The document summarizes a presentation on zeolite applications for clean fossil and biofuels given at the European Federation of Catalysis conference in Kazan, Russia in September 2015. It discusses the use of zeolites in fluid catalytic cracking (FCC) processes to produce gasoline from heavy oils as well as their use in Fischer-Tropsch wax cracking and biomass catalytic pyrolysis. The presentation outlines the FCC process and how zeolite properties like acidity and pore size affect product yields and compositions. It also summarizes results from pilot plant and commercial FCC units. For FT wax cracking and biomass pyrolysis, the effects of different zeolites on product distributions are presented.

1. 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

2. Outline
Introduction
Zeolites in FCC
Zeolites in F-T Waxes
Zeolites in Biomass Catalytic
Pyrolysis
Conclusions

3. International Conference:
European Federation of Catalysis
Zeolites in Fluid Catalytic Cracking
Kazan, Russia, September 2015

4. FCC PROCESS

5. FCC REGENERATOR
(C, H, S, N) REACTIONS
C
+1/2O2
+O2 CO2
CO
+1/2O2
N
+1/2O2
+O2 NO2
NO
+1/2O2
NO + CO 1/2N2 + CO2
4H + O2 2H2O
S + O2 SO2
SO2 + 1/2O2 SO3

6. PROCESS AND CATALYST EVOLUTION IN
CATALYTIC CRACKING

7. Carbon Intensity vs Cat Type
0
2
4
6
8
10
12
14
16
18
HIGH ALUMINA ZEOLITE+RISER CO BURNING ZEOLITE 2015
CarbonIntensity(grCO2producedperkg
coke/MJgasoline)
CARBON INTENSITY vs CAT TYPE

8. 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

9. 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%

10. 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

11. FCC Pilot Plant to Commercial FCCU Unit
Comparison
Parameters
Ratio of Commercial
to Pilot Plant
Pilot 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.

12. 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
74
75
76
77
78
79
80
81
82
83
84
4 5 6 7 8 9 10 11 12 13 14
C/O
conversion,%wt
Y-ECAT
FCC Pilot Plant
35
37
39
41
43
45
47
49
51
53
55
75 77 79 81 83 85
conversion, %wt
gasoline,%wt
Y-ECAT
Com Data

13. Gasoline vs UCS (65wt%)
Wallenstein et al., Applied Catalysis A: General 502 (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)
Gasoline(wt%)
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)
Gasoline(wt%)
GASOLINE vs UCS AT CONSTANT
CONVERSION

14. UCS vs Re2O3
Wallenstein et al., Applied Catalysis A: General 502 (2015) 27-41
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
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
Re2O3 (wt%)
UCS(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

15. C4 OLEFINICITY vs Re2O3 AT CONSTANT
CONVERSION
C4 olefinicity vs Re2O3 (75wt%)
0.46
0.48
0.50
0.52
0.54
0.56
0.58
0.60
0.62
0.64
0.66
0.68
0.70
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%)
C4olefinicity
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

16. Wt-% Conversion vs Wt-% Slurry (343C+)
7
9
11
13
15
65 67 69 71 73 75 77 79
Conversion, wt-%
Slurry(343C+),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.

17. 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.

18. 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.

19. International Conference:
European Federation of Catalysis
Zeolites in F-T Wax Cracking
Kazan, Russia, September 2015

20. THERMOCHEMICAL PROCESSES
Fast Pyrolysis
Catalytic
Cracking
Thermal HP
Catalytic HP
Biomass Bio-oil
Veg. Oil
VGO
VGO
Gasification
Fischer-
Tropsch
wax

21. 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
Cokeyield,
%wtonfeed
Y
ZSM-5
WAX CATALYTIC CRACKING
ZSM-5 additive decreases considerable the coke yield due to lower hydrogen
transfer activity
EFFECT OF ZSM-5 ON COKE YIELD
A.A. Lappas, D.K. Iatridis and I.A. Vasalos, Ind. Eng. Chem. Res. 2011, 50, 531-538

22. EFFECT OF ZSM-5 ON GASOLINE & C3H6 YIELDS
A.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, %wt
C3H6yield,
%wtonfeed
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
gasoline(C5-216°C)yield,
%wtonfeed
Y
ZSM-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

23. EFFECT OF ZSM-5 ON GASOLINE COMPOSITION
A.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
0
5
10
15
20
25
30
35
40
45
N-
PARAFFINS
BR-
PARAFFINS
SAT-NAPH
UNSAT-
NAPH
N-OLEFINS
BR-OLEFINS
AROMATICS
Gasolinecomposition(%wt)
Y
Y+4% ZSM-5
Y+8%ZSM-5
Y+12%ZSM-5
Y+50% ZSM-5
ZSM-5

24. International Conference:
European Federation of Catalysis
Biomass Catalytic Pyrolysis
Kazan, Russia, September 2015

25. 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

26. CIRCULATING FLUID BED BIOMASS PYROLYSIS PILOT
PLANT UNIT

27. BFCP CFB UNIT (Lignocell, T=450°C, S/B=10-14)
0
20
40
60
80
Non-catalytic ZSM5-5 FCC
Bio-oilyield(%wtonbiomass)
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 FCC
Gasyield(%wtonbiomass)
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 FCC
Cokeyield(%wtonbiomass)
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
BFCPCFB 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) FCCOxygenates
%w t in Bio-Oil
%w t on Biomass
EFFECT OF Y ZEOLITE vs ZSM-5
Y Y
Y Y

28. Reaction chemistry for the catalytic fast
pyrolysis of glucose with ZSM-5
Source: PhD Thesis, T. Carlson, UMass, 2010

29. 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

30. 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)
%onbio-oil
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)
Brönstedacidsites(µmol/g)
Temperature (
o
C)
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 – acidity
K.S. Triantafyllidis et al., Proceedings Cat4Bio Conference, Thessaloniki, 2012

31. 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%
%FEEDCARBONTOOIL
COM ZSM-5_LIGNOCEL

32. 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
%FEEDCARBON

33. 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

34. 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

35. 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

36. ACKNOWLEDGEMENTS
(for granting the award)
• EFCATS SELECTION COMMITTEE
• PROF. JOHANNES LERCHER
• PROF. ANGELIKI LEMONIDOU
• Dr. ANGELOS LAPPAS
• Dr. BRUCE COOK
• Dr. CHERYL JOYAL

37. 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

39. ACKNOWLEDGEMENTS
MY FAMILY
My Thanks and
Gratitude to my
Family