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Thermochemical Conversion
Submitted by:.
MANAOIS, Marybhel D.
Submitted to:
ENGR. M. CABANGON
Thermochemical conversion
Thermochemical technologies are used for converting biomass into fuel
gases and chemicals. The thermochemical process involves multiple stages. The
first stage involves converting solid biomass into gases. In the second stage the
gases are condensed into oils. In the third and final stage the oils are
conditioned and synthesized to produce syngas. Syngas contains carbon and
hydrogen and can be used to produce ammonia, lubricants, and through the
Fischer-Tropsch process can be used to produce biodiesel.
Gasification
that leads to nearly all of the biomass being converted into gas. This takes place in two
stages: partial combustion to form producer gas and charcoal, followed by chemical
reduction. These stages are spatially separated in the gasifier, with gasifier design very
much dependant on the feedstock characteristics. Gasification requires temperatures
of about 800C. Gasification technology has existed since the turn of the century when
History
The process of producing energy using the gasification method has been
in use for more than 180 years. During that time coal and peat were used to
power these plants. Initially developed to produce town gas for lighting &
cooking in 1800s, this was replaced by electricity and natural gas, it was also
used in blast furnaces but the bigger role was played in the production of
synthetic chemicals where it has been in use since the 1920s.
During both world wars especially the Second World War the need of
gasification produced fuel reemerged due to the shortage of petroleum. Wood
gas generators, called Gasogene or Gazogne, were used to power motor
vehicles in Europe. By 1945 there were trucks, buses and agricultural
machines that were powered by gasification. It is estimated that there were
close to 9,000,000 vehicles running on producer gas all over the world.
Chemical reactions
The chemical reactions in gasification process take place in the presence
of steam in an oxygen-lean,reducing atmosphere. The ratio of oxygen molecules
to carbon molecules is far less than one in the gasification reactor.
Gasification process
Gasification is a flexible, reliable, and clean energy technology that can turn a
variety of low-value feedstocks into high-value products, help reduce our dependence
on foreign oil and natural gas, and can provide a clean alternative source of baseload
electricity, fertilizers, fuels, and chemicals.
tar compounds) and the residuum from this process will be mainly activated
carbon.
Reduction, where the activated carbon reacts with water vapour and carbon
dioxide to form combustible gases such as hydrogen and carbon oxide. The
reduction (or gasification) process is carried out in the temperature ranging up
to about 1100C.
Oxidation, where part of the carbon is burned to provide heat for the
previously described processes.
The gas composition is also a function of gasifier design and thus, the same
fuel may give different calorific value as when used in two different
gasifiers. Table therefore shows approximate values of gas from different fuels.
Syngas Cleanup
Syngas Contaminant Removal and Conditioning
Raw synthesis gas (syngas) from the high temperature gas cooling
(HTGC) system needs to be cleaned to remove contaminants including fine
particulates, sulfur, ammonia, chlorides, mercury, and other trace heavy
metals to meet environmental emission regulations, as well as to protect
downstream processes. In the case of carbon sequestration, carbon dioxide
(CO2) is also removed. Depending on the application, syngas may need to be
conditioned to adjust the hydrogen-to-carbon monoxide (H2-to-CO) ratio to
meet downstream process requirement. In applications where very low sulfur
(<10 ppmv) syngas is required, converting carbonyl sulfide (COS) to hydrogen
sulfide (H2S) before sulfur removal may also be needed. Typical cleanup and
conditioning processes include cyclone and filters for bulk particulates removal;
wet scrubbing to remove fine particulates, ammonia and chlorides; solid
absorbents for mercury and trace heavy metal removal; water gas shift (WGS)
for H2-to-CO ratio adjustment; catalytic hydrolysis for converting COS to H2S;
and acid gas removal (AGR) for extracting sulfur-bearing gases and CO2
removal.
High Temperature Syngas Cooling and Heat Recovery
Synthesis gas (syngas) leaving the reactor is at high temperature;
typically 2,500F to 2,800F for an entrained-flow gasifier. Recovery of heat
from the syngas is essential for attaining process efficiency. Heat recovery
systems can reclaim a significant portion (5-25%) of the energy in the feed,
depending on the technology employed. The actual design of a syngas cooling
and heat recovery system has to consider the characteristics of the coal feed,
syngas produced, and the overall gasification process application.
The raw syngas leaving the gasifier can be cooled by a radiant and/or
convective heat exchanger and/or by a direct quench system, wherein water or
cool recycled gas is injected into the hot raw syngas. Then, the syngas typically
passes through a series of heat exchangers for heat recovery at a lower
temperature. In all cases, steam is produced for in-plant power generation or
process heating. The steam and water systems are integrated and optimized
within the overall gasification facility.
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Wet Scrubbing
In most commercial gasification operations, syngas leaving the filter is
quenched and scrubbed with water for final particulate removal. Water
scrubbing takes place below the dew point temperature of the syngas so that
the finest solid particles can act as nuclei for condensation, thus ensuring that
all solids can be removed
efficiently.Scrubbing
also
removes chlorides, ammonia,
some hydrogen sulfide (H2S) and
other trace contaminants from
the
syngas.
Typically,
the
scrubbed syngas is reheated for
carbonyl sulfide (COS) hydrolysis
and/or a sour water gas shift
(WGS) if required, followed by
cooling in a low temperature gas
cooling
(LTGC)
system
to
generate low pressure steam.
After these processes, the syngas
is sent downstream for sulfur
and mercury removal.
Spent water from the scrubber
column is directed to a gray
water treatment system where it
is depressurized and vacuum flashed. The spent water is then decanted into a
gravity settler to remove particulates. Solid-concentrated underflows from the
settler bottom are filtered to recover the fine particulate as a filter cake, which
is then either discarded or recycled to the gasifier depending on its carbon
content. Water from the settler is recycled for gasification reuse, with excess
being sent to the wastewater treatment system for disposal.
Mercury and Trace Elements
Current commercial practice is to pass cooled syngas from LTGC through
sulfided, activated carbon beds to remove over 90% of the mercury and a
significant amount of other heavy metal contaminants. Due to sulfur in the
activated carbon, these beds are normally placed ahead of the AGR system to
minimize the possibility of sulfur slipping back into and contaminating the
cleaned syngas.
Water Gas Shift
In applications where scrubbed syngas H2/CO ratio must be
increased/adjusted to meet downstream process requirements, the syngas is
passed through a multi-stage, fixed-bed reactor containing shift catalysts to
convert carbon monoxide (CO) and water into additional H2 and CO2 according
to the following reaction known as the water-gas shift (WGS) reaction:
The shift reaction will operate with a variety of catalysts between 400F and
900F. The reaction does not change molar totals and therefore the effect of
pressure on the reaction is minimal. However, the equilibrium for H2
production is favored by high moisture content and low temperature for the
exothermic reaction. Normally, excess moisture is present in the scrubber
syngas from slurry-fed gasifiers sufficient to drive the shift reaction to achieve
the required H2-to-CO ratio. Indeed, for some slurry-fed gasification systems, a
portion of the syngas feed may need to be bypassed around the sour shift
reactor to avoid exceeding the required product H2-to-CO ratio. On the other
hand, additional steam injection before the shift may be needed for syngas
output by dry-fed gasifiers.
In any case, the scrubber syngas feed is normally reheated to 30 to 50F above
saturation temperature to avoid catalyst damage by condensation of liquid
water in the shift reactor. Shifted syngas is cooled in the low temperature gas
cooling (LTGC) system by generating low pressure steam, preheating boiler feed
water, and heat exchanging against cooling water before going through the acid
gas removal system for sulfur removal.
There is some flexibility for locating the WGS reactor: it can be located either
before the sulfur removal step (sour shift) or after sulfur removal (sweet shift).
Sour shift uses a cobalt-molybdenum catalyst and is normally located after the
water scrubber, where syngas is saturated with water at about 450F to 500F,
depending on the gasification conditions and the amount of high temperature
heat recovery. An important benefit of sour shift is its ability to also convert
COS and other organic sulfur compounds into H2S to make downstream sulfur
removal easier. Therefore, syngas treated through WGS does not need separate
COS hydrolysis conditioning.
A conventional high temperature (HT) sweet shifting operates between 550F to
900F and uses chromium or copper promoted iron-based catalysts. Because
syngas from the sulfur removal process is saturated with water at either near
or below ambient temperature, steam injection or other means to add moisture
to the feed is normally needed for HT sweet shifting.
A conventional low temperature (LT) sweet shift, typically used to reduce
residual CO content to below 1%, operates between 400F to 500F and uses a
copper-zinc-aluminum catalyst. LT sweet shifting catalysts are extremely
sensitive to sulfur and chloride poisoning and are normally not used in coal
gasification plants.
Sweet shift is normally not used for coal gasification applications, given the
problems of sulfur and chloride poisoning as mentioned above, in addition to
the inefficiency of having to cool the syngas before sulfur removal, which
condenses out all of the moisture gained in the water scrubber, and then
reheating and re-injecting the steam into the treated gas after H2S removal to
provide moisture for shift. Sour shift is normally preferred for coal gasification
applications since the moisture gained in the water scrubber is used to drive
the shift reaction to meet the required H2/CO ratio.
Selexol Process
The solvent, with dissolved CO2, is then removed from the chamber. The N2 is
released as it is not absorbed in the solvent. The recovery of CO2 from the
solvent is called desorption. The usual process for recovery of CO2 from the
solvent is temperature change. Other methods include pressure changes and
the use of membranes with solvents.
Fischer-Tropsch diesel
The Fischer-Tropsch process is one of the advanced biofuel conversion
technologies that comprise gasification of biomass feedstocks, cleaning and
conditioning of the produced synthesis gas, and subsequent synthesis to liquid
(or gaseous) biofuels. The Fischer-Tropsch process has been known since the
1920s in Germany, but in the past it was mainly used for the production of
liquid fuels from coal or natural gas. However, the process using biomass as
feedstock is still under development. Any type of biomass can be used as a
feedstock, including woody and grassy materials and agricultural and forestry
residues. The biomass is gasified to produce synthesis gas, which is a mixture
of carbon monoxide (CO) and hydrogen (H2). Prior to synthesis, this gas can be
conditioned using the water gas shift to achieve the required H2/CO ratio for
the synthesis. The liquids produced from the syngas, which comprise various
hydrocarbon fractions, are very clean (sulphur free) straight-chain
hydrocarbons, and can be converted further to automotive fuels. FischerTropsch diesel can be produced directly, but a higher yield is achieved if first
Modern gasification has been used in the chemical industry since the
1950s. Typically, the chemical industry uses gasification to produce methanol
as well as chemicals, such as ammonia and urea, which form the foundation of
nitrogen-based fertilizers. The majority of the operating gasification plants
worldwide produce chemicals and fertilizers. And, as natural gas and oil prices
continue to increase, the chemical industry is developing additional coal
gasification plants to generate these basic chemical building blocks.
Eastman Chemical Company helped advance the use of coal gasification
technology for chemicals production in the U.S. Eastman's coal-to-chemicals
plant in Kingsport, Tennessee converts Appalachian coals to methanol and
acetyl chemicals. The plant began operating in 1983 and has gasified
approximately 10 million tons of coal with a 98 to 99 percent on-stream
availability rate.
Power Generation with Gasification
Coal can be used as a feedstock to produce electricity via gasification,
commonly referred to as Integrated Gasification Combined Cycle (IGCC). This
particular coal-to-power technology allows the continued use of coal without
the high level of air emissions associated with conventional coal-burning
technologies. In gasification power plants, the pollutants in the syngas are
removed before the syngas is combusted in the turbines. In contrast,
conventional coal combustion technologies capture the pollutants after
combustion, which requires cleaning a much larger volume of the exhaust gas.
This increases costs, reduces reliability, and generates large volumes of sulfurladen wastes that must be disposed of in landfills or lagoons.
Today, there are 15 gasification-based power plants operating
successfully around the world. There are three such plants operating in the
United States. Plants in Terre Haute, Indiana and Tampa, Florida provide
baseload electric power, and the third, in Delaware City, Delaware provides
electricity to a Valero refinery.
Substitute Natural Gas
Gasification can also be used to create substitute natural gas (SNG) from
coal and other feedstocks, supplementing U.S. natural gas reserves. Using a
"methanation" reaction, the coal-based syngaschiefly carbon monoxide (CO)