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Episode 3 : Production of

Synthesis Gas by Steam


Methane Reforming
SAJJAD KHUDHUR ABBAS
Ceo , Founder & Head of SHacademy
Chemical Engineering , Al-Muthanna University, Iraq
Oil & Gas Safety and Health Professional OSHACADEMY
Trainer of Trainers (TOT) - Canadian Center of Human
Development

History of Synthesis Gas

In 1780, Felice Fontana discovered that


combustible gas develops if water vapor is
passed over carbon at temperatures over 500
C. This CO and H2 containing gas was called
water gas and mainly used for lighting
purposes in the19th century.

As of the beginning of the 20th century,


H2/CO-mixtures were used for syntheses of
hydrocarbons and then, as a consequence,
also called synthesis gas.

Haber and Bosch discovered the synthesis of ammonia


from H2 and N2 in 1910 and the first industrial ammonia
synthesis plant was commissioned in 1913.
The production of liquid hydrocarbons and oxygenates
from syngas conversion over iron catalysts was
discovered in 1923 by Fischer and Tropsch.
Much of the syngas conversion processes were being
developed in Germany during the first and second
world wars at a time when natural resources were
becoming scare and alternative routes for hydrogen
production, ammonia synthesis, and transportation fuels
were a necessity.
In 1943/44, this was applied for large-scale production
of artificial fuels from synthesis gas in Germany.

To this day, however, methanol

and ammonia are still produced


from syngas using essentially the
same processes originally
developed and, apart from
hydrogen production, constitute
the major uses of syngas.

What is synthesis gas ?


In its simplest form, syngas (also called producer gas, town
gas, blue water gas, and synthesis gas) is composed of carbon
monoxide (CO) and hydrogen (H2). The name comes from its
use.
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 can be produced from any hydrocarbon


feedstock, including: natural gas, naphtha, residual
oil, petroleum coke, and coal.
The lowest cost routes for syngas production,
however, are based on natural gas, the cheapest
option.
The choice of technology for syngas production
also depends on the scale of the synthesis
operation.

Syngas production from solid fuels can require an


even greater capital investment with the addition of
feedstock handling and more complex syngas
purification operations.
The syngas composition, most importantly the H2/CO
ratio, varies as a function of production technology and
feedstock.
Steam methane reforming yields H2/CO ratios of 3/1,
while coal gasification yields ratios closer to unity or
lower.

Physical Properties of Hydrogen (H2):


With only one proton and one electron, hydrogen is the lightest of all chemical
elements. At ambient temperature, molecular hydrogen, H2, is a colourless and
odorless gas.
hydrogen condenses to a colorless liquid, it freezes at 259.15 C.
H2 is14 times lighter than air.
property

Unit

Value

Molar mass

g mol1

2.016

Heat of vaporization

J mol1

898

Properties at 273.15 K, 101.3 kPa

Density

kg m3

0.0899

Thermal conductivity

W m1 K1

0.1645

Molar heat

J mol1 K1

Cp = 22.0, Cv = 6.51

Property

Unit

Value

Boiling point (101.3 kPa)


Temperature

20.37

Density (liquid)

kg m3

70.00

Density (gas)

kg m3

1.319

Liquid at boiling point (101.3 kPa)

Molar heat

J mol1 K1

Cp = 22.0, Cv = 6.51

Enthalpy

J mol1

7918

Thermal conductivity

W m1 K1

0.117

Gas at boiling point (101.3 kPa)


Specific heatcapacity

J mol1 K1

Cp = 23.49, Cv = 12.8

Enthalpy

J mol1

7020

Thermal conductivity

W m1 K1

0.0185

Critical Point
Temperature

33.00

Pressure

kPa

1339

Density

kg m3

30.09

Chemical properties of hydrogen


In air, H2 combusts to water with a hardly visible,
weakly bluish flame. Hydrogen combines with almost
any other element. Metal compounds with
negatively charged hydrogen are called metal
hydrides (e.g. CaH2, NaH, LiH).Hydrogen has a
reducing effect on a lot of metal oxides when
heated. Thus CuO with H2, for example, reacts to Cu
and H2O. Hydrogen has a reducing
effect on a lot of metal oxides when heated.

Physical and Chemical Properties of Carbon


Monoxide (CO):

Carbon monoxide is colourless, odourless and tasteless. It is


highly toxic,poorly soluble in water (solubility: 23 mL L1 at 20
C and 1 bar).
Property

Unit

Value

Molar mass

g mol1

28.010

Explosion range
(in air at 101.3 kPa)

% Volume
fraction

10.9 76

Properties at 273.15 K, 101.3 kPa


Density

kg m3

1.250

Molar heat

J mol1 K1

Cp = 29.05,Cv =
20.68

Thermal
conductivity

W m1 K1

0.02324

Property

Unit
Boiling point (101.3 kPa)

Value

K
Melting point (101.3 kPa)
Temperature
K
Critical point
Temperature
K
Pressure
Kpa
Density
kg m3

81.65

Temperature

74.15
132.29
3496

301

Chemical properties of CO
Together with air, carbon monoxide forms explosive
mixtures in the concentration range of a CO-volume
fraction of (10.9-76%).In engineering, it is obtained by
separation from synthesis gas.
The reason for its toxicity is its property to displace
the oxygen from the hemoglobin-complex of blood,
since the affinity of hemoglobin (Hb) to CO is about
300 times higher than to O2. The hemoglobin of a
heavy smoker of cigarettes can reach a COsaturation of up to 15% in the course of a day.

Uses of syngas
1. Syngas can be used to produce a variety of chemicals like
ammonia and methanol.
2. Syngas itself can be used as a fuel in internal combustion
engine.
3. 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.
4. syngas can be used to produce organic molecules such as
synthetic natural gas (SNG-methane).

At these days, synthesis gas is mainly used for production of the


products listed:

Product

Uses

H2 and N2

Ammonia

CO

Formic acid

H2 and CO

Acetic acid

Mixtures of (H2, CO and CO2)

Methanol

Production of Synthesis Gas from Hydrocarbons:


In the production of synthesis gases from hydrocarbons,
the components hydrogen and carbon monoxide
usually appear as complementary products, carbon
dioxide can be obtained as a by-product.

There are Several Methods to Production the


Synthesis Gas from Hydrocarbons :
1.Steam Reforming
2.Partial Oxidation (PO ).
3.Autothermal Reforming ( ATR).

The Process Selection depends on Two factors:


1. The desired product composition (H2/CO ratio ).
2. The feedstock available like natural gas, residual gases
from refineries,LPG(Liquefied Petroleum Gas), naphtha,
heavy oils, distillation residues, pitch and coal.
The selected process in this project is Production
Synthesis Gas by steam reforming of Methane Gas
due to ratio (H2/CO)is equal to 3/1 and the feed is
methane gas. the economic cost of the steam must
be taken into account

The Advantages of (SMR):

Steam reforming of natural gas are :


Efficient
Economical
widely used process for hydrogen and monoxide
production
provides near- and mid-term energy security and
environmental benefits
The SMR produces a H2/CO ratio equal to three

We choose methane as a feed because of :

Methane is a wide distribution in nature.


cheap
Make a Less problems with the reformer.
Make a longer age for reformer than other
feed stockes.

Methane

Methane is a chemical compound with the chemical formula CH4 (one


atom of carbon and four atoms of hydrogen). It is the simplest alkane and
the main component of natural gas.
Methane is a colorless, odorless gas with a wide distribution in nature. It is
the principal component of natural gas, a mixture containing about 75%
CH4, 15% ethane (C2H6), and 5% other hydrocarbons, such as propane
(C3H8) and butane (C4H10).
Property

Unit

Molecular formula

Value
CH4

Molar Mass

g mol-1

16.04

Density at 25 C , 1
atm

g cm-3

0.656

Viscosity at -170 C

mPa.s

0.142

Specific heat
capacity at -100 C

J g-1 k-1

5.34

Melting point

-182

Flame Velocity

cm s-1

43.4

Critical Values
Temperature

- 82.5

Pressure

MPa

4.67

Density

g cm-3

0.162

Sources of Methane
Natural sources
1. Wetlands
2. Oceans
3. Geological sources
4. Wild animals
5. Wildfires

Non Natural sources


(Artificiality)
1. Oil and Gas System
2. Landfills
3. Wastewater
4. Coal Mines
5. Agriculture

Steam Reforming (Tubular Reforming)


Steam Reforming Methane (SMR) has been used for several decades
since it has been developed in 1926 and over the years substantial
improvements have been introduced. SMR process consists of gas
feed pre-heating and pre-treatment, reforming.
Steam reforming of methane is the main industrial route to produce
synthesis gas (a mixture of hydrogen and carbon monoxide).
In the steam reforming process, a light hydrocarbon feedstock (such
as natural gas, refinery gas, LNG, or naphtha) is reacted with steam
at elevated temperatures(typically 700 C to 900 C), and elevated
pressures (15 to 30 bar) in nickel-based catalyst filled tubes to
produce a synthesis gas. This gas consists primarily of hydrogen and
carbon monoxide. , but other gases such as carbon dioxide and
nitrogen, as well as water vapor are also present.The typical steam to
carbon ratio falls in the range of (2.8 to 3.2 to 1).

steam reforming (SR) is highly endothermic and it is carried


out at high temperature (700 - 900 C) and at pressures
between 15 and 30 bar.

Reactions and thermodynamics


The standard enthalpies of reaction (at 298 K) are given in brackets.
The most important reactions in steam reforming (SR) of methane are:

1. CH4(g) + H2O(g) CO(g) + 3H2(g)


2. CO(g) + H2O(g) CO2(g) + H2(g)

(H = +206 kJ/mol)
(H = -41 kJ/mol)

Catalyst
All tubular reformers use catalyst inside the
tubes in order to reduce the operating
temperature. This is important in order to
reduce the tube stresses resulting from high
pressure and high temperatures The Nicatalyst is needed since methane is a very
thermodynamically stable molecule even
at high temperatures. nickel catalyst filled
tubes to produce a synthesis gas.
Ni-catalyst is often in the form of thickwalled Raschig rings, with 16 mm in
diameter and height, and a 6 8 mm hole
in the middle.

Challenges
During the production of Synthesis gas, CO2
is also produced. The SMR process in
centralized plants emits more than twice the
CO2 than hydrogen produced. To avoid
emission of CO2 into the atmosphere, CO2
can be concentrated, captured, and
sequestered.

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