Beruflich Dokumente
Kultur Dokumente
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
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
31
Nomenclature
CR
^
D
Ei
F
kMA
kD
K
KE
KS
I
mb
mp
MW
N
rJ
rP
R
RG
RSS
x
t
t1
t2
t3
T
U0
vi
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
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
32
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.
s s0 exp
U 0 cr
RG T
Table 1
Experimental milling conditions utilized in the present work and the corresponding
milling intensities.
Reagent
ratio R
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
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
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)
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
v 1 1 RK D^ exp RK D^
K mol
Reagent MW wt
K
Pollutant MW
10
1.4266 102
1.6065 101
1.8120 102
[27]
11
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
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)
20
3.6982 101
1.5855 102
1.4322 103
RSS
KE
[5]
Proposed model
Exponential model
References
r J X x2
r P X2
Milling device
CaO to pollutant
weight ratio
12
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
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
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).
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.
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
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
5.3132 103
5.6542 103
5.8029 103
7.2498 103
1.1084 102
1.8810 102
4.1731 103
9.9493 103
RSS
3.6260 101
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
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).
References
[1] IUPAC, Compendium of Chemical Technology (the Gold Book), second ed.,
Blackwell Scientific Publication, Oxford, 1997. <http://goldbook.iupac.org>.
[2] L. Takacs, The historical development of mechanochemistry, Chem. Soc. Rev.
42 (2013) 7649, http://dx.doi.org/10.1039/c2cs35442j.
[3] L. Takacs, What is unique about mechanochemical reactions?, Acta Phys Pol. A
126 (2014) 10401043, http://dx.doi.org/10.12693/APhysPolA.126.1040.
[4] V.V. Boldyrev, K. Tkcov, Mechanochemistry of solids: past, present, and
prospects, J. Mater. Synth. Process. 8 (2000) 121132.
[5] Y. Nomura, S. Nakai, M. Hosomi, Elucidation of degradation mechanism of
dioxins during mechanochemical treatment, Environ. Sci. Technol. 39 (2005)
37993804, http://dx.doi.org/10.1021/es049446w.
[6] W. Zhang, J. Huang, G. Yu, S. Deng, W. Zhu, Mechanochemical destruction of
dechlorane plus with calcium oxide, Chemosphere 81 (2010) 345350, http://
dx.doi.org/10.1016/j.chemosphere.2010.07.025.
37
38
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]