Chemical Engineering Journal 291 (2016) 3038

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

A comprehensive kinetic model for mechanochemical destruction

of persistent organic pollutants
Giovanni Cagnetta, Jun Huang , Bin Wang, Shubo Deng, Gang Yu
State Key Joint Laboratory of Environment Simulation and Pollution Control (SKJLESPC), School of Environment, POPs Research Center, Tsinghua University, Beijing 100084, PR China

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

The POPs destruction kinetic model

includes all mechanochemical

parameters.

It was validated successfully with 10
different chlorinated POPs.

It predicts correctly the reaction rate
with various reagent ratios.

CaO mechanical activation during MC
POPs destruction was ascertained.

a r t i c l e

i n f o

Article history:
Received 9 September 2015
Received in revised form 24 November 2015
Accepted 16 January 2016
Available online 4 February 2016
Keywords:
Mechanochemistry
Reaction kinetic
Persistent organic pollutants

a b s t r a c t
In the last 20 years, mechanochemical technology has shown a remarkable potential to destroy halogenated pollutants in safe manner. Being a solvent-free treatment that operates at environmental conditions, it is a good candidate to be a non-thermal alternative for disposal of persistent organic pollutants
stockpiles. However, there are many aspects that need further developments. One of them is the assessment of reaction kinetic. In the present work, a kinetic model that is commonly utilized to describe
mechanochemical transformations is adapted and applied for the first time to destruction of organic
molecules. In particular, it was modified to include all fundamental parameters related to the
mechanochemical degradation of halogenated persistent organic pollutants. Validation with literature
and experimental data proves the soundness of the proposed model and confirms that solid reagents activation is a necessary step to achieve pollutants destruction.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Mechanochemistry (MC) deals with chemical reactions that
are induced by mechanical energy, as defined by IUPAC [1]. The
energy transfer can be realized by grinding in mortar with pestle,
or more often utilizing special milling devices, called high energy
mills or MC activators.
Starting from the groundbreaking experiments of Spring and
Lea some 120 years ago, MC has grown into a well-established field
with increasing research activity and some actual and many more
Corresponding author.
E-mail address: huangjun@mail.tsinghua.edu.cn (J. Huang).
http://dx.doi.org/10.1016/j.cej.2016.01.079
1385-8947/ 2016 Elsevier B.V. All rights reserved.

potential applications [2]. In particular, by MC methods it is possible to prepare compounds, phases, and microstructures that are
essentially different from the products of ordinary reactions [3].
Moreover, it is an environmentally friendly technology. Milling is
conducted in solid phase (without solvents) at environmental temperature and pressure, so the whole process is simpler than traditional one and does not require any exhausted solvent
regeneration/disposal [4]. This feature counterbalances the costs
due to energy demand of milling devices.
MC has a remarkable potential for environmental applications,
because it has been recognized as a good non-combustion technology capable to destroy a large variety of chlorinated, brominated,
and fluorinated persistent organic pollutants (POPs), usually

G. Cagnetta et al. / Chemical Engineering Journal 291 (2016) 3038

31

Nomenclature
CR
^
D
Ei
F
kMA
kD
K
KE
KS
I
mb
mp
MW
N
rJ
rP
R
RG
RSS
x

charge ratio (ball-to-powder ratio)

specific energy dose [J g1]
ball impact energy [J]
ball hit frequency in ball mills [Hz]
kinetic rate constant of mechanical activation reaction
kinetic rate constant of pollutant destruction reaction
rate constant of the model proposed in the present work
[g J1]
rate constant of the exponential model [g J1]
rate constant of the sigmoid model [g J1]
energy intensity [W g1]
ball mass [g]
powder mass [g]
molecular weight [g mol1]
number of balls
jar radius [m]
planetary disk radius [m]
reagent-to-pollutant ratio
gas constant [8.3145 J mol1 K1]
residual sum of squares
fraction of the powder mixture

co-milled with other reagents in solid phase [511]. Hence, it is one

of the most suitable technologies that can be employed to achieve
safe destruction of POPs at large scale, by virtue of (I) high conversion percentages (near 100%) of pollutants into nonhazardous
mineral form (common products are halides and amorphous carbon); (II) relatively short treatment time (few hours); (III) cheap
dehalogenating/destroying reagents (e.g. calcium oxide, quartz,
etc.); (IV) low temperatures (few tens K higher than room temperature) reached during high-energy milling, which assures that POPlike by-products are not generated unintentionally. However, pilot/
full-scale applications are very few [1214], so it would be premature to consider MC treatment a well-defined technology viable for
POPs waste disposal. Many aspects require further investigations
and clarifications. One of them is the prediction of reaction rates
under different conditions, which is fundamental for full-scale
development of new technologies. In fact, kinetic models are
required not only to calculate technical parameters (e.g. treatment
time), but also to assess economic factors (e.g. operating costs).
The POPs destruction kinetic in high energy mills has been studied in few works, modeled either as a pseudo-first order reaction
[15] or with a sigmoid trend [16,17]. The latter takes into account
the existence of an initial lag time, reported by some authors
[16,1820], which is required to generate new surfaces with reactive centers on solids. Actually, most of the published works are
focused on determination of the milling time necessary to achieve
a complete dehalogenation or destruction of the pollutant, so they
rarely investigate what happens during the early milling phase.
Nevertheless this is a crucial issue, because the existence of an initial period with slow reaction rate proves that during high energy
milling solid activation not only occurs, but also is necessary to
realize pollutants MC destruction (as explained in the next paragraph). Hence, this aspect needs clarification.
Another issue that has never been investigated in kinetic studies is the influence of the reagent ratio. It has a fundamental role in
determining pollutants MC destruction rates [6,21], but, to the best
of our knowledge, this parameter has not been included yet in any
kinetic model.
In this work, we utilize and validate a model for generic MC
transformations of inorganic materials to describe MC dehalogenation/destruction reactions of (chlorinated) POPs. In particular, we

t
t1
t2
t3
T
U0

vi

time of milling [s]

time of ball detachment [s]
time of ball flight [s]
time of return to the repeating cycle position [s]
temperature [K]
bond energy in solids [J]
ball impact velocity [m s1]

Greek letters
/
ball angular position in the jar [rad]
ball angular postion at detachment from jar wall [rad]
/1
c
constant of Zhurkovs model [J MPa1]
r
tensile stress [MPa]
v
reaction conversion
v(calc)
conversion value calculated by the model
i

v(xp)
i
s
s0
x
X

conversion value obtained from experimetal data

lifetime before bond rupture [s]
period of atomic oscillation [s]
rotation speed of the jar [rad s1]
rotation speed of the planetary disk [rad s1]

use the specific energy dose as the parameter that indicates the
reaction progress: In this way the model is roughly independent
from specific milling conditions. Besides, the equation is modified
to take into account the reagent ratio.
1.1. The mechanochemical destruction of POPs
The main purpose of the MC destruction technology is to
employ a cheap non-toxic reagent that firstly is able to induce
halogen atoms release as halides from the pollutant molecule,
and then provokes the collapse of the carbon structure of the latter,
which is usually broken apart in light gases and/or amorphous carbon [10,22]. Both effects lead to molecule mineralization, which is
considered necessary for safe disposal of toxic pollutants [23].
Many reagents, with a reducing or oxidant nature under milling
conditions, have been tested with satisfying results. Almost all
comply with the basic requirement of averting toxic (by-) products
generation. Among co-milling reagents, CaO is the most important,
because it can dehalogenate and destroy (if milling is enough energetic) a copious variety of POPs, and it is also a cheap and largely
available material. In addition, other more efficient agents with
very interesting secondary effects (dehalogenation boost, catalysts
production, waste beneficial reuse) were already investigated
[8,10,22,24,25].
MC activators play a key role in the pollutant MC destruction.
They allow the reaction between POPs and the substantially inert
material typically used as reagent by providing the required activation energy for reactions in the form of mechanical energy, at room
temperature and pressure, and without solvents. Milling conditions have to be chosen carefully because frequently there is an
optimal value for milling parameters; they are also directly responsible for the most critical disadvantage of MC treatment, namely
the energy consumption.
The peculiar effect of milling devices, i.e. the capability of realize particular reactions, is clearly evident from the dehalogenation/
destruction reaction mechanisms. For chlorinated and brominated
pollutants, very mild Lewis bases and reducing reagents are
induced by mechanical activation to transfer electrons to pollutant
molecules, provoking the rupture of the carbon halogen bond; the
high energy milling of bland neutral and oxidant reagents can

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G. Cagnetta et al. / Chemical Engineering Journal 291 (2016) 3038

produce new crystals surfaces with active centers, which dismantle the carbon structure, inducing halides release as collateral
effect.
Current knowledge soundly suggests that the mechanism of
pollutants MC destruction may be summarized in a two-step reaction: Firstly, the reagent (C) is activated by ball milling (to the state
C), and then it reacts with the pollutant (P). Hence, the following
chemical equations can be written:
kMA

C ! C 


kD

C P ! products

This mechanism has been ascertained for CaO. The oxide centers in the CaO lattice are activated by milling and are induced to
transfer electrons to the carbon atoms of organic pollutants. These
atoms are more electrophilic if they are bound with a halogen.
Then, an electron is transferred to the halogen atom, which
detaches from pollutant molecule, and a CO bond is created
[26,27]. Anyway, this mechanism of activation and charge transfer
is supposed to be similar for other reagents.
Consequently, the kinetic differential equations are the
following:

8
dxC
>
>
< dt

dxC
dt
>
>
: dxP
dt

kMA xC
kMA xC  kD xP xC

kD xP xC

To the best of our knowledge, an algebraic solution for this system has not been achieved, but a graphical representation of a
numerical solution is shown in Fig. 1. It is evident that the pollutant degradation trend is a sigmoid. Indeed, the initial conversion
rate is slow because of the low fraction of activated centers C;
as the number of the latter grows in exponential manner, the fraction of P decreases similarly; in the last phase, the P fraction is low
and the rate is slowed down. The existence of a slow reaction rate
during the early milling phase would confirm that the mechanism
described by Eqs. (1) and (2) is correct.
Solid state reaction kinetic has been widely investigated, in particular for inorganic systems. Many models have been developed,
which are based on different mechanistic assumptions as nucleation, geometrical contraction, diffusion, and reaction order. A
summary of commonly employed kinetic equations and their
mathematical development can be found in Ref. [28]. However,
these models do not consider specific chemical aspects of MC
activation.

Probably, the first MC transformation model, which takes into

account chemical bond breaking in the particles to form new surfaces and give chemical reactions under stress field in MC activators, was proposed by Zhurkov and co-workers in 1950s [29,30].
According to their theory, the exact moment at which a solid is
destroyed by a mechanical load depends on the lifetime before
rupture of deformed interatomic bonds:

s s0 exp



U 0  cr
RG T

where the product cr is equivalent to the deformation energy,

which reduces the activation energy necessary for bond breaking.
Butyagin and Streletskiy developed Zhurkovs theory, introducing energetic considerations on the processes of deformation and
fracture of solids; they found a dependence of the kinetic of structure defect formation and chemical reactions on the expended
energy [31].
In fact, today most of the models that have been developed for
MC transformations of materials are based on energetic considerations. For example, Padella et al. employ the total power transferred to powder [32], while Kwade and co-workers devised the
concept of stress energy, defined as the maximum amount of
energy that can be supplied to the milled particles at one collision
event [33]; both authors utilize computer simulations to assess the
velocity distribution of the balls and calculate their kinetic energy.
Furthermore, it is worth mentioning the model developed by Delogu and co-workers, which is based on the probability that a certain volume of powder can be compressed by hitting balls and
undergo MC transformations/reactions [34,35].
The model we propose in the present work is based on Zhurkov
and Butyagins one, in particular on the elaboration made by Delogu et al. [36]. However, we implemented some novel features:
It is applied to planetary ball mills utilizing single ball kinematics,
so it does not require any numerical simulation of milling device
operation to calculate ball velocities; it includes the reagent ratio,
comprising in this way both operational and chemical aspects of
the MC reaction; it is applied for the first time to pollutants MC
destruction and validated with literature and experimental data.
2. Materials and methods
Hexachlorobenzene (HCB, purity 99.9%, Sinopharm Chemical
Reagent Co. Ltd, China) was utilized as model pollutant for MC
treatment with calcium oxide (Beijing Modern Eastern Fine Chemicals Corp., China) as co-milling reagent. The latter was heated at
800 C for 4 h and stored in a desiccator prior to use. Both reagents
were already employed by us in another work, using the planetary
ball mill model QM-3SP2 (Nanjing University Instrument Corp.,
China) [8]. In order to point out possible differences deriving from

Table 1
Experimental milling conditions utilized in the present work and the corresponding
milling intensities.
Reagent
ratio R

Planetary and jar

rotation speed Xx [rpm]

Charge
ratio CR

Milling intensity
I [W/g]

10

150300
225450
300600
150300
225450

30
30
30
30
15
30
45
30
30
30
30

0.404
1.366
3.238
0.404
0.683
1.366
2.048
3.238
0.404
1.366
3.238

20

30
Fig. 1. Numerical solution for the differential equations system (Eq. (3)), with
kMA = kD = 1, and initial conditions xC,0 = xP,0 = 1, xC ;0 0.

300600
150300
225450
300600

33

G. Cagnetta et al. / Chemical Engineering Journal 291 (2016) 3038

MC activator, in the present work experiments were carried out

utilizing the planetary ball mill Pulverisette-4 (Fritsch GmbH, Germany), with stainless steel jars and balls (10 mm, in number of
30, total weight of 120 g). Reagents mixtures were co-milled for
0.5, 1, 2, and 4 h, while milling parameters and reagent ratio were
varied to investigate different operating conditions, which are
summarized in Table 1.
A portion of the milled mixture (0.05 g) was extracted with hexane (50 mL) by ultrasonication for 30 min. Then the extract was filtered by 0.22 lm polytetrafluoroethylene (PTFE) filters and
analyzed for HCB concentration by GCMS (QP 2010 Plus,
Shimadzu, Japan), utilizing the same conditions and method
previously described [8].

and that it is substantially independent from how this accumulation is obtained, namely it is not influenced by milling intensity.
Delogu et al. [40,36,43] employing Zhurkov and Butyagins theory find that, to describe MC transformations, two kinds of trend of
the conversion, expressed as a function of the specific energy dose,
are followed: the exponential and the sigmoid one. Transformations of single phase systems (e.g. polymorphic transformations,
amorphization, etc.) follow the exponential trend (Eq. (7)), which
correspond to a first-order reaction; binary systems, in which
two solids react one with the other (e.g. mechanical alloying of
two metals), generally are better described by a sigmoid trend
(Eq. (8)). In particular, the transformation conversions are formulated as:

v 1  exp K E D^

3. The model

7


3.1. The concept of energy dose

v 1  1 K S D^ exp K S D^

Energy delivery mode and estimation are fundamental to comprehend and describe MC phenomena. Two quantities, defined by
Pavel Yurievich Butyagin in the 1970s, can be used to this end:
the milling intensity (I), which is the rate of energy transfer to
milled powder; and the energy dose, which is the total amount of
mechanical energy transferred to powder, usually utilized as speci^
fic quantity per unit of powder mass, namely the specific dose (D)

Both equations were never validated for MC organic reactions.

The model proposed in this work is based on Eq. (8), but we apply
it for the first time to an organicinorganic system, and, in addition, the equation is modified to take into account the reagent ratio
R. The final form is:

[37]; both quantities are defined as follows:

1
I mb v 2i NF Ei NF
2

^ It 1 Nmb v 2 F t 1 C R v 2 Ft
D
i
mp 2 mp i
2

In words, the milling intensity is the kinetic energy (mbv2i )

delivered to the powder through the N balls by F hits per time unit,
while the specific dose is the intensity transferred for a milling
time of t to an mp amount of powder.
The above defined specific dose provides a useful description of
the milling progress for different devices and milling conditions. In
fact, the energy dose required to obtain a certain degree of structural transformations is a characteristic invariant quantity of the
system that undergoes high energy milling. Specifically, the transformation degree depends only on the total amount of energy supplied to the material and not on the energy intensity of the
treatment, within reasonable limits of the latter (from 103 to tens
W/g). This finding has been amply demonstrated for inorganic systems [36,3841]. Moreover, the specific dose is comparable when
milling devices with different type of action are used to achieve
the same refinement degree of the material [42].
The specific dose is utilized in the proposed model as the
parameter that indicates the reaction progress, instead of the usual
time of milling. This choice allows us to condensate all main information on milling in only one quantity that directly estimates the
energy input provided by the device. In fact, in order to quantify
the energy dose, the impact velocity and the impact frequency of
the balls have to be known, which depend on milling parameters
(i.e. rotational speed or vibration frequency, charge ratio, vial filling ratio, etc.) and the geometry of the MC activator.
3.2. MC destruction reaction model
The idea of utilize the specific energy dose as a reaction progress parameter is based on the assumption that the MC dehalogenation/destruction reaction is determined only (or, at least,
strongly) by the accumulation of energy in the ground powder,

v 1  1 RK D^ exp RK D^

It is noteworthy that R can be expressed both in term of weight

ratio or molar one, because an adjustment of the rate constant K is
always possible:

K mol

Reagent MW wt
K
Pollutant MW

10

This correlation is derived from the relationship between R(mol)

and R(wt), which is analogous to Eq. (10). In the present work the
reagent weight ratio is utilized for all computations.
3.3. Validation with literature data
In order to make a preliminary validation of the model, a kinetic
analysis on degradation of 10 chlorinated pollutants with CaO by
MC treatment was carried out (Table 2), correlating the pollutants
abatement conversions with the specific dose supplied to reaction
mixture. Calcium oxide was chosen as the model reagent because a
fair corpus of studies is available (see references in Table 2).
Dechlorination kinetic data were inferred from graphs on articles,
so conversions were estimated with 2 significant figures. Geometrical characteristics of milling devices were retrieved from constructors web-sites.
3.4. Calculation procedure
All computations were carried out utilizing an electronic
spreadsheet (MS Excel 2003).
First of all, conversion time of milling data were translated into
conversion specific dose. In other words, the specific dose, corresponding to a certain time of milling, rotation speed, charge ratio,
and in a specific milling device, was calculated; then all conversion
data were expressed as a function of this parameter.
Two kinds of high energy mill were considered, because they
are the most employed equipments in environmental MC (and
not only): planetary ball mills and vibrational mills (in particular
Spex 8000 mixer/mill). The kinematic of a single ball motion for
both equipments is utilized to evaluate the quantities required
for dose estimation.

1.4266  102
1.6065  101
1.8120  102
[27]

11

Actually, in the present work no computations are made for this

mill, because the two quantities calculated above are exactly the
ones required for the energy dose estimation.
Evaluation of average ball velocity and hit frequency in planetary ball mills is based on the kinematic motion equations of a single ball, according to the work of Chattopadhyay et al. [49].
Basically, the authors explain that the motion of the ball can be
divided in 3 phases (Fig. 2): initially, the ball, starting from the
angular position of / = 0, moves along the jar wall for a time of
t1; then, when the detachment criterion is satisfied (i.e. the resultant of the centrifugal forces, deriving from the planetary disc rotation and the jar rotation on its own axis, is directed toward the jar
inner part), the ball, in the position / = /1, detaches from the jar
wall and flies with constant velocity vi for a time of t2; finally,
the ball hits the wall and moves along it for a time of t3 until the
cycle is repeated again.
The detachment criterion allows us to calculate the position /1
where the ball starts its flight:

8.8274  103

2.9646  102
8.3101  102
3.2999  102
[47]

1.8592  102

1.1462  105
1.1451  102
1.1667  101
[46]

2.2328  103

8.5885  102
4.6374  101
6.3153  102
[17]

6.8469  103

4.2928  102
2.9756  101
1.2943  102
[7]

2.8244  103

9.9493  103
3.6260  101
3.2302  102
[8]

4.1731  103

6.2372  103
6.3515  101
7.2625  102
[6]

6.7065  103

5.4721  104
9.8995  102
2.7114  102
[45]

7.9617  103

2.4083  103
5.3231  103
5.8804  104
4.1422  102
[44]

cos /1 

1,2,3-Trichlorobenzene

Pentachlorophenol

Octachloronaphthalene

Mirex

c-Hexachlorocyclohexane

Hexachlorobenzene

Dechlorane plus

DDT

3-Chlorobiphenyl

Value inferred from data available on the paper.

9*
4.2*

35*

25*
91*

3.71

36
24

98*
11.7*

15

36

275
(9g)
275
(9g)
700
(38g)
275
(9g)
700
(38g)
400
(13g)
700
(38g)
36

10
7

25

42*
20

700
(38g)
700
(38g)

Planetary ball mill

Pulverisette 7, Fritsch, D
Planetary ball mill
Pulverisette 7, Fritsch, D
Vibration mill
8000 mixer/mill, SPEX, US
Planetary ball mill
QM-3SP2, Nanjing University Instrument, PRC
Planetary ball mill
QM-3SP2, Nanjing University Instrument, PRC
Planetary ball mill
Pulverisette 7, Fritsch, D
Planetary ball mill
QM-3SP2, Nanjing University Instrument, PRC
Planetary ball mill
Pulverisette 7, Fritsch, D
Planetary ball mill
XQM-0.4L, Kexi, PRC
Planetary ball mill
Pulverisette 7, Fritsch, D
4-Chlorobenzene

20

3.6982  101
1.5855  102

1.4322  103

RSS
KE

[5]

Proposed model
Exponential model
References

Rotation speed [rpm]

(centrifugal factor)
Charge
ratio

v i 4:169 m s1 ; F 142:04 Hz

r J X  x2
r P X2

v 2i Xr2p X  x2 r2J 2XX  xrJ rp cos /1

Milling device

CaO to pollutant
weight ratio

Concas et al. already made calculations on Spex mixer/mill [48].

The authors assert that, in standard operation mode, the average
ball velocity and hit frequency have the following values:

12

Subsequently, it is possible to compute the ball velocity and the

impact frequency:

Contaminant

Table 2
Summary of literature data employed to validate the proposed kinetic model. In bold the rate constant values with lowest RSS.

6.0090  103

G. Cagnetta et al. / Chemical Engineering Journal 291 (2016) 3038

RSS

34

1
t1 t2 t3

13
14

(See Ref. [49] for t1, t2, and t3 detailed calculation). These parameters, together with the charge ratio and the time of milling, are
required to quantify the specific energy dose (according to Eq. (6)).
However, this simple method for the computation of the energy
amount transferred to the powder requires a caveat. In fact, only a
fraction of the energy is really used to activate the powder mixture
and induce the reaction. Generally speaking, milling devices deliver energy in at least two ways: one contributes more to the
mechanical dose transferred to the powder, while the other dissipates energy in the form of heat. In their simulation of a planetary
mill, Shelekhov et al. [50] identify normal and tangential contributions to the energy dissipation that can loosely be associated with
plastic deformation due to compression versus heating by friction
[51]. Reliable assessments of dissipated energy or, otherwise, of
effective energy dose are difficult to achieve, and experimentally
validated values are necessary to obtain a convincing model of
energy delivery [42]. Therefore, for the sake of simplification, the
total specific energy dose was employed to estimate reaction progress instead of the effective energy share. Nonetheless, in proper
milling conditions (e.g. optimal jar filling ratio, 1 6 |x/X| 6 3,
etc.) the kinetic energy possessed by a hitting ball is almost completely transferred to the trapped powder [52], so this resolution
does not invalidate the efficacy of the model, as also demonstrated
by present works results.
Afterward, experimental points are fitted by models. Together
with our proposed model (Eq. (9)), the exponential one (Eq. (7))
is also utilized for comparison, being often used as pseudo-first
order approximation. The residual sum of squares (RSS) is calculated to assess the performances of experimental data best fitting,
defined as:

RSS

n
X
calc
xp 2
vi
 vi
i1

15

G. Cagnetta et al. / Chemical Engineering Journal 291 (2016) 3038

35

Fig. 3. Experimental points (from Ref. [6]) and proposed model fitting lines (with
K = 6.6901  103) of declorane plus co-milled with CaO, with different reagent
ratios (R).
Fig. 2. Schematic motion of a single ball in planetary ball mills, according the
mathematical elaboration of Chattopadhyay et al. [49] (see text for further
explanations).

4. Results and discussion

best operating conditions (and the related costs) for the MC treatment of POPs. Increasing R entails the enhancement of reaction
rate and the consequent energy expenditure reduction, but also
implies the decrease of treated pollutant amount as well as a larger
consumption of co-milling reagent. As usual, cost analysis can be
utilized to assess the optimal value of R.

4.1. Validation with literature data

4.2. Experimental results
The proposed sigmoid model is the best fit (corresponding to
the lowest RSS) for 9 pollutants out of 10 (Table 2). This result
strengthens the idea that a slow initial rate in the reaction kinetic
exists, and it is caused by a certain time required to gain intimate
contact of reagents and accumulation of crystal defects (i.e. the
activation) of CaO. Nevertheless, because of large excess of the
oxide, necessary mixing and activation are quickly obtained and
the initial slow reaction rate is negligible, so the exponential model
(or rather the pseudo-first order approximation of the reaction
kinetic) is still a good estimation of destruction rate. The existence
of a lag time for CaO is ascertained in the Section 4.2, because available data are not detailed enough at low energy doses, i.e. short
milling times.
In our previous work, we studied the influence and the importance of the reagent ratio R on MC destruction of dechlorane plus
(a chlorinated flame retardant) co-milled with CaO, using R = 10,
15, and 25 [6]. We found that higher reagent ratios improve significantly the conversion at shorter milling times. The same data are
utilized in this study to validate the proposed sigmoid model with
different reagent ratios. The values of the kinetic constants are
reported in Table 3. Again, the proposed model fits data very well
but the pseudo-first order approximation is quite satisfying too,
and fits data even better than sigmoid trend in one case (with
R = 15). The average value of K (6.6901  103) is adopted in
Fig. 3 to construct the fitting curves with various R values.
Results confirm that the influence of the reagent ratio on the
reaction rate is significant. In fact, it improves remarkably the pollutant degradation rate, so plays a primary role in determining the

Table 3
Rate constants obtained from the best fitting of dechlorane plus degradation kinetic
(experimental data taken from Ref. [6]). In bold the rate constant values with lowest
RSS.
R

10
15
25

Exponential model

Proposed model

KE

RSS

RSS

2.8074  102
5.4533  102
7.2625  102

8.7723  102
2.5845  103
6.3657  101

5.9984  103
7.3654  103
6.7065  103

3.6818  102
4.4417  103
6.2989  103

Fig. 4 shows the experimental points of HCB destruction conversions at different milling intensities varying with milling time
(with R = 20), as well as the curve referred to the specific energy
dose. Once more time, the proposed model is the best-fit of the
experimental data respect to the pseudo-first order approximation
(Table 4, values with R = 20).
According to Delogu et al. [36], the fact that all experimental
points stand near the same fitting line (Fig. 4b) is a proof that
the MC reaction between HCB and CaO does not require an energy
dose threshold that must be surpassed before the reaction can happen. In fact, the authors found that in some binary systems with
immiscible components (i.e. with positive enthalpy of mixing), part
of the energy dose must be spent to generate metastable crystalline solid solutions. In this case, in order to obtain coherent
experimental data (i.e. points that show a unique trend), the
energy dose must be corrected, subtracting the threshold value
from the estimated one.
Comparison between the calculated kinetic constant of our
model with the Pulverisette-4 ball mill and of the one obtained
with previous works data employing the QM-3SP2 mill [8] for
the same pollutant (Table 4) indicates that their values are sensibly
different (the average value estimated in this work
K = 5.5901  103 is 34% greater than the one calculated from preceding works data). Apart from the obvious uncertainty due to
experimental errors, this difference is probably determined by
the milling device utilized in this work, which was chosen intentionally of a different model. Although both mills have planetary
motion, however the geometry and other features are dissimilar.
Actually, it is demonstrated that the charge ratio and the rotation
speed are the most significant milling parameters, but they are
not enough to determine completely the milling conditions [53].
Other parameters like the jar volume, its filling ratio, and the balls
diameter are important too. For instance, in this work we used
10 mm balls, while in the precedent work were utilized
5 mm balls. These little differences may have a role in determining the variance between the two values of K, such as causing slight
disparity in the energy share effectively transferred to the powder
and/or its delivery mode (i.e. impact or attrition). The reaction rate

36

G. Cagnetta et al. / Chemical Engineering Journal 291 (2016) 3038

Fig. 4. HCB destruction conversion co-milled with CaO (R = 20) at different milling intensities (see Table 3 for the corresponding milling parameters), reported as a function of
milling time (a) and specific energy dose (b).

Table 4
Comparison of the rate constants obtained from experimental results of the present
work and the one taken from Ref. [8] utilizing different planetary ball mills. In bold
the rate constant values with lowest RSS.
R

Exponential model

Proposed model

KE

RSS

Pulverisette-4 ball mill (present work)

10
1.8493  102
3.5884  102
20
4.3527  102
1.2531  101
30
7.0086  102
5.5461  101

5.3132  103
5.6542  103
5.8029  103

7.2498  103
1.1084  102
1.8810  102

QM-3SP2 ball mill ([8])

15
3.2302  102

4.1731  103

9.9493  103

RSS

3.6260  101

modeling in diverse devices, also with different type of action, is an

interesting topic for future research, which has been rarely tackled
in MC destruction of pollutants.
Results confirm that the energy dose is an invariant quantity;
videlicet, independently from the milling intensity, the energy
dose provided to the HCBCaO system determines its transformation degree, specifically the pollutant destruction conversion
(Fig. 4b). This finding is not surprising, because it is well known
that the energy dose is invariant for inorganic systems. Therefore,
the activation of CaO, in particular of the oxides centers in the lattice that are responsible for the pollutant dehalogenation and
destruction, is independent from milling intensity too. Indeed this
result corroborates the existence of a CaO activation step, before
the pollutant destruction (as proposed in chemical Eqs. (1) and
(2)).
Another proof of solids activation is the evident sigmoid trend
of the degradation reaction (Fig. 4). Short milling times and low
rotational speeds (corresponding to low specific energy doses)
were purposely chosen to investigate the early reaction phase.
The reaction rate is clearly slow during the first hour of milling.
This time, called by other authors induction time [18,19], is
required to achieve a relevant number of active centers on the sur-

Fig. 5. HCB destruction conversion with different CaO/HCB reagent ratio (R). The
fitting lines are generated with the average value of K = 5.5901  103.

face (and to create brand new surfaces) of CaO particles, which are
necessary to start the pollutant degradation (Eqs. (1) and (2)).
Experimental results confirm, from the kinetic point of view, that
the oxide centers in the CaO lattice are induced by mechanical
force to transfer electrons to C atoms of the pollutants [26]. Consequently, chlorine atoms hold electrons and detach from the molecule as chlorides.
The effect of reagent ratio on the reaction rate was also studied.
Three different ratios were utilized for milling under various intensities (Fig. 5). The proposed model succeeds to predict the change
of this parameter, seeing that the three kinetic constants (estimated by the best-fitting of experimental data) are quite similar
(Table 4).
Reasonably, the values of K found in this work should be correlated only with the chemical properties of the two reagents and, to
a lesser extent, on the milling device. Especially, the energy dose
includes milling conditions, while the reagent ratio takes into

G. Cagnetta et al. / Chemical Engineering Journal 291 (2016) 3038

account the reaction stoichiometry. Hence, it is very likely that the

calculated rate constants are independent from the two mentioned
parameters and are a function of reagents characteristics. Actually,
we found similar values but with a sizable discrepancy (30%) for
the same reagents utilizing two planetary ball mills with diverse
geometric configurations. Model improvement to estimate differences in milling devices, in particular their scale (viz. laboratory-,
pilot- and industrial-scale), is an interesting research issue for
the future. Moreover, identifying a relationship between chemical
properties of the reagents and the constant rate would make the
model independent from direct measurements.
5. Conclusions
A kinetic model that describes the MC destruction of POPs was
presented in this work. It includes all fundamental parameters (i.e.
milling conditions and regent ratio) that influence the reaction
rate. It was validated successfully utilizing literature data of 10
chlorinated POPs and experimental data on CaO and HCB comilled in a planetary ball mill under various conditions.
(1) The invariance of the energy dose was confirmed for the
HCBCaO system. It means that the reaction progress is
independent (within reasonable limits) from the milling
intensity and depends only on the total energy amount
delivered to the powder (i.e. the reaction mixture).
(2) The proposed model is based on a sigmoid equation of the
reaction conversion as a function of the specific energy dose,
and fits satisfactorily all available kinetic data. This result
confirms that an activation step of the solids (in particular
of CaO) occurs before the pollutant destruction reaction
happens.
(3) The model was also successfully employed to predict the
reaction rate with different reagent ratios. Hence, this is
the first model that comprehends all fundamental parameters required for a complete description of POPs destruction
reactions in MC activators.
(4) Results reveal that sensible differences in estimation of
kinetic constants are observed if different milling devices
are utilized. In order to assess this variance, future research
will be carried out on different activators. Moreover, pilotscale mills will be utilized to verify predictions of the model
and whether it suffers a scale-up effect.

Acknowledgements
The project was supported by the National Natural Science
Fund (No. 51278270), the National High-Tech Research and Development Program (No. 2013AA06A305), and Tsinghua University
Initiative Scientific Research Program (20131089251).
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