DK9448_C003.

fm Page 51 Tuesday, March 28, 2006 2:44 PM

3 Landfill Gas to
Methanol
William H. Wisbrock
President, Biofuels of Missouri, Inc., St. Louis

CONTENTS

Landfills and Landfill Gas ..................................................................................51

Methanol, Present, and Future............................................................................53
Landfill Gas to Methanol....................................................................................54
Renewable Methanol...........................................................................................56
New Uses for Domestic Methanol .....................................................................57

Abstract An explanation of how market forces, governmental mandates, and tax

incentives have placed the use of landfill gas as an alternative energy source into
a growing industry in the United States. Also included is a description of the
opportunities and challenges that face this emerging domestic energy industry,
along with a description of the Acrion Technology CO2 Wash process that cleans
landfill gas, so that it can be utilized for the manufacture of methanol.

LANDFILLS AND LANDFILL GAS

Landfills are physical facilities used for the disposal of residual solid wastes in
the surface soils of the earth. Historically, landfills have been the most economical
and environmentally acceptable method for the disposal of solid wastes, both in
the United States and throughout the world. Even with the implementation of
waste reduction, recycling, and transformation technologies, nearly all of the
residual solid waste in the United States today is deposited in landfills. Further-
more, landfills are not going to disappear, rather they will continue to be an
important component of solid waste management strategy far into the twenty-
first century.
Landfills produce a large amount of gas. Anaerobic decomposition of the
biodegradable portion of the municipal solid waste produces methane and carbon
dioxide in roughly equal amounts. These two principal components, together with
atmospheric nitrogen and oxygen and trace organic compounds, comprise landfill
gas, LFG. According to the Environmental Protection Agency (EPA) Landfill

51

© 2006 by Taylor & Francis Group, LLC

 DK9448_C003.fm Page 52 Tuesday, March 28, 2006 2:44 PM

52 Alcoholic Fuels

Methanol Outreach Program (LMOP) statistics, each pound of organic waste

biodegrades into 10 to 12 standard cubic feet of gas during its landfill residence
of approximately 25 years. Modest size landfills produce one to five million
standard cubic feet of landfill gas daily. By way of example, one of the largest
landfills in the United States, Fresh Kills, Staten Island, NY, produces more than
30 million cubic feet of landfill gas daily. Landfill gas generation increases while
the landfill is active and decays three to five percent annually beginning several
years after the landfill is closed. Significant landfill gas is generated for up to 25
years after closure of the landfill.
The 1986 Clean Air Act (CAA) requires that landfills containing over 2.5
million tons of municipal solid waste be required to collect and flare the landfill
gas in order to prevent methane migration and control the odor associated with
the landfill. This requirement helps prevent methane migration, which contributes
to local smog and global climate change. Methane will try and escape into the
atmosphere from the landfill either through fissures in the lining of the landfill
or through the surface cover. Landfills are the largest human-related source of
methane in the United States, accounting for about 34% of all methane emissions.
The amount of methane created depends on the quantity and moisture content of
the waste and the design and management and environmental practices of the
landfill.
In order to comply with the CAA, LFG is extracted from the landfill by an
engineered system of liners, pipes, wells, wellhead monitors, and a vacuum
system to move the collected gas to a metering device and then to the constant
temperature flare. Significant amounts of landfill gas that are now flared could
be utilized for economically viable projects. The EPA estimates that there are
between 800 and 1000 domestic landfills that are currently flaring landfill gas
that could be converted to energy and energy-related projects, thereby reducing
dependence on fossil energy. Methane vented or flared from existing U.S. landfills
was estimated by the LMOP in 2001 to equal about 5% of domestic natural gas
consumption or about 1% of domestic total energy needs.
Landfill gas is similar to low-quality natural gas in that it requires the removal
of the volatile organic contaminants and the CO2 to realize substantial commercial
value. Landfill gas contaminants challenge separation technology because the
potential contaminants can number in the hundreds of chemical compounds and
various toxic species such as vinyl chloride and hydrogen sulfide. Additionally,
no two landfills have the same contaminants and these contaminants are constantly
changing over the gas production life of the landfill as the decomposition occurs.
The conventional uses of landfill gas to energy include electricity generation
using internal combustion engines, turbines, micro turbines and fuel cells; direct
use, which would include boiler, dryer, kiln, greenhouse, wastewater treatment;
cogeneration, also known as combined heat, and power that enjoys the efficiency
of capturing the thermal energy in addition to electricity generation; and alterna-
tive fuels that include pipeline quality gas, compressed natural gas, liquefied
natural gas, methanol, and hydrogen.

© 2006 by Taylor & Francis Group, LLC

 DK9448_C003.fm Page 53 Tuesday, March 28, 2006 2:44 PM

Landfill Gas to Methanol 53

Landfill ownership is either public or private. Solid waste disposal firms

generally own and operate the majority of the private landfills. Privately owned
landfills tend to promote their gas resource and solicit buyers or users of the gas
more aggressively than their public counterparts. The process of obtaining and
acquiring landfill gas rights is essentially the same for either case. Such a process
usually consists of the following: a review of the proposal by the owner or
appropriate public officials, the negotiation of the business plan and definition of
responsibilities and liabilities, and an execution of a contractual agreement gov-
erning the gas rights, responsibilities of the parties, term of the agreement, price
for the gas, and other details of mutual concern.
Establishing a price for landfill gas and other project considerations requires
the examination and negotiation of many factors, including but not limited to the
following:

• Amount of landfill gas available and the projections of future gas

generation rates.
• Gas composition or gas quality.
• Environmental regulations and permits required.
• Ownership of gas collection system and responsibility for its mainte-
nance.
• Competing prices for natural gas and electric in the area.
• IRS Section 29 tax credit availability.
• Building permits and access to landfill.
• Local air quality conditions and regulations.

The IRS Section 29 tax credits were an attempt to provide a financial incentive
for the utilization of the landfill gas for energy projects. The IRS Code provided
for a $1.05 per million BTU tax credit to a landfill gas developer if such an energy
project were started prior to June 30, 1998. These tax credits will expire on
December 31, 2007, and no longer provide financial incentive to promote tradi-
tional landfill gas to energy projects.

METHANOL, PRESENT, AND FUTURE

Methanol (chemical formula CH3OH and also known as methyl alcohol or wood
alcohol) is a clear, colorless liquid that is water soluble and readily biodegradable.
Methanol occurs naturally in the atmosphere as a by-product of biomass and
landfill decomposition. As an industrial product, methanol is a liquid petrochem-
ical that can be made from renewable and nonrenewable fossil fuels containing
carbon and hydrogen. Since natural gas costs account for the major portion of
the operating costs of domestic methanol producers and are followed in impor-
tance by distribution costs and operating costs, virtually all new methanol pro-
duction has been moved offshore near low cost or “stranded” natural gas locations.
Large world-scale or megamethanol plants are being built in these stranded
gas areas, such as Chile, Trinidad, Qatar, Equatorial Guinea, and Saudi Arabia.

© 2006 by Taylor & Francis Group, LLC

 DK9448_C003.fm Page 54 Tuesday, March 28, 2006 2:44 PM

54 Alcoholic Fuels

Each plant can produce 300 million gallons annually of methanol and costs more
than $350 million to construct. The construction of these megaplants has rein-
forced the characterization of methanol as a “typical” commodity as cycles of
oversupply resulting in lower prices and idled capacity are followed by periods
of shortage and rapidly rising prices as demand catches up and exceeds supply
until increased prices justify new plant investment.
Prior to the 1980s, methanol was produced and consumed locally in North
America primarily as an intermediate feedstock for derivatives such as formal-
dehyde, acetic acid, and plastics recycling in packaging. Limited international
trade was seen mostly through U.S. exports. U.S. natural gas feedstock, at that
time, was reasonably competitive. Today methanol is a global commodity and
the United States has gone from the position of largest producer in the world, to
the largest net importer in less than a decade.
The American Methanol Institute, the trade organization for the methanol
industry, has changed its name to the Methanol Institute and predicts that there
will be no U.S.-produced methanol within five years due primarily to high and
volatile natural gas prices. With the controversy surrounding methyl-tertiary-
butyl-ether (MTBE), significant demand for methanol has disappeared from the
domestic market. While it was widely predicted that methanol prices over the
past several years would be extremely weak, the recovery of the international
economy and demand from China and India have virtually made up for the rapid
decline for the demand of methanol for MTBE.
MTBE was developed in the early 1990s as an oxygenate to improve more
complete combustion of gasoline. This was done at the behest of the EPA.
However, leaking underground storage tanks at automobile service stations caused
ground water contamination and MTBE was found to be a possible carcinogen.
As a result, California, New York, and several other states have banned MTBE.
It has largely been replaced by ethanol as an oxygenate for gasoline.

LANDFILL GAS TO METHANOL

Most existing and proposed landfill gas recovery projects simply combust raw or
minimally treated landfill gas to generate heat or electricity. No competitive
technology for landfill gas recovery has yet to capture any significant market
share of the available landfill gas resources. Landfill gas to methanol is technically
the most challenging issue since contaminant removal to parts per billion is
required to manufacture methanol and made possible only by the CO2 Wash™
technology developed and patented by Acrion Technology, Inc. of Cleveland, OH.
The CO2 Wash™ process is shown in Figure 3.1.
CO2 Wash™ removes the contaminants from landfill gas using liquid carbon
dioxide condensed directly from the landfill gas. A stream of contaminant-free
methane and carbon dioxide is produced, along with a condensed stream of
contaminants in carbon dioxide. This intermediate stream of clean methane and
carbon dioxide can be used as fuel gas or as feedstock to make methanol. This
second process is shown in Figure 3.2. In the alternative, this intermediate stream

© 2006 by Taylor & Francis Group, LLC

 DK9448_C003.fm Page 55 Tuesday, March 28, 2006 2:44 PM

Landfill Gas to Methanol 55

Liquid CO2 Wash™ Process

CH4, CO2 (no VOC’s)

Refrigeration
Liquid CO2
(no VOC’s)

Dry, Compressed Landfill

Gas with VOC’s
Liquid CO2 and VOC’s

FIGURE 3.1 The CO2 wash process.

can be further processed to separate the carbon dioxide from the methane to
produce methane as pipeline gas or transportation fuel (compressed or liquid)
and liquid carbon dioxide. The contaminant-laden carbon dioxide stream is incin-
erated in the landfill flare in all cases as is being done if there were no LFG to
energy project.

Alco2hol
Solutions
Schematic Process Flowsheet
Natural Gas
(methane)
Methane Methanol →
Recycle Purge

Synthesis Gas Crude Chemical Grade

Reforming Synthesis Purification
(CO2, H2, CO) (CH3OH + H2O) (CH3OH)
methanol + water methanol

Steam
Overall Reaction: CH4 + H2O = CH3OH + H2

Alcohol Solutions, LLC

98708 Big Bend
St. Louis, MO 63122
(314) 962-1770

FIGURE 3.2 The methane-to-methanol process.

© 2006 by Taylor & Francis Group, LLC

 DK9448_C003.fm Page 56 Tuesday, March 28, 2006 2:44 PM

56 Alcoholic Fuels

Landfill gas is pretreated to remove water and hydrogen sulfides and then
compressed to about 400 psi. Dry, compressed landfill gas is introduced to a
conventional packed tower where the contaminants are removed. Pure liquid
carbon dioxide condenses from the treated landfill gas at the top of the column.
A small portion of the liquid carbon dioxide is sent down the column (descending
drops) where, in intimate contact with rising landfill gas, it absorbs (or washes)
contaminants from the landfill gas. The larger portion of this condensed liquid
is available as liquid carbon dioxide product at the top of the column. Clean
landfill gas feedstock for methanol synthesis is at the top of the column, with a
composition of 75% methane, 25% carbon dioxide.
In 1998, Acrion completed successful field tests of the CO2 Wash at the Al
Turi Landfill in Goshen, NY, under a grant from the U.S. Department of Energy
(DOE). In the fall of 2001, a demonstration CO2 Wash™ skid, also funded by a
U.S. DOE grant, was operated successfully at the New Jersey EcoComplex,
Burlington County, NJ. Continuity and quality of products were established in
an extended 100+-hour run producing over 3500 lbs of liquid carbon dioxide
(>0.9999 purity). Atlantic Analytical Laboratory and the EPA approved the facil-
ity for landfill gas testing and confirmed the product gas streams purity. Mack
Truck has verified technology veracity in 2003–2004 trials and is proceeding with
additional liquid natural gas production programs.
This CO2 Wash™ process experience, combined with the extensive experi-
ence that HydroChem, a subsidiary of Linde, AG, has had in building modular
hydrogen/methanol plants, has reduced significantly the investment and business
concerns associated with landfill gas to methanol projects.

RENEWABLE METHANOL
Utilizing landfill gas to manufacture methanol has many significant advantages
over the current suppliers of methanol.

• A known price for the raw material and the known price of the plant
allows the producer to control the production costs of methanol over
the productive life of the landfill, typically the remaining years that
the landfill will be open and then 25 years after it is closed.
• The ability to determine production costs enables the manufacturer to
offer long-term, price-stable contracts to customers who have tradi-
tionally experienced wide fluctuations in the price of methanol.
• The proximity of the production site to the methanol customers results
in considerably lower transportation costs and more dependable deliv-
ery.
• Being classified as a renewable resource, the manufacturer of methanol
from landfill gas enjoys a “green” reputation in the United States. A
number of Fortune 500 companies have a corporate policy to purchase
a certain percentage of their raw material needs from renewable
sources.

© 2006 by Taylor & Francis Group, LLC

 DK9448_C003.fm Page 57 Tuesday, March 28, 2006 2:44 PM

Landfill Gas to Methanol 57

• “Green methanol” will allow the manufacturer to take advantage of

various tax credits and incentives passed by the United States Congress
to promote renewable products and fuels. One example is the 60-cents-
per-gallon “alcohol fuel credit” that applies to methanol used in trans-
portation fuels.
• The utilization of landfill gas in the manufacture of methanol results
in the sequestering of methane and carbon dioxide, this process is
credited with reducing greenhouse gas emissions.

The emerging markets for renewable methanol are becoming more defined
and mature as demand is being driven by environmental statutory requirements
and U.S. government mandates regarding the reduction of global warming gases
and ending U.S. reliance upon foreign oil and energy. To that end, landfill gas to
methanol offers a compelling opportunity to develop a significantly large domestic
industry to support the growing demand for domestic renewable fuels and energy.

NEW USES FOR DOMESTIC METHANOL

• Methanol fuel cells: transportation, stationary, and portable power.

• Production of biodiesel.
• Sewerage treatment denitrification.
• Fuel for standby turbine electric generators.
• Pulp and paper bleaching replacing chlorine.
• Stock-car racing fuel.
• Replacement for diesel fuel for stationary diesel engines.
• Converting methanol to hydrogen. Eliminating storage and trans-
portation.
• Fuel additives for diesel fuel. Preventing gelling and fuel line freeze.
• Intermediate for production of dimethyl ether, acetic acid, and form-
aldehyde.
• Environmental cleanup of perchlorate at military installations.

All referenced data in this chapter comes from the U.S. Environmental Pro-
tection Agency (http://www.epa.gov).

© 2006 by Taylor & Francis Group, LLC