2015 europacat zeolite applications
TRANSCRIPT
International Conference:
European Federation of Catalysis
Zeolite applications for the production of
clean fossil fuels and biofuels
Dr. Iacovos Vasalos
CPERI/CERTH
Kazan, Russia, September 2015
Outline
� Introduction
� Zeolites in FCC
� Zeolites in F-T Waxes
� Zeolites in Biomass Catalytic Pyrolysis
� Conclusions
International Conference:
European Federation of Catalysis
Zeolites in Fluid Catalytic Cracking
Kazan, Russia, September 2015
FCC PROCESS
FCC REGENERATOR
(C, H, S, N) REACTIONS
C
+1/2O2
+O2 CO
2
CO
+1/2O2
N
+1/2O2
+O2 NO
2
NO
+1/2O2
NO + CO 1/2N2
+ CO2
4H + O2
2H2O
S + O2
SO2
SO2
+ 1/2O2
SO3
PROCESS AND CATALYST EVOLUTION IN
CATALYTIC CRACKING
Carbon Intensity vs Cat Type
0
2
4
6
8
10
12
14
16
18
HIGH ALUMINA ZEOLITE+RISER CO BURNING ZEOLITE 2015
Car
bon
Inte
nsity
(gr
CO
2 pr
oduc
ed p
er k
g co
ke/M
J ga
solin
e)
CARBON INTENSITY vs CAT TYPE
What is a Zeolite?
� Crystalline
� Aluminosilicate open framework
� Unit Cell
� Exchangeable cations (for change balance)
� Molecular sieving properties
A. Dyer, 1988
Different representations of TO4
tetrahydra
T = Si or Al
T-Site
exchangeable
cation
zeolitic water
Anatomy of a Cracking Catalyst
Matrix
Zeolite Y
70 Microns
Matrix Zeolite
Silica
Silica-alumina Ultra Stable Y
Clay REY, CREY (rare earth-Y, calcined REY)
Alumina Reduced NonFramework Species USY
Zeolite Levels, wt%
REY, CREY USY
Range 5 to 20% 25 to 50%
Typical 10 to 15% 40%
ACE R+ unit
�Confined (fixed) fluid bed reactor (CFBR)
Circulating Riser Reactor (CRR)
�Catalyst circulation with continuous
regeneration
EXPERIMENTAL UNITS
“Feedstock and catalyst effects in fluid catalytic cracking – Comparative yields in
bench scale and pilot plant reactors”, A.A. Lappas et al. / Chemical Engineering
Journal 278 (2015) 140–149
SCT-MAT unit
�Fixed bed microactivity unit
FCC Pilot Plant to Commercial FCCU Unit
Comparison
ParametersRatio of Commercial
to Pilot PlantPilot Plant Commercial
Feed Rate (BPD) 476190 0.126 60000
Feed Preheat Temp (F) 210 – 585 375 – 550
Riser Outlet Temp (F) 960 – 1025 960 – 1000
Cat to Oil for lab catalyst 4 – 12
Cat to Oil for commercial catalyst 0.67 6 – 16 4 – 9
“Pilot Plant Evaluation of FCCU Catalyst Technology and Use of Data for Commercial Catalyst
Applications” by Cheryl Joyal (BP) et al.
CATALYST ACTIVITY & GASOLINE YIELD vs CONVERSION
Lappas, A.A., “Refinery Benefits from an External FCC Catalyst Testing Laboratory (CPERI). Pilot
Plant Evaluation of FCCU Catalyst Technology”, Grace Davison FCC Technology Conference
September 7- 9, 2011, Munich
FCC Pilot Plant
7475767778798081828384
4 5 6 7 8 9 10 11 12 13 14
C/O
conv
ersi
on,
%w
t
Y-ECATFCC Pilot Plant
3537394143454749515355
75 77 79 81 83 85
conversion, %wt
gaso
line,
%w
t
Y-ECAT
Com Data
Gasoline vs UCS (65wt%)Wallenstein et al., Applied Catalysis A: General 50 2 (2015) 27-41
44
46
48
50
52
54
24.24 24.26 24.28 24.30 24.32 24.34 24.36 24.38 24.40 24.42 24.44 24.46 24.48
UCS (Å)
Gas
olin
e (w
t%)
Gasoline vs UCS (68wt%)
40
42
44
46
48
50
52
54
24.22 24.24 24.26 24.28 24.30 24.32 24.34 24.36 24.38 24.40 24.42 24.44
UCS (Å)
Gas
olin
e (w
t%)
GASOLINE vs UCS AT CONSTANT CONVERSION
UCS vs Re2O3Wallenstein et al., Applied Catalysis A: General 50 2 (2015) 27-41
24.2424.2624.2824.3024.3224.3424.3624.3824.4024.4224.4424.4624.48
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
Re2O3 (wt%)
UC
S (
Å)
Applied Catalysis A: General 502 (2015) 27-41
"Impact of rare earth concentration and matrix modification in FCC catalysts
on their catalytic performance in a wide array of operational parameters"
D. Wallenstein, K. Schäfer, R.H. Harding
C4 OLEFINICITY vs Re2O3 AT CONSTANT CONVERSION
C4 olefinicity vs Re2O3 (75wt%)
0.46
0.480.50
0.520.54
0.560.58
0.600.62
0.640.66
0.680.70
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
Re2O3 (wt%)
C4
olef
inic
ity
Studies in Surface Science and Catalysis 134 (2001) 71-85
“Effect of catalyst properties and feedstock composition on
the evaluation of cracking catalysts"
A.A. Lappas, Z.A. Tsagrasouli, I.A. Vasalos and A. Humphries
Wt-% Conversion vs Wt-% Slurry (343C+)
7
9
11
13
15
65 67 69 71 73 75 77 79
Conversion, wt-%
Slu
rry
(343
C+)
, wt-%
Decrease of 1.5 wt%
Catalyst 2Catalyst 3
Pilot Plant Slurry Yield Comparison
“Pilot Plant Evaluation of FCCU Catalyst Technology and Use of Data for Commercial Catalyst
Applications” by Cheryl Joyal (BP) et al.
Slurry Yield, wt%
10
11
12
13
14
15
16
17
Mar-04 May-04 Jul-04 Sep-04 Nov-04 Jan-05 Mar-05 May-05 Jul-05 Sep-05
Catalyst-2
Catalyst-3
Time
FCC Commercial Slurry Yield
“Pilot Plant Evaluation of FCCU Catalyst Technology and Use of Data for Commercial Catalyst
Applications” by Cheryl Joyal (BP) et al.
FUTURE FCC DEVELOPMENTS
• DEVELOPMENT OF HYBRID MICRO-
MESOPOROUS BASED CATALYSTS
• HIGH ACCESSIBILITY ZEOLITE VS ACTIVE
MATRIX
• SITE SPECIFIC COPROCESSING OF BIOFEEDS
• CATALYSTS RESISTANT TO METAL
DEACTIVATION INCLUDING Ca, Mg, etc.
International Conference:
European Federation of Catalysis
Zeolites in F-T Wax Cracking
Kazan, Russia, September 2015
THERMOCHEMICAL PROCESSES
Fast Pyrolysis
Catalytic
Cracking
Thermal HP
Catalytic HP
Biomass Bio-oil
Veg. Oil
VGO
VGO
GasificationFischer-
Tropsch
wax
FCC pp, T=538°C
0.0
0.2
0.4
0.6
0.8
1.0
70 75 80 85 90 95 100
conversion, %wt
Cok
e yi
eld,
%w
t on
feed
YZSM-5
WAX CATALYTIC CRACKING
ZSM-5 additive decreases considerable the coke yield due to lower hydrogen
transfer activity
EFFECT OF ZSM-5 ON COKE YIELDA.A. Lappas, D.K. Iatridis and I.A. Vasalos, Ind. Eng. Chem. Res. 2011, 50, 531-538
EFFECT OF ZSM-5 ON GASOLINE & C3H6 YIELDSA.A. Lappas, D.K. Iatridis and I.A. Vasalos, Ind. Eng. Chem. Res. 2011, 50, 531-538
19%wt
FCC pp, T=538°C
6
8
10
12
14
16
18
20
70 75 80 85 90 95 100
conversion, %wtC
3H6
yiel
d,%
wt o
n fe
ed
Y
ZSM-5
19%wt
WAX CATALYTIC CRACKING
FCC pp, T=538°C
30
34
38
42
46
50
54
58
70 75 80 85 90 95 100
conversion, %wt
gaso
line(
C5-
216°
C)
yiel
d,%
wt o
n fe
ed
YZSM-5
18%wt
drop
Effect of ZSM-5 on Wax cracking: similar trends with VGO
The effect of ZSM-5 is more pronounced with Wax than with VGO
Incremental decrease of gasoline very low after 12%wt ZSM-5
EFFECT OF ZSM-5 ON GASOLINE COMPOSITIONA.A. Lappas, D.K. Iatridis and I.A. Vasalos, Ind. Eng. Chem. Res. 2011, 50, 531-538
� Gasoline quality with ZSM-5 is significantly different
� ZSM-5 affects strongly n- and br-paraffins
� The effect on olefins is not so significant while aromatics are still low
WAX CATALYTIC CRACKING
Isoconv=85%wt, T=538°C
05
1015202530354045
N-
PA
RA
FF
INS
BR
-P
AR
AF
FIN
S
SA
T-N
AP
H
UN
SA
T-N
AP
H
N-O
LEF
INS
BR
-OLE
FIN
S
AR
OM
AT
ICS
Gas
olin
e co
mpo
sitio
n (%
wt)
Y
Y+4% ZSM-5
Y+8%ZSM-5
Y+12%ZSM-5
Y+50% ZSM-5
ZSM-5
International Conference:
European Federation of Catalysis
Biomass Catalytic Pyrolysis
Kazan, Russia, September 2015
BIOMASS FAST PYROLYSIS PROCESS
� Biomass pyrolysis: a thermo-chemical process for the production of liquids,
solids and gaseous products
� A solid heat carrier is used
� Biomass Catalytic Pyrolysis: Use a solid catalyst as heat carrier for the in-
situ upgrading of the pyrolysis products
CIRCULATING FLUID BED BIOMASS PYROLYSIS PILOT
PLANT UNIT
BFCP CFB UNIT (Lignocell, T=450°C, S/B=10-14)
0
20
40
60
80
Non-catalytic ZSM5-5 FCCBio
-oil
yie
ld (
%w
t o
n b
iom
as
s)
BFCP CFB UNIT (Lignocell, T=450°C, S/B=10-14)
0.0
5.0
10.0
15.0
20.0
25.0
Non-catalyt ic ZSM5-5 FCC
Gas
yie
ld (
%w
t o
n b
iom
ass)
BFCP CFB UNIT (Lignocell, T=450°C, S/B=10-14)
0.0
5.0
10.0
15.0
20.0
25.0
Non-catalytic ZSM5-5 FCCCok
e y
ield
(%
wt
on b
iom
ass)
� The catalysts decrease the production of liquids and increase the water, coke and gas production
• The presence of catalyst favors the secondary cracking of vapors and the de-oxygenation reactions
� ZSM-5 is a better catalyst that Y
BFCP CFB UNIT (Lignocell, T=450°C, S/B=10-14)
0.00
3.00
6.00
9.00
12.00
15.00
18.00
Non-catalytic ZSM-5 (Cat.-5) FCCO
xyge
nate
s
%w t in Bio-Oil
%w t on Biomass
EFFECT OF Y ZEOLITE vs ZSM-5
Y Y
Y Y
Reaction chemistry for the catalytic fast
pyrolysis of glucose with ZSM-5
Source: PhD Thesis, T. Carlson, UMass, 2010
Jae, J., Tompsett, G.A., Foster, A.J., Hammond, K.D., Auerbach, S.M., Lobo,
R.F. and Huber, G.W., “Investigation into the shape selectivity of zeolite
catalysts for biomass conversion”, Journal of Catalysis, 279, (2011), 257-268
Schematic of zeolite pore diameter (dN) compared to the kinetic diameter of
feedstocks and oxygenate and hydrocarbon catalytic pyrolysis products
Bio-oil main components
* Values refer to ~ 12% organic phase on biomass for catalytic experiments
0
20
40
60
80
100
Non-catalytic Silicalite ZSM-5 (11.5) ZSM-5 (25) ZSM-5 (40)
% o
n b
io-o
il
Heavy PAHs Aromatics
Acids Ketones Phenols
Relative strength of Brönsted acid sites
100 150 200 250 300 350 400 450 500
0
200
400
600 silica sand silicalite ZSM-5 (11.5)
ZSM-5 (40) ZSM-5 (25)
Brö
nst
ed
aci
d si
tes
(µm
ol/g
)
Temperature (oC)
� The stronger Brönsted acidity of ZSM-5 with higher Si/Al favors the formation of
aromatics, and decreases acids and slightly phenols
ZSM-5 zeolite: Effect of Si/Al ratio – acidityK.S. Triantafyllidis et al., Proceedings Cat4Bio Conference, Thessaloniki, 2012
Pyrolysis Carbon Efficiency for commercial
ZSM-5 and Lignocel
PYROLYSIS CARBON EFFICIENCY VS OXYGEN IN OIL
34
36
38
40
42
44
17.0 17.5 18.0 18.5 19.0 19.5 20.0 20.5 21.0
OXYGEN IN OIL, wt%
% F
EE
D C
AR
BO
N T
O O
IL
COM ZSM-5_LIGNOCEL
Pyrolysis Carbon Efficiency at 20wt% oxygen in
oil – commercial ZSM-5/Lignocel
PYROLYSIS CARBON EFFICIENCY AT 20wt% OXYGEN IN OIL
0
5
10
15
20
25
30
35
40
45
OIL COKE CO CO2 LIGHT GASES
% F
EE
D C
AR
BO
N
Catalytic fast pyrolysis of pine wood with a fresh ZSM-5,
the ZSM-5 after 5 reaction–regeneration cycles and the
ZSM-5 after 30 reaction–regeneration cycles.
Huber et al., “Catalytic fast pyrolysis of lignocellulosic biomass in a process development unit with
continual catalyst addition and removal”, Chemical Engineering Science 108 (2014) 33-46
FUTURE R&D NEEDS
• THERMOCHEMICAL PATHWAY
– Syngas Purification & Catalyst Development
– Catalytic Upgrading
• PYROLYSIS PATHWAY
– Bio oil Production & Recovery
– Catalyst Development
– Co processing bio oil in refining
Conclusions:Energy for Sustainable Development
• Zeolites key to sustainable development
• Zeolite applications in FCC major motivation
• ZSM-5 a key for successful implementation of
catalytic pyrolysis
• Hybrid processes combining fossil with biomass
resources to exploit idle refining assets
ACKNOWLEDGEMENTS
(for granting the award)
• EFCATS SELECTION COMMITTEE
• PROF. JOHANNES LERCHER
• PROF. ANGELIKI LEMONIDOU
• Dr. ANGELOS LAPPAS
• Dr. BRUCE COOK
• Dr. CHERYL JOYAL
ACKNOWLEDGEMENTS
(A tribute to all)
• The EU and Greek Authorities for financial support
• Amoco Oil and BP people for their moral and financial
support
• Department of Chemical Engineering– Aristotle University
of Thessaloniki
• The scientific, technical and management personnel –
CPERI & CERTH
• The team scientific, technical and support personnel
• My family
ACKNOWLEDGEMENTS
MY FAMILY
My Thanks and Gratitude to my Family