Nikos Papayannakos, Professor National Technical University of Athens
School of Chemical Engineering Unit of Hydrocarbons and Biofuels Processing
Catalytic Hydrotreatment of Triglycerides and Free Fatty Acids for Green Diesel Production
1 March 2013
UGent Francqui Chair 2013 / 3rd Lecture
• Introduction • Laboratory Research
HDO reactions Equipment Conventional HDS in the presence of V.O. Deep HDS in the presence of V.O.
• Industrial Reactor Simulation • Conclusions
Presentation Outline UGent/FCh13/3L
1 March 2013
Direct Use of V.O. in diesel engines
Not recommended Use of refined VO Long - term use causes problems in engine parts (gumming-up of injectors and coking-up of valves and exhaust)
1 March 2013
Biofuels from Vegetable Oils and Fats UGent/FCh13/3L
V.O./Fats Conversion to Biodiesel (FAME) Main Process / Product Characteristics New production equipment Consumption of catalyst and methanol Product compliance with standards By - product glycerin Biodiesel oxidation during storage
V.O./Fats Conversion to Green Diesel
Main Process / Product Characteristics Use of existing equipment in refineries Known technology – Hydrotreatment Use of conventional hydrotreating catalysts Product fully compatible with diesel Product cetane number up to 85 Storage stability
Biofuels from Vegetable Oils and Fats UGent/FCh13/3L
• GOAL Replacement of part of petro-diesel with renewable diesel produced in a refinery via an existing process • Target The prediction of the operation of Industrial Units fed with Gas Oil /V.O. mixtures The suggestion of the necessary modifications to the existing Units for successful operation
Processing of V.O./Fats in Refineries
1 March 2013
CO2 + H2 CO + H2O
CO2 + 4H2 CH4 + 2H2O
+ 4 H2 R3-CH3 + C3H8 + 2H2O
+ 2 H2 R2-H + CO + C3H8 + H2O
+ H2 R1-H + CO2 + C3H8 O
O
C
C
O C
O
O R1
R2
R3
O
Triglyceride Green Diesel
Decarboxylation
Decarbonylation
Hydrogenation/ Dehydration
Liquid Phase
Gas Phase
C3H8 + H2O CO + 2H2O
Propane
HDO Reactions UGent/FCh13/3L
1 March 2013
S
E
S.C.
R
F
P
H2
PI PT
FT
PdT
WGM
• F: Liquid feed tank • P: Pump • R: Reactor • S: Gas - Liquid separator • WGM: Wet Gas Meter • Red Lines : Upflow Operation
Laboratory Unit UGent/FCh13/3L
1 March 2013
Inert
Glass wool
Glass wool
Diluted Catalytic Bed
Inert
1 March 2013
Laboratory Reactor UGent/FCh13/3L
Catalyst : 5 g CoMo/γ-Al2O3 (Albemarle KF 757)
Experimental Conditions Liquid Feed: 10% wt Cotton Seed Oil in Diesel (S < 20 ppm).
Reaction Temparatures : 305 – 320 – 335 °C Pressure : 30 bar
Liquid feed : 25-125 g/h, WHSV : 5-25 goil/gcat/h
Gas feed : 24 NlΗ2/h
Gas composition : 1% vol/vol H2S / H2 (DMDS)
Analysis Saponification Number (ASTM D94-02 )
Fatty_Acids Type Form Formula % (kg/kg)
Palmitic 16:0 C16H32O2 22.96
Palmitoleic 16:1 C16H30O2 0.90
Stearic 18:0 C18H36O2 2.30
Oleic 18:1 C18H34O2 16.70
Trans-Oleic 18:1 C18H34O2 0.10
Linoleic 18:2 C18H32O2 55.40
Trans-Linoleic 18:2 C18H32O2 0.02
Linolenic 18:3 C18H30O2 0.20
Composition of Cotton Seed Oil
HDO Experiments UGent/FCh13/3L
1 March 2013
0est( ) (1 )HDO HDOr k C x− = ⋅ ⋅ −
HDO Catalytic Reaction rates
0
10
20
30
40
50
60
70
80
0 2 4 6 8 10 12 14 16
WHSV (h-1)
Este
r Con
vers
ion,
x
experimentalmodel prediction
T=305 oC
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30
WHSV (h-1)
Este
r Con
vers
ion,
x
experimentalmodel prediction
T=335 oC
Hydrodeoxygenation Kinetics UGent/FCh13/3L
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30
WHSV (h-1)
Este
r Con
vers
ion,
x
experimentalmodel prediction
T=320oC
1 March 2013
QL WHSV = Vcat
1
10
100
0,0016 0,00162 0,00164 0,00166 0,00168 0,0017 0,00172 0,00174
1/T (K-1)
k (h
-1)
k HD
O, h
-1
Hydrodeoxygenation Kinetics UGent/FCh13/3L
Estimated Parameters
1 March 2013
kHDO,0 EHDO
kgfeed/hr/kgcat kJ/mol
3.18x1010 108
Properties Diesel Diesel/GD, 9/1
Density (g/ml) 0,8533 0,8497
Cetane Number 50,6 53,6
Cetane Index 51,8 53,9
100
150
200
250
300
350
400
IBP 5% 10% 20% 30% 40% 50% 60% 70% 80% 85% 90% 95% FBP
Αποθειωμένο ντίζελ Βιολογικό ντίζελ (βαμβακέλαιο 10%)
T, o C
Distillation Curve
Product Properties UGent/FCh13/3L
1 March 2013
• : Desulphurized Diesel o : Diesel / Green Diesel 9/10
HDS / HDO Set 1
Experimental Conditions Liquid Feed : Gasoil (0.88% S) / Palm Oil (0, 2.5, 5.0 and 10.0 % wt) mixtures:
Catalyst : 40 g CoMo/γ-Al2O3 (Albemarle KF 757), diluted with 50 g SiC.
Reaction Temperature : 310 – 330 – 350 °C Reactor Pressure : 33 bar
Liquid flow rate : 56, 40 and 28 g/h, WHSV : 1.4, 1.0 and 0.7 goil/gcat/h
Gas flow rate : 20 NlΗ2/h
Analysis Sulphur content in product oil, Exit gas composition
Co-hydroprocessing UGent/FCh13/3L
1 March 2013
Liquid feeds properties
Fatty Acids Form Formula % wt
Lauric 12:0 C12H24O2 0.3
Myristic 14:0 C14H28O2 0.8
Palmitic 16:0 C16H32O2 44.3
Palmitoleic 16:1 C16H30O2 0.2
Stearic 18:0 C18H36O2 5.0
Oleic 18:1 C18H34O2 39.1
Linoleic 18:2 C18H32O2 10.1
Linolenic 18:3 C18H30O2 0.1
Property Value
Density (g/ml) 0.865
Water (ppm) 250
Sulphur (% w/w) 0.88
Cetane Number 48.3
Palm Oil composition
Gasoil Distillation Curve (%-οC)
IBP 5% 10% 20% 30% 40% 50% 60% 70% 80% 85% 90% 95% FBP
174 233 248 264 274 284 294 305 317 331 338 348 360 368
Gas Oil Properties
Experiments UGent/FCh13/3L
1 March 2013
1 March 2013
Experimental Results for Set 1 UGent/FCh13/3L
Τ=310 C
40
50
60
70
80
90
100
0,0 2,5 5,0 7,5 10,0% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
HCON
_tot
(N
LH2/K
g _fe
ed)
WHSV=0,7 h^-1 WHSV=1,0 h^-1 WHSV=1,4 h^-1
% VEGETABLE OIL h-1 h-1 h-1
Τ=310 C
0
500
1000
1500
2000
2500
0,0 2,5 5,0 7,5 10,0% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
Cs p
pm
WHSV=0,7 h^-1 WHSV=1,0 h^-1 WHSV=1,4 h^-1h-1 h-1 h-1 % VEGETABLE OIL
Τ=330 C
0150300450600750900
10501200
0,0 2,5 5,0 7,5 10,0% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
Cs p
pm
WHSV=0,7 h^-1 WHSV=1,0 h^-1 WHSV=1,4 h^-1h-1 h-1 h-1
% VEGETABLE OIL
Τ=330 C
40
50
60
70
80
90
100
0,0 2,5 5,0 7,5 10,0% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
HCON
_tot
(NL
H 2/K
g _fe
ed)
WHSV=0,7 h^-1 WHSV=1,0 h^-1 WHSV=1,4 h^-1h-1 h-1 h-1 % VEGETABLE OIL
Τ=350 C
40
50
60
70
80
90
100
0,0 2,5 5,0 7,5 10,0% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
HC
ON
_tot
(
NL H
2/Kg _
feed
)
WHSV=0,7 h^-1 WHSV=1,0 h^-1 WHSV=1,4 h^-1% VEGETABLE OIL
T=350 C
050
100150200250300350400450
0,0 2,5 5,0 7,5 10,0
% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
Cs p
pm
WHSV=0,7 h^-1 WHSV=1,0 h^-1 WHSV=1,4 h^-1
% VEGETABLE OIL % VEGETABLE OIL
0,00
0,20
0,40
0,60
0,80
1,00
0 5 10 15 20 25 30 35
time (days)
activ
ity a
Experimental Results for Set 1 UGent/FCh13/3L
1 March 2013
Experimental Reactor Model I
Kinetic Equations Hydrodesulphurization
Gasoil Hydrogen Consumption
R HDS k HDS C Sn⋅ RHDS k HDSo
e
E HDS−
R T⋅⋅ C Sn⋅
ppms Kgfeed⋅
hr Kgcat⋅
R HCON_GO k HCON_GOoe
E HCON_GO−
R T⋅⋅ CHTGO HCONGO−( )2⋅
Reactor Modeling UGent/FCh13/3L
1 March 2013
VO Hydrogen Consumption
Experimental Reactor Model II
RHDO kHDOoe
EHDO−
R T⋅⋅ CVO( )INITIAL
⋅ 1 X−( )⋅ KgVO
hr Kgcat⋅
R HCONVOR HDO CHTVO⋅ x z( )
HCON VO z( )
CHT VO
R HCONVOk HDOo
e
E HDO−
R T⋅⋅ CVO( )INITIAL
⋅ 1HCONVOCHTVO
−
⋅ CHTVO⋅NLH2VO
hr Kgcat⋅
Reactor Modeling UGent/FCh13/3L
1 March 2013
Experimental Reactor Model III
Mass Balances
ppms( )dCSR HDS−
MFEEDdmcat⋅
Organic Sulphur
Hydrogen Sulphide
NLH2Shr
dNV H2S22.4
MB S 10 6−⋅R HDS⋅ dm cat⋅
Hydrogen
NLH2hr
dNV H2 R HCON_GO R HCON_VO+( )− dm cat⋅
Reactor Modeling UGent/FCh13/3L
1 March 2013
Gasoil Hydrogen Consumption
Experimental Reactor Model IV
NLH2Kggasoil
d HCONGO
R HCON_GOMfeed 1 CVO( )
0−
⋅dm cat⋅
Vegetable Oil Hydrogen Consumption
NLH2Kgvo
d HCONVO
R HCON_VOMfeed CVO( )
0⋅
dm cat⋅
Total Hydrogen Consumption
NLH2Kgfeed
HCONTOT HCONGO 1 CVO( )0
−
⋅ HCONVO CVO( )0
⋅+
Reactor Modeling UGent/FCh13/3L
1 March 2013
Y k HDS X⋅
X1
WHSV
Y1a
C Sin( )1 n− C Sout( )1 n−−
n 1−( )
⋅
T=350 C
R2 = 0,9246 R2 = 0,9464 R2 = 0,9583 R2 = 0,984
0,00
0,05
0,10
0,15
0,20
0,25
0,65 0,85 1,05 1,25 1,45X
Y
0.0% 2.5% 5.0% 10.0%
T=330 C R2 = 0,9775 R2 = 0,9993 R2 = 0,9251 R2 = 0,9485
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,65 0,75 0,85 0,95 1,05 1,15 1,25 1,35 1,45X
Y
0.0% 2.5% 5.0% 10.0%
T=310 C
R2 = 0,9282 R2 = 0,9976 R2 = 0,9992 R2 = 0,8392
0,00
0,01
0,02
0,03
0,04
0,05
0,65 0,75 0,85 0,95 1,05 1,15 1,25 1,35 1,45X
Y
0.0% 2.5% 5.0% 10.0%
1 March 2013
Estimation of HDS Kinetic Constants UGent/FCh13/3L
R2 = 0,9955R2 = 0,9835R2 = 0,9953R2 = 0,986
1,2
1,7
2,2
2,7
3,2
3,7
4,2
4,7
0,00159 0,00164 0,00169 0,001741/T
- LN
(K
_HD
S)
0.0% 2.5% 5.0% 10.0%
0
300
600
900
1200
1500
1800
0 300 600 900 1200 1500 1800
Cs_exp_corr (ppmwS)
Cs_c
alc
(ppm
wS)
Oil Content wt
kHDS 0
n=1,6
0,00
0,03
0,05
0,08
0,10
0,13
0,15
0,0 2,5 5,0 7,5 10,0
% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
K_H
DS
ppm
s^(1
-n )/
Kg_
feed
/Kg_
cat /
hr) 350 C
330 C310 C
k HD
S
% Vegetable Oil
HDS Kinetic Constants UGent/FCh13/3L
1 March 2013
T=350 C R2 = 0,9971 R2 = 0,9722 R2 = 0,9215 R2 = 0,9107
0,005
0,010
0,015
0,020
0,025
0,030
0,035
0,040
0,65 0,85 1,05 1,25 1,45 1,65Χ
Υ
0.0% 2.5% 5.0% 10.0%
T=330 C
R2 = 0,9143 R2 = 0,9745 R2 = 0,9217 R2 = 0,8662
0,005
0,010
0,015
0,020
0,025
0,030
0,65 0,85 1,05 1,25 1,45 1,65X
Y
0.0% 2.5% 5.0% 10.0%
T=310 C
R2 = 0,8115 R2 = 0,9586 R2 = 0,978 R2 = 0,9908
0,000
0,005
0,010
0,015
0,020
0,025
0,65 0,85 1,05 1,25 1,45 1,65Χ
Υ
0.0% 2.5% 5.0% 10.0%
HCONGO
HCONTOT( )exp
CHTVO CVO( )0
⋅−
1 CVO( )0
−
Y k HCONGOX⋅
X1
WHSV 1 CVO( )0
−
⋅
Y1a
1CHTGO HCONGO−
1CHTGO
−
⋅
Estimation of Hydrogen Consumption Kinetic Constants UGent/FCh13/3L
1 March 2013
2030405060708090
100
20 40 60 80 100HCON_exp_corr (NLH2/Kg_feed)
HC
ON
_cal
c (N
LH2/K
g _fe
ed)
x=y 0% 2.50% 5% 10%
NLH2KgVO
CHTVO 210
0,0178
0,0137
0,0108
0,0050,0 2,5 5,0 7,5 10,0
% ΠΕΡΙΕΚΤΙΚΟΤΗΤΑ V.O.
K_H
CO
N_G
O
(Kg _
go2 /
NL H
2/hr/K
g _ca
t)
350 C 330 C 310 C% VEGETABLE OIL
Hydrogen Consumption Kinetic Constants UGent/FCh13/3L
1 March 2013
40 % Selectivity towards Hydrogenation/Hydration
HDS / HDO Set 2
Experimental Conditions
Liquid Feed : Gasoil (0.5% S) neat or in mixtures with Palm Oil (5.0 and 10.0 % wt):
• Catalyst : 40 g CoMo/γ-Al2O3 (Albemarle KF 757), diluted with 50 g SiC.
• Reaction Temperature : 330 – 350 – 365 °C
• Reactor Pressure : 33 bar
• Liquid flow rate : 56, 40 and 34 g/h, WHSV : 1.4, 1.0 and 0.85 goil/gcat/h
• Gas flow rate : 20 NlΗ2/h
Analysis
• Sulphur content in product oil, Exit gas composition
1 March 2013
Co-hydroprocessing UGent/FCh13/3L
Experimental Results for Set 2
T=350 oC
0
50
100
150
200
250
0,0 5,0 10,0% VEGETABLE OIL
Cs
(ppm
w S
)
WHSV=0.85 (1/h) WHSV=1.0 (1/h) WHSV=1.4 (1/h)
T=330 oC
0
100
200
300
400
500
600
0,0 5,0 10,0% VEGETABLE OIL
Cs
(ppm
w S
)
WHSV=0.85 (1/h) WHSV=1.0 (1/h) WHSV=1.4 (1/h)
T=365 oC
0
25
50
75
100
125
0,0 5,0 10,0% VEGETABLE OIL
Cs
(ppm
w S
)
WHSV=0.85 (1/h) WHSV=1.0 (1/h) WHSV=1.4 (1/h)
0,00,10,20,30,40,50,60,70,80,91,0
0 5 10 15 20 25 30time (days)
activ
ity a
1 March 2013
Experiments / Set II UGent/FCh13/3L
Y k HDS X⋅
X1
WHSV
Y1a
C Sin( )1 n− C Sout( )1 n−−
n 1−( )
⋅
T=350 C R2 = 0.9983 R2 = 0.9999 R2 = 0.9027
0.00
0.10
0.20
0.30
0.40
0.65 0.75 0.85 0.95 1.05 1.15 1.25X
Y
0.0% 5.0% 10.0%
T=365 C R2 = 0.9804 R2 = 0.9932 R2 = 0.9995
0.00
0.15
0.30
0.45
0.60
0.75
0.90
0.65 0.75 0.85 0.95 1.05 1.15 1.25X
Y
0.0% 5.0% 10.0%
T=330 C R2 = 0.913 R2 = 0.9901 R2 = 0.9601
0.00
0.05
0.10
0.15
0.20
0.25
0.65 0.85 1.05 1.25 1.45X
Y
0.0% 5.0% 10.0%
1 March 2013
Estimation of HDS kinetic constants / Set II UGent/FCh13/3L
R2 = 0.9821R2 = 0.9983R2 = 0.9999
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0.00156 0.00158 0.00160 0.00162 0.00164 0.00166
1/T
- LN
(K_H
DS)
0.0 % 5.0 % 10.0 %
0
100
200
300
400
500
600
0 100 200 300 400 500 600Cs_exp (ppmwS)
Cs_
calc
(pp
mw
S)CONTENT kHDS o EHDS
% wt Palm oil (ppms(1-n) * Kgfeed)/h/Kgcat) (KJ/mol)0.0 5.20E+11 1455.0 8.19E+07 10410.0 2.59E+07 98
n=1,55
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,0 2,5 5,0 7,5 10,0% VEGETABLE OIL
k HD
S
(ppm
s(1-n
) kg f
eed/k
g cat
/h)
330 C350 C365 C
1 March 2013
HDS kinetic constants / Set II UGent/FCh13/3L
Gas analysis 330oC/1.4 h-1 350oC/1.4 h-1 350oC/1.0 h-1
Gas %v/v %v/v %v/v
H2 96.73 96.83 97.62
H2S 0.94 1.12 0.59
CO 0.69 0.64 0.36
CO2 0.69 0.44 0.54
CH4 0.51 0.55 0.51
C3H8 0.44 0.42 0.39
Vegetable Oil in Feed : 10 wt %
Gas Phase UGent/FCh13/3L
1 March 2013
G
L Reactor Outlet, zi
Separator Inlet , zi
Gas Outlet, yi
Algorithm of calculations
1. Determination of gaseous molar fractions, yi from the gas analysis.
2. By fitting this molar fractions, the ones in the separator’s inlet, zi were calculated using a cubic equation of state.
3. These molar fractions are the same at the reactor’s outlet.
4. Molar flows of the gaseous products calculated from the molar fractions are used for further calculations.
Estimation of Selectivity UGent/FCh13/3L
1 March 2013
System
• The sum of CO, CO2 and CH4 molar flows at Reactor Outlet give the amount of ester bonds following the paths of decarboxylation and decarbonylation
• Combining with V.O. structure calculate catalyst selectivity
Dehydration pathway is preferred by 38% of the total ester bonds and the remaining (62%) follow the other two paths
Industrial Hydrotreatment Unit
1 March 2013
Mild Hydrotreatment Unit UGent/FCh13/3L
Operating Parameters of the Industrial Unit
• Liquid Inlet Flow Rate = 120 - 170 tn/hr
• Gas Inlet Flow Rate (Recycle + Make-up) = 48000 - 55000 Νm3 /hr • Quench 1 Flow Rate = 3000 Νm3 /hr ( 75 % vol/vol Hydrogen ) • Quench 2 Flow Rate = 2000 Νm3 /hr ( 75 % vol/vol Hydrogen )
• TInlet = 280 - 345 oC
• P = 34 - 39 bar
• Catalyst Mass Μcat = 120 tn
1 March 2013
Industrial Unit UGent/FCh13/3L
Industrial Reactor Model
Vegetable Oil Hydrogen Consumption
Mass Balances
Organic Sulphur
Hydrogen Sulphide
Gasoil Hydrogen Consumption
Energy Balance
dTR HCON_GO ∆HR_GO⋅ T( ) R HCON_VO ∆HR_VO⋅ T( )+
i
F i Cp i T( )⋅∑dmcat⋅
Unsaturated C-C bonds : ΔΗR_GO=1.4 KJ/NLH2
Ester bonds deoxygenation ΔΗR_VO=2.5 KJ/NLH2
1 March 2013
Reactor Modeling UGent/FCh13/3L
Hydrogen Consumption and Temperature Profiles
Low Sulphur Gasoil Cs_in = 5000 ppm
T=350 C, WHSV=1.4 h-1, 0 % V.O
0
10
20
30
40
50
60
0 2 4 6 8 10 12 14 16 18 20ύψος m
HCO
N_to
t (NL
H2/K
g _fe
ed)
Reactor Length, m
T=350 C, WHSV=1.4 h-1, 0 % V.O
348350352354356358360362364366368
0 2 4 6 8 10 12 14 16 18 20ύψος m
T (C
)
Reactor Length, m
T=350 C, WHSV=1.4 h-1, 5% V.O
0
50
100
150
200
250
0 2 4 6 8 10 12 14 16 18 20ύψος m
HC
ON
_VO
(NLH
2/K
g _VO
)
Reactor Length, m
T=350 C, WHSV=1.4 h-1, 5% V.O
0
10
20
30
40
50
60
70
0 2 4 6 8 10 12 14 16 18 20ύψος m
HCO
N _G
O (N
L H2/K
g _G
O)
Reactor Length, m
T=350 C, WHSV=1.4 h-1, 5% V.O
345
350
355
360
365
370
375
0 2 4 6 8 10 12 14 16 18 20ύψος m
T (C
) Reactor Length, m
1 March 2013
Results UGent/FCh13/3L
Organic Sulphur and Hydrogen Flow Rate Profiles
T=350 C, WHSV=1.4 h-1, 0 % V.O
0
1000
2000
3000
4000
5000
0 2 4 6 8 10 12 14 16 18 20
ύψος m
Cs
ppm
w S
Reactor Length, m
T=350 C, WHSV=1.4 h-1, 0 % V.O
42000
44000
46000
48000
50000
0 2 4 6 8 10 12 14 16 18 20ύψος m
NV H
2 Nm
3 /hr
Reactor Length, m
T=350 C, WHSV=1.4 h-1, 5% V.O
0
1000
2000
3000
4000
5000
0 2 4 6 8 10 12 14 16 18 20
ύψος m
Cs
ppm
w S
Reactor Length, m
T=350 C, WHSV=1.4 h-1, 5% V.O
42000
44000
46000
48000
50000
0 2 4 6 8 10 12 14 16 18 20ύψος m
NVH
2 Nm
3 /hr
Reactor Length, m
1 March 2013
Results UGent/FCh13/3L
Effects of the Operating Parameters
Cs <10 ppm
0,7 0,9 1,1 1,3 1,5 1,7 1,9 2,1 2,3
370
360
350
T_in
( o C
)
WHSV (h-1)
10%
5%
0 %
Cs <10 ppm
0,7 0,9 1,1 1,3 1,5 1,7 1,9 2,1 2,3
370
360
T_in
( o C)
WHSV (h-1)
0 %
WHSV=1.4 h-1
020406080
100120140160
0,0 5,0 10,0
% V.O.
Cs_
out
( ppm
)
330
340
350
360
370
WHSV=1.4 h-1
050
100150
200250
300350
400
0,0 2,5 5,0 7,5 10,0
% V.O.
Cs_
out
( ppm
)
330
340
350
360
370
HEAVY FEED (Csin=8800 ppm) LIGHT FEED ΚΚ3 (Csin=5000 ppm)
1 March 2013
Results UGent/FCh13/3L
HCON + 2,0-2,3 NLH2/Kg_feed per 1 % V.O. T_out + 1,3 oC per 1 % V.O.
WHSV=1.4 h-1
2030405060708090
100
0,0 5,0 10,0
% V.O.
HC
ON
(NL H
2/Kg_
feed
) 300310320330340350360370
WHSV=1.4 h-1
310320330340350360370380390400
0,0 5,0 10,0
% V.O.
T_ou
t (C
)
300310320330340350360370
Effects of the V.O. Content / Light Feed
1 March 2013
Results UGent/FCh13/3L
HCON + 2,6-3,1 NLH2/Kg_feed per ΔΤin=10 oC T_out + 1,0 oC per ΔΤin=1 oC
WHSV=1.4 h-1
40
50
60
70
80
90
100
310 320 330 340 350 360 370
T_in ( oC)
HC
ON
(NL H
2/Kg _
feed
)
0.0% V.O. 5.0 % V.O. 10.0 % V.O.
WHSV=1.4 h-1
320330340350360370380390400
310 320 330 340 350 360 370
T_in ( oC)
T_ou
t (C
)
0.0% V.O. 5.0 % V.O. 10.0 % V.O.
WHSV=1.4 h-1
0
100
200
300
400
500
310 320 330 340 350 360 370
T_in ( oC)
CS_
out (
ppm
)
0.0% V.O. 5.0 % V.O. 10.0 % V.O.
Effects of the Inlet Temperature/ Light Feed
1 March 2013
Results UGent/FCh13/3L
0.0 % V.O.
020406080
100120140160180200220
0,5 1,0 1,5 2,0 2,5
WHSV (h-1)
Cs_
out
(ppm
)
330
340
350
360
370
10.0 % V.O.
0
40
80
120
160
200
240
280
0,5 1,0 1,5 2,0 2,5
WHSV (h-1)
Cs_
out
(ppm
)
330
340
350
360
370
0.0 % V.O.
300
310
320
330340
350
360
370
380
0,5 1,0 1,5 2,0 2,5
WHSV (h-1)
T_ou
t (C
)
300
310
320
330
340
350
360
10.0 % V.O.
320
330
340
350
360
370
380
390
0,5 1,0 1,5 2,0 2,5
WHSV (h-1)
T_ou
t (C
)
300
310
320
330
340
350
360
Effects of the Space Velocity / Light Feed I
1 March 2013
Results UGent/FCh13/3L
HCON - 1,5-1,9 NLH2/Kg_feed per ΔWHSV=0,1 h-1
0.0 % V.O.
20,0
30,0
40,0
50,0
60,0
70,0
80,0
90,0
100,0
0,5 1,0 1,5 2,0 2,5
WHSV (h-1)
HC
ON
(NL H
2/K
g _fe
ed)
300
310
320
330
340
350
360
370
10.0 % V.O.
20,0
30,0
40,0
50,0
60,0
70,0
80,0
90,0
100,0
0,5 1,0 1,5 2,0 2,5
WHSV (h-1)H
CO
N (N
L H2/K
g _fe
ed)
300
310
320
330
340
350
360
370
Effects of the Space Velocity / Light Feed II
1 March 2013
Results UGent/FCh13/3L
Βιοdiesel (FAME)
Green Diesel
% Ο
Density, g/ml
11 0
Sulfur Content, ppm
Energy Content MJ/kg
% Difference in NOx Emissions
Neat
Distillation 10 – 90 %
Cetane Number
0.88 0.78
< 10 < 10
38 44
+10 0 – (-10)
Liquid Solid
340 - 355 265 - 320
50 80 - 90
Green Diesel vs Biodiesel UGent/FCh13/3L
1 March 2013
Conclusions The Co-processing of Gasoil – V.O. mixtures in conventional
hydrotreaters results in Petro – Diesel and Green Diesel mixtures
At conventional HDT conditions total V.O. conversion to Green Diesel is achieved
Deactivation of Co-hydroprocessing is similar to that during Gasoil HDT
The increase of the V.O. content up to 5 % in the reactor feed results in a decrease of HDS reaction rates, but for a further increase up to 10 % the desulphurization rates remained unchanged
The selectivity of the CoMo/Al2O3 catalyst is 38 % for hehydration reactions and 62 % for hydro- decarbonylation/decarboxylation
The increase of the V.O. content in the feed results in increase of the produced heat in the reactor and the temperature difference TOUT – TIN
1 March 2013
UGent/FCh13/3L
Acknowledgements • Collaborators : Matsoukas Andreas M.Sc. Student Sebos Ioannis Ph.D. Student Templis Chrysovalantis Ph. D. Student Vonortas Andreas Ph. D. Student • Supporters Motor Oil Hellas Refinery Hellenic Petroleum Refinery GF Energy
1 March 2013
UGent/FCh13/3L
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