Documenti di Didattica
Documenti di Professioni
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Dr G Murali Dhar
Heavy Oil
1
End 1970 Protect Environment from Noxious Emissions Strong Impact on Refining
Oxygenates (2.7%)
1994
1995
2000
2005
2010
<10
Gasoline
Sulfur (ppm) max
1000
500
150
50/10
--
<1
Aromatics (Vol%)
max
--
--
42
35
< 35
--
--
18
18
< 10
--
2.7
2.7
2.7
--
--
--
95/98
95/98
95/98 (?)
80
--
60
--
-6
1994
1995
2000
2005
2010
Diesel Oil
Density (g/ ml) max
0.845
0.8450.840
0.84-0.82
49
51
51-53
> 55
2000
350
50/10
< 10
Distillation, 95% TC
max
370
360
360340
< 340
11
11-3
<2
PolyNuclear Aromatics
PNA (wt%) max
Pollutant
400
1700
NOx mg/Nm3
450
450
50
50
4.0
3.0
2.0
1.0
0.0
Gasoline
LPG
Gasoil
Jet/ Kerosene
Petroleum Refining
10
Hydrocracking
12
Hydrotreating
Relative activity
0
1965
1980
1990
2000
2005 Years
13
14
Relative Rate
R
+ H2
40 f
+ H2S
S
R2
R1
+ H2
+ H2S
10 f
S
R2
R2
R1
+ H2
S
R1
+ H2S
R3
R2
R2
R1
Intermediate
R3
+ H2
R1
+ H2S
f
(slowest)
S
R4
R3
R4
R3
15
16
Co Mo cat
Ni Mo cat
200
Oxidative Desulfurization
Sulfur Compounds Sulphones / Extracted with solvent
Oxidizing Agents: H2O2, Organic Peroxides
Hydrocarbon Sulphones Adsorbed on Alumina/
Adsorbents.
100
50
0
Low Temperature
High Temperature
17
18
Alkylation
Catalysts : Since 1940 - To Date - Liquid Catalysts HF & Conc. Sulfuric Acid
1990 Solid Catalysts : BF3/ Al2O3, BF3/Amberlite,Supported SbF5,
Sulfated Zirconia, Zeolites Shell/Akzo- Not Yet Commercial
World Production Alkylates --- 40% From HF Catalyst
--- 60% From Sulfuric Acid
19
20
Isomerization
Creating future fuels
Catalytic Reforming
Process Conditions : Fixed Bed, Temp. 200 -250oC, Pressure 10 -15 bar
Today
Catalytic reforming is aimed to produce:-
Pt /Zeolite Superior over Pt/Al2O3 in Better Activity, Regenerability, Longer life, Resistant
to Poisons
21
Reforming
Reforming
22
Catalysts :
5-25 bar
Amer. Oil Co
Fixed Bed / SR UOP
,,
/ SR
Chevron
,,
,,
Moving Bed/CCR UOP
Thermodynamics/ Kinetics:
Reaction
Rate
Site
Thermal Effect Favorable Conditions
Dehydrogenation
Very rapid Metal
Endothermic
Low Press./High Temp
Dehydrocyclization Slow
Metal/Acid Endothermic
,,
Isomerization
Rapid
Acid
Mild Exothermic
Press. No Effect
Hydrocracking
Very Slow
Metal/Acid Exothermic
24
Gasoline Blend
Light Naphtha
Alkylation / Isomerization
Heavy Naphtha
Cat. Reforming
Reformulated
Gasoline (RFG )
Light Olefins
MTBE
FCC Gasoline
DHDS/ Isomerization
25
26
Alternative Fuels
Creating future fuels
Natural Gas
Hydrogen Production :
Catalytic Reforming of Naphtha
Steam Reforming of Light Naphtha
Steam Reforming of Natural Gas
Gasification of Coal / Petroleum residues
Syn Gas / WGS Reaction
Bio- Mass
Electrolysis
-!
3H2+ CO
Co / Alumina
28
Year
Steam reforming
Partial oxidation
2000
MeOH
DME
Alcohols
DMC
(Dimethyl
Carbonate
solvent)
DMM
(Dimethoxy
Methane
CCR Reforming
Fischer Tropsch
Olefins
Ethers (MTBE)
(TAME)
Gasoline
Heavy Oil
1950
Paraffins
Hydrotreating
Cat cracking + alkylation + polymerization
UPGRADING
Kerosene
Zeolites in FCC
Platforming
Hydrogenation
Thermal Cracking
Diesel
Speciality
product
29
1900
Continuous distillatioin
30
Alternative Fuels :
Natural Gas
GTL Syn Gas -- FT HC ( Diesel/ Gasoline )
DME ( Diesel)
Bio-mass Jatropha Seeds Diesel
Methane Activation
C1 C4 Alkane Oligomerization ( Aromatics)
Hydrogen Fuel Cell
Catalytic Combustion :
Petrochemicals
BTX
31
Thank You
33
32