Electronic Supplementary Materials

Modification of H-[B]-ZSM-5 zeolite for methanol to

propylene (MTP) conversion: investigation of extrusion and

steaming treatments on physico-chemical characteristics and

catalytic performance

Maryam Sadat Beheshtia, Mahdi Behzada,*, Javad Ahmadpourb, Hassan Arabic

aFaculty of chemistry, Semnan University, P.O. Box:19111-35131, Semnan, Iran

bDepartment of Chemical Engineering, Babol Noshirvani University of Technology,

P.O. Box: 47148-71167, Babol, Iran

cGroup of Polymerization catalyst, Faculty of Engineering, Iran Polymer and

Petrochemical Institute, P.O. Box: 13115-14977, Tehran, Iran

Corresponding author. E-mail addresses: mbehzad@semnan.ac.ir

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Catalytic performance tests

The reactor system was entirely placed in a temperature-controlled three-zone furnace,

so that, the feed could be preheated and the products could be avoided from

condensation. In a typical run, 4 g of catalyst (size 16-25 mesh) was loaded in the

middle section of the reactor tube and methanol-water mixture (mass ratio: 1) was

injected into the catalyst bed by a WellChrom HPLC K-120 pump to provide a

methanol weight hourly space velocity (WHSV) of 0.9 h-1. Prior to the catalytic activity

tests, the sample was activated in-situ, at a heating rate of 3 °C/min under N2 flow at

300 °C for 2 h. After that, the flow of nitrogen gas was stopped and then, mixture of

methanol and water, as the feed, was pumped from the feed tank to pre-heater and

performance tests were conducted at 480 °C and atmospheric pressure. The reaction

temperature was controlled and measured by a temperature controller and a K-type

thermocouple probe was placed very close to the catalyst bed inside the reactor. To

avoid any product condensation, the transfer line from the reactor outlet to the separator

vessel was externally heated and maintained at 120 °C. On-line analysis of gas phase

was performed by a micro gas chromatograph (Varian CP-4900) equipped with a TCD

detector, in which four channels were used to separate the products [(CH4, C2-C5

olefin/paraffin, DME, C6-cut) and (H2, CO and CO2)]. Separated aqueous part of the

liquid product was analyzed by gas chromatograph of Varian CP-3800 equipped with

FID and TCD detectors, in which a CP-Wax52CB column was used to separate the

component (methanol and water). The organic part was also analyzed with the gas

chromatograph of Varian CP-3800 equipped with a FID detector, in which a PIONA

column was used to separate the component (C6-C16 hydrocarbons).

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Fig. S1. Schematic flow diagram of the experimental setup for the catalytic activity tests.

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Fig. S2. TGA curve of the H-[B]-ZSM-5 powder as the dry sample (before calcination) at the heating rate of 10 oC/min.

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Fig. S3. FT-IR spectra of H-[B]-ZSM-5 zeolite powder (BZP), extrudes (BZE) and steam-treated extruded (BZEH) samples.

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BZP

BZE

BZEHFig. S4. Images of elemental analysis: Red dots (Si mapping) and blue dots (Al mapping).

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Fig. S5. Average products distributions of MTP reaction over the H-[B]-ZSM-5 powder, extrudes and steam-treated extruded samples.

(Reaction conditions: T = 480 °C, P = 1 atm, WHSV= 0.9 h-1, feed: 50 wt% methanol in water, compositions are averages over useful catalyst lifetime.)

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Fig. S6. TGA/DTA patterns (a), the coke content and coke distribution (b) and coke deposition rate (c) of the deactivated H-[B]-ZSM-5 catalysts for MTP reaction at different

reaction times. (Reaction conditions: T = 480 °C, P = 1 atm, WHSV= 0.9 h-1, feed: 50 wt% methanol in water.)

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Fig. S7. NH3-TPD profiles of the regenerated H-[B]-ZSM-5 zeolite powder, extruded and steam-extruded samples.

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