Europe User Conference: ADNOC optimization of hydrocracking process as a func...
2010 ISPC Presentation
1. José Luis Barrios Goicetty
Universidad de Oriente
Applied Science and Engineering School
Chemistry Department
Academic
Advisor
Yaneis Obando, MSc.
Industrial
Advisor
Rafael D’Elía
3. Introduction H2S Generation Project Development Application & Conclusions
• Sulfide stress cracking
• Hydrogen induced cracking
• Toxicity of the workplace
• Personnel risk
• Environmental footprint
• Mechanical Integrity of the facilities
• Increase of medium/long term
expenses and investments
Problems
Consequences
4. • No initial H2S
• Negligible for T > 140 ºF
• High temperature and pressure
• Aquous saturation
Introduction H2S Generation Project Development Application & Conclusions
• No initial H2S
• No anhydrite
5. Introduction H2S Generation Project Development Application & Conclusions
Steam Generator
Injector
Well
Tanks
Producer
Steam and
Condensed Water
Hot
Water Heavy
Oil
Water and
Hevy Oil
Zone
H2O
Heavy Oil
6. Introduction H2S Generation Project Development Application & Conclusions
1 Heavy oil
2 Water
3 HP/HT Reactor vessel
4 Temperature/Pressure controller
5 Flash separation vessel
6 Gasometer
7 Dragger tube for H2S
8 Asphaltene content (IP 143/2004)
7. Introduction H2S Generation Project Development Application & Conclusions
Pressure
< 1400 psi
Temperature
200 – 300 ºC
W/O Ratio
Aqueous saturation
Sand Presence
Interaction with the porous media
8. Introduction H2S Generation Project Development Application & Conclusions
Water/oil input into the reactor’s cell
Closure of the cell and placement on the oven
Temperature set-up and system’s pressurization
Sampling and flash separation
Storage of the gaseous phase
Dragger tube / Asphaltene content analyses
9. Introduction H2S Generation Project Development Application & Conclusions
Hydrogen Sulfide Asphaltene Content
S
A
M
P
L
E
I
S
A
M
P
L
E
II
H2S Concentration
<10 ppm
Exposure limit
100 ppm
Lethal (3-15 min)
>700ppm
Unconsciousness
10. Introduction H2S Generation Project Development Application & Conclusions
y = -5,9771E-04x + 8,0731E-02
R² = 8,5540E-01
y = -1,2726E-03x + 8,0404E-02
R² = 8,9464E-01
y = -8,9815E-04x + 8,0606E-02
R² = 8,8744E-01
0,072
0,073
0,074
0,075
0,076
0,077
0,078
0,079
0,080
0,081
0,082
0 1 2 3 4 5 6
Casf(mol/L)
Tiempo de reacción (h)
225 ºC 250 ºC 275 ºC
y = -1,9317E-03x + 7,1833E-02
R² = 7,7905E-01
y = -3,1947E-03x + 6,8869E-02
R² = 9,5633E-01
y = -2,0595E-03x + 6,9416E-02
R² = 9,6925E-01
0,045
0,050
0,055
0,060
0,065
0,070
0,075
0 1 2 3 4 5 6
Casf(mol/L)
Tiempo de reacción (h)
225 ºC 250 ºC 275 ºC
y = 7,5326E-03x + 2,5167E+00
R² = 8,5735E-01
y = 1,6468E-02x + 2,5208E+00
R² = 8,9976E-01
y = 1,1451E-02x + 2,5183E+00
R² = 8,9092E-01
2,500
2,520
2,540
2,560
2,580
2,600
2,620
2,640
0 1 2 3 4 5 6
-Ln(Casf)
Tiempo de reacción (h)
225ºC 250ºC 275ºC
y = 3,0144E-02x + 2,6305E+00
R² = 7,7667E-01
y = 5,3283E-02x + 2,6744E+00
R² = 9,7114E-01
y = 3,2345E-02x + 2,6671E+00
R² = 9,7733E-01
2,600
2,650
2,700
2,750
2,800
2,850
2,900
2,950
3,000
3,050
0 1 2 3 4 5 6
-Ln(Casf)
Tiempo de reacción (h)
225ºC 250ºC 275ºC
y = 9,4944E-02x + 1,2388E+01
R² = 8,5931E-01
y = 2,1327E-01x + 1,2441E+01
R² = 9,0490E-01
y = 1,4605E-01x + 1,2408E+01
R² = 8,9441E-01
12,20
12,40
12,60
12,80
13,00
13,20
13,40
13,60
13,80
0 1 2 3 4 5 6
1/Casf(L·mol-1)
Tiempo de reacción (h)
225ºC 250ºC 275ºC
y = 4,7167E-01x + 1,3834E+01
R² = 7,7441E-01
y = 8,9627E-01x + 1,4477E+01
R² = 9,8343E-01
y = 5,0959E-01x + 1,4386E+01
R² = 9,8436E-01
13,00
14,00
15,00
16,00
17,00
18,00
19,00
20,00
21,00
0 1 2 3 4 5 6
1/Casf(L·mol-1)
Tiempo de reacción (h)
225ºC 250ºC 275ºC
y = 2,3938E+00x + 1,5349E+02
R² = 8,6129E-01
y = 5,5283E+00x + 1,5482E+02
R² = 9,1003E-01
y = 3,7270E+00x + 1,5399E+02
R² = 8,9791E-01
145,00
150,00
155,00
160,00
165,00
170,00
175,00
180,00
185,00
190,00
195,00
0 1 2 3 4 5 6
1/Casf(L2·mol-2)
Tiempo de reacción (h)
225 ºC 250 ºC 275 ºC
y = 1,4801E+01x + 1,8986E+02
R² = 7,7229E-01
y = 3,0409E+01x + 2,0833E+02
R² = 9,9260E-01
y = 1,6107E+01x + 2,0656E+02
R² = 9,9021E-01
160,00
210,00
260,00
310,00
360,00
410,00
0 1 2 3 4 5 6
1/Casf(L2·mol-2)
Tiempo de reacción (h)
225 ºC 250 ºC 275 ºC
n=1 n=2 n=3n=0
S
A
M
P
L
E
I
S
A
M
P
L
E
II
11. 200 – 300
1 3,5·1015 209
2 1,1·1015 181
3 1,5·107 102
4 2,1·1023 327
5 1,2·106 97
Belgrave y Col.
(1994)
(*) Units vary depending on the value on n
200 – 300
I 4,7·1013 137
II 2,0·1038 385
T
(ºC)
Sample
A
(*)
Ea·10-3
(KJ/Kmol)
Barrios.
(2009)
Introduction H2S Generation Project Development Application & Conclusions
13. Initial asphaltene content did not show a direct relation with hydrogen sulfide
generation
Hydrogen sulfide generation through aquatermolysis is feasible in the temperature
range between 225-275 ºC, reaching a maximum at 250 ºC (for the studied samples)
The estimation of hydrogen sulfide generation is feasible through the experimental
procedure designed in this work.
Hydrogen sulfide estimations, obtained from an experimental procedure such as
described in this work, are specific for each fluid as they depend on composition and
the fluid properties
Due to the important effect it has over the operations, estimations of H2S generation
must be included in every steam injection project
Introduction H2S Generation Project Development Application & Conclusions
14. Rafael D’Elía (Schlumberger)
Yaneis Obando, MSc (U de Oriente)
