
concentration after 16 months of operation. ~3000 ppmw bicine.
Iron concentration, • During the trial, Unit 2 maintained iron concentrations • Units operating on a MDEA/DEA blend from June 2009 to Nov
ppmw between 1-4 ppmw, indicating very low corrosion rates. 2012 averaged 18 ppmw iron. Typical iron range is 8-20 ppmw.
Operational reliability, • 100% amine operational reliability during the trial. • 95% amine operational reliability during the trial. Unit 1 shut
% of time treating gas Unit 2 shut down due to boiler issues. down twice during the trial due to severe amine foaming events.
Table 6
another unit, this lost revenue “CO2-only” gas, the operator esti- These cost estimates and payback
would further increase the cost mated equipment repairs to pumps, calculations do not take into
advantage. valves and piping due to corrosion account the lost revenue for unit
(corrosion maintenance) at $20 000/ down time or additional opera-
Operations cost comparison year for the MDEA/DEA blend. tional expenses, such as filter
The operator estimated first-year The operator concluded that the cartridges, which would further
and annual operating expenses for payback is 0.36 years for a new 300 reduce the payback time. The reve-
a new 300 gpm facility, based on gpm facility using solvent in place nue of any additional gas
MDEA/DEA blend operational of their standard MDEA/DEA processed, total sweet gas sold to
experience and trial data (see Table blend. the pipeline (treated and bypassed),
4). A new facility requires an initial Note: due to pricing confidential- was also not included.
fill of either amine. The annual ity of amine and antifoam, specific The operator also estimated first-
operating cost of the MDEA/DEA amine and antifoam costs are not year and annual operating expenses
blend requires the addition of provided. All operational cost for an existing 300 gpm facility
chemical additives at $22 752/year comparison tables provide the upgraded from MDEA/DEA blend
for a unit this size. MDEA/DEA pounds of amine for a system fill, to Ucarsol solvent, based on
make-up amine, based on operator estimated pounds of annual MDEA/DEA blend operational
experience and trial results, was make-up amine, estimated annual experience and trial experience (see
estimated to be two times the cost of antifoam, operator-provided Table 5). An existing facility would
make-up requirement for Ucarsol cost of annual chemical additives, require the removal of the MDEA/
solvent. Antifoam usage for the and operator-estimated cost of DEA blend and an initial fill of the
MDEA/DEA blend, based on the corrosion maintenance in a MDEA/ solvent. All other costs — make-up
trial, was estimated at three times DEA system for a 300 gpm facility. amine, antifoam, chemical additives
that for the Ucarsol solvent. From Payback calculations are based on and the estimated cost of corrosion
10 years of operational experience antifoam and amine costs at the maintenance — remain the same
with MDEA/DEA blends in time of the trial. for the cost comparison. The cost of