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VÚAnCh - UniCRE
Czech Republic
Ústí nad Labem; HQ & inorganic technologies
Litvínov – Chempark; UniCRE
Ústí nad Labem
Prague
Litvínov
█ More than 20 units (plug-flow
reactors…)
█ Catalyst loading: 5-250 ml
█ Testing conditions: lup to 550° C
l20 MPa
lvarious technical gases
█ Operation 24/7
█ Catalyst synthesis, scale-up, shaping
█ Detailed / advanced analytics
UniCRE – CATPRO infrastructure
Triglycerides to Fuels
Gre
en d
iese
l
+ CH 3O Hcat.
H 2
cat.
H 2
cat.
H 2
cat.
CH3COO R1,2,3
CH3 R1,2,3
H R1,2,3
H R1,2,3
+
+
+
+
C3H8O3
C3H8
C3H83 CO2
+
+
+3 CO
6 H2O
3 H2OC3H8 +
1)
2)
3)
4)
T, (cat.)
Organic liquid products Gases+ 5)
CR1 OO
CH2
CR2 OO
CH
CR3 OO
CH2
OLP + +Solids H2O
Kubičková, I.; Kubička, D. Waste Biomass. Valor. 2010, 1, 293-308.
Comparison of diesel fuels
ULSD Biodiesel Green Diesel
O, % 0 11 0
Density, kg/m3 840 880 780
S, ppm <10 <5 <1
LHV, MJ/kg 43 38 44
Cloud point, °C -5 -5 - +10 -20 - +20
Cetane number 51 50-65 70-90
Stability good poor good
Energy & GHG Savings
Fossil CED, GJ/t 0 26.3 – 35.5 40.3 – 42.9
GHG, t CO2eq./t 0 1.2 - 2.4 1.8 – 3.2
UOP, 1st Alternative Fuels Technology Conference, 18.2.2008, Prague
.Biodiesel (FAME) - transesterification Selected issues
Basics of triglycerides to FAME
catalyst
R3COOCH3
R2COOCH3
R1COOCH3
CH-OH
CH2-OH
CH2-OH
+CH2-O-CO-R1
CH-O-CO-R2
CH2-O-CO-R3
3 CH3-OH+
R1, R2, R3 = CnH2n-1+x, where n = 13-21, x = -6, -4, -2, or 0
Reaction conditionsT: 60°CP: 1 atmMeOH/oil: 5-6 mol/molcatalyst: NaOH, CH3ONacatNaOH/oil: 0.007 g/g
pictures from the Internet
FAME – European situation.2009-28-EC:•GHG savings.Now: 35%.2017: 50%.2018: 60%
GHG savings.RS-BD: 38%.RS-GD: 47%.SF-BD: 51%.SF-GD: 62%
data from www.ebb-eu.org (includes green diesel capacity and production), EU Directive 2009 28EC
Alternative to the traditional process .Esterfip-H•160-250 kt/y•1.5 Mt/y
.Conditions•Zn-Al catalyst•200 – 250°C
Vegetable oil
Partial evap. Partial evap.
Full evap.
R1 R2
Methyl esters (> 99%)
Glycerol (> 98%)
Methanol
Bournay, L.; Casanave, D.; Delfort, B.; Hillion, G.; Chodorge, J. Catal. Today 2005, 106, 190–192.
.Green diesel - deoxygenation Industrial processes
Commercial applications
Pretreated feedstock
Hydro-treating
H2
NExBTL Product
stabilization
Flare gases
Gasoline
Gas treating
Iso-merization
Sour water unit
H2S recovery
Sulfur recovery unit
SO2
NexBTL process (Hodge, 2006)
.NexBTL█ Neste Oil, stand-alone units
Commercial applications
Feed
Two stage reactor system
Water
Make-up hydrogen (2-3.5 wt.%)
Acid gas removal CO2
Propane & light ends
Green diesel (88-98 vol.%)
Naphtha (1-10 vol.%)
Distillation Separator
Ecofining process (Frey, 2011, UOP, 2012)
.Ecofining█ UOP / ENI, stand-alone
Commercial units
Name Technology developer
Location Company Capacity, kt/a
Status
NexBTL NesteOil FinlandFinland
SingaporeNetherlands
NesteOilNesteOil
190190
800800
20072009
20102011
Ecofining UOP/Eni USA
Italy, Venice
Diamond Green Diesel
400
300 (500)
2013
2014 (2015)
(Neste Oil, 2012, C. Perego, Liblice, 2014)
Commercial applications
Atmospheric distillation
Vacuum distillation
Delayed cooking
FCC Existing HDT
Process H-BIO
Diesel
Diesel DD
Oil
Gas-oil
Diesel coke
Vacuum residue
Atmospheric residue
Vegetable oil Other fraction of diesel
H-Bio process (Costa, 2007)
.H-Bio█ Petrobras, co-processing units
Commercial applications
LGO feed
Product
Heat exchanger
Hot separator
Fired heater
Hydrotreating reactor with 4 catalyst beds
Make-up recycle H2
To amine unit
RTD
Co-processing of tall oil with LGO in Preem refinery (Egeberg et al., 2011)
.Preem refinery█ Haldor Topsoe, co-processing
units
Stand-alone vs. co-processing & challenges
.Stand-alone█ Investment intensive█ Flexible
lPremium products (green diesel x green jet)
.Co-processing█ Directly or revamp█ Low flexibility
lEN590 constraintsLow temperature properties
(CFPP)Sulfur
lBy-products (CO, CO2, CH4, C3H8, H2O)
lCatalyst deactivation
.Deoxygenation of triglycerides Fundamental aspects
+ 3 H2
CH2-O-CO-C17H33
CH-O-CO-C17H33
CH2-O-CO-C17H33
CH2-O-CO-C17H35
CH-O-CO-C17H35
CH2-O-CO-C17H35
+ 12 H 2
3 C18H38
3 C17H35COOH
- 6
H2O
3 C17H36
hydrogenation
hydrodeoxygenation
hydrodecarboxylation
- C3H8
+ 3 H2
+ 9
H2
+ 3 H2
- C3 H
8 ; - 3 CO2
- C 3H 8
; - 6 H 2
O
+ 6 H2
- 3 H2O3 C17H35CH2OH
- 3 H2 O
+ 3 H2
3 C17 H
35 CO
OH
- 3 H2 O
3 C17H35COOC18H37
Reaction pathways in deoxygenation
█ Initial hydrogenation of double bonds
█ HDO (H2O), HDC (CO2) accompanied by CO2 hydrogenation
█ Mechanism determines H2 consumption
Collect Czech Chem Commun 2008, 73 1015
X
Key aspects
.Reaction pathways█ Product selectivity█ Hydrogen consumption
.Raw materials quality█ Cost█ Deactivation
.Active phase selection█ Noble metals catalysts – decarboxylation
█ Sulfided (hydrotreating) catalysts – HDO and HDC
Dealing with H2 consumption
0
10
20
30
40
50
60
0 10 20 30 40 50 60 70 80 90 100 110
Yield HC, %
Yie
ld C
17
, %
NiMo
Ni
Mo
Appl. Cat A: Gen. 372 (2010) 199–208
CS II – Triglycerides – Green diesel
Kubička, D. Collect. Czech. Chem. Commun. 2008, 73, 1015–1044
.Support influence█ Active phase
█ Modifying active phase properties
Dealing with H2 consumption
Appl. Cat. B: Environ. 145 (2014) 101-107
Deactivation of sulfided catalysts
Sulfur depletion Feedstock impurities
RO
RO-S
50
55
60
65
70
75
80
85
90
95
100
0 24 48 72 96 120 144 168 192 216 240 264 288
Time-on-stream, h
Yie
ld o
f HC
, %
RO
50
55
60
65
70
75
80
85
90
95
100
0 24 48 72 96 120 144 168 192 216 240 264 288
Time-on-stream, h
Yie
ld o
f HC
, %
DMDS pulse
0
20
40
60
80
100
120
0 24 48 72 96 120 144 168
Time-on-stream, h
Yie
ld o
f HC
, %
NRORRO-I
RRO-II
WRO
Appl. Cat A: Gen. 394 (2011) 9–17
mmol/kg M eq. P
NRO 6.003 6.070
RRO-I 0.237 <0.016
RRO-II 0.197 0.023
WRO 2.035 1.224
Deactivation of sulfided catalysts
Sulfur depletion Feedstock impurities
RO
RO-S
50
55
60
65
70
75
80
85
90
95
100
0 24 48 72 96 120 144 168 192 216 240 264 288
Time-on-stream, h
Yie
ld o
f HC
, %
RO
50
55
60
65
70
75
80
85
90
95
100
0 24 48 72 96 120 144 168 192 216 240 264 288
Time-on-stream, h
Yie
ld o
f HC
, %
DMDS pulse
0
10
20
30
40
50
60
70
80
90
100
0 24 48 72 96 120 144 168
Time-on-stream, h
Yie
ld o
f HC
, %
TGROG
RO
Appl. Cat A: Gen. 394 (2011) 9–17
mmol/kg M eq. P
RO 0.197 0.023
ROG* 0.279 3.351
TG 0.444 10.009
Deactivation of sulfided catalysts
Sulfur depletion Feedstock impurities
RO
RO-S
50
55
60
65
70
75
80
85
90
95
100
0 24 48 72 96 120 144 168 192 216 240 264 288
Time-on-stream, h
Yie
ld o
f HC
, %
RO
50
55
60
65
70
75
80
85
90
95
100
0 24 48 72 96 120 144 168 192 216 240 264 288
Time-on-stream, h
Yie
ld o
f HC
, %
DMDS pulse
0
1
2
3
4
5
6
7
8
9
0 24 48 72 96 120 144 168
Time-on-stream, h
Yie
ld o
f Est
ers,
%
TG
ROG RO
0
5
10
15
20
25
30
35
40
45
0 24 48 72 96 120 144 168
Time-on-stream, h
Yie
ld o
f Aci
ds, %
TG
ROG
RO
Appl. Cat A: Gen. 394 (2011) 9–17
. Feedstock – price / quality /
availability
.Hydrogen consumption – HDO / HDC
. Single step hydrogenation /
isomerization
.Full refinery integration
. Robust non-sulfided catalysts
Challenges
Acknowledgements
█ N. Žilková, J. Vlk – mesoporous materials█ L. Kaluža – NiMo, Ni, Mo catalysts█ P. Priecel, L. Čapek – NiMo catalysts with
different Ni coordination
█ P. Šimáček, J. Chudoba – GC-MS identification█ J. Horáček, F. Homola – deoxygenation
experiments█ R. Bulánek, M. Setnička – active-phase–support
interactions
█ FT-TA3/074, P106/12/G015, CZ.1.05/2.1.00/03.0071
THANK YOU!
Contacts
Areál Chempark, Záluží 1, Litvínov, Postal Code 436 70
UniCRE is a part ofResearch Institute of Inorganic ChemistryRevoluční 1521/84, Ústí nad Labem, Postal Code 400 01Reg. No.: 62243136, TAX ID No.: CZ62243136Phone: +420 475 309 211, +420 475 309 222e-mail: [email protected], www.vuanch.czRegistered in the Commercial Register at the Regional Courtin Ústí n. L., Part B, File 664Banking information: 7009 411/0100, KB Ústí n. L.
the presentation was part of the projectUniCRE – Unipetrol Centre for Research and EducationSupported under the Operational Programme of Research and Development for InnovationNo. CZ.1.05/2.1.00/03.0071From EU and the Ministry of Education, Youth and Sports funds
