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