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Energy Procedia 75 (2015) 554 559

The 7th International Conference on Applied Energy ICAE2015

Gasoline production by dehydration of dimethyl ether with

NH4-ZSM-5 catalyst
Kuo-Chao Liang*, Feng-Mei Yeh, Cheng-Gang Wu, How-Ming Lee
Physics Division, Institute of Nuclear Energy Research, Atomic Energy Council
No. 1000, Wenhua Rd., Jiaan Village, Longtan Township,Taoyuan County 32546, Taiwan (R.O.C.)

Abstract

NH4-ZSM-5 is employed for converting dimethyl ether to gasoline (DTG) with the fixed-bed reactor. The lifetime of
the catalyst can be extended from 10 hours to 197 hours and the aromatic content can be decreased from 56.6 vol.%
to 30.2 vol.% as H-ZSM-5 replaced by NH4-ZSM-5 for DTG reaction at the experimental conditions of P = 1 atm, T
= 300 oC, and WHSV (Weight Hourly Space Velocity) = 6.5 h-1. The durability of NH4-ZSM-5 is performed by the
reaction (1 atm/300 oC/WHSV 6.5 h-1) - regeneration (air 0.5 lpm/570 oC/10 hrs) cycle test. The product distribution
of the DTG with the NH4-ZSM-5 undergone 6 times regeneration is similar to the fresh one. Moreover, the products
were analyzed by the in-line GC-MS. The product distribution is similar ether the sample from starting or the sample
from the 240 hours on stream running at the reaction conditions of P = 1 atm, T = 400 oC, and WHSV = 3.6 h-1.
2015
2015 The Authors.
The Authors. Published byPublished by isElsevier
Elsevier Ltd. This
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Ltd.
an open access article under the CC BY-NC-ND license

Selection
Peer-review and/or
under peer-review
responsibility underInnovation
of Applied Energy responsibility
Institute of ICAE
Keywords: dimethyl ether; gasoline; zeolite, ammonium

1. Introduction

Gasoline is essential for the transportation industry. Traditionally, gasoline is produced from petroleum.
In 1973, the beginning of the first energy crisis, interest in synthesis fuels drove the methanol-to-
hydrocarbon research. The most successful synthesized gasoline process is the methanol-to-gasoline
(MTG) process developed by ExxonMobil[1, 2]. A plant for a gasoline production of 14,500 bpd over a
H-ZSM-5 catalyst was started up in 1986. Due to the fall in crude oil prices, the gasoline synthesis
department of the plant was shutdown in 1997. Recently, the MTG is revived because the fluctuation of
cruel oil price and the peak oil issue.
DME is the first intermediate of MTG process. The process can be simplified if gasoline is synthesized
from DME. The Topse Integrated Gasoline Synthesis (TIGAS) process of Haldor Topse AS, based on

* Corresponding author. Tel.: +886-3-471-1400 EXT. 7553; fax: +886-3-471-5617.

E-mail address: garyliang@iner.gov.tw.

1876-6102 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Applied Energy Innovation Institute
doi:10.1016/j.egypro.2015.07.452
 Kuo-Chao Liang et al. / Energy Procedia 75 (2015) 554 559 555

DME as reactant and H-ZSM-5 as catalyst, was developed in 1980s. A new pilot plant integrated the
biomass gasification, the one-step DME synthesis, and the TIGAS gasoline production has been installed
and tested since 2013[3, 4].
The ZSM-5 catalyst is the key factor for MTG or DTG process. The catalyst lifetime and product
distribution were influenced by the acidity of ZSM-5 zeolite. For acidity modification, typical methods are
the alkali silicon removing[5, 6], the acid aluminum leaching[7], and the ion exchanging. Typical NH3-
TPD spectrum of the ZSM-5 is shown in Figure 1. The ammonium on the NH4-ZSM-5 can be desorbed
by the heat treatment. The amount of ammonium desorption was depended on heating rate and
temperature. Therefore, the concentration of the surface acid sites can be controlled by the temperature
programming method. In present work, an heat treatment was applied on the NH4-ZSM-5 catalyst. The
performance of the heat treated NH4-ZSM-5 for DTG reaction was tested with the fixed-bed reactor.

Fig. 1. NH3-TPD diagram of ZSM-5 (heating rate 10 oC/min).

Nomenclature

MTG methanol to gasoline

DME dimethyl ether
DTG dimethyl ether to gasoline
bpd barrels per day
TIGAS Topse Integrated Gasoline Synthesis
TPD temperature programming desorption
GC-MS gas chromatography-mass spectrometry
PONA paraffins, olefins, naphthenes, and aromatics
WHSV weight hourly space velocity
lpm liter per minute
556 Kuo-Chao Liang et al. / Energy Procedia 75 (2015) 554 559

2. Materials and methods

The schematic diagram of DTG system is depicted in Figure 2. The untreated NH4-ZSM-5 (Si/Al = 50)
was supplied by Zeolyst. The H-ZSM-5 was prepared by the high temperature calcination (1 atm/570
o
C/10 hrs) of NH4-ZSM-5. The 5 g catalyst was mixed with 5 g of silica and filled into the reactor. The
reactant was DME (96.5 vol.% DME balanced N2). The flow rate of reactant was controlled by MFC. The
reactant was preheated to 190 oC then introduced into the fixed-EHGUHDFWRU7KHUHDFWRU[PP
is made of SUS316L stainless steel tube. The temperature of the reactor was controlled by the furnace.
The product distribution was monitored by the in-line GC-MS system (Agilent, column: DB-1ms 0.25
PP  [  P 7KH OLTXLG SURGXFWV RLO DQG DTXHRXV SKDVH ZHUH FROOHFWHG E\ WKH GHFDQWHU DW URRP
temperature and the atmospheric pressure.

Fig. 2. Schematic diagram of the DTG system: (1) DME cylinder; (2) MFC, (3) preheater, (4) fixed-bed reactor, (5) furnace, (6) GC-
MS, and (7) decanter.

The gas phase products was vented directly. The oil phase was separated then analyzed with the
ASTM D6730 detailed hydrocarbon (PONA) method. The DTG reaction was stopped as the
DFFXPXODWLRQUDWHRIDTXHRXVSKDVHOHVVWKDQPOG. The reactor was purged by N2 with the flow rate of
1 lpm and the period of 10 minutes. The deposited coke is removed by the regeneration procedure (air 0.5
lpm/1 atm/570 oC/10 hrs) then the activity of the catalyst will be restored. The lifetime of the catalyst was
defined as the time passed between the reaction start and the moment of the DME signal shown at the
spectrum of GC-MS. Moreover, the treated NH4-ZSM-5 was obtained by heat treatment (1.2 atm/570
o
C/10 hrs) of the catalyst placed in the closed DTG reactor.

3. Results and discussion

Figure 3 shows the lifetime of the DTG reaction with the catalyst of treated NH4-ZSM-5, untreated
NH4-ZSM-5, and H-ZSM-5 respectively. The lifetime of H-ZSM-5 was around 10 hours at the reaction
conditions of P = 1 atm, T = 300 oC, and WHSV = 6.5 h-1. There was no any DTG product as the
untreated NH4-ZSM-5 employed. However, the lifetime was extended to 197 hours as the treated NH4-
ZSM-5 used. The results of the PONA analysis for oil phase products were illustrated in Figure 4. The
aromatic content was reduced from 56.2 vol.% to 30.2 vol.% as the H-ZSM-5 replaced by the treated
NH4-ZSM-5. The acidity of the catalyst is the key factor for DTG reaction. The acidic sites on ZSM-5
occupied by ammonium were inactive. According to the methanol-to-hydrocarbon reaction path[2, 8], the
first step of MTG (or DTG) was methanol/DME converted to light olefins then the light olefins reacted to
form paraffins, heavy olefins, naphthenes, and aromatics. The reactivity of the catalyst was inversely
 Kuo-Chao Liang et al. / Energy Procedia 75 (2015) 554 559 557

proportional to the amount of adsorbed ammonium. Therefore, the yield of aromatics were decreased as
NH4-ZSM-5 employed.

Fig. 3. The catalytic lifetime of DME dehydration with NH4-ZSM-5 or H-ZSM-5 at the reaction conditions of T = 300oC, P = 1
atm, and WHSV = 6.5 h-1. The catalyst treatment: (a) NH4-ZSM-5 heat treatment h in the fixed-bed reactor with 570 oC/10 h, (b)
NH4-ZSM-5 untreated, and (3) H-ZSM-5.

The durability of the catalyst was carried out with the reaction-regeneration cycle test. The conditions
of the reaction and the regeneration were listed in Table 1.
Table 1.Conditions for reaction and regeneration

reaction regeneration
reactant DME air
reation time - 10 hrs
WHSV (h-1) 6.5 -
flow rate (lpm) - 0.5
pressure (atm) 1 1
temperature (oC) 300 570

Fig. 4. The PONA analysis of DME dehydration with NH4-ZSM-5 or H-ZSM-5catalysts at the reaction conditions of T = 300oC, P
= 1 atm, and WHSV = 6.5 h-1. (P: paraffins, I: iso-paraffins, O: olefins, N: naphthenes, A: aromatics, U: unknown)
558 Kuo-Chao Liang et al. / Energy Procedia 75 (2015) 554 559

The product distribution analyzed by the in-line GC-MS was shown in Figure 5. After 120 hours of on
stream running, the total ion current spectra of DTG with the catalyst of the fresh, 3rd regeneration, and
6th regeneration were taken respectively. There was no significantly difference. The results indicated the
characteristics of NH4-ZSM-5 were unchanged even undergone 6 times of the high temperature coke
burning process.
The thermal stability of NH4-ZSM-5 was tested under the reaction conditions of T = 400 oC, P = 1 atm,
and WHSV = 3.6 h-1. The GC-MS data DQG WKH DSSHDUDQFH RI RLO SKDVH OLTXLGV show in Figure 6. The
results indicated the characteristics of the NH4-ZSM-5 catalyst was changed insignificantly after 240
hours on stream reaction. Therefore, the heat treated NH4-ZSM-5 can work well under the high
temperature DTG environment.

Fig. 5. The PONA analysis of DME dehydration with NH4-ZSM-5 or H-ZSM-5 at the reaction conditions of T = 300oC, P = 1 atm,
WHSV = 6.5 h-1, and on stream times = 120 hrs. The regeneration: (a) fresh, (b) 3 times, and (c) 6 times.

Fig. 6. The GC-MS spectrum and the pictures of oil phase OLTXLG from the DME dehydration with NH4-ZSM-5 catalyst at the
reaction conditions of T = 400 oC, P = 1 atm, and WHSV = 3.6 h-1. On stream time of catalysts: (a) 24 hrs and (b) 240 hrs.
 Kuo-Chao Liang et al. / Energy Procedia 75 (2015) 554 559 559

4. Conclusion

NH4-ZSM-5 activated by in-line desorption of ammonia is suitable for DTG process. The lifetime of
the catalyst can be extended from 10 hours to 197 hours. 7KHDURPDWLFFRQWHQWRIWKHRLOSKDVHOLTXLGLV
reduced from 56.2 vol.% to 30.2 vol.%. The stability of NH4-ZSM-5 is good either reaction-regeneration
cycle test or high temperature longtime reaction. However, the future study is needed to clarify the
relationship among the acidity, selectivity, reactivity, and ammonia desorption.

Acknowledgements

The authors acknowledge the financial support of the Ministry of Science and Technology, Taiwan,
ROC, in this work (Grant No. MOST 103-3111-Y-042A-047).

References

[1] Liederman D, Jacob SM, Voltz SE, Wise JJ. Process Variable Effects in the Conversion of Methanol to Gasoline in a Fluid
Bed Reactor. Ind Eng Chern Process Des Dev. 1978;17:340-6.
[2] Stocker M. Methanol-to-hydrocarbons: catalytic materials and their behavior. Microporous and Mesoporous Materials.
1999;29:3-48.
[3] Keil FJ. Methanol-to-hydrocarbons: process technology. Microporous and Mesoporous Materials. 1999;29:49-66.
[4] Olsbye U, Svelle S, Bjorgen M, Beato P, Janssens TVW, Joensen F, et al. Conversion of Methanol to Hydrocarbons: How
Zeolite Cavity and Pore Size Controls Product Selectivity. Angewandte Chemie-International Edition. 2012;51:5810-31.
[5] Bjorgen M, Joensen F, Holm MS, Olsbye U, Lillerud KP, Svelle S. Methanol to gasoline over zeolite H-ZSM-5: Improved
catalyst performance by treatment with NaOH. Applied Catalysis a-General. 2008;345:43-50.
[6] Su L, Liu L, Zhuang J, Wang H, Li Y, Shen W, et al. Creating mesopores in ZSM-5 zeolite by alkali treatment: a new way to
enhance the catalytic performance of methane dehydroaromatization on Mo/HZSM-5 catalysts. Catalysis Letters. 2003;91:115-27.
[7] van Donk S, Janssen AH, Bitter JH, de Jong KP. Generation, characterization, and impact of mesopores in zeolite catalysts.
Catalysis Reviews-Science and Engineering. 2003;45:297-319.
>@ /DFDUULHUH $ /XFN ) ZLHUF]\VNL ' )DMXOD ) +XOHD 9. Methanol to hydrocarbons over zeolites with MWW topology:
Effect of zeolite texture and acidity. Applied Catalysis A: General. 2011;402:208-17.

Biography
Dr. Liang has more than twenty years of research and product development experience in plasma-
assisted chemical vapor deposition, plasma etching, and plasma cleaning. He also works on the
renewable energy area and focus on the biomass-to-OLTXLGSURFHVV