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Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology


Chemical Engineering Department

OBJECTIVES

General:
To determine different types of fuel gases and its uses
To determine the raw materials and manufacturing process involved in
making different types of fuel gases

Specific:

To determine the processes involved in producing natural gas


To determine the raw materials and manufacturing process involved and
companies producing manufactured gas (syngas and biogas)
To determine the raw materials and manufacturing process involved and
companies producing petroleum gas (LPG)

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

INTRODUCTION

Fuels are any materials that store potential energy in forms that can be
practicably released and used as heat energy. It is originally applied to the materials
that stores chemical energy that can be released through combustion in particular,
but nowadays, the heat energy can also be in the form of nuclear energy via nuclear
fusion and non-combustion/oxidation, like in fuel cells.

Fuel has three types: solid fuel, liquid fuel, and fuel gas. Any fuel that is
usually composed of hydrocarbons, carbon monoxide, hydrogen, or their
combinations, and is gaseous in ordinary conditions is called a fuel gas. The
hydrocarbons mentioned can be methane or propane. Usually, it is transported
directly from its manufacturing plant to the corresponding place of consumption.
Some, however, are liquefying it first for transport.

Fuel gases has its advantages because of its form, this is because it can
avoid the difficulty of transporting solid fuel and the dangers of spillage inherent in
liquid fuels. But on the other hand, it also has its disadvantages, since fuel gases
cannot be detected and collected in certain areas. This can lead to the risk of gas
explosions. To stop this, odorizers are added to most fuel gases so that they can be
detected by a distinct smell.

A. DEFINITION OF TERMS

1. Liquefied Petroleum Gas - a mixture of light gaseous hydrocarbons, made


liquid by pressure and used as fuel
2. Heating value the amount of heat produced by a substance when it is
combusted
3. Oil reservoir a collection of oil which is usually found underground
4. Synthetic Natural Gas (SNG) - also referred to as substitute natural gas,
created through converting or reforming carbonaceous feedstocks (coal,
biomass) and can be used in almost every way that natural gas can be
used
5. Synthetic Petroleum/Synthetic Fuel - a liquid fuel obtained from coal,
natural gas, oil shale, or biomass
6. Pyrolysis - a thermochemical decomposition of organic material at
elevated temperatures in the absence of oxygen (or any halogen)
7. Digestate the solid remnants of the original input material to the
digesters that the microbes cannot use
8. Biomethane purified biogas

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College of Engineering and Technology
Chemical Engineering Department

9. Offshore Drilling - refers to a mechanical process where a wellbore is


drilled through the seabed. It is typically carried out in order to explore
for and subsequently extract petroleum which lies in rock formations
beneath the seabed. Most commonly, the term is used to describe drilling
activities on the continental shelf, though the term can also be applied to
drilling in lakes, inshore waters and inland seas.

B. BRIEF HISTORY

Natural gas was actually known by the ancients, but it was considered
by them to be a supernatural manifestation. Noticed only when ignited, it appeared
as a mysterious fire bursting from fissures in the ground. The use of gas was
mentioned in China about 900 B.C. Apparently, natural gas was unknown in Europe
until its discovery in England in 1659. However, even though this discovery occurs,
the natural gas still remained unpopular.

The first attempts to manufacture fuel gas in a commercial way starts to


be made in the period 17951805 in France by Philippe Lebon. Philippe Lebon was a
French civil engineer working in the public engineering corps who became interested
while at university in distillation as an industrial process for the manufacturing of
materials such as tar and oil. As he investigated distillation, he discovered that the
gas produced in the distillation of wood and coal could also be a useful for lighting,
heating, and even as an energy source in engines.

This discovery lead to the first company to provide manufactured gas to


consumer as a utility was the London based Gas Light and Coke Company. It was
founded through the efforts of a German migr, Frederick Winsor, who had
witnessed Lebon's demonstrations in Paris. This is incorporated and legalized by the
royal charter in April 1812.

From 1812 to approximately 1825, manufactured gas was predominantly


an English technology. A number of new gas utilities were founded to serve London
and other cities in the UK in the years after 1812. Liverpool, Exeter, and Preston
were the first in 1816. Soon enough, other places followed, so that by 1821, no town
in England with population less than 50,000 was without gaslight.

France's first gas company was also promoted by Frederick Winsor after
he had to flee England in 1814. Unfortunately, the company had failed. To continue
the operation of using manufactured gas as a source of illumination, the government
of France, which was also interested in promoting the industry, commissioned

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College of Engineering and Technology
Chemical Engineering Department

Chabrol de Volvic to study the technology and build a prototype plant in 1817, also
in Paris. The plant provided gas for lighting the hpital Saint Louis, and the
experiment was judged successful. This result to a public company that provides
manufactured gas in 1818. Private companies soon followed, and by 1822, when the
government moved to regulate the industry, there were four in operation in the
capital.

Gaslight was first introduced to the US in 1816 in Baltimore by


Rembrandt and Rubens Peale, who lit their museum with gaslight, which they had
seen on a trip to Europe. Baltimore, Maryland began the first commercial gas lighting
of residences, streets, and businesses in 1816.

Up until 1824, manufactured gas was used as a source of heat and light
and in other industrial companies. The natural gas came in 1824, as one attempts to
harness the natural gas for economic use occurred in Fredonia, New York. This led to
the formation of the first natural gas company in the United States, the Fredonia Gas
Light Company, in 1859. Toward the latter part of the nineteenth century large
industrial cities began to use natural gas.

Soon enough, in 1840, LPG was used for a portable fuel source, and its
use has expanded and developed dramatically ever since. Liquefied petroleum gas is
primarily and widely used in rural areas where piped natural gas is not available. A
large oil company introduced LPG to France in the mid 1930's. And a large gas
company built a bottling plant in Italy, near Venice, in 1938. By the early 1950's,
companies were producing LPG cylinders for household use and these were being
marketed elsewhere under license.

C. TYPES OF FUEL GAS

These two broad types of fuel gases are based on their corresponding
sources.

1. Found Naturally
a. Natural Gas

- a fossil fuel formed when layers of buried plants and animals


are exposed to intense heat and pressure over thousands of
years

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College of Engineering and Technology
Chemical Engineering Department

- a hydrocarbon gas mixture consisting primarily of methane,


but commonly includes varying amounts of other higher
alkanes and even a lesser percentage of carbon dioxide,
nitrogen, and hydrogen sulphide
b. Petroleum Gas
- a flammable mixture of hydrocarbon gases used as a fuel in
heating appliances and vehicles
- usually liquefied for easy transportation

- when specifically used as a vehicle fuel it is often referred to as


autogas

2. Manufactured from Other Materials (Manufactured Fuel Gases)


- also called as artificial gas
- those produced through an artificial process, usually
gasification, at a location known as a gasworks
- used as a replacement to natural gas when the supply in
natural gases in unexpectedly high

NATURAL GAS

The Malampaya Deep Water Gas to Power Project

INTRODUCTION

The Malampaya Deep Water Gas-to-Power project represents the largest and
most significant industrial investment in the history of the Philippines. It heralds the
birth of the countrys natural gas industry that will enable the supply of clean,
environment-friendly fuel slated to provide 2,700 megawatts of power to Luzon for a
period of 20 years starting January 2002. This meets 30% of the whole countrys
power generation requirements (Bayquen, 2007).

Natural gas is a fossil fuel made up of 80% to 95% methane and varying
amounts of ethane, propane, butane and other hydrocarbon compounds and a lesser
percentage of carbon dioxide, nitrogen, and hydrogen sulfide. There will always be
some condensate and/or oil associated with the gas. In its natural state, the gas is
colorless, odorless and lighter than air. It occurs naturally in underground structures

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College of Engineering and Technology
Chemical Engineering Department

similar to those containing crude oil. Natural gas has been dubbed the fuel of the
future or green fuel due to its clean qualities relative to other fossil fuels like oil
and coal.

Natural gas possesses remarkable qualities. Among the fossil fuels, it has the
lowest carbon intensity, emitting less CO2 per unit of energy generated than other
fossil fuels. It burns cleanly and efficiently, with very few non-carbon emissions.
Unlike oil, natural gas generally requires limited processing to prepare it for end use.
These favorable characteristics have enabled natural gas to penetrate many markets,
including domestic and commercial heating, multiple industrial processes and
electrical power. Natural gas also has favorable characteristics with respect to its
development and production. The high compressibility and low viscosity of natural
gas allows high recoveries from conventional reservoirs at relatively low cost, and also
enables natural gas to be economically recovered from even the most unfavorable
subsurface environments, as recent developments in shale formations have
demonstrated.

Natural gas is found in deep underground rock formations or associated with


other hydrocarbon reservoirs in coal beds and as methane clathrates. Petroleum is
another resource found in proximity to and with natural gas. Most natural gas was
created over time by two mechanisms: biogenic and thermogenic. Biogenic gas is
created by methanogenic organisms in marshes, bogs, landfills, and shallow
sediments. Deeper in the earth, at greater temperature and pressure, thermogenic
gas is created from buried organic material. Before natural gas can be used as a fuel,
it must be processed to remove impurities, including water, to meet the specifications
of marketable natural gas. The by-products of this processing
include ethane, propane, butanes, pentanes, and higher molecular weight
hydrocarbons, hydrogen sulfide (which may be converted into pure sulfur), carbon
dioxide, water vapor, and sometimes helium and nitrogen.

MANUFACTURING PROCESS

The Malampaya Deep Water Gas to Power project delivers gas from an off-shore
gas field to three power plants near the city of Batangas (100 kilometers south of
Manila) in the Philippines. The project consists of an off-shore production platform, a
504 km subsea pipeline, and an on-shore gas treatment plant.

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Chemical Engineering Department

Malampaya Development

The offshore field contains recoverable natural gas reserves of some 2.7 trillion
cubic feet and 85 million barrels of condensate. The gas is extracted from 2,200
meters below the seabed, which is at a water depth of 830 meters. This project to
extract natural gas deposits from over 3,000 meters below sea level and transport
this to a market over 500 kilometers away posed one of the greatest deep-water
challenges in the world and required the use of the latest in gas technology and
skills.

Gas from five subsea wellheads is transported via two 30 km flow lines to a
production platform that sits in shallow water. On the platform the condensate is
removed from the gas and stored for retrieval by tankers using a catenary anchored
leg mooring (CALM) buoy. Then the gas is compressed for export to the gas treatment
plant through the 504 km pipeline.

For the off-shore platform Yokogawa has delivered all safety systems, including
an inherent safe high integrity pressure protection system (HIPPS) that contains SIL4
loops and two PLCs controlling the emergency shutdown (ESD) and fire & gas (F&G)
functions. As it was a requirement of Shell to standardize on one safety PLC type, the
safety functions of the Cooper Rolls gas compressors (2x) and the solar turbines (3x)

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College of Engineering and Technology
Chemical Engineering Department

were implemented on a Yokogawa ProSafe-PLC, in close co-operation with the


package suppliers. All Yokogawa safety systems are integrated into one redundant
safety network. The engineering work station (EWS) includes a FAST/TOOLS
application for maintenance override scheduling. Via a redundant ProSafe-COM
MULCOM interface, data is transferred via the OPC (OLE for process control) protocol
to the DCS.

For the on-shore gas plant, Yokogawa has again delivered all safety systems,
including an inherent safe HIPPS that contains the SIL4 loops, two PLCs for the ESD
and F&G functions, and four safety systems for burner management control. The
safety functions of the solar turbines (2x) are also implemented on Yokogawa
ProSafe-PLC. All Yokogawa safety systems are integrated into one redundant safety
network. The EWS includes a FAST/TOOLS application for maintenance override
scheduling. Via a redundant MULCOM interface, data is transferred via the OPC
protocol to the local DCS.

Three combined-cycle gas turbine power plants are being supplied with the
processed gas to generate power: the 1,000 MW Sta. Rita power plant, the 500 MW
San Lorenzo power plant and the 1,200 MW Ilijan power plant. The National Power
Corporation (NAPOCOR), a government-owned power distribution company, owns the
Ilijan power plant, while First Gas Power Corporation and FGP Corporation are the
developers and operators of the Sta. Rita and San Lorenzo power plants.

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College of Engineering and Technology
Chemical Engineering Department

PROCESS FLOW

Wellbore is drilled through the seabed. It is typically carried


RIG DRILLING out in order to explore for and subsequently extract petroleum
which lies in rock formations beneath the seabed.

Natural gas dehydration is a treatment that removes most of


the water vapor content before forwarding the gas to
pipelines.
GAS DEHYDRATION Dehydration treatment to remove water vapor from natural
gas is needed to prevent hydrate formation and pipeline acid
corrosion, and to guarantee compliance with the dewpoint
required by the standard specifications.

The drying of natural gas to a dew point lower than the


operating temperature of the chiller plant is of obvious
GAS DEWPOINTING importance to prevent freeze up problems, causing flow
restriction, with resulting consequences in terms of plant
operating efficiency.

The condensate is stabilised on the topsides, stored in the


CGS and then exported to a shuttle tanker through a
CONDENSATE catenary anchored leg mooring system (CALM).
STABILISATION The Malampaya CALM transfers condensate from the concrete
gravity Production Platform to tankers through a 2.5km long
24-in pipeline. tankers.

The processed gas is compressed and exported through a


EXPORT 504km pipeline to the Batangas onshore facility at Luzon
COMPRESSION Island, in the Philippines.

Hydrogen sulfide is a highly corrosive gas and often the cost


of ongoing maintenance and replacement of pipelines, tubing
H2S REMOVAL and other equipment make the prospect of operating natural
gas with high levels of H2S to be breakeven at best.

Natural Gas is then delivered to three combined-cycle gas


DISTRIBUTION turbine power plants.

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College of Engineering and Technology
Chemical Engineering Department

Summary

This involves the extraction of gas from a reservoir located 3,000 meters below
sea level. The gas will flow through five sub-sea wellheads to a manifold in 820-meter
water depth, through two 30-kilometer pipelines to a shallow water production
platform where the gas is dried. The dried gas is then transported through a 504-
kilometer sub-sea pipeline from the platform in offshore Palawan to the on-shore gas
plant in Batangas where gas is further processed with the removal of hydrogen
sulfide and finally delivered to three combined-cycle gas turbine power plants.

This natural gas will be used as fuel for three power plants in Batangas, which
can provide up to 2,700 MW of electricity, representing 30% of the installed capacity
of the Luzon grid.

LIQUEFIED PETROLEUM GAS PRODUCTION

OBJECTIVES

To liquid petroleum and its characteristics


To name the different companies LPG providers in the Philippines
To determine the different manufacturing process, chemical reactions and
equipment involved in the production LPG

INTRODUCTION

Liquefied petroleum gas, or LP gas, is one of the most


common alternative fuels used in the world today. In fact, in
many places, it isn't an alternative fuel at all: LP gas is a
mainstay for heating and cooking in certain areas of India and
some rural areas of the United States.

It is a mixture of light gaseous hydrocarbons made liquid by pressure inside of


the propane tanks. Liquefied petroleum gas (LPG) is a different chemical compound
to natural gas even though they are both hydrocarbons. Although gaseous under

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College of Engineering and Technology
Chemical Engineering Department

normal atmospheric conditions, LPG is stored under modest pressures in liquid


form. In this way LPG can be transported and stored in a concentrated form to
provide a source of high-energy fuel.

LPG is highly inflammable and must therefore be stored away from sources of
ignition and in a well-ventilated area, so that any leak can disperse safely.

Another reason why care should be taken during storage is that LPG vapour is
heavier than air, so any leakage will sink to the ground and accumulate in low lying
areas and may be difficult to disperse.

LPG expands rapidly when its temperature rises. So whenever a container is


filled, sufficient space is left to allow for such expansion. LPG will cause natural
rubber and some plastics to deteriorate. This is why only hoses and other equipment
specifically designed for LPG should be used.

USES

LPG which is otherwise known as Liquefied Petroleum Gas, has many industrial as
well as domestic uses. Some of its uses are:

1. Motor Fuel - The top most use of LPG is to use as the main fuel for vehicles. It
burns better than diesel or petrol and hence, the top most use for LPG is to
use it as ignition fuel. It is also more energy efficient and is said to leave lesser
damaging impact on the atmosphere and the environment. When LPG is used
to fuel internal combustion engines, it is often referred to as auto gas or auto
propane.

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College of Engineering and Technology
Chemical Engineering Department

2. Refrigerant - LPG is also popularly used as a refrigerant, this is because


butane and propane are both considered to be energy efficient.

3. Cooking Fuel - The other main use of LPG is as domestic fuel or what we
know as cooking fuel. LPG gas is a combination of propane and butane. Even
these individual components have many domestic uses. Like propane is used
in portable stoves as well as barbeques and butane is used in deodorants and
even gas lighters used to light gas ovens in the kitchens and even cigarettes.

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College of Engineering and Technology
Chemical Engineering Department

COMPOSITION

The normal components of LPG are propane and butane. Small concentrations of
other hydrocarbons may also be present. The percentage composition of liquefied
petroleum gas is as follows:

COMPONENT PERCENTAGE
0.20%

Ethane
57.30%

Propane
41.10%

Butane

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College of Engineering and Technology
Chemical Engineering Department

1.40%

Pentane

COMPANIES

COMPANY NAME LOCATION

2101 Ibarra st, cor. Dapitan,


Sampaloc

Solane LPG

Blk. 159 Lot 22-B Felix Avenue,


Karangalan Vill., Brgy. San Isidro,
Cainta Rizal

PR Gaz

Madrigal Business Park Ayala


Alabang, Muntinlupa, 1780

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College of Engineering and Technology
Chemical Engineering Department

Liquigaz

PROCESS FLOW

LPG is produced during the oil refining process or is extracted during the
natural gas production process. In the production of liquefied natural gas or LNG,
petroleum gas is one of the by-products. It is separated from the gas stream for
further processing. While in the oil refining process, petroleum gas is one of the
many products that could be produced. The process flow of the production of LPG is
as follows:

DRILLING

EXTRACTION

DISTILLATION

DESULFURIZATION

BOTTLING

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College of Engineering and Technology
Chemical Engineering Department

PRODUCTION PROCESS

1. Drilling - A drilling rig drills unto the ground until the oil reservoir is clear of
obstruction and can be extracted using the oil rig.

MECHANISM METHOD OF OUTPUT EQUIPMENT


TRANSPORT
The rigs turntable turns No method of No
the drill making it drill into transport is product
the ground. Water is used is
pumped into the hole to produced
ease the drilling, the
resulting mud is sucked out
of the hole through a hose,
it is then passed through a
machine called a shale
shaker which filters out the
solids, the filtered mud is
then pumped back again to
the hole and sucked backed
out again until the drill
reaches the oil reservoir
DRILL RIG

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College of Engineering and Technology
Chemical Engineering Department

2. Extraction - An oil rig extracts the oil from the ground using a stainless rod.

MECHANISM METHOD OF OUTPU EQUIPMENT


TRANSPORT T
A motor turns two Pipes are Extract
crank rods aided with used to ed
counter weights transport the crude
which is attached to a extracted oil
pitman arm which in crude oil to a
turn, is attached to collection
what is called a plant. After
walking beam. The which, some
circular motion of the of the
crank rods force the collected is
walking beam to transported
rotate back and forth. to an oil
Attached to the other refinery
end of the beam is the
horses head which is
attached to the bridal
wherein a polished
rod is attached. The
momentum of the rod OIL RIG
sucks out the oil from
the reservoir unto the
valves on the surface.

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College of Engineering and Technology
Chemical Engineering Department

3. Distillation - The oil is heated up to a temperature of 600oC, the gas is then


pumped into a distillation column. Petroleum gas is drawn from the top.

MECHANISM METHOD OF OUTPUT EQUIPMENT


TRANSPORT
The different Pipes are Petroleum
components of the used to gas
crude oil is transport the
separated from each extracted
other by utilizing crude oil to
their boiling point the
difference. The gas distillation
resulting from column. After
boiling the crude oil which, the
is put into a extracted
distillation column. petroleum
The higher the gas is
compound goes, the transported
cooler it gets, and again
because the through
liquefaction point of pipes to a
compounds are hydrotreater
different, they are
separated into the
DISTILLATION
different points of
COLUMN
the column

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4. Desulfurization - The petroleum gas is then transported into a desulfurization


tank to remove sulphur. The purpose of removing the sulfur is to reduce the sulfur
dioxide emissions that result from using those fuels in automotive vehicles, aircraft,
railroad locomotives, ships, gas or oil burning power plants, residential and
industrial furnaces, and other forms of fuel combustion.

MECHANISM METHOD OF OUTPUT EQUIPMENT


TRANSPORT
H2 gas is added to the Petroleum Desulfurized
petroleum gas to gas is Petroleum
desulfurize it. This is transported gas
sometimes aided by into the
catalysts like Nickel hydrotreater
and Molybdenum. using pipes.
Propanethiol+ The

Hydrogen desulfurized

Propane + Hydrogen petroleum

sulfide gas is then


transported
to the
bottling
plants

HYDROTREATER

5. Bottling - The petroleum gas is bottled into what is commonly called LPG tanks or
propane tanks. Because of the pressure inside the tank, the gas liquefies.

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College of Engineering and Technology
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MECHANISM METHOD OF OUTPUT EQUIPMENT


TRANSPORT
Hoses fill the propane Pipes Liquefied
tanks up to 80% of its transport Petroleum
capacity, this is to desulfurized Gas
ensure that the gas petroleum
liquefies. After the gas into the
propane tank is filled, it bottling
is sealed by the machine plants
and a conveyor
transports it to the
loading bay

LPG FILLING CAROUSEL

Manufactured Fuel Gas


Manufactured fuel gases are those produced through an artificial process.
Manufactured fuel gases include:

Producer gas
Water gas
Syngas
Coal gas
Wood gas
Blast furnace gas
Biogas

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a. Producer Gas (air gas)

It is a mixture of flammable gases (principally carbon monoxide and hydrogen) and


nonflammable gases (mainly nitrogen and carbon dioxide) made by the passing air
with steam over burning carbonaceous substances, usually coal, in a furnace. It is
used as fuel, certain gas engines and in the manufacture of ammonia.
Producer gas has lower heating value than other gaseous fuels, but it can be
manufactured with relatively simple equipment. (Encyclopaedia Britannica)

Producer Gas Components

b. Water Gas (blue gas)


Water gas, colorless poisonous gas that burns with an intensely hot, bluish (nearly
colorless) flame. The synthesis gas is a mixture of carbon monoxide and hydrogen
(about 50 percent carbon monoxide, 40 percent hydrogen, and small amounts of
methane, carbon dioxide, and nitrogen) and is almost entirely combustible as a
result. Water gas is so named because of the use of water (steam) in its preparation.
This process involves treating white-hot hard coal or coke with a blast of steam;
carbon monoxide and hydrogen are formed. The gas is manufactured in vast
quantities for commercial use. It is of much importance in the preparation of
hydrogen and as a fuel in the making of steel and in other industrial processes, e.g.,
the Fischer-Tropsch process.

H2O + C H2 + CO (H = +131 kJ/mol)

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The reaction is endothermic so the fuel must be continually re-heated to keep the
reaction going. In order to do this, an air stream, which alternates with the vapor
stream, is introduced for the combustion of carbon to take place.

O2 + C CO2 (H = 393.5 kJ/mol)

Variations of Water Gas


i. Carburetted water gas
Water gas had a lower calorific value than coal gas so the calorific value
was often boosted by passing the gas through a heated retort into which
oil was sprayed. The resulting mixed gas was called carburetted water
gas.
ii. Semi-water gas
Semi-water gas is a mixture of water gas and producer gas made by
passing a mixture of air and steam through heated coke. The heat
generated when producer gas is formed keeps the temperature of the
coke high enough to allow water gas to be formed.

c. Synthesis Gas (Syngas)


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) and for
producing ammonia or methanol. Syngas is also used as an intermediate in
producing synthetic petroleum for use as a fuel or lubricant via the FischerTropsch
process. Syngas is combustible and often used as a fuel of internal combustion
engines. It has less than half the energy density of natural gas.
Syngas Composition

The following table provides a typical range for the composition of syngases. This will
be dependent upon the specific chemical composition of the feedstock to the gasifier.

Substance Composition (%)


H2 20-40
CO 35-40
CO2 25-35

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CH4 0-15
N2 2-5

d. Coal Gas
Coal gas is a gaseous mixture of mainly hydrogen, methane, and carbon monoxide
and formed by the destructive distillation (i.e., heating in the absence of air) of
bituminous coal and used as a fuel. Sometimes steam is added to react with the
hot coke, thus increasing the yield of gas. Coal tar and coke are obtained as by-
products. (Encyclopedia Britannica, 2008)

Substance Composition (%)


Hydrogen (H2) 14.0%
Carbon Monoxide (CO) 27.0%
Carbon Dioxide (CO2) 4.5%
Oxygen (O2) 0.6%
Methane (CH4) 3.0%
Nitrogen (N2) 50.9%

e. Wood Gas
Wood gas is a syngas fuel which can be used as a fuel for furnaces, stoves and
vehicles in place of gasoline, diesel or other fuels. During the production
process biomass or other carbon-containing materials are gasified within the oxygen-
limited environment of a wood gas generator to produce hydrogen and carbon
monoxide. These gases can then be burnt as a fuel within an oxygen rich
environment to produce carbon dioxide, water and heat. In some gasifiers this
process is preceded by pyrolysis, where the biomass or coal is first converted to char,
releasing methane and tar rich in polycyclic aromatic hydrocarbons.

Substance Composition (%)


Hydrogen (H2) 14.0%
Carbon Monoxide (CO) 27.0%

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Carbon Dioxide (CO2) 4.5%


Oxygen (O2) 0.6%.
Methane (CH4) 3.0%
Nitrogen (N2) 50.9%

It is pointed out, that the gas composition is strongly dependent on the gasification
process, the gasification medium (air, oxygen or steam) and the fuel moisture. Steam-
gasification processes typically yield high hydrogen contents, downdraft fixed bed
gasifiers yield high nitrogen concentrations and low tar loads, while updraft fixed bed
gasifiers yield high tar loads.

f. Blast Furnace Gas


Blast furnace gas (BFG) is a by-product of blast furnaces that is generated when
the iron ore is reduced with coke to metallic iron. It has a very low calorific heating
value, about 93 BTU/cubic foot, because it consists of about 60 percent nitrogen, 18-
20% carbon dioxide and some oxygen, which are not flammable. The rest is
mostly carbon monoxide, which has a fairly low heating value already. It is commonly
used as a fuel within the steel works, but it can be used in boilers and power
plants equipped to burn it. It may be combined with natural gas or coke oven gas
before combustion or a flame support with richer gas or oil is provided to sustain
combustion. Particulate matter is removed so that it can be burned more cleanly.
Blast furnace gas is sometimes flared without generating heat or electricity.

g. BioGas
Biogas typically refers to a gas produced by the anaerobic digestion or fermentation
of organic matter including manure, sewage sludge, municipal solid waste,
biodegradable waste, energy crops or any other biodegradable feedstock. Biogas is
comprised primarily of methane and carbon dioxide.

One main advantage of biogas is the waste reduction potential. Biogas production by
anaerobic digestion is popular for treating biodegradable waste because valuable fuel
can be produced while destroying disease-causing pathogens and reducing the
volume of disposed waste products.

Biogas burns more cleanly than coal, and emits less carbon dioxide per unit of
energy. The carbon in biogas was recently extracted from the atmosphere by

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photosynthetic plants. Releasing it back into the atmosphere adds less total
atmospheric carbon than burning fossil fuels.

Thus, biogas production kills two birds with one stone: it reduces waste and
produces energy. In addition, the residues from the digestation process can be used
as high quality fertilizer. This closes the nutrient cycle.

Characteristics

The product of digestion is Biogas, a combination of methane and carbon dioxide,


typically in the ratio of 6:4 (55-80 % methane). In addition, there are small quantities
of hydrogen sulfide and other trace gases.

Typical composition of
biogas
Methane 50-80 %
Carbon dioxide 25-50 %
Nitrogen 0-10 %
Hydrogen 0-1 %
Hydrogen
0-3 %
sulphide

Use

Biogas containing methane is a valuable product of anaerobic digestion which can be


utilised in the production of renewable energy. Biogas can be used for generating
electricity and heat. It can also be burned directly for cooking, heating, lighting and
process heat. Furthermore, even pilot fuel cells installations are operated with by
biogas.

In addition, biogas can be cleaned and upgraded to natural gas quality. The final
product is biomethane, which has methane content between 95 and 100%. This
biomethane is suitable for all natural gas applications: for instance, it can be fed into
the natural gas grid or used for transport in vehicles.

Raw Materials

In biogas plants, biogas can be produced by using numerous different input


substrates. Organic materials are essential as substrates for generating biogas and
the key starting point for the production process. The organic material should be free

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from wood (lignin) because the bacteria in the plant are unable to process this
substance. There are seven categories of organic materials which are suitable
substrates:

Domestic (communal) Organic waste means separate collected fruit and


organic waste vegetable wastes, flower soil, flowers, eggshells, coffee and
tee filters and other organic leftovers. The percentage of
dry matter varies between 10 and 30 %.
Green and plant Loppings and leftovers from cutting gardens or parks
wastes which do not contain woody matter (lignin).
Communal sewage The leftover from communal waste water treatment is
sludge sludge, which must be decontaminated to be used for
biogas production. This sewage sludge can contain
phosphor, nitrate and heavy metals. Experience shows
that sludge from waste water treatment is suitable in
biogas plants, but is not considered as a high quality
substrate. It is illegal to use sludge from non-public
sources because of the higher content of heavy metals or
genetically modified organisms or hormones. The
percentage of dry matter varies between 20 and 30 %.
Liquid or solid Liquid or solid manure from animal farming is one of the
manure main substrates for the digestion process. Cow manure is
best, whereas chicken manure for example has a high
output, but might contain sand. The dry matter of solid
manure varies between 15 and 30% and of liquid manure
between 5 and 7 %.
Energy crops Energy crops are primarily cultivated on otherwise
disused fields, such as corn, Sudan grass, millet, white
sweet-clover.
Industrial food waste Industrial food wastes come from food and meat
production sites or processes such as whey, potato mash,
vegetable leftovers, brewer grains, apple marc. These
kinds of substrates are usually very suitable and do not
contain harmful substances. Substrates from meat
production, like slaughterhouse waste, are good organic
materials but need special treatment to reduce health
risks and odour.

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Maximal potential of gas production per ton of substrate

Cow manure 25 m3/t


Pig manure 36 m3/t
Whey 55 m3/t
Spent grains, duff 75 m3/t
Loppings 110 m3/t
Domestic organic waste 120 m3/t
Industrial food waste 220 m3/t
Flotation slurry 400 m3/t
Waste food grease and oils 600 m3/t

Process Lay-out

Anaerobic Biogas Upgrading


Pre-treatment
Digestion (Water Scrubbing)

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Equipment Lay-out

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Plant Lay-out

Manufacturing Process of BioGas

1. Pre-treatment Collected manure was pre-treated prior to introduction in an


anaerobic digester. It includes grinding, screening, grit removal, and mixing. It
is used to adjust the manure or slurry water content to meet process
requirements of the selected digestion technology. A concrete or metal
collection/mix tank may be used to accumulate manure, process water and/or
flush water.

Proper design of a mix tank prior to the digester can limit the introduction of
sand and rocks into the anaerobic digester itself. If the digestion processes

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requires a thick manure slurry, a mix tank serves a control point where water
can be added to dry manure or dry manure can be added to dilute manure.

Equipment Mechanism Reagent Used Product/


and Feed Outcome
Autogenous Mill Waste is fed in the none Homogenize
autogenous mill where mixtures of
it is crushed into small waste
particles and screened materials are
to remove some yielded.
unnecessary dirts.
Then, it is mixed to
Mixing Tank homogenize it.

2. Anaerobic digestion is a purely bacterial process. The process works in the


absence of air. The digestion process can be divided into four phases.

In the first phase anaerobic bacteria use enzymes to decompose high


molecular organic substances such as proteins, carbohydrates, cellulose and
fats into low molecular compounds. During the second phase acid forming
bacteria continue the decomposition process into organic acids, carbon dioxide,
hydrogen sulphide and ammonia. Acid bacteria form acetate, carbon dioxide
and hydrogen during the third phase, the acetogenesis. The fourth phase, the
methanogenesis, involves methane forming bacteria producing methane,
carbon dioxide and alkaline water.

The bacteria can digest any kind of biological material except solid biofuels
with a high quantity of lignin, such as wood.

The bacteria in the methane phase need a longer reproduction time than the
bacteria in the acid phase. Therefore the speed and scale of the fermentation
depend on the metabolism of the methane bacteria. On the other hand the
methane bacteria need the metabolism products from the acid bacteria. Thus,

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they are in symbiosis and the necessary conditions for both bacteria types are
imperative for a smooth flow.

Hydrolysis
In general, hydrolysis is a chemical reaction in which the breakdown of water occurs
to form H+ cations and OH- anions. Hydrolysis is often used to break down larger
polymers, often in the presence of an acidic catalyst. In anaerobic digestion,
hydrolysis is the essential first step, as Biomass is normally comprised of very large
organic polymers, which are otherwise unusable. Through hydrolysis, these large
polymers, namely proteins, fats and carbohydrates, are broken down into smaller
molecules such as amino acids, fatty acids, and simple sugars. While some of the
products of hydrolysis, including hydrogen and acetate, may be used by
methanogens later in the anaerobic digestion process, the majority of the molecules,
which are still relatively large, must be further broken down in the process of
acidogenesis so that they may be used to create methane.

Acidogenesis
Acidogenesis is the next step of anaerobic digestion in which acidogenic
microorganisms further break down the Biomass products after hydrolysis. These
fermentative bacteria produce an acidic environment in the digestive tank while
creating ammonia, H2, CO2, H2S, shorter volatile fatty acids, carbonic acids, alcohols,
as well as trace amounts of other byproducts. While acidogenic bacteria further
breaks down the organic matter, it is still too large and unusable for the ultimate goal
of methane production, so the biomass must next undergo the process of
acetogenesis.

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Acetogenesis
In general, acetogenesis is the creation of acetate, a derivative of acetic acid, from
carbon and energy sources by acetogens. These microorganisms catabolize many of
the products created in acidogenesis into acetic acid, CO2 and H2. Acetogens break
down the Biomass to a point to which Methanogens can utilize much of the
remaining material to create Methane as a Biofuel.

Methanogenesis
Methanogenesis constitutes the final stage of anaerobic digestion in which
methanogens create methane from the final products of acetogenesis as well as from
some of the intermediate products from hydrolysis and acidogenesis. There are two
general pathways involving the use of acetic acid and carbon dioxide, the two main
products of the first three steps of anaerobic digestion, to create methane in
methanogenesis:

CO2 + 4 H2 CH4 + 2H2O


CH3COOH CH4 + CO2

While CO2 can be converted into methane and water through the reaction, the main
mechanism to create methane in methanogenesis is the path involving acetic acid.
This path creates methane and CO2, the two main products of anaerobic digestion.

An anaerobic digester is an engineered containment vessel designed to exclude


air and promote the growth of methane bacteria. The digester may be a tank, a
covered lagoon, or a more complex design, such as a tank provided with
internal baffles or with surfaces for attached bacterial growth. It may be
designed to heat or mix the organic material.

Equipment Mechanism Reagent Product/


Used and Outcome
Feed
Digester There are four fundamental None Biogas are
steps of anaerobic digestion yielded after the
that include hydrolysis, methanogenesis
acidogenesis, acetogenesis, as well as
and methanogenesis. digestate and
Throughout this entire wastewater.
process, large organic
polymers that make up waste
materials (biomass) are broken
down into smaller molecules
by chemicals and
microorganisms. Upon

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completion of the anaerobic


digestion process, the biomass
is converted into Biogas,
namely carbon dioxide and
methane, as well as digestate
and wastewater.
3. Biogas Upgrading - Raw biogas produced from digestion is roughly 60%
methane and 29% CO2 with trace elements of H2S; it is not high quality enough
to be used as fuel gas for machinery. The corrosive nature of H2S alone is
enough to destroy the internals of a plant.
Methane in biogas can be concentrated via a biogas upgrader to the same
standards as fossil natural gas, which itself has had to go through a cleaning
process, and becomes biomethane. Carbon dioxide, water, hydrogen sulfide,
and particulates must be removed if present.
There are four main methods of upgrading: water washing/scrubbing, pressure
swing absorption, selexol absorption, and amine gas treating.
The most prevalent method is water washing where high pressure gas flows
into a column where the carbon dioxide and other trace elements are scrubbed
by cascading water running counter-flow to the gas. This arrangement could
deliver 98% methane with manufacturers guaranteeing maximum 2% methane
loss in the system. It takes roughly between 3% and 6% of the total energy
output in gas to run a biogas upgrading system.

High pressure water scrubbing

High pressure water scrubbing is a technique based on the physical absorption of


dissolving gases in liquid. In the case of upgrading biogas, it can be used because the
dissolubility of CO2 and H2S is much larger compared to the dissolubility of CH4.
Also, the dissolubility of all components increases when the pressure is higher. The
principle of the process is shown in the figure.

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First, the biogas enters an input separator where the pressure is increased to 2
bars. If the biogas contained any water it will be condensed here together with
some contaminants. Then, the gas is compressed to 10 bars and injected into
the bottom of the scrubber while water is sprayed from the top of the column.
The gas leaving at the top of the scrubber needs to be dried. After this drying
step, the obtained CH4 purity is approximately 98%. The water used in the
process can be regenerated by decreasing the pressure to 1 bar.

The main advantage of high pressure water scrubbing is its simplicity. This
technique only requires water and an absorption column. This technique does
not need any expensive chemicals or equipment so it is also economical feasible.

The water scrubbing process has two main waste streams. The first one is the
air exhaust. This one mainly consists of air with higher than normal percentages
of CO2. But, the stream also contains some H2S which is poisonous and
therefore this stream needs to be treated.

The second waste stream is water that is been purged. The amount of H2S and
CO2 are that low that this stream does not need to be treated.

Companies

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asiaBIOGAS Co. Ltd. (ABC)


AsiaBIOGAS Co. Ltd. (ABC) is Southeast Asias largest biogas systems design,
engineering, construction and operating company. Headquartered in Bangkok,
Thailand, the firm currently operates in Thailand, The Philippines, Vietnam,
Indonesia and Malaysia. Focusing primarily on renewable waste to energy generation,
asiaBIOGAS designs, builds and operates power plants
Asiabiogas Philippines
12th floor, 1205 West Tower,
Philippine Stock Exchange Building,
Exchange Road, Ortigas Centre,
Pasig City Philippines
Tel: +63 2 661 7552
Email: info@asiabiogas.com

Pangea Green Energy Philippines


PGEP is a renewable energy project development and consulting company providing
solid technical advise, innovative financial solutions, and environmental expertise
that balance economic and environmental benefits.
Address: 68 Zamboanga Street, Area B, Barangay Payatas,
Quezon City 1119, Philippines
Phone: +63.2.4890646 / +63.2.9134988 / +63.2.4272086
Fax: +63.2.4210133 / +63.2.4272086
Email: info@pgephil.com

SYNTHESIS GAS MANUFACTURING

A. Introduction
a. Definition

As mentioned above, there are three types of fuel, the solid, the liquid
and the gas. The fuel gas is further divided into two major divisions according to their
sources, the fuel gas that is found naturally and the fuel gas that is manufactured
from other materials. One type of manufactured fuel gas is the synthesis gas.

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Synthesis gas, often abbreviated as syngas, is a mixture comprising of


carbon monoxide, carbon dioxide, and hydrogen. It is mainly used as an intermediary
building block for the final production (synthesis) of various fuels, as its name
implies. However, Syngas is combustible and has less than half the energy density of
natural gas, making it a common source of fuel of internal combustion
engines/transportation fuel.

b. Uses

Syngas is a very diverse product with many far reaching and potential
uses. Aside from being a fuel for transportation and other processes itself, it also acts
as an intermediate in creating different products such as:

1. Synthetic natural gas (SNG)


- Using a "methanation" reaction, the coal-based syngaschiefly
carbon monoxide (CO) and hydrogen (H2)can be profitably converted
to methane (CH4).
2. Methanol and Ammonia
- Methanol: Methanol is used as the feedstock for production of
formaldehyde, acetic acid, propylene and various esters. These in turn
are the chemical building block in the production of plastics, resins,
pharmaceuticals, adhesives, paints and much more. Methanol is also
used as a component of fuels. Biodiesel is normally made using
methanol.

-Ammonia: Ammonia is the base for nitrogen fertilizers, including


ammonium, nitrate and urea fertilizers. These fertilizers play an
important role in attaining high agricultural yields and are the key to
our ability to provide sufficient food for growing populations.
- Ammonia is also the feedstock for most synthetic nitrogen-containing
compounds including amine and nitro compounds. Ammonia plays an
important role in the production of plastics like nylon and
polyurethane.
3. Hydrogen
- Hydrogen is used in the oil refining industry to strip impurities from
gasoline, diesel fuel, and jet fuel, thereby producing the clean fuels
required by state and federal clean air regulations. Hydrogen is also
used to upgrade heavy crude oil. It is also been promoted as the
energy carrier and fuel of the future. It is now been considered

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because a fuel based on hydrogen combust only in the form of water.


It is a preferred fuel for fuel cells.
4. Synthetic Petroleum/Synthetic Fuel
- Synthetic petroleum is for use as a fuel or lubricant via the Fischer
Tropsch process and previously the Mobil methanol to gasoline
process. Syngas is processed into a liquid transportation fuel using
one of a number of different conversion techniques depending on the
desired end product. The Fischer-Tropsch process reacts syngas with
typically a cobalt or iron-based catalyst, and transforms the gas into
liquid products (primarily diesel fuel and jet fuel) and potentially
waxes (depending on the FT process employed).

B. MANUFACTURING PROCESS
a. Layouts

Process Layout:

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Process Flowchart:

Feedstock
Dehydration Pyrolysis
Preparation

Combustion and
Purification Catalysis
Gasification

b. Raw Materials

Raw Materials and its Function

Raw Material Function


Coal

Feedstock

Natural Gas

Feedstock

Biomass

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Feedstock

Oxygen and Steam Responsible for producing


carbon monoxide and some
carbon dioxide in combustion
and gasification

c. Product

Table 2. The Product and its Composition

The following table provides a typical range for the composition of


syngas. This will be dependent upon the specific chemical composition of the
feedstock to the gasifier.

Substance Composition (%)


H2 20-40
CO 35-40
CO2 25-35
CH4 0-15
N2 2-5

d. Manufacturing Process

Process Mechanism/Description Equipment


Feedstock The raw materials, such
Preparation as coal, petroleum based
materials, biomass and
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other materials that


could be rejected as
waste are prepared and
processed separately to
form different feedstocks
that will be into the
gasifier. It is often dried
and pulverized. The
quality of the syngas will
depend on the quality of
the feedstocks formed.
Dehydration This is also called as the Gasifier
drying process. This
occurs at temperature
around 100C. The water
content in the feedstock
is removed and the
resulting steam/water is
mixed into the gas flow.

Aside from that, the


resulting steam may also
be involved with
subsequent chemical
reactions, notably the
water-gas reaction if the
temperature is
sufficiently high enough.
In this water gas
reaction, balances the
concentrations of carbon
monoxide, steam, carbon
dioxide and hydrogen.

Chemical Reaction:
CO + H2O CO2 + H2

Pyrolysis This process is also Gasifier


called as devolatilization
process. This process
occurs at temperatures
about 200-300C.

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Volatiles are released and


char is produced,
resulting in up to 70%
weight loss for the
feedstock. The process is
dependent on the
properties of the
feedstock, as mentioned
earlier, and determines
the structure and
composition of the char,
which will then undergo
gasification reactions.
Combustion and Combustion is an Gasifier
Gasification exothermic (heat
releasing) reaction
between a high carbon
fuel and an oxidizer (a
substance that supports
combustion, usually
oxygen) in which the fuel
is burned to produce
heat as an energy source.
Gasification is an
exothermic reaction
between a high carbon
fuel and a carefully
controlled and limited
supply of oxidizer, in
which the fuel yields
useful elemental and
compound gases that can
be made into other
products.

The combustion process


occurs as the volatile
products and some of the
char reacts with oxygen
to primarily form carbon
dioxide and small
amounts of carbon
monoxide, which
provides heat for the

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subsequent gasification
reactions. The
gasification process
occurs as the char reacts
with carbon and steam to
produce carbon
monoxide and hydrogen.

Chemical Reactions:
For combustion: C + O2
CO2
For gasification: C + H2O
CO2 + H2
Purification The result of gasification CO2 Membrane (removal of
is a raw syngas that is carbon dioxide and
not yet clean enough to nitrogen)
use. A purification
process takes care of
impurities such as
carbon dioxide, water
vapor, methane, sulfur
compounds, tar and ash.
Sulfur is recovered in the
elemental form or as
sulfuric acid and both of
these can be marketed. If Amine Scrubber (removal
syngas contains a of sulphur)
considerable quantity of
nitrogen, the nitrogen
must be separated to
avoid production of nitric
oxides, which are
pollutants and contribute
to acid rain production.

The proportion between


hydrogen and carbon
monoxide is also
adjusted depending on
what the syngas will be
used for.

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The gasifier systems mentioned above has three types, according to its
gasifier bed type. All of these types can be used in producing syngas and has the
same mechanism. The only difference between then is the addition of some raw
materials and how the individual process mentioned (dehydration, pyrolysis,
combustion and gasification) are achieved.

1. Fixed Bed Gasifier/Moving Bed Gasifier (Lurgi Process)

In this process, the gas will be needed to be purified or scrubbed after by


a circulating gas liquor and then cooled to a temperature at which the gas is
saturated with steam because the gas produced is still not pure.

This gasifier has a pressurized (up to 2800 kPa) moving-bed system that
operates with either air or oxygen. The feedstock is fed at the top of the gasifier and
steam or oxygen are injected at the bottom. The temperature of gasification is lower
than with the other types of beds. As the feedstock gravitates downward and is
heated, devolatilization took place and, from a temperature of 620 to 760C upward,
devolatilization is accompanied by gasification of the resulting char. The crude gas
leaves the gasifier at temperatures between 370 and 575C, depending on the type of
feedstock.

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2. Fluidized Bed Gasifier (Winkler Process)

This gasifier has the advantage of uniform temperature distribution and


excellent solid-gas contact. Crushed or fine feedstock is fed to the top and oxygen
and steam is fed into the bottom. Aside from that, some type of coals and other
feedstock must be preheated first before being fed to the process. This is because its
operating temperatures are really high. Also, the resulting gas has high dust content,
so it needs to be treated.

In this system, the fuel is fluidized in oxygen and steam or air. The
oxygen and steam is passed through the feedstock, which is granular in form, at high
enough velocities to suspend the solid and cause it to behave as though it were a
fluid. This will form the gas and the ash.

3. Entrained Flow Gasifier (Koppers-Totzek Process)

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This gasifier has the highest capacity per unit volume of the three
processes. It produces a gas free of tars and phenols. Also, the overall gas production
rates are higher than either the fixed bed or the entrained bed. However, it requires
high temperatures, to 1900C, and high amounts of oxygen.

In this gasifier, the pulverized feedstock, oxygen and steam are fed
together. The fuel particles must be much smaller than for other types of gasifiers.
This means the fuel must be pulverized, which requires somewhat more energy than
for the other types of gasifiers. The feedstock is then gasified in suspension. The
gasification reactions take place in a dense cloud of very fine particles.

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References

Austin, G. T. (1984). Shreve's Chemical Process Industries (5th ed.). (J. Zseleczky, &
R. Margolies, Eds.) United States of America: McGraw-Hill, Inc.

Beychock, Milton. "Hydrodesulfurization." The Encyclopedia of Earth. N.p., 15 Dec.


2013. Web. 23 Feb. 2014.

BiofuelOrgUK. (2010). Biofuel.org.UK. Retrieved February 24, 2014, from What is


SynGas?: http://biofuel.org.uk/what-is-syngas.html

Biogas. Retrieved on February 20, 2014 at http://en.wikipedia.org/wiki/Biogas.

Clarke Energy. (n.d.). Clarke Energy. Retrieved February 25, 2014, from Syngas
Cogeneration / Combined Heat & Power: http://www.clarke-energy.com/gas-
type/synthesis-gas-syngas/

Fraham, John. "What Is the Composition of Lpg Gas?" WikiAnswers. Answers


Corporation, n.d. Web. 24 Feb. 2014.

Gable, C., & Gable, S. (n.d.). about.com. Retrieved February 24, 2014, from What is
Gasification?:
http://alternativefuels.about.com/od/researchdevelopment/a/gasification.htm

Grabianowski, Ed. "How Liquefied Petroleum Gas Works." HowStuffWorks. N.p., n.d.
Web. 23 Feb. 2014.

Lwnertz, P. (2008). ChemRec: Energy to Succeed. Retrieved February 25, 2014, from
The Magic of SynGas:
http://chemrec.se/Syngas_the_link_from_feedstock_to_synthetic_product.aspx

"LPG - Liquefied Petroleum Gas." LPG - Liquefied Petroleum Gas. N.p., n.d. Web. 23
Feb. 2014.

"LPG." LPG RSS. N.p., n.d. Web. 23 Feb. 2014.

"What Is LPG?" Origin News RSS. ORIGIN, n.d. Web. 24 Feb. 2014.

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