2015 EUROPACAT ZEOLITE APPLICATIONS
-
Upload
iacovos-vasalos -
Category
Documents
-
view
61 -
download
0
Transcript of 2015 EUROPACAT ZEOLITE APPLICATIONS
![Page 1: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/1.jpg)
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
![Page 2: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/2.jpg)
Outline
� Introduction
� Zeolites in FCC
� Zeolites in F-T Waxes
� Zeolites in Biomass Catalytic Pyrolysis
� Conclusions
![Page 3: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/3.jpg)
International Conference:
European Federation of Catalysis
Zeolites in Fluid Catalytic Cracking
Kazan, Russia, September 2015
![Page 4: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/4.jpg)
FCC PROCESS
![Page 5: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/5.jpg)
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
![Page 6: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/6.jpg)
PROCESS AND CATALYST EVOLUTION IN
CATALYTIC CRACKING
![Page 7: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/7.jpg)
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
![Page 8: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/8.jpg)
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
![Page 9: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/9.jpg)
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%
![Page 10: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/10.jpg)
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
![Page 11: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/11.jpg)
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.
![Page 12: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/12.jpg)
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
![Page 13: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/13.jpg)
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
![Page 14: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/14.jpg)
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
![Page 15: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/15.jpg)
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
![Page 16: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/16.jpg)
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.
![Page 17: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/17.jpg)
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.
![Page 18: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/18.jpg)
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.
![Page 19: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/19.jpg)
International Conference:
European Federation of Catalysis
Zeolites in F-T Wax Cracking
Kazan, Russia, September 2015
![Page 20: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/20.jpg)
THERMOCHEMICAL PROCESSES
Fast Pyrolysis
Catalytic
Cracking
Thermal HP
Catalytic HP
Biomass Bio-oil
Veg. Oil
VGO
VGO
GasificationFischer-
Tropsch
wax
![Page 21: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/21.jpg)
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
![Page 22: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/22.jpg)
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
![Page 23: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/23.jpg)
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
![Page 24: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/24.jpg)
International Conference:
European Federation of Catalysis
Biomass Catalytic Pyrolysis
Kazan, Russia, September 2015
![Page 25: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/25.jpg)
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
![Page 26: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/26.jpg)
CIRCULATING FLUID BED BIOMASS PYROLYSIS PILOT
PLANT UNIT
![Page 27: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/27.jpg)
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
![Page 28: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/28.jpg)
Reaction chemistry for the catalytic fast
pyrolysis of glucose with ZSM-5
Source: PhD Thesis, T. Carlson, UMass, 2010
![Page 29: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/29.jpg)
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
![Page 30: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/30.jpg)
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
![Page 31: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/31.jpg)
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
![Page 32: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/32.jpg)
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
![Page 33: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/33.jpg)
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
![Page 34: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/34.jpg)
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
![Page 35: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/35.jpg)
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
![Page 36: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/36.jpg)
ACKNOWLEDGEMENTS
(for granting the award)
• EFCATS SELECTION COMMITTEE
• PROF. JOHANNES LERCHER
• PROF. ANGELIKI LEMONIDOU
• Dr. ANGELOS LAPPAS
• Dr. BRUCE COOK
• Dr. CHERYL JOYAL
![Page 37: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/37.jpg)
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
![Page 38: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/38.jpg)
![Page 39: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/39.jpg)
ACKNOWLEDGEMENTS
MY FAMILY
My Thanks and Gratitude to my Family
![Page 40: 2015 EUROPACAT ZEOLITE APPLICATIONS](https://reader031.fdocuments.in/reader031/viewer/2022030316/587401f31a28ab6f1d8b5553/html5/thumbnails/40.jpg)