Conversion of C2 & C3 alkanes to aromatics

Starting points for discussion

•existing technology (UOP CyclarTM process)

•catalysts reported to be metal-containing zeolites

•substantial research reported for such conversions

•related issue topic covered yesterday:

methane conversion to aromatics
Thermodynamically, conversion of
propane to aromatics
less uphill than
methane to aromatics

reaction ΔG◦400 (kJ/mol)

6 CH4 → C6H6 + 9 H2 399

2 C3H8 → C6H6 + 5 H2 136

 REPORTED CATALYSTS

acidic zeolite (e.g., HZSM-5) or, better,

zeolite-supported metals such as Zn, Ga, Mo
(also used for methane conversion)
less than fully characterized
metals possibly present as carbides (or oxycarbides);
not in metallic state
both inside & outside zeolite pores
 CATALYSTS UNDERGO RAPID DEACTIVATION

• catalysts rapidly coked

• require frequent regeneration

• regeneration might contribute to

catalyst deactivation
 Feed propane
&/ or but ane

Light gas
product s

endot hermic

UOP Cyclar TM Process, developed by BP & UOP Sabic process operat ing in Saudi Arabia

Source: www.uop.com/ cyclar- process- produces- high- quality - aromatic- products

 SUGGESTED REACTION NETWORK

Numerous authors suggest dehydrogenation catalyzed by

metal-containing function (e.g., molybdenum carbide)—slow reaction—
& subsequent oligomerization & cyclization catalyzed by zeolite acidic sites

Source of figure: www.uop.com/cyclar-process-produces-high-quality -aromatic-products

 CyclarTM Process
Feed: propane and/or butane

Aromatic (benzene, toluene, xylenes) yields said to be 58-

60%

H2 product (may be ~5% yield)

Rapid catalyst deactivation requires

“continuous” regeneration,
moving bed reactors
(catalyst residence time presumably of days)

Catalyst lifetime said to be not short

Source: www.uop.com/ cyclar- process- produces- high- quality - aromatic- products

Possible opportunities for discovery of improved catalysts

Metal-containing molecular sieves

Active for reactions including (de)hydrogenation

large & growing class of catalytic materials

many structurally nonuniform & less than well characterized

Catalytic performance depends strongly on structure of

metal-containing species

Synthetic routes allow some tuning of structure & catalytic properties

less common routes include

organometallic synthesis
atomic layer deposition
Example: Catalysts made by ALD with
dimethyl zinc (among others)

Characterized by IR, NMR, XAS, TPR, …..

Reaction at atmospheric pressure, 823 K

Zinc species not simple (not molecular)

Are there good opportunities to make well-defined

species containing metals such as Zn, Ga, &/or Mo in
zeolites?
Single-site catalysts?
E. J. M. Hensen et al. ACS Catal. 2012, 2, 71.
 Candidate research directions
Vary
metal or combination of metals in molecular sieve

molecular sieve (& pore structure)

Attempt to tailor metal-containing catalytic sites

single sites on/in molecular sieve framework

multi-atom sites (clusters)

Understand chemistry of synthesis & catalysis

Relate catalytic activity, selectivity, stability to structure

(use theory, spectroscopy of functioning catalysts)

Deeper characterization of catalysts

Investigate co-feeds with methane

 Comparison process: Chevron AromaxTM

Feed: alkanes such as n-hexane, n-heptane

Products: aromatics such as benzene & toluene

Catalyst: Pt clusters in LTL zeolite with exchange ions

such as Ba2+ & promoters such as halides

This is naphtha reforming without the acidic function in the catalyst.