Syngas: Production, Applications and Environmental Impact

Editor: A. Indarto and J. Palgunadi © 2011 Nova Science Publishers, Inc.

Chapter 1

SYNTHESIS GAS
PRODUCTION BY REFORMING METHANE IN A
CHEMICAL COMPRESSION REACTOR

V. Shmelev*
Combustion Lab, Institution of Russian Academy of Sciences Semenov Institute of
Chemical Physics RAS, Russia

Abstract
The various technologies are studied to convert methane, a main ingredient of natural
gas, into hydrogen. These investigations are part of the total efforts to develop new low
pollution energies and reduce greenhouse gases. The discussion, different from existing
methods of reformation, suggests several steps in approach to a noncatalytic partial
oxidation methane in the methane-air mixture with usage of the internal combustion engine,
which can be modified to a chemical compression reactor with the heat recuperation. The
use of a chemical compression reactor (CCR) is quite promising for syngas and hydrogen
production. There is wide industrial base for manufacturing cheap CCRs on the base of
internal combustion engine. However, analysis shows that it is required to use additional
techniques for ensuring ignition and the occurrence of the chemical conversion of rich
hydrocarbon-air mixtures. Such effective method is preheating of the mixture prior to supply
to a reaction vessel. It is considered several methods. The mixture can be heated directly
outside the CCR, for example, in an electrical heater or by heat regeneration, and internal
heat recovery processes can be used. The outside preheating is the simplest method and can
be considered as a first step for investigation and development of this technology.
This chapter includes the theoretical analysis for CCR with external electrical heating
mixture and experimental results with the methane-air mixtures; a method for noncatalytic
partial oxidation of methane in a CCR with heat regeneration is proposed and the appropriate
theory is developed. The heat regenerator is located in the channel of a combined exhaust
and intake manifold, through which reaction products and reactants alternately pass; a
method for the partial oxidation of methane in a CCR with internal heat recovery is proposed
and examined. The reactor cylinder divided by a partition with a cross flow orifice into two
chambers is considering. Internal heat recovery is implemented using a thermal activator
installed in the smaller (auxiliary) chamber.
__________________________
* e-mail: shmelev@chph.ras.ru
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Nomenclature

α air– methane equivalence ratio ICE Internal Combustion Engine

ε burning completeness coefficient K rate constants of the reaction, m3⋅mol-1⋅sec-1
θ dimensionless temperature ma mass of thermal activator, kg
τ dimensionless time N crankshaft speed, rpm
χ fraction of reacted methane Ni concentrations of the components, %
ρ gas density, kg⋅m-3 Nu Nusselt number
ω parameter of the heat exchange P pressure, Pa

η volume of syngas produced per unit energy, Pe Peclet number

m3⋅kWh-1 q overall mixture consumption rate, kg⋅sec-1
β volume ratio for the working and auxiliary Qf total flow, L⋅min-1
chambers
R universal gas constant, J⋅mol-1⋅K-1
λ volumetric compression ratio
Sa heat transfer surface area, m2
ξ volumetric concentrations of the
components T temperature, K

δ width of slot channels, m t time, sec

αa -1 -2
coefficient of heat transfer, J⋅sec ⋅m ⋅K -1 TA Thermal Activator

φ volume of syngas produced per unit time per U piston velocity, m3⋅sec-1
unit volu me, m3⋅h-1⋅L-1 V volume, m3
A empirical parameter, W power per unit volume and per cycle, kW⋅L-1
(mol⋅m-3)1-A-B-C⋅sec-1⋅K-d
Wi heat release rate or heat transfer, J⋅sec-1
C specific heat, J⋅kg-1⋅K-1
Wm overall hydrocarbon oxidation rate,
CCR Chemical Compression Reactor mol⋅m-3⋅sec-1
d orifice diameter, mm xi molar coefficients
E specific internal energy, J⋅kg-1
Ea effective activation energy, J⋅mol-1
H specific enthalpy, J⋅kg-1
HRE Heat-Retaining Element
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Introduction

The widespread use of natural gas and hydrogen in the power industry, transport, and as raw
materials for the chemical industry is one of the primary contemporary technological
tendencies. An overwhelming share of hydrogen is synthesized in the processes of natural gas
and coal conversion into synthesis gas, and also in reforming and other oil refining and
petrochemical processes. From an ecological point of view, it is attractive to use hydrogen in
motor transport for the power supply of onboard fuel cell–based engines. However, there are
some serious problems in the way of its practical realization; one of them is creation an
efficient infrastructure for hydrogen production and distribution. Because of their technical
complexity and high-energy consumption, the contemporary industrial hydrogen synthesis
methods, which are based on steam or steam–oxygen natural gas conversion, will hardly be
able to claim a significant role in a scattered production of hydrogen.
It is necessary to note, that the specified method is a catalytic conversion. The use of
catalysts considerably complicates the process of hydrocarbon oxidation. Therefore, in some
cases, it is expedient to aim for the noncatalytic and cheaper process of conversion. Such a
promising method for producing synthesis gas is the partial oxidation of methane in
exothermal reactions. Thereby, one of the important problems of chemical engineering is the
development of new economically and ecologically efficient methods for processing natural
reactants into a final target product and the development of apparatuses for their
implementation.
A rather attractive process of noncatalytic partial oxidation of methane is the combustion
of hydrocarbon-rich mixtures in a chemical compression reactor (CCR) that uses the
operating principle of an internal combustion engine (ICE) [1-5]. Such a CCR is a heat engine
of cyclic operation in which adiabatic (ideally) a piston accomplishes compression of
reactants up to the temperature necessary for rapid occurrence of chemical conversion. In
the subsequent expansion stroke, the reaction products are cooled and hardened, and
the mechanical energy supplied to the gas during its compression is returned during
the expansion as useful work. Under conditions of a sufficient heat effect of the chemical
conversion, the reactor can produce excess mechanical energy. This makes it possible to
organize a high-efficiency system for recovering the heat of chemical conversion during the
operation of the reactor.
Thus, a CCR combines in itself a heater; a reactor; a hardening device; and, probably, an
energy generator and is a unique apparatus in chemical engineering that combines in itself so
many necessary qualities. However, there is a principal limitation on the wide application of
these reactors for carrying out many reactions of practical importance [1,6], in particular, for
partial oxidation of hydrocarbons. It is hardly possible to heat a rich hydrocarbon–air mixture
without adding oxygen with a low adiabatic exponent by compression to the necessary
ignition temperature or reach the reaction temperature (~1200 - 1500 K) of very rich
hydrocarbon–air mixture at a limited compression pressure (~100 atm). To achieve this
temperature, too high a pressure of compression of about 1000 atm is necessary, which is
intolerable for state-of-the-art ICEs. It is required to use additional techniques for ensuring
ignition and the occurrence of the chemical conversion of rich hydrocarbon–air mixtures.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Studies of “explosive” methane reforming in internal combustion engines were begun in

Russian and German [2,3] in the last century. The relatively slow speed spark ignition-type
engine was used [2-4]. It was shown that syngas could be produced in an engine with spark
ignition when the mixture is enriched to an air–fuel equivalence ratio α = 0.38. However, to
sustain the process the air should be enriched with oxygen to 80%. Nevertheless, it was stated
that in view of the additional oxygen cost the production of syngas in an internal combustion
engine can be profitable and attractive and that a large-scale production could be easily
implemented. In addition to syngas, the process could concurrently produce power at a high
efficiency. The use of a high-speed compression ignition engine for synthesis gas production
was very attractive. As a very powerful ignition system was needed to ignite this mixture, a
more suitable option was an engine with compression ignition. The pilot liquid fuel in [5]
provided ignition sources distributed over a large gas volume. The engine with a compression
ratio of 14.2 operated by a two-component fuel mixture consisting of methane and 10% diesel
fuel was used to achieve a syngas content up to 80% in the exhaust gases at α = 0.42 under of
1000 rpm.
The partial oxidation of methane was also accomplished by the method of pulsed
mixture compression in free-piston ballistic compressors [1]. A high conversion of methane
was reached when a mixture with a CH4 /O2 ≈ 2 ratio was compressed to a temperature higher
than 1500 K. However, to reach this temperature, it was necessary to dilute the mixture with
argon to its concentration in the mixture exceeding 80%. This resulted in an increase in the
mixture adiabatic index, which made it possible to reach the required temperature at a limited
compression ratio of about 30.
The authors of [7] proposed a method for the partial oxidation of methane with air in a
CCR constructed on the basis of an ICE. In this apparatus, a rich mixture, with an air excess
ratio of ~ 0.5, is inflamed by a torch of combustion products of a stoichiometric mixture. The
authors of [8] proposed idea of preliminarily heating the reaction mixture to 200 - 450°C
before it is introduced into the reactor. In [6,10,11], a method for gas heating in the mode of
“superadiabatic” compression in the CCR cylinder is proposed that makes it possible to attain
higher temperatures in comparison to adiabatic compression to the same maximum pressure
or compression ratio. This process can be organized in multistage (in particular, two-stage)
compression of gas during its flow from one vessel to another (with an increase in entropy),
for example, in a divided cylinder of an ICE. An increase in entropy occurs when gas flows
through a hole in a partition between the vessels. The effect of a rise in temperature is
explained by the possibility of delivering larger work on the gas (as a result of one or more
intermediate stages of compression to a maximum pressure). In [6], it is proposed to heat the
gas in two sequential strokes with superadiabatic compression in order to considerably
increase the temperature.
Further development of the considered technology is connected with improvement of the
combustion process in ICE reactors and improvement of the gasdynamic and thermodynamic
processes in pulse compressive reactors with the free piston of the single and two stages
compression [12-14].
In this chapter, the partial oxidation of methane in a CCR with a outside preheater or
hypothetical regenerators that are set outside or inside the cylinder space is theoretically
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
studied, and the capabilities of these methods are evaluated. The outside preheating is the
simplest method and can be considered as a first step for investigation and development of
this direction.

Reactor with Internal Heat Recovery

A method for heating a gas in the superadiabatic regime in an ICE cylinder was developed as
mention in [11]. Among other things, it involves the internal recovery of heat, a technique
that makes it possible to use low exothermic mixtures. It is implemented as follows: an ICE
cylinder is divided into two chambers (working and auxiliary) by a partition with a crossflow
orifice. The auxiliary chamber accommodates a heat recuperator with a developed surface
(also known as a thermal activator (TA) [11]), for example, a set of metal plates or a porous
metallic or ceramic body (Figure 1.1). The TA absorbs part of the heat ∆Q stored by the
reaction products during the expansion stroke and releases it into the initial mixture during the
compression stroke, thereby increasing the temperature and entropy of the mixture. During
the intake and exhaust strokes, the TA only slightly interacts with the mixture and reaction
products, since it is separated from the working chamber by the partition. Thus, a closed cycle
of heat transfer is realized immediately in the ICE. The superadiabatic regime of compression
of the reaction mixture to a higher temperature occurs without cycle-average energy
expenditures on the heating of the TA. The use of a TA makes it possible to extend the region
of chemical transformations to fuel-richer mixtures.
A similar idea, the use of a porous medium in the cylinders of a diesel engine for
enhancing fuel evaporation, was put forward and realized in [15]. The authors of [11]
experimentally demonstrated that this idea can be implemented in a simple way in an ICE.
The aim of this paragraph is to theoretically analyze whether the partial oxidation of
methane in rich methane–air mixtures can be accomplished using an CCR on the basis of an
ICE with internal heat recovery by means of a TA [16].
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

a. b.
Note: 1. Cylinder, 2. Piston, 3. Intake valve, 4. Exhaust valve, and 5. Thermal activator.

Figure 1.1. Schematic of a CCR with internal heat recovery:

(a) Compression stroke; (b) Expansion stroke.

Calculation Model

Consider the partial oxidation of methane in rich methane–air mixtures containing

ξm0 = 0.17–0.3 mole fractions of methane. At the two limiting methane concentrations, this
process can be approximately described by the equations

CH4 + O2 = CO + H2 + H2O ξm0 = 0.173, ∆H = - 277.5 kJ/mol (1.1)

CH4 + ½ O2 = CO + 2 H2 ξm0 = 0.3, ∆H = - 35.6 kJ/mol (1.2)

where ∆H is heat of the reaction.

Part of the thermal energy released by the first reaction can be converted into useful
work. Note, however, that the conversion of methane according to the second equation
releases only a small amount of heat, and, therefore, it needs an external energy input to
occur.
We calculated the characteristics of the partial oxidation of methane in an ICE-based
CCR with a two chamber cylinder (separated by a partition with a crossflow orifice shown in
Figure 1.1). Let the volumes of the working and auxiliary chambers be V1 and V2,
respectively, with β = V2 / V0 << 1, where V0 = V1 + V2 is the volume of the cylinder and let
the auxiliary chamber accommodate a TA. As the piston moves toward the partition, it
compresses the gas mixture in the working chamber, with the final degree of compression
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
being λ ≤ 1/β (the maximum degree of compression λ = 1/β is attained when all the gas
overflows into the auxiliary chamber). It was assumed that, at the initial instant of time,
the piston is positioned at the bottom dead center, with the mixture being uniformly
distributed over the cylinder at pressure P0 and temperature T0. As the piston moves to the top
dead center, it forces the cold mixture to flow into the auxiliary chamber, where it receives
heat from the TA heated in the previous cycle to a temperature Ta. The superadiabatic heating
of the mixture occurs due to the joint action of three factors: compression, inflow with
entropy increase [9], and heat transfer from the TA. We numerically simulated only two
stages, the compression and expansion strokes, assuming that the intake and exhaust strokes
are not accompanied by changes in the thermal parameters of the TA.
The chemical conversion of methane was described using global modeling [17].
According to this method, a detailed kinetic scheme can be reduced to a limited number of
kinetic equations. In principle, the consumption of a hydrocarbon can be described with
acceptable accuracy by one equation. In this case, the reaction orders with respect to the
reactants and the effective activation energy of the process are determined from experiment.
The overall hydrocarbon oxidation rate Wm is given by the global kinetic equation

d Nm
Wm = = − A N ma N oxb N nc T d exp(− E a / R T ) , (1.3)
dt

where А, a, b, c, d are empirical parameters; Ea is the effective activation energy; Nm , Nox, and
Nn are, respectively, the molar concentrations of hydrocarbon, oxygen, and nitrogen in the
hydrocarbon–air mixture; t is the time; T is the current temperature; and R is the universal gas
constant. The empirical coefficients were chosen based on the results of experiments with rich
methane-air mixtures [18-20].
At high temperatures, it took into account the dissociation of water vapor, with the
composition of the reaction products being calculated with consideration given to the
processes involving water gas. An analysis demonstrated that the extent of conversion of
methane can be estimated rather accurately without performing detailed kinetic calculations
of the composition of the reaction products. The dissociation of water is described by the
equation:

d N H 2O
= K1 N H 2 O N g − K 2 N r2 N g (1.4)
dt

where Ng, Nr are the molar concentrations of the gaseous components and dissociation
products (R0 = H or OH) and K1 and K2 are the rate constants of the direct and reverse
reactions, respectively [21,22].
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

The reaction of water gas can be described as:

d N CO2
= K 3 N CO N H 2 O − K 4 N CO2 N H 2 (1.5)
dt

where NCO2, NCO, NH2O, and NH2 are the molar concentrations of carbon dioxide, carbon
monoxide, water vapor, and hydrogen, respectively, and K3 and K4 are the rate constant of the
direct and reverse reactions [22].
In some calculations, the kinetics of soot formation was described [22]. It turned out,
however, that the process was too short to produce an appreciable amount of soot; therefore,
we report here no data on soot formation. We solved a system of equations describing the
changes in the internal energy and mass of the methane-air reaction mixture in the working
and auxiliary chambers of the reactor during compression, crossflow, and expansion
[6,10,24]:

d (E i m i ) dV gi
= Pi + H k q k + Wci − Wti + Wai
dt dt
d mi
= qk
dt
dξ ji
= w ji + q~ jk (1.6)
dt
d V gi
= U (t )
dt
d (c a m a Ta )
= −α a S a (Ta −T2 ) = − Wa 2
dt

Equation set of (1.6) was supplemented with the Clapeyron equation.

The last equation in (1.6) describes the temperature of the TA, which is controlled by
heat transfer between it and the gas mixture in the auxiliary chamber. Here, H and E are the
specific enthalpy and internal energy of the gas mixture; P is the pressure; Vgi is the volume of
the compressed gas (Vg2 = V2); i and k (i, k = 1, 2) are the indices that denote the chambers of
the reactor, with k = i if the gas outflows from the ith chamber; Wc is the heat release rate;
Wt is the heat transfer (or heat loss) rate, which was determined using the Woshni model [25];
Wa2 is the rate of heat transfer from the TA to the gas mixture and vice versa (Wa1 = 0,
Wai = –Wa2); ξj and wj are, respectively, the relative concentrations of the initial components
in the gas mixture with mass mi or those of the reaction products (СH4, CO, CO2, H2, H2O,
and R0) that are labeled by j and the dimensionless rate of their transformations in the
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
~ are the overall mixture consumption rate and the relative cross-flow rates
reaction; q and q j

of the components, respectively [24]; U is the piston velocity [25]; ca is the specific heat of
the material of the TA; ma, Sa, and Ta are the mass, heat transfer surface area, and temperature
of the TA; and αa is the coefficient of heat transfer between the TA and gas mixture.
The temperature dependences of the heat capacities of air, methane, and the reaction product
components were borrowed from [26].
The concentrations of the reaction products were found from the material balance
equation in view of kinetic equations (1.3) and (1.4):

xmCH4 + O2 → (1 – χ)(xmCH4 + O2) +χ(x1CO + x2H2 + x3CO2 + x4H2O) (1.7)

where xm is the input parameter of the problem, and the unknown molar coefficients x1, x2,
and x4 were calculated from the carbon, hydrogen, and oxygen balance; the coefficient x3 was
calculated from kinetic equation (1.5); and the fraction of reacted methane χ was calculated
from kinetic equation (1.3). The process of water dissociation, equation (1.4) was not
included in the consideration of the material balance due to the insignificance of its
contribution.
The calculations were performed at the following values of the input parameters: the
cylinder diameter, 10 cm; working chamber length, 10 cm; piston stroke length, 10 cm;
crossflow orifice diameter, d = 5 - 15 mm; β = 0.01 - 0.1; crankshaft rotational speed,
N = 1000 rpm; and working cylinder wall temperature, T0 = 360 K. The maximum pressure
during compression and chemical reaction did not exceed 100 - 200 atm, whereas the final
degree of compression was λ = 10 - 20, with the geometric degree of compression in the
working chamber being:

1− β
λ1 = λ (1.8)
1 − λβ

The TA was modeled by a 0.1-mm-thick ribbon wound into a spiral with an intercoil
distance of 1 mm, a heat transfer surface area of Sa = 790 - 1710 cm2, and a mass of
ma = 30 - 70 g.

Calculation Results

The calculation results show that, for the conventional one-stage compression of a mixture
with a methane concentration of ξm0 = 0.167 to a degree of λ = 20 (typical of diesels), no
methane conversion is observed. At a crossflow orifice diameter of d = 5 mm, N = 1000 rpm,
and β = 0.048, the maximum temperature in the working chamber Tf1 attains a temperature of
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

nearly 900 K at a pressure of Pf1 = 65 atm; in the auxiliary chamber, Tf2 ≈ 1000 K at a peak
pressure of Pf2 = 55 atm. These conditions proved to be too mild to initiate the reaction.

a b
Note: τ is the dimensionless time (current time in units of crankshaft rotational period).

Figure 1.2. Time evolution of the (a) temperature and (b) methane concentration in
(1) working and (2) auxiliary chambers and (3) the temperature of the TA in the auxiliary chamber
at ξm0 = 0.22, λ = 15, β = 0.064, d = 0.47 cm, and Ta = 1140 K.

When the thermal activator (Figure 1.1) was installed in the auxiliary chamber,
the picture changed drastically, even for mixtures with ξm0 > 0.167.
At the very beginning of the compression stroke, the mixture is additionally heated by
the TA (heated to Ta = 1140 K in the previous cycle) and explodes at a temperature just above
1000K, with the degree of methane conversion attaining χ = 0.87. Initially, the temperature of
the TA decreases by 3.7 K (curve 3 of Figure 1.2b), but, as the process of compression
continues and the chemical reaction occurs, the temperature of the mixture grows and
eventually exceeds that of the thermal activator. The ensuing heat transfer from the mixture to
the activator raises its temperature by about ∆Ta = 1 K compared to the steady-state
temperature Ta. Once the steady state of the periodic process is established, the TA
temperature at the end of the expansion stroke attains its initial value, Ta = 1140 K; i.e.,
the temperature at the end of each cycle remains unchanged (curve 3 of Figure 1.2b), a
behavior indicative of internal heat recovery. The peak temperatures and pressures in the
working and auxiliary chambers were found to be Tf1 = 1410 K, Pf1 = 79.2 atm and Tf2 = 1710
K, Pf2 = 53.8 atm, respectively. The composition of the conversion products for a number of
calculation variants (at λ = 15) and other parameters of the cycle are given in the table. Here
W is the power per unit volume of the setup (1 litter) per cycle, that is, per two crankshaft
revolutions (a positive value corresponds to energy production, and a negative value to a
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
process powered by an external drive); η is the energy cost of 1 m3 of synthesis gas; φ is the
volume yield of synthesis gas per hour per 1 liter of the setup; and ξmk, ξH2, ξCO, ξH2O, and ξCO2
are the final mole fractions of CH4, H2, CO, H2O, and CO2 in reaction products.
Note that, for a given mixture and fixed values of the input parameters of compression,
the condition of the cycle being closed in Ta (the equality of the temperatures at the beginning
and end of the thermodynamic cycle) can be met at various values of Ta, in particular,
Ta = 1140 K and Ta = 1090 K (the second and third row of the table). At Ta = 1090 K, the
peak pressures and temperatures in the chambers are lower than those at Ta = 1140 K; as
a result, the extent of conversion is lower (χ = 0.7), as are the concentrations of the partial
oxidation products (H2 and CO).
Figure 1.3 shows the regions of existence of a recovery cycle. In the region to the left of
the curves, the regime of closed recovery is realized, for which the temperatures at
the beginning and end of the cycle are equal to each other. To the right of the curves,
the condition of existence of a closed cycle for the TA temperature is not satisfied. As
the concentration ξm0 increases (even at a higher degree of compression λ), the region of
existence of a recovery cycle shifts to smaller crossflow orifice diameters d. This is associated
with the fact that the compression temperature needed to ignite the mixture increases with
the fuel-to-air ratio. At a fixed ξm0 (curves 2 and 3), a decrease in λ does not results in an
appreciable change in the crossflow orifice diameter, a behavior that can be explained by the
fact that the parameter d produces a stronger effect on the compression temperature than λ
does.

Note: The numbers at the curves denote extent of methane conversion χ.

Figure 1.3. The temperature dependence of the TA on the crossflow orifice diameter (boundaries
of the region of existence of a heat recovery cycle) at (1) ξm0 = 0.167, λ = 12, and β = 0.081;
(2) ξm0 = 0.22, λ = 15, and β = 0.064; (3) ξm0 = 0.22, λ = 12, and β = 0.081.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Figure 1.4 shows how the crossflow orifice diameter d, TA temperature Ta, and the
output (input) energy W depend on the degree of compression λ for methane–air mixtures
with various fuel-to-air ratios at various extents of conversion χ. As can be seen from Figure
1.4a, the diameter d increases with the degree of compression λ at all ξm0 values, since the
decrease in the compression temperature in the working chamber V1 caused by an increase in
d is compensated for by its increase associated with an increase in λ. At all ξm0 values,
Ta monotonically decreases with increasing λ. In this case, the decrease in the temperature of
the mixture due to the decrease in Ta is compensated for by the appropriate increase in λ. As
can be seen from Figure 1.4c, when operating with mixtures with ξm0 = 0.167 and ξm0 = 0.22,
the CCR produces concurrently syngas and useful work (except for a small area near λ = 10 at
ξm0 = 0.22). At ξm0 = 0.24, a small amount of energy can be generated only at λ > 18.

a. b. c.
Note: The regions of intermediate χ values are hatched.

Figure 1.4. (a) Crossflow orifice diameter, (b) TA temperature, and (c) power released (absorbed)
per unit volume of the reactor as functions of the degree of compression
at (1) ξm0 = 0.167, χ = 0.99; (2) ξm0 = 0.22, χ = 0.93; (3) ξm0 = 0.22, χ = 0.97;
(4) ξm0 = 0.242, χ = 0.9; and (5) ξm0 = 0.242, χ = 0.93.

Table 1.1. Composition of the conversion product and other parameters of the cycle
ξm0 d, Ta, Pf1, Pf2, Tf1, Tf2, W, η, m3/ φ, χ ξmk ξH2 ξCO ξH2O ξCO2
cm K atm atm K K kW/l (kWh) m3/hl
0.167 0.95 1280 81.0 81.1 2160 2280 +5.22 +1.37 6.02 0.99 0.002 0.18 0.103 0.103 0.039
0.219 0.47 1140 79.2 53.8 1410 1710 +1.4 +6.89 8.1 0.87 0.03 0.246 0.132 0.048 0.015
0.219 0.47 1090 78.9 45.8 1210 1560 +0.76 +10.24 6.56 0.70 0.068 0.195 0.108 0.041 0.01
0.242 0.41 1130 125.1 54.8 1245 1560 -0.4 -26.18 8.77 0.83 0.043 0.27 0.142 0.029 0.008
Note: W is the power per unit volume and per cycle (two rotations of the crankshaft) (the positive and negative signs
correspond to energy generation and consumption, respectively); η is the volume of syngas produced per unit
energy; φ is the volume of syngas produced per unit time per unit volume of the reactor; and ξmk, ξH2, ξCO, ξH2O and
ξCO2 are the final mole fractions of CH4, H2, CO, H2O, and CO2 in the reaction products.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
We simulated the composition of the products of the oxidation of methane in rich
methane–air mixtures in an ICE cylinder measured in [7, 8]. Unfortunately, the authors of [8]
failed to report the degree of compression, whereas the authors of [7] provide no information
on either the degree of compression or the crankshaft rotational speed. Nevertheless, using
typical values of these parameters, λ = 10 - 15 and N = 350 - 1000 rpm, we satisfactorily
predicted the extent of methane conversion, oxidation temperature, and concentrations of
the reaction products. The calculated and measured concentrations of hydrogen, carbon
monoxide, carbon dioxide, and water vapor were found to range within ξH2 = 0.18 - 0.22,
ξCO = 0.10–0.12, ξCO2 = 0.02–0.04, and ξH2O = 0.08–0.11, respectively.

Reactor with Outside Heat Regeneration

a b)
Note: 1. Cylinder; 2. Piston; 3. Intake valve; 4. Exhaust valve; 5. Regenerator (HRE); 6. Inlet pipe; 7. Outlet pipe.

Figure 1.5. Scheme of the CCR based on the ICE with a regenerator:
(a) exhaust stroke, (b) intake stroke.

Consider another variant of heat recuperation [27]. It is proposed to place the regenerator,
i.e. a heat-retaining element (HRE) outside the CCR cylinder so that reaction products and
reactants alternately pass through it (Figure 1.5). In the exhaust stroke, when the piston moves
to the top dead center (Figure 1.5a), highly heated reaction products, passing through the
regenerator, give a portion of the heat ∆Q to the regenerator, which results in the heating of
the HRE. In the intake stroke, when the piston moves to the bottom dead center (Figure 1.5b),
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

the reactants take a portion of the heat ∆Q, thus cooling the HRE and heating up to the
necessary temperature. Thus, it becomes possible to use a CCR for the chemical conversion
of rich hydrocarbon–air mixtures with retention of all of its known advantages due to the
preheating of the original mixture in a regenerative cycle.
Different designs of the regenerator are possible. For example, the motion of the reaction
products and reactants in the regenerator can occur in separated flows through adjoining and
alternating channels. In the other variant, the motion of the reaction products and reactants
can occur alternately through all the channels in the total flow. In this case, the regenerator
space will be filled with residual reaction products or reactants upon completion of the
exhaust and intake strokes, respectively. This leads to undesirable dilution of the fresh
mixture and products with the opposite component.
In this paragraph, the partial oxidation of methane in a CCR with a hypothetical
regenerator that is set outside the cylinder space is theoretically studied, and the capabilities
of this method are evaluated.

Calculation Model

A mathematical model of the process is described in detail above. However, there are
some changes in equations of 1.6 because a single chamber cylinder, i = 1 only and all
crossflow rates are zero. Beside we have to write additional equation reflecting
preheating gas mixture:

d ( Em )
= α a S a ( Ta − T ) (1.9)
dt

where m ≡ m1 and T ≡ T1 are the gas mass and temperature respectively. The initial
conditions for the intake stroke of a fresh mixture of reactants in the regenerator are as
follows: T = T0, ξj = 0, ξm = ξm0 , Ta = Ta0 ; in cylinder: T = Tr0 , ξj = ξrj , ξm = ξm0 , V = V0/ λ .
Here, T0 is the initial temperature of the mixture; ξrj is the concentration of components in the
residual gases of the cylinder; Tr0 is the temperature of the residual gas of the cylinder; V0 is
the volume of the cylinder.
An important issue of the problem is the choice of the regenerator design and
parameters. The regenerator operates under non-steady-state conditions according to the
following scheme: cooling of the reaction products and heating of the regenerator mass →
cooling of the regenerator mass and heating of the reactants that enter the reactor →
the expectation stage. Note that, instead of the stage of expectation, active operation of the
regenerator in the intake and exhaust strokes of the second cylinder of the reactor is possible.
To ensure the efficient operation of the regenerator, it is required that the characteristic time
of the heating of the reactants in the intake stroke of a working mixture in the cylinder should
be comparable to the characteristic time of the piston motion t0 = 60/4N, where N is the
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
crankshaft speed. Let us write the equation (1.9) that describes the heat exchange of the gas
mixture with the HRE in the dimensionless form:

dθ
= ω( θ a − θ ) (1.10)
dτ
mc
Here, θ = T/T0; θa = Ta/T0, ω = is the parameter of the heat exchange, which is about
α a S a t0
unity; c is the specific heat of gas; and τ = t/tс, where tс = 4t0 is the characteristic time of a
complete cycle.
Let the regenerator, which is constructed in cylindrical or rectangular geometry, consists
of thin metal plates that are separated by slot channels with width δ. We express the mass of
the gas and the reach of the heat exchange through the volume of the cylinder V0 and the
volume of the HRE Va, respectively. Since m = ρ⋅V0 (ρ is the gas density) and the reach of the
heat exchange at a large number of plates and their small thickness as compared to δ is
Sa ≈ Va/δ, we derive a relationship between the volumes:

Va ρ cδ
= (1.11)
V0 α at0ω
2 δ Pe
The Nusselt number Nu for a flat slot at laminar flow and the parameter < 70
la
almost do not depend on the rate of the gas flow and Nu = 7.5 [28], where Pe is the Peclet
number and la is the characteristic length of the volume of the heat exchange. The value of
the heat transfer coefficient αa between the gas and the plates of the regenerator can be
estimated to be αa = 50 - 100 W/(m2 K).
If the motion of the reaction products and the reactants in the regenerator occurs in
separated flows through adjoining and alternating channels, the estimates by formula (1.9)
yield the ratio Va/V0 ≈ 1 - 2 at ω = 1.
If the motion of the reaction products and the reactants in the regenerator occurs
alternately through all the channels in the total flow, the estimates by formula (1.9) yield
Va/V0 ≈ 0.5 - 1, since the area of the heat exchange in this case is doubled (gas flows past
the inner plates of the HRE from both sides). Introduction of additional cross partitions into
the design of the regenerator will probably make it possible to lower the ratio Va/V0 down to
the limiting value Va/V0 ≈ 0.3 - 0.5. In the regenerator of the given design, upon completion of
the exhaust and intake strokes, there is a relatively large quantity of reaction products or a
fresh mixture of reactants, respectively. Residual reaction products are returned to the
cylinder of the reactor in the intake stroke, which should lead to an abrupt decrease in the
production rate of the reactor and even the impossibility of its operation. The reaction
products that leave the reactor are diluted with the reactants of the fresh mixture, which
considerably decreases the quality of the final product. This situation can be improved by
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

different methods, in particular, by pumping residual reaction products and a

residual fresh mixture from the regenerator to the corresponding phases of the cycles.

Calculation Results

Calculations were carried out at the following input parameters of the problem: the cylinder
diameter is 0.1 m, the piston stroke is 0.1 m, and the compression ratio is 14 - 30. The initial
concentration of methane in the methane–air mixture is 0.138 - 0.242, and the crankshaft
speed is 500 - 3000 rpm. The initial temperature of the mixture of reactants was chosen to be
300 K, and the temperature of the cylinder walls was taken to be 360 K. The final pressure of
the compression was limited to a value of approximately 100 atm at a compression ratio of
30.

a b

Figure 1.6. (a) Variation of (1) pressure and (2) temperature in the cylinder of the CCR;
(b) Variation of the concentration of (1) methane, (2) hydrogen, (3) carbon monoxide,
(4) steam, and (5) carbon dioxide in the cylinder of the CCR
at ξm0 = 0.231, λ = 18, N = 1000 rpm, and Ta0 = 620 K.

The parameter of the heat exchange of the regenerator ω varied in the range of 0.2 - 1
depending on the crankshaft speed. The regenerator with the given values of the parameter ω
can be represented, for example, as a set of concentric ring layers made of metal foil with a
thickness of 0.1 mm with a gap between the layers of 1 mm, which are located in a heat-
insulated vessel. The diameter of the HRE is 0.066 m, its length is 0.3 m, the total area of the
heat exchange is 2 m2, and mass is 0.8 kg. Thus, the volume of the regenerator was
comparable to the volume of the cylinder. To ensure the operation of this regenerator in the
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
mode of the flows of the reaction products and reactants that are alternating and not separated
in channels, the removal of the residual reaction products from the volume of the regenerator
prior to the stage of the intake of a fresh mixture of reactants was supposed in the
computational model.
Figure 1.6 shows the variation of the pressure and temperatures in the CCR cylinder and
in the HRE as a function of the dimensionless time τ = t/tc in the working cycle of the CCR.
The initial and final temperature of the regenerator Ta0 was taken to be 620 K, the initial
concentration of methane in the mixture ξm0 was 0.231, the compression ratio λ was 18, and
the speed N was 1000 rpm.

Figure 1.7. Degree of methane conversion (solid lines 1 - 4) and the H2/CO ratio in the conversion
products (dotted lines 5 - 8) as a function of the speed of the CCR crankshaft at λ = 18 and
ξm0 = 0.242 (line 1 and 5), 0.231 (line 2 and 6), 0.193 (line 3 and 7), and 0.138 (line 4 and 8).

It is seen from Figure 1.6a that the maximum pressure in the CCR cylinder does not
exceed 60 atm, and the maximum temperature of the gas in the cylinder reaches 2010 K.
The temperature of the HRE changes little (the maximum change in temperature ∆Ta was less
than one degree) due to the higher heat capacity of the material of the regenerator as
compared to the heat capacity of the gas mixture. In launching the CCR with a cold HRE, the
system reaches a quasi-steady-state mode in ~ Ta0/∆Ta ~ 1000 - 3000 cycles; i.e., the HRE
heating up to the maximum temperature of the regenerative cycle Ta0 occurs for 1 - 3 min of
the operation of the CCR. In the quasi-steady-state mode of the reactor operation, a high
degree of methane conversion to products η = 99% is attained (Figure 1.6b, curve 1). In this
case, the concentrations of carbon monoxide ξCO = 0.16 and hydrogen ξH2 = 0.305 in the
reaction products are 0.16 and 0.305, respectively (the ratio of H2/CO is 1.91). The
concentrations of the remaining products (carbon dioxide and water vapor) are as follows:
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

ξCO2 = 0.015 and ξH2O = 0.044 (CO/CO2 = 10.7, H2/H2O = 6.9); i.e., the amount of the
products of complete oxidation does not exceed 6%. In this case, in the complete duty cycle,
the reactor can produce energy that is 1.15 kW/(L⋅s) from the unity volume of the setup, and
the energy price of 1 m3 of the synthesis gas is 0.07 kW h at the volumetric yield of the
synthesis gas of 13.5 m3/h from 1 L of the setup.
A decrease in the reactor crankshaft speed leads to an increase in the degree of methane
conversion at any composition of the original mixture ξm0 = 0.138 - 0.242, since the mixture
residence time at the maximum temperature increases (Figure 1.7). At ξm0 = 0.242, the degree
of methane conversion increases from η = 74.2 to 97.4% with a decrease in N from 1500 to
500 rpm (curve 1). In the case of less rich mixtures, the degree of methane conversion is not
less than 90% at N ≤ 3000 rpm (curves 2 - 4) and is not less than 98% at N ≤ 1000 rpm. This
means that the factor of the time of the reaction occurrence is very substantial. For a rich
mixture with ξm0 = 0.242 (curve 1) at N > 1500 rpm, it is not possible to satisfy the condition
of the closure of the regeneration “ring”, i.e., the equality of the temperature Ta0 at the
beginning of the compression stroke and at the end of the expansion stroke, due to the low
calorific value of the mixture.
The ratio of H2/CO in the synthesis gas increases (Figure 1.7) with the enrichment of the
mixture with methane and a decrease in N. The ratio of H2/CO reaches 1.9 - 1.95 at
N = 500 rpm for all the studied compositions of the original mixture.
With the enrichment of the mixture, the ratio of unoxidized products or the products of
incomplete oxidation to the corresponding products of complete oxidation, i.e., the ratio of
H2/CO and CO/CO2, increases, whereas their dependence on the reactor crankshaft speed is
insignificant. For example, the ratio of CO/CO2 increases approximately from 1 to 15 and the
ratio of H2/H2O increases from 1 to 10 at N = 1000 rpm and λ = 18 with an increase in the
concentration of methane in the original mixture from ξm0 = 0.138 to 0.242. At N = 3000 rpm
(a decrease in the time of the reaction), the ratio of CO/CO2 increases approximately from
1 to 13 and the ratio of H2/H2O increases from 1 to 7 with an increase in the concentration of
methane in the original mixture from ξm0 = 0.138 to 0.231.
The temperature of the HRE Ta0 rises with an increase in the calorific value of the
mixture when approaching the stoichiometric composition, but the dependence of Ta0 on the
reactor crankshaft speed is insignificant. For example, Ta0 increases approximately from
600 to 1050 K at N = 1000 rpm and a pressure of compression of 60 atm with a decrease in
the concentration of methane in the original mixture from ξm0 = 0.242 to 0.138. At
N = 3000 rpm, Ta0 increases approximately from 700 to 1020 K with a decrease in the
concentration of methane in the original mixture from ξm0 = 0.231 to 0.138.
An increase in the compression ratio λ leads to an increase in the degree of methane
conversion η at any composition of the original mixture (Figure 1.8), since the maximum
temperature of the mixture in the cylinder of the reactor rises. For ξm0 = 0.242, the degree of
methane conversion increases from η = 88.9 to 95.7% with an increase in λ from 18 to 30
(curve 1). At λ < 18, it is not possible to satisfy the condition of the closure of the
regeneration ring due to the low calorific value of the mixture. In the case of less rich
mixtures, the degree of methane conversion exceeds 98.6% at all the values of λ ≥ 14 (curves
2 and 3).
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Figure 1.8. Degree of methane conversion (solid lines 1–3) in the methane–air mixture and
the H2/CO ratio in the conversion products (dotted lines 4–6) as a function of the compression
ratio in the CCR at N = 1000 rpm and ξm0 = 0.242 (line 1 and 4), 0.219 (line 2 and 5), and
0.193 (line 3 and 6).

With an increase in the compression ratio, the value of the H2/CO in the reaction
products decreases (Figure 1.8); the value of H2/CO is lower the closer the composition of the
mixture is to the stoichiometrical composition. This can be associated with a decrease in the
maximum temperature of the regenerative cycle with an increase in λ and with the depletion
of the mixture in methane.
With the enrichment of the mixture, the ratio of unoxidized products or the products of
incomplete oxidation to the corresponding products of complete oxidation, i.e., the ratio of
H2/CO and CO/CO2, increases, whereas their dependence on the compression ratio is
insignificant. The ratio of CO/CO2 increases approximately from 4 to 15 and the ratio of
H2/H2O increases from 3 to 10 at λ = 18 and N = 1000 rpm with an increase in the
concentration of methane in the original mixture from ξm0 = 0.193 to 0.242.
The temperature of the HRE Ta0 decreases with an increase in the compression ratio at
any composition of the original mixture, since a decrease in Ta0 is offset by a corresponding
increase in λ. With an increase in the calorific value of the mixture, i.e., with a decrease in the
content of methane in the mixture and approaching the stoichiometric composition, the value
of Ta0 increases. For example, Ta0 increases approximately from 580 to 830 K at λ = 18 and
N = 1000 rpm with a decrease in the concentration of methane in the original mixture from
ξm0 = 0.242 to 0.193. At λ = 30 Ta0 increases approximately from 490 to 760 K with a
decrease in the concentration of methane in the same interval.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Reactor with Outside Heater

Consider the simplest method of outside preheating mixture, which can be considered as a
first step for investigation of reforming methane in a chemical compression reactor. It is
proposed to place the electrical heater outside the CCR cylinder so preheating of the mixture
prior to supply to a reaction vessel (Figure 1.9).
In the intake stroke, when the piston moves to the bottom dead center (Figure 1.9), the
reactants take a portion of the heat ∆Q , thus heating up to the necessary temperature. Thus, it
becomes possible to use a CCR for the chemical conversion of rich hydrocarbon–air mixtures
with retention of all of its known advantages due to the outside preheating of the original
mixture. In principle, the electrical heating can be changed by thermo heating.

Note: 1. Cylinder; 2. Piston; 3. Intake valve; 4. Exhaust valve; 5. Heater.

Figure 1.9. Scheme of the CCR based on the ICE with outside electrical heater.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Calculation Model

A mathematical model of the process is described in detail above with reference to a

CCR with a outside heat regenerator. The calculations were carried out at input values of the
problem applicable to design of the diesel engine, which was used in the experiment. The
temperature of the engine walls was chosen 360 K, the total flow rate Qf (cold air + methane)
was changed from 40 up to 150 L/min. Because not all intake mixture could take part in the
chemical reaction, the burning completeness coefficient ε was used, which was varied in the
interval of 0.7 ≤ ε ≤ 1.

Experimental Method

Experiments were carried out in Prof. Y. N. Chun laboratory of Chusun University,

Republic of Korea. A commercial diesel engine ND130DIE was used as a CCR and its
technical data are following: cylinder bore of 94.5mm, the stroke 90.5 mm, replacement
volume 670cm3. The compression ratio λs was 18, the crankshaft speed N changed from 1000
up to 2000 rpm.
The gas supply line was composed of the methane supply line and air supply line.
Methane was supplied through the Compressed Natural Gas (CNG) cylinder filled up with
a high pressure of 220 atm and was injected through the mixer via a regulator, a flowmeter
(Dwyer, RMB-5, USA) and a surge tank (7.5 L) for mixture with air. The air supply line
consist of an orifice flow meter (KFE, OLA-N, Korea), a surge tank (19 L), a diaphragm
with a 10 mm orifice diameter, a safety valve and 6 kW electric heater. A mixer from an
LPG motor vehicle was used for preparing the methane-air mixture. The spark ignition of
the mixture was used to avoid hard operation of the engine.
The measuring system is composed of the devices for measurement of the temperature
and the engine’s rotational frequency. For measurement of the temperature, a thermocouple
(K-type, outside diameter of 6 mm) was installed onto the intake manifold and exhaust
manifold and a data logger (FLUKE, Hydra Data Logger 2625A, USA) was used for the
temperature monitoring. A magnetic-type temperature control device was also made and
used to control the temperature of the heater. For measurement of the rotational frequency,
a tachometer (HIOKI, 3404 TACHO HiTESTER, Japan) was installed. As for the exhaust
gas analysis system, a sampling probe was inserted into the exhaust line at the point of 390
mm away from the exhaust valve. Exhaust gas was inhaled through a vacuum pump (Gast
Manufacturing Inc., 15D1150-102-1021, USA) and then passed through the impinger so
that soot and moisture could be got rid of. After that, the waste gas was analyzed by the gas
chromatograph (SHIMADZU, 14B, Japan). A thermal conductive detector (TCD) detector
was used for the analysis, with Molecular Sieve 5A (80/100 mesh) for hydrogen, Molecular
Sieve 13X (80/100 mesh) for carbon monoxide and HayeSep R (100/120 mesh) for carbon
dioxide and CmHn.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

The engine was first test-run with gasoline during 15 minutes and, only after
stabilization of the temperature inside the engine, the refining fuels of methane and air were
injected. Then, experiments were carried out in accordance with each of the variables,
including an oxygen/methane ratio, a total flow rate under fixed intake preheating
temperature.

Results and Discussion

The intake temperature T1 of the gas mixture was kept of 600K in the all presented
experiments. The respective calculations predicts that the hydrogen concentration have to
reach the great value ~ 30 % at the equivalence ratio α ≈ 0.35 and the total intake flow Qf of
106.5 L/min if all methane - air mixture has time for conversion. However, experiment shows
the maximum value was near 20 % (Figure 1.10). As the equivalence ratio decreased, so the
hydrogen concentration fell. If the equivalence ratio increased at α > 0.35 the hydrogen
concentration fell again. The curve 4 reflects the measured crankshaft speed of the engine.
The theory provides a satisfied fit if to suppose that only some part of the mixture has time for
burning. It means that the crankshaft speed in the experiments was too high so required time
τb for complete burning all mixture exceeds the characteristic time of the piston displacement
τd. Calculation shows of 20-30% unburned mixture, i.e. the burning completeness coefficient
ε = 0.7 – 0,8 (Figure 1.10).

Figure 1.10. Comparison of experiment (point) and model prediction (curves 1 - 3) for the
hydrogen concentration in the dry combustion products at ε = 1 (line 1), 0.8 (line 2),
0.7 (line 3) and the experimental engine speed (line 4).
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor
Decreasing hydrogen yield for α < 0.35 is because of the combustibility of the rich
mixture is worsened due to the insufficient supply of oxygen, which untenable to promote
quick partial oxidation, i.e. τb > τd in spite of decreasing the crankshaft speed. On the
contrary, the hydrogen concentration decreases after it has reached the maximum point,
despite the continual increase in the equivalence ratio. It is because of the excessive
crankshaft speed, which does not provide full burning the mixture, i.e. τb > τd is conserved
in this region of α. Similar dependences were found out for the carbon monoxide
(Figure 1.11).

Figure 1.11. Comparison of experiment (point) and model prediction (curves 1 - 3) for the carbon
monoxide concentration in the dry combustion products at ε = 1 (line 1), 0.8 (line 2),
0.7 (line 3) and the experimental engine speed (line 4).

The results of uncompleted burning are displayed in Figure 1.12. The carbon dioxide
and rest methane concentrations in the combustion products increase with decreasing
equivalence ratio while the oxygen concentration grows.
It can be noted when the equivalence ratio was below 0.3, the lack of fuel and the
discharge losses caused misfire. In the area where the ratio got above 0.7, a normal engine
operation became difficult due to the pre-ignition and knocking.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Figure 1.12. Dependence on the carbon dioxide (1), oxygen (2) and rest methane (3)
concentrations in the dry combustion products from equivalence ratio
for CH4/Air mixture at ε = 0.8.

The measurement of the H2 and CO concentrations in the dry combustion products of

reformed gas and the engine operation speed are displayed in Figure 1.13 and 1.14, where
the total flow is changed between 40 and 130 L/min. The equivalence ratio was fixed at
0.35 and the intake preheating temperature was T1 = 600K.
When the total gas flow stood at 110 - 120 L/min, the concentration of hydrogen and
carbon monoxide reached the maximum of ~ 20 and 15%, respectively. As the total flow
decreases from Qf = 120 L/min, amount of hydrogen and carbon monoxide in the synthesis
gas also decreased, due to reducing the chemical reaction rate under the dropping pressure
in spite of increasing τd.
For Qf > 120 L/min the hydrogen and carbon monoxide concentration fall down after
reaching the peak. It is because the increased amount of mixed gas causes reducing the
coefficient ε in region of the great crankshaft speed.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

Figure 1.13. The hydrogen yield (1) and crankshaft speed (2) for variable gas consumption
at ε = 0.8.

Figure 1.14. The carbon monoxide concentration (1) and crankshaft speed (2)
for variable gas consumption at ε = 0.8.

The concentrations of methane and oxygen in the reformed gas are displayed in Figure
1.15 and 1.16. Here the crankshaft speed dependence is same as for Figure 1.13 and 1.14.
The theory satisfactorily describes the experiment in the region 80 > Qf > 120 L/min.
For Qf > 120 L/min the experimental oxygen and rest methane concentrations in the
combustion products increase unlike the theoretical values. The explanation of this effect is
like as for hydrogen. Increased amount of the mixture causes reducing the coefficient ε in
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

region of the great crankshaft speed. Besides the value ε can be function from Qf, ε = f(Qf)
reducing if Qf grows.

Figure 1.15. Dependence on the oxygen concentration in the combustion products from the gas
consumption at ε = 0.8.

Figure 1.16. Dependence on the rest methane concentration in the combustion from the gas
consumption at ε = 0.8.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

It was difficult to expect the good describing experimental data by the theoretical
simulation because of the simplified 1D theoretical model has been used. There are several
particularities, which used model does not take into account. In first, the theoretical model
makes assumption on space ignition of the mixture by compression while the distributed
burning occurs from spark ignition in the real experiment. In second, the model proposes the
temperature homogeneity of the mixture in the cylinder. The real picture has 3D natures. It is
possible strong cooling the heated mixture in the boundary layers in the intake pipe and
cylinder when filling the cylinder by fresh heated mixture. The mixture in the cylinder will
not be space uniform in the temperature. Because ignition time delay is sensitive to the gas
temperature that a chemical conversion is possible only in the volumes, where the mixture
temperature exceeds the critical value. The small characteristic time of the piston
displacement τd (great speed of the crankshaft) aggravate this situation. Effect of the partial
combustion of the mixture is confirmed that circumstance that the engine power falls (speed
of the crankshaft decreases) and experimental points of the hydrogen and carbon monoxide
concentrations (Figure 1.13 and 1.14) lies noticeably below calculations at increasing the gas
consumption in the high magnitudes Qf region. Simultaneously, the concentration of
unburned methane is found above the theoretical curve. So using the fitting parameter ε, it
takes into account the share of the mixture taking part in the chemical reaction, wholly
justified. If we presume that the mixture is temperature uniform in the volume, that is possible
to enter a correction in the heat exchange coefficient αa or in the initial gas temperature T1.
However, the calculations show, that increase of αa or reduction of T1 cause a shift of the
maximum on the hydrogen and carbon monoxide yields in the area of high α comparatively
to the experimental data. Herewith, if there is a satisfactory description of the experiment
NH(α) that the dependency NH (Qf) impossible to describe.
However the comparison of the experimental data with calculations with using simple
theoretical model is useful because allows us to conclude about strong effect of the crankshaft
speed on the syngas yield.

Conclusions

In this chapter, a method for noncatalytic partial oxidation of methane in methane–air

mixtures in a chemical compression reactor is proposed and the appropriate theory is
developed. Several reactors was considered that uses the operating principle of an internal
combustion engine with an internal heat recovery, heat regenerator located in the channel of a
combined exhaust and intake manifold, through which reaction products and reactants
alternately pass, and with external electrical heating mixture.
It was demonstrated that internal heat recovery in a CCR equipped with a thermal
activator makes it possible to conduct the conversion of methane in methane-air mixtures
with a hydrocarbon content of up to 24% and degrees of compression of 10 to 20, and a peak
pressure of less than 200 atm. A region (determined by the crossflow orifice diameter, degree
of compression, and initial mixture composition) within which the condition of existence of a
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

heat recovery cycle is met was identified. It was demonstrated that, for mixtures containing
22% methane or less, the extent of conversion exceeds 93%, a value that makes it possible to
generate useful energy at degrees of compression above 10.
Reactor with heat regenerator makes it possible to implement noncatalytic conversion of
methane in methane-air mixtures with the content of a hydrocarbon of up to 24% at ratios of
compression of 14 - 30; the degree of methane conversion can reach above 97%, and, in this
case, useful power is produced.
The theoretical analysis for CCR with external electrical heating mixture was done and
the experiments were carried out with the methane-air mixtures. Results showed that the
concentration of hydrogen and carbon monoxide could reach almost 20% and 15%,
respectively, under the optimal standard conditions with equivalence ratio of 0.35, total
flow rate of 106.5 L/min and intake preheating temperature of 600 K. It was shown the
considerable role of the crankshaft speed on syngas yield.
The crucial issues of the possibility of practical implementation of these methods are
associated with further detailed calculations and design study of the reactors.

Acknowledgments

I thank Dr. V. Nikolaev for help in calculations and students of Chosun University
Mr. Mun Sup Lim, and Mr. Myung Seok Hong for participation in the experiments.
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

References

[1] Yu. A. Kolbanovskii, et al., Pulse Compression of Gases in Chemistry and Technology,
Nauka, Moscow (1982), [in Russian].
[2] N. I. Kobozev, et al., The Explosive Conversion of Methane, Trudy Vses. Sov. Po Kom.
Khim. Per. Neft., Report in Three parts, Acad. Sci. USSR, Moscow (1956), [in
Russian].
[3] Von I. Szesich, Riv. Combust. 3, 204 (1956).
[4] T. Yamamoto, et al., “Production of Synthesis Gas by an Internal Combustion Engine”,
6th World Petroleum Congress, Sec. IV-Paper 42-PD, 9, 1963 (Frankfurt am Main,
Germ.) pp429-437.
[5] G. A. Karim, British Chemical Engineering, 8, 392 (1963).
[6] V. M. Shmelev, and V. M. Nikolaev, Theor. Found. Chem. Eng. 42, 19 (2008).
[7] Vladimir Genkin, et al., Russian Federation Patent No. 2120913, Febr. 24, 1998.
[8] Vladimir Grunval’d, et al., Russian Federation Patent No. 2096313, Nov. 20, 1997.
[9] V. M. Shmelev, and V. M. Nikolaev, Problemy Mashinostroeniya Avtomatizatsii, 4, 57
(2002), [in Russian].
[10] V. M Nikolaev, and V. M. Shmelev, “Combustin of the Lean Mixtures in an ICE with
Superadiabatic Compression”, Proc. X Int. Symp. on Fundametal and Applied
Problems of Improvement of Reciprocating Engines, Vladimirsk. Gos. Univ., CD paper
no. 05-01-043, 2005 (Vladimir, Russia), [in Russian].
[11] V. M Shmelev, and et al., “The fuel gasification in an ICE cylinder”, Proceeding of X
International Symposium on Fundametal and Applied Problems of Improvement of
Reciprocating Engines, Vladimirsk. Gos. Univ., CD paper no. 05-01-044, 2005
(Vladimir, Russia), [in Russian].
[12] M. Glouchenkov, and A. Kronberg, “Pulsed Compression Technology”, A
Breakthrough in the Production of Hydrogen, 16th World Hydrogen Energy
Conference (WHEC), 7, 2006. (Lyon, France) pp1-7.
[13] V. M. Shmelev, and et al., High Temperature, 46, 77 (2008).
[14] V. M. Shmelev., and et al., Combustion and Explosive, Edited by S. Frolov, Torus
Press, Moscow, 2, 12 (2009), [in Russian].
[15] F. Durst, and M. Weclas, Proc. Proc. Inst. Mech. Eng., Part D, 215, 63 (2001).
[16] V. M. Shmelev, and V. M. Nikolaev, Russian Journal of Physical Chemistry B,
Pleiades Publishing, Ltd., 2, 431 (2008).
[17] V. M. Zamanskii, , and A. A. Borisov, Itogi Nauki Tekhn., Ser. Kinet. Katal., 19, 156
(1989), [in Russian].
[18] G. I. Kozlov, Proc. 3rd All-Union Meeting on the Theory of Combustion, Akad. Nauk
SSSR, Moscow, 1, 30 (1960), [in Russian].
 Chapter 1
Synthesis Gas Production by Reforming Methane in a Chemical Compression Reactor

[19] A. Nemeth, and R. Sawyer, J. Phys. Chem., 73, 2421 (1969).

[20] E. L. Petersen, , and et al., Combust. Flame, 117, 272 (1999).
[21] V. Ya. Basevich, and et al., Khim. Fiz., 17, 112 (1998), [in Russian].
[22] N. A. Dvornikov, Combustion, Explosion and Shock Waves, 35, 230 (1999).
[23] Z. A. Mansurov, Combustion, Explosion and Shock Waves, 41, 727 (2005).
[24] V. M. Shmelev, and et al., Khim. Fiz., 25, 42 (2006), [in Russian].
[25] J. I. Ramos, Internal Combustion Engine Modelling, HPB, New York (1989).
[26] R. C. Reid, and et al., Properties of Gases and Liquids, McGraw-Hill, New York
(1977).
[27] V. M Shmelev, and V.M. Nikolaev, Theor. Found. Chem. Eng., Pleiades Publishing,
Ltd., 43, 50 (2009).
[28] V. N. Lukanin, et al. Teplotekhnika (Heat Engineering),Vysshaya shkola, Moscow
(2002), [in Russian].

Author biography
Vladimir Shmelev was born in Russia on June 30, 1940. He received the B.S. degree from
Moscow Engineering Physical Institute, Moscow, Russia, in 1964 and the Ph.D. and D.Sc.
degrees in physics from the Institute of Chemical Physics, Russian Academy of Science,
Moscow, in 1968 and 1982, respectively. Since 1964, he has been with the Institute of
Chemical Physics, Russian Academy of Science, where he is currently the Head of the
Combustion Laboratory. His current research interests include the fundamentals of the
combustion theory, gas lasers on combustion, plasma chemistry. He has developed some
technologies in the combustion field, which were marked by golden medals on the
international exhibitions “Arhimed”.