Ind. Eng. Chem. Prod. Res. Dev.

lB86, 25, 627-630 627

On an equimolar basis, ZDTPs exhibit lower an-
tioxidant capabilities than MPH.
Antioxidant capabilities of equimolar mixtures of
ZDTPs and MPH are determined by capabilities of
MPH and are not improved by the presence of
ZDTPs despite a significant decrease of hydroper-
oxide concentration due to ZDTP-induced decom-
position. This behavior of ZDTPs could be explained
by free radical formation from ZDTP-induced de-
composition of hydroperoxides and by depletion of
ZDTP before MPH capabilities are exhausted.
Also, the degree of oxidative degradation of used oils
during service or laboratory testing can be monitored.
Registry No. MPH, 128-37-0;n-C8ZDTP, 7059-16-7;i-
CSZDTP, 2929-95-5.
Literature Cited
ASTM Spectral Technical Publication, 315H, Part 2, "Multlcyllnder Test Se-
quences for Evaluating Automotive Englne Oils"; American Society for
Testing and Materials: Philadelphia, PA, 1980.
Hsu, S. M.; Ku, C. S.;Becker, D. A. SA€ Tech. Pap. Ser. 1082, No.
821240.
Jensen, R. K.; Korcek, S.;Mahoney, L. R.; Zinbo, M. J . Am. Chem. SOC.
1870, 101 7574-7584.
I

Antioxidant capabilities of MPH can be improved
by addition of i-C,ZDTP in an amount greater than
the amount of MPH. It was not determined what
this limiting amount must be; however, when the
amount of i-C3ZDTP was greater by a factor of 2 (on
a molar basis), significant improvement of anti-
oxidant capabilities was observed.
Similarly, the method can be used to characterize the
antioxidant capabilities of base oils, to assess consistency
of engine oil formulation, and to determine oxidation
properties of engine oils. The effects of base oil-additive
package interactions and formulation changes on high-
temperature antioxidant capability can be investigated.
Johnson, M. D.; Korcek, S.; Zinbo, M. SA€ Tech. Pap. Ser. 1083, No.
83 1 684.
Johnson, M. D.; Korcek. S.; Zinbo, M. ASLE Trans. 1986, 2 9 , 136-140.
Korcek, S.; Mahoney, L. R.; Johnson, M. D.; Hoffman, S. SA€ Trans. 1070,
8 7 , 3568-3596.
Korcek, S.;Mahoney. L. R.; Johnson, M. D.; Siegl, W. 0. SA€ Tech. Pap.
Ser. 1081, No. 810014.
Mahoney, L. R.; Korcek, S.;Hoffman, S.; Willermet, P. A. Ind. €ng. Chem.
Prod. Res. Dev. 1878, 17, 250.
Mahoney. L. R.; Otto, K.; Korcek, S.;Johnson, M. D. Ind. Eng. Chem. Prod.
Res. Dev. 1080, 19, 11-15.
Murray, D. W.; Clarke, C. T.; MacAlpine, G. A.; Wright, P. G. SA€ Tech. Pap.
Ser. 1082 No. 821236.
Wlllermet, P. A. ASLE Trans. 1070, 2 2 , 301-306.
Received for review March 28, 1986
Accepted July 31, 1986

Corrosivity of Diethanolamine Solutions and Their Degradation

Products

Amitabha Chakma and Axel Meisen"

Department of Chemical €ngineering, The University of Britlsh Columbia, Vancouver, British Columbia V6T 1 W5, Canada

Weight loss and potentiodynamic tests were performed to determine the corrosivity of AISI-ASE 1020 carbon
steel in aqueous solutions containing diethanolamine (DEA) and/or its principal degradation products. The solutions
were either free from or saturated with CO,. The amine solutions were found to be corrosive in the presence
of CO,, and corrosion rates at 100 O C and atmospheric pressure r a n w from approximately 1.6 to 2.1 mm/year
for DEA concentrations of 30-60 wt %, respectively. 3-(Hydroxyethyl)-2-oxazolidone, which is a major degradation
compound of DEA, was found to be most corrosive. The corrosivity of DEA solutions in the presence of C02 is
explained qualitatlvely in terms of the reduction in solution pH and the enlargement of the corrosion region in the
Pourbaix diagram due to metal complexing.

Introduction corrosivity of degradation products is a matter of consid-

Corrosion is a major problem for alkanolamine-based
gas-sweetening planta since it may Tesult in metal failure
(especially in heat-exchanger tubes and absorber/regen-
erator trays), equipment fouling, and foaming. Di-
ethanolamine (DEA) plants generally experience less
corrosion than mqmoethanolamine plants (Kohl and
Riesenfeld, 1979), but corrosion is also a concern for DEA
planta (Polderman and Steele, 1956; Moore, 1960; Fitzerald
and Richardson, 1966; Smith and Younger, 1972; Hall and
Barron, 1981). It is now well established (McMin and
Farmer, 1969; Maddox, 1977) that the corrosion rate in-
creases with temperature and "acid gas loading", i.e., the
concentration of C02 and H2Sin solution. Industrial so-
lutions usually contain, apart from DEA, water, and ab-
sorbed acid gases, significant quantities of amine degra-
dation products. The latter are formed by irreversible
reactions which DEA undergoes mainly with C02. The
0196-4321/06/ 1225-0627$01.50/0
erable controversy and practical importance.
In 1956 Polderman and Steele reported simple experi-
ments which indicated that the products corrode steel.
Moore (1960) subsequently published some industrial data
and showed that the corrosion rate increases with the
concentration of degradation products. Values as high as
1 mm/year (40 mpy) were found for carbon steel. The
corrosivityof degradation products has also been reported
by others (Smith and Younger, 1972; Nonhebel, 1972).
However, Blanc et al. (1982) recently published data in
support of their claim that DEA degradation products are
not corrosive under conditions typically encountered in
gas-treating plants. Their main argument was that the pH
of a DEA solution of 30%-all percentages used in this
paper are weight percent-(or 3 mol/L) lies between 11.5
and 10 for temperatures ranging from 20 to 100 "C; the
precise pH value depends on the concentration of the
0 1986 American Chemical Society
828 Ind. Eng. Chem. Prod. Res. Dev., Vol. 25, No. 4, 1986
2.4
2 .o
I .6
I .2
-
>
1
0.8
-I
4 0.4
L
z
w 0.0
I-
O
a -0.4
-0.8
-I I
- I .6
-2 0 2
IMMUNITY
4 6
PH
8
CORROSION/
IO 12 14
Figure 1. Pourbaix potential-pH diagram for the iron-water system
at 25 "C (Pourbaix, 1974).
degradation products. They concluded that, under these
conditions, iron and carbon steel are either noncorrosive
or passive according to the Pourbaix potential-pH diagram
(see Figure 1;Pourbaix, 1974). However, Pourbaix dia-
grams do not provide absolute proof of the feasibility of
corrosion. A better understanding of corrosion is obtained
from kinetic studies, such as plotting potentiodynamic
polarization curves (Pourbaix, 1974). Furthermore, the
Pourbaix diagram that Blanc et al. (1982) used was only
representative of the iron-water system at 25 OC. In-
dustrial DEA systems are more complicated because they
consist of iron, water, DEA, carbon dioxide, hydrogen
sulfide, degradation products, and heat-stable salts. The
heat-stable salts as well as the degradation products may
form metal complexes which impair the use of Pourbaix
diagrams. In addition, the Pourbaix diagrams are tem-
perature dependent. As the temperature increases, the
regions of corrosion widen and the region of passivity
narrows for the iron-water system.
Blanc et al. (1982) also performed corrosion experiments
by immersing SI 1018 carbon steel coupons in 30%
aqueous DEA solutions at 80 OC and a Ha partial pressure
of 2000 kPa (290 psi). After 500 h, the weight-loss mea-
surements implied a corrosion rate of 0.05 mm/year (2
mpy). In another similar test, Blanc et al. (1982) used a
mixture of DEA and the degradation compound N,N-
bis(hydroxyethy1)piperazine (BHEP) and obtained a
corrosion rate of 0.02 mm/year (0.8 mpy).
Recent extensive work on DEA degradation by Kennard
and Meisen (1985) revealed that, in addition to BHEP,
3-(hydroxyethyl)-2-oxazolidone(HEOD) and N,N,N'-
tris(hydroxyethy1)ethylenediamine (THEED) are major
DEA degradation products. Therefore, the statement by
Blanc et al. (1982) that degradation products of amines,
DEA and MDEA, have no practical effect upon the cor-
rosion rate of carbon steel cannot be regarded as proven
since some major products were excluded from their tests.
The basic objective of this paper is therefore to report
results of corrosion studies undertaken with DEA solutions
and their degradation products.
Experimental Procedures
1. Preparation of Partially Degraded DEA Solu-
tion. A solution containing initially 30% DEA in water
was degraded in a heat-transfer loop under a CO, partial
pressure of 4.13 MPa. Details of the degradation exper-
16
7
0 40 80 120 160 200 240
T I M E (Hours)
Figure 2. Typical pH change of a DEA solution degrading in a
heat-transfer loop (Chakma, 1984). (Conditions: initial DEA con-
centration 30%; inlet temperature 60 OC, outlet temperature 195 "C,
heating fluid temperature 250 "C; flow rate 0.011 L/s.)
iment have already been reported (Chakma, 1984). The
final degraded solution contained about 8.7% of degra-
dation products; its composition was 2.13 mol/L of DEA,
0.58 mol/L of HEOD, 0.10 mol/L of THEED and 0.02
mol/L of BHEP.
As the degradation progressed, the pH of the solution
decreased substantially as shown in Figure 2.
2. Potentiodynamic Tests. Polished coupons of
AISI-ASE 1020 carbon steel with a surface area of 6.44 cm2
were immersed in corrosion cells containing either unde-
graded or partially degraded DEA solutions. The corrosion
cells were then connected to a corrosion measurement
system (Model 350A, Princeton Applied Research,
Princeton, NJ). A calomel electrode containing saturated
KC1 solution was used as the reference electrode. The
electrode was equipped with a heat-shrink Teflon bridge
tube having a 4-mm-diameter Vycor disk at the tip (Model
K65, Princeton Applied Research) in order to minimize
diffusion of chloride ions to the specimen while a low
electrical resistance was maintained. Potentiodynamic
polarization curves were obtained at 1 mV/s scanning
rates, and the free corrosion currents were determined by
the built-in microcomputer via Tafel slope extrapolation
(Uhlig, 1965). The experiments were conducted at 25 "C.
3. Weight-Loss Tests. Weight-loss tests were carried
out in accordance with procedures specified by the Na-
tional Association of Corrosion Engineers (1969). All but
the high-pressure experiments were performed by using
a Pyrex flask. The high-pressure corrosion experiments
were conducted using a 600-mL stainless steel autoclave
containing a Pyrex liner (Model 4563, Parr Instrument Co.,
IL). The solutions for the atmospheric pressure tests were
either free of or saturated with COz at room temperature
by bubbling COz through an extra-coarse fritted glass gas
dispersion tube (8-mm diameter, 20 nim long) placed inside
the Pyrex flask. The solutions for the high-pressure ex-
periments were saturated with C 0 2 by introducing CO,
into the autoclave containing the solutions.
Results and Discussion
1. Corrosion Rates in Undegraded DEA Solution.
The corrosion rate of carbon steel in an undegraded
C0,-free DEA solution was determined via Tafel slope
 Ind. Eng. Chem. Prod. Res. Dev., Vol. 25, No. 4, 1986 629

> >
-E E
1

z
a
c
v)

CURRENT D E N S I T Y ( n A / c m 2 ) CURRENT D E N S I T Y ( n A / c m 2 )

Figure 3. Potentiodynamic polarization curve of a 30% undegraded Figure 4. Potentiodynamic polarization curve of a partially de-
DEA solution (corrosion potential = -0.897 V SCE, corrosion current graded aqueous DEA solution containing 22.5% DEA, 4.65% HEO-
= 5.751 X lo3nA/cm2, corrosion rate 2.654 mpy, temperature 25 "C). D, 2.49% THEED, and 0.37% BHEP (corrosionpotential = -0.832
V SCE, corrosion current = 3.49 X lo4 nA/cm2, corrosion rate =
Table I. Corrosivity of DEA Solutions" at 100 "C (Boiling 16.10 mpy, temperature = 25 "C).
Condition) Using Weight-Loss Tests
Table 111. Effect of Degradation Compounds on Corrosion
corrosion rates Rates at 100 "C (Boiling Condition) Using Weight-Loss
solution mm/year mPY Tests"
30% DEA 0.0025 0.098 corrosion rates
40% DEA 0.003 0.12
sample mm/year mpy
60% DEA 0.0035 0.137
30% DEA + Cop 1.60 63.10 15% DEA + COP 0.13 5.1
40% DEA + COB 1.84 72.32 15% BHEP + COS 0.16 6.3
60% DEA + COS 2.070 81.60 15% HEOD + COz 1.95 76.6
30% DEA + COZ 1.60 63.1
a The DEA solutions were either free from or initially saturated 30% DEA + 5% BHEP + Cop 1.57 62.0
with C o pat room temperature and atmospheric pressure. 30% DEA + 5% HEOD + COZ 1.91 75.0
"The solutions were initially saturated with COz at room tem-
Table 11. Effect of C 0 2 Partial Pressure at 100 "C on perature and atmospheric pressure.
Corrosion Rate of 30% DEA Solutions" Using Weight-Loss
Tests 2. Corrosion Rates in Solutions Containing DEA
total pressure, C O partial
~ pressure, corrosion 'at's and/or Its Degradation Products. The partially de-
MPa MPa mm/year mpy graded DEA solution yielded a corrosion rate of 0.4
1.48 1.38 0.61 24.0 mm/year (16.1 mpy) at 25 "C according to the poten-
2.88 2.78 0.65 25.6 tiodynamic method (see Figure 4). This value is about
4.23 4.13 0.8 31.5 6.1 times higher than that obtained for an undegraded
"The solutions were saturated with COPinside the autoclave at solution and proves that degraded DEA solutions con-
various partial pressures. taining HEOD, THEED, and BHEP are, in fact, corrosive
toward carbon steel. The earlier claims by Blanc et al.
extrapolation of the polarization curve obtained at 25 "C (1982) are thereby contradicted.
at the free current potential. The rate was found to be Table I11 summarizes the results of weight-loss tests with
0.067 mm/year or 2.65 mpy (see Figure 3). This value is DEA and various degradation compounds. The corrosion
very similar to that reported by Blanc et al. (1982) for one rate in a solution containing DEA and BHEP is about the
of their tests using the Fe-H2S-DEA system. same as when BHEP is absent. This confirms the non-
When the solutions were saturated with COz at room corrosive nature of BHEP and agrees with the findings of
temperature and atmospheric pressure before they were Blanc et al. (1982). However, the corrosion rates in solu-
heated to 100 "C, they became far more corrosive. This tions containing HEOD were significantly higher than
can be concluded from results summarized in Table I. those in other solutions.
The corrosion rates increase with the DEA concentration, 3. Passivity. Amines are known to be fair corrosion
which is probably due to the fact that the COz concen- inhibitors. For example, Ballard (1966) claims that DEA
tration in the solution increases as the DEA concentration used in gas-sweetening plants forms good, but not tena-
is raised. cious, films on metal surfaces. He therefore recommends
The corrosion rates obtained in the presence of C 0 2are low fluid velocities to avoid destroying the protective films.
very high. The probable reason is that all experiments An examination of the polarization curves for both the
were carried out at 100 "C and atmospheric pressure so undegraded and the degraded samples (Figures 3 and 4)
that the solutions were nearly boiling. The presence of indicates that, although regions of passivity do exist, the
vapor bubbles disturbed the layer of protective corrosion films are not quite stable. Particularly in the case of un-
products on the steel surfaces and therefore enhanced the degraded DEA solutions, the films seem to be very un-
corrosion rates. When the tests were conducted at elevated stable. Furthermore, the passive films seem to offer very
pressures, boiling was prevented and the corrosion rates little protection since the corrosion current in the passive
were significantly reduced (see Table 11). Table I1 also region is very close to the critical corrosion current.
shows that the corrosion rates increase with COz partial 4. Pitting. Unlike undegraded DEA solutions, the
pressure. pitting potential of degraded DEA solutions is clearly
630 I d . Eng. Chem. Rod. Res. Dev.. Vol. 25. No. 4. 1986
Finure 5. Electron mieroeraohic Dhoto of AISI-ASE 1020 carbon
detectable (see Figure 4). This indicates that degraded
DEA solutions mieht induce Dittine corrosion under certain
conditions. Eledron micrograpkc photos of mild steel
coupons revealed pitting after exposure to DEA and
HEOD solutions. The pitting is more severe in the case
of HEOD as shown by Figure 5 (left) and Figure 5 (right),
respectively.
Qualitative Explanation
The corrosivity of DEA solutions in the presence of C02
and degradation compounds can be explained as follows:
The pH of typical industrial DEA solutions usually falls
between 10 and 12. As C02 is absorbed hy the solutions,
their pHs decrease. In addition, the solution pH falls as
DEA degrades because the principal degradation com-
pounds are less alkaline than DEA (Hakka et al., 1968).
Hall and Barron (1981) presented industrial data showing
a gradual reduction in solution pH upon the formation of
heat-stable salts. These fmdings are also in agreement with
our experimental results as shown by Figure 2. The initial
sharp decrease is due to C02 absorption, and the subse-
quent gradual decrease results from the formation of
degradation compounds. The reduction in pH gradually
brings the system close to the left corrosion triangle of the
pH-potential diagram.
Metal complexing also plays an important role in the
corrosion due to the presence of degradation products.
Degradation products probably form iron chelates because
Comeaux (1962) reported the formation of such chelates
with similar compounds. Hall and Barron (1981) also
reported the presence of iron chelates in industrial DEA
solutions.
The main effect of metal complexing is the reduction
of the potential of the metal-ionjmetal equilibrium rep-
resented by
Fez+ -k 2e- - Fe
The reduction in this equilibrium potential enlarges the
corrosion region corresponding to the left corrosion triangle
in the pH-potential diagram (see Figure 1).
Hence the pH reduction due to CO, absorption and
degradation-product formation as well as metal-complex
formation enhances the corrosivity of DEA solutions.
Conclusions
The following conclusions concerning the corrosivity of
DEA solutions toward AISI-ASE 1020 carbon steel may
,.\--.
be drawn:
. ..
. .
sponsible for corrosion.
. ~Corrosion
(3) , ~~~~~~ ~ .~
in the nresence of COOand deeradation
~ ~ ~~
products can be attributed to the redugion in soiution pH
and to the enlargement of the corrosion region due to metal
complexing.
Acknowledgment
The financial support of the Canadian Gas Processors
Association and the Natural Sciences and Engineering
Research Council of Canada are gratefully acknowledged.
Registry No. DEA, 111-42-2; HEOD, 3356-885: AIS1 1020,
12725-36-9; CO,, 124-38-9.
Literature Cited
Ballad. D. Hyaocarba, R-s. 1988, 45(4). 137.
Blanc. C.; olall. M.; Demarak. 0. R o c . Gas Cond. Conf. 1982. 32.
Chakma. A. M.A.Sc. TMsk. UnlvsrsHy 01 81Moh miumbla, 1984.
Comeaux. R. V. Roc.-Am. Pel. I n d . . Mv. Rem. 1982. 42, 4.31.
Fn2eram. K. J.; Richardson. J. A. HyhocarBon R-ss. 1988. 45(7). 125.
Hakka. L. E.: Slcgh. K. P.: Bata. 0. L.: Testart. A. 0.: AMejchyshyn. W. M.
Gas Proms. Can. 1988, 6 1 . 3 2 .
Hall. W. 0.;Barnon. J. G. Roc. Gas cond.Conf. 1981. 37.
Kennard. M. L.: Me)sL)n. A. Id. Eng. Chem. Furlem. 1985. 2 4 , 129.
Kohl. A. L.; Rlesenleld. F. C. Gas Rriricatiar: Gult Houslon, TX. 1979.
Maddcx. R. N. Gas and L @ M Sweetening: Campbell Petroleum: Naman.
OK, 1977.
McMin. R. E.: Farm%. F. Conhnence on S W Rscovsry RoMsdings: Okla-
homa state unksrsny: s1111water. M(. 196s.
W e . K. L. carosion(Hwot0n) 1080, 76. 111.
N.A.C.E. Standard TM01-69 "Laborat- Cmosbn Testing 01 Metals lw mS
Process Industries": National ASSOClatkm 01 Cwrorion Enginems: Hous-
tan. TX. 1969.
Nanhebei. 0. Gas pL*IAcaHon IW A* PoMlllon Contml. 2nd ed.; Newness-
Bunemorths: ~ d m1972. .
Polderman. L. D.: Steele. A. S. OU uls J . 1950. 54. 206.
Pourbaix. M. AHas Of E/- EqUlIlbriB bl A q m s S h i b r k S . 2nd
English ed.; National ASSOClatlon 01 Conorion Engineers: Houslm. TX.
,-,..
."7,
SmMh. R. F.; Younw, A. H. WkOCBrba, Rocepo. 1972. 51(7). 98.
uhlig. H. H. camsian and Conosion ConfrokWiley: New Yo*. 1965
Received for reuiew November 25,1985
Accepted April 7, 1986