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DME: Multi-Source, Multi-Purpose Clean Fuel

Article · July 2014

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 DME: Multi-Source, Multi-Purpose Clean Fuel
Dr. C. Samanta Dr. R. K. Voolapalli
Manager Chief Manager
(R&D) BPCL (R&D) BPCL
E
nergy security through sustainable
development is the vision 2030 for India and
the government is promoting cleaner fuels
to curb polluting emissions from transportation. At
present, transportation fuels are primarily produced
from crude oil, with alternative sources viz. natural
gas, coal and biomass having only a small market
share. This trend is going to change, since crude oil
is not an infinite resource. In this context,
development of an alternative energy basket based
on unconventional and renewable energy is one of
the key research and development areas.Along with
bio-ethanol and biodiesel, OME (oxymethylene
ether) is also gaining importance as an alternative
synthetic fuel.
What is DME? Dimethyl ether (DME), also known
as methoxymethane, with the formula CH3-O-CH3
is the simplest OME with no C-C bond. It is a
colourless gas and a useful precursor to other
organic compounds and an aerosol propellant. DME
is easy to liquefy and transport and it has remarkable
potential for use as an automotive fuel, for electric
power generation, and in domestic applications
Fig 1: DME: A multipurpose fuel
Dr. Ankur Bordoloi Dr. M.O. Garg
Scientist Director
IIP, Dehradun IIP, Dehradun
such as heating and cooking and as a chemical and
chemical intermediate (Fig 1.)
Why DME?: DME can be derived from many
sources, including renewable materials (biomass,
including municipal waste and waste from paper and
pulp mills, wood, or agricultural products) and from
fossil fuels (natural gas and coal).Thus, DME
production offers greater flexibility w.r.t feedstock
(Fig 2). In terms of properties, like LPG, DME is gas
at normal temperature and pressure, but changes
to a liquid when subjected to modest pressure or
cooling. This easy liquefaction makes DME easy to
transport and store. This and other properties,
including a high oxygen content, lack of sulfur or
other noxious compounds, and ultra clean
combustion make DME a versatile and promising
solution in the mixture of clean renewable and low-
carbon fuels under consideration worldwide. The
comparative properties of DME with other commonly
used fuels are given in Table 1. DME is also a
promising diesel alternative because of its clean
burning properties (Fig.3).
 Table 1: Comparison among the properties of DME and other fuels

Properties DME Propane n-Butane Methane Methanol Diesel

Net calorific value 6,900 11,100 10,930 12,000 4,800 10,000
(kcal/kg)
Net calorific value 4,620 5,440 6,230 5,040 3,790 8,400
(kcal/l)
Net calorific value 14,200 21,800 28,300 8,600 n.a n.a
(kcal/Nm3)
Explosion limit (%) 3.4~ 17 2.1~9.4 1.9~8.4 5~15 5.5~36 0.6~6.5
Cetane number 55~ 60 5 10 0 5 40~55
Viscosity 0.12~ 0.15 0.2 0.2 - 0.7 2~4
(Kg/m3 at 25°C)
Liquid density 0.67 0.49 0.57 0.42 0.79 0.84
(Kg/m3 at 25°C)
Boiling pt (°C) -25 -42 -0.5 -162 65 180~370

Fig 2: DME can be produced from multiple feedstock through direct and indirect syn-gas conversion routes

Synthesis of DME
Two processes have been claimed so far ‘Indirect DME synthesis’ and ‘Direct DME synthesis’
for the production of DME known as (Fig 2).

Fig 3: DME a promising fuel alterative for diesel engines.

 Indirect DME synthesis
The indirect synthesis is a well-established process
and several plants are operating worldwide. Haldor
Topsoe, Lurgi, Mitsubishi Gas Chemical, Udhe, Total,
ICI, Shell have developed their proprietary
technology for DME production though indirect
process.
The indirect DME synthesis reaction from syn-gas
consists of three main reactions: (1) the methanol
synthesis reaction, (2) methanol dehydration and
finally (3) the water gas shift reaction. Indirect
process of DME synthesis employs two different
catalysts and two separate reactors for reaction
i and ii. On the other hand, direct conversion process
could be carried out using a single catalyst for
carrying out reaction i and ii and/or reaction iii
simultaneously. In both the processes reaction iv
takes place as a side reaction.
Copper based catalyst promoted with ZnO, Al2O3
and various other rare earth oxides is commercially
used for methanol production from syn-gas via
reaction (i). Copper based catalyst also inherently
possesses water gas shift activity (reaction iv) which
generates CO2 within the system. The CO2 so formed
can also react with H2 to form methanol as per
reaction (reaction vi).

(i) 2 CO + 4 H2 ! 2 CH3OH G0 = -58.0 kJ/mol, H0 = -182.2 kJ/mol

(ii) 2 CH3OH ! CH3OCH3 + H2 O G0 = -4.5 kJ/mol, H0 = -23.5 kJ/mol

This leads to following global reaction (iii).

(iii) 2CO + 4H2 ! CH3OCH3 + H2O G0 = -62.5 kJ/mol, H0 = -205.7 kJ/mol

In case the water gas shift reaction (4) supported by the catalyst

(iv) CO + H2O ! CO2 + H2 G0 = -28.6kJ/mol, H0 = -41.2 kJ/mol

A new global reaction result (v) as

(v) 3CO + 3H2 ! CH3OCH3 + CO2 G0 = -91.10 kJ/mol, H0 = -246.6 kJ/mol

(vi) CO2 + 3H2 ! CH3OH + H2O H0 = -50.1 kJ/mol

Methanol Synthesis
Commercial Reactors used for methanol
Operating conditions synthesis
Catalyst: CuO (60-70%)-ZnO (20-30%)-Al2O3 Several types of methanol reactor have been
(5-15%) or Cr2O3 (5-15%) developed by leading methanol producers, some
Temperature: 220-300 0C of these include

Pressure: 50-100 Atm ( 5-10MPa)
Composition of the feed : 59-74 H2, 15-27%
CO, 8% CO2, 3 % CH4,
Conversion of CO to methanol per pass is
normally : 16-40%
H2 : CO ratio : 2.17
The selectivity to methanol: ~99.8%.
Under normal commercial operating conditions,
CuO/ZnO/Al2O3 methanol catalysts have quite long
lifetimes, up to 2-5 years.
ICI adiabatic single bed reactor: the heat of
reaction is removed by adding cold reagent at
different heights in the bed.
Haldor Topse adiabatic reactors: arranged in
series intermediate cooler remove hear of
reaction.
Lurgi two multitubular reactor: the heat of
reaction is removed in the first reactor by boiling
water around bed in the second reactor by gas.
Air product-Chem System three phase
fluidized bed: reactor an inert hydrocarbon
liquid inside the reactor remove the heat.
 Casale isothermal reactor: the heat is removed
by plates immersed in the catalysts.
Methanol dehydration to DME
Operating conditions
Reactor: Tubular fixed bed reactor
Temperature: 200-250 0 C and the outlet is
300-350 0C
Pressure: 1.0-2.0 MPa
Catalyst: Haldor Topsoe's state-of-the-art methanol-
to-DME synthesis catalyst (DME-99) is three lobes
shape activated alumina. The operating range for
methanol dehydration is 250-400 0C. The other
methanol-to-DME catalyst is manufactured by
SudChemie, Germany. The catalyst is delivered in
pellet form and has the chemical composition-
Al2O3. The feed methanol is fed to a DME reactor
after vaporization. Methanol one pass conversion
to DME is 70-85% in the reactor. Lurgi offers
technology for the production of DME via their
MegaDME process.
Direct DME synthesis:
Challenges and Opportunities
While most of DME is currently produced by the
indirect method, it can also be produced through
direct synthesis using a dual-catalyst system which
permits both methanol synthesis and dehydration
Fig 4: Scopus search data on publications with key words in topics “Direct DME Synthesis”, vs Years.
in the same process unit, with no intermediate
methanol separation. There is significant scope in
improving overall process efficiency by overcoming
equilibrium limitation of methanol formation by
converting the methanol to DME within the catalyst
pores and thereby increasing the overall per pass
conversion.The direct DME synthesis eliminates the
intermediate methanol synthesis stage and the
licensors claim promises efficiency advantages and
cost benefits.
A Scopus search has been made on the topic direct
DME synthesis (Fig 4) which shows a steady
increase in the number of publications on the topic
in recent times, revealing the renewed interest on
the direct DME synthesis. Although direct DME
synthesis offers attractive advantages over its
indirect counterpart, the direct process has inherent
challenges associated with integrating two different
types of catalytic reactions in a single reactor unit.
For example, syngas conversion to methanol
requires high pressure (more than 3 MPa) and high
temperature and is limited by equilibrium. On the
other hand, methanol dehydration to DME occurs
at low pressure and temperature depending upon
the solid acid catalyst. In addition, an active and
selective catalyst is required that will not break C-O
bond since C-O bond cleavage will lead to methane
and other hydrocarbon formation. Development of
a highly active and selective bi-functional catalyst
possesses significant challenges in the direct DME
synthesis.
JFE, Haldor Topsoe and KOGAS have emerged as
leading players of direct synthesis of DME using bi-
functional catalyst. However, these technologies are
Fig 5: Schematic overview of direct DME synthesis from syngas (source JFE)
Global Scenario of DME
China is by far the world's largest consumer of DME,
accounting for about 90% of global consumption.
In China, DME made from coal is used for residential
heating and cooking as well as for industrial uses.
The city of Shanghai recently announced plans for
a pilot program to burn DME in test fleets of buses,
taxis and commercial trucks in a bid to reduce
particulate emissions while also reducing
dependence on oil imports. Some of the prominent
Chinese companies active in DME include China
Energy Ltd, ENN Energy Holdings Ltd. Ningxia Coal
Group etc.
Aiming to promote the wide-spread of DME fuel, nine
Japanese companies; Mitsubishi Gas Chemical,
ITOCHU, JAPEX, Taiyo Oil, Total Di-Methyl Japan,
Toyota Tsusho, JGC, Mitsubishi Heavy Industries and
Mitsubishi Chemical, established a joint venture
company “Fuel DME Production Co. Ltd.” to
produce annually 80,000 tons of DME (potential
expansion up to 100,000 tons). The DME production
plant was constructed in Niigata factory of Mitsubishi
Gas Chemical, and started the operation in August,
2008 (source: Japan DME association (JDA).
The world’s first bioDME demonstration plant in
Piteå, Sweden (operating since 2010), is the only
gasification plant worldwide producing high-quality
synthesis gas based on 100% renewable
yet at the pilot stage and there is no commercial
scale syn-gas to DME plant. A schematic diagram
of direct DME synthesis process is shown in Fig. 5.
feedstocks. The raw material used is black liquor, a
high-energy residual product of chemical paper and
pulp manufacture which is usually burnt to recover
the spent sulphur.
In February 2014, ASTM International, a globally
recognized organization that develops
technical standards, released a specification for
DME as a fuel. ASTM D7901 provides guidance for
fuel producers, engine and component suppliers,
and infrastructure developers on DME purity, testing,
safety, and handling.
Recently the California-based Oberon Fuels Inc. has
received EPA’s approval of biogas-based DMEunder
renewable fuel standard. The EPA determined that
biogas-based DMEproduced from the Oberon
process resulted in an approximate 68% reduction
in greenhouse gases when compared to baseline
diesel fuel. This is one of the latest milestones for
the growing DME industry. Oberon makes DME and
methanol from methane and carbon dioxide using
its proprietary skid-mounted, small-scale production
units. The small-scale process avoids financial,
infrastructure, and regulatory challenges that large-
scale projects confront. In 2013, Oberon Fuels' pilot
plant in Brawley, California produced the first fuel-
grade DME in North America, which is currently
being used by Volvo Trucks. Auto manufacturers
Shanghai Diesel Co, AB Volvo, Isuzu Trucks, and
Nissan Diesel are actively developingDME fuelled
heavy duty vehicles.
Recent R&D Activities on DME in India
Realizing the importance of DME as one of the
promising future fuels, a consortium of Indian and
Australian research institutes has been formed to
develop a small scale DME production technology.
A project proposal by the consortium of Indian and
Australian Institution(s), “Mini DME: A custom
designed solution to bring stranded gas to the
energy markets”, was shortlisted for funding under
“Grand challenge” fund by Australia-India Strategic
Research Fund (AISRF). AISRF is a platform for
bilateral collaboration in science, jointly managed
and funded by the Governments of India and
Australia. The “Grand Challenge” Fund is jointly
managed by Australia's Department of Industry,
Innovation, Science, Research and Tertiary
Education (DIISRTE) and India's Department of
Science and Technology (DST). The Fund is
designed to support collaborative projects that
address a problem considered by both countries to
be significant enough to be characterised as a
‘grand challenge’.
Both Australia and India have abundant reserves of
NG. However, many of these reserves are in remote
locations and are hence difficult to bring to market
and are currently considered to be sub-economic.
In India NG reserves are located in the hilly areas of
Tripura and the deserts of Rajasthan (Gotaro mines),
while NG associated with oil production is produced
on the offshore platforms of Bombay High. Much of
the associated gas is partly flared, both wasting a
valuable resource and releasing CO2, a greenhouse
gas, into the atmosphere. In Australia remote NG
reserves are located both on- and offshore in inland
parts of Queensland and north Western Australia,
respectively. For large reserves liquefaction and
cryogenic transport are feasible, but for smaller
reserves this approach is more challenging.
Consequently many small reserves located in
remote regions are effectively stranded from
markets. An attractive solution for the
commercialization of such stranded reserves, and
for the productive utilization of associated NG, is
the conversion of the NG into a more easily
transportable, higher value product. For the reasons
outlined above, in Australia and India the conversion
to DME is particularly attractive.
The mini DME project involves partners from
Australia consists of CSIRO, RMIT University and
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University of Melbourne, while Indian partners
include IIP Dehradun, IIT Roorkee and BPCL
(CRDC). BPCL is the sole industrial partner in the
project. Apart of investigating various syn-gas
generation and syn-gas conversion technology
integration options, the main projectobjective is the
development of mini DME prototype, which would
be skid mounted to convert natural gas to DME.
A research proposal entitled “Development of
catalyst and process studies for direct synthesis of
dimethyl ether from syn-gas” had also been awarded
in 2012 by Petrotech Society of India in which a
student is pursing Ph.D.
Summary
DME is emerging as an alternative renewable fuel
and has potential to replace crude oil derived fuels
viz. diesel and LPG. Since DME can be produced
from a variety of locally available feedstock DME
production is not dependent upon the price of crude
oil which will help in offering its competitive price
with that of diesel. China, Japan, European Union
and North America are aggressively promoting DME
as a cleaner fuel for transportation.
The recent EPA’s approval of biogas-based DME is
a significant milestone for DME industry which is
going to greatly promote the use of DME as an
environmentally friendly renewable fuel in the years
to come. Leading automobile industry giants such
as Renault and Volvo have developed DME based
fuel engine for buses.
In India, LPG is used for cooking in more than
33 million homes, and the demand is increasing with
imports rising rapidly. In Australia, over half a million
vehicles use LPG - all of which could be powered
using DME. In both cases, DME can immediately
be used as a blend with LPG without the need to
change infrastructure. While renewables are still
being developed, DME has huge potential to help
both India and Australia to move from a high carbon
society to a low one.
One of the major hurdles for DME to be used a
commercial transportation fuel is however, cost
involved in investment and setup of distribution
infrastructure. Development of efficient small-scale
DME plant based on direct DME synthesis would
drastically reduce DME production cost. In addition,
due to its lower viscosity and lubricity than diesel
DME needs purpose built fuel injection systems.
Requirements for modifications to the fuel
distribution infrastructure and vehicle engine parts
to accommodate the use of DME will influence the
market introduction from bus and truck fleets to
passenger diesel cars.