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The technologies for transforming biomass into energy, fuels, chemicals or other value-added

products come in one of two varieties. One is founded on the natural biological processes
carried out by microbes, or they're dependent on the calibrations of heat, pressure and/or
oxygen that define various thermochemical reactions generally referred to as gasification. At
the moment, the former is the glitzy star at the center of the renewable fuels stage, while the
latter-the understudy to these microbial wonders-is gaining a reputation for robust consistency
and efficiency.

"Syngas production is sort of an orphan," says Alexander Koukoulas, senior technology


consultant for ANL Consultants LLC, which services the pulp and paper, packaging, chemicals and
bioenergy industries. "It hasn't really seen much in the way of publicity even though it's a much
more mature technology that has been used at commercial scale for quite sometime."

To harness the energy stored in the chemical bonds of agricultural waste, forest residues or any
other of the profusion of carbohydrate-containing leftovers that can serve as renewable energy
feedstocks, engineers tinker with the deforming powers of heat and pressure with the aim of
breaking the linkages that hold these molecules together and capturing the chemical energy
released in the process. This chemical energy is contained in a mixture of molecules collectively
called synthesis gas because it's suitable for the synthesis of various fuels and chemicals. The
principal components of syngas are carbon monoxide and hydrogen but the concentrations of
these and the presence of other minor molecules can be tailored by using different
thermochemical reaction conditions.

This star diagram shows the multitude of biobased products that can be produced from syngas.

The main method of producing syngas from biomass feedstocks is called gasification. Although
gasification reactions can take many forms, these processes are defined by cranking up the
temperature to between 650 and 1,400 degrees Celsius (1,202-2,552 Fahrenheit). There are two
approaches to achieving these elevated temperatures: direct heating and indirect heating. In
direct heating, a relatively small amount of oxygen is added to the reactor. If this gas is made up
of more than 90 percent oxygen, the resulting syngas will be rich in carbon monoxide and
hydrogen, explains Jerod Smeenk, engineering manager for Frontline BioEnergy LLC, a biomass
gasifier developer and process engineering firm. A contrasting approach uses various means of
indirect heat transfer to achieve high operating temperatures, including hot sand circulation and
exotic alloy heat exchangers, Smeenk says. "It comes down to an economic consideration," he
says. "One must consider many factors including simplicity of design, upfront costs, operating
costs, scale-up potential and the potential replacement costs for exotic alloy heat exchange
components."

The least expensive approach to biomass gasification is the direct approach, which adds air-not
pure oxygen-to the system with simple blower technology. The gas released from this approach
is called producer gas because although this method is a money saver, nitrogen from the air
becomes a major component of the gas. Although producer gas doesn't have as high a
concentration of carbon monoxide and hydrogen as syngas, it can be made very clean with
appropriate gas conditioning and as such it can be used as a replacement for natural gas and
burned to fuel equipment like fired boilers and direct-fired dryers, Smeenk explains.

This is the type of system that Frontline is in the process of installing at Chippewa Valley Ethanol
Co. LLC in Benson, Minn. The gasification system will be constructed as an island so as not to
disrupt the primary workings of the facility. The burners at the boilers and dryers will be
replaced with special multi-fuel burners that can run on producer gas, natural gas or a
combination of both. "Whereas some other biomass systems require a complete overhaul, our
technology lends itself to doing a retrofit of an existing facility," Smeenk says. The first phase of
the CVEC project, which is expected to be complete in February, will process 75 tons of locally
available wood waste thereby displacing 25 percent of the natural gas consumed by the plant.
"Ultimately our objective is to displace more than 90 percent of the plant's natural gas
requirement."

But what if the goal of the ethanol producer or pulp and paper mill owner is to produce a rich
syngas for the production of electricity? The method of choice in this case is a thermochemical
reaction called steam reforming. It's a type of indirect gasification that is also referred to as high-
temperature pyrolysis.

In pyrolysis, biomass is heated to temperatures ranging from 400 to 800 C (752 to 1,472 F) in an
oxygen-starved reactor. In fast pyrolysis, the reaction is run in the middle of this temperature
range and the amount of time that the biomass is exposed to heat is limited. These conditions
maximize the production of a liquid product called pyrolysis oil or py-oil, "which can be used in
much the same way as a crude oil can be used," Koukoulas says.

In high-temperature pyrolysis, steam is used to heat the biomass. "We put energy in but convert
all the biomass to syngas," explains Dan Burciaga, president of ThermoChem Recovery
International Inc., a biomass-to-energy company that commercializes gasification technologies.
"This makes it a very thermally efficient process." TRI's steam reformer technology is currently
being used at the Norampac Inc. containerboard mill in Trenton, Ontario. The feedstock for the
steam reformer is black liquor, which is essentially the lignin left over from the pulping process.
The syngas that's made is combusted in a boiler to produce steam, which offsets some natural
gas requirements. The system started up in September 2003 and transitioned from
commissioning to full commercial operation in October 2006.

The use of syngas as a natural gas replacement is just the start. "Once you have syngas you have
optionality," says Chris Doherty, vice president of contracts for TRI. "Syngas has the building
blocks to create all the products and chemicals currently generated in the petrochemical
industry." Perhaps the ultimate and most demanding application of syngas is as a precursor for
liquid fuel.

Producing this liquid fuel is the goal of a new partnership between TRI, Flambeau River Papers
LLC of Park Falls, Wis., and Syntroleum Corp. of Tulsa, Okla. TRI and Syntroleum will serve as
technology partners for Flambeau's planned 37 MMgy wood-to-syngas-to-liquid fuel plant
colocated with the company's paper mill. TRI will provide the gasification technology for the
project while Syntroleum will provide the gas-to-liquids technology. The latter converts syngas
into a low-sulfur replacement to crude oil through a cobalt catalyzed process called Fischer-
Tropsch. "We're very excited about this biofuels plant," says Bob Byrne, president of Flambeau
River Biofuels LLC. In mid-August, the company submitted a grant application to the U.S. DOE to
help fund the construction of the plant. Byrne says they expect to hear from the agency this
month. "If we get a government grant it will be a significant tail wind for us to put this project
together and move quickly to funding, permitting, construction and startup," he says. However,
the development of the biofuels plant doesn't hinge on this grant. "If we don't get the grant, I
still expect that we will put the project together but it may take us longer to get it funded."
Either way, Byrne expects to break ground this spring. "And that's not the end all," he says.
"We're hopefully establishing the model that helps make the North American pulp and paper
industry that much more competitive with the global economy that we face," says Bill Johnson,
director of government affairs and public relations for Flambeau.

Coal gasification
From Wikipedia, the free encyclopedia

Coal gasification is the process of producing syngas–a mixture consisting primarily of carbon
monoxide (CO), hydrogen (H2), carbon dioxide (CO2), methane (CH4), and water vapor (H2O)–
from coal and water, air and/or oxygen.

Historically, coal was gasified using early technology to produce coal gas (also known as "town
gas"), which is a combustible gas traditionally used for municipal lighting and heating before the
advent of industrial-scale production of natural gas.

In current practice, large-scale instances of coal gasification are primarily for electricity
generation, such as in integrated gasification combined cycle power plants, for production of
chemical feedstocks, or for production of synthetic natural gas. The hydrogen obtained from coal
gasification can be used for various purposes such as making ammonia, powering a hydrogen
economy, or upgrading fossil fuels.

Alternatively, coal-derived syngas can be converted into transportation fuels such as gasoline and
diesel through additional treatment via the Fischer-Tropsch process or into methanol which itself
can be used as transportation fuel or fuel additive, or which can be converted into gasoline by
the methanol to gasoline process. Methane from coal gasification can be converted into LNG for
use as a fuel in the transport sector.[

During gasification, the coal is blown through with oxygen and steam (water vapor) while also
being heated (and in some cases pressurized). If the coal is heated by external heat sources the
process is called "allothermal", while "autothermal" process assumes heating of the coal via
exothermal chemical reactions occurring inside the gasifier itself. It is essential that the oxidizer
supplied is insufficient for complete oxidizing (combustion) of the fuel. During the reactions
mentioned, oxygen and water molecules oxidize the coal and produce a gaseous mixture of
carbon dioxide (CO2), carbon monoxide (CO), water vapour (H2O), and molecular hydrogen (H2).
(Some by-products like tar, phenols, etc. are also possible end products, depending on the
specific gasification technology utilized.) This process has been conducted in-situ within natural
coal seams (referred to as underground coal gasification) and in coal refineries. The desired end
product is usually syngas (i.e., a combination of H2 + CO), but the produced coal gas may also be
further refined to produce additional quantities of H2:
3C (i.e., coal) + O2 + H2O → H2 + 3CO

If the refiner wants to produce alkanes (i.e., hydrocarbons present in natural gas, gasoline, and
diesel fuel), the coal gas is collected at this state and routed to a Fischer-Tropsch reactor. If,
however, hydrogen is the desired end-product, the coal gas (primarily the CO product)
undergoes the water gas shift reaction where more hydrogen is produced by additional reaction
with water vapor:

CO + H2O → CO2 + H2

Although other technologies for coal gasification currently exist, all employ, in general, the same
chemical processes. For low-grade coals (i.e., "brown coals") which contain significant amounts
of water, there are technologies in which no steam is required during the reaction, with coal
(carbon) and oxygen being the only reactants. As well, some coal gasification technologies do
not require high pressures. Some utilize pulverized coal as fuel while others work with relatively
large fractions of coal. Gasification technologies also vary in the way the blowing is supplied.

Syngas

From Wikipedia, the free encyclopedia

Not to be confused with synthetic gasoline.

Syngas, or synthesis gas, is a fuel gas mixture consisting primarily of hydrogen, carbon monoxide,
and very often some carbon dioxide. The name comes from its use as intermediates in creating
synthetic natural gas (SNG)[1] and for producing ammonia or methanol. Syngas is usually a
product of gasification and the main application is electricity generation. Syngas is combustible
and often used as a fuel of internal combustion engines.[2][3][4] It has less than half the energy
density of natural gas.

Syngas can be produced from many sources, including natural gas, coal, biomass, or virtually any
hydrocarbon feedstock, by reaction with steam (steam reforming), carbon dioxide (dry
reforming) or oxygen (partial oxidation). Syngas is a crucial intermediate resource for production
of hydrogen, ammonia, methanol, and synthetic hydrocarbon fuels. Syngas is also used as an
intermediate in producing synthetic petroleum for use as a fuel or lubricant via the Fischer–
Tropsch process and previously the Mobil methanol to gasoline process.

Production methods include steam reforming of natural gas or liquid hydrocarbons to produce
hydrogen, the gasification of coal,[5] biomass, and in some types of waste-to-energy gasification
facilities.

Syngas can be used in the Fischer–Tropsch process to produce diesel, or converted into e.g.
methane, methanol, and dimethyl ether in catalytic processes.

If the syngas is post-treated by cryogenic processing, it should be taken into account that
this technology has great difficulty in recovering pure carbon monoxide if relatively large
volumes of nitrogen are present due to carbon monoxide and nitrogen having very similar
boiling points which are –191.5 °C and –195.79 °C respectively. Certain process technology
selectively removes carbon monoxide by complexation/decomplexation of carbon monoxide
with cuprous aluminum chloride (CuAlCl

4) dissolved in an organic liquid such as toluene. The purified carbon monoxide can have a
purity greater than 99%, which makes it a good feedstock for the chemical industry. The
reject gas from the system can contain carbon dioxide, nitrogen, methane, ethane, and
hydrogen. The reject gas can be further processed on a pressure swing adsorption system to
remove hydrogen, and the hydrogen and carbon monoxide can be recombined in the proper
ratio for catalytic methanol production, Fischer-Tropsch diesel, etc. Cryogenic purification,
being very energy-intensive, is not well suited to simply making fuel, because of the greatly
reduced net energy gain.[citation needed]

The chemical composition of syngas varies based on the raw materials and the processes.
Syngas produced by coal gasification generally is a mixture of 30 to 60% carbon monoxide,
25 to 30% hydrogen, 5 to 15% carbon dioxide, and 0 to 5% methane. It also contains lesser
amount of other gases.[6]
The main reaction that produces syngas, steam reforming, is an endothermic reaction with
206 kJ/mol methane needed for conversion.

The first reaction, between incandescent coke and steam, is strongly endothermic,
producing carbon monoxide (CO), and hydrogen H

2 (water gas in older terminology). When the coke bed has cooled to a temperature at which
the endothermic reaction can no longer proceed, the steam is then replaced by a blast of air.

The second and third reactions then take place, producing an exothermic reaction—forming
initially carbon dioxide and raising the temperature of the coke bed—followed by the
second endothermic reaction, in which the latter is converted to carbon monoxide, CO. The
overall reaction is exothermic, forming "producer gas" (older terminology). Steam can then
be re-injected, then air etc., to give an endless series of cycles until the coke is finally
consumed. Producer gas has a much lower energy value, relative to water gas, due primarily
to dilution with atmospheric nitrogen. Pure oxygen can be substituted for air to avoid the
dilution effect, producing gas of much higher calorific value.

When used as an intermediate in the large-scale, industrial synthesis of hydrogen


(principally used in the production of ammonia), it is also produced from natural gas (via
the steam reforming reaction) as follows:

CH

4+H

2O → CO + 3H

In order to produce more hydrogen from this mixture, more steam is added and the water
gas shift reaction is carried out:
Coal gasification

From Wikipedia, the free encyclopedia

Coal gasification is the process of producing syngas–a mixture consisting primarily of


carbon monoxide (CO), hydrogen (H2), carbon dioxide (CO2), methane (CH4), and water
vapor (H2O)–from coal and water, air and/or oxygen.

Historically, coal was gasified using early technology to produce coal gas (also known as
"town gas"), which is a combustible gas traditionally used for municipal lighting and heating
before the advent of industrial-scale production of natural gas.

In current practice, large-scale instances of coal gasification are primarily for electricity
generation, such as in integrated gasification combined cycle power plants, for production of
chemical feedstocks, or for production of synthetic natural gas. The hydrogen obtained from
coal gasification can be used for various purposes such as making ammonia, powering a
hydrogen economy, or upgrading fossil fuels.

Alternatively, coal-derived syngas can be converted into transportation fuels such as


gasoline and diesel through additional treatment via the Fischer-Tropsch process or into
methanol which itself can be used as transportation fuel or fuel additive, or which can be
converted into gasoline by the methanol to gasoline process. Methane from coal gasification
can be converted into LNG for use as a fuel in the transport sector.[1]

CO + H

2O → CO

2+H

The hydrogen must be separated from the CO2 to be able to use it. This is primarily done by
pressure swing adsorption (PSA), amine scrubbing, and membrane reactors.