Catalytic Hydrotreatment of Triglycerides and Free Fatty ... 2... · Product cetane number up to 85...

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


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


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


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


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


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


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⋅


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⋅


1 March 2013


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

⋅+


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


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


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


Cs

(ppm

w S

)


T=365 oC

0

25

50

75

100

125


Cs

(ppm

w S

)


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


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


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


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


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


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


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


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


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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