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Journal article Chern Model Devolatilization Coal Particle

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A model for the devolatilization of a coal particle

sufciently large to be controlled by heat transfer

Jyuung-Shiauu Chern

1

, Allan N. Hayhurst

Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK

Received 12 August 2005; received in revised form 7 April 2006; accepted 11 April 2006

Available online 19 June 2006

Abstract

This study follows previous experimental work showing that the shrinking-core model applies to the pyrolysis

(i.e., heating in the absence of oxygen) of particles (diam. 14 mm) of a bituminous coal or a lignite in a uidized

bed at 700950

C. These experimental facts are in accord with the production of volatile matter being endothermic

and not thermoneutral, as often assumed. Also, the rate at which volatile matter is produced in the presence of

oxygen (i.e., devolatilization) or in its absence (pyrolysis) is demonstrated here to be controlled not at all by mass

transfer, but by heat conduction to a moving reaction front inside a coal particle, provided its diameter exceeds

3 mm. The resulting steady-state model of devolatilization indicates that six dimensionless groups are required

to describe the rate of

(I) coal char +volatile matter

for a nonfragmenting and nonswelling coal. This reaction occurs for a total time of

c

1

r

0

+c

2

r

2

0

for a coal of radius r

0

. Experimental measurements of the times for pyrolysis in a bed of hot sand uidized by

N

2

indicate this dependence on r

0

holds much better than the usually accepted one of ar

n

0

. The measurements

also indicate that the enthalpy change of reaction (I) is 9.4 4.0 MJ/(kg of volatile matter) and the thermal

conductivity of char is 1.2 0.5 Wm

1

K

1

. In addition, it was deduced that reaction (I) occurs at 500 K

and that (of the heat released by burning the volatile material, a fraction is fed back to a parent coal particle

devolatilizing in a bed uidized by, e.g., air) is less than unity. These numerical considerations enable the model

of devolatilization to be simplied; it turns out that a heated particles core of virgin coal shrinks mostly with

a constant velocity, characterized by only four dimensionless groupsi.e., two of them usually turn out to be

unimportant. The important groups include a Biot number for the char, Bi

char

, and = 1 + H

comb

/

H

v

.

Given that =0 and =1 for pyrolysis, the kinetics in that case are characterized entirely by three dimensionless

groups, including Bi

char

. The conditions for the shrinking core model to apply to devolatilization and pyrolysis

are discussed and are found not to apply, e.g., toward the end of devolatilization and for coals with low volatile

contents. The model was used to calculate when reaction (I) starts after an initial heating period for a coal particle.

*

Corresponding author. Fax: +44 1223 334796.

E-mail address: allan_hayhurst@cheng.cam.ac.uk (A.N. Hayhurst).

1

Current address: Energy Commission, Ministry of Economic Affairs, 2 Fu-Hsing North Road, Taipei 104, Taiwan.

0010-2180/$ see front matter 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

doi:10.1016/j.combustame.2006.04.011

554 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

The results are compared with experimental measurements (using gas chromatography of the volatiles released)

of when various species (e.g., CO, CO

2,

NO

x

, C

2

H

4

, C

2

H

6

, HCN) rst appear from a pyrolyzing coal particle.

These measurements conrm that reaction (I) can be assumed to occur at a mean temperature of 500 K.

2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Keywords: Fluidized beds; Coal; Pyrolysis and devolatilization

1. Introduction

A previous study [1] showed that the thermal de-

composition of a large (diam. 14 mm) particle of a

bituminous coal or a lignite in an electrically heated

uidized bed occurs [1] within a narrow reaction

zone, which behaves like a moving boundary in each

particle. No reaction is observed at a point inside

a heated coal particle before this boundary arrives,

whereas the coals volatile matter is fully removed af-

ter this front has passed [1]. Thus, this reaction zone

behaves as in the shrinking-core model [2]. An expla-

nation for this narrow reaction zone comes from con-

sidering the relative rates of reaction and heat conduc-

tion. The rate of thermal decomposition, whose exact

mechanism is not fully understood, is expected to be

proportional to exp(E/T

f

), where T

f

is the temper-

ature of the moving reaction zone. Thus, a higher T

f

will increase the rate of reaction considerably. On the

other hand, the rate of internal heat transfer to the

decomposition front only varies linearly with the tem-

perature in the reaction zone. This means that if T

f

is sufciently high, the rate of thermal decomposi-

tion will be inherently faster than heat transfer. The

result is large gradients in temperature inside a de-

volatilizing or pyrolyzing particle [3], coupled with a

moving temperature front, which causes the reaction

zone to be narrow. Thus, if a coals thermal decompo-

sition is endothermic, the rate of devolatilization can

be governed by the supply of enthalpy to sustain ther-

mal decomposition; i.e., internal heat transfer is rate-

controlling. To be explicit, for internal heat conduc-

tion to be slower than reaction (I) requires [4] that the

heating-up time for the particle be much longer than

the time constant for reaction (I); i.e., r

2

0

/ 1/k

1

or r

2

0

/Aexp(E/RT ). Substituting typical val-

ues [4] indicates that this requires r

0

> 1.5 mm for a

uidized bed at 900

on previous experimental observations [1,3] of py-

rolysis in hot beds uidized by N

2

is developed for

devolatilization (i.e., when the released volatile matter

burns in air around the coal particle), whereas py-

rolysis (i.e., in the absence of O

2

) is a special case.

Various assumptions will simplify the model and pro-

vide analytical solutions.

2. The importance of mass transfer

Previous work [1,4] has shown that if a piece

of devolatilizing bituminous coal or a lignite (diam.

15 mm) is extracted froma uidized bed at 800

C

and quenched rapidly in N

2

, its external layer of char

is very porous. However, a central core of undecom-

posed virgin coal is found if the coal is withdrawn

before all the volatile matter has been liberated. Evi-

dently during devolatilization, thermal decomposition

in (I) occurs at the interface between the central un-

decomposed coal and the char around it. This section

describes measurements of the pore sizes, etc. in the

char to ascertain whether the rate of devolatilization

is controlled by mass transfer of the volatile matter

through the outer layer of char. Such a check is im-

portant, because it has been asserted [5,6] that internal

mass transfer of the released volatile species can be

the rate-controlling step for devolatilization.

The experiments and coals have been described

[1]. Briey, a coal particle (2 g) was added to an

electrically heated bed (750950

C) of sand uidized

by N

2

at U/U

mf

= 3. After 10 min, pyrolysis was

easily complete, so the remaining char was extracted

and quenched in N

2

. After the char was crushed

into smaller particles, the diameters and volumes of

the pores were measured with a mercury porosime-

ter (Micromeritics Autopore II 9220). These results

were found to be reproducible and independent of

the size of the char particles; this provides important

validation for the mercury porosimetry. In addition,

internal surface areas in pores of different diameters

were measured with a BET analyzer (Micromeritics

ASAP 2000) using N

2

as the adsorbing gas. Such a

technique inevitably has errors, e.g., underestimating

the areas within smaller micropores. These measure-

ments also provided the porosity, (the ratio of the

volume of voids to the bulk volume), which is dis-

played in Fig. 1. The chars are more porous than

the original coal, but Fig. 1 shows that their porosity,

when they are made at 750950

C, is almost constant

and as high as 0.5.

In Fig. 2a, the volume inside the pores is plotted

against the corresponding internal diameter. It will be

noticed that most of the voidage inside the char from

Baddesley coal is in pores of diameter >0.1 m, i.e.,

macropores. The internal surface area per unit mass

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 555

Nomenclature

A pre-exponential factor dened by k

1

=

Aexp(E/RT ) (s

1

)

a a constant of proportionality in Eq. (30)

Bi Biot number =r

0

h

l

/k

C

p

heat capacity (J/kg K)

c

1

c

1

=

H

v

Y

c

X/3h

l

(T

T

f

)

c

2

c

2

=

H

v

Y

c

/6k

char

(T

T

f

)

E mean activation energy for devolatiliza-

tion (kJ/mol)

Fo pseudo-Fourier number (dimensionless)

as dened in Eq. (18)

H

comb

heat of combustion per unit mass of

volatile matter (J/kg)

H

v

heat of devolatilization per unit mass of

volatile matter (J/kg)

H

v

apparent heat of devolatilization per

unit mass of volatile matter (J/kg); see

Eq. (1)

H

w

heat of vaporization per unit mass of

moisture (J/kg)

h convective heat transfer coefcient be-

tween a uidized bed and a devolatiliz-

ing coal

h

l

heat transfer coefcient (W/m

2

K), de-

ned in Eq. (3)

Kn Knudsen number

k thermal conductivity (W/mK)

k

1

rst-order rate constant for thermal de-

composition in (I) (s

1

)

L characteristic distance for a transport

process (m)

Le pseudo-Lewis number

M

A

relative molecular mass of species A

(kg/kmol)

n an exponent in Eq. (30) (dimensionless)

n

p

number of pores per unit external surface

area of char (m

2

)

Q rate of exchange of enthalpy (W)

R universal gas constant = 8.31441

(J/Kmol)

r radial position inside a particle of

coal/char (m)

r

f

the radial position where thermal decom-

position occurs (m)

r

p

radius of a pore (m)

r

0

radius of a coal particle (m)

S

g

internal surface area per unit mass of

char (m

2

/kg)

T temperature (K)

T

f

mean temperature of the devolatilization

front

t time (s)

U supercial velocity of the gas uidizing

a bed of sand (m/s)

U

mf

minimum value of U for incipient u-

idization (m/s)

V

g

volume of the voids in a unit mass of

char (m

3

/kg)

W

moisture-free original coal (kg/kg)

Y

unit mass of moisture-free original coal

(kg/kg)

thermal diffusivity (m

2

/s)

m

mth eigenvalue of Eq. (51) (dimension-

less)

rad

emissivity at the surface of a coal parti-

cle

the fraction of the enthalpy from com-

bustion reaching the particle

H

v

/C

p,v

(T

T

f

)

=Bi

c

1, as dened in Eq. (52)

Y

H

v

/

char

C

p,char

(T

T

f

)(1 Y

)

mean free path

voidage or porosity of a char

density (kg/m

3

)

r

f

/r

0

, dimensionless radius

rad

StefanBoltzmann constant = 5.67

10

8

(W/m

2

K

4

)

tortuosity of the pores in a char

X dened by Eq. (33)

1 +H

comb

/

H

v

Superscript

dimensionless quantity

Subscript

c of or pertaining to coal

char of or pertaining to char

devo of or pertaining to devolatilization

l of or pertaining to the surrounding gases

pyro of or pertaining to pyrolysis

s of or pertaining to the external surface of

a particle

v of or pertaining to volatile material

w of or pertaining to water

0 initial value

nal value

556 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

Fig. 1. The porosity of the char from Baddesley coal pyrolyzed at different temperatures for 10 min at 850

C.

Fig. 2. For the pores of different diameters in char from

Baddesley coal after pyrolysis at 850

volumes, (b) the internal surface areas.

is plotted in Fig. 2b against the internal diameter of

the pores. Most of the internal surface area is located

in narrow pores of diameter <0.1 m, i.e., meso- and

micropores; for macropores (>0.1 m), no signicant

contribution to the internal surface area is found. In

Fig. 2 different roles for the macropores and micro-

pores are revealed: porosity is mainly contributed by

macropores, whereas the micropores possess most of

the internal surface area. This agrees with the litera-

ture [7,8]. Knowing the sizes of all the pores is useful,

but inconvenient, so an average pore radius will be de-

vised for further discussion. Using the parallel-pore

model [9], the average pore radius is dened as r

p

=

2V

g

/S

g

. Here, V

g

is the void volume, and S

g

is the

internal surface area, both per unit mass of char. Such

average pore radii are shown in Fig. 3a, where it will

be noticed that r

p

is larger for chars made in a hot-

ter bed. The original coal has about the same average

pore radius as the chars. In the following discussion,

the average radius for the macropores will be arbitrar-

ily designated as r

macro

= 10r

p

, and for the average

radius in the micropores, r

micro

= r

p

/10. Using the

parallel-pore model [9], if all the pores are distributed

homogeneously inside the char, the area of the pores

per unit outer surface area will equal the porosity [10].

If the pores meet the outer surface of the particle at

an average angle of 45

unit outer surface area is [10]: n

p

= /

2r

p

2

. The

resulting values of n

p

are shown in Fig. 3b, which in-

dicates that a lower temperature in the uidized bed

produces more, but smaller pores (see Fig. 3a) in a

char. However, the macropores do not appear to be

inuenced by temperature, because the porosity (see

Fig. 1) is fairly constant after pyrolysis at different

temperatures.

During pyrolysis or devolatilization, the volatiles

generated in the reaction zone must transfer through

the outer layer of char to the surroundings. To forecast

the rate of mass transfer of various chemical species

inside the char, their effective diffusivities are now

estimated. The binary diffusion coefcients of CH

4

,

HCN, H

2

S, N

2

O, and COS in nitrogen were chosen

as examples; these chemical species are commonly

found in the volatiles [11]. The rst thing to be es-

tablished is what type of diffusion dominates inside

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 557

Fig. 3. For the chars from Baddesley coal pyrolyzed at dif-

ferent temperatures for 10 min: (a) the average pore radii,

(b) the number of pores per unit external surface area.

a char particle: is it Knudsen or bulk (i.e., molec-

ular) diffusion? This question can be answered by

examining the magnitude of the mean free path, ,

of the volatiles inside the pores. For CH

4

at a pres-

sure of 1 atm and 0

number Kn = /2r

p

lies in the range 1 to 20 for the

above gases. Now when Kn 10, Knudsen diffusion

dominates; i.e., the diffusion of a molecule is con-

trolled more by collisions with the pores walls than

with other gaseous molecules, whereas molecular dif-

fusion prevails for Kn 0.1 [10], when the pores

are relatively wide. It must be concluded that for the

chars in this study, diffusion inside the pores of ra-

dius r

p

, i.e., the average, is either Knudsen or in the

transitional region between molecular and Knudsen

diffusion. Hence, Knudsen diffusion should prevail

in the micropores, whereas bulk diffusion dominates

in the macropores. The diffusivities of the volatiles

for bulk and also Knudsen diffusion are now esti-

mated.

First, a binary bulk diffusion coefcient was pre-

dicted using the ChapmanEnskog equation [12].

Then, the effective diffusivity for bulk diffusion in

the macropores is [13] D

macro

=D

AB

/ for the two

gases A and B, i.e., for N

2

and another gas. Here, the

tortuosity was assumed to be 1.5 (for most circum-

stances, lies between 1 and 2) to account for the

irregular shapes of the pores. For the micropores, the

Knudsen diffusion coefcient was calculated [10] for

a species A from D

micro

= 9700r

micro

(T/M

A

)

1/2

.

The diffusivities for the macropores are about 100

times bigger than those for the micropores. A higher

temperature results in both D

macro

and D

micro

being

increased. With the above estimates of D

macro

and

D

micro

, the relative rates of mass transfer and thermal

conduction inside a char particle can be investigated.

The characteristic times for mass transfer and thermal

conduction are L

2

/D and L

2

/ [13], where L is the

characteristic distance. For a particle of coal during

pyrolysis or devolatilization, the radius of the particle

is the characteristic distance for both bulk diffusion

and thermal conduction, because the volatiles must

diffuse to the surroundings; also, thermal conduction

occurs inside all the particle. However, the gas in a

micropore needs only to diffuse to the nearest macro-

pore; hence, the characteristic distance for Knudsen

diffusion, L

micro

, is roughly half the thickness of

the solid skeleton between macropores. Because the

porosity of chars is 0.5 (see Fig. 1), the thickness

of the solid part between the pores is expected (if a

regular hexagonal array of holes is assumed) to be

roughly the mean diameter of the macropores; i.e.,

L

micro

= 10r

p

. The ratio of the characteristic times

for mass transfer and thermal conduction is a pseudo-

Lewis number:

Le =

L

2

mass

/D

L

2

cond

/

.

When Le 1, mass transfer is much slower than ther-

mal conduction, whereas Le 1 corresponds to the

opposite situation. The thermal diffusivity,

char

, of

the char was taken as 10

7

m

2

/s, a typical value for

a char [14]. The resulting pseudo-Lewis numbers for

the various gases mentioned above in either macro- or

micropores are plotted against temperature in Fig. 4

for a particle of radius 5 mm. All the values are

10

3

or less, i.e., very much smaller than 1; this

means that mass transfer inside such a char particle

is always very much faster than internal heat conduc-

tion. Such a conclusion still holds if the above argu-

ment is adjusted for errors in V

g

, S

g

, and L

micro

. In

the real situation of a devolatilizing or pyrolyzing coal

particle, there are forced ows of the volatiles (often

giving jets [15]), because of pressure differences, so

that mass transfer will be even quicker than the above

estimate. Thus, it is clear that devolatilization and py-

rolysis are denitely not controlled by mass transfer

of gaseous volatiles within the pores of a coal particle.

On the contrary, it is likely that internal heat transfer

is rate-controlling.

558 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

Fig. 4. The pseudo-Lewis numbers for various gases diffusing inside macro- and micropores of Baddesley chars prepared at

different temperatures.

3. An approximate model of devolatilization

A shrinking-core model [1] is rened below to

describe devolatilization under heat transfer control,

with the volatiles burning. However, this model is not

universally valid for all coals undergoing devolatiliza-

tion. One requirement is a sharp, spatial change of

the volatile content in a coal particle during its de-

volatilization. To have a sharp temperature change in

space, the particle of coal must be big enough to be

nonisothermal. This requires that the Biot number of,

e.g., a near-spherical coal particle, Bi

c

r

0

h

l

/k

c

, has

to be larger than 1/2 [16]. Here, h

l

and k

c

are, re-

spectively, the external heat transfer coefcient [1]

and the thermal conductivity of coal; r

0

is the radius

of the coal particle. However, if the thermal conduc-

tivity, k

char

, of the char produced is much smaller than

k

c

, the particle can also be nonisothermal, even when

Bi

c

< 1/2 during devolatilization or pyrolysis. Thus,

it is also possible to use Bi

char

(r

0

h

l

/k

char

) > 1/2

as the requirement for nonisothermality. Whether it is

better to use Bi

c

or Bi

char

will be examined below, but

at this stage it can be noted that Bi

char

>0.5 requires

r

0

> 1.4 mm, using values of h

l

and k

char

deduced

below. The situations for which this model is valid

are discussed in Section 5.3. The physical properties

of the coals considered below have been given previ-

ously [1].

3.1. The assumptions of the model

A spherical coal particle is considered for sim-

plicity. During devolatilization the reaction zone is

located at r

f

, as illustrated in Fig. 5. For r < r

f

, the

coal remains unreacted. The reacted coal, i.e., char,

lies between r

f

and r

0

. The temperature in the reaction

Fig. 5. The radial prole of temperature in a devolatilizing

coal particle. The temperature in the uidized bed is T

(at

r =), at the particles exterior (r =r

0

) it is T

s

, and in the

reaction zone (r =r

f

) it is T

f

.

front at r

f

is T

f

, which in this model will be assumed

to be a constant during devolatilization. For simplic-

ity, fragmentation, swelling and any change of shape

are assumed not to happen. Although the concept of

one single primary reaction is questionable [17], the

phenomenological statement

(I) coal

(s)

volatiles

(g)

+char

(s)

will be assumed to describe thermal decomposition.

Thus, although several parallel paths for reaction (I)

are likely [17], it is assumed that all of them are suf-

ciently rapid for the rate of (I) to be controlled by

heat transfer. Consequently, the idea of thermal de-

composition via many parallel reactions is preserved,

but only one step is needed in this model, because the

kinetics of each step contributing to (I) is fast enough

not to be rate-controlling. For the same reason, only

one heat of devolatilization is dened and employed

for reaction (I), whose overall rate is determined by

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 559

heat conduction through the char. The rate of de-

volatilization will be expressed by the advancement of

only one reaction front (i.e., dr

f

/dt , as indicated by

microscopic examination of sectioned particles [1]),

in spite of some volatile matter being more tightly

bound than the remainder. Any secondary reactions of

the volatile material (e.g., with the char to yield soot)

will be ignored.

Evaporation of water in a coal occurs at 100

C

and complicates this model. When a thin thermocou-

ple (see below) was cemented into a coal particle to

measure the temperature midway between its exterior

and center, the temperature was found to be 100

C

for 25 s during its pyrolysis or devolatilization. Of

course, drying and the evolution of volatile matter

will occur simultaneously, but at different places. It

was noticed [3] that water in the particle delays the

subsequent increase of temperature and eventually

lengthens the time of devolatilization (or pyrolysis).

Such effects have been reported before [1820]. To

incorporate drying into this model, two approaches

seem possible. First, a narrow moving zone for evap-

oration at 100

devolatilization, there are two reaction fronts. Each

reaction front has its own specic temperature and

requires a distinctive amount of enthalpy to effect a

change of phase. The second approach is to treat water

as the least tightly bound volatile species and assume

it is included in reaction (I). Hence, the latent heat of

vaporization of water is part of the apparent heat of

devolatilization,

H

v

, per unit mass of (true) volatile

matter, and only one reaction front is required, in view

of the steep temperature gradients at r =r

f

in Fig. 5.

Furthermore, the sensible heat, from T

0

to T

f

, of the

unreacted coal at r

f

is incorporated into

H

v

for sim-

plicity. This inclusion of sensible heat will contradict

the treatment in Section 5.1 for predicting the heat-

ing time before drying; however, the error is expected

to be small. The apparent heat of devolatilization (per

unit mass of true volatile matter) is thus dened as

H

v

=H

v

+

_

H

w

+C

p,w

(T

f

373)

_

W

/Y

(1) +C

p,c

(T

f

T

0

)/Y

.

Here, W

and Y

volatile material, respectively, per unit mass of mois-

ture-free original coal. In addition, H

w

is the latent

heat of vaporization per unit mass of water at 373 K,

and H

v

is the overall enthalpy of devolatilization

per unit mass of the volatiles for reaction (I) at tem-

perature T

f

. In Eq. (1), T

0

was taken to be the initial

temperature. Although the rst method seems more

realistic, various attempts at using the rst one failed

to give a simple, analytical solution for the time of

devolatilization. Furthermore, the inadequacy of de-

scribing drying as a reaction front will be demon-

strated in Sections 5.2 and 5.3. Thus here the second

method is adopted.

The rate at which enthalpy is transferred from the

surroundings to the particles exterior is

(2) Q

r

0

=4r

2

0

h

l

(T

T

s

).

Here the overall heat transfer coefcient includes con-

vective and radiative contributions and so is

(3) h

l

=h +

rad

rad

_

T

3

+T

2

T

s

+T

T

2

s

+T

3

s

_

.

The temperature of the volatile matter is assumed to

be T

f

at r

f

, but T

transpirational enthalpy per unit time is assumed to

be

(4) Q

t

=4r

2

f

C

p,v

Y

c

(T

T

f

)

dr

f

dt

.

Here, C

p,v

is the mean heat capacity of the volatile

material (including water) between T

and T

f

. Be-

cause water is treated as part of the volatile matter, the

value of C

p,v

will depend on the water content. Inside

the particle, a quasi-steady state is assumed between

r

0

and r

f

, i.e., across the char. The change of sensible

heat and the enthalpy ow across the char layer are

treated separately. Without considering any change of

sensible heat in the char, the resulting enthalpy ow

by conduction [21] is

(5) Q

r

0

r

f

=4k

char

(T

s

T

f

)r

0

r

f

/(r

0

r

f

).

The change in the sensible heat of the char layer (pre-

viously neglected [1]) is

(6) Q

sen

=4

char

C

p,char

d

dt

r

0

_

r

f

T r

2

dr.

However, it is difcult to derive an analytical solution

if Eq. (6) is used. Consequently, a perfectly good ap-

proximation, found using the temperature distribution

(shown in Fig. 13) in a particle, after considering non-

steady conduction of heat, was employed:

(7) Q

sen

=

4

3

char

C

p,char

(T

T

f

)r

2

0

dr

f

dt

.

The rate of enthalpy consumption in the endothermic

reaction (I) is

(8) Q

chem

=4r

2

f

H

v

Y

c

dr

f

dt

.

The enthalpy to heat up the unreacted central part,

i.e., a change of sensible heat of the raw coal (again

neglected previously [1]), has already been incorpo-

rated into Eq. (1) as part of the apparent enthalpy of

devolatilization.

If there is enough oxygen in the uidizing gas,

e.g., the bed is uidized by air, and if the temperature

560 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

of the bed is high enough (>850

C [22]) to ignite

the volatile matter, these vapors start to burn. Such

combustion around a coal particle liberates heat and

provides enthalpy for devolatilization. The rate of lib-

eration of enthalpy, Q

comb

, from burning the volatiles

is

(9) Q

comb

=4r

2

f

c

H

comb

Y

dr

f

dt

.

Although the volatile matter burns, probably fairly

rapidly, the vigorous ow of uidizing gas might

carry much of the liberated enthalpy away from the

particle; hence not all the liberated heat of combus-

tion will be used in heating the coal particle. Here it

is assumed that Q

comb

is the enthalpy of combus-

tion that reaches the particle and thus contributes to

its heating, with 0 1. This was of course ig-

nored in the previous [1] treatment of pyrolysis. If the

bed is cooler than 850

self-ignite [22], so =0 even for devolatilization. If

equals 0, this model can also be used for the pyrolysis

of coal; no other modication is needed. Hence, the

steady-state relationship between the above enthalpy

ow rates is

(10)

Q

r

0

+Q

comb

=Q

r

0

r

f

+Q

sen

+Q

t

(at r =r

0

)

and

(11) Q

r

0

r

f

=Q

chem

(at r =r

f

),

where every quantity is positive for simplicity.

In summary, the assumptions of this steady-state

model include the following:

(a) The primary reaction, (I), with one dominant

path, occurs irreversibly in a moving front at r

f

.

(b) The temperature at the reaction front, T

f

, is con-

stant during devolatilization.

(c) Mass transfer of the volatile material across the

layer of char is not rate-controlling.

(d) Bi

char

or Bi

c

>1/2 to ensure that the distribution

of temperature inside the particle is not uniform.

(e) The changes of the sensible heat of both the unre-

acted coal and the layer of char are approximated

as in Eqs. (1) and (7).

(f) Fragmentation, swelling, and change of shape of

the particle do not occur.

(g) The latent heat of evaporation of water is viewed

as part of the apparent heat of devolatilization;

i.e., drying and the primary reaction (I) in effect

occur simultaneously.

(h) From burning the released volatile material, the

fraction of its heat of combustion that is used for

further heating of the particle is . This parameter

is estimated below, but for the pyrolysis of a coal,

is zero.

(i) The particle is large enough for r

2

0

/

Aexp(E/RT ), as discussed above. As an

aside, this could mean that if reaction (I) were

really several reactions in parallel, any steps with

a very large activation energy, E, could be ki-

netically controlled. Such a possibility is ignored

below.

3.2. Derivation of the model

Equation (10) gives

4r

2

0

h

l

(T

T

s

) +4r

2

f

c

Y

C

p,v

(T

T

f

)

dr

f

dt

+

4

3

char

C

p,char

(T

T

f

)r

2

0

dr

f

dt

+4r

2

f

c

H

comb

Y

dr

f

dt

(12) =4k

char

(T

s

T

f

)r

0

r

f

/(r

0

r

f

).

Rearranging the above equation gives the temperature

at the outer surface of the particle as

(13)

T

s

=

_

_

_

r

2

0

h

l

T

+T

f

k

char

r

0

r

f

/(r

0

r

f

)

+r

2

f

c

Y

[H

comb

+C

p,v

(T

T

f

)]

dr

f

dt

+r

2

0

char

C

p,char

(1 Y

)(T

T

f

)

dr

f

dt

/3

_

_

r

2

0

h

l

+k

char

r

0

r

f

/(r

0

r

f

)

.

Also, Eq. (11) gives

4k

char

(T

T

s

)r

0

r

f

/(r

0

r

f

)

(14) =4r

2

f

H

v

Y

c

dr

f

dt

.

Furthermore, T

s

can be eliminated from Eqs. (13)

and (14) to give

(15)

dr

f

dt

=

(T

T

f

)r

2

0

h

l

_

_

r

2

f

Y

c

[

H

v

H

v

r

0

h

l

/k

char

+H

comb

+C

p,v

(T

T

f

)]

+r

f

(

H

v

Y

c

r

2

0

h

l

/k

char

)

+r

2

0

char

C

p,char

(T

T

f

)(1 Y

)/3

_

_

.

After integration, Eq. (15) becomes

t =r

3

f

c

Y

3r

2

0

h

l

(T

T

f

)

_

H

v

_

1

r

0

h

l

k

char

_

+H

comb

+C

p,v

(T

T

f

)

_

r

2

f

c

Y

2r

0

h

l

(T

T

f

)

H

v

r

0

h

l

k

char

r

f

char

C

p,char

(1 Y

)

3h

l

+

r

0

c

Y

3h

l

(T

T

f

)

_

H

v

_

1 +

r

0

h

l

2k

char

_

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 561

+H

comb

+C

p,v

(T

T

f

)

(16) +C

p,char

(T

T

f

)

(1 Y

)

char

Y

c

_

.

Two boundary conditions were employed for Eq. (16),

viz., r

f

= r

0

at zero time, and r

f

= r

f

at time t . The

time t = 0 is chosen as the moment volatile material

starts to evolve. The time interval between inserting

a coal particle into a uidized bed and when volatiles

start to evolve is designated as the time of heating; it

will be dealt with in Sections 5.1 and 5.2.

Six dimensionless parameters are employed to

simplify Eq. (16); they are

(17) Bi

char

r

0

h

l

/k

char

,

(18) Fo k

char

t /

c

C

p,v

r

2

0

h

l

t /Bi

char

c

C

p,v

r

0

,

(19)

H

v

/C

p,v

(T

T

f

),

(20)

Y

H

v

/

char

C

p,char

(T

T

f

)(1 Y

),

(21) 1 +H

comb

/

H

v

,

(22) r

f

/r

0

.

The pseudo-Fourier number, Fo, is an arbitrary mea-

sure of time. It differs from its conventional den-

ition [21], because here Fo uses physical properties

from different materials, namely, the heat capacity of

the volatile matter, the thermal conductivity of the

char, and the density of the original coal. The ratio

of the apparent heat of devolatilization to the change

of the sensible heat of the volatile material is des-

ignated as . The relative importance of the heat

of devolatilization and the sensible heat of the char

is . Furthermore, indicates the contribution to the

heat of devolatilization fromburning the volatiles. Be-

cause combustion is exothermic and the pyrolysis of

coal is probably endothermic, 1. The dimension-

less position of the reaction front, , varies from 1 to

zero. Using these dimensionless groups, Eq. (16) be-

comes

Fo

Y

=

3

3

_

1

Bi

char

1

Bi

char

2

2

3Bi

char

(23)

+

1

3

_

1

2

+

Bi

char

+

1

Bi

char

+

1

Bi

char

_

.

The signicance of the cubic Eq. (23) is that the rela-

tionship between Fo and , i.e., the movement of the

reaction front, is characterized by only ve dimen-

sionless groups, namely, Y

, Bi

char

, , , and .

For the pyrolysis of coal, both Eq. (16) and its dimen-

sionless version, Eq. (23), are applicable, provided

equals zero, i.e., = 1. Hence, in this model, only

four parameters, i.e., Y

, Bi

char

, , and , govern

the relationship between Fo and for the pyrolysis of

any solid fuel.

4. The time of devolatilization

The time of devolatilization is the interval of time

from the beginning to the end of volatile material be-

ing released in (I), when oxygen is present in the sur-

roundings, i.e., the time for the reaction front to move

from = 1 to 0. From Eq. (23), the dimensionless

time of devolatilization is

Fo

devo

=Y

/6 +Y

/3Bi

char

(24) +Y

/3Bi

char

+Y

/3Bi

char

.

Similarly, the time of pyrolysis is given when =1

in Eq. (24); hence,

Fo

pyro

=Y

/6 +Y

/3Bi

char

(25) +Y

/3Bi

char

+Y

/3Bi

char

.

The difference between the above two times is

Fo Fo

devo

Fo

pyro

(26) =( 1)Y

/3Bi

char

.

Equations (24)(26) can be revamped into the dimen-

sional expressions

(27)

t

devo

=

Y

H

v

c

3(T

T

f

)

_

r

2

0

2k

char

+

_

1 +

H

comb

H

v

+

C

p,v

(T

T

f

)

H

v

+

C

p,char

char

(T

T

f

)(1 Y

)

Y

H

v

_

r

0

h

l

_

,

(28)

t

pyro

=

Y

H

v

c

3(T

T

f

)

_

r

2

0

2k

char

+

_

1 +

C

p,v

(T

T

f

)

H

v

+

C

p,char

char

(T

T

f

)(1 Y

)

Y

H

v

_

r

0

h

l

_

,

(29)

t t

devo

t

pyro

=Y

H

comb

c

r

0

/3h

l

(T

T

f

).

The time required to heat up the particle, before the

volatiles appear, is explored below. It is worth not-

ing that Eqs. (27) and (28) both contain terms in r

0

and r

2

0

. In fact, if either t

devo

or t

pyro

is proportional

562 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

to r

2

0

, heat conduction through the outer layer of char

is totally rate-controlling. Also, Eqs. (27) and (28)

conrm that t

devo

and t

pyro

are both characterized by

k

char

, not k

c

.

4.1. Comparison with the conventional expression

for the time of devolatilization

A comparison of Eq. (27) with the conventional

empirical expression,

(30) t

devo

=ar

n

0

(with r

0

in mm and t

devo

in s),

for the time of devolatilization is made here. The

value of n can be deduced from

(31) n = lnt

devo

/ lnr

0

.

Hence, using Eq. (27) for t

devo

, the value of n is

n =

lnr

0

_

ln

_

r

2

0

2k

char

+

_

1 +

H

comb

H

v

+

1

+

1

_

r

0

h

l

_

_

=r

0

r

0

_

ln

_

r

2

0

2k

char

+X

r

0

h

l

__

(32) =

X r

0

/h

l

+r

2

0

/k

char

X r

0

/h

l

+r

2

0

/2k

char

,

where a new quantity

X1 +

H

comb

H

v

+

C

p,v

(T

T

f

)

Y

H

v

(33) +

C

p,char

char

(T

T

f

)(1 Y

)

Y

char

H

v

has been used in Eq. (32) for simplicity. It should be

noticed that using the Biot number for char, Eq. (32)

can be simplied to

(34) n =(X+Bi

char

)/(X+Bi

char

/2).

After rearrangement, Eq. (34) gives

(35) Bi

char

=X(n 1)/(1 0.5n).

Hence, using Eq. (35), the value of n can indicate

Bi

char

, which reveals whether external or internal heat

transfer is rate-controlling. Therefore, the common

practice of using n to identify the rate-controlling

process, in spite of Eq. (30) being empirical, has some

theoretical basis. A small Bi

char

(i.e., Bi

char

X)

gives n 1, which seems to jeopardize the idea of

an uneven temperature distribution inside the parti-

cle (because it will be found later that X 1.3),

and hence invalidate this model. However, it will be

demonstrated in Section 4.3 that Bi

c

, the Biot number

for coal, is more relevant for establishing a sharp re-

action front. Hence, a small Bi

char

, or n 1, will not

alter the validity of this model, provided Bi

c

>1/2.

4.2. Estimates of the values of the governing

parameters

Equation (27) can be simplied to t

devo

=c

1

r

0

+

c

2

r

2

0

, with two parameters, c

1

and c

2

, to be deter-

mined. Here, c

1

=

H

v

Y

c

X/3h

l

(T

T

f

) and

c

2

=

H

v

Y

c

/6k

char

(T

T

f

). The values of c

1

and c

2

can be obtained from the slope and intercept

at r

0

= 0 on a plot of measured values of t

devo

/r

0

against r

0

. The ratio of these two parameters,

(36) c

2

/c

1

=h

l

/2Xk

char

,

can be employed to give the Biot number for the char,

i.e.,

(37) Bi

char

=2Xr

0

c

2

/c

1

.

The major unknown quantities are T

f

and

H

v

, which

cannot be obtained directly from c

1

and c

2

.

It was noticed that, if a coal particle was pyrolyzed

in a hot bed of silica sand uidized by N

2

, ames

were seen on top of the quartz tube housing the bed.

These ames were of the released volatile material

burning in the laboratory air. The duration of one of

these ames was taken as a crude measure of the

time for pyrolysis; in fact it will probably be an un-

derestimate. These t

pyro

measured for three bitumi-

nous coals in a uidized bed at 950

C are plotted

in Fig. 6 as t

pyro

/r

0

against r

0

. Given that results

for coal are expected to be scattered, it is notewor-

thy that a fairly good straight line can be tted to

Fig. 6 for all three coals, which appear to be simi-

lar in Fig. 6. Linear regression gives the intercept as

c

1

=4200 s/m and the slope as c

2

=6.410

5

s/m

2

.

If X is taken as 1.3 (from an estimate of

H

v

made

after trial and error below in this section) for pyrol-

ysis and h

l

= 460 W/m

2

K [1], these values of the

slope and intercept give the thermal conductivity of

the char as 1.2 0.5 W/mK over the temperature in-

terval between T

f

and T

s

, using Eq. (36). For a coal

particle of radius 7 mm, Bi

char

equals 2.8. Hence,

for applying this model, the assumption (d) in Sec-

tion 3.1 is not violated for these coals. The slope

of Fig. 6 is c

2

, whose value gives

H

v

/(T

T

f

).

However, continuous measurements [3] with a ther-

mocouple cemented in a pyrolyzing particle of Daw

Mill indicated that the temperature in the reaction

front was 230

C. If T

f

is accordingly taken as

500 K, the value of c

2

from Fig. 6 gives

H

v

=

7.7 4.2 MJ/(kg of volatile matter). In conclusion,

because of its theoretical background and the con-

sistency of its dimensions, the expression t

devo

=

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 563

Fig. 6. The ratio of the duration of the ame of burning volatile material to the initial radius of the coal particle plotted against

the initial radius. The bed was uidized with N

2

at 950

C.

c

1

r

0

+c

2

r

2

0

is more meaningful than the conventional

empirical expression t

devo

= ar

n

0

for correlating ex-

perimental results for large particles of coal.

For a typical coal particle devolatilizing in a u-

idized bed, the governing parameters Bi

char

, , ,

and can now be estimated using the following val-

ues: the initial radius of the coal particle, r

0

=7 mm;

h

l

= 460 W/m

2

K [1]; the thermal conductivity of

char, k

char

= 1.2 W/mK (from above and compara-

ble to a previous estimate [1] of 1.7 0.9 W/mK);

the heat of combustion, H

comb

= 33 MJ/kg; the

temperature of the surroundings, T

= 1123 K; and

the heat capacity of the gaseous volatile matter,

C

p,v

= 1390 J/kgK. These values are for Daw Mill,

whose initial volatile content, Y

mate of C

p,v

was made from the assumptions that,

rst, the average molecular weight of the volatile

matter is 30 g/mol (bearing in mind that H

2

and

hydrocarbons from CH

4

up to tars are present), and

second, the heat capacity per mole of volatile mat-

ter is 5R [23]; here, R is the universal gas constant.

However, the heat of devolatilization

H

v

and T

f

are,

strictly speaking, unknown. Hence, and cannot

be estimated accurately. The values of , and hence

, are uncertain, but are estimated as follows using

previous experimental observations [1].

For pyrolysis, Eq. (23) gives

(38) =Fo/Y

f

1

() f

2

()/f

1

()Bi

char

,

where

(39)

f

1

() =

_

1 +2

3

3

2

+2(1

3

)/Bi

char

+2(1 )/Bi

char

__

6,

(40) f

2

() =(1

3

)/3.

The ratio of the two items on the right-hand side of

Eq. (38),

_

Fo/Y

f

1

()

___

f

2

()/f

1

()Bi

char

_

(41) =h

l

t /

_

r

0

c

C

p,v

Y

f

2

()

_

,

is 22, i.e., much larger than unity, when = 0.75

at t 30 s. Therefore, is mainly determined by

Fo/Y

f

1

(), so that f

2

()/f

1

()Bi

char

can be ig-

nored. In this case, after transformation into dimen-

sional form, Eq. (38) becomes

(42)

H

v

T

T

f

=

k

char

t

f

1

()Y

c

r

2

0

.

Let t

A

and t

B

be the times for the reaction front in

two identical particles to reach a specic dimension-

less radius

x

, for bed temperatures T

,A

and T

,B

,

respectively. Inserting these values into Eq. (42), the

values of T

f

and

H

v

can be estimated because

(43) T

f

=(t

B

T

,B

t

A

T

,A

)/(t

B

t

A

)

and

(44)

H

v

=k

char

t

A

(T

,A

T

f

)

__

f

1

(

x

)Y

c

r

2

0

_

.

When a particle of Daw Mill was pyrolyzed at 750

and 950

tion front to reach = 0.75 were 42.8 and 26.3 s,

respectively. However, these two times are subject

to two errors. First, the initial heating times were

not deducted. Second, the quenching of the parti-

cle by nitrogen is not perfect; hence, the time re-

quired to reach a specic radius is underestimated,

so it seemed reasonable to add 3 and 7 s to the

above times to compensate for the extra heating

time due to improper quenching at 750 and 950

C,

respectively. Taking

c

= 1200 kg/m

3

and r

0

=

564 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

7 mm, after deduction of the initial heating times

(see Section 5.1), Eqs. (43) and (44) give

H

v

=

10.5 MJ/(kg of the volatiles) (after trial and error,

since

H

v

changes f

1

(

x

)) and T

f

= 500 K. This

value of

H

v

is higher, but more accurate than the

estimate of 7.7 4.2 MJ/(kg of volatile matter) from

Fig. 6. However, the estimate of T

f

agrees perfectly

with the value (see above) indicated by thermocou-

ples inserted into a coal particle. With the denition

of

H

v

in Eq. (1), the true heat of devolatilization

is H

v

=9.4 4 MJ/(kg of volatiles), assuming the

following values: W

=0.065, H

w

=2257 kJ/kg,

C

p,w

= 2000 J/kgK, C

p,c

= 890 J/kgK. It must

be noted that the values of

H

v

and T

f

are very

sensitive to the values used above for t

A

and t

B

;

without deducting the errors mentioned above, the

times 42.8 and 26.3 s give

H

v

= 5000 kJ/kg

and T

f

= 700 K. Furthermore, because the thick-

ness of the char layer obtained [1] has great vari-

ation due to inhomogeneities of a coals composi-

tion, T

f

and

H

v

derived using Eqs. (43) and (44)

have resulting uncertainties. However, the values

H

v

=10.5 4 MJ/(kg of volatile matter) and T

f

=

500 K will be adopted as the most accurate esti-

mates for all three coals in Fig. 6. These values com-

pare with previous estimates [1] of

H

v

= 9.2

3.5 MJ/(kg of volatile matter) and the signicantly

higher T

f

= 550 100

value of T

f

is discussed again below.

The temperature measurements in a particle of

Daw Mill coal of radius 7 mm [3] revealed that the

time for the reaction front to reach 0.5 during

devolatilization is 40 s shorter than during pyrol-

ysis at the same bed temperature of 850

C. Using

Eq. (23) or (29) with the typical physical properties

listed above, the value of is 0.85 for this case.

However, the difference of only 10 s between the

times of devolatilization and pyrolysis for the differ-

ent coal Reitspruit indicates that 0.21. Such a

low value of suggests that the volatiles mainly burn

away from such a coal particle in a uidized bed. The

difference in for these two coals might be caused by

the different chemical compositions of their volatiles,

especially their concentrations of H

2

.

With the above physical properties for Daw Mill,

typical values of Bi

char

2.8 (r

0

=7 mm), 0.7

( = 0.20.9), 22, and 12 for devolatiliza-

tion are obtained.

4.3. Inuence of each governing parameter in this

model

The inuence of the dimensionless groups Bi

char

,

, and will now be examined. For simplicity, the

following values are adopted for discussion: =10,

= 20, = 1 (i.e., pyrolysis), Bi

char

= 5 (r

0

=

12.5 mm). Another governing parameter, Y

, inu-

ences both and ; however, for simplicity, these

three parameters will be treated as if they were uncor-

related. The inuence of (the ratio of the apparent

heat of devolatilization to the increase in sensible heat

of the volatile material: see Eq. (19)) on the motion of

the reaction front is demonstrated in Fig. 7. This is

a plot of against Fo/Y

(a dimensionless time)

for different values of with Bi

char

= 5, = 20,

and =1 (i.e., pyrolysis). Little difference exists be-

tween = 10 and 100, whereas the velocity is very

sensitive to when < 1. Because a typical value

of is actually larger than 10, the value of will not

inuence the relationship between Fo/Y

and .

The inuence of Bi

char

is illustrated in Fig. 8,

where again is plotted against Fo/Y

, for =

Fig. 7. Results of the shrinking-core model plotted as (dimensionless radial position of the reaction front) against dimensionless

time for the parameters =0.1, 1, 10, and 100, Bi

char

=1, 5, 10, and 100, =20, =1.

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 565

Fig. 8. Results of the shrinking-core model, again plotted as versus Fo/Y

char

=1, 5, 10,

and 100, =20, =1.

Fig. 9. Results of the shrinking-core model for the parameters =10, Bi

char

=5, =20, =1, 0.5, and 0.

10, = 20, and = 1. The velocity of the reac-

tion front for pyrolysis is more sensitive to Bi

char

for Bi

char

< 5 than when Bi

char

> 10, e.g., for r

0

>

25 mm. A larger Bi

char

gives a smaller Fo

pyro

/Y

,

i.e., the dimensionless time of pyrolysis; however, it is

misleading, from Fig. 8, to deduce that a larger Bi

char

results in a shorter time of pyrolysis. The reason is

that when Bi

char

is changed, Fo/Y

is also altered.

The position of the reaction front, , is again plot-

ted in Fig. 9 against Fo/Y

(a measure of ) to investigate any effect of burn-

ing the volatiles. According to Eq. (21), = 1 for

pyrolysis, whereas any heating of a coal particle from

the combustion of the volatiles gives a smaller . In

Fig. 9, for the reaction front to reach the same ,

a smaller results in a smaller Fo/Y

; i.e., the

burning of the volatile matter shortens the time of de-

volatilization.

The inuence of on the motion of the reaction

front is demonstrated in Fig. 10, which is a plot of

against Fo/Y

cation of the ratio of the enthalpy of devolatilization

and the sensible heat of the char) with Bi

char

= 5,

=10, and =1 (i.e., pyrolysis). Little difference

exists between =10 and 100, whereas the velocity

is very sensitive to when <1. Because a typical

value of is actually larger than 10, the value of

will not inuence the relationship between Fo/Y

0

, etc.

It will be noticed in Figs. 79 that, for some com-

binations of parameters, an almost linear relationship

exists between and Fo/Y

terval between equal to unity and zero. For exam-

ple, the dimensionless velocity of the reaction front is

d/d(Fo/Y

tity) against in Fig. 11 for = 1, 0.5, or 0. There

566 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

Fig. 10. Results of the shrinking-core model for the parameters =10, Bi

char

=5, =0.1, 1, 10, and 100, =1.

Fig. 11. Calculated velocity (dimensionless) of the reaction front plotted against for the parameters = 10, Bi

char

= 5,

=20, =1, 0.5, and 0.

are two regions of , one near the exterior and the

other close to the center, where according to Fig. 11,

the reaction front moves much quicker than else-

where. For pyrolysis, the reaction front moves at a

nearly constant rate for between 0.15 and 0.95. This

demonstrates that the velocity of the reaction front is

nearly constant, and explains why the char layer is

found [1] to increase in thickness at a nearly constant

rate. If the volatiles burn, the reaction front moves

quicker than during pyrolysis for > 0.7; however,

any effect of the volatiles burning is insignicant for

<0.7, i.e., near the end of devolatilization.

The rate at which volatile matter is released at

a particular time is

2

d/d(Fo/Y

) in dimen-

sionless form. Values of

2

d/d(Fo/Y

), with

= 10, = 20, and Bi

char

= 5, are plotted in

Fig. 12 against Fo/Y

for = 1, 0.5, or 0. At

an early stage, the rate of devolatilization or pyrolysis

is high, but decreases while time progresses; in fact,

for Fo/Y

evolution is found. This long and low rate of evolu-

tion explains the uncertainty of determining the end

of devolatilization. A smaller value of , i.e., with

combustion of the volatiles, results in a quicker ini-

tial, but slower nal, stage of evolution. The plots in

Fig. 12 are very similar in shape to the measured rates

of evolution [3].

With the estimates of =10, =20, =1, and

Bi

char

=5, i.e., for r

0

=12.5 mm, the above analysis

shows that and exert little inuence on the re-

lationship between Fo/Y

four dimensionless parameters (, Bi

char

, Fo/Y

,

) and one equation, i.e., Eq. (23), determine the

behavior of devolatilization. Consequently, there are

three degrees of freedom and the parameter =r

f

/r

0

is characterized by three other parameters, together

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 567

Fig. 12. The dimensionless rate of the release of volatile matter as dened by Eq. (52). The parameters used were = 10,

=20, Bi

char

=5, =1, 0.5, or 0.

with Eq. (23). Hence, for characterizing devolatiliza-

tion, three independent dimensionless groups are rel-

evant; they can be chosen to be

Fo/Y

k

char

t (T

T

f

)/Y

H

v

r

2

0

,

Bi

char

=r

0

h

l

/k

char

, 1 +H

comb

/

H

v

.

For pyrolysis, only Bi

char

and Fo/Y

are relevant.

Here is the demonstration that Bi

char

and not Bi

c

is

important for characterizing devolatilization times.

4.4. The inuence of moisture content

The amount of water in a particle of coal can be al-

tered before its insertion into a uidized bed. Hence,

water content is a variable and therefore controllable.

According to Eq. (1), different water contents of a

coal particle alter the value of the apparent heat of

devolatilization, and eventually change the time of

devolatilization. This inuence can be seen by using

Eq. (27) to give

(45)

t

devo

W

=

c

3(T

T

f

)

_

r

2

0

2k

char

+

r

0

h

l

_

.

Because all the items on the right-hand side of

Eq. (45) are positive, t

devo

/W

water content increases the time for devolatilization.

The literature [46] conrms this prediction.

5. The temperature on the exterior of a particle

When a particle of coal is inserted into a hot (700

950

the insertion and when volatile matter starts to be

evolved can be deduced with the above model. The

primary reaction (I) is assumed to proceed (like a

change of phase) at a temperature T

f

; therefore, the

start of pyrolysis, i.e., the time when the temperature

of the outer surface of the particle reaches T

f

, can be

obtained by solving the corresponding heat conduc-

tion problem. However, it is found experimentally [3]

that different chemical species in the volatile matter

evolve after different residence times, so that choos-

ing the starting time of one species is somewhat ar-

bitrary and will result in uncertainties. Furthermore,

the removal of moisture from a coal particle makes

an estimate of when volatiles emerge complicated.

Because drying occurs at a lower temperature than

T

f

, and so requires a latent heat of vaporization, the

presence of moisture in a coal particle lengthens the

time of heating. Temperature measurements [3] with

a thin thermocouple (diam. 0.2 mm) cemented in a

coal particle revealed that the evaporation of water

lasts a fairly long time (25 s) at a radial position

r/r

0

=0.5. Hence, the initial heating can be roughly

separated into two stages according to the temper-

ature at the particles exterior; when this is below

100

C to

T

f

, is the second stage. It must be noticed that dry-

ing in the interior and thermal decomposition on the

exterior of the particle may occur simultaneously. Be-

cause this initial heating time concerns phenomena

before the evolution of any volatile matter, the dis-

cussion in this section should be applicable for both

pyrolysis and devolatilization. The assumption, used

in the above shrinking-core model, of regarding wa-

ter as part of the volatile matter will not be employed

in Sections 5.1 and 5.2.

5.1. The heating of the particle before drying

For the rst stage, the equation for heat transfer

inside a spherical particle of coal is

568 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

(46)

T

t

=

c

_

2

T

r

2

+

2

r

T

r

_

and the corresponding boundary conditions are

T

r

r=r

0

=

h

l

k

c

(T

T ) +

rad

rad

k

c

_

T

4

T

4

_

(47) =

h

l

k

c

(T

T )

and

(48)

T

r

r=0

=0,

where the thermal diffusivity of coal,

c

k

c

/

c

C

p,c

,

is used, and h

l

is dened in Eq. (3). The initial condi-

tion is that throughout the coal

(49) T =T

0

.

Equations (46)(49) can be transformed with the fol-

lowing three dimensionless parameters: T

=(T

T )/(T

T

0

), r

=r/r

0

, t

=

c

t /r

2

0

. The resulting

dimensionless forms are

(46a)

T

=

2

T

r

2

+

2

r

,

(47a)

T

+Bi

c

T

=0 for r

=1,

(48a)

T

=0 for r

=0,

(49a) T

=1 for t =0.

The Biot number for coal, Bi

c

r

0

h

l

/k

c

, is used in

Eq. (47a). The solution of Eqs. (46a)(49a) is [13]

T

(r

, t

) =

2

r

m=1

exp

_

2

m

t

_

2

m

+

2

(

2

m

+

2

) +

(50) sin(

m

r

)

r

_

0

r

#

sin(

m

r

#

) dr

#

.

Here,

m

is the mth eigenvalue of the eigenfunction

(51)

m

cot

m

+ =0

and

(52) =Bi

c

1 =r

0

h

l

/k

c

1.

Because of the presence of exp(

2

m

t

) in Eq. (50),

only the rst eigenvalue

1

[13] is important. Further-

more, the initial condition Eq. (49a), i.e.,

T

(r

=1, t

=0) =1

=

2

r

2

1

+

2

(

2

1

+

2

) +

(53) sin(

1

r

)

r

_

0

r

#

sin(

1

r

#

) dr

#

,

must be fullled. Thus, inserting Eq. (53) into

Eq. (50), the simplied solution

(54)

T

T

s

T

T

0

exp

_

2

1

t

r

2

0

_

is obtained for the surface temperature. The heating

time in the rst stage is accordingly

(55) t

1

=

_

r

2

0

/

c

2

1

_

ln

_

(T

T

0

)/(T

373)

_

from letting T

s

= 373 K. The value of

1

can be

found [13] for different values of ; in fact, for Bi

c

(= + 1) > 10,

1

3; for Bi

c

= 1,

1

1.6.

The following values are adopted to estimate t

1

:

T

0

= 298 K; T

= 1123 K (850

C); r

0

= 7 mm;

c

= 1200 kg/m

3

for Baddesley coal. The thermal

conductivity of coal at (298 + 373)/2 = 336 K can

be estimated from Merricks correlation [24] to be

0.30 W/mK (based on the ultimate analysis of Bad-

desley [1]). Likewise, the heat capacity of Baddesley

coal at 336 K is estimated [24] to be 890 J/kg K.

Therefore,

c

= 2.8 10

7

m

2

/s and Bi

c

= 11;

hence

1

= 3.07 [13]. With the above values, t

1

=

1.8 s for Baddesley of radius 7 mm. Furthermore, if

the particle is moisture-free, Eq. (55) can be used up

to T

f

, when reaction (I) starts on the surface of the

particle; this occurs after a further time of t

2

=3.4 s,

i.e., after a total of 5.2 s.

5.2. The heating during and after drying

After the surface temperature of a coal particle

reaches 100

ration inside the particle occurs in a moving reac-

tion front at 100

shrinking-core model. Hence, that model can be used

with only slight modications. The validity of this

treatment of drying using a shrinking-core model will

be examined later. The primary reaction (I) begins

after a further heating time, t

2

, when the particles

exterior reaches T

f

. Let the vaporization front be at

radius r

w

and temperature T

w

(=100

C). Of course,

there is no contribution from any combustion of the

volatiles. The governing equation, derived in the same

way as above, is

Fo

w

W

w

=

3

w

3

_

1

1

Bi

c

1

Bi

c

w

_

2

w

2

w

3Bi

c

w

(56)

+

1

3

_

1

2

+

1

Bi

c

+

1

Bi

c

w

+

1

Bi

c

w

_

,

where

(57) Fo

w

k

c

t /

c

C

p,w

r

2

0

=h

l

t /Bi

c

c

C

p,w

r

0

,

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 569

(58)

w

H

w

/C

p,w

(T

T

w

),

(59)

w

r

w

/r

0

,

(60)

w

H

w

W

/C

p,c

(T

T

w

)(1 W

).

The temperature at the external surface of the particle

is

T

s

=

T

+T

w

w

/Bi

c

(1

w

)

1 +

w

/Bi

c

(1

w

)

(61)

+

(

2

w

+

w

/3

w

)W

(T

T

w

)/Bi

c

d

w

dFo

w

1 +

w

/Bi

c

(1

w

)

fromrearranging terms in Eq. (13). Hence, the heating

time in the second stage, t

2

, is given when T

s

= T

f

.

This time was computed as follows: rst, values of

w

were tabulated from 1 to 0 at intervals of, say,

0.01; second, using Eq. (56), the values of Fo

w

for

each

w

were derived. Then the derivative d

w

/dFo

w

was obtained numerically. The value of T

s

is given

by Eq. (61). Finally, choosing the value of Fo

w

, for

which T

s

= T

f

, the heating time t

2

was obtained us-

ing Eq. (57).

The following parameters for the pyrolysis of

a Baddesley coal particle were adopted for these

computations: T

= 1123 K, T

f

= 500 K, T

w

=

373 K, r

0

=7 mm, W

=0.065, h

l

=460 W/m

2

K,

C

p,w

= 2000 J/kgK, H

w

= 2257 kJ/kg (hence

H

w

= 3380 kJ/kg), and

c

= 1200 kg/m

3

. The

thermal conductivity for Baddesley at a temperature

(T

w

+T

f

)/2 is 0.37 W/mK. The value of Bi

c

is 8.7,

w

= 0.32, and

w

= 2.3. Using the above values,

t

2

2.2 s, which is smaller than t

2

=3.4 s, from us-

ing Eq. (55) for a moisture-free particle. Because the

time estimated using Eq. (55) did not consider the de-

lay of drying, it should give a shorter time than that

using Eqs. (56) and (61). Therefore, a re-examination

of the shrinking-core model is now in order.

5.3. Discussion: validity of the shrinking-core model

The region of validity of the shrinking-core model

has not been explored fully. The unreasonable pre-

diction of t

2

in Section 5.2 gives a good example

of blindly and wrongly applying the shrinking-core

model. The reason that drying cannot be described

using this model is probably that assumption (e) in

Section 3.1 is being violated. Continuous measure-

ments of the temperature inside a pyrolyzing coal par-

ticle [3] using inserted thermocouples revealed that

drying probably occurs over a wide region, rather than

at a sharp front. As a result, assumption (e) underesti-

mates the enthalpy required for drying. Another way

of violating assumption (e) is for the neglect of sensi-

ble heat from Eq. (7) to be serious and problematic.

Because the changes of sensible heat are approxi-

mated using Eqs. (1) and (7), errors from using these

two approximate expressions will be signicant when

the volatile content is low ( < 1). Hence, for high

rank coals, this model might well be inadequate. For

the same reason, when 1, i.e., near the end of

devolatilization, this model may be inadequate. Sim-

ilarly, for coals of low water content, this model is

potentially wrong.

Another assumption that is probably wrong is (a),

i.e., that one primary reaction occurs at a sharp front.

It is clear [17,25,26] that several reactions of ther-

mal decomposition occur at different temperatures

and hence at different spatial locations. However, the

high thermal conductivity in the outer layer of char

(1.2 W/mK; see Section 4.1) and a relatively low one

(0.30 W/mK, from Merricks correlation [24]) for

the inner core of virgin coal help to maintain a sharp

temperature front, i.e., a quick temperature change

before reaction occurs. It is very likely that this tem-

perature front leads to the appearance of a shrinking

core. Hence, for the bituminous coals in this study,

this model is still correct, in spite of assumption (a) in

Section 3.1 probably being violated.

5.4. The temperature within a moisture-free particle

of coal in a hot uidized bed

If a coal particle contains water, as yet no sat-

isfactory way of calculating the temperature, T

s

, at

its outer surface has been presented. However, for

a moisture-free particle of coal, the relationship be-

tween time and T

s

is described by Eq. (54), before

T

f

is reached at the particles exterior. Afterward, the

temperature at the surface of a pyrolyzing particle is

T

s

=

T

+T

f

/Bi

char

(1 )

1 +/Bi

char

(1 )

(62)

+

(

2

+/3)Y

(T

T

f

)/Bi

char

d

dFo

1 +/Bi

char

(1 )

.

The solution of Eq. (62) was explained in Sec-

tion 5.2 for the case of drying, when Eq. (61) was

used. The following physical properties for dry Bad-

desley can be used: T

= 1123 K, T

f

= 500 K,

T

w

= 373 K, T

0

= 298 K, r

0

= 7 mm, Y

= 0.402,

h

l

= 460 W/m

2

K, C

p,v

= 1390 J/kgK, H

v

=

9.4 MJ/kg, and

c

= 1200 kg/m

3

. Again, the ther-

mal conductivity for Baddesley coal at a tempera-

ture (T

w

+ T

0

)/2 = 336 K is 0.30 W/mK; but it is

1.2 W/mK for its char at (T

f

+T

Section 5.1). The value of T

s

(i.e., at r = r

0

) is plot-

ted against residence time in Fig. 13. Furthermore, the

temperatures throughout the particle are also plotted

in Fig. 13. The temperature T at r/r

0

, with r > r

f

,

570 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571

Fig. 13. The temperature of the outer surface of a particle of Baddesley coal (radius 7 mm) during pyrolysis at 850

C. The

position of the reaction front is also displayed using the axis on the right.

Table 1

The temperature and the starting time the evolution of vari-

ous chemical species during the pyrolysis of Baddesley in a

uidized bed at 850

C

Chemical species CO CO

2

NO

x

C

2

H

4

C

2

H

6

HCN

Starting time of 7.5 7 9.5 20 20 50

evolution (s)

Temperature of 260 250 280 380 380 570

exterior (

C)

was obtained from Eq. (6); the nal form is

T =

(63)

T

s

(r/r

0

)/[1 (r/r

0

)] +T

f

(r/r

0

)/[(r/r

0

) ]

(r/r

0

)/[1 (r/r

0

)] +(r/r

0

)/[(r/r

0

) ]

.

Here, < r/r

0

< 1, where r

f

/r

0

. Because dry-

ing has not been considered, these temperatures at

each residence time are slightly overestimated in

Fig. 13.

Table 1 lists the times when various chemical

species were rst detected [3] gas chromatographi-

cally in the off-gases after one particle of Baddesley

coal had been added to a bed of sand at 850

C when

uidized by N

2

. Table 1 also lists the corresponding

external temperatures calculated from Eq. (62) for the

pyrolysis of Baddesley coal at 850

C. Of course, as

already mentioned, these temperatures are overesti-

mates, because moisture in the coal delays its heating.

However, the results in Table 1 and Fig. 13 are in-

teresting. The reason for different chemical species

appearing at different times is that different parallel

steps in reaction (I) occur [17,25,26] at different tem-

peratures. Certainly, Table 1 indicates that the mean

value of T

f

is much less than 570

C. This conrms

that the previous estimate [1] of T

f

= 550 100

C

is too high. The difculty of estimating a mean value

for T

f

was noted in Section 4.2. The nal estimate

of 500 K was made above from measured tempera-

tures of devolatilization inside one of these particles,

as well as a consideration (see Section 4.2) of the

times for the devolatilization front to reach =0.75.

It is also worth noting that when small particles of

bituminous coals are heated slowly, after losing mois-

ture they start to lose mass, probably by releasing tars

at 500 K [7,27,28]. The relatively late appearance

of HCN is due to the fact that it requires a compara-

tively high temperature to generate it. If a temperature

of almost 570

trogen may be bound relatively tightly, e.g., in some

aromatic structure in the coal. On the other hand, one

unknown, unidentied nitrogenous compound (possi-

bly NH

3

), which is one of the precursors of N

2

O, was

found [3] to start to evolve at a time much earlier than

HCN, but similar to those for C

2

H

4

or C

2

H

6

. Hence,

the temperature at which what is conjectured as NH

3

is generated is below 380

2

H

4

or C

2

H

6

. This suggests that the source of the nitrogen

for this NH

3

is some less tightly bound structure in

coal, bearing in mind that C

2

H

4

and C

2

H

6

are likely

to be the products of decomposition of aliphatic hy-

drocarbons of higher molecular weight.

6. Conclusions

This steady-state, shrinking-core model is a rene-

ment of a previous one [1]. It cannot be applied to the

devolatilization or pyrolysis of all coals. In particular,

for a coal of low volatile content, e.g., an anthracite,

this model might be inadequate. In any event, assump-

tion (f) is far from true in this case, because an an-

thracite rapidly fragments when added to a uidized

J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 571

bed [1,4]. Within the range of validity (e.g., with lig-

nite and bituminous coals, where such reaction fronts

have been observed visually [1]), the predictions of

this model agree qualitatively with the literature. The

time of devolatilization or pyrolysis can be predicted.

Dimensionless forms of the relevant parameters have

been found. The equation governing the devolatiliza-

tion of a largish coal particle is Eq. (23); the analyses

revealed that the following four dimensionless groups

are important:

Fo/Y

k

char

t (T

T

f

)/Y

H

v

r

2

0

,

r

f

/r

0

, Bi

char

=r

0

h

l

/k

char

,

1 +H

comb

/

H

v

.

The initial heating time can be predicted using

Eq. (55) for a moisture-free coal. To correlate exper-

imental measurements of the time of devolatilization

(or pyrolysis), the expression t

devo

= c

1

r

0

+ c

2

r

2

0

is more useful and meaningful than the commonly

used empirical expression t

devo

= ar

n

0

. Measure-

ments of c

1

and c

2

provided values of k

char

, Bi

char

,

and

H

v

/(T

T

f

).

The time of pyrolysis or devolatilization is deter-

mined by the Biot number for char, Bi

char

, not Bi

c

,

based on the coals properties. However, for the ini-

tial heating time, Bi

c

is the relevant parameter. The

heat of devolatilization turns out to be much larger

than the usually assumed negligible quantity. The

value of H

v

is 9.4 MJ/(kg of volatile matter)

for Daw Mill, whose char has a thermal conductiv-

ity of 1.2 0.5 Wm

1

K

1

. A mean temperature at

the reaction front for Daw Mill equal to T

f

= 500 K

(230

these bituminous coals and char are 2.8 10

8

and

8.8 10

7

m

2

/s, respectively.

The above model has the attraction that its basic

equations have analytical solutions. Detailed consid-

eration of the model indicates that in reality a de-

volatilizing or pyrolyzing particle of coal initially has

a fairly wide drying front passing from its exterior to

its middle. This is followed at progressively higher

temperatures by a succession of other fronts, so close

to one another that they were modeled above as one

front. Each front corresponds to one of the individ-

ual steps for thermal decomposition in (I) and has

its own activation energy and pre-exponential factor.

The velocities of these fonts are controlled by heat

conduction inside the particles outer layer of char.

However, of course, it could well be that, for a coal

of a given size, some steps in (I) have activation ener-

gies large enough to be kinetically controlled. These

steps release the most tightly bound volatiles and oc-

cur near the end of devolatilization without a front

moving inside a particle, whose temperature is uni-

form and close to that of the uidized bed.

Acknowledgments

Financial support from B.C.U.R.A. and from The

Ministry of Education, Republic of China (Taiwan),

is gratefully acknowledged.

References

[1] J.-S. Chern, A.N. Hayhurst, Combust. Flame 139

(2004) 208221.

[2] O. Levenspiel, Chemical Reaction Engineering, second

ed., Wiley, New York, 1972.

[3] J.-S. Chern, Ph.D. thesis, University of Cambridge,

1997.

[4] J.-S. Chern, A.N. Hayhurst, J. Energy Inst. 78 (2005)

6275.

[5] R.D. La Nauze, Fuel 61 (1982) 771774.

[6] R.H. Essenhigh, Trans. Am. Soc. Mech. Eng. J. Eng.

Power 85 (1963) 183188.

[7] D.W. van Krevelen, Coal, Elsevier, Amsterdam, 1961.

[8] W.E. White, C.H. Bartholomew, W.C. Hecker, D.M.

Smith, Adsorpt. Sci. Technol. 7 (1991) 180.

[9] A. Wheeler, in: L.K. Doraiswamy, M.M. Sharma

(Eds.), Heterogeneous Reactions: Analysis, Examples

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[10] L.K. Doraiswamy, M.M. Sharma (Eds.), Heteroge-

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[11] P.R. Solomon, M.A. Serio, E.M. Suuberg, Prog. Energy

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[12] R.M. Fristrom, Flame Structure and Processes, Oxford

Univ. Press, Oxford, 1995, p. 240.

[13] M.N. zisik, Heat Conduction, second ed., Wiley, New

York, 1993.

[14] K. Annamalai, W. Ryan, Prog. Energy Combust.

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[15] M.A. Andrei, A.F. Sarom, J.M. Ber, Combust.

Flame 61 (1985) 1727.

[16] O. Levenspiel, Engineering Flow and Heat Exchange,

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[17] D.B. Anthony, J.B. Howard, AIChE J. 22 (1976) 625

655.

[18] J.F. Stubington, J. Inst. Energy 53 (1980) 191195.

[19] W. Prins, R. Siemons, W.P.M. van Swaaij, M. Rado-

vanovic, Combust. Flame 75 (1989) 5779.

[20] M.K. Urkan, M. Arikol, Fuel 73 (1994) 768772.

[21] M.N. zisik, Heat Transfer, Wiley, New York, 1985.

[22] J.S. Dennis, A.N. Hayhurst, I.G. Mackley, Proc. Com-

bust. Inst. 19 (1982) 12051212.

[23] R. Hill, An Introduction to Statistical Thermodynam-

ics, AddisonWesley, 1960.

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