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Fuel 168 (2016) 91106

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Fuel
journal homepage: www.elsevier.com/locate/fuel

A semi-empirical approach to the thermodynamic analysis of downdraft


gasification
Denis A. Svishchev a,b,, Alexander N. Kozlov a, Igor G. Donskoy a,b, Alexander F. Ryzhkov b
a
Laboratory of Thermodynamics, Melentiev Energy Systems Institute (ESI), Siberian Branch of Russian Academy of Sciences, 130 Lermontov Street, Irkutsk 664033, Russia
b
Ural Federal University (UrFU), 19 Mir Street, Yekaterinburg 620002, Russia

h i g h l i g h t s

 We suggest an approach to the analysis and optimization of process parameters.


 The approach was tested by the experiments on downdraft gasifier.
 For the charcoal and biomass cases the mass and energy balances were made up.
 The results are generalized as cold gas efficiency constraints.
 A hypothesis about the wood gasification mechanism is put forward.

a r t i c l e i n f o a b s t r a c t

Article history: For most commercial biomass gasifiers the cold gas efficiency makes up 5070%. However, thermody-
Received 23 September 2015 namic modeling demonstrates the possibility of its increase to 8085%. Thermodynamic models predict
Received in revised form 14 November 2015 an optimal composition of flows coming to the gasifier, and a temperature. These parameters are hard to
Accepted 17 November 2015
reproduce at gasifier since they often depend on the operating parameters. This paper proposes a semi-
Available online 28 November 2015
empirical approach which makes it possible to carry out a thermodynamic analysis of operating param-
eters and optimization of gasifier operation.
Keywords:
To test the approach we did experiments on charcoal and biomass gasification in a downdraft gasifier.
Equilibrium model
Semi-empirical approach
Modeling was done on a non-stoichiometric model maximizing the reaction system entropy.
Carbon boundary point The semi-empirical approach reveals three limitations of the cold gas efficiency of the experimentally
Downdraft gasifier observed process. The first limitation is related to the attainment of a carbon boundary line (which is esti-
Cold gas efficiency mated thermodynamically) by the reaction system. This line corresponds to the maximum cold gas effi-
Biomass gasification mechanism ciency of the process. The second limitation deals with a shift along the carbon boundary line. The third
limitation is a stoichiometric limitation on the formation of combustible gas components.
The process of wood gasification is characterized by a number of phenomena which are untypical of the
downdraft process. These phenomena underlie the hypothesis about the wood gasification mechanism.
According to this hypothesis the process of gasification runs in the layers of individual particles. At the
same time there is either no fuel bed stratification or it does not manifest itself.
2015 Elsevier Ltd. All rights reserved.

1. Introduction considered to be a carbon neutral fuel, which makes it possible to


reduce carbon dioxide emissions; its use may contribute to an
1.1. Background increase in the energy security of the countries importing energy
resources, decrease their dependence on fossil and nuclear fuel
Biomass is a promising renewable energy source. Its advantages supplies; an increase in the energy use of biomass is an additional
compared to the traditional types of fuel are as follows: biomass is factor of economic support to the agricultural regions [1]. A specific
feature of biomass is low density of its distribution across the ter-
ritory, which limits the cost effective radius of its collection and
Corresponding author at: Melentiev Energy Systems Institute (ESI), Siberian
arouses interest in the energy plants of small unit capacity [2].
Branch of Russian Academy of Sciences, 130 Lermontov Street, Irkutsk 664033,
Russia. Tel.: +7 (902)17 19 199; fax: +7 (3952)42 67 96. One of the efficient biomass processing methods is gasification.
E-mail addresses: denis.svishchev@gmail.com (D.A. Svishchev), kozlov@isem.irk. This is the process of thermochemical fuel conversion under the
ru (A.N. Kozlov), donskoy.chem@mail.ru (I.G. Donskoy), af.ryzhkov@mail.ru effect of gaseous oxidizers or supercritical water [3]. Unlike other
(A.F. Ryzhkov).

http://dx.doi.org/10.1016/j.fuel.2015.11.066
0016-2361/ 2015 Elsevier Ltd. All rights reserved.
92 D.A. Svishchev et al. / Fuel 168 (2016) 91106

processes of thermochemical conversion such as burning, pyroly- equilibrium approximation. This is why the assumptions made in
sis, liquefaction, carbonization and torrefaction, the target product the models were as follows:
of gasification is gas intended for energy and production purposes.
Gasification of solid fuel is not a new technology and over the 1. Consideration is given to a steady-state process which occurs in
last century and a half several periods of its development have a continuous stirred-tank reactor. Thermodynamic models are
changed one another [3]. Since early 2000s again there has been zero-dimensional. They do not take into account possible gasi-
an increase in the interest in this technology, which was caused fier configurations, such as fixed bed, fluidized bed and pneu-
by the following factors: the aims to reduce carbon dioxide emis- matic transport [21].
sions and improve the environmental friendliness of the energy 2. Chemical system is supposed to attain equilibrium. There is a
industry; a considerable increase in the cost of hydrocarbon feed- systematic deviation between equilibrium and experimental
stock; an intensive development of the economy and growing yield of substances. The measured yield of tar, C2-
energy consumption in China and India [4]. hydrocarbons, methane and char often exceeds the equilibrium
Despite the existing potential, the gasification technologies values [22,23]. The calculated equilibrium ratio H2/CO exceeds
have not been widely commercialized [5], so far and the major the experimental one.
share of energy produced from biomass falls on the process of 3. Mineral part of the fuel is represented by a mechanical mixture
direct combustion [6]. This situation can be explained by a number of metal oxides and silicon oxide [24]. Chemical transforma-
of technological problems characteristic of gasifiers [7,8]. Research tions of these components are either not considered [24] or
into the production process line of biomass processing has shown are limited by pure condensed substances carbonates, sili-
that the main difficulties are related to the stages of gasification cates, aluminum silicates, etc. [25,26]. Such an approximation
and gas cleaning [8]. is related to the insufficient accuracy and stability of thermody-
One of the technological barriers to the gasification commer- namic data for phases and components of ash, and the presence
cialization is insufficiently high cold gas efficiency of the existing of liquid and glass phase, etc. [27].
plants. This characteristic reflects the share of chemical energy of
the fuel which is transferred to the chemical energy of gas. Sensible In order to take into account the non-equilibrium composition
heat of gas in this case is not considered. The overwhelming major- of reaction products, which is experimentally observed, research-
ity of commercial plants are characterized by comparatively low ers introduce mass constraints on the formation or consumption
cold gas efficiency, about 5070% (Table 1). Interestingly, this level of one substance or another. The constraints are caused by insuffi-
is typical of the plants of different capacity, which have different cient residence time of the substances in the reaction zone, and are
design and conditions of process organization, and process fuel of of a kinetic nature. They are formed on the basis of experimental
different origin and composition. At the same time there are exper- data obtained at gasifiers. The constraints can be taken into
imental studies demonstrating the possibility of increasing the account in the model by applying quasi-equilibrium temperature,
cold gas efficiency. In the autothermal process that occurs without which is lower than the temperature of the process and better sim-
external heat supply the cold gas efficiency of 77% was reached [9]. ulates the yield of char residue and methane [28,29]. In stoichio-
With heat supplied, in the allothermal process it is possible to metric models, constraints are introduced by adjusting the
achieve higher efficiency values, reaching 124% [10]. This value is equilibrium constants of watergas shift reaction and methane for-
indicative of the fact that the energy of gas exceeds the energy of mation. The equilibrium constants are multiplied by coefficients
fuel used to produce this gas. Additional energy comes to the pro- depending on the process temperature, oxygen content or equiva-
cess in the form of heat and is converted to the chemical energy of lence ratio [30,31]. Non-equilibrium content of substances can be
gas. taken into account directly in the mass balance. In this case the
Comparatively low efficiency of demonstration and pilot plants required mass of the substance is stoichiometrically excluded from
is related to the non-optimal conditions for the operation of reac- the initial matter of the system, is sent through bypass and mixed
tors, and in some cases to the non-optimal choice of gasification with equilibrium products of the reaction [32,33]. Additional mod-
method of one or another fuel type. This research aims to enhance els can be used to describe the conversions of substances that pass
the cold gas efficiency of gasification process. through the bypass [34].
Thermodynamic models make it possible to find optimal oper-
1.2. Thermodynamic modeling of gasification ating conditions of a certain reactor or an entire plant. The opti-
mized parameters include energy and exergy efficiency,
A widely spread approach to the research into the gasification hydrogen and carbon dioxide yield, gas heating value and its out-
process and assessment of the degree to which it is perfect is a put with a certain ratio of H2 to CO [3539]. The result of modeling
thermodynamic approach [19,20]. The approach is based on the represents an optimal set of input parameters that mirrors the

Table 1
Performance characteristics of commercial biomass gasifiers.

Size, MW(th) Scale Gasifier type Agent type Feedstock Moisture wb, % Ash db, % CGEa, % Carbon conv., % Refs.
26.5 Commercial Shaft-furnace Oxygen-rich air Municipal solid waste 44.0 16.3 49.2 95.3 [11]
18.9 Commercial Shaft-furnace Oxygen-rich air Municipal solid waste 42.8 32.3 54.6 91.7 [11]
2.0 Pilot Bubbling fluidized bed Air/steam Sewage sludge 38 39.5 70 n/a [12]
1.2 Pilot Two-stage downdraft Air Wood chips 12.3 0.6 53 74 [13]
1.1 Demonstration Updraft Air, Air/steam Municipal solid waste 30.0 11.7 3258b n/a [14]
0.5 Demonstration Bubbling fluidized bed Air Sewage sludge 38 57 66 n/a [12]
0.4 Pilot Entrained-flow (cyclone) Air Peat, rice husk, bark, wood <15 0.619.3 4352 7095 [15]
0.3 Pilot Entrained-flow O2/N2 Wood powder 3.0 0.9 58 89 [16]
0.25 Pilot Downdraft Air Wood sawdust, pellets 9.5 2.1 68 n/a [17]
0.060.08 Pilot Bubbling fluidized bed Air Wood pellets 6.3 0.7 5560 8995 [18]
0.040.07 Pilot Bubbling fluidized bed Air Olive oil waste (orujillo) 8.7 14.2 5360 7094 [18]
a
Cold gas efficiency.
b
The calculations considered heat supplied to the process.
D.A. Svishchev et al. / Fuel 168 (2016) 91106 93

initial composition of the system and includes the reaction temper- We will consider the last two points in more detail.
ature (Fig. 1). To determine optimal parameters of the model, In practice, the gasification agent to fuel ratio is maintained
graphical approaches are often used, including those based on through the control of mass flows coming to the reactor. Flow rate
ternary diagrams [40,41]. Also, the response surface methodology of gaseous substances is regulated with the equipment pushing
is applied which allows optimization of several input model them to the reactor or pulling producer gas from the reactor. A
parameters simultaneously [42]. number of specialized mechanical systems were developed to con-
In equilibrium state the reaction products can contain thermo- trol and measure fuel flow rate [51,52]. At the same time there is
dynamically stable solid carbon. Its quantity can decrease due to still a question about the choice of intensity of fuel and gasification
changing initial composition of the system and temperature. The agent supply to the reactor, since it is impossible to estimate it
conditions when solid carbon is consumed completely are called with the thermodynamic models. The rate of substance supply
solid carbon boundary [43] or carbon boundary point [44] and should correspond to the rates of their conversion in the process.
the corresponding temperature is called carbon boundary temper- Too intensive supply will decrease the fuel conversion rate and
ature [45]. In these conditions the maximum energy and exergy increase the residual char, whereas the presence of oxygen in the
efficiency of the process is achieved [43,44]. At carbon dioxide gasification agent will lead to excessive oxidation of the com-
gasification, the carbon boundary point also corresponds to the bustible gas components.
maximum conversion of the gasification agent [46]. To determine There are fixed bed reactors simple in design. Fuel flow rate in
the carbon boundary point, special models have been developed them is not an independent and controlled parameter and is deter-
[47,48]. mined by gasification process demand [53]. This circumstance can
complicate experimental reproduction of the optimal equivalence
2. Materials and methods ratio, which is estimated thermodynamically.
Temperature is an input parameter of the thermodynamic
2.1. Operating parameters optimization model. At the same time it turns out to be dependent on the pro-
cess that occurs in the reactor. To one extent or another, tempera-
In the Section 1.1 it is shown that the cold gas efficiency of the ture is determined by all operating parameters and this causes the
implemented commercial plants is comparatively low and makes greatest difficulties in its reproduction. Moreover, the reactor vol-
up 5070%. Thermodynamic calculations demonstrate the princi- ume is characterized by temperature variation, which can reach
pal capability to enhance the gasification process. Calculated cold 700800 C between different areas of the fixed bed [54,55].
gas efficiency of the autothermal process under optimal conditions Non-stoichiometric models allow the use of the principle of
reaches 8085% [40,49,50]. In this case the potential of enhancing entropy maximization instead of the principle of free energy min-
the efficiency makes up 1035%. This potential can be imple- imization [56,57]. In this case instead of temperature we use heat
mented by applying the results of thermodynamic modeling to exchange between reactor and thermal reservoir. In the experi-
the optimization of gasifier operation. To this end it is necessary ment this parameter corresponds to the difference between exter-
to experimentally reproduce optimal input parameters of the nal heat supply and reactor heat losses. Such an approach makes it
model, i.e. the initial composition of the reaction system and tem- possible to take into account the temperature variation in the reac-
perature. Such a reproduction, however, is hindered by a number tor and provide better comparability of modeled and experimental
of factors. Comparison of the input thermodynamic model param- data.
eters and process parameters (Fig. 1) reveals the following: There can be two ways of solving the problems related to the
application of thermodynamic modeling for the optimization of
1. The number of operating parameters exceeds the number of gasification processes. The first way is traditional and it can be
input model parameters. The thermodynamic model can take characterized as a movement from model to experiment. This
into account such parameters as size of the particles, geometri- approach lies in the improvement of thermodynamic models
cal dimensions of reactor and bed voidage only indirectly. through the involvement of unconsidered operating parameters
2. The thermodynamic model does not consider the intensity of in the calculation. This direction is developed by Gmez-Barea
flows of the substances coming to the reactor or leaving it. and Leckner [58].
3. Some input parameters of the model are the process dependent The second way can be characterized as a movement from
variables, for example temperature, and, in some cases, the experiment to model. It suggests finding the relationships
ratio of gasification agent to fuel. between the operating parameters of the process and input

Fig. 1. Comparison of process parameters and input parameters of the model.


94 D.A. Svishchev et al. / Fuel 168 (2016) 91106

parameters of the model. The main tool of such a research is exper- thermodynamics. Sections 2.32.5 consider in detail both parts of
imental studies which imply the estimation of an impact of indi- the semi-empirical approach scheme and the examples of graphi-
vidual operating parameters on the initial composition of the cal analysis are presented in Section 3.
system and its heat exchange with the environment. The experi-
ments aim to reveal the factors that either facilitate or limit the
attainment of optimal gasification conditions which were obtained
2.3. Experimental rig
in thermodynamic modeling. This way of research is of a semi-
empirical nature.
The experiments had the following distinctive features:

2.2. Semi-empirical approach 1. Fuel flow rate in the studied process has to be determined by
the needs of the gasification process. To this end, we chose fixed
The scheme of an approach proposed in the research includes bed process without forced removal of the bed from reactor.
the experimental and calculation parts (Fig. 2). The experimental 2. The gasification process should be organized in the way that the
part can be represented by one or several experimental cases. Each yield of the reaction products be comparable with the equilib-
case requires that the dependent variables be determined. These rium yield estimated on the model. For this purpose, we used
are equivalence ratio and heat exchange between reactor and the a downdraft process which made it possible to achieve deep
environment. The calculation part generates a set of model cases tar decomposition. Along with the biomass, charcoal character-
obtained on a preliminarily verified thermodynamic model. ized by lower volatile product yield was used as a fuel.
Fig. 1 demonstrates a relationship between the input model 3. It is necessary to study the operating parameters which are not
parameters and process dependent variables that hinder the repro- considered in the model. One such parameter, namely gasifica-
duction of optimal model cases. In Fig. 2 there is no such a relation- tion agent flow rate, was varied in the experiments.
ship. To this end the equivalence ratio and heat exchange between 4. Heat exchange between the reactor and the environment
the reactor and the environment are varied in wider ranges of val- should be changed in a wide range of values. In the experiments
ues. These ranges are selected randomly but should include exper- the value of the reactor heat losses was determined by the
imental values. thickness of heat insulation, and the external heat supply was
The key part of the semi-empirical approach is an analysis of controlled by heating the gasification agent.
experimental cases with respect to a set of modeled ones (Fig. 2).
The analysis makes it possible to investigate the capabilities and The experiments were done on a laboratory rig (Fig. 3). The rig
ways of reaching the gasification conditions optimal in terms of includes a downdraft reactor without throat, with an internal

Fig. 2. A general scheme of the semi-empirical approach.


D.A. Svishchev et al. / Fuel 168 (2016) 91106 95

Fig. 3. Schematic diagram of the rig: 1 fuel hopper, 2 rotameter, 3 air heater, 4 wall tuyeres, 5 thermal insulation, 6 grate, 7 thermocouples, 8 receivers for
liquids, 9 cyclone, 10 heat exchanger, 11 fine filter, 12 blower, 13 chromatograph.

diameter of 80 mm. Maximum heating capacity of the reactor in


Table 2
the conducted experiments made up 8.5 kW. Properties of the fuel and char residue.
Fuel comes to the reactor from the fuel hopper (1). Air is sup-
Sample Birch char Aspen chips Aspen char
plied to the reactor through the electric air heater (3) and six tuy-
eres (4) located evenly along the reactor perimeter. The reactor has Run ID C1 C2 C3 B1B3 B3
Moisture content, % wb 3.6 4.4 2.6 6.8 0.9
a heat insulation layer (5). The fuel bed rests on the grate (6) which
Ultimate analysis, % daf
can be installed at any height inside the reactor. The grate makes it C 82.5 49.3 86.6
possible to specify the height of the bed, which varies from the H 3.6 5.5 1.7
minimum (grate is opposite the tuyeres) up to 455 mm. O 13.9 45.2 11.7
Temperature is measured with the thermocouples of type K Proximate analysis, % db
Volatile matter 18.9 84.9 13.0
(7), whose junctions are located near the inner surface of the reac- Fixed carbon 77.6 14.7 84.7
tor. Such a location of thermocouples almost does not prevent bed Ash 3.5 0.4 2.3
movement. Solid particles are separated from producer gas in Decomposition temperature (C) 232 315
cyclone (9). The cyclone also allows collecting liquid products.
Gas from the cyclone is cooled in the heat exchanger (10) and
passes through the fine filter (11). Gas movement through the rig ply to the hopper it was carefully mixed and its sample was taken
is provided by the blower (12). It creates a negative pressure inside for the analysis. The data of ultimate and proximate analysis of the
the rig of about 26 kPa, thus excluding leakage of producer gas to samples are presented in Table 2. The Table also presents the prop-
the laboratory premises. Air flow rate is controlled by the blower erties of the aspen char obtained in one of the experimental runs.
and is measured by rotameter (2). Unlike the wood, birch char was not stored in the hermetically
closed container and its moisture varied from run to run.
In the downdraft gasifiers, it is recommended that the used bio-
2.4. Instrumentation and procedures mass should have a moisture content not exceeding 20% [60]. In
the case where the fuel hopper is heated by producer gas and in
Gas composition was determined by the method of gas chro- staged reactors it is possible to apply fuel with a moisture content
matography. Chromatograph SRI 8610C, equipped with succes- up to 3045% [6163]. However, this considerably decreases heat-
sively connected columns with silica gel and zeolite of 13X type, ing value of the gas and gasification efficiency. For the biomass
makes it possible to determine all gas components including C2- gasification experiments, we took sufficiently dry fuel with a mois-
hydrocarbons. With helium, being a gas carrier, the analysis rapid- ture content of 7% (Table 2).
ity makes up about 12.5 min. The sum of absolute errors in the Table 2 also shows the temperature of thermal decomposition
measurement of gas component concentrations does not exceed of a fuel sample. It was measured with the thermal analyzer Net-
1%. zsch 449C Jupiter. The dry fuel sample was heated at the rate of
The yield of liquid products of gasification was evaluated by the 10/min, in the air flow of 30 ml/min. The temperature of thermal
mass of samples taken from the cyclone and heat exchanger. Tar decomposition corresponds to the middle of the temperature range
content in the samples was determined by the weight of the resi- during which the dry sample lost 1% of the initial weight.
due obtained after drying a part of the averaged sample (10 ml) in Each fuel type took part in three experimental runs with air. In
the drying oven at 70 C during 4050 min. An analogous approach one run we recorded several cases that differed in the air flow rate.
was used earlier in the research by Bhattacharya and Dutta [59]. The runs differed from one another in air heating and thickness of
In the experiments we used aspen chips, 911 mm in size, and the reactor heat insulation (Table 3). The total number of the
birch char crushed into particles, 812 mm in size. Before fuel sup- experimental cases obtained in six runs made up 27.
96 D.A. Svishchev et al. / Fuel 168 (2016) 91106

Table 3 V air
Operating parameters of tested experimental runs. ER 2
V air;fullOx
Fuel Run Air flow rate (wet) Air temperature Insulation thickness
ID (Nm3/h) (C) (cm)
Cold gas efficiency (gcg) of the process was calculated as a ratio
of the lower heating value of gas to the lower heating value of fuel
Birch C1 0.82.5 20 5
char C2 20 10
from which the gas was produced:
C3 270450 10
LHV gas V gas
Biomass B1 0.82.8 20 0 gcg  100; % 3
B2 20 10 LHV fuel mfuel
B3 330370 10
Energy balance was made up on the basis of mass balance. Heat
losses were calculated according to the equation:
P
LHV fuel mfuel Q air  j LHV j mj Q j
For each experimental case a stationary state was attained HL  100; % 4
LHV fuel mfuel
which was characterized by constant mass and energy flows dur-
ing a certain time. Depending on the conditions of the process, it where Q stands for sensible heat of a respective mass flow, index j
took 40120 min to reach the stable condition. The attainment of corresponds to the outgoing flow, namely gas, char residue or tar.
the stable condition was testified by the steady temperature profile Heat exchange between the reactor and the environment corre-
and gas composition. sponded to the expression:
The height of fuel bed had to be sufficient for the gassolid reac-
tions to occur. The fuel bed section along which these reactions Q air
HEx HL   100; % 5
mainly run and end is called the reaction zone. For the stratified LHV fuel mfuel
downdraft reactor this zone appears to be limited from above by
the unburned fuel zone and from the bottom by the inert char
2.5. Equilibrium model
zone [60,64].
According to the estimations made by Jayah et al. [65], the
This research is based on the thermodynamic models for a
height of the reaction zone makes up about 240 mm for the down-
closed reaction system [57]. The equilibrium composition of the
draft reactor fed by the wood chips 10 mm in size. For charcoal the
reaction products is calculated on the model with constant
typical height of the reaction zone is lower than for the wood. The
enthalpy and pressure. In terms of mathematical programming,
studies on the air gasification of charcoal were conducted by
the model has the form:
Kolodtsev [66] in the top-lit downdraft reactor. The results of the
Find
studies are indicative of the fact that the conversion reactions
X
run within first three particles of the bed. In the experiments on max Sx; T Sj x; Txj 6
the charcoal conversion in the updraft reactor that were conducted j
by Hallett et al. [67], the height of the reaction zone approximately
corresponded to five diameters of the fuel particles. In this research subject to
the height of the fuel bed was measured from the tuyeres to the X
n
grate and was assumed redundant. It made up 80 mm for birch aij xj bi ; i 1; m 7
char and 300 mm for aspen chips. j1

Gas leaving the reaction zone was further cooled in the inert
char zone. In order to correctly characterize the running thermo- xj P 0; 8j 1; n 8
chemical process, the temperature of the off gases should be mea-
sured not immediately after the bed, but at the end of the reaction where S(x, T) and Sj(x, T) are entropy of the reaction system and
zone. Otherwise, the gas temperature will turn out to be underes- specific entropy of its j-th chemical substance; x = (x1, . . . , xn)T is
timated. In the experiments on charcoal the temperature was mea- the vector of amounts of substances of the system with dimension
sured by a thermocouple located directly in the fuel bed at a n; aij is the number of atoms of element i in a molecule of substance
distance of 52 mm below tuyeres. Readings from this thermocou- j; bi is the amount of substance of element i in the system. The right-
ple were also taken in the experiments on wood for which the hand side of expression (6) presents the total entropy of reacting
reaction zone sizes appeared to be comparable with the reaction substances. Eq. (7) specifies the mass balance condition and in com-
zone sizes for charcoal. More details can be found in Section 3.2. bination with inequality (8) determines the range of physical values
Total mass and energy balances were made up for each experi- of variables x.
mental case. Tar deposits on the inner surface of rotameter hinder Energy balance between the reaction system and thermal reser-
the measurement of gas flow rate by this method. Therefore, the voir is specified by the following equations:
flow rate was calculated by the nitrogen balance as in [68,69]: X
Hhr Hj T in xin
j H 9
j
V air Nair
V gas 2
1 X
N gas
2 H Hj Txj 10
j
where Vgas and Vair gas yield and air flow rate, Nm /h; and 3
Ngas
2 N air
2
nitrogen content in gas and air, vol.%. Since nitrogen content in the where H(x, T) and Hj(T) are enthalpy of the entire system and speci-
fuel is relatively small, it may be ignored in Eq. (1) [70]. Fuel flow fic enthalpy of its j-th substance; Htr is change in the enthalpy of
rate was calculated by the carbon balance as in the research by thermal reservoir which exchanges heat with the studied system.
Rutberg et al. [71]. This parameter corresponds to the heat exchange between the reac-
Equivalence ratio (ER) was specified as a ratio of actual air flow tor and the environment, which is estimated by the experimental
rate (Vair) to the air quantity which is theoretically necessary for data. For the autothermal process, the value Htr is positive and cor-
full combustion of the initial fuel (Vair,fullOx): responds to heat losses to the environment. In adiabatic conditions
D.A. Svishchev et al. / Fuel 168 (2016) 91106 97

it equals zero. For the allothermal process, Htr can be negative. are well in line with classical studies conducted in the first half
Index in denotes the initial state of the system. of the last century [66,74,75].

T f x 11 3.1.1. Model verification


Temperature of the system is calculated by Eq. (11) at each step Model (6)(11) requires information about the initial composi-
of the algorithm optimizing the objective function (6). tion of the reaction system and its heat exchange with the environ-
In this research, the thermodynamic properties of individual ment. For runs on the charcoal the data are presented in Tables 2
substances were estimated based on the data from [72]. Ash was and 4. Fig. 4 compares the composition of raw gas that is estimated
modeled as a chemically inert mixture of pure condensed sub- by the model with that measured in the experiments.
stances. The content of ash components was specified based on The products of birch char gasification leave the rig reactor in
the data from [27] and made up in wt%: SiO2 23.0, CaO 44.5, the amounts differing from the equilibrium ones. For the majority
K2O 7.7, Al2O3 5.3, MgO 6.3, Fe2O3 3.6, K2SO4 6.3, Na2O of cases the equilibrium yield of hydrogen and carbon dioxide is
3.0 and TiO2 0.3. A method for the calculation of thermody- higher and equilibrium steam yield is lower than the measured
namic properties of fuel and specific features of residual char rep- one. Such a difference between the experimental and modeled
resentation in the model are presented in Appendix A. Atomic results is partly explained by the fact that according to the shift
weights of the elements were assumed by the data of IUPAC [73]. reaction equilibrium is not attained:

CO H2 O CO2 H2 12

3. Results and discussion In the experiments, conversion of the initial substances (CO and
H2O) into the reaction products (CO2 and H2) proves to be kineti-
3.1. Charcoal gasification cally limited.
According to Eq. (12), we can expect a lower equilibrium yield
Table 4 presents the data of mass balances and some indices of carbon monoxide as compared to the experimental yield. It
made up for runs on charcoal. It is obvious that in all the cases should be consumed in the shift reaction. However, Fig. 4 does
gas has 0.10.8 vol.% of unreacted oxygen, which is typical of not allow us to make the conclusion on such an effect. It is proba-
downdraft gasifiers [60]. Complete consumption of oxygen does bly leveled down for the above reasons.
not occur since part of the air is not filtered through the fuel bed, Firstly, the model predicts an almost zero yield of oxygen and
but goes through the reactor, through the near-wall space where residual char. Only for case C1.1 the equilibrium graphite yield
bed void volume is higher. This part of the air is mixed with burn- makes up 0.1 mol/kg (fuel wb). In the experiments these sub-
ing producer gas outside the reaction zone, where temperature and stances are not fully consumed (Table 4). Hence, the equilibrium
concentration of radicals is insufficiently high for triggering the content of carbon oxides formed in accordance with Eq. (13) will
oxidation reaction. exceed the experimental one.
Volatiles contained in the birch char, whose yield is 19% cause a bC a=2 bO2 aCO bCO2 13
methane concentration in gas at the level of 0.20.5 vol.%. High
temperature in the fuel bed in the intensive allothermal cases Secondly, the modeled content of methane in raw gas is low and
C3.2C3.4 reaches 9001000 C, and fosters almost complete does not exceed 0.010.02 vol.%, and its concentration in the
methane oxidation. Its concentration drops below the limit of experiments reaches 0.5 vol.%. The model predicts deeper methane
detection by the chromatography method. Tar is not considered decomposition. Since in the calculations the graphite is not formed,
in the balances because its yield with volatiles is negligibly small. such decomposition can run with formation of carbon monoxide
An increase in the air flow rate, its heating, as well as heat insu- and hydrogen in accordance with the general reaction:
lation of the reactor cause rise in the content of combustible com- CH4 Ox 2H2 CO 14
ponents in producer gas, increase in heating value of the gas and
cold gas efficiency of the process on the whole. These regularities where Ox substance that is an oxygen donor (O2, H2O, CO2).

Table 4
Summary data for charcoal gasification cases.

Case ID C1.1 C1.2 C1.3 C1.4 C1.5 C2.1 C2.2 C2.3 C2.4 C2.5 C3.1 C3.2 C3.3 C3.4
Insulation thickness cm 5 5 5 5 5 10 10 10 10 10 10 10 10 10
Air flow rate (wet) Nm3/h 0.82 1.22 1.62 2.04 2.43 0.83 1.23 1.67 2.06 2.49 0.82 1.21 1.62 2.03
Air temperature C 23 23 23 23 23 19.9 19.9 20 20 20 270 355 415 450
Air moisture content vol.% 1.0 1.0 1.0 1.0 1.0 0.9 0.9 0.9 0.9 0.9 0.7 0.7 0.7 0.7
Raw fuel consumption kg/h 0.20 0.34 0.49 0.62 0.73 0.20 0.36 0.52 0.66 0.82 0.24 0.37 0.50 0.64
Equivalence ratio 0.567 0.491 0.449 0.446 0.454 0.577 0.473 0.445 0.431 0.416 0.468 0.436 0.434 0.427
Average raw gas composition
H2 % 5.5 7.3 7.9 7.4 7.6 5.2 7.1 7.5 8.8 9.8 7.3 8.5 8.6 10.4
O2 % 0.2 0.1 0.1 0.1 0.2 0.2 0.1 0.1 0.2 0.2 0.3 0.2 0.4 0.8
N2 + Ar % 63.8 60.8 58.5 58.7 58.9 63.8 58.9 57.6 57.0 55.6 58.6 57.5 57.1 55.4
CO % 19.1 24.8 28.5 29.5 28.7 17.5 25.1 28.3 29.7 30.5 26.8 31.0 31.7 31.4
CH4 % 0.3 0.3 0.4 0.3 0.2 0.5 0.5 0.4 0.3 0.4 0.4 0.0 0.0 0.0
CO2 % 8.1 5.1 3.0 2.4 2.8 9.1 4.8 3.0 2.4 1.9 3.5 1.2 0.6 0.4
H2O % 3.0 1.6 1.6 1.6 1.6 3.7 3.5 3.1 1.6 1.6 3.1 1.6 1.6 1.6
Gas flow rate (raw) Nm3/h 1.00 1.57 2.17 2.72 3.23 1.02 1.64 2.27 2.83 3.51 1.09 1.66 2.22 2.87
Gas temperature C 598 720 778 791 812 640 746 817 867 873 733 894 974 1031
Charcoal residue yield g/h 2.5 4.2 6.2 7.8 9.2 2.5 4.5 6.4 8.2 10.3 3.0 4.8 6.4 8.2
Mass balance closure % 99.7 99.3 99.6 99.4 99.5 100.4 101.0 100.7 100.1 100.5 100.9 99.7 99.7 100.5
Heat exchange % 27.8 16.3 11.0 10.9 10.9 28.3 14.8 10.5 6.6 4.0 13.1 5.5 2.4 2.7
Cold gas efficiency % 56.1 66.1 71.0 71.1 70.3 54.0 67.0 70.5 73.6 76.3 69.3 74.2 75.6 79.1
98 D.A. Svishchev et al. / Fuel 168 (2016) 91106

In the experiments the producer gas is the main product of fuel


conversion. By-products, such as tar and charcoal residue are
formed in negligible amounts. This fact explains a good agreement
between the cold gas efficiency values that are obtained in the
experiments and those obtained on the model. Almost in all the
cases their discrepancies do not exceed 2% abs. and only in case
C3.4 the discrepancy is 4.0% abs.

3.1.2. Cold gas efficiency limitations


While verifying the model we changed its four input parame-
ters, namely air and fuel moisture content, the equivalence ratio
and heat exchange with the environment (enthalpy of a thermal
reservoir). The rest of the input parameters remained constant.
The number of variable input parameters in the model can be
reduced to two by assuming that the moisture of birch char and
air does not change and is equal to average values across the runs.
Under these assumptions any experimental case can be character-
ized by equivalence ratio and heat exchange. The study included a
series of variant calculations, in which these two parameters were
varied with small increments.
Fig. 5 presents some results of modeling. The dotted line with a
zero yield of condensed carbon corresponds to the set of carbon
boundary points. Similarly, we designate this line as a carbon
boundary line. For the specified heat exchange level the maximum
cold gas efficiency will be observed in the point resting on this line.
To the right of the carbon boundary line the process shifts to com-
bustion, to the left of the line to pyrolysis. Fig. 5 represents a
region of model cases which can be potentially realized on the
rig. In the shaded region the modeled process temperature does
not exceed the charcoal decomposition temperature (Table 2). It
is probable that the process with the parameters from the consid-
ered region cannot be realized in practice.
Points in Fig. 5 show all the experimental cases for birch char. It
is noteworthy to indicate that the points occupy the same region in
the Figure, close to the carbon boundary line. Above the 5% heat
exchange level the points have virtually a linear arrangement.
Experimental cases differ from each other in the reactor insulation
thickness, air temperature and flow rate. Despite the different nat-
ure of operating parameters they have an equivalent impact on rel-
ative indices of the process. For example, in Fig. 5 the rectangular
frame indicates cases C1.3C1.5 and C2.3, differing in air flow rate
and thermal insulation thickness. Nonetheless, the gas composi-
tions and the cold gas efficiency for them prove to be close to each
other (see Table 4). This fact allows the conclusion about thermo-
dynamic equivalency of the considered operating parameters, i.e.
the parameters can alternatively substitute each other.
For each experimental case the values of equivalence ratio and
heat exchange are such that the reaction system turns out to be
near the carbon boundary line (Fig. 5). When gas passes through
the fuel bed its composition should tend to an equilibrium one. If
the gas and fuel phases are in equilibrium, the system will be on
the carbon boundary line. In the experiments the fuel bed height
exceeded the reaction zone height, which explains disposition of
the experimental cases in Fig. 5. To study this phenomenon in
detail we applied experimental data of Nicholls [75]. He studied
gas composition variation along the coke bed height.
Nicholls carried out experiments on the combustor, whose
design corresponded to the updraft fixed bed gasifier. Air of differ-
ent temperatures and coke were fed into it. The fuel bed was situ-
ated on the grate and its height was maintained constant and equal
to 61 cm. Before taking measurements, the combustor was heated
for 2 h. Gas samples were taken and temperature was measured
through special holes located along the reactor height.
Fig. 4. Comparison of the modeled and measured composition of raw gas. Fig. 6 presents results of the experiments for air temperature
Experiments on the birch char, runs C1C3.
204 C. Continuous change in gas composition which weakens by
D.A. Svishchev et al. / Fuel 168 (2016) 91106 99

Fig. 5. Results of variant calculations of charcoal gasification. Solid isolines demonstrate modeled cold gas efficiency (%), dotted lines equilibrium graphite yield (kg/kg
(fuel)), points experimental cases.

While moving from section to section the reaction system nears


the carbon boundary line, shifting from the combustion region to
the gasification one (Fig. 7). The system tends to attain an equilib-
rium between the gas and solid phases. Point e with a quadratic
label shown in Fig. 7 corresponds to the end of the reaction zone
(Fig. 6), in which the rate of gas composition change and corre-
spondingly the rate of heterogeneous reactions decrease. Such
reduction is caused by the fact that the system approaches the
equilibrium state.
The thermodynamic analysis of the experiments by Nicholls
explains disposition of the experimental cases for birch char that
are shown in Fig. 5. If the fuel bed height is sufficient and exceeds
the reaction zone height or is comparable with it, the reaction sys-
tem reaches a region close to the carbon boundary line. Besides,
the system tends to maximize cold gas efficiency and reach the
maximum conversion of its sensible heat into chemical energy of
gas. This conclusion makes it possible to formulate the first limita-
Fig. 6. Fixed-bed coke gasification by air of temperature 204 C [75]. tion of gasification efficiency: the carbon boundary line and the
maximum cold gas efficiency can be attained by providing suffi-
the end of the reduction zone is observed along the whole fuel bed cient time for the reaction between gas and solid fuel.
height. The reaction zone sizes are comparable to the fuel bed The air flow rate, its heating and also thermal insulation of the
sizes. reactor determine thermal conditions and heat exchange of the
We perform a thermodynamic analysis of gas formation process reaction zone. These parameters are thermodynamically equiva-
in the coke bed in accordance with the scheme in Fig. 2. The whole lent. Changes in any parameter lead to changes in thermal condi-
bed along the height is divided into sections and each section is tions of the process and the reaction system shifts along the
associated with gas of a certain composition and temperature. carbon boundary line (Fig. 5).
Between the sections, the equivalence ratio and heat exchange The second limitation of cold gas efficiency is associated with
with the environment vary. These parameters were calculated the thermal process condition that determines the reaction system
using the data of Nicholls for each section. position along the carbon boundary line. For the autothermal gasi-
Variant calculations of coke combustion were made by analogy fication the heat losses can be reduced only to a certain level mak-
with the thermodynamic analysis of charcoal gasification. The rel- ing up 24%. Gasification efficiency can further be increased only
evant results are presented in Fig. 7. Solid isolines show an equilib- by heat supply from outside.
rium yield of graphite. Points denote experimentally observable In the allothermal process heat can be supplied not only by the
states of the reaction system for each bed section. Shaded region gasification agent heating, but also by heat transfer through the
includes cases in which the temperature was not higher than the reactor wall, heat carrier heating and preliminary fuel heating.
fuel decomposition temperature that is equal to 430 C. The latter Heating of the gasification agent by using the plasma torch is con-
was measured by the thermogravimetric analysis for the graphite sidered to be the most effective method despite its high cost [76].
sample, because we did not have the coke sample. For the allothermal conditions there also exists an efficiency
100 D.A. Svishchev et al. / Fuel 168 (2016) 91106

Fig. 7. Modeled results of coke combustion. Isolines present equilibrium graphite yield (kg/kg (fuel)), points reactive system states in the experiments.

Table 5
Summary data for biomass gasification cases.

Case ID B1.1 B1.2 B1.3 B1.4 B1.5 B1.6 B2.3 B2.4 B2.5 B3.1 B3.2 B3.3 B3.4
Insulation thickness cm 0 0 0 0 0 0 10 10 10 10 10 10 10
Air flow rate (wet) Nm3/h 0.82 1.21 1.62 2.03 2.46 2.79 1.62 2.04 2.33 0.82 1.22 1.63 2.05
Air temperature C 24 25 25 24 24 23 24 24 24 331 361 370 369
Air moisture content vol.% 1.4 1.4 1.3 1.3 1.3 1.3 0.9 0.9 1.0 0.6 0.7 0.7 0.6
Raw fuel consumption kg/h 0.52 0.81 1.04 1.29 1.53 1.78 1.26 1.52 1.77 0.69 1.06 1.43 1.83
Equivalence ratio 0.383 0.365 0.379 0.387 0.393 0.382 0.316 0.328 0.323 0.294 0.284 0.280 0.276
Average raw gas composition
H2 % 14.0 15.0 14.5 14.5 14.4 14.6 16.2 16.3 16.8 17.5 18.3 18.3 17.6
N2 + Ar % 46.5 44.6 45.0 45.4 45.4 44.8 40.7 41.7 41.5 39.8 38.8 38.2 38.1
CO % 16.4 16.5 16.0 15.7 15.9 16.2 19.8 19.9 20.0 23.1 23.8 23.0 23.6
CH4 % 2.1 2.3 2.2 2.1 1.9 2.1 2.8 2.5 2.6 2.6 2.8 2.9 3.1
CO2 % 13.0 12.8 12.7 12.7 12.4 12.2 10.8 10.7 10.8 9.7 9.2 9.7 9.1
C2H4 % 0.3 0.4 0.3 0.3 0.3 0.3 0.4 0.3 0.3 0.3 0.3 0.3 0.4
C2H6 % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
H2O % 7.6 8.3 9.2 9.2 9.6 9.7 9.3 8.6 8.0 6.9 6.8 7.4 8.0
Gas flow rate (raw) Nm3/h 1.37 2.12 2.80 3.49 4.21 4.84 3.12 3.82 4.39 1.62 2.48 3.35 4.23
Gas temperature C 220 295 344 418 475 499 654 677 682 598 670 688 718
Char residue yield g/h 0.6 1.0 1.2 1.5 1.8 2.1 1.6 2.0 2.3 0.9 1.4 1.8 2.4
Tar yield with raw gas g/Nm3 0.20 0.12 0.13 0.11 0.14 0.14 0.46 0.45 0.39 0.23 0.24 0.31 0.31
Mass balance closure % 99.3 100.4 100.8 100.7 100.8 100.9 101.4 100.6 100.3 99.9 99.8 100.7 100.7
Heat exchange % 21.4 17.0 16.7 15.0 13.8 11.9 1.8 2.0 1.2 1.9 1.9 2.1 3.3
Cold gas efficiency % 73.8 76.6 75.5 75.2 74.9 76.3 83.4 82.6 83.5 85.6 87.9 87.7 88.2

Table 6
Runs with different heights of the wood fuel bed.

Case ID Bed height (cm) Insulation (cm) Air flow rate (Nm3/h) Dry gas composition (vol.%) Tar yield with dry gas (g/Nm3)
H2 N2 + Ar CO CH4 CO2 C2
B2.4 30.0 10 2.04 17.8 45.6 21.7 2.7 11.7 0.4 0.49
B4.1 3.5 10 1.19 14.6 52.6 21.3 1.1 10.2 0.2 0.34
B4.2 3.5 10 3.59 14.5 50.8 21.8 2.1 10.4 0.4 0.18
D.A. Svishchev et al. / Fuel 168 (2016) 91106 101

limitation. It becomes evident, when additional heat supplied to


the reactor is used to increase temperature rather than chemical
energy of producer gas. Such a limitation is typical of air and oxy-
gen gasification of high carbon fuels. For example, in oxygen gasi-
fication of condensed carbon by reaction (13) the cold gas
efficiency will depend on the ratio of carbon oxides. The efficiency
of the limiting case, where gas consists practically entirely of car-
bon monoxide, will be limited stoichiometrically. The considered
limitation is removed with a change in the chemical composition
of the gasification agent, for example, when steam is added to
oxygen.

3.2. Wood biomass gasification

Table 5 presents mass balances for experimental runs made


using wood biomass. Each run suggested testing the cases which
differ in air flow rate from one another. Unlike the regularities
observed in char conversion the efficiency of wood gasification vir-
tually does not depend on air flow rate. There are no considerable
changes in the composition of raw gas and equivalence ratio,
despite a 33.5-fold increase in the air flow rate. This phenomenon
is not characteristic of the downdraft gasifiers. The published data
indicate that gas composition changes with air flow rate. Depend-
ing on the process conditions, hydrogen and carbon monoxide con-
tent can both increase and decrease when air flow rate grows
[77,78].
When studying a downdraft process, Jayah et al. [65] found out
that the reaction zone makes up 240 mm. In our experiments bed
height was 300 mm. Run B1 is characterized by the absence of
insulation on the reactor walls. In case B 1.1 gas temperature mea-
sured at a distance of 52 mm from tuyeres makes up only 220 C
(Table 5). However, the process is characterized by quite high effi-
ciency 72%. This circumstance allows us to suppose that the
height of the reaction zone is considerably lower than the height
Fig. 8. Comparison of modeled and measured gas composition. Gasification of
of the fuel bed, equal to 300 mm. For the gas to have such a low
aspen chips, runs B2 and B3.
temperature, the conversion reactions should end at a bed with a
height lower than 52 mm. This supposition was confirmed in run
B4 in which the fuel bed height made up only 35 mm. and light hydrocarbons are lower than the corresponding mea-
Characteristics of some experimental cases tested in runs B2 sured values (Fig. 8). These differences qualitatively correspond
and B4 are presented in Table 6. Gas composition proves compara- to the results obtained by Kangas et al. [22].
ble in the experiments with different heights of the bed. Further- There are virtually no hydrocarbons in equilibrium and their
more, a decrease in the fuel bed height does not lead to a rise in yield in the process is as follows: 2.53.1 vol.% of methane, 0.3
the tar yield. The reactions of fuel gasification and decomposition 0.5 vol.% of C2-hydrocabons. In the model, the matter of hydrocar-
of most tar products occur and mainly end in the pre-tuyere space bons transfers to hydrogen and carbon monoxide according to
of the gasifier. reaction (15):
Experiments with charcoal and wood have cases which are
comparable with one another, for example cases C2.3C2.5 and
Cx Hy Ox y=2H2 xCO 15
B2.3B2.5 respectively. The fuel used in them was different, but
heat insulation of reactor was the same and air flow rates without As well as in expression (14), Ox denotes an oxidizing agent act-
heating were close. Heat losses in the reaction zone in the experi- ing as an oxygen donor (O2, H2O, CO2). Unlike the model, in the
ment on wood turn out to be 39% abs. lower than those in the experiment part of the oxidizing agent remains unreacted which
experiment on charcoal. This fact is also indicative of small sizes explains higher measured concentrations of steam and carbon
of this zone in the experiments on wood biomass. dioxide in gas.
Run B3 differs from B2 by air heating to the temperature of
3.2.1. Model verification 330370 C (Table 5). We can suppose that the external heat sup-
Input model parameters (i.e. air moisture content, equivalence ply should positively affect the equilibrium state attainment in the
ratio, fuel composition and heat exchange) were assumed for each reactor, and the measured concentrations of substances should
case according to Tables 2 and 5. Equilibrium model of wood gasi- approach the modeled concentrations. This supposition is not con-
fication was verified by the experimental data. Fig. 8 presents the firmed. On the one hand, the experimental data are indicative of
results of comparing equilibrium and measured compositions of the fact that in the case of air heating the temperature of gases
gas for runs B2 and B3. The cases of run B1 were not considered leaving the reaction zone rises only by 3540 C (Table 5). On the
since for them the heat exchange with the environment was deter- other hand, the comparison of Fig. 8B2 and B3 does not show qual-
mined incorrectly. For more details see Section 3.2.2. itative changes between the gas composition differences which are
There are systematic deviations between the modeled and determined in the experiment and in the model.
experimental values. The equilibrium concentrations of H2 and It should be noted that the modeled values of the cold gas effi-
CO are higher and the equilibrium concentrations of CO2, H2O ciency differ little from the experimental ones. Average difference
102 D.A. Svishchev et al. / Fuel 168 (2016) 91106

Fig. 9. Results of wood gasification modeling. Solid lines show modeled cold gas efficiency (%), dotted lines equilibrium graphite yield (kg/kg (biomass)), points
experimental cases.

between them is 1% abs. This allows us not to consider the limita- In certain conditions, biomass pyrolysis occurs with a consider-
tions on the yield of non-equilibrium amounts of substances in the able endothermic heat effect. This circumstance can be used to
model (6)(11). supply heat to the process. Similar principle is implemented in a
two-stage Viking gasifier [79]. Its design includes a screw pyroly-
zer heated by gas from the engine and the gasifier. The tempera-
3.2.2. Limitations of cold gas efficiency ture at the end of the pyrolyzer makes up 600 C. The plant
The verified model cases differed from one another first of all by makes it possible to produce gas with low tar yield, hydrogen con-
such input parameters as equivalence ratio and heat exchange centration of 3034 vol.%, carbon monoxide 1517 vol.%, and
between the reactor and the environment. The moisture of fuel methane 23 vol.%
and air changed little from run to run. This affords the opportunity The third limitation of the efficiency is related to the possibility
to analyze the experimental cases on a set of modeled cases by of its enhancement with a shift of the system along the carbon
graphical method (Fig. 9). boundary line. It proves significant in the case of air gasification
By analogy with charcoal gasification the experiments on bio- of dry biomass. For the case of conversion of absolutely dry aspen
mass are mainly located along the carbon boundary line (Fig. 9). the limiting temperature of the process makes up 930 C. Above
The experimental cases of run B1 (quadratic markers, Fig. 9) do this value a considerable part of the supplied heat will be
not show the above described effect. They are located not exactly consumed to heat substances in the reactor but not to increase
on the carbon boundary line but on the line going along the heat chemical energy of gas.
exchange axis. The expected location of points of run B1 is demon-
strated by a shaded region in the Figure. In run B1 there is no heat
insulation on the reactor walls. This results in a sharp cooling of 3.2.3. Hypothesis about the process mechanism
gases leaving the reaction zone, and overestimation of heat losses, Gasification in the high carbon fuel bed causes the formation of
which explains the shift of points in the Figure. Fig. 9 shows the individual reaction zones in this bed [66,67,75]. In the oxidation
shaded region where the process cannot be realized, since the zone the oxygen of the gasification agent is consumed (see
equilibrium temperature does not exceed the wood decomposition Fig. 6). The main product of this process is carbon dioxide. Gas from
temperature (315 C). the oxygen zone goes to the reduction zone where carbon dioxide
Proximity of points to the carbon boundary line is indicative of reacts with the fuel and monoxide is formed. Enthalpy of the pro-
the reaction system proximity to the equilibrium between gas and cess appears to be negative in the oxidation zone and positive in
fuel phase. For the cases of charcoal gasification the first limitation the reduction zone. In other words, heat is produced in some par-
of cold gas efficiency is related to the time of fuel and gasification ticles of the bed and it is absorbed in the other ones. Heat is
agent reaction. For the experiments involving wood biomass this transferred from one zone to another. This process is accompanied
limitation appears to be less significant due to high conversion by loss of heat part which decreases with an increase in the air flow
rates. The process runs in a narrow reaction zone, with a width rate and gasification intensity.
not exceeding 35 mm. To explain the processes that occur in the downdraft gasification
As well as in the case of charcoal conversion the thermal condi- of the high volatile fuels (biomass, lignite), the mechanism with
tion of wood gasification determines the location of cases along the stratification of reactor zones is applied [80,81]. Four individual
carbon boundary line. In the autothermal conditions the efficiency zones are distinguished in the fuel bed: (1) drying; (2) pyrolysis;
of gasification reaches 83.5% at heat losses of 12%. Further (3) partial oxidation and (4) gasification of char residue. In the
increase in the efficiency can be achieved only if heat is externally research by Reed and Das [60] the zones of biomass pyrolysis and
supplied to the process. oxidation are connected by the zone of flaming pyrolysis. After this
D.A. Svishchev et al. / Fuel 168 (2016) 91106 103

Fig. 10. Hypothetical mechanism of wood particle gasification.

zone the oxidation products are reduced in the char bed located 4. Conclusions
below.
The process in runs B1B4 is characterized by the following fea- Thermodynamic analysis of the experiments done on a down-
tures: (1) a small size of reaction zone; (2) low sensitivity of gas draft gasifier revealed three limitations on the cold gas efficiency.
composition to air flow rate; (3) small heat losses compared to The first limitation is connected to the kinetics of interaction
the case of charcoal gasification; (4) low tar yield; (5) proximity between gas and fuel, and manifests itself when the time of their
of the reaction system to the state of equilibrium between gas reaction is insufficient (insufficient height of the fuel bed). The
and fuel phase. In order to explain these phenomena we put for- reaction system tends to the attainment of the carbon boundary
ward a hypothesis about the mechanism of thermochemical con- line and maximum conversion of available thermal energy to
version of the wood biomass. This mechanism differs from chemical energy of gas. The cold gas efficiency can be further
classical ideas about the combustion process. The reaction zones enhanced when the system moves along the carbon boundary line.
are located not in different parts of the fuel bed but within the vol- Such a movement is determined by heat exchange between the
ume of individual reacting particles (Fig. 10). The char oxidation system and the environment. The second limitation of the effi-
zone is formed in the surface layer of a particle. Under this layer ciency is characteristic of autothermal processes which may lack
there is a zone of biomass pyrolysis which is limited by the inert their own heat. The third limitation of the efficiency arises when
core. Flow of heat is transferred from surface to the inner layers the system energy conversion to the gas energy is restrained by
of the particle. the stoichiometric factors. In this case heat, supplied from the out-
A sequence of stages of the biomass pyrolytic decomposition is side is mainly consumed for heating the substances and walls of
presented in expression (16). Fresh layers of wood are heated to the reactor. All the three limitations to one extent or another are
the temperature of thermal decomposition. Then the fuel conversion characteristic of the gasification processes of both charcoal and
takes place and char, tar and gas are formed. The stages of wood.
heating and pyrolysis are accompanied by a weak endothermic The regularities of biomass gasification process appeared to be
effect. Enthalpy of such a process makes up 10.5 kJ/mol (biomass) uncharacteristic and different from the data available in publica-
[82]. tions. Based on the actual data, we formulated a hypothesis about
the biomass gasification mechanism. According to this mechanism,
DHh individual stages of the process run within individual particles
Biomass 298 K ! Biomass T rather than in different zones of the fuel bed. At the particle surface
heating
Dr H p Dr Hdec=red a layer of char is formed. It reacts with oxygen, releasing heat. This
! Char; tar; gas ! Char&gas heat is absorbed by the certain processes. These are pyrolysis of an
pyrolysis decomposition=reduction
internal layer of biomass, tar decomposition processes and reduc-
16 tion of pyrolysis products at their filtering through the surface
In the final stage, the pyrolysis products are filtered through the layer of char. This hypothesis requires further development and
superheated surface char layer. In this process the tar is decom- testing.
posed, and steam and carbon dioxide are reduced. This stage can The results of the experiments will be useful for the verification
be accompanied by a considerable endothermic effect. of mathematical models. For all the runs the complete data are pre-
Heat is produced and consumed by the processes that occur on sented. These data are sufficient to make up mass and energy bal-
the same fuel particles. Heat is not transferred between different ances. The untypical cases of biomass gasification are attractive
reaction zones of the bed, and the gasification process turns out to from the practical viewpoint. They are characterized by a compact
be almost insensitive to the air flow rate. Tar is mainly decomposed reaction zone, high cold gas efficiency, low tar yield, and stability of
in the superheated surface char layer. The suggested mechanism of gas composition under changing reactor capacity.
biomass gasification also explains the low height of the reaction In the research we suggest a semi-empirical approach. The
zone and comparatively small heat losses to the environment. It is approach makes it possible to conduct a thermodynamic analysis
of a hypothetical character and requires additional research. of experimental cases, study the impact of operating parameters
104 D.A. Svishchev et al. / Fuel 168 (2016) 91106

Table A Standard entropy of the dry, ash-free fuel formation is calcu-


Modeling of air gasification of wood biomass. Residual char is represented by graphite lated by the technique assumed for fossil coals [84]:
(Case 1) or aspen char according to Table 2 (Case 2).
    
H O
Input parameters of the model Case 1 Case 2 Df S298fuel a1 a2 exp a3 a4
CN CN
Equivalence ratio () 0.15 0.15    
Enthalpy of thermal reservoir (Htr), kJ/mol (fuel daf) 0 0 N S
a5 a6 J=mol=K A:4
Biomass and air temperature (C) 25 25 CN CN
Equilibrium composition, mol/mol (fuel daf)
Aspen (CH1.49O0.69) 0.00E+00 0.00E+00 where ax empirical coefficients (a1 = 37.1653, a2 = 31.4767,
Aspen char (CH0.23O0.10) 3.93E34
a3 = 0.564682, a4 = 20.1145, a5 = 54.3111, a6 = 44.6712) and C, H,
C (graphite) 0.327
CH4 0.043 0.226 O, N coefficients in the empirical formula of fuel. The fuel entropy
CO 0.356 0.508 is calculated by the equation:
CO2 0.274 0.267 Z
H2 0.561 0.332
T
cp T
H2O 0.198 0.061
STfuel Df S298fuel dT A:5
298 T
N2 + Ar 0.580 0.580
Temperature (C) 637 588 Heat capacity is calculated as a function of temperature and volatile
G, kJ/mol (fuel daf) 580.0 554.8
matter by the Kirov method, which is presented in detail in [84].
S, kJ/mol (fuel daf)/K 0.467 0.464
Entropy of formation and heat capacity of fuel do not affect the
results of thermodynamic calculations. Their use in the equilib-
rium model (6)(11) is justified only in terms of the completeness
and optimize them. This approach can be applied to study the
of thermodynamic description. This is explained by the absence of
operating parameters of reactors that differ in design and capacity,
the initial fuel in equilibrium (Table A).
and compare them with one another.
Char residue is one of the main gasification products. Technique
(A.1)(A.5) can be used to replace graphite by char in the model.
Acknowledgments Such an improvement looks logic since it takes into account the
residual quantities of hydrogen and oxygen, contained in char.
Thermodynamic calculations for gasification processes were However, thermodynamic stability of char is less than that of gra-
carried out at UrFU and supported by the Russian Science Founda- phite and its equilibrium quantity appears to be extremely small
tion by Grant 14-19-00524 (to D.A.S., I.G.D. and A.F.R.). The other (Table A). To better simulate the experimental data, mass con-
parts of the study are funded by the Russian Foundation for Basic straints that increase the graphite yield are often introduced into
Research (Grant 14-08-31666). Instrumental studies are supported the model. Replacement of graphite by char in the model increases
by Baikal Analytical Center of Irkutsk Scientific Center of the Rus- the differences between the experimental and modeled data, and
sian Academy of Sciences. turns out to be rational only if mass constraints on its consumption
are additionally used.
Appendix A. Thermodynamic properties of fuel
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