MAY 28, 2014

Is there a better alternative to

ethanol in gasoline? The Dimethyl
Carbonate Story
The following is an excerpt from a Technical Research Proposal I helped
to develop and submit in conjunction with the National Alternative Fuels
Foundation (now defunct). Although some of the content is a bit dated, it
speaks to a promising pathway to lower gasoline costs and provide clean
energy from other sources such as coal, natural gas and biomass
(assuming research success).
Background & Research Concept (The Need, The technology and its
Benefits, Research)
Dimethyl Carbonate (DMC) is a biodegradable, high-octane compound
that can be used to significantly reduce U.S. dependency on foreign oil,
assuming an economically feasible and environmentally acceptable
catalyst and process for its manufacture. The research project described
in this proposal (Research) will explore two catalytic/process
pathways that have a high probability of achieving this end. These
pathways (assuming success) would enable economically production of
large quantities of DMC from synthesis gas or methanol (either of which
can be produced from renewable biomass, including forest products and
agricultural wastes, as well as from domestic coal or natural gas) and
sequestered CO2.
There is a need for a domestically produced, renewable fuel to reduce
national
dependency
on
imported
fuels.
In 1985, imported petroleum represented only 4 million barrels/day
(hereinafter b/d) or 27% of US domestic consumption. In 2002, it
represented nearly 11.4 million barrels per day or 58 % of US domestic
consumption. At the same time, US dependency on Middle East oil
increased by more than five times to approximately 2.3 million b/d

(from .35 million b/d). In-spite of improvements to todays energy

diversity, a clear and present need exists to reduce this dependency,
while
simultaneously
mitigating
environmental
risk.
An emission-reducing low-cost fuel component that can replace MTBE
and be used immediately in existing vehicle/ fuel distribution system,
absent engine or system modification, is needed.
DMC can be blended into gasoline at the refinery level and utilized
within existing fleet and fuel distribution systems without modification
or retrofit. It has the potential to improve the combustion and fuel
efficiency of the entire gasoline pool, simultaneously reducing harmful
emissions. MTBE was phased out due to concerns over its toxicity and
groundwater contamination. The other major oxygenate, ethanol, while
environmentally sound fuel, is solely dependent upon tax subsidy, and
has deleterious hydroscopic tendencies, which make it unsuitable for
pipelines. Furthermore, ethanol is not readily used in diesel, fuel oils
and/or aviation fuels.
DMC is a low vapor pressure, low-toxicity, higher boiling point, nonhygroscopic, fully miscible/fungible fuel component, having attractive
octane, cetane and emissions characteristics, especially when used in
gasoline, diesel, fuel oils, aviation and other transportation fuels. DMC
can be manufactured from domestic and renewable feedstock,
transported in existing fuel pipelines and be used without any
modification
to
engines
or
fuel
distribution
systems.
There is a need for a New Fuel and supplement to Ethanol?
US refining capacity is close to maximum capacity and ethanol
production has recently declined. The newest refinery in the United
States began operating in 2008 in Douglas, Wyoming. However, the
newest refinery with atmospheric distillation capacity greater than
100,000 barrels per day began operating in 1977 in Garyville, Louisiana
(source: EIA). As energy demand is likely to increase, octane costs
associated with high severity processes, shrinking the pool even more is
likely to persist beyond the replacement potential of Ethanol.

A large viable economic fuel use of sequestered CO2 is needed.

Due to environmental greenhouse concerns, there is justification to
remove and sequester large quantities of CO2. However, there is a
challenge in finding acceptable places to dispose of CO2. If successful,
the proposed catalyst/process would use massive amounts of CO2 as
feedstock. The prospect of such significant CO2 use in the economic
production of transportation fuels represents a break-through in
alternative fuel production.
There is a need for a hydrogen carrier fuel (HCF) that is safe,
affordable, and widely distributable before the USs conversion to a
hydrogen economy:
Title VIII Hydrogen provisions require the DOE to encourage programs
that would facilitate the production of hydrogen carrier fuels from
diverse sources, and to support the research, development, and
demonstration activities necessary to meet these program goals. DMC is
potentially one of the most attractive hydrogen carrier fuels anywhere. It
is potable, relatively non toxic and can be manufactured from a host of
different feeds (assuming success of this project). As additive to
hydrocarbon fuels, it could drive the creation of large-scale HCF
production facilities, enable utilization of existing distribution systems,
and create the preexisting HCF supply necessary for easy transition to a
hydrogen fuel economy.
There is a need for a safe, potable, low toxic, fungible, nonhygroscopic fuel for future fuel cell vehicles.
Some experts agree that the ultimate solution for a clean, sustainable
transportation system will be a conversion from internal combustion
engines to fuel cells. Methanol and hydrogen are both currently used in
fuel cells. However, each has it limitations. Methanol is toxic and highly
hydroscopic (therefore not fungible). Hydrogen, on the other hand, is a
gas that requires special handling, which is highly explosive. DMC, is a
potable liquid, which is a non-hygroscopic/fully fungible, relatively nonexplosive and non-toxic, essentially consisting of two molecules of
methanol and one of CO2.

Toyota is moving away from building longer-range battery-electric

vehicles (EV) in favor of its effort in hydrogen fuel cell vehicles, its top
North American executive said. Jim Lentz, CEO of Toyotas North
American region, said Toyota sees battery-electric vehicles as viable
only in a select way, in short-range vehicles that take you that extra
mile, from the office to the train, or home to the train, as well as being
used on large campuses. 5/20/2014 autonews.com
The Technology and its Benefits (Advantages over current
technologies)
The benefits a potential new pathway for the safe and economical (fuel
commodity) production of DMC are substantial and many. They fall into
two categories: process benefits and usage benefits. Each of these
includes stand-alone and combined technology benefits, as
discussed below:
Stand alone process benefits
These benefits are defined as those based solely on production/use of
DMC as a refinery stream component:
Reduction in the use/or supplement of petroleum based fuels from
DMC produced from natural gas, coal, biomass feedstock (either
directly or indirectly via methanol or ethanol) and CO2
These feedstock are not traditional petroleum material and represent
alternative fuel sources. As a fuel additive DMC could easily
replace/supplement the equivalent of 4.47 million barrels per day of
finished US petroleum products within the next decade (1.48 million b/d
biomass, 0.490 sequestered CO2, 2.5 million b/d natural gas or coal).
DMC from Biomass
The DOE estimates over 2.45 billion metric tons of biomass are
available for methanol conversion each year . Assuming a 5%
conversion rate, an additional 1.48 million b/d of methanol derived from
biomass could be produced within the next decade. Given the expected
conversion rates, DMC catalyst process should be the same as

methanols. Thus, 1.48 million b/d of DMC could be realistically

produced from biomass within the next decade.
DMC Produced from Sequestered CO2
Proposed DMC reaction pathway (equation 11 Appendix 1), will utilize
CO2 as a feed material. For every 1.0 kilogram (kg) of DMC produced
0.5 kg of sequestered CO2 will be consumed. The use of sequestered
CO2 to produce DMC effectively reduces energy/fuel otherwise required
to produce CO2 from non-sequestered sources. This translates into
annual energy process savings of 0.89 quadrillion BTU (or about 490
thousand b/d) within the next decade. Moreover, the net effect of using
sequestered CO2 and biomass in the production of DMC, effectively
results in net zero CO2 emissions when DMC is ultimately combusted as
additive.
DMC
from
Natural
Gas
The quantity of recoverable natural gas in the United States is vastly
greater than that of petroleum. To the extent clean natural gas can
substitute for petroleum feedstock in transportation fuels, it could greatly
improve both our domestic energy and environmental sustainability.
Alternatively, clean coal syn-gas may be used. A successful DMC
production pathway from synthesis gas or methanol will create an
unprecedented use for natural gas or clean coal syn-gas with a realistic
potential of displacing 2.5 million b/d of the US petroleum based fuels
by 2020. According to Lurgi (a proposed industry process engineering
contractor see below) by 2030, the share of European petroleum-based
fuels will drop from its current 90% to below 40%, while the share of
natural gas-based synthetic fuels will rise by a similar percentage.
2.) Significant reductions in environmentally harmful by-products and
energy requirements (compared to current DMC processes)
Reductions
in
environmentally
harmful
by-products:
Compared to the phosgene DMC process, based on the NAFFs
proposed catalyst/process pathways, there is a reduction of 1.3 g of NaCl
per g of DMC formed, as well as the elimination of hazardous HCL as a

byproduct.. Additionally, because CO2 is used instead of CO and NO,

the risk of explosion and accidental release of toxic CO and NO during
manufacture is virtually eliminated.
Reduced
Energy
Requirements
Current DMC production technologies are geared more for
pharmaceutical grade production, and hence are energy/capital intensive,
unable to deliver DMC in volume and at prices competitive to other fuel
additives (ethanol, MTBE, and petroleum based octane enhancers).
Under NAFFs proposed development plan, stringent decision points
will be required/maintained (see below) to insure that critical
yields/costs can be demonstrated (to insure that NAFFs catalyst/process
can distinguished over the existing uneconomical processes) prior to
entry into Phase II catalyst improvement/development, or Phase III pilot
plant feasibility studies. Anticipated reductions in energy requirements
are dependent upon selected starting material, catalytic efficiency and
process conditions. [It is believed Dow invested $8MM in DMC process
research, which lead to energy cost reductions from over $1.00/lb to less
than $0.10/lb, before abandoning its effort in the mid 1980s after MTBE
became the premier oxygenate. A NAFF team member [Harold Myers]
was intimately involved in Dows effort. Another team member [Dr.
Scott Cowley] was intimately associated with another big dollar dialkyl
carbonate catalyst/process initiative. Based on the combined expertise of
NAFFs team, which has benefited from substantial preexisting research,
that NAFFs proposed research pathways could result savings of
between 58 and 93 percent over existing DMC processes. Such savings
are necessary if DMC is to become a low cost commodity fuel or fuel
additive.

Usage Benefits (benefits associated with the use of DMC as a Fuel

Additive)

DMC represents a new, commercially-viable pathway for the creation of

a near-term hydrogen carrier fuel production. Furthermore, this pathway
may represent the safest, fastest, and potentially the most cost-effective
way
to
deliver
hydrogen
into
the
marketplace.
Why the safest? Unlike pure hydrogen or compressed natural gas, DMC
does not require costly/potentially dangerous high-pressure storage and
delivery tanks. For safety reasons, federal regulations prohibit siting
hydrogen-fueling equipment within 75 feet of gasoline fueling
equipment, effectively pushing hydrogen out the footprint of most
existing energy retailers. Moreover, the storage of gaseous hydrogen at
pressures of 5,000 to 10,000 psi on board vehicles represents a
considerable danger, since a traffic accident or an intended act of
terrorism could rupture the storage tank and cause a large explosion,
potentially killing hundreds.
Ethanol, MTBE, and natural are among the leading commercial
hydrogen carrier fuels currently in the marketplace. Like DMC, ethanol
and MTBE do not require high-pressure storage/transport and delivery
tanks. However, MTBE will gradually be phased out. Ethanol, a safer
alternative is limited due to feedstock limitations and need for Federal
subsidies. Natural gas requires special handling and distribution
facilities. Conversion of natural gas, and MTBE to hydrogen yields
CO2, a green house gas. The conversion of DMC to hydrogen would not
yield any new CO2, as sequestered CO2 was the original feed.
Why the Fastest? Safe and economical near term fuel additive demand
for DMC will drive plant construction. Given DMCs superior energy
and environmental advantages, DMC supplies will likely grow faster
than any other HCF.
Why the most cost effective? Domestic natural gas prices are now quite
high. Reliance upon natural gas as the premier HCF (even assuming cost
effective hydrogen conversion) would translate into extremely high
hydrogen fuel costs. Other the hand, relying upon DMC, which can be
produced from a basket of feed stock material, including biomass and

coal, would tend to hedge against price swings of a single feed.

Furthermore, unlike hydrogen or any other commercially available
hydrogen carrier fuels, DMC is the only fuel that can be used safely and
seamlessly in current transportation fleets and fuel distribution networks.
The US fuel distribution system is a major piece of our national energy
infrastructure. Replacing it with a separate hydrogen system will require
massive expenditures. (Unlike natural gas or hydrogen, DMC can be
supplied at existing fueling facilities and be potentially utilized in a yet
to be invented on board hydrogen fuel conversion/energy system,
negating the hazards of converting to hydrogen before delivery).
Superior Oxygen content can translate into superior emission
benefits
DMCs superior oxygen content can result in significantly lower CO2,
CO, NOx, and toxic emissions. DMC contains 53.3% oxygen by weight,
far greater than any other available oxygenate. By comparison, ethanol
contains 34.8% oxygen by weight, and MTBE contains 18.2% oxygen
by weight. According to the EPA: Oxygen helps gasoline burn more
completely, reducing harmful tailpipe emissions from motor vehicles. In
one respect, the oxygen dilutes or displaces gasoline components such as
aromatics (These aromatics such as benzene are responsible for
disproportionate amounts of carbon monoxide and hydrocarbon exhaust
emissions) and sulfur. In another respect, oxygen optimizes the oxidation
during combustion. Oxygenates can increase the combustion efficiency
of gasoline, thereby reducing vehicle emissions of carbon monoxide. It
has been established that tail pipe emissions are generally independent
of the type of oxygenate added to gasoline (Reuter et al 1992), thus
making DMC the most valuable oxygenate on a weight basis, assuming
all else is equal.
DMC has low toxicity and is biodegradable.
Unlike MTBE, there is no ground water contamination risk associated
with DMC as a fuel additive. DMC is biodegradable and reacts in the
presence of a catalytic amount of base thereby avoiding the formation of
undesirable inorganic salts as by-products. Unlike MTBE and certain

petroleum-based fuels, DMC is not especially carcinogenic. In

laboratory toxicology tests, the lethal dose of DMC required to kill 50%
of rat population is 13,000 mg/kg, more than 3.25 the amount of MTBE
(4000mg/kg) required.
DMC has no transportability or RVP disadvantages (unlike ethanol)
Transportability Advantages: Unlike ethanol, DMC is not hydroscopic
and does not separate from gasoline if stored for an extended period of
time, or if exposed to water or water vapor (as in a pipeline). Because of
its inherent problems, ethanol is shipped separately from gasoline
(typically by rail car or truck but not in pipelines) and is blended with
the gasoline at the distribution terminal. This disability costs ethanol 2
cents a gallon or more, in terms of additional handling.
RVP Advantages: EPA regulates the vapor pressure of all gasoline during
the summer months (June 1 to September 15 at retail stations). These
rules reduce gasoline emissions of volatile organic compounds (VOC)
that are a major contributor to ground-level ozone. DMC is a desirable
fuel additive because (unlike ethanol) it does not increase fuel vapor
pressure (evaporative emissions), which makes it particularly attractive
in RFG fuels. With DMC, low cost, high vapor pressure components
such as butane and pentanes may not need to be removed, translating
into greater profitability and reduced petroleum waste. (See Attachment
1, Letter from Herb Bruch, Former Technical Director, National
Petroleum Refiners Association)
Why
a
DMC
pathway
from
Methanol?
Methanol, a chemical that may be produced from biomass, coal, fuel oil,
or natural gas is likely to be the principal feedstock in NAFFs DMC
catalyst/process effort. According to the Methanol Institute, US
methanol capacity totals 2.2 billion gallons/annually, meeting s of US
demand, of which, MTBE production accounts for 41%.
Because of MTBE phase out, methanol prices have softened. At the
same-time, at least 12 million tonnes/year (88 million barrels) of new
capacity worldwide is expected. Chemical Market Associates predicts a

significant over capacity of methanol will exist, unless a new market is

found/created.
Assuming success of NAFFs effort, limited industrial-scale production
of DMC could be in place as early as 2008. In view of the anticipated
increases in both domestic and worldwide methanol capacity, as well as
the phase-out of MTBE, methanol should be in sufficient quantities for
the near term and intermediate production of DMC. Intermediate and
longer term DMC production from methanol will almost certainly
require significant new methanol production.
Why a DMC pathway from Synthesis gas?
While technically more challenging, DMC produced directly from syngas represents the lowest possible cost option (One-Step Syn-Gas
Process). Biomass syn-gas to DMC would be a highly desirable option
and is an integral component of NAFFs Research effort. Lurgi would be
a particularly suitable down-stream process engineering contractor, due
to their experience in biomass and other synthesis gas to methanol.
Notes
EIA
country
[US]
Analysis
Brief
October
2003
athttp://www.eia.doe.gov/emeu/cabs/usa.html
This is defined as benefits associated with a successful DMC process
development according to proposed catalytic pathways, the use of
desired
feedstocks,
and
projected
market
conditions.
http://www.ott.doe.gov/biofuels/pdfs/methanol_from_biomass.pdf(1995)
According to DOE: One ton of biomass feedstock can be converted to
721
liters
(186
gallons)
of
methanol.
Source:http://www.ott.doe.gov/biofuels/pdfs/methanol_from_biomass.p
df
Given the current availability of sequestered CO2 coupled with the fact
that through international mandates, sequestered CO2 capacity is quickly
emerging, it is anticipated that sufficient CO2 will be commercially

available at competitive prices to meet 100% of the capacity to produce

DMC derived from a biomass feedstock by 2024.
This assumes that the marketplace for sequestered CO2 will be
sufficiently large and prices competitive.
On a BTU energy basis, the energy available from US proven natural
gas reserves (183 TCF) exceeds the amount of available energy from US
proven petroleum reserves (22.4 billion barrels) by approximately
182,900 quadrillion BTU (or 1694 times) (5.83 mbtu = 1 barrel
petroleum, 1000 cuft= 1MBTU natural gas) sources EIA country
Analysis Brief October 2003 and EIA Apples, Oranges and Btu doc
athttp://www.eia.doe.gov
Official Inauguration of the HP POX High Pressure Synthesis Gas
Plant Built by Lurgi and the IEC in Freiberg on 21 November 2003
athttp://www.lurgi.com/english/nbsp/index.html
EIA, Motor Gasoline Outlook and State MTBE Bans Table 1 , April
6,2003 at http://www.eia.doe.gov
Increased olefins translate into increased profitability due to decreased
processing requirements in addition to the cost savings associated with
the reduced amount of paraffin required.
Reduced aromatic content is not required to meet complex model
emissions under Phase II of CAA as long as VOCs and NOx emissions
are met.
Dolan, Gregory In search of the Perfect clean-fuel options
Hydrocarbon
Processing,
March
2002
athttp://www.methanol.org/pdf/HP03Editorial.pdf p.2
Pacheco, Michael A. Review of Dimethyl Carbonate Manufacture and
Its characteristics as a Fuel additive Table 5 American Chemical
Society,
1997.
http://www.epa.gov/mtbe/faq.htm

Cleaner Gasoline for Cleaner Air Better for Your Health EPA 420-F-95005
April
1995
EPA
Office
of
Mobile
Sources
athttp://www.epa.gov/otaq/rfgheal.htm
Tundo P. New Developments in DMC chemistry pure Appl Chem Vol.
73
No.7 pp.1117,2001 athttp://www.iupac.org/publications/pac/2001/pdf/73
071117.pdf
Oxford Physical and Theoretical Chemistry Lab
http://physchem.ox.ac.uk/MSDS/DI/dimethyl_carbonate.htmlandhttp://p
tcl.chem.ox.ac.uk/MSDS/BU/tert-butyl_methyl_ether.html
http://www.eia.doe.gov/emeu/steo/pub/special/mtbeban.html#MTBE
%20Supply%20and%20Demand
http://www.epa.gov/otaq/volatility.htm
Katrib Y. Uptake measurements of carbonates by aqueous phase
Universite
louis
Pasteur,
Strasbourg
at http://imkaida.fzk.de/CMD/AR2000/HEP06.pdf
The Federal RFG program requires a minimum 2.1 percent oxygen by
weight when averaging. This minimum oxygen requirement can be
satisfied by blending approximately 5.5 volume percent ethanol or 11
volume
percent
MTBE.
http://www.eia.doe.gov/emeu/steo/pub/special/mtbeban.html#MTBE
%20Supply%20and%20Demand
http://www.methanol.org/methanol/fact/methanol.cfm
Oil & Gas Journal Week of November 17th 2003 (Industry Trends) p.7
It is anticipated that the catalyst/pathway converting methanol into DMC
would also likely include an ability to convert ethanol into diethyl
carbonate (DEC). Thus, ethanol may also be included as a possible feed,
if DEC was the desired product.