Supporting Information

Conversion of dimethyl ether to olefins over nanosized mordenite fabricated

by a combined high-energy ball milling with recrystallization

Teguh Kurniawan1, Oki Muraza1*, Koji Miyake2, Abbas S. Hakeem1, Yuichiro Hirota2, Adnan
M. Al-Amer1*, Norikazu Nishiyama2

1
Center of Research Excellence in Nanotechnology and Chemical Engineering Department King
Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
2
Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University,
1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan

*Corresponding author
*E-mail: alamer@kfupm.edu.sa; omuraza@kfupm.edu.sa

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 The material presented in the Supporting Information of the manuscript: Highlight of zeolite 1D

performance on olefinic target from dimethyl ether (DME)/methanol feed. XRF analysis of

natural zeolite as received. Milling operational cost calculation. Recrystallization cost

calculation. This material is available free of charge via the Internet at http://pubs.acs.org.

Table S1 summarizes the performance of various modified one-dimensional (1D) zeolites for

dimethyl ether/methanol to olefin reaction from the open literature. The catalysts activity over

the dealuminated 1D mordenite was reported relatively low as compared with the others 1D

zeolite.

Table S1. Highlight of zeolite 1D performance on olefinic target from dimethyl ether

(DME)/methanol feed

Zeolite Feed Conversion Olefinsa P/Eb TOSc T WHSV Ref.

[%] selectivity [-] [min] [K] [h-1]

[%]
1
Dealuminated DME 16.9 33 0.7 5 623 1.18

Mordenite (3M-6h) (6.3) (0) (-) (60) (623) (1.18)

2
Desilicated EU-1 DME 17 19 3.3 5 623 1.18

(0.25 M) (3) (0) (-) (60) (623) (1.18)

3
Desilicated- DME 48 36 2.1 5 623 1.18

dealuminated EU-1
4
Milled-alkaline-acid Methanol 100 42 7.4 5 673 2

treated-ZSM-22 (90) (18) (8) (500) (673) (2)

a
(ethylene + propylene). bratio propylene to ethylene
c
Time on stream. The numbers inside the bracket are data of different time on stream.

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Table S2 shows the oxide and elemental composition of natural zeolites as-received by XRF

analysis. The natural zeolites contain high silicon to aluminum ratio ca. 6. Some metal

impurities were also detected such as iron oxide, titanium oxide and phosphorus oxide.

Table S2. XRF analysis of natural zeolite as received

Oxide form % Elemental %

Al2O3 6.61 Al 3.50

SiO2 44.38 Si 20.74

P2O5 0.62 P 0.27

K2O 0.99 K 0.83

CaO 3.44 Ca 2.46

TiO2 0.35 Ti 0.21

Fe2O3 1.99 Fe 1.39

Table S3 & S4 show the economic evaluation of high-energy ball milling and recrystallization

process. The price of natural zeolite as received was only ca. $ 0.3 per kg (USD) which we

obtained from a company in Indonesia. From the literature survey, we find the synthetic zeolite
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price was $ 247 /kg for commercial scale in the industry. The laboratory grade of synthetic
6 7
mordenite was more expensive such as $ 558 in sodium form and 720 $ /kg in the

ammonium form. The ball milling is an efficient unit operation which is widely practiced in the

industrial process. The recrystallization process was a very fast hydrothermal process with 2 h

only as compared with the synthetic MOR with 48 h of hydrothermal treatment. Moreover, there

is no need for OSDA (organic solvent directing agent) and alumina in the recrystallization

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process which will cut the chemical cost as compared with the synthetic mordenite preparation.

In addition, the OSDA free of the recrystallization process is environmentally friendly. From our

laboratory scale calculation (Table S3 and S4), the ball milling operation cost was ca. $ 2.9 per

kg and the recrystallization step cost was ca. $ 3.8 per kg. Hence, the recrystallized-milled

mordenite derived from natural zeolites was ca. $ 7.0 per kg which is still far cheaper than the

synthetic one (ca. $ 247 to 720/kg).

Table S3. Milling operational cost calculation

Sample Power Time Total power Power cost Total power cost Power cost per kg
(kg) (kW) (h) (kWh) (USD/kWh) (USD) (USD/kg)
0.2 0.6 8 4.8 0.12 0.576 2.9

Table S4. Recrystallization cost calculation

Chemical Mass required Price Total Cost per kg sample
Sample (kg) (kg) (USD/kg) (USD) (USD/kg)
0.005 Silica gel 0.00347 5 0.01735 3.5
NaOH 0.00154 1 0.00154 0.3

References

(1) Nasser, G.; Kurniawan, T.; Miyake, K.; Galadima, A.; Hirota, Y.; Nishiyama, N.; Muraza,
O., Dimethyl ether to olefins over dealuminated mordenite (MOR) zeolites derived from natural
minerals. J. Nat. Gas Sci. Eng. 2016, 28, 566-571.
(2) Ahmed, M. H. M.; Muraza, O.; Al Amer, A. M.; Sugiura, Y.; Nishiyama, N., Development
of desilicated EU-1 zeolite and its application in conversion of dimethyl ether to olefins.
Microporous Mesoporous Mater. 2015, 207, 9-16.
(3) Ahmed, M. H. M.; Muraza, O.; Al-Amer, A. M.; Miyake, K.; Nishiyama, N., Development
of hierarchical EU-1 zeolite by sequential alkaline and acid treatments for selective dimethyl
ether to propylene (DTP). Appl. Catal., A 2015, 497, 127-134.
(4) Wang, J.; Xu, S.; Li, J.; Zhi, Y.; Zhang, M.; He, Y.; Wei, Y.; Guo, X.; Liu, Z., An approach
to prepare nanosized HZSM-22 with enhanced lifetime in the methanol to hydrocarbon (MTH)
reaction. RSC Adv. 2015, 5, 88928-88935.
(5) Shemfe, M.; Gu, S.; Fidalgo, B., Techno-economic analysis of biofuel production via bio-oil
zeolite upgrading: An evaluation of two catalyst regeneration systems. Biomass Bioenergy 2017,
98, 182-193.
(6) https://us.vwr.com/store/product/9881375/zeolite-mordenite-sodium.
(7) https://www.alfa.com/en/catalog/045877/.

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