Methanol to Olefins (MTO):

Development of a Commercial
Catalytic Process
Simon R. Bare
Advanced Characterization, UOP LLC

Modern Methods in
Heterogeneous Catalysis Research
FHI Lecture November 30, 2007
1 © 2007 UOP LLC, All Rights Reserved
 Polyethylene and Polypropylene

• Thousands of uses of polyethylene and

polypropylene.

2
 Polyethylene and Polypropylene

• Main source of the ethylene and propylene

(monomer feedstock for polyethylene and
polypropylene) is steam cracking of naphtha or
other hydrocarbon.
Naphtha
(C5-C9) Steam Cracking
C2= + C3= + C3+
Ethane
>850°C, millisec
HCBN

3
 Methanol To Olefins (MTO) Reaction

• Methanol is an alternate source of light olefins.

• Dehydration with shape selective transformation
to low molecular weight alkenes.
Ethylene
SAPO-34
Catalyst
Methanol Propylene
Δ

Butenes
Other By-Products
H2O
H2 , COX
C1-C5 Paraffins
C5+
4 Coke
 UOP/Hydro MTO Process

SAPO-34 Catalyst

H 2O

CH3OH

Courtesy to Unni Olsbye,

5 University of Oslo
 MTO Reaction

• High selectivity and yield to light olefins.

Material SAPO-34

T atom % 10% Si (gel)

Selectivities (2 hr)
C2-C4 olefins 96
CH4 1.4
C2H6 0.3
C3H8 0.9
Stability
hr at >50% >40
conversion
Coking
carbon on 19% after
used catalyst 54 HOS

• Many acid catalysts are active for the methanol

dehydration – what makes SAPO-34 the preferred
catalyst?
Yuen, et al., Microporous Materials, 2 (1994) 105
6
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol & natural gas
• Discovery to commercialization

7
 What is a Zeolite?

• Zeolites occur in nature.

Mordenite Chabazite Natrolite

8
 Zeolites

• Zeolites consist of a framework built of tetrahedra.

• Each tetrahedron comprises a T-atom bound to four
O atoms.
• Oxygen bridges connect the tetrahedra.
• T-atoms are Si or Al.

Courtesy to Francesca Bleken,

9 University of Oslo
 Zeolites

• Alumino-silicate framework
• Crystalline, microporous (pore diameter 3-14Å)
• Framework density <20 T-atoms/1000Å3

LTA = Zeolite A
10
 Ways to Visualize a Zeolite: ZSM-5 (MFI)

• Medium pore size 5.1 x 5.5Å

- Wire frame structure showing only T-
atoms
- Pore structure – critical for thinking
about a molecule diffusing through the
structure.

11
 Range of Pore Sizes

• Zeolites exhibit a range of pore sizes of molecular

dimensions (molecular sieves).
Small Large
8-ring 12-ring
~ 4A ~ 6-8A

Very Large
Medium >12-ring
10-ring >8A
~ 5-6A

12
 Acid Sites in Zeolites

• Substitute Al3+ for Si4+: charge imbalance – need

additional cation to compensate.
O
Si • No total charge.

• One extra charge per

H Al atom introduced
into the lattice.
• Cations compensate
Al
for total charge.
• Protons as cations
give Brønsted acid
properties. Courtesy to Francesca Bleken,
13 University of Oslo
Evolution of Molecular Sieve Compositions

Time of Initial Discovery Composition

Late 40's to Early 50's Low Si/Al Ratio Zeolites
Mid 50's to late 60's High Si/Al Ratio Zeolites
Early 70's Pure SiO2 Molecular Sieves
Late 70's AlPO4 Molecular Sieves
Late 70's to Early 80's SAPO and MeAPO Molecular Sieves
Late 70's Metallo-silicates, -aluminosilicates
Early to Mid 90's Mesoporous Molecular Sieves
Octahedral-tetrahedral Frameworks

14
 Framework Types

• 176 framework types recognized by the International Zeolite

Association (IZA) (http://www.iza-online.org/).
• IZA Structure Commission assigns framework type codes to
all unique and confirmed framework topologies.

ABW ACO AEI AEL AEN AET AFG AFI AFN AFO AFR AFS
AFT AFX AFY AHT ANA APC APD AST ASV ATN ATO ATS
ATT ATV AWO AWW BCT *BEA BEC BIK BOG BPH BRE CAN
CAS CDO CFI CGF CGS CHA -CHI -CLO CON CZP DAC DDR
DFO DFT DOH DON EAB EDI EMT EON EPI ERI ESV ETR
EUO FAU FER FRA GIS GIU GME GON GOO HEU IFR IHW
ISV ITE ITH ITW IWR IWW JBW KFI LAU LEV LIO -LIT
LOS LOV LTA LTL LTN MAR MAZ MEI MEL MEP MER MFI
MFS MON MOR MOZ MSO MTF MTN MTT MTW MWW NAB NAT
NES NON NPO NSI OBW OFF OSI OSO OWE -PAR PAU PHI
PON RHO -RON RRO RSN RTE RTH RUT RWR RWY SAO SAS
SAT SAV SBE SBS SBT SFE SFF SFG SFH SFN SFO SGT
SOD SOS SSY STF STI STT TER THO TON TSC UEI UFI
UOZ USI UTL VET VFI VNI VSV WEI -WEN YUG ZON

15
 Zeolites as Industrial Catalysts

• But only ~18 framework types have seen

commercial utility.

ABW ACO AEI AEL

AEL AEN AET AFG AFI AFN AFO AFR AFS
AFT AFX AFY AHT ANA APC APD AST ASV ATN ATO ATS
ATT ATVBEAAWO AWW BCT *BEA BEC BIK BOG BPH BRE CAN
CAS CDO CFI CGF CGS CHA -CHI -CLO CON CZP DAC DDR
DFO DFTCHADOH DON EAB EDI EMT EON EPI ERI
ERI ESV ETR
EUO FAU FER GIS
EUO FAU FER FRA GIS GIU GME GON GOO HEU
HEU IFR IHW
ISV ITE ITH ITW IWR IWW JBW KFI LAU LEV LIO -LIT
LTA LTL
LOS LOV LTA LTL LTN MAR MAZ MEI MEL MEP MER MFI
MFI
MFS
NESMOR
MON
NON
MOR
NPO
MOZ
NSI
MSO
OBW
MTF
OFF
MTN
OSI
MTW MWW
MTT
OSO
MTW
OWE
MWW
-PAR
NAB
PAU
NAT
PHI
RHO
PON RHO -RON RRO RSN RTE RTH RUT RWR RWY SAO SAS
SAT SAV SBE SBS SBT SFE SFF SFG SFH SFN SFO SGT
SOD SOS SSY STF STI STT TER THO TON TSC UEI UFI
UOZ USI UTL VET VFI VNI VSV WEI -WEN YUG ZON

16
Commercial Catalytic Uses of Zeolites (Refining &
Petrochemicals)

Process FAU LTL MOR BEA MWW MFI AEL FER RHO CHA ???
Ethylbenzene x x x
Cumene x x x x x
Other aromatics x
Xylene isom x x
C4 isom x
C4= isom x x x
C5= isom x x
Iso-dewaxing x
Amination x x x x
C3,C4 arom x
Naphtha arom x
FCC x x
Dewaxing x
Hydrocracking x x
MTG x
MTO x x
Toluene x x
trans-alkylation

FAU = Y, USY LTL = Linde L, K-L MOR = mordenite BEA = beta

MWW = MCM-22 MFI = ZSM-5 AEL = SAPO-11, SM-3 FER = ferrierite
RHO = zeolite RHO CHA = chabazite, SAPO-34

17 K. Tanabe and W. Holderich, Appl. Catal. A, 399 (1999) 181

Alumino-phosphate (AlPO4) Molecular Sieves

• Microporous solids similar to silico-aluminate

zeolites – but composed of interlinked tetrahedra of
AlO4 and PO4 vs. AlO4 and SiO4.
• Alternating Al-O-P bonds
• Almost never Al-O-Al, and never P-O-P (due to
charge and lack of hydrothermal stability).

Al P

18
 Idealized 2D Connectivity of tetrahedral AlPO4
framework
• Al and P strictly alternating.
• Neutral framework.

Al P Al P Al P Al P

P Al P Al P Al P Al

Al P Al P Al P Al P

P Al P Al P Al P Al

Al P Al P Al P Al P

P Al P Al P Al P Al

Al P Al P Al P Al P

P Al P Al P Al P Al
19
Si Substitution for P in AlPO4 to give SAPO

• Si substitution for P in AlPO4 yields negative

framework charge and Brønsted acid sites.

Isolated Si: Si+4 →P+5

Al P Al P Al P Al P

Negative framework P Al P Al P Al P Al
charge H
Al Si Al P Al P Al P
Template P Al P Al P Al P Al
decomposition →H+
Al P Al P Al P Al P

No Si-O-P P Al P Al P Al P Al

No P-O-P Al P Al P Al P Al P

P Al P Al P Al P Al
20
 Si Substitution Produces Brønsted Acid Sties

Si island
Al P Al P Al P Al P
Isolated Si 5 Si = 4P + 1 Al
1 Si = 1P P Al P Al P Al P Al 5 Si = 3 H+
H
1 Si = 1 H+ H
Al Si Al P Al Si Al P
H
P Al P Al Si Si Si Al
Yes
Al P Al P Al Si H Al P
Al-O-P
Adjacent H
isolated Si P Al Si Al P Al P Al Si-O-Al
H Si-O-Si
2 Si = 2P Al Si Al P Al P Al P No
2 Si = 2 H+ P Al P Al P Al P Al Al-O-Al
P-O-P
Si-O-P
21
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol & natural gas
• Discovery to commercialization

22
 Characterization Methods for Zeolites

• NH3 TPD
• Hydroxyl FTIR
• Pyridine FTIR
• Framework FTIR
• Low temperature CO FTIR
• Solid State NMR
• Electron microscopy: SEM/TEM

• XPS
• XRD
• EXAFS
• Many others…..

23
 Acidic Sites: Use of Base for Characterization

• Acidic catalyst surface may expose both protic

(Brønsted) and aprotic (Lewis) sites.
• Protic sites in a zeolite are surface hydroxyl groups
OH.
• Aprotic sites in zeolite are typically extraframework
Al surface cations.
• Basic probe molecule will interact with OH via
hydrogen bonding:
OHs + B ⇔ OHs…Β
• If OH is sufficiently acidic then proton transfer:
OHs…Β ⇔ Os−…Η+Β
• For aprotic sites the base will form a Lewis acid-
base adduct:
L + B ⇔ L←B

24
 Ammonia Temperature Programmed Desorption

• NH3 TPD is used to measure the amount and relative

strength of the acid sites.
• NH3 small molecule but not very specific.

H
H
H H
H H
N
N

N oo H+
O
H
H Al
H Al

Ammonia Lewis acid (electron acceptor) Brønsted acid (proton

donor)

25
Ammonia Temperature Programmed Desorption

Linear temperature ramp. Amount of ammonia

desorbed as a function of temperature
recorded and quantified.

700 18

16
600
14

Rate of NH3 Desorption

500
12
Temperature (°C)

400 10

300 8

6
200
4
100
2

0 0
0 10 20 30 40 50 60 70 80
Time (minutes)

26
 Hydroxyl FTIR

• Use FTIR to measure the infra red spectrum of the zeolite.

• The vibrational frequency of the hydroxyl species in the
sample is dependent on the type of hydroxyl species present.
• Can differentiate between framework and extraframework
species.

Terminal Si-OH

BEA
Terminal Si-OH

.4
Absorbance

.3

Extra-framework Al-OH
.2 Non-framework Al-OH

Bridging Si-OH-Al
3Bridging OH

Extra-framework
.1
Al-OH
Terminal Al-OH

0
3900 3800 3700 3600 3500 3400 3300 3200 3100 3000
Wavenumber (cm-1)
Normalized

27 H. Knözinger in Handbook of Heterogeneous Catalysis, Vol 2, p. 707

 Hydroxyl FTIR

• Transformation of IR spectrum on steaming of

zeolite BEA.
• Dealumination of framework Al species.

Terminal Si-OH Starting Material

Terminal Si-OH Steamed 5%; 550C; 24hrs
Steamed 10%; 600C; 24hrs
.4
Absorbance

.3

Extra-framework Al-OH
.2 Non-framework Al-OH
Bridging Si-OH-Al
Bridging OH

Extra-framework
.1 Al-OH
Terminal Al-OH

0
3900 3800 3700 3600 3500 3400 3300 3200 3100 3000
Wavenumber (cm-1)
Normalized

28
 Pyridine FTIR: Basics

• Pyridine is a weak base which coordinates with both Brønsted

and Lewis acid sites.
• Distinct FTIR-active bands are observed for each type of acid
site.
• The integrated intensity provides a relative measure of the
number of each site.
• The desorption temperature provides a relative measure of the
acid site strength.
• Most useful when comparing a series of samples.

Ring vibrational
modes
+
N
1450 cm-1 H 1550 cm-1
N O-
L B
Lewis (aprotic) Brønsted (protic)
29
 Pyridine FTIR: Spectrum
Hydroxyl Region Pyridine Adsorption
1.5
Pyridine adsorption attenuates
bridging OH groups; bands are
Bridging OH restored upon pyridine desorption
Absorbance

1
N-H bands

.5

Si-OH
0
3900 3800 3700 3600 3500 3400 3300 3200 3100 3000
Wavenumber (cm-1)
File # 1 : Y-64PRTC

Pyridine Adsorption Spectral Region

Pyridine adsorption yields
Brønsted/Lewis
distinct Brønsted and Lewis
1.5
acid site absorbance bands
Absorbance

in this region
1
Brønsted/Lewis
Key: Pretreated .5
Brønsted Lewis
After 150C
After 300C 0
1650 1600 1550 1500 1450 1400 1350 1300
After 450C Wavenumber (cm-1)
30 File # 1 : Y-64PRTC
 Pyridine FTIR: Acid Site Distribution

Pyridine Adsorption IR
Integrated area of pyridine adsorbed
Brönsted Acid Site Distribution
1.2 on Brønsted acid site; ~ 1550 cm-1
Integrated Area/mg

0.8

0.6

0.4

0.2
Integrated area of pyridine adsorbed
0
Sample 1 on Lewis acid site; ~1450 cm -1.

Weak Moderate Strong Total

Pyridine Adsorption IR
Weak Site: pyridine desorbed between 150ºC Lewis Acid Site Distribution
0.6
and 300ºC Integrated Area/mg
0.5

0.4
Moderate site: pyridine desorbed between 0.3

300ºC and 450ºC 0.2

0.1

Strong site: pyridine remaining after 450 ºC 0

Sample 1

desorption
Weak Moderate Strong Total
31
 Framework FTIR

• Framework region (1400 - 400 cm-1) contains

information on T-O-T modes, ring modes of zeolites
• T-O-T(asym) frequency shifts with Si/Al2 ratio.

T-O-T stretch
Before calcination – 1091.4 cm -1
325C Steamed - 1095.6 cm -1
Absorbance

2
550C Steamed - 1098.9 cm -1
Loss of framework aluminum
610C steamed - 1100.8 cm -1
1.5 from higher temp steaming
results in shift of T-O-T stretch
1

.5

0
1600 1400 1200 1000 800 600

Wavenumber(cm-1)
Wavenumber

32
 Low Temperature CO FTIR

• CO is a small, very weak, soft base

- Accessible to small pores
• Reversible adsorption at <150K
• Number/strength distributions without high
temperature desorption
• Can detect very low levels of Brønsted acidity
• Complimentary, more detailed information
- ν(CO) 2160-2190 cm-1(B)
- ν(CO) 2160-2240 cm-1(L)
- Δν(OH) 0-350 cm-1(B)
• Shift in OH band gives measure of acid site strength

33
 Low Temperature CO Adsorption

OH bands shift due to interaction

Hydroxyl Brønsted
with CO CO
O-H
O--H-CO Physisorbed

CO Addition

3800 3600 3400 3200 2300 2200 2100 2000

Wavenumber (cm-1) Wavenumber (cm-1)

• All acid sites accessible to CO

• Interaction of CO with acid hydroxyl results in frequency shift → strength of sites
• Integrated CO band area → number of sites
• Difference spectra clarify OH band shifts

34
 Low Temp CO Adsorption on Different Materials

• Low temp CO adsorption clearly shows strength

difference in Brønsted acidity of SAPO and zeolitic
materials

BEA SAPO
Before CO Adsorption Before CO Adsorption
After CO Adsorption 280 cm-1
After CO Adsorption
Absorbance

Absorbance
.1
.4

322 cm-1

0
0
4000 3800 3600 3400 3200 3000 4000 3800 3600 3400 3200 3000
Wavenumber (cm-1) Wavenumber (cm-1)

35
 Solid State NMR

Si/Al ratio from 29Si NMR

36 Engelhardt and Michel (1987); Eckert (1991); Fyfe et al (1991)

 29SiNMR of SAPO-34: Effect of Sample
Preparation Conditions
Synthesis Route # 1 Synthesis Route # 2
x97x98_x97
x102x104x100_x102
Isolated Si Isolated Si
Si islands Route #2
has no Si islands
Sample D
Sample A

Sample B
Sample E
Sample C

-60 -80 -100 -120 -140

-60 -80 -100 -120 -140
29 29
Si Chemical shift (ppm from TMS) Si Chemical shift (ppm from TMS)

• Route #1 produce more silica islands than Route #2

• Silica islands result in lower acidity

37
 High Resolution TEM

• High resolution TEM powerful technique for

“visualizing” pore structure and any non-crystalline
material in zeolites.
• Can also be used for structure determination using
imaging and electron diffraction, e.g. determination
of structure of new UOP zeolite UZM-5.
- UZM-5: Rietveld refinement by XRD was not definitive due to
broadening of the peaks due to the morphology of the
zeolite (thin plates).

consists of thin plates, with c axis

⊥ to plates (broadening in XRD)

38
 High Resolution TEM

• Combination of high resolution imaging together

with electron diffraction.

simulated image
with overlay

[110] High-resolution image

showing surface termination

39
 Structure of UZM-5 (UZF)

“Chalice”

Ang. Chem. Int. Ed. (2003) 42, 1737

40
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol & natural gas
• Discovery to commercialization

41
 SAPO-34

• The particular molecular sieve of interest to the MTO

process is SAPO-34.
• This material is structurally analogous to, but
compositionally distinct, from the silico-aluminate
zeolite mineral chabazite (CHA).
• In chabazite all T sites are occupied by either Si4+ or
Al3+.
• In SAPO-34 Al and P atoms occupy alternately, and
some Si atoms occupy sites normally occupied by
P.

42
 SAPO-34 (CHA) Structure

• Three-dimensional pore system consisting of large cavities

(about 9.4Å in diameter) separated by small windows (3.8 x 3.8Å)
• Periodic building unit is the double 6-ring layer – connected
through 4-rings.

D6R 8-ring

SEM of SAPO-34 crystals

~1 μm

43
 Structural Characteristics of CHA Framework

• The CHA cage. 4-rings inaccessible

to most molecules
(door closed)

Cage bounded by 36 TO2

Dimensions: 7.5 x 8.2Å
Pore opening: 4.4 x 3.6A
Every TO2 shared by 3 cages

44
 SAPO vs. Zeolite Synthesis

Zeolite SAPO
Oxide Reactants Alumina Alumina
Silica Silica
H3PO4
Alkali hydroxide Common Almost never

Organic structure- Common Required

directing agent
pH Usually > 11 Usually < 9

Temperature 25 – 200°C 100 – 200°C

Time Hours – weeks Usually < 3 days

45
 Template Packing in SAPO-34

• >30 templates make SAPO CHA framework type.

- Most not well studied
- TEAOH is most common

N-Mebutylamine Morpholine Cyclam

46
 Calculating Acid Site Density of CHA Framework

• Elemental analysis of SAPO best expressed as mole

fraction:
- SixAlyPzO2 where x + y + z = 1.00
• Framework charge = [Al – P] = [Si] if Si is isolated

• Each cage bounded by 36 TO2

• Each TO2 is shared by 3 cages
• 1 acid site per cage = 0.03 Si

47
 Acid Site Location: Dehydrated D-SAPO-34

• Neutron diffraction used to locate the actual

position of the acid sites in CHA cage.

Protons attached to
O4 (4.0% occupancy)
More acidic
3630 cm-1
8-ring

Protons attached to
O2 (3.4% occupancy)
Less acidic
8-ring 3601 cm-1

L. Smith et al, Catal. Lett. 1996, 41, 13

48
 Discovery of ALPO and SAPO Materials

• In late 70’s Edith Flanigen’s group at Union Carbide

given the challenge:

“Discover the next generation of molecular

sieve materials”

• Words of Edith Flanigen ……

49
 Discovery of ALPO and SAPO Materials

• A commitment on part of management to support

long-range innovative discovery with no guarantee
for commercial success.
• Willingness to take that risk and to assign
significant resources to back up that commitment.
• Patience to allow major discoveries to find their
place in the commercial world.
• Creating an environment and culture that fostered
innovation and that attracted the best scientists and
challenged them to their limits.
• Allowing them freedom to dream, and trusting that
they would succeed.
• Recognizing and rewarding them when they did
succeed.
50
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol & natural gas
• Discovery to commercialization

51
 Methanol Conversion using Zeolites

• 1975 – Mobil Oil discloses ZSM-5 catalyst for conversion

of methanol to gasoline (MTG)

-H2O
2 CH3OH CH3-O-CH3
+H2O
-H2O
Isoparaffins
Aromatics C2 - C5 olefins
C6+ olefins

Chang, Silvestri, and Smith, US 3894103 and 3928483

52
 Methanol Conversion over Zeolites

• Several zeolites with Brønsted acid sites show

activity for methanol conversion.

Pore Size Examples Performance Performance

(low (high
conversion) conversion)
Small ERI Light olefins Paraffins
ERI/OFF
KFI
Medium MFI Olefins Paraffins
FER Aromatics
MTT
Large MOR Olefins
FAU Aromatics
Paraffins

G.F. Froment et al, Catalysis (London), 9, 1 (1992)

53
 Methanol to Hydrocarbons

CHA, SAPO-34

MTO

MTG

Methanol to Hydrocarbon Catalysis, J. F.Haw, et al., Acc. Chem. Res. 2003, 36, 317
54
 MTO Catalysts

• Medium-pore zeolites (ZSM-5)

- Major olefin product is Propylene
- Significant C5+/aromatics by-products
- Slow deactivation

• Small-pore molecular sieves (SAPO-34)

- Major olefin products are Ethylene and Propylene
- Fast deactivation by aromatic coke
- SAPO molecular sieves more stable than corresponding
zeolite structure

Shape Selectivity

55
 Structural Comparison

5.5 Ă
3.8 Ă

H H
O O
(Al-O)3Si Al(O-P)3 (Si/Al-O)3Si Al(O-Si)3

Small Pore Medium Pore

Weak Acid Sites Strong Acid Sites

56
 Small, Medium & Large Pore
• Small, medium and large pore SAPO’s show MTO activity – but
distinct selectivity differences.

SAPO-34 SAPO-11 SAPO-5

C7+ Small Medium Large

C6
C5
C2-C4=
C1-C4
CO

0 20 40 60 80 0 20 40 60 80 0 20 40 60 80
Wt% selectivity
350C, WHSV = 0.3 h-1,
57 MeOH = 0.02 bar, N2 = 0.98 bar S.M. Yang et al, Stud. Surf. Sci. Catal., 61, 429 (1991)
 SAPO-34 vs. SSZ-13

• SSZ-13 has same structure (CHA) as SAPO-34 but is

an aluminosilicate zeolite.
• Selectivity to olefins substantially less in SSZ-13.
Material SAPO-34 SSZ-13 SSZ-13 SSZ-13
(Chabazite) (Chabazite) (Chabazite)
T atom % 10% Si (gel) 18% Al 10% Al 3.3% Al
Selectivities (2 hr)
C2-C4 olefins 96 69 75 87
CH4 1.4 3.9
C2H6 0.3 5.4
C3H8 0.9 18.9
Stability
hr at >50% >40 6 13 7
conversion
Coking
carbon on 19% after 16.6% after 19.3% after 15.0% after
used catalyst 54 HOS 18 HOS 18 HOS 18 HOS

Yuen, et al., Microporous Materials, 2 (1994) 105

58
 Another Twist in the Story…….

• SAPO-34 has CHA topology. Related framework type

is AEI.
Structures depicted as layers of D6R

CHA AEI

Layers of a, a, a Alternating layers of b, a, b, a

59
 AEI and CHA

• Exxon and Hydro patents teach that intergrowth of

AEI and CHA topology are readily formed and are
also active in MTO.
AEI cage
AEI

CHA CHA cage

AEI
WO 02 70407 (2002); WO 98/15496
60 and US 6334994 (2002)
 AEI and CHA Intergrowths

%CHA
85
75
70
70
70
80
60
10

20

ExxonMobil PCT WO 02/070407

61
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol & natural gas
• Discovery to commercialization

62
 MTO Mechanism

• More than 20 proposed mechanisms during the past

30 years (Involving intermediates such as radicals,
carbenes, oxonium ions, carbocations)

H2O H2O Hydrogen transfers

Alkanes
2CH3OH CH3OCH3 Alkenes
Aromatics

• How can two or more C1-entities react so that C-C

bonds are formed?
• No simple β-hydride elimination so no
straightforward mechanism to olefins from
methanol.
• Don’t have time to go into great detail on some of
the elegant mechanistic work performed.
63
 Hydrocarbon Pool Mechanism

C2 H4
C3 H6
-nH2O
nCH3OH (CH2)n
saturated hydrocarbons
aromatics
C4 H8

• What is the identity of the hydrocarbon pool?

• How does it operate?

I.M. Dahl and S. Kolboe, J. Catal. 149 (1994) 329,

64 I.M. Dahl and S. Kolboe, J. Catal. 161 (1996) 304.

 Zeolite Beta as a Model System
• The beta zeolite is a wide pore zeolite allowing direct
introduction of rather large molecules.
• It is not interesting as a commercial catalyst for
MTO/MTH chemistry.
Model: Beta, BEA-topology
Cages = Windows

12-ring window, substituted

aromatic hydrocarbons can
enter. 7.7 x 6.6 Å
65
 Methanol over H-Beta at 400°C

Aliphatics Aromatics
Ethane/ethene

Isobutane
Propane/propene

Hexamethyl benzene
Methanol

Pentamethyl benzene
2-methyl-2-butane
Dimethylether

trans-2-butene

cis-2-butene
1/i-butene
n-butane
Methane

4 5 6 7 8 26 28
Retention time (minutes)

Hexamethylbenzene is a dominant gas phase product

Bjørgen, M. and Kolboe, S. Appl. Catal. A 2002, 225, 285-290.
Courtesy Unni Olsbye, Univ. Oslo
66
 Hydrocarbon Pool

Hydrocarbon
He Methanol
pool
Alkenes
H2O

H-zeolite

The olefin production goes on for several minutes after the

methanol feeding has been terminated

What is the active pool contained inside the zeolite?

Courtesy Unni Olsbye, Univ. Oslo

67
 Hydrocarbons Retained in Zeolite Pores

Analysis (GC-MS,
HRMS, NMR)

9 Analyzed ex-situ by:

9 Quenching the reaction (after a set time, few mins)
9 Dissolving the zeolite (15% HF)
9 Extracting the organic material from the water
phase
9 Trapped organic species are liberated and can be
analyzed Courtesy Unni Olsbye, Univ. Oslo
68
 Trapped Hydrocarbons

• Methanol reacted over the H-beta zeolite (GC-MS)

The trapped
Stability material
of the retainedis hydrocarbons
nearly exclusively composed
was probed of
by stopping the
Hexamethylbenzene is a dominant retained species
polymethylated
feed and flushingaromatics
the catalyst with carrier gas for 1 minute
Tetramethylbenzene

Hexamethylnaphthalene
Hexamethylbenzene
Pentamethylbenzene

Among the trapped

hydrocarbons, hexaMB
shows the fastest
decomposition

8 10 12 14 16 18 20
Retention time (minutes)
Courtesy Unni Olsbye, Univ. Oslo
69
 Hexamethylbenzene over H-Beta

• The same gas phase products as observed when

methanol was reacted
• The retained compounds were the same as those
obtained from methanol

13

Propane/propene
Ethane/ethene

Isobutane

2-methylbutane
12
Aliphatics

n-butane
11
Detector response (mV)

10

4 .0 4 .2 4 .4 4 .6 4 .8 5 .0 5 .2 5 .4 6 .4 6 .6
24

PentaMB
22
TetraMB

Aromatics

HexaMB
14
TriMB

12

10
19 20 21 22 23 24 25 28 29
R e te n tio n tim e (m in u te s )

Bjørgen, M.; Olsbye, U.; Kolboe, S. J. Catal. 2003, 215, 30-44.

70 Courtesy Unni Olsbye, Univ. Oslo

 Initial formation of HMB and heptaMP+

13
CH3
H313C 13
CH3
13 13
H3 C CH3 H313C 13
CH3
13 13
6 CH3OH CH3OH +
H-Zeolite
H-Zeolite H313C 13
CH3 H313C 13
CH3
13
CH3 13
CH3
6H2O H2O -
Zeolite

Hexamethylbenzene: Heptamethylbenzenium:
Six labelled atoms Seven labelled atoms

Hexamethylbenzene in zeolite pore can take up

another CH3 to form heptamethylbenzenium ion

M. Bjørgen, U. Olsbye, D. Petersen and S. Kolboe, J. Catal. (2004), 221, 1-10.

71
 Exocyclic Mechanism

• Deprotonation of heptaMB+
• Exocyclic double bond reacts with
incoming CH3OH resulting in ethyl group
on benzene ring
• Subsequent dealkylation to ethylene

• Essential intermediate in cycle is

formation of two gem-methyl groups
attached to benzene ring.
M. Bjørgen, U. Olsbye, D. Petersen and S.
72 Kolboe, J. Catal. (2004), 221, 1-10.
 Paring Mechanism
* *
Iso-butene
Alkyl side chain growth Zeolite *

by ring *
*
* *

contraction/expansion *
*
+ *
*
+ *

* *
Leads predominantly to *
* *
*
propylene and isobutene

*
Methanol *
* *
*
* + *

+ *
*
* * *
Leads to carbon atom * *

interchange between Propene

ring and substituents *
*
*
*
*
*
* *
+
*
* * *

M. Bjørgen, U. Olsbye, D. Petersen and S.

73 Kolboe, J. Catal. (2004), 221, 1-10.
 MTO Site – Organic-Inorganic Hybrid

74 Courtesy Unni Olsbye, Univ. Oslo

 SAPO-34

• SAPO-34 (CHA) has large cages connected with

small windows.
• Large aromatics are accumulated in these cages
during the reaction.
• An array of nanoreactors!

Courtesy Unni Olsbye, Univ. Oslo

75 (001) projection
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol & natural gas
• Discovery to commercialization

76
 Fixed Bed MTO Performance

• SAPO-34 catalyst highly active with good

selectivity then conversion drops rapidly.

100
C o n versio n /S electivity, %

80 Total
Olefins
Conversion
60
Ethylene

40
Propylene
20
Propane
0
Time
77
 Molecular View of Initial Deactivation

• Hexamethylbenzene in
CHA cage
• With increasing TOS
some methylbenzenes
age into
methylnaphthalenes.
• Further aging to
phenanthrene causes
loss of activity
• Largest ring system to
form in SAPO-34 is
pyrene.

Haw, Accts. Chem. Res. 36 (2003) 317

78
 MTO Reactor Design

• Fixed Bed Reactor

- rapid deactivation due to coke formation
- reactor would have to swing between process &
regeneration
- product composition varies with time
- expensive high-temperature valves required

• Fluidized-Bed Reactor
- transport reactor, internal catalyst circulation
- continuous movement of portion of used catalyst to
separate regenerator
- reduced catalyst inventory, increased capacity
- uniform product distribution with time

79
 Fluidized Bed Reactor

Fast Fluidized-Bed Regenerator

Product Offgas

MeOH Air

80
 Fluidized Bed Reactor Results

• Conversion and selectivity remain high over months

of operation.

Conversion
Conversion or Selectivity, %

100

80

60
Selectivity to C2=
40
Often in
20
catalysis some clever
Selectivitychemical
to C3= engineering
required to make the catalytic process commercially
0 viable.
0 10 20 30 40 50 60 70 80 90
Time on-stream, days

81
 UOP/HYDRO MTO Process Flow Scheme
• The catalytic reactor is only one small part of the overall
process!
Quench Caustic C2 C3
Reactor Regenerator Tower Wash De-
De-C2 De-
De-C1 Splitter De-
De-C3 Splitter De-
De-C4
Tail Gas

Regen Gas Ethylene

Propylene
Dryer
Mixed C4

DME
Recovery
C2H2
Reactor

C5+
Air Water
Propane

Methanol Ethane

82
 Olefin Cracking Technology

• Another piece of the process…..

• Production of propylene and ethylene from C4 to C8
olefins.

Catalyst
C4 to C8 Propylene
Olefin Cracking
Olefins & Ethylene
C4H8 to C8H16
−Δ T
C3H6 & C2H4

83
 Olefin Cracking integration with MTO

• Upgrade C4+ MTO product to C2= and C3=.

MeOH MTO C2= • 20% increase in light

olefin yields
Unit C3=
• Nearly 80% reduction in
C4-C5 Light C4+ by-products
Olefins Olefins
• Can achieve 2:1
propylene/ethylene
OCP product ratio
C4+
Unit

84
 MTO Reaction with Olefin Cracking

Ethylene
SAPO-34
Catalyst
Methanol Propylene
Δ

X
Butenes

Other By-Products
H2O
H2 , COX
C1-C5 Paraffins
C5+
Coke

85
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol & natural gas
• Discovery to commercialization

86
 Why Natural Gas Conversion?

• Large reserves of remote natural gas.

• Environmental need to minimize venting or flaring of
associated gas from oil fields.
• Existing technologies for methane conversion
limited by market size or marginal economics.

87
 World Natural Gas Reserves

Egypt
Canada Others
Netherlands
Kazakhstan
Uzbekistan Russia
Turkmenistan
Malaysia World Total =
Norway
Australia
Indonesia 179 x 1012
Iraq
Nigeria
Venezuela Cubic Meters
Algeria
United States
United Arab Iran
Emirates Saudi
Qatar Source Oil & Gas Journal 2003
Arabia

• Natural gas utilization is desired by many companies and nations

- Monetization of stranded gas reserves
- Reduced gas flaring
- Less dependence on crude oil
88
 Ethylene Supply & Demand

• Demand for ethylene predicted to increase: source

will have to come from new capacity.
2004 Supply (PG) 150,000
103 MM MTA
(steam crackers) 140,000
Gas Oil
6% d
130,000 an a ne
?
Naphtha Others em -E
th
D

kMTA
n
54% 2% No
120,000

Ethane e?
ha n
27% 110,000 Et

Butane Current Capacity

4% Propane 100,000
7%

10
04

06

08

12

14
20

20

20

20

20

20
“PG” = polymer-grade

89 Data Source: CMAI 2005

 Propylene Supply & Demand

• Propylene demand also predicted to rise.

100,000
2004 Supply
61 mm MTA
90,000

nd
a
Refinery 80,000 em

?
D

kMTA
70,000
Steam Steam Crackers, Refineries
Naphtha Dehydro PDH, Olefin Conversion, MTO
Cracker 60,000
Others
Current Capacity
50,000
04

06

08

10

12

14
20

20

20

20

20

20
90 Data Source: CMAI 2005
 Stranded Gas Monetization Processes

Production Liquefaction
Revapor- Natural
Shipping ization gas LNG

Hydrocarbon
synthesis Upgrading Liquid fuels GTL
Synthesis gas
production
Methanol Ethylene
synthesis MTO GTO
CO + H2 Propylene

Polyethylene
Polymers
Polypropylene
GTP

91
 Value of Products Produced from 1 MM BTU of
Natural Gas

12

10
Value of Products, $

0
Natural LNG Gasoline Methanol Olefins Polymers
Gas

Polymers are highest value product

92
 Large Gas Fields by Size

• Substantially more fields economically viable for

GTP technology than other technologies.

50 - 500 Tcf 15 86
Suitable
320
for
Size of Fields

5-50 Tcf Suitable

71 LNG & GTL
for
GTP
1 - 5 Tcf 234

0.5 - 1 Tcf 269

0 50 100 150 200 250 300

Number of Fields
Total = 589 Large Fields
93
1 Trillion cf = 28.2 BCM Source: Oil & Gas Journal
 Methanol to Olefins Process

• MTO process is new viable route to polymer grade

ethylene and propylene.
Natural Gas
Bio-Mass

Synthesis Methanol Ethylene &

Gas
Production
Methanol
Synthesis MTO Propylene

Coal
SAPO-34 Catalyst
HCHC
+H O CO→CO
+H + CH
H23OH
→ CH3OH → C2CH2H +C H
2+ H2O 2 4 4+ C33H6

94
 MTO Commercial Status

• MTO Demo Unit

- Started-up in 1995 at Norsk Hydro
facilities in Norway
- Used commercial methanol
feedstock
• UOP and Total Petrochemicals
announced in Dec 2005 an
integrated demonstration unit
consisting of both a
UOP/HYDRO Methanol-to-Olefins
unit and a Total
Petrochemicals/UOP Olefin
Cracking unit.
• Construction started at Total’s
petrochemical complex in Feluy,
Belgium. Start-up in 2008.
95
 Outline

• Zeolites
• Zeolites as industrial catalysts
• Acid sites in molecular sieves
• Aluminum phosphate (AlPO4) molecular sieves
• Characterization methods for molecular sieves
• SAPO-34
• Methanol conversion using zeolites
• Zeolites vs. SAPO’s in methanol conversion
• CHA and AEI
• MTO mechanism
• MTO reactor design
• Putting it all together: methanol
• Discovery to commercialization

96
 SAPO-34 vs UZM’s

• For SAPO-34 it took 20+ years from discovery of the

material to its use in a commercial process.
• In 1998 New Materials Group formed at UOP to
discover new zeolites.
• UZM-8 discovered in late 2000, patent issued 2004.
• Identified as a candidate for ethylbenzene
production.
C6H6 + C2H4 C6H5CH2CH3
benzene ethylene ethylbenzene
• Performance of UZM-8 allowed for the design of a
more economical process.
• New process with new catalyst for EB production
offered for sale in late 2006.
6 years to commercialization!
97
 Acknowledgements

• John Chen
• Paul Barger
• Steve Wilson
• Hayim Abreveya
• Edith Flanigen

• Wharton Sinkler
• Sue Wojnicki
• Emmanuelle Siler
• Sesh Prabhakar

• Prof. Unni Olsbye, University of Oslo.

98