Hydrolysis of 1,3,5-Tris(2-hydroxyethyl)hexahydro-s-triazine and Its

Reaction with H
2
S
J an M. Bakke,* J anne Buhaug, and J aroslav Riha
Department of Chemistry, Norwegian University of Scienceand Technology, NO-7491 Trondheim, Norway
The rate of hydrol ysi s of 1,3,5-tri s(2-hydroxyethyl )hexahydro-s-tri azi ne (tri azi ne, 1) was shown
to be strongl y dependent on the pH of the aqueous sol uti on: d[tri azi ne]/dt ) 2.6 10
-5
[tri azi ne]
+ 2.2 10
6
[tri azi ne][H
+
] at 22 C; d[tri azi ne]/dt ) 4.8 10
-4
[tri azi ne] + 3.5 10
8
[tri azi ne]-
[H
+
] at 60 C. Furthermore, we have establ i shed the structures of the products from the reacti on
of tri azi ne wi th S
2-
/HS
-
to be 3,5-bi s(2-hydroxyethyl )hexahydro-1,3,5-thi adi azi ne (thi adi azi ne,
2) and 5-(2-hydroxyethyl )hexahydro-1,3,5-di thi azi ne (di thi azi ne, 3) by I R and NMR spectroscopy
together wi th combusti on anal yses. 3was not hydrol yzed and di d not react wi th S
2-
/HS
-
at pH
from 10 to 2.
Introduction
Hydrogen sul fi de i s present i n natural gas from many
gas fi el ds. I t i s a hi ghl y undesi rabl e consti tuent because
i t i s toxi c and corrosi ve and has a very foul odor.
Therefore, several methods for i ts removal have been
devel oped. One such method i s the i njecti on of an
aqueous sol uti on of 1,3,5-tri s(2-hydroxyethyl )hexahydro-
s-tri azi ne (l ater cal l ed tri azi ne, 1) i nto the gas stream.
Thi s l i qui d scavenger process i s economi cal up to
approxi matel y 50 kg of H
2
S/day
1
and wi l l remove H
2
S
down to ca. 5 ppm i n streams wi th rel ati vel y l ow
concentrati ons of H
2
S. However, because the products
and the detai l s of the reacti on are not known, the
opti mal condi ti ons for the H
2
S removal may not al ways
be appl i ed. We have, therefore, i ni ti ated a study of the
reacti on between tri azi ne and H
2
S.
The mai n product of thi s reacti on i s general l y as-
sumed
2
to be 5-(2-hydroxyethyl )hexahydro-1,3,5-di thi -
azi ne (3), presumabl y formed as i ndi cated i n Scheme
1. However, we have not been abl e to fi nd any i nforma-
ti on supporti ng thi s. We, therefore, report the resul ts
from a study of the structure of the reacti on products.
An i mportant si de reacti on of tri azi ne i s i ts hydrol ysi s.
To study the reacti on of tri azi ne (1) wi th H
2
S, i t woul d
be necessary to carry out the reacti ons at a pH where
the hydrol ysi s reacti on was sl ow or even negl i gi bl e.
Hence, we have made an esti mate of the rate of
hydrol ysi s at di fferent pHs and temperatures.
Rate of Hydrolysis of Triazine
The ki neti cs of the hydrol ysi s of tri azi ne were studi ed
by
1
H NMR spectroscopy, compari ng the area of one
tri azi ne si gnal (2.7 ppm) wi th the si gnal of acetoni tri l e
(1.94 ppm), an i nternal standard not taki ng part i n the
reacti on. At hi gh pH, the hydrol ysi s was sl ow enough
to be moni tored di rectl y i n the NMR spectrometer. At
l ower pH, sampl es were quenched by addi ti on of a
buffered basi c sol uti on. The observed pseudo-fi rst-order
rate constants at temperatures of 22 and 60 C are gi ven
i n Tabl e 1.
The data i n Tabl e 1 can be fi tted to a rate l aw:
wi th k
obs
) k
1
+ k
2
[H
+
].
From the data i n Tabl e 1, the rate constants k
1
and
k
2
can be cal cul ated:
The rate constant k
1
onl y becomes si gni fi cant at hi gh
pHs and l ow temperatures. From (1) the hal f-l i fe of
tri azi ne at vari ous pHs can be esti mated. The resul ts
are pl otted i n Fi gure 1. These resul ts may be of some
i nterest for H
2
S removal i n gas mi xtures wi th a si gni fi -
cant content of carbon di oxi de.
Structure of the Reaction Products
To avoi d the aci d-catal yzed hydrol ysi s of tri azi ne, we
carri ed out the i nvesti gati on on the structure of the
reacti on products by usi ng Na
2
S at pH 10.0 i nstead of
gaseous H
2
S. I ntroductory experi ments showed the pH
of the sol uti on to i ncrease duri ng the reacti on. To obtai n
a constant pH, a buffer was used and aqueous HCl was
automati cal l y added when the pH rose.
The reacti on was moni tored by
1
H NMR spectroscopy.
The spectrum (Fi gure 2) di spl ayed the si gnal s from
monoethanol ami ne (MEA) together wi th si gnal s from
an ethyl ene group. Traces of unreacted tri azi ne gave the
tri pl et at 2.69 ppm, and the formed MEA gave the
tri pl ets at 2.91 and 3.71 ppm.
Proton COSY NMR spectroscopy showed the tri pl et
at 3.03 ppm to be coupl ed to the one at 3.66 ppm. Of
* To whom correspondence shoul d be addressed.
Phone: +47 73594095. Fax: +47 73594256. E-mai l :
jan.magnus.bakke@chembi o.ntnu.no.
Table 1. Observed First-Order Rate Constants for the
Hydrolysis of 1
kobs (s
-1
)
pH 22 C 60 C
10.9 (5.6 ( 0.2) 10
-5
(3.7 ( 0.1) 10
-3
9.5 (7.2 ( 0.5) 10
-4
0.11 ( 0.01
8.0 (2.2 ( 0.2) 10
-2
-
d[tri azi ne]/dt ) k
1
[tri azi ne] + k
2
[tri azi ne][H
+
] (1)
k
1
22 C
) 2.6 10
-5
s
-1
k
2
22 C
) 2.2 10
6
s
-1
M
-1
k
1
60 C
) 4.8 10
-4
s
-1
k
2
60 C
) 3.5 10
8
s
-1
M
-1
6051 I nd. Eng. Chem. Res. 2001, 40, 6051-6054
10.1021/i e010311y CCC: $20.00 2001 Ameri can Chemi cal Soci ety
Publ i shed on Web 11/21/2001
these two, the one at 3.03 ppm woul d be assi gned to
the protons at a ni trogen-substi tuted carbon and the one
at 3.66 ppm to those at an oxygen-substi tuted carbon.
I n addi ti on to the ethyl ene si gnal s, two si ngl ets at
3.92 and 4.26 ppm were promi nent i n the spectrum. The
COSY spectrum di d not i ndi cate a scal ar coupl i ng
between these two or to the ethyl ene groups.
However, NOE experi ments showed a weak cross-
rel axati on (2.0%) and by that proxi mi ty of the protons
gi vi ng ri se to the two si ngl ets. Furthermore, i rradi ati on
of the si gnal s at 3.92 and 4.26 ppm al so resul ted i n a
smal l but si gni fi cant posi ti ve NOE (3.2% and 1.5%,
respecti vel y) for the si gnal at 3.03 ppm. Correspond-
i ngl y, i rradi ati on of the si gnal at 3.03 ppm gave a
posi ti ve NOE for the si gnal s at 3.92 ppm (5.8%) and 4.26
ppm (1.6%). These resul ts suggest that the tri pl ets at
3.03 and 3.66 ppm and the si ngl ets at 3.92 and 4.26 ppm
ar i se fr om one compound, 3,5-bi s(2-hydr oxyethyl )-
hexahydro-1,3,5-thi adi azi ne (thi adi azi ne, 2). The
13
C
NMR spectrum of the mi xture was correl ated wi th the
1
H NMR spectrum shown i n Fi gure 1 by proton-carbon
COSY. The
13
C si gnal s correspondi ng to the
1
H NMR
si gnal s tentati vel y assi gned to 2 were i denti fi ed and
compared to the cal cul ated
13
C NMR data for 2. There
i s a good correspondence between the two sets of data,
gi vi ng further support to compound 2 bei ng the major
product from the reacti on of sul fi de i ons wi th tri azi ne.
Usi ng l i qui d-l i qui d extracti on, we were abl e to i sol ate
compound 2 onl y partl y contami nated by other com-
pounds. El emental anal ysi s supported the expected
el emental composi ti on of the compound, al though not
wi thi n the (0.5%l i mi ts. Furthermore, l ow-temperature
NMR spectra of thi s product showed the si ngl et si gnal s
at 3.92 and 4.26 ppm to spl i t i nto doubl ets as woul d be
expected from the ri ng protons of 2at temperatures l ow
enough to sl ow the ri ng fl i ppi ng. The same effect was
observed for tri azi ne i tsel f.
3
By these combi ned resul ts,
we consi der i t reasonabl e to assi gn structure 2 to the
mai n product from the reacti on of tri azi ne wi th Na
2
S.
The puri fi ed thi adi azi ne (2) was reacted further wi th
NaHS. At pH 10.0 the reacti on was sl ower than the
correspondi ng reacti on wi th tri azi ne. However, from
1
H
NMR spectroscopy the reacti on gave onl y one product
i n addi ti on to MEA. Thi s product gave two tri pl ets
together wi th two broad si ngl ets i n the regi on 4.1-4.5
ppm. The structure of the compound gi vi ng ri se to those
si gnal s was el uci dated by the techni ques used for
thi adi azi ne.
Scheme 1
Figure1. Hal f-l i fe of 1as a functi on of the temperature and pH.
Figure 2.
1
H NMR spectrum (300 MHz, D2O, pH 10); generati on of 2.
6052 I nd. Eng. Chem. Res., Vol . 40, No. 26, 2001
The data both from the NMR spectroscopy methods
and from el emental anal ysi s were i n accordance wi th
those of structure 3.
I n anal ogy wi th the reacti ons of 1and 2, i t woul d be
reasonabl e to assume that the reacti on of 3 wi th H
2
S
woul d gi ve the tri thi ane 4 as a product.
However, we found 3 to be much l ess reacti ve than
ei ther 1 or 2 both toward sul fi de i ons and hydrol ysi s.
The reacti on wi th HS
-
/H
2
S was attempted at pH from
10 to 2. No reacti on wi th HS
-
/H
2
S or hydrol ysi s was
observed under any of these condi ti ons. I t shoul d be
noti ced that, at pH 8, the l i feti me of tri azi ne under
hydrol ysi s condi ti ons was about 20 mi n and, at pH 4, i t
was 3 10
-3
s (see above).
The
1
H NMR spectra of an actual spent scavenger
from an oi l fi el d i n the North Sea showed the same
compounds as those i denti fi ed i n thi s work.
The i mportance of the pH of the reacti on mi xture for
both the hydrol ysi s and the reacti on wi th sul fi de i ons
strongl y suggests that protonati on of the ri ng ni trogen
atom was necessary for the reacti on to proceed. From
thi s, we propose the reacti on path i n Scheme 2:
Conclusions
We have establ i shed that the reacti on of 1wi th sul fi de
i ons gi ves 2 and that thi s reacts further to gi ve 3. 2
reacted sl ower than 1, and 3was even l ess reacti ve. 3
was not hydrol yzed at pH as l ow as 2, and i t di d not
react wi th HS
-
/H
2
S at pH from 10 to 2. For both 1and
2, the reacti on wi th sul fi de i ons competed wi th the
hydrol ysi s reacti on.
Experimental Section
The spectroscopi c and anal yti cal equi pment used has
been reported el sewhere.
4
El emental anal yses were
carri ed out by Dr. L. Hel esi c, Prague I nsti tute of
Chemi cal Technol ogy, Czech Republ i c.
Hydrolysis of 1. The rates of hydrol ysi s of 1 at pH
10.9, 9.5, and 8 and at temperatures of 22 and 60 C
were determi ned by the use of
1
H NMR spectroscopy.
At 22 C and pH 6 and 4, the reacti on was too fast to be
moni tored by thi s techni que. At 60 C, the reacti on coul d
onl y be moni tored at pH 10.9 and 9.5.
The concentrati on of 1 i n sol uti ons for ki neti c mea-
surements was 0.1 vol %. 1 (200 L of a 5% sol uti on)
was added to the buffer sol uti on (10 mL). Sampl es were
taken from the reacti on mi xture, quenched by addi ti on
of a potassi um carbonate sol uti on, and stored i n an i ce
bath. The concentrati ons of 1 i n these sampl es were
determi ned by
1
H NMR spectroscopy. For 1a si gnal at
2.7 ppm i n the NMR spectra was used to determi ne i ts
concentrati on. Acetoni tri l e was used as an i nternal
standard.
Generationof 2. 1(0.10 g, 0.46 mmol ) was di ssol ved
i n a buffered water sol uti on at pH 10.0 (10 mL), and
Na
2
S (0.036 g, 0.46 mmol ) was added. The reacti on was
run at room temperature and moni tored by
1
H NMR
spectroscopy. Most of 1 had reacted after 1 h. The
si gnal s of the
1
H NMR spectrum (Fi gure 2) and the
13
C
NMR spectrum were assi gned to MEA and 2.
2 was i sol ated usi ng conti nuous water-di chl oro-
methane extracti on.
1
H NMR (300 MHz, D
2
O, pH 10):
3.03 (t, J ) 5.7 Hz, N-CH
2
-CH
2
-OH), 3.66 (t, J )
5.7 Hz, N-CH
2
-CH
2
-OH), 3.92 (s, N-CH
2
-N), 4.26
(s, S-CH
2
-N).
13
C NMR: cal cd
5
55.3, 58.3, 59.0, 75.2;
found (75 MHz, D
2
O, pH 10) 56.7 (N-CH
2
-CH
2
-OH),
57.5 (N-CH
2
-S), 61.5 (N-CH
2
-CH
2
-OH), 76.4 (N-
CH
2
-N). I R (neat): /cm
-1
3378 (s), 2913 (s), 1429 (m),
1285 (m), 1176 (w), 1048 (m), 938 (w), 880 (w), 691 (w),
668 (w). El em anal . Cal cd: C, 43.7; H, 8.4; N, 14.6; S,
16.7. Found: C, 42.4; H, 8.1; N, 14.0; S, 16.6.
Generation of 3. 2 (0.010 g, 0.052 mmol ) was
di ssol ved i n a buffered water sol uti on at pH 10.0 (10
mL), and NaHS (0.0029 g, 0.052 mmol ) was added. The
reacti on was l eft for several days for compl eti on. The
si gnal s of the
1
H NMR spectrum and the
13
C NMR
spectrum were assi gned to MEA and 3.
3was i sol ated by di chl oromethane extracti on from the
water phase.
1
H NMR (300 MHz, D
2
O, pH 10): 3.19
(t, J ) 5.7 Hz, N-CH
2
-CH
2
-OH), 3.71 (t, J ) 5.7 Hz,
N-CH
2
-CH
2
-OH), 4.16 (s, S-CH
2
-S), 4.49 (s, S-CH
2
-
N).
13
C NMR: cal cd
5
33.8, 56.6, 58.8, 58.8; found (75
MHz, D
2
O, pH 10) 35.1 (S-CH
2
-S), 53.0 (N-CH
2
-
CH
2
-OH), 60.1 (N-CH
2
-S), 61.0 (N-CH
2
-CH
2
-OH).
I R (neat): /cm
-1
3394 (s), 2915 (s), 1429 (s), 1283 (s),
1195 (m), 1059 (s), 941 (m), 873 (m), 689 (m). El em anal .
Cal cd: C, 36.3; H, 6.7; N, 8.5; S, 38.8. Found: C, 35.7;
H, 6.5; N, 8.4; S, 37.2.
Acknowledgment
Generous support from the Norwegi an Research
Counci l and Statoi l ASA i s grateful l y acknowl edged.
Scheme 2
I nd. Eng. Chem. Res., Vol . 40, No. 26, 2001 6053
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(5) ACD/I -l ab ChemSketch versi on 4.5.
Received for review Apri l 9, 2001
Revised manuscript received Jul y 20, 2001
Accepted September 13, 2001
I E010311Y
6054 I nd. Eng. Chem. Res., Vol . 40, No. 26, 2001