Exothermic Oxidation

Related terms:

Coal, Reactor, Oxidation Reaction, Catalyst, Hydrogen, Syngas, Temperature, oxy-

gen carrier, steam reforming, Higher Temperature

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Learn more about Exothermic Oxidation

Carbon capture from power generation

Stephen A. Rackley, in Carbon Capture and Storage (Second Edition), 2017

4.1 Introduction
The fundamental chemical process involved in the generation of power from car-
bon-based fuel is the exothermic oxidation of carbon, as described in Section 3.1,
and since CO2 is the lowest-energy end-point of the oxidative reaction chain, its
production is unavoidable. The elimination of carbon from power plant emissions
therefore requires either:

• Decarbonation of the fuel prior to combustion (pre-combustion capture)

• Separation of CO2 from the products of combustion (post-combustion cap-

ture)
• Reengineering the combustion process to produce CO2 as a pure combustion
product, obviating the need for its separation (oxyfuel or chemical looping
combustion)

These approaches are illustrated schematically in Figure 4.1.

Figure 4.1. Options for CO2 capture from power generation.

As shown in the figure, the pre- and post-combustion approaches both require
technologies to separate CO2 from a gas mixture comprising CO2+H2 or CO2+N2,
respectively. For oxyfueling, the oxygen supply can be achieved either through a
separation of O2 from air (O2+N2+trace gases) or by the delivery of oxygen to
the combustion process in the form of a solid oxide (chemical looping). Some
advantages and disadvantages of these capture options are summarized in Table
4.1.

Table 4.1. Advantages and disadvantages of capture options

Capture option Advantages Disadvantages

Pre-combustion Lower energy requirements for Temperature and efficiency-
CO2 capture and compres- issues associated with hydro-
sion; fully developed technol- gen-rich gas turbine fuel
ogy, commercially deployed at
the required scale in other in-
dustries
Post-combustion Fully developed technology, High parasitic power require-
commercially deployed at the ment for solvent regeneration;
required scale in other indus- low [CO2] impacts capture ef-
tries ficiency
Opportunity for retrofit to existing plant High capital and operating costs for current ab-
sorption systems
Oxyfuel combustion Mature air separation tech- Costly and energy intensive air
nologies available; very high separation step; significant
[CO2] simplifies capture plant impact makes retrofit un-
process attractive
Chemical looping combustion Very high [CO2] simplifies cap- Immature technology, currently
ture process under development

Several fundamental technology areas are in use or under development to address

these gas separation challenges, including absorption, adsorption, hydrate-based
separation, membranes, chemical looping. and cryogenic separation systems. The
application of these technologies to pre- and post-combustion capture and to
oxyfuel/chemical looping combustion is outlined in the following sections, and the
technologies are described in detail in Chapters 6–9Chapter 6Chapter 7Chapter
8Chapter 9.

> Read full chapter

The role of the fuel in the operation,

performance and degradation of fuel
cells
D.J.L. Brett, ... I. Staffell, in Functional Materials for Sustainable Energy Applications,
2012

9.3.3 Autothermal reforming

Autothermal reforming (ATR) combines the steam reforming reaction and fuel
oxidation into a single unit, the exothermic oxidation providing the heat for the en-
dothermic reforming process. ATR is popular for smallerscale hydrogen generation
and affords higher H2 production than POX and faster start-up and response times
than steam reforming. Independent control of the steam-to-carbon and air-to-fuel
ratios means that effective heat management can be achieved.

Early ATR systems were composed of separate, but thermally integrated, burner and
steam reformer. The challenge for single-unit ATR is that the catalyst must service (or
at least be compatible with) both the steam reforming and partial oxidation reactions
and their environment. Again, the choice of catalyst must be matched to the type of
fuel used. Lighter hydrocarbons can use copper-based catalysts with longer chain
molecules using Pt, Rh and Ru or ionconduction ceria supported non-noble metal
formulation: Fe, Co, Ni (Ghenciu, 2002). PGM cermet catalysts with bi-functional
properties have more recently been developed for ATR: the PGM services the dehy-
drogenation role and the oxide ion conducting properties of the ceramic component
(e.g., CeO2, ZrO2, Bi2O5) perform the selective oxidation function (Ghenciu, 2002).

> Read full chapter

Fuels and fuel processing for low tem-

perature fuel cells
D.J.L. Brett, ... I. Staffell, in Polymer Electrolyte Membrane and Direct Methanol Fuel
Cell Technology: Fundamentals and Performance of Low Temperature Fuel Cells,
2012

1.4.3 Autothermal reforming

Autothermal reforming (ATR) combines the steam reforming reaction and fuel
oxidation into a single unit, the exothermic oxidation providing the heat for the en-
dothermic reforming process. ATR is popular for smaller scale hydrogen generation
and affords higher H2 production than POX and faster start-up and response times
than steam reforming. Independent control of the steam-to-carbon and air-to-fuel
ratios means that effective heat management can be achieved.

Early ATR systems were composed of separate, but thermally integrated, burner and
steam reformer. The challenge for single-unit ATR is that the catalyst must service
(or at least be compatible with) both the steam reforming and partial oxidation
reactions and their environment. Again, the choice of catalyst must be matched to
the type of fuel used. Lighter hydrocarbons can use copper-based catalysts with
longer chain molecules using Pt, Rh, and Ru or ion-conduction ceria-supported
non-noble metal formulation: Fe, Co, Ni (Ghenciu, 2002). PGM cermet catalysts
with bifunctional properties have more recently been developed for ATR: the PGM
serves the dehydrogenation role and the oxide ion conducting properties of the
ceramic component (e.g. CeO2, ZrO2, Bi2O5) perform the selective oxidation function
(Ghenciu, 2002).

> Read full chapter

Laser Cutting Process

ProfessorBekir Sami Yilbas, in Laser Heating Applications, 2012

4.4 Analysis for Heat Transfer to Liquid Metals with the Pres-
ence of Assisting Gas
In the laser cutting process an assisting gas is used either to protect the surface from
high-temperature exothermic oxidation reactions, such as argon, or to produce an
exothermic reaction, such as oxygen. A jet of gas, which produces an exothermic
reaction, results in an increase in the rate of cutting; however, the accuracy and
the fineness of the cut are partly affected by the addition of the gas stream for
certain gas stream velocities. In an attempt to investigate the forces exerted by an
inert gas jet on the thin molten layer, the equations of motion of the gas flow were
solved previously [9,10]. In the analysis, the gas flow was assumed to be laminar and
the chemical reaction contribution was disregarded. Therefore, an extension of the
previous models became necessary. Dorrance [7], using a simple model reacting gas
mixture flowing over a heated flat plate, was able to demonstrate that boundary layer
equations applied up to the point where the reaction zone became attached to the
flat plate. In the model proposed, the reaction zone was assumed to be attached to
the liquid surface; reactions were considered to take place at the gas–liquid interface
with the rest of the gas phase being frozen (the mass rate of change of species
i per unit volume is constant). It has been demonstrated that the heat transfer
from a boundary layer composed of reacting gas is independent of the location
of the reaction zone within the boundary layer to a first order of approximation
[9,10]. This approximation includes the assumption that the transport properties
are independent of the boundary layer gas mixture, or at least their variation with
the composition is of secondary importance compared with their variation with
temperature. Since it is assumed that the chemical reactions are taking place at the
liquid–gas interface and the rest of the gas phase is frozen, the composition of the
gas mixture throughout the boundary layer will be determined by convection and
diffusion of the products and reactants through the boundary layer, the gas species
present in the external stream, and the gas species at the interface. The analysis
related to the heat transfer into the liquid metal is presented below in the light of
the previous study [9].

To derive equations for the heat transfer into liquid metal, which is experiencing
chemical reactions at the surface (i.e., the gas–liquid interface), an equation can be
written for the heat balance at the interface. Considering Figure 4.6, a heat balance
at the gas–liquid interface gives

Figure 4.6. A schematic view of the liquid–gas interface.

(4.90)

where denotes the chemical symbol for the material content undergoing a chem-
ical reaction, ( V)g is the volume flow of vapor phase escaping from surface, is heat
transfer to the liquid metal surface due to conduction and diffusion , and is the heat
transfer from the gas boundary to the liquid metal in the presence of mass transfer
occurring at the surface of the liquid. For material content

(4.91)

where h is the enthalpy and Lv = heat of vaporization of material content .

Combining Eqns (4.90) and (4.91) gives

(4.92)

Introducing Eqn (4.91) into Eqn (4.92) results in

(4.93)

where I is the total enthalpy , e is the free stream gas density, Ue is the free stream
gas velocity, CH is the heat transfer coefficient, Ci is the species mass fraction, MT1
is the mass transfer parameter, and Lv is the heat of vaporization. The heat transfer
to the liquid metal surface is [9]

(4.94)

Zi is the reduced mass fraction and

(4.95)

and

and MT1 is a mass transfer parameter defined by

(4.96)

Inserting total enthalpy in Eqn (4.93) gives

(4.97)

where MT2 in Eqn (4.97) is defined by .

Define another form called the chemical enthalpy potential hc as

(4.98)

Since the enthalpy of a gas mixture is , then

(4.99)

where , since all species leaving the liquid surface are confined to the boundary
layer, according to the assumption made earlier.
Combining Eqns (4.97) and (4.99) gives

(4.100)

In Eqn (4.100), is the heat transfer to the liquid metal in the presence of mass transfer
occurring at the surface of the liquid. The term hc represents the heat released or
absorbed due to a chemical reaction among the gas species near the surface.

To determine the heat transfer rate, one has to find the mass fractions of various
species at the surface and the edge of the boundary layer (which are used to
determine hc from Eqn (4.99)). It is also necessary to develop a method to calculate
( V)g as a function of the surface chemistry.

To calculate ( V)g the following equation can be considered [9]:

(4.101)

At the surface (liquid)

(4.102)

Therefore,

(4.103)

where

(4.104)

since

(4.105)

where is the density of the total mixture. Once the pressure at the edge of the
boundary layer and the interface temperature are known, species mass fractions Ci
can be calculated. Consequently, f(0) and hence ( V)g can be determined.

> Read full chapter

Natural Gas Conversion VI

T.J. Mazanec, ... E.T. Robinson, in Studies in Surface Science and Catalysis, 2001

2.4 Reactor Modeling

OTM syngas production combines oxygen separation with steam reforming and
partial oxidation of methane. Heat integration of the very exothermic oxidation and
endothermic reforming reactions is critical to achieve good process intensification
and high yields of syngas. Computational models have been developed that permit
various reactor designs to be evaluated. These models are based on fundamental
equations for mass and heat transfer as well as kinetics of the chemical reactions.

Figure 7 presents the calculated temperature profile for a counter-current tubular

OTM syngas process. In this model the air is fed from the bottom in the left hand
segment and the process gas is fed from the top of the figure in the right hand
segment. The white space represents the membrane.

Fig. 7. Temperature profiles calculated for OTM syngas process. The left segment
shows the air stream and the right segment shows the process gas. Temperature in
Kelvin.

> Read full chapter

Recent Advances in Polyethylene-Based

Biocomposites
Muhd R. Mansor, ... Mohd Z. Akop, in Natural Fibre Reinforced Vinyl Ester and Vinyl
Polymer Composites, 2018

3.5.2.1 Differential scanning calorimetry

This equipment is used to learn the degradation of oxidative in PE composites.
For a standard test, the composites are heated in nitrogen atmosphere to 200°C,
then oxygen is added and the beginning time of exothermic oxidation is noted.
Differential scanning calorimetry also can be used to evaluate the temperature of
glass transition (Tg) of PE. Addition of fiber or filler to the PE affects the temperature
of melting and crystallization and the crystallization percentage due to change in
the agents of nucleating (Zhang et al., 2006). Fibers behave as agents of nucleating
that rise the crystallinity percentage while fillers cause a reduction in movement of
the crystalline areas and the crystallite’s size. Natural fibers as agents of nucleating
in doum(5 wt.%)/LDPE composites show a wide melting peak as there were more
crystallites formed (Arrakhiz et al., 2013). The reinforcement and nucleating in
CaCO3-PE micrometric composite causes the increase of bulk crystallinity and the
decrease of spherulite size (Tanniru and Misra, 2005). The addition of HA nanopar-
ticles and aging of HDPE in HA nanoparticles/HDPE composites cause a change
in Tg, crystallinity, and temperature of melting (Jaggi et al., 2012). SEBS-g-MA and
PE-g-MA can cause an induce in fractional crystallization of the nylon-6 component
for banana fiber (BaF)-filled composites based on HDPE/nylon-6 blends (Liu et al.,
2009).

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Behavior of Radionuclides in the Envi-

ronment
Gregory Choppin, ... Christian Ekberg, in Radiochemistry and Nuclear Chemistry
(Fourth Edition), 2013

22.3.2 Fukushima
On the 11th of March 2011 an earthquake of the magnitude 9.0 on the Richter scale
occurred outside the eastern coast of Japan. All affected nuclear reactors shut down
as planned as a response to the earthquake. However, an unusually large tsunami
hit the Fukushima Daiichi nuclear power station afterwards causing a total blackout.
As the fuel heated up the zircaloy cladding underwent a highly exothermic oxidation
reaction according to eqn. (19.44).

(19.44)

The hydrogen produced escaped up into the secondary reactor building where it
accumulated and later exploded. Such explosions occurred in two reactors, but at
different times. This nuclear accident and its release was more fully described earlier,
see §13.10.2.
In comparison, the total releases of 900 PBq total into the air from Fukushima are
modest when compared to the 5200 PBq total from Chernobyl. The fallout in Japan
resulted in evacuation of many of the most afflicted areas. The effect of rain on the
fallout was rather similar in the two cases.

> Read full chapter

Geophysical Studies of Pyrometamor-

phic and Hydrothermal Rocks of the
Nabi Musa Mottled Zone, Vicinity of
the Dead Sea Transform, Israel
Yevgeny Vapnik, ... Sonia Itkis, in Coal and Peat Fires: A Global Perspective, 2015

Mineral Precursors of Magnetic Phases

The precursors of magnetic phases in CM rocks are often problematic. The oxidation
of pyrite to magnetite and/or hematite was suggested to be responsible for much
of the observed enhancement of magnetization (Cisowski and Fuller, 1987; Ron and
Kolodny, 1992). The oxidation of pyrite was postulated as a primary mechanism of
magnetic matter formation for MZ (Ron and Kolodny, 1992; Vandamme et al., 2003).
It was assumed that “oil shales” were rich in pyrite, the low-temperature exothermic
oxidation of which led to spontaneous combustion of rocks and enhancement of
their magnetic susceptibility. In addition to pyrite we infer at least partial inflow of
matter and mobility of iron during combustion (Masalehdani et al., 2007) and low-T
hydrothermal processes. Further reduction of iron compounds by hot reducing
gases (Thorpe et al., 1998; Heffern et al., 2007) led to the appearance of magnetic
phases. Thus, it is likely that clay minerals, Fe-oxides, and hydroxides were also the
Fe-bearing precursor minerals of magnetic minerals in MZ. Such precursors de-
termined the Ca–Fe-rich content of some minerals (perovskite and brownmillerite)
and most abundant cations (Al, Mg, Ti, and Cr) substituting for Fe in observed iron
oxides and ferrites.

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Oxidative Steam Reforming

Daniel J. Haynes, Dushyant Shekhawat, in Fuel Cells: Technologies for Fuel Process-
ing, 2011
Publisher Summary
This chapter explores aspects of oxidative steam reforming (OSR) chemistry that are
important in a fuel-reforming process. In this method, steam and oxygen are fed
together as oxidants to reform the hydrocarbon fuel into a H2-rich fuel stream suit-
able for fuel cells. OSR is generally considered as a combination of partial oxidation
and steam reforming. Feeding air and steam together utilizes the heat generated
from exothermic oxidation of the fuel to promote the endothermic steam-reform-
ing reactions. OSR has been an established technology for H2 generation since
the late 1950s. It is capable of producing H2 efficiently at high throughputs,
which generally makes it the preferred method for industrial use in petrochemical
production. However, using OSR for such applications requires a separation plant
to remove N2 from air to reduce process gas volumes. Oxygen separation is very
capital intensive (almost 40% of total cost) and generally precludes the use of OSR for
large-scale applications. However, OSR does have some disadvantages. Using steam
requires a water storage and supply system, which adds weight, complexity, and cost
to the process. Also, as with any system that uses water, appropriate insulation is
needed for applications in colder climates, and added space would be required for a
reservoir in an already confined area (assuming for transportation use). Attempts to
mitigate storage problems have looked into recycling the fuel cell exhaust to provide
the necessary water requirements to maintain reforming capabilities under OSR
conditions.

> Read full chapter

Design of Biomass Gasifiers

Prabir Basu, in Biomass Gasification and Pyrolysis, 2010

Gasification Temperature
Because lignin, a refractory component of biomass, does not gasify well at lower
temperatures, thermal gasification of ligno-cellulosic biomass prefers a minimum
gasification temperature in the range 800 to 900 °C. For biomass, an entrained-flow
gasifier typically maintains a gasification temperature well exceeding 900 °C. For
coal, the minimum is 900 °C for most gasifier types (Higman and van der Burgt,
2008, p. 163).

A higher peak gasification temperature is chosen for an entrained-flow gasifier. The

higher the ash-melting temperature, the higher the design value of the gasifier
 temperature. This temperature is raised through the gasifier's exothermic oxidation
reactions, so a high reaction temperature also means a high oxygen demand.

In entrained-flow gasifiers, the peak gasification temperature is typically in the range

1400 to 1700 °C, as it is necessary to melt the ash; however, the exit gas temperature
is much lower. The peak temperature of a fluidized-bed gasifier is in the range of
700 to 900 °C to avoid softening of bed materials. It is about the same as the gas
exit temperature in a fluidized-bed gasifier. In a crossdraft gasifier the gasification
temperature is about 1250 °C, whereas the peak gasification temperature is about
1500 °C. The exit-gas temperature of a downdraft gasifier is about 700 °C, but its
peak gasifier temperature at the throat is 1000 °C. The updraft gasifier has the lowest
gas-exit temperature (200–400 °C), while its gasification temperature may be up to
900 °C (Knoef, 2005). Once the gasification temperature is known, the designer can
turn to the heat balance on this basis.

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