Synthesis and performance evaluation of

1,3,5-tris(2-hydroxyethyl)-hexahydro-striazinane liquid H2S scavenger

H2S

1,3,5-2-
- FT-IRGC-MSMS1H NMR13C NMR
0 1.5
mL/min
1H NMR
pH

pH

H2S 600
1000 ppm 1.0 mL 2.0 V% 10 V%
0.22 0.30 mg H2S 10 70 pH=6.86 9.18 2
4 h 90.0 %
N2

H2S 740 760 cm3

30 70 mL 0.10 V% 10 V% 0.960 1.06 g
H2SN2 20 50 mL/min 11 31 h
90.0 %

1,3,5-2--
H2S

ABSTRACT
Triazine hydrogen sulfide scavenger has a very promising future as a kind of
liquid hydrogen sulfide scavenger with a direct injection method for its
convenient-preparation, low-cost, occupied small space, direct injection into the
offshore oil pipeline, and high-efficiency.Various H2S removal processes at present
arent available for offshore oil-drilling due to limited space and cost. Developing
triazine direct-injected H2S scavenger has being received more and more attention.
But the domestic research is still less.
In this thesis, 1,3,5-tris(2-hydroxyethyl)-hexahydro-s-triazinane as a kind of
triazine hydrogen sulfide scavenger was synthesized by using formaldehyde and
ethanolamine. The structure was confirmed by FT-IR, GC-MS, GC, 1H NMR and 13C
NMR. These characterization methods can reflect optimal synthetic condition of
triazine was that: 1:1 mol ratio of reagent, 0 ice water bath, the formaldehyde was
added as a dropping rate of 1.5 mL/ min, ethanol was added as an anti-polymerization
agent.
Stability of triazine H2S scavenger in different condition was investigated by 1H
NMR. The triazine was more stable when triazine concentration increased, solution
pH value was higher, the temperature was lower and the reaction time was shorter.
Water solution was more likely to lead to the hydrolysis of the triazine than alcohol
solution.The most significant factors affecting the stability were solvent type and
tempreture, the secondary were triazine concentration and solution pH value, and the
last was reaction time.
Methods for evaluation of the H2S removal of triazine were designed including
static and dynamic H2S removal. The static H2S removal efficiency was higher when
the temperature was higher, triazine concentration increased, the reaction time was
longer, and the injection rate of triazine was faster. Water solution was better than
alcohol solution. 0.22-0.30 mg H2S was removed by 1.0 mL 2.0 V%-10 V% triazine
in water solution while H2S volume was 600-1000 ppm.The static H2S removal
efficiency reached 90.0 % above with the condition adjusted appropriate as follows:
10-70 , pH = 6.86-9.18, the reaction time was 2-4 h.

Dynamic H2S removal efficiency and capability was higher when triazine
concentration increased and reaction time was longer. N2 gas flow rate was confirmed
by field test suitably. The volume of triazine only affected H2S removal capability
instead of efficiency, and was decided to add in accordance with the actual situation.
0.960-1.06 g H2S was removed by 30-70 mL 0.10 V%-10 V% traizine in water
solution while 740-760 cm3 H2S was produced.The dynamic H2S removal efficiency
reached 90.0 % above with the condition adjusted appropriate as follows: room
tempreture, 20-50 mL/min N2 gas flow rate, the reaction time was 11-31 h.

KEY WORDS1,3,5-tris(2-hydroxyethyl)-hexahydro-s-triazinane, direct injection

method, liquid hydrogen sulfide scavenger, H2S, performance evaluation of H2S
removal

............................................................................................................................1

..........................................................................................................1
1.1 H2S ......................................................................................1
1.2 H2S ...............................................................................................2
1.2.1 H2S ............................................................................2
1.2.2 H2S ................................................................................4
1.2.3 ..........................................................................................4
1.3 .....................................................................................7
1.3.1 ......................................................................7
1.3.2 ..................................................................8
1.4 .......................................................................................13
1.5 ...........................................................................................14
1.6 .......................................................................................15
........................................................................................................17
2.1 ...........................................................................................................17
2.2 ...............................................................................................17
2.3 ...............................................................................................19
2.3.1 ....................................................................................................19
2.3.2 ....................................................................................................19
2.3.3 H2S ..............................................................................................22
H2S .......................................................................24
3.1 ...........................................................................................24
3.2 ...................................................................................................25

3.2.1 ................................................................................................25
3.2.2 - ...................................................................................26
3.2.3 ....................................................................................................27
3.2.4 ....................................................................................................29
3.3 .......................................................................31
3.3.1 ....................................................................................................31
3.3.2 ............................................................................................32
3.3.3 ........................................................................................................33
3.3.4 ....................................................................................................34
3.3.5 ............................................................................................35
3.4 ...........................................................................................................36
3.5 ...........................................................................................................36
H2S ...................................................................37
4.1 ...............................................................................................37
4.2 ...................................................................................37
4.2.1 ................................................................................................37
4.2.2 pH ......................................................................................38
4.2.3 ............................................................................................39
4.2.4 ....................................................................................................40
4.3 ...........................................................................................................40
H2S .......................................................41
5.1 ...................................................................................41
5.2 ...........................................................................42
5.2.1 ....................................................................................................42
5.2.2 ................................................................................................43
5.2.3 pH ..........................................................................................44
5.2.4 ....................................................................................................45

5.2.5 ........................................................................................46
5.2.6 ............................................................................................47
5.2.7 ................................................................................................47
5.2.8 ....................................................48
5.3 ...........................................................................................................49
H2S .......................................................50
6.1 ...................................................................................50
6.2 ...........................................................................52
6.2.1 N2 .........................................................................................................52
6.2.2 ................................................................................................52
6.2.3 ....................................................................................................53
6.2.4 ................................................................................................54
6.2.5 ............................................................................................54
6.3 ...........................................................................................................55
....................................................................................................56
7.1 ...................................................................................................................56
7.2 ...................................................................................................................57
......................................................................................................................58
..................................................................................67

......................................................................................................................68

H2SH2S

80

H2S

Gas
Technology Institute, GTI

H2S

1,3,5-(2-
)-1,3,5-
H2S

pH

1.1 H2S
30
20 90
1-1[1]

1-1 1990-2010
Figure 1-1 Petroleum consumption and production in 1990-2010 of China

1-2
Figure 1-2 Flow path and flow regimes of the chemical system
1

1050
2000
1-2

300
[2] CO2 H2S
H2S
[3]
Rajagopal [4]
Campos BasinH2S

H2S
H2S
1-2 3000m
13 8
8
H2S

H2S

1.2 H2S
H2S

1.2.1 H2S

1.2.1.1 [5-9]

(CNG)
ZnO/MnO2

[10]
1.2.1.2 [5,6,11,12]

H2SCO2
H2S
N--2N---
HPF DIPA
MDEASulfinol Amisol
FRC

1.2.1.3 [5,12]
H2S 20 50
20 90 ,

1.2.1.4 [11,13]
( H2S CO2)

MEADGA

DEADIPA
TEAN-
3

MDEA()

1.2.1.5 [5,7,11,12]
H2S
H2S

H2S H2S

LO-CAT [14]
Sulfint
Sulferox [15]Stretford/ADA
PDS

()
Claus

1.2.2 H2S
H2S H2S [16]

[17-22] H2S
H2S

1.2.3
H2S
LO-CAT H2S
Claus [23]
1.2.1.1
1.2.1.2
4

1,3,5

[24][25][26][27][28]
[29][30][31][32]
[33][40]

1-1
[5,11,12,45,46]
1-1 4
Table 1-1 Comparison of four methods of H2S removal

70-100%

99%

80%

90%

/%

[34]

H2S

H2S

H2S

200ppm[35]

[36]

H2S

[37, 38]

[39]


1-1 4
Table 1-1 Comparison of four methods of H2S removal

H2S

[40]

[41]

[42]

pH

H2S

[43]CaCO3

[44]

1-1 H2S

(MEAMDEA ) H2S
(MEA)N-
(MDEA)( H2S, CO2 )
H2S CO2 H2S , H2S
CO2 H2S CO2
H2S ()
() CO2
( N-) CO2 H2S

N-
H2S [13]
6

98%
[47]
H2S
39 , 48
162
N-
20 80 [48]
[49] MDEA H2S
MDEA
MDEA 2,2-()
()

[50]

1.3
1.3.1
H2S
H2S H2S
H2S
//
H2S [51]
sweeten
H2S
H2S
H2S

MEA DEA
H2S CO2DEA CO2 carbamate
bicarbonateMDEA H2S
MDEAMDEA
CO2 CO2 /
H2S
CO2
DGA[2-(2-)]
DGA CO2 H2S
H2S
H2S NMP N-

H2S CO2
H2S
LRSR 10-12

1.3.2
H2S ppm
H2S

1.
2.
3.
4.
5.
H2S
2-6 [42] H2S

Linga [52] H2S 30-35

1.3.2.1

H2S[2]
FeS2

1.3.2.2
NaClO2
NaBrO3 NaNO2[53,54]
H2S
H2S

H2S [55]

H2S[56]

H2S [57]
O-O

H2S

1.3.2.3
H2S
[58-60]

1-1
H2S 1,2,3-1-1

HMTA
[61]
H2S
[62] H2S

98-99 50

H2S
SRBs H2S[63]
SRB H2S
H2S
[64,65] H2S
[66]
H2S
H2S
H2S

H2S
pH H2S

H2S
[61]HMTA HMTA pH
7.5 HTMA
H2S

[67]
1999 Baker Hughes [68] 30min H2S
99.5%
2002 Nasr-El-Din [61] HMTA H2S
HMTA

10

1.3.2.4
1mol 1,3,5-
IUPAC triazinane N,N'-

H2S [69] 1,3,5-

1,3,5-hexahydrotriazines
[70]
-S-triazinetrione[71]
1,3,5--2-
--S-N,N'- H2S
[72]

1,3,5-- H2S
3-MOPA

H2S [73,74]
H2S [75]
H2S HS-[76]
H2S 50kg H2S/day
5ppm

[70]
[77]
1,3,5--2---S- H2S 5-2-
-1,3,5 --2 -3,5 --2--1,3,5 - 1,3,5 pH pH=2-10 1,3,5-[78]

20

[34]1,3,5 --2---S-
H2S

1,3,5 --1,3,5--S-[79]

11

H2S pH
H2S
pH [80]
H2S
H2S
[81][82]
1995
Leppin [83] H2S

H2S 19cm3/m3 0.1cm3/m32000

PDVSA-Intevep[84]
CO2 H2S
2007 Nasr-El-Din [42]

H2S
2009 Xiao [85]

2012 Angelis[86]
H2S [35]
1994 Baker Hughes [87]
3- H2S
2008 Baker Hughes [36]
Baker Petrolite
HSW700 H2S HSW700 15%2011
Grahame [88]

Gas Technology InstituteGTI

2001 JIP North Sea Gas Production

GTI
12

H2S
Scavenger
CalcBase [40]
1.3.2.5

H2S [89]
IIIIIEDTA
[90]
H2S S[91]
N-2- H2S
O2

EDTA
H2S
1200 ppm H2S [90]
H2S ZnS

1.4
1,3,5-2--
H2S 1:3 H2S
1 mol 3 mol H2S H2S

1,3,5-[78]
1-3 1 1 H2S 3,52--1,3,5 - 2 2 H2S
5-2--1,3,5- 3
[78]-H2S
[92] 3 H2S

13

1-3 H2S
Figure 1-3 H2S removal process of triazine

1-4 H2S
Figure 1-4 Nucleophilic substitution reaction path of triazine with H2S

H2S pH pH
pH pH [78]
pH pH
H2S
1-4

1.5

14

1. pH

2.

H2S H2S
[93] CO2
H2S-CO2 CO2
[94]

CO2 H2S

pH

N2

[95]

1.6
H2S

1.
-

15

2.
pH

3.

pH
N2

16

2.1
2-1
2-1
Table 2-1 Chemical reagents

3-

2.2
2-2

17


2-2
Table 2-2 Apparatus for experiments

SCION 456-GC

(Bruker
Daltonics Inc.)

Agilent 6890/5975

Agilent 7890A/5975C

TENSOR 27

Bruker

VARIAN INOVA 500MHz

Varian

AL204

Mettler Toledo

DF-101S

EMS-20

SHZ-D()

DGG-103

DZG-403

2XZ-2

LABOROTA 4000

Heidolph

0.1 mL~1.0 mL

SL-1000XLS

Rainin

pH

PHS-25

WE-3

H2S

200-5000 ppm 10-200

ppm

100mL

ZG-1

H-06APD

100g

HK-02A

300

KF-003

LZB-3WB

18

2.3
2.3.1

Bruker TENSOR 27
400-4000 cm-1
0.6 cm-1
Agilent 6890/5975
NIST

Bruker SCION 456-GC

GC-MS
GC
VARIAN INOVA 500MHz 1H
13

C 11.75 T3 Hz/h

1H330:113C250:11H0.45 Hz D2O
CDCl3

2.3.2

[99]
Rf

19

Taylor [96]
1,3- 2-1

2-1 1,3-
Figure 2-1 Reaction scheme for the thermolysis of 1,3,5-tris(2-hydroxyethyl)
hexahydro-s-triazine to oxazolidine

3.2.3 4.48min 1,3-

100 %3.2.4

1,3-

2.25~2.75 ppm

2-12-2

20

AS
MS
ns

AR
MR
nR

2-1

AS 2.25~2.75 ppm ns
6M S
219.284 g/ molAR 2.25~2.75 ppm
nR 2

M R 61.084 g/mol

f1 A1 f 2 A2
AR

2-2

f1 f 2 1,3-
A1 A2 1,3-
AR

2-3 2-4
2-3
Table 2-3 Calculation result of first triazine in the 1H NMR

mol/L

g/mol

g/L

0.17000

219.28

37.278

0.060000

61.084

3.6650

1.0200

0.12000

10.171

2-4
Table 2-4 Calculation result of second triazine in the 1H NMR

mol/L

g/mol

g/L

0.17167

219.28

37.644

0.050000

61.084

3.0542

1.0300

0.10000

12.325
21

2-5
Table 2-5 Peak areas of triazine in the gas chromatograph spectra
%

1,3-

20.869

54.306

18.034

10.171

22.890

54.701

15.267

12.325

f1 20.869 f 2 54.306
10.171
18.034
f1 22.890 f 2 54.701
12.325
15.267

f1 1.1480

2-3

2-4

f 2 3.0370

f1 f 2 1,3-

2-5

1.1480 A1 3.0370 A2
2-5
AR

2.3.3 H2S
H2S H2S
H2S
H2S

SN/T 2943-2011
2011 12 1
200 5000 ppm 10 200
ppm H2S H2S
22

1.
2.
3.

4. 100 mL
100 mL
5. 100 mL 2-3
6.
7.
8.
9.
10. 100 mL
100 mL

23

 H2S

H2S

H2S

H2S 4 ppm
RSH R2S
CH3SHCOS
H2S

3.1

1. 250 mL
2.
3.

4. 30 min
5. 1h
6.
R

3-1

24

 H2S

3.2
3.2.1
0
3-1

1.00
0.95

Transmittance[%]

0.90
0.85
0.80
0.75
0.70
0.65
0.60
3000

2000

1000

Wavenumber(cm )
-1

3-1
Figure 3-1 FT-IR spectra comparison of the triazinane

4000 ~ 3200 cm-1 OH 3-1

3459.8 cm-1 O-H 1051.1 cm-1
C-O 3000 ~ 2700 cm-1
C-H 3-1 2944.9 cm-1 1462.9 cm-1
C-H
CH2 1179.9 cm-1 C-N
2500 ~ 2000 cm-1
1660.3 ~ 1614.8 cm-1

H2S

25

 H2S

3.2.2 -
Agilent 6890/5975 3.2.1
EIFID

HP-5MS 30 m0.25 mm0.25 m

50 10 /min 100 20
/min 280 5 min
325
250
40 mL/min450 mL/min45 mL/min
3-2

T I C :

. D \ d a t a . m s

1 . 3 e + 0 7
1 . 2 e + 0 7
1 . 1 e + 0 7
1 e + 0 7
9 0 0 0 0 0 0
8 0 0 0 0 0 0
7 0 0 0 0 0 0
6 0 0 0 0 0 0
5 0 0 0 0 0 0
4 0 0 0 0 0 0
3 0 0 0 0 0 0
2 0 0 0 0 0 0
1 0 0 0 0 0 0
2 . 0 0

4 . 0 0

6 . 0 0

8 . 0 0

1 0 . 0 0

1 2 . 0 0

1 4 . 0 0

1 6 . 0 0

1 8 . 0 0

2 0 . 0 0

2 2 . 0 0

- - >

3-2 GC-MS
Figure 3-2 The gas chromatography spectrum of GC-MS analysis results of product

NIST
13.838 min
3-3

26

 H2S

a
86

100
56

OH

N
50
N

HO

42
98
28

OH
44

128

72

158

49
0
20
30
40
50
60
70
80
(mainlib) 1,3,5-Triazine-1,3,5(2H,4H,6H)-triethanol

90

100

110

120

130

140

150

160

170

b
3-3 GC-MS EI
a 13.838 min
bNIST
Figure 3-3 Mass spectra of GC-MS analysis results of product, (a) mass spectra at 13.838min, (b)
research result of NIST

3.2.3
Bruker SCION 456GC 3.2.1

BR-5MS Bruker 30 m0.25 mm0.25 m

40 20 /min 300 10 min
280
27

 H2S

310
30 mL/min300 mL/min25 mL/min

3-4

3-4
Figure 3-4 The gas chromatography spectrum of analysis results of product

GC-MS Taylor [96]

Bruker
3-1
3-1
Table 3-1 Peak order of triazine in the gas chromatography

3.42

3.50

4.31

4.48

1,3-

8.81

9.18

28

 H2S

3.2.4
3.2.4.1 1H NMR
VARIAN INOVA 500MHz
3-53-6

3-5 1H NMR 500MHzD2O

Figure 3-5 1H NMR spectra of the triazine500MHzD2O

H 3-5 1H NMR 2.46 3.47 ppm

3.47 ppm N-CH2-CH2-OH OH C H2.46 ppm

N-CH2-CH2-OH N C H 3.30 ppm H
C H N-CH2-N
H
29

 H2S

3.38 ppm
NH2-CH2-CH2-OH OH C H2.51 ppm NH2-CH2-CH2-OH
N C H4.65 ppm

3-6 1H NMR 500MHzCDCl3

Figure 3-6 1H NMR spectra of the triazine500MHzCDCl3

TMS1H NMR 3-6

3.63 2.59 H3.30 ppm H3.58
2.78 ppm H7.26 ppm 0 ppm
TMS OH

3.2.4.2 13C NMR

VARIAN INOVA 500MHz
3-7

30

 H2S

3-7 13C NMR 500MHzD2O

Figure 3-7 13C NMR spectra of the triazine500MHzD2O

C H 3-7 13C NMR

73.0358.79 53.82 ppm 63.10 42.45
ppm C
2.3.2 CH3-CH2-OH C
58.05 ppm-CH2- 47.19 ppm[97]
58.79 53.82 ppm N-CH2-CH2-OH OH C
N-CH2-CH2-OH N C 73.03 ppm N-CH2-N C
63.10 42.45 ppm NH2-CH2-CH2-OH
OH C N C[98]

3.3
3.3.1
6.108 g 7.508
g 1.5 mL/min 0306090
31

 H2S

60

60

55

55

50

50

45

45

40

40

35

35

30

30

25

1,3-

20
15
10

25
20
15
10

5
0

20

40

60

80

5
100

3-8
Figure 3-8 Effect of reaction temperature on the mass concentration of triazine

3-8
3-8
0 60 0
60

2.3.2 3-8
1,3- 1,3-

3.3.2
6.108 g 7.508
g

32

 H2S

3-9
3-9 6.0
mL/min 3.0 mL/min 6.0 mL/min
12.0 mL/min 3.0 mL/min
1.5 mL/min
12.0 mL/min

60

60

50

50

40

40

30

30

1,3-

20

10

1.5 mL/min

20

10
2

10

12

mL/min

3-9
Figure 3-9 Effect of dropping rate on the mass concentration of triazine

3.3.3
6.108 g 7.508 g
1.5 mL/min
3-2
Rivers [87]3-

33

 H2S
3-2
Table 3-2 Effect of different additives on the mass concentration of triazine
%

1,3-

38.494

42.893

8.6540

59.232

10.815

41.797

12.715

22.396

28.151

46.302

6.5140

53.897

3-

3.3.4
6.108 g 7.508
g 1.5 mL/min 0.5 g
3-3
Table 3-3 Effect of different purification methods on the mass concentration of triazine

1,3-

38.494

42.893

8.6540

59.232

20.590

53.652

18.344

32.514

23.052

54.421

15.557

37.081

19.765

53.951

18.377

31.600

0.38100

5.8310

2.4120

7.7800

17.351

32.096

36.721

22.567

3.2280

2.6940

0.41800

23.279

0.08 MPa
55 ~ 64 66 ~
70 78 ~ 120 75 min
37.6% 0.085 MPa
60 90 35 min 47.6%
0.98 MPa U
56 ~ 68 68 ~ 74
83 min 61.7%

34

 H2S

3-3

[72]

3.3.5
3-4
Table 3-4 Effect of different mol ratios of reagent on the mass concentration of triazine
%

1,3-

2:1

8.4300

46.496

13.397

20.216

1.6:1

11.490

56.080

14.135

25.237

1.2:1

15.351

65.799

14.539

31.363

1:1

19.765

53.951

18.377

31.600

1:1.2

23.954

47.691

6.0340

51.496

1:1.6

38.971

2.8770

21.283

455.29

1:2

38.954

10.827

1.5 mL/min 0.5 g

3-4

1:2 49.81 %
1:1 [72]
35

 H2S

3.4
Bakke [78]
pH
3-5
Table 3-5 Peak order of triazine in the gas chromatography

pH
pH 11.3 12h

9.75 12h

10

9.30 pH

pH

3.5
1-

30
1.5 mL/min
4

36

 H2S

H2S
4.1
3.4 H2S pH

H2S

1. pH pH 46.86
9.18
2. 6 V%
16 V% 26 V%
3. 20 22 h 70 6 h
4.

4.2
4.2.1
4-1 70 6 hpH=4
Table 4-1 Effect of different volume percentage concentrations on the stability of triazine70
6 hpH=4

V%

%
/

7.8900

3.9450

18.480

14.535

78.653

16

38.010

19.005

73.635

54.630

74.190

26

200.80

100.40

291.02

190.62

65.501

37

 H2S

80

75

70

65

2022hpH=4
2022hpH=6.86
2022hpH=9.18
706hpH=4
706hpH=6.86
706hpH=9.18

60

55

50
5

10

15

20

25

30

V%

4-1
Figure 4-1 Effect of volume percentage concentration on the stability of triazine

4-1 4-1

4-1 6
70
4

pH

4.2.2 pH
pH
4-2
4-2 6 pH
70 20 6 V% pH
4
pH
pH
38

 H2S

pH

75

70

65

20 22 h6 v%
20 22 h16 v%
20 22 h26 v%
70 6 h6 v%
70 6 h16 v%
70 6 h26 v%

60

55

50
4

pH

4-2 pH
Figure 4-2 Effect of pH of the solution on the stability of triazine

4.2.3
4-2 20 22 h
Table 4-1 Effect of different volume percentage concentrations on the stability of triazine20
22 h
V%

%pH=4

%pH=6.86

%pH=9.18

52.941

50.625

50.501

16

52.300

50.444

49.961

26

50.207

50.000

48.980

4-3 70 6 h
Table 4-1 Effect of different volume percentage concentrations on the stability of triazine70
22 h
V%

%pH=4

%pH=6.86

%pH=9.18

78.653

75.027

73.148

16

74.190

64.397

64.983

26

65.501

64.344

61.576

39

 H2S

4-24-3
20
42.980 % 52.941 % 70 61.576 % 78.653 %
16 V% 6 V% 16
V% pH

pH

4.2.4

pH

4.3
1

2pH

pH
3

40

 H2S

H2S

5.1
H2S
ASTM D4810-06 H2S
H2S
H2S 5-1

1 8.4 g Na2S9H2O 20 mL 1.8 mol/L Na2S

2 12 mol/L 5.0 mL 10 mL
3 H2S

4 20 mL 1.0 mL
1.0 mL Na2S
1 h
5 1.0 mL
H2S
H2S 2 min
50 mL H2S A
ppm 2 min 50 mL 100 mL
Appm
6 NaOH H2S
7 H2S
B ppm Bppm

%=B-A/ B100%

5-1

H2S /

H2S
41

 H2S

1. Na2S
2 Na2S

3. H2S
H2S
4. AB 2 AB
5.

5-1 H2S
(a)(b) Na2S (c) H2S
Figure 5-1 Illustration of static H2S removal efficiency determination of triazinane
(a) distilled water or methanol; (b) Na2S solution and HCl solution; (c) H2S gas

5.2

pH

0
1.5 mL/min
1:1

5.2.1
50

42

 H2S

4 h 1 s 5-2

100

90

80

70

60

50

40
10

20

30

40

50

60

70

5-2
Figure 5-2 Effect of reaction temperature on the static H2S removal efficiency of triazine

5-2
H2S
H2S
[40,43,55]
50
70 H2S

50

5.2.2

50 4 h 1 s 5-3
5-3 250 50 10

2.0 V%

43

 H2S

100
95

90

85
80
75
70
65
60
55
0

10

V%

5-3
Figure 5-3 Effect of volume percentage concentration on the static H2S removal efficiency of
triazine

5.2.3 pH

98
96

94
92

90
88
86
84
82
80
78
4

10

pH

5-4 pH
Figure 5-4 Effect of pH of the solution on the static H2S removal efficiency of triazine

pH 50
44

 H2S

4 h 1 s 50 5-4
H+ OH-
pH pH
pH
H2S

pH 7 [80]

5.2.4

100
95
90

85
80
75
70
65
60
55

50
45
40
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5-5
Figure 5-5 Effect of reaction time on the static H2S removal efficiency of triazine

50 1 s 50 5-5
H2S
1 2.6 H2S
H2S H2S

H2S

45

 H2S

H2S

H2S

5.2.5

50 50 4 h 0.5 h 5-15-2
0.5 h 1 s 5 s 13 %

4 h 1 s 5 s 1.7 %

5-1 50 4 h
Table 5-1 Effect of different injection rate of triazine on the static H2S removal efficiency of
triazine50 4 h

97.5

70.0

95.8

63.0

5-2 50 0.5 h
Table 5-1 Effect of different injection rate of triazine on the static H2S removal efficiency of
triazine50 0.5 h

72.5

55.0

70.0

42.0

46

 H2S

5.2.6
5-2 5-1 5-2

H2S H2S H2S

H2S
H2S

5.2.7
5.2.7 5.2.8

50 1 s 50 4 h 5-3
5-3
Table 5-3 Effect of different additives on the static H2S removal efficiency of triazine

97.5

70.0

3-
98.1

71.9

93.1

63.1

5-3 3-
4:1
3-

[87]

5-3 Owens
[34]

90 % H2S

47

 H2S

5.2.8
3.3.5

50
1 s 50 4 h
5-6 1:1

1:1

[88] 1.2:1 2:1

[61]
5-6
1:1.2 1:2

100
95

90

4 h
4 h

85
80
75
70
65
60
55
50
0.5

1.0

1.5

2.0

5-6
Figure 5-6 Effect of mol ratio of reagent on the static H2S removal efficiency of triazine

48

 H2S

5.3
1.

2.

3. H2S 600 1000 ppm 1.0 mL

2.0 V% 10 V% 0.22 0.30 mg H2S
10 70
pH=6.86 9.18 2 4 h
90.0 % 1:1 2.0
V% 50 pH=6.86 1 s 4 h
97.5 %
40.0 % 75.0 %
4.

49

 H2S

H2S
6.1

H2S 6-1

1. FeS 1.0 min

300

2. 3CdSO48H2O CdSO4
3. NaOH H2S
4. H2S

5. FeS
6. 6-1 N2
N2

7. 10wt%
8.
CdSO4 H2S NaOH
10. G5 CdSO4
11. FeS m1 g
3CdSO48H2O V1mLN2
CdSO4 CdS m2g
pH 5.0 mL 20 mL 1.0 min N2

50

 H2S

FeS+2HCl=FeCl2+H2S
H2S+CdSO4=CdS+H2SO4

m1
m2

M
M CdS
% FeS
100%
m1
M FeS

6-1

H2S /
m1
m2

22.4
M FeS M CdS

V1 10 3

6-2

6-1 H2S
(a) (b) (c) FeS (d) (e) (f) CdSO4
(g) CdS (h) NaOH
Figure 6-1 Illustration of dynamic H2S removal efficiency determination of triazinane
(a) HCl solution; (b) gas rotameter; (c) FeS powder; (d) magnetic stirrer bar; (e) triazinane;
(f) CdSO4 solution; (g) CdS deposition; (h) NaOH solution

1. FeS SO2 FeS

2. FeS

3. H2S
4.
51

 H2S

6.2
N2

pH
0 1.5 mL/min
1:1

6.2.1 N2
FeS 3.0 g10 wt% 30 g3CdSO48H2O
15 g 1.0 % 30 mL 21 hNaOH
4.0 g
6-1 N2
Table 6-1 Effect of N2 flow rates on the dynamic H2S removal efficiency of triazine
N2 mL/min

pH

20

7.6

22.7

91.2

50

7.5

24.7

97.6

80

7.8

22.4

89.2

= H2S mL/mL

6-1 N2 50 mL/min
20 mL/min 80 mL/min 6-1
N2 1 N2 H2S
N2 H2S
H2S 3 N2
1 H2S N2
H2S H2S
50 mL/min

6.2.2
FeS 3.0 g10 wt% 30 g3CdSO48H2O
15 gN2 50 mL/min 30 mL 21 hNaOH
52

 H2S

4.0 g
6-2
Table 6-2 Effect of volume percentage concentrations on the dynamic H2S removal efficiency of
triazine
V%

pH

0.10

7.0

23.0

91.4

1.0

7.5

24.7

97.6

10

8.4

24.6

98.1

= H2S mL/mL

6-2

pH

6.2.3
6-3
Table 6-3 Effect of reaction times on the dynamic H2S removal efficiency of triazine
h

pH

11

8.8

23.4

92.3

21

7.5

24.7

97.6

31

7.4

24.8

97.7

= H2S mL/mL

FeS 3.0 g10 wt% 30 g3CdSO48H2O

15 gN2 50 mL/min 1 % 30 mLNaOH
4.0 g
6-3
21 h 31 h
53

 H2S

pH pH

6.2.4
FeS 3.0 g10 wt% 30 g3CdSO48H2O
15 g 1 %N2 50 mL/min 21 hNaOH 4.0
g
6-4
Table 6-4 Effect of volumes on the dynamic H2S removal efficiency of triazine
mL

pH

30

7.5

24.7

97.6

50

7.5

14.7

97.6

70

7.5

10.6

97.6

= H2S mL/mL

6-4
pH

H2S

6.2.5
FeS 3.0 g10 wt% 30 g3CdSO48H2O
15 gN2 50 mL/min 1 % 30 mL
21 hNaOH 4.0 g
6-5
Table 6-5 Effect of different additives on the dynamic H2S removal efficiency of triazine

pH

7.5

24.7

97.6

3-

7.2

24.8

97.9

7.5

24.4

96.6

= H2S mL/mL

54

 H2S

6-5 3-
5.0 mL 30 mL 6-5
3-

5.2.7
5.0 mL

pH

6.3
1.

2.

N2

3. H2S 740 760 cm3 30 70 mL

0.10 V% 10 V% 0.960 1.06 g H2SN2
20 50 mL/min 11 31 h
90.0 % FeS 3.0 g 10 wt% 30 g
50 mL/min N2 H2S 1.0 V%
30 mL 21 h 3CdSO48H2O 15 g CdSO4
H2S CdSO4 CdS NaOH 4.0 g
97.6 %
22.3 24.8

55

7.1

1,3,5-2-

1. NMR GC
0 1.5
mL/min
2. NMR
pH

pH
3.

4. H2S 600
1000 ppm 1.0 mL 2.0 V% 10 V%
0.22 0.30 mg H2S 10 70 pH=6.86 9.18 2
4 h 90.0 %
1:1 2.0 V% 50 pH=6.86
1 s 4 h 97.5 %
40.0 %
75.0 %
5. H2S 740
56

760 cm3 30 70 mL 0.10 V% 10 V%

0.960 1.06 g H2SN2 20 50 mL/min 11
31 h 90.0 % FeS
3.0 g 10 wt% 30 g 50 mL/min N2 H2S
1 V% 30 mL 21 h
3CdSO48H2O 15 g CdSO4 H2S CdSO4
CdS NaOH 4.0 g
97.6 %
22.3 24.8

7.2
1.

2. pH
[82]

3.

4.
N,N'-

57

[1] . . 201242(7)1~5
[2] Wilson D R. Hydrogen sulphide scavengers: recent experience in a major North
Sea field. SPE 36943 presented at the SPE European Petroleum Conference.
Milan, Italy: Society of Petroleum Engineers press, 1996
[3] Lee J, Kumar R. Laboratory study of hydrogen sulfide removal in slug flows in a
high pressure crude oil loop. Journal of Petroleum Science and Engineering, 2013,
103: 72~79
[4] Rajagopal K, Lacerda R, Slobodcicov I, et al. Modeling and simulation of
hydrogen sulfide removal from petroleum production lines by chemical
scavengers. Chemical Engineering Communications, 2009, 196(10):1237~1248
[5] . H2S .
201128(2)136~138
[6] . H2S . 2012
33(8)37
[7] . . 2004
30(5)33~37
[8] . . 201035
(2)23~27
[9] . . 200223(1)
29~33
[10] . H2S .
() 200931(1)121~124
[11] . []
2006
[12] . .
201230(4)365~369
[13] . H2S .
() 200228(2)127~130152

58

[14] . H2S LO-CAT. 200737(11)

30~35
[15] . .
200324(5)41~44
[16] H2S []
2012
[17] . H2S . 2009
28(7)42
[18] . . 200827(8)6~8
[19] . .
201010(4)886~890
[20] . .
200819(6)35~36
[21] . .
200822(6)126~125
[22] . . 200141(5)
650~653
[23] . 2000
(). 2001(6)11~15
[24] Noblet J A, Smith L A, Suffet I H. Influence of natural dissolved organic matter,
temperature,

and

mixing

on

the

abiotic

hydrolysis

of

triazine

and

organophosphate pesticides. Journal of Agricultural and Food Chemistry, 1996,

44: 3685~3693
[25] Plust S J, Loehe J R, Feher F J, et al. Kinetics and mechanism of hydrolysis of
chloro-1,3,5-triazines. Atrazine. The Journal of Organic Chemistry, 1981, 46:
3661~3665
[26] Hawari J, Halasz A, Sheremata T, et al. Characterization of metabolites during
biodegradation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) with municipal
anaerobic sludge. Applied and Environmental Microbiology, 2000, 66(6):
2652~2657
[27] Veleva S, Valcheva E, Valchev I, et al. Application of an exponential kinetic
equation to the interaction of optical brighteners with pulp. Reaction Kinetics and
Catalysis Letters, 2001, 72(2): 355~364
59

[28] Camino G, Costa L. Performance and mechanisms of fire retardants in

polymers-a review. Polymer Degradation and Stability, 1988, 20(3~4): 271~294
[29] Lupton J M, Hemingway L R , Samuel I D W, et al. Electroluminescence from a
new distyrylbenzene based triazine dendrimer. Journal of Materials Chemistry,
2000, 10: 867~871
[30] Bojinov V B, Panova L P, Simeonov D B. Design and synthesis of polymerizable
yellow-green emitting 1,8-naphthalimides containing built-in s-triazine UV
absorber and hindered amine light stabilizer fragments. Dyes and Pigments, 2008,
78(2): 101~110
[31] Khwaja T A, Pentecost S, Selassie C D, et al. Comparison of quantitative
structure-activity relationships of the inhibition of leukemia cells in culture with
the inhibition of dihydrofolate reductase from leukemia cells and other cell types.
Journal of Medicinal Chemistry, 1982, 25(2): 153~156
[32] Srinivas K, Srinivas U, Bhanuprakash K, et al. Synthesis and antibacterial
activity of various substituted s-triazines. European Journal of Medicinal
Chemistry, 2006, 41(11): 1240~1246
[33] Ren T, Liu W, Xue Q, et al. The effect of molecular structure of N-containing
heterocyclic compounds on their wear properties. Lubrication Science, 1993, 5(3):
205~212
[34] Owens T R. Formulation for hydrogen sulfide scavenging from hydrocarbon
streams and use thereof. WO, 2008/049188-A1. 2008-05-02
[35] Foral A J, AI-Ubaidi B H. Evaluation of H2S scavenger technologies. Houston,
Texas, USA: M W Kellogg Company, 1994
[36] Salma T, Lambert A A, Rivers G T. Fast high capacity hydrogen sulfide
scavengers. US, 2008/0056974 A1. 2008-03-06
[37] Taylor G N, Prince P, Matherly R, et al. Identification of the molecular species
responsible for the initiation of amorphous dithiazine formation in laboratory
studies of 1,3,5-tris(hydroxyethyl)-hexahydro-s-triazinane as a hydrogen sulfide
scavenger. Industrial & Engineering Chemistry Research, 2012, 51(36):
11613~11617
[38] Taylor G N, Matherly R. Structural elucidation of the solid byproduct from the
use of 1,3,5-tris(hydroxyalkyl)hexahydro-s-triazine based hydrogen sulfide
scavengers. Industrial & Engineering Chemistry Research, 2011, 50(2): 735~740
60

[39] Nagl G J. Removing H2S from gas streams: four leading technologies are
compared here. Chemical Engineering, 2001, 108(7): 97~100
[40] Fish K S, Leppin D, Palla R, et al. Process engineering for natural gas treatment
using direct-injection H2S scavengers. GasTIPS, 2003, 9(2):12~17
[41] Arnold T, Graham W R, Cranmer J D. Process for mitigation of wellbore
contaminants. US, 6942037. 2005-09-13
[42] Nasr-El-Din H A, Zabihi M, Kelkar S K, et al. Development and field application
of a new hydrogen sulfide scavenger for acidizing sour-water injectors. SPE
106442 presented at SPE International Symposium on Oilfield Chemistry.
Houston, Texas, USA: Society of Petroleum Engineers press, 2007
[43] Amosa M K, et al. Sulphide scavengers in oil and gas industrya review. NAFTA
Croatian Scientific Journal, 2010, 61 (2): 85~92
[44] Jordan M M, Mackin K, Johnston C J, et al. Control of hydrogen sulfide
scavenger induced scale and the associated challenge of sulfide scale formation
within a North Sea high temperature/high salinity field production wells:
laboratory evaluation to field application. SPE 87433 presented at SPE
International Symposium on Oilfield Scale. Aberdeen, UK: Society of Petroleum
Engineers press, 2004
[45] . H2S . 200922(1)71~74
[46] . .
200331(2)51~54
[47] . . 200127(1)5~7
[48] .
. 201129(1)15~21
[49] . N-.
199928(1)25~27
[50] . .
199925(3)265~268
[51] Pandey M. Process optimization in gas sweetening unit- a case study. SPE 17305
presented at International Petroleum Technology Conference International
Petroleum Technology Conference. Doha, Qatar: Society of Petroleum Engineers
press, 2005

61

[52] Linga H, Nilsen F P, Abiven R, et al. Multi fluid injection mixer. WO,
2006/038810. 2006-04-13
[53] Burnes E E, Bhatia K. Process of removing hydrogen sulfide from gas mixtures.
US, 4515759. 1985-05-07
[54] Geverte D, Jenneman G E. Reduction of sulfide in fluids. US, 5820766,
1998-10-13
[55] Hunton A G, Read P A, Wilson R D. Evaluation and field application of a new
hydrogen sulfide scavenger. Paper presented at the 10th International Oil Field
Chemical Symposium. Fagernes, Norway: 1999
[56] Sturman P J, Goeres D M. Control of hydrogen sulfide in oil and gas wells with
nitrite injection. SPE 56772 presented at SPE Annual Technical Conference and
Exhibition. Houston, Texas, USA: Society of Petroleum Engineers press, 1999
[57] Knudsen B, Tjelle S, Linga H. A new approach towards environmentally friendly
desulfurization. SPE 73957 presented at SPE International Conference on Health,
Safety and Environment in Oil and Gas Exploration and Production. Kuala
Lumpur, Malaysia: Society of Petroleum Engineers press, 2002
[58] Edmondson J G. Method of scavenging hydrogen sulfide. US, 4680127 A.
1987-07-14
[59] Hardy J A, Georgie J W. Hydrogen sulphide scavenging method. US application,
20040074813. 2004-04-22
[60] Elliott J R, Raymond M B, Kalpakci B, et al. Theory and measurements of fates
of H2S scavengers. SPE 28949 presented at the SPE International Symposium on
Oilfield Chemistry. San Antonio, Texas, USA: Society of Petroleum Engineers
press, 1995
[61] Nasr-El-Din H A, Al-Humaidan A Y, Fadhel B A, et al. Investigation of sulfide
scavengers in well-acidizing fluids. SPE Production & Facilities, 2002, 17(4):
229~235
[62] Bedford C T, Fallah A, Mentzer E, et al. The first characterisation of a
glyoxal-hydrogen sulfide adduct. Journal of the Chemical Society, Chemical
Communications, 1992, (15): 1035~1036

62

[63] Kriel B G, Crews A B, Burger E D, et al. The efficacy of formaldehyde for the
control of biogenic sulfide production in porous media. SPE 25196 presented at
SPE International Symposium on Oilfield Chemistry. New Orleans, Louisiana
USA: Society of Petroleum Engineers press, 1993
[64] Penkala J E, Reed C, Foshee J. Acrolein application to mitigate biogenic sulfides
and remediate injection well damage in a gas plant water-disposal system. SPE
98067 presented at International Symposium and Exhibition on Formation
Damage Control. Lafayette, Louisiana, USA: Society of Petroleum Engineers
press, 2006
[65] Salma T. Cost effective removal of iron sulfide and hydrogen sulfide from water
using acrolein. SPE 59708 presented at SPE Permian Basin Oil and Gas Recovery
Conference. Midland, Texas, USA: Society of Petroleum Engineers press, 2000
[66] Penkala J E, Reed C, Foshee J. Acrolein application to mitigate biogenic sulfides
and remediate injection well damage in a gas plant water-disposal system. SPE
98067 presented at International Symposium and Exhibition on Formation
Damage Control. Lafayette, Louisiana, USA: Society of Petroleum Engineers
press, 2006
[67] Al-Humaidan A Y, Nasr-El-Din H A. Optimization of hydrogen sulfide
scavengers used during well stimulation. SPE 50765 presented at SPE
International Symposium on Oilfield Chemistry. Houston, Texas, USA: Society
of Petroleum Engineers press, 1999
[68] Callaway M, Rivers G T. Abatement of hydrogen sulfide with an aldehyde
ammonia trimer. US, 5958352. 1999-09-28
[69] Rivers G T, Hackerott J T. Method of making reduced water content
bisoxazolidine hydrogen sulfide scavengers. US, 6339153. 2002-01-15
[70] Salma T, Briggs M L, Herrmann D T, et al. Hydrogen sulfide removal from sour
condensate using non-regenerable liquid sulfide scavengers: a case study. SPE
71078 presented at SPE Rocky Mountain Petroleum Technology Conference.
Keystone, Colorado, USA: Society of Petroleum Engineers press, 2001
[71] Allison J D, Wimberley J W. Processes and oxidizing agents for oxidizing sulfide
ion to innocuous, soluble sulfur species. US, 4710305 A. 1987-12-01
[72] Dillon E T. Composition and method for sweetening hydrocarbons. US, 4978512.
1990-12-18
63

[73] Rivers G T, Rybacki R L. Mixtures of hexahydrotriazines useful as H2S

scavengers. US, 5347004. 1994-09-13
[74] Rivers G T, Rybacki R L. Process for scavenging H2S by mixtures of
hexahydrotriazines. US, 5554349. 1996-09-10
[75] Galloway A J. Method for removing sulphide(s) from sour gas. US, 5405591 A.
1995-04-11
[76] Bakke J M, Buhaug J B. Hydrogen sulfide scavenging by 1,3,5-triazinanes.
Comparison of the rates of reaction. Industrial & Engineering Chemistry
Research, 2004, 43(9): 1962~1965
[77] Trauffer, E A, Evans R D. Methods for regenerating a sulfur scavenging
compound from a product of a sulfur scavenging reaction. US, 5347003.
1994-09-13
[78] Bakke J M, Buhaug J, Riha J. Hydrolysis of 1,3,5-tris(2-hydroxyethyl)hexahydros-triazine and its reaction with H2S. Industrial & Engineering Chemistry Research,
2001, 40 (26): 6051~6054
[79] Sullivan D S, Thomas A R, Edward M A, et al. Method of treating sour gas and
liquid hydrocarbon. US, 5674377. 1997-10-07
[80] Millan J C, Dubey S, Koot W. Accelerated mechanism of scale deposition in UW
production operation. SPE 87446 presented at SPE International Symposium on
Oilfield Scale. Aberdeen, U K: Society of Petroleum Engineers press, 2004
[81] Sitz C D, Barbin D K, Hampton B J. Scale control in a hydrogen sulfide
treatment program. SPE 80235 presented at International Symposium on Oilfield
Chemistry. Houston, Texas, USA: Society of Petroleum Engineers press, 2003
[82] Eylander J G R, Holtman H A, Salma T, et al. The development of low-sour gas
reserves utilizing direct-injection liquid hydrogen sulphide scavengers. SPE
71541 presented at SPE Annual Technical Conference and Exhibition. New
Orleans, Louisiana, USA: Society of Petroleum Engineers press, 2001
[83] Leppin D. Natural gas production: performance of commercial technology for
removing small amounts of hydrogen sulfide. SPE 29743 presented at SPE/EPA
Exploration and Production Environmental Conference. Houston, Texas, USA:
Society of Petroleum Engineers press, 2005

64

[84] Castillo M, Avila Y S, Rodriguez R E, et al. Liquid scavengers-their

effectiveness

and

compatibility

with

downstream

processes.

Materials

performance, 2000, 39(12): 54~58

[85] Xiao Z, Morgenthaler L N, Cowan M K, et al. Evaluation of H2S scavengers for
matrix-acidizing treatment. SPE 121698 presented at SPE International
Symposium on Oilfield Chemistry. The Woodlands, Texas, USA: Society of
Petroleum Engineers press, 2009
[86] Angelis A. Natural gas removal of hydrogen sulphide and mercaptans. Applied
Catalysis B: Environmental, 2012, 113~114: 37~42
[87] Rivers G T, Rybacki R L. Mixtures of hexahydrotriazines useful as H2S
scavengers. WO, 94/08980. 1994-04-28
[88] Taylor G N, Matherly R. The laboratory evaluation and optimization of hydrogen
sulphide

scavengers

using

sulphur

specific

flame

photometric

gas

chromatography. SPE 140401 presented at SPE International Symposium on

Oilfield Chemistry. The Woodlands, Texas, USA: Society of Petroleum
Engineers press, 2011
[89] Davidson E, Hall J, Temple C. A new iron-based, environmentally friendly
hydrogen sulfide scavenger for drilling fluids. SPE Drilling & Completion, 2004,
19(4): 229~234
[90] Buller J and Carpenter J F. H2S scavengers for non-aqueous systems. SPE
International Symposium on Oilfield Chemistry. The Woodlands, Texas, USA:
Society of Petroleum Engineers press, 2005
[91] Pich S, Larachi F. Dynamics of pH on the oxidation of HS with iron(III)
chelates in anoxic conditions. Chemical Engineering Science, 2006, 61(23):
7673~7683
[92] Williams H, Dyer S, Bezerra M C M, et al. The effect of sulphide scavengers on
scaling tendency and scale inhibitor performance. SPE 131115 presented at SPE
International Conference on Oil Field Scale. Aberdeen, UK: Society of Petroleum
Engineers press, 2010
[93] . .
201333(2)54~58

65

[94] Salma T. Effect of carbon dioxide on hydrogen sulfide scavenging. SPE 59765
presented at SPE/CERI Gas Technology Symposium. Calgary, Alberta, CA:
Society of Petroleum Engineers press, 2000
[95] . -.
201131(9)1~4
[96] Taylor G N, Matherly R. Gas chromatography mass spectrometric analysis of
chemically derivatized hexahydrotriazine-based hydrogen sulfide scavengers: 1.
Industrial & Engineering Chemistry Research, 2010, 49(13): 5977~5980
[97] Gottlieb H E, Kotlyar V, Nudelman A. NMR chemical shifts of common
laboratory solvents as trace impurities. Journal of Organic Chemistry, 1997, 62:
7512~7515
[98] Refsdal A. Examination of the reaction between hydrogen sulfide and cyclic
amines. Trondheim: Norwegian University of Science and Technology, 1997
[99] . .
200322(6)101~103

66

[1] . .

[2] . CO2
.

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