CHE 410: Heterogeneous Catalysis Prepared by: K. Bjorkman, A. Korinda, N. Mashayekhi, D. Petrone, P. Ryan, C. Wilmer and W. C.

Wong Presented by: Chris Wilmer June 6, 2008

Methanol-to-olefin synthesis is a commercially valuable process, particularly because of the high-demand for propylene and ethylene. Today these compounds are created mainly through the non-catalytic cracking of naphtha under steam. The methanol-to-olefin (MTO) process, however, uses a novel molecular-sieve catalyst that efficiently converts methanol into propylene and ethylene. The molecular-sieve under consideration is silicon, aluminum, phosphate and oxygen based, and is hence called SAPO-34. Our literature review of the MTO process seeks to investigate: the mechanisms leading to the creation of large organic compounds inside the pores of the catalyst, the role of these organic compounds in the formation of propylene and ethylene, the discrepancy between observed product ratios of propylene and ethylene and corresponding thermodynamic predictions, and finally, the reactivity of the products under MTO conditions. We discovered that the large organic compounds are typically N-methyl-benzenes formed after a kinetic induction period, and only in the presence of impurities in the methanol feed. The successive methlyation of N-methyl-benzene is followed by de-ethylation and de-propylation to produce ethylene and propylene respectively; the more methyl substituted the benzene is, the higher the selectivity for propylene. Under typical reaction temperatures (~650 K), thermodynamics predicts that the ratio of propylene to ethylene is between 5-10, but experimentally the ratio is observed to be between 0.5 and 1. Feeding ethylene back into the catalyst lowers selectivity for ethylene, indicating that it can act as both a product and a reactant. The same holds true for propylene.

Brief Introduction
What is SAPO-34? What is the MTO reaction? What is interesting about this reaction?

Brief Introduction
What is SAPO-34?
It is a porous mineral
A crystalline silicon aluminum phosphate molecular sieve (zeolite is a crystalline aluminum silicate)

Brief Introduction
What is SAPO-34?
It is a porous mineral
A crystalline silicon aluminum phosphate molecular sieve (zeolite is a crystalline aluminum silicate)

The pores are 0.38nm across (about 3-4 atoms)

It has a chabazite framework (CHA). It is a 3dimensional 8-membered-ring molecular sieve. The cage size 0.63 nm

Brief Introduction
What is SAPO-34?
It is like aluminum-phosphate with some of the phosphorous (P+5) atoms substituted by silicon (S+4) atoms. Hydrogen (H+) are added to balance the framework charge.

Brief Introduction
What is SAPO-34?
It is like aluminum-phosphate with some of the phosphorous (P+5) atoms substituted by silicon (S+4) atoms. Hydrogen (H+) are added to balance the framework charge It is a catalyst for the methanol-to-olefin reaction

Brief Introduction
What is the methanol-to-olefin (MTO) reaction?
In general, it is the conversion of the alcohol, methanol, into a light alkene
for example:

2CH 3OH C2 H 4 + 2 H 2O 3CH 3OH C3 H 6 + 3H 2O

Brief Introduction
What is interesting about this reaction?
The cages allow for the trapping of organic molecules which act as organic reaction centers
that catalyze the reaction in cooperation with active sites over the surface of the catalyst. This is in contrast to more typical catalysis that merely involves active sites on the framework

Brief Introduction
What is interesting about this reaction?
The cages allow for the trapping of organic molecules which act as organic reaction centers
that catalyze the reaction in cooperation with active sites over the surface of the catalyst. This is in contrast to more typical catalysis that merely involves active sites on the framework

The reaction intermediates are long-lived (and this is not typical) to the extent that they can be characterized after being trapped in the catalyst

Presentation Outline
We are going to try to answer the following questions: How are the organic reaction centers formed? How are the reaction products, ethylene and propylene, formed? How does the observed ratio of propylene to ethylene compare to the thermodynamic prediction? Are the primary products, ethylene and propylene, reactive under MTO conditions?

Question One:
How are the organic reaction centers formed?

Light Olefins Are Made from Methylbenzenes as Feed over Zeolite Beta GC-MS of volatile products over Si/Al2
The yield of olefins and the selectivity to propylene increases with the number of methyl groups on benzene 38% of ethylene made by cofeeding 5 moles 13C-methanol: 1 mole 12C-hexamethylbenzene was 12C, indicating that HMB continued to be source of light olefins even in the presence of methanol
=75 Beta at 450C using various methylbenzenes as feed

44

54

104

204
18 21 24 25

15

Retention time (min)

J. Phys. Chem. B 106 (2002) 2294, Sassi

Methylbenzenes Are Suggested to be the Trapped Reaction Centers for MTO over SAPO-34
methanol methylmethoxy substituted aromatics

8 Si/100T, ~2 micron crystals

4 sec of reaction following 1st methanol pulse (0.053 g/g cat) at t=0 sec leads to 14% conversion

4 sec of reaction following 2nd methanol pulse (0.053 g/g cat) at t=360 sec leads to 100% conversion

CP/MAS NMR spectra of products retained in SAPO-34 after various reaction times, following each time, a pulse of methanol (0.053 g/g cat) at 673K

13C

GC analyses of volatile products formed after 1 and 2 pulses of methanol at 673K J. Am. Chem. Soc. 122 (2000) 10726, Song

The Induction Period during MTO

T=673o K Initial Pulse of unpurified solvent-grade MeOH 14% conversion

Second pulse after 6 minutes nearly 100% conversion with much greater product seen
Haw, J.; Marcus, D. Well-defined (supra)molecular structures in zeolite MTO catalysis. Top. In Cat. 34. (2005). 41-48.

Proposed Function of Organic Reaction Centers

3 C3H6 3 C3H8 3 CH3OH

3 C3H6

Input
Output C2H4 CH3OH

nCH3OH n=1 n=2

Schematic of how the organic 3H2O reaction center facilitates the reaction of methanol to ethylene or propylene Here, the organic reaction nH2O center is formed by the trimerization of propylene , however, organic reaction centers appear even when only methanol is fed to a fresh catalyst
Haw, J.; Marcus, D. Well-defined (supra)molecular UOP 4813C-34 structures in zeolite MTO catalysis. Top. In Cat. 34. (2005). 41-48.

H2O

Output C3H6

Formation of Organic Reaction Centers

Hypothetically, the organic reaction centers can be formed from: Organic impurities In the catalyst In the feed Or from methanol Once the initial organic reaction centers are formed, products can create more reaction centers (autocatalytic)

Organic Impurities in Catalyst

T=648o K

Methanol does not react with the rigorously calcined catalyst at typical operating temperatures. Gas chromatography with a rigorously calcined catalyst showed very little MTO conversion

Regularly calcined

Rigorously calcined

Haw, J.; Song, W.; Marcus, D.; Nicholas, J. The Mechanism of Methanol to Hydrocarbon Catalysis. Am. Chem. Soc. 36. (2003). 317-326.

The Feed Impurities mechanism

Concept
Organic impurities, that are very difficult to remove from a methanol feed, initiate the formation of organic reaction centers However, large hydrocarbons (such as benzene) cannot come directly from the impurities, because they would not enter the catalyst:

Aromatics, even benzene, cannot pass through the eightring windows that interconnect the cages of HSAPO-34, but must be prepared in place by ship-in-a-bottle routes from olefins or other precursors. - Sassi, 2002

The Feed Impurities mechanism

Possible Mechanism
Acetone, perhaps present as an impurity (ethanol has also been suggested), is converted to acetic acid inside the catalyst cage, and then to isobutylene.

Isobutylene is the first component to get stuck in the cage; it is too big. Isobutylene, and possibly 2-butene, trimerize and rearrange to form a heptamethylcyclopentenyl cation:

Question Two:
How are the reaction products, ethylene and propylene, formed?

Product Mechanism Comparison

Ethylene

E=26.4 kcal/mol E=20.8 kcal/mol

Propylene

E=22.5 kcal/mol E=10.8 kcal/mol

The more methyl branches exist on the benzene ring, the more energetically favorable is the detachment of an alkene fragment The number of methyl branches has a stronger influence on the reaction energies when forming propylene versus ethylene
Arstad, B., et. al. J. Am. Chem. Soc. (2004) 126: 2991-3001.

Product Mechanism Comparison

Ethylene
Few methyl groups on organic reaction center Reaction energy
20.8-26.4 kcal/mol

Propylene
Many methyl groups on organic reaction center Reaction energy
10.8-22.5 kcal/mol

Occurs over weak acid sites

Better selectivity with coking

Requires stronger acid sites Decreasing selectivity with coking Reduces strong acid sites Makes pores smaller Napthalenes rather than benzenes become ORCs

Arstad, B., et. al. J. Am. Chem. Soc. (2004) 126: 2991-3001. Haw, J. F., et. al. Acc. Chem. Res. (2003) 36: 317-326. Haw et. al. US Patent 2006.

How are the reaction products formed?

Meave avg. number of methyls per benzene
Increasing space velocity of methanol, increased Meave and decreased ethylene selectivity Increasing substituted number of methyls on benzene, Meave, increases selectivity towards propene Addition of water increased ethylene selectivity When benzenes approximately have 2 methyls, then transition occurs for making more propylene

Weiguo Song, Hui Fu, and James F. Haw, 2000 Supramolecular Origins of Product Selectivity for Methanol-to-Olefin Catalysis on HSAPO-34

How are the reaction products formed?

Fresh catalyst subjected to 13Cmethanol at 400C Methanol feed then cut off and products retained on the catalyst examined after various durations CP/MAS NMR spectra indicate number of methyl groups decrease with time (due to dealkylation)
13C

Examination of volatile products show increase in ethylene selectivity (higher ethylene with decreased ethyl groups is consistent with Beta)

Weiguo Song, Hui Fu, and James F. Haw, 2000 Supramolecular Origins of Product Selectivity for Methanol-to-Olefin Catalysis on HSAPO-34

Question Three:
How does the observed ratio of propylene to ethylene compare to the thermodynamic prediction?

How does the observed ratio of propylene to ethylene compare to the thermodynamic prediction?
Molar ratio of Ethylene/Propylene

2 C3H6 <-> 3 C2H4 H = 117 kJ/mol (Endothermic)

From experiment, SAPO-34 is more selective towards ethylene at elevated temperatures Both correlations increase ethylene content with increasing temperature because they are endothermic SAPO-34 has a higher molar ratio because of its selective characteristics described earlier

2.5

Experimental, SAPO-34, Wilson 1998 Thermodynamic Equilbrium

1.5

0.5

0
645 665 685 705 725

Temperature (K)

Question Four:
Are the primary products, ethylene and propylene, reactive under MTO conditions?

Product Reactivity
Ethylene in Feed Propylene in Feed

Time on Stream

10 hours

Time on Stream

10 hours

Selectivity for ethylene decreases with additional ethylene in the feed Indicates that ethylene is being consumed to form other products ethylene to propylene

Selectivity for propylene decreases with additional propylene in the feed Indicates that propylene is being consumed to form other products propylene to ethylene

Wu, X. Applied Catalysis A. (2001) 218: 241-250.

Acknowledgements
CHE-410 classmates
K. Bjorkman, A. Korinda, N. Mashayekhi, D. Petrone, P. Ryan, W. C. Wong

Prof. Hayim Abrevaya