Exothermic Oxidation

Related terms:

Coal, Reactor, Oxidation Reaction, Catalyst, Hydrogen, Syngas, Temperature, oxy- gen
carrier, steam reforming, Higher Temperature

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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- ment
commercially deployed at the for solvent regeneration; low [CO2]
required scale in other indus- impacts capture ef- ficiency
tries
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 plant
[CO2] simplifies capture impact makes retrofit un- attractive
process
Immature technology, currently under
Chemical looping combustion Very high [CO2] simplifies cap- development
ture process

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.

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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).

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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 heattransfer to the liquid metalin 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.

Tocalculate (□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.

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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.

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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 etal.,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.

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Design of Biomass Gasifters

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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