Chemical Engineering Science 142 (2016) 310317

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Chemical Engineering Science

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

Kinetic modeling of gas phase synthesis of ethyl chloride from ethanol

and HCl in xed bed reactor
Natalia Bukhanko a, Johan Wrn a,b,n, Ajaikumar Samikannu a, Jyri-Pekka Mikkola a,b
a

Technical Chemistry, Department of Chemistry, Chemical-Biological Center, Ume University, SE-90187 Ume, Sweden
Laboratory of Industrial Chemistry and Reaction Engineering, Johan Gadolin Process Chemistry Centre, bo Akademi University, Biskopsgatan 8, FIN-20500,
Turku/bo, Finland
b

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

Gas-phase process of ethyl chloride

synthesis from ethanol and HCl over
high porous Al2O3-based catalysts in
a bed-xed reactor was investigated.

Two rival kinetic models for the
description of process kinetic were
proposed.

The values of rate constants, reaction
equilibrium constants and activation
energy were calculated for both
kinetic models.

art ic l e i nf o

a b s t r a c t

Article history:
Received 15 June 2015
Received in revised form
11 December 2015
Accepted 13 December 2015
Available online 21 December 2015

Kinetic modeling of gas-phase synthesis of ethyl chloride from ethanol and hydrochloric acid over high
porous Al2O3 and 2 wt% ZnCl2/Al2O3 catalysts was studied in a continuous plug ow reactor in the
temperature range of 200325 C. Two rival kinetic models were proposed that both describe the
kinetics well. The kinetic parameters of the reaction were determined and activation energy values for
ethyl chloride formation from ethyl alcohol and diethyl ether reactions were calculated.
& 2015 Published by Elsevier Ltd.

Keywords:
Ethyl chloride
Kinetic modeling
Gas-phase reaction
Heterogeneous catalysis

1. Introduction
Fixed bed reactors are widely used for various industrial processes, e.g. homogeneous and heterogeneous reactions. In industrial scale, when the tube is packed with catalyst, signicant
operational and cost advantages can be achieved (Kayode Coker,
2001; Salmi et al., 2010). Consequently, high-throughput reactors
with little or no back mixing render plug ow reactors suitable for
various reactions in large-scale production. Also, modeling of
tubular plug ow reactors has been reviewed in detail in literature
n

Corresponding author.
E-mail address: jwarna@abo. (J. Wrn).

http://dx.doi.org/10.1016/j.ces.2015.12.005
0009-2509/& 2015 Published by Elsevier Ltd.

(Kayode Coker, 2001; Salmi et al., 2010; Froment and Bischoff,

1990; Metcalfe, 1997).
The reaction of ethanol and HCl is a green route to produce
ethyl chloride, an ethylating agent for a number of various
industries and can be used to produce e.g. cellulose derivatives,
polymers, freons and ionic liquids (Summary of Emissions Associated with Sources of Ethyl Chloride, 1988; Savage et al., 1954;
Karlson et al., 2008; Holbrey et al., 2001). High product selectivity
and, in essence, full conversion of reactants, absence of hazardous
by-products and wastes as well as the use of bioethanol produced
from renewable resources along with low cost and non-toxic
alumina catalysts supports this route as an environmentally
friendly industrial process (Bukhanko et al., 2013). However, the
information about kinetics and mechanism of ethanol

N. Bukhanko et al. / Chemical Engineering Science 142 (2016) 310317

hydrochlorination is mostly limited to liquid phase processes at

low temperatures (Korgesaar, Palm, 1974; Korgesaar, Palm, 1975;
Gezalov et al., 1988; Vigdorovich, Gorelkin, 1973). Most of the
earlier publications report about the inuence of experimental
conditions on product selectivity but the kinetics was not analyzed. Thus, kinetic investigations of gas-phase ethanol hydrochlorination process are needed.
In this work, two kinetic models of gas-phase synthesis of ethyl
chloride from ethanol and hydrochloric acid are discussed and
reaction kinetics as well as thermodynamics were studied. Both
pure alumina and ZnCl2 impregnated highly porous alumina were
used as catalysts in the reaction. Still, variations in feedstock
composition (pure ethanol and ethanol-water mixtures) and differences in the catalyst materials are compared.

2. Experimental setup
2.1. Catalysts preparation and precursors
High-porous aluminum oxide prepared by solgel method
(Bukhanko et al., 2013) and zinc chloride salt (analytical grade,
498%, Merck) were used for the preparation of the catalysts. The
modied alumina catalysts (2 wt% ZnCl2/Al2O3) were prepared by
Table 1
BET surface area, pore size and pore volume data for the catalytic materials
(Bukhanko et al., 2013).
Catalyst

SBET, m2/g

Pore size, nm

Pore volume, cm3/g

Al2O3
2 wt%ZnCl2/Al2O3

429.1
400.2

18.0
6.3

1.9
0.6

311

means of impregnation (Bukhanko et al., 2013). The reactants,

ethyl alcohol (99.5 vol%, i.e. 98.3 mol% and 95 vol%, i.e. 85.3 mol%;
analytical grade, Solveco) and anhydrous HCl (99.999%, PRAXAIR)
were used as received. The catalytic materials were characterized
by means of TEM, XPS, XRD and nitrogen physisorption (BET) and
described in detail in our previous work (Bukhanko et al., 2013)
and shortly presented in Table 1.
2.2. Catalytic experiments
Catalytic reactions were performed in a tailor-made, pressurized xed bed reactor (ID 10 mm, length 260 mm) constructed of
stainless steel tube with tantalum lining inside to eliminate the
corrosion processes induced by the HCl (Fig. 1). The catalyst bed
consisted of the catalyst of choice (mcat 0.25 g, lbed 3 cm) and
glass beads as spacers in the reactor. Ethyl alcohol was fed with an
HPLC-pump and vaporized at 250 C before feeding into the
reactor. The reaction was carried out at different temperatures:
200, 250, 275, 300 and 325 C, respectively, both under atmospheric conditions and under elevated pressure of 6 bar. The
contact time values were calculated using these parameters settings and presented in Table 2 (Supplementary content 1). The
molar ratio of ethanol and hydrochloric acid n(C2H5OH): n(HCl)
was varied from 1.05:1, 1.025:1 to 1:1, respectively. In addition,
experiments with ethanolwater mixtures, containing 50, 70 and
90 mol% of ethanol, were carried out. The ow rates of the reactants were controlled by means of PC-operated mass ow controllers and calibrated before each and every experiment. The
mixture of products from the reactor outlet was passed through a
vessel containing crushed CaO (heated to 105 C,) in order to
remove traces of water and unreacted acid. The reaction products
were collected in a cooling trap (T  5 C) for further sampling.

Fig. 1. The scheme of reactor setup for gas phase synthesis of ethyl chloride.

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N. Bukhanko et al. / Chemical Engineering Science 142 (2016) 310317

Table 2a
The reaction equilibrium constants calculated from thermodynamic theoriesmodel 1.
T, C

Keq1

Keq2

Keq3

200
250
275
300
325

635.6
332.6
251.6
195.0
154.4

14.12
8.45
6.80
5.59
4.68

45.01
39.38
37.02
34.90
32.99

The rst reaction scheme (model 1) is similar to that for methyl

chloride synthesis and described in detail (Schmidt et al., 2013).
This model assumes three main steps for the reaction (listed
below). The step 1, ethyl chloride formation directly from ethanol
and HCl, is the main rate determining step (RDS), step 2 describes
the formation of the main by-product, diethyl ether, form ethanol
and, nally, step 3, describes the reaction of diethyl ether with HCl
to form ethyl chloride.
I EtOH HClEtCl H2O
II 2EtOHDEE H2O

Table 2b
The reaction equilibrium constants calculated from thermodynamic theoriesmodel 2.
T (C)

Keq2

Keq3

Keq4

200
250
275
300
325

635.6
332.6
251.6
195.0
154.4

2.0366E-04
1.1186E-04
8.6875E-05
6.9189E-05
5.6309E-05

45.01
39.38
37.02
34.90
32.99

III DEE HClEtCl EtOH

The reaction rates can be written as follows:
r 1 k1s
C EtOH
C HCl  C EtCl
C H2O =K eq1 =D2

r 2 k2s
C EtOH 2  C DEE
C H2O =K eq2 =D2

r 3 k3s
C DEE
C HCl  C EtCl
C EtOH =K eq3 =D2

where the denominator D can be written as:

cooling was necessary at  5 C because of the high volatility of
ethyl chloride.
The liquid-phase products were analyzed using a gas chromatograph (Agilent 6890 N) equipped with a ame ionized detector
(FID) and HP-PLOT/U capillary column. The molar uxes of products were calculated from the GC data. The experimental conditions and molar uxes of reactants and products are presented in
Table 2 (Supplementary content 1).

3. Reactor model
For the packed bed reactor, the ideal plug ow model is used:
dn_ i
r i B
dx
.
where ni molar ow of i-component (mol/min), ri-the component
generation rates (mol/min) and B is the bulk density of the catalyst in the reactor (catalyst mass/volume).
Packed bed reactors operate under kinetic and/or diffusion
limited regime, depending on the catalyst particle size, reaction
rates and diffusion rates. In order to investigate whether our system operated under kinetic regime or under diffusion control, the
effectiveness factor at the reaction conditions for highest reaction
rates was calculated. The effectiveness factor can be calculated
from the Thiele modulus. Thiele modulus is q
a function
between

reaction rate and diffusion coefcient

K
Di L

The diffusion

coefcient Di was calculated by using of semi-empirical Fuller

SchettlerGiddings equation (Reid et al., 1988) and was found to
be 5.8.10  6 m2/s. The values of Thiele modulus, and the effectiveness factor, , were calculated by approximating the reaction
to follow rst order kinetics in the beginning of the reaction when
the reaction rate is highest. The Thiele modulus and effectiveness
factor obtained values 0.08 and 0.99, respectively. Thereby, it was
shown that under these experimental conditions the reaction was
carried out under kinetic regime.

4. Rival models for the reaction kinetics

To describe the reaction kinetics, two slightly different models
were developed and proposed, assuming that ethyl chloride can be
formed from both ethanol and diethyl ether.

D 1 K HCl
C HCl C EtOH
K EtOH

The reactor model including the generation rates for all compounds becomes as follows
dcEtOH =dt  r 1  2
r 2 r 3 B

dcHCl =dt  r 1  r 3
B

dcEtCl =dt r 1 r 3
B

dcH2O =dt r 1 r 2
B

dcDEE =dt r 2  r 3
B

The alternative, second model (model 2) is also based on the

assumption that ethyl chloride is produced from ethanol and
diethyl ether, but via intermediate states. This approach of ethyl
chloride formation via various parallel reactions was proposed in
our previous work (Bukhanko et al., 2013). Thus, according to the
following reaction scheme, 3 main reactions can be listed as RDS
for ethyl chloride formation. The initial step, the ethoxy formation
from ethanol is very fast and the concentration of H species,
formed at this step, is negligible low and has no effect on further
steps. In the calculations the concentration of the ethoxy species
was taken as equal to the ethanol concentration. The reaction I in
this model can be considered as not RDS step and the equilibrium
constant for this step was not calculated. The last step V was not
considered as RDS. The derivation of this model is presented in the
Electronic Supplementary Content 1.
I EtOHEtOx H
II EtOx HCl HEtCl H2O
III 3EtOx HCl HDEE H2O EtCl
IV DEE HClEtCl EtOH
V DEE HEtOx HC
The nal reaction rates for the model can be described as follows:
r 1 k1
C EtOH  C EtOx
C H =K eq1 =D2

10

r 2 k2s
C EtOx
C HCl  C EtCl
C H2O =K eq2 =D2

11

r 3 k3s
C EtOx 3
C HCl  C EtCl
C DEE
C H2O =K eq3 =D3

12

N. Bukhanko et al. / Chemical Engineering Science 142 (2016) 310317

313

Table 3a
The numerical values of the estimated kinetic parameters for reaction scheme 1.
Catalyst Al2O3 Degree of explanation 99.1%

Correlation matrix

parameter

value

/

k1

k2

k3

Ea1

Ea2

Ea3

k1
k2
k3
Ea1
Ea2
Ea3

9.76E-07
4.27E-08
3.66E-11
1.05E 05
4.48E 04
2.35E 04

8.82E-08
2.12E-08
2.88E-11
4.44E 03
5.26E 04
2.12E 04

1
0.045
 0.01
0.756
 0.013
0.017

1
0.018
0.045
 0.168
 0.01

1
 0.01
0.017
 0.22

1
 0.054
0.016

1
0.001

Units: k1, k2, k3-m3/molmin; Ea J/mol; Tmean 300 C, kis ki exp(1/T  1/Tmean).

Table 3b
The numerical values of the estimated kinetic parameters for reaction scheme 2.
Catalyst Al2O3 Degree of explanation 98.8%

Correlation matrix

parameter

value

/

k2

k3

k4

Ea2

Ea3

Ea4

k2
k3
k4
Ea2
Ea3
Ea4

8.16E-07
1.37E-10
3.94E-11
9.48E 04
8.14E 04
6.20E 04

5.16E-11
7.00E-15
1.47E-15
4.02E 00
3.02E 00
1.78E 00

1
0.745
0.22
 0.38
0.353
 0.218

1
 0.469
 0.138
0.721
0.473

1
 0.251
 0.548
 0.974

1
0.565
0.249

1
0.55

Units: k3 (m3/mol)3min, k2,k4,-m3/molmin; Ea J/mol; Tmean 300 C, kis ki exp(1/T-1/Tmean).

Table 3c
The numerical values of the estimated kinetic parameters for reaction scheme 1.
Catalyst 2 wt.% ZnCl2/Al2O3 Degree of explanation
99.12%

Correlation matrix

parameter

value

/

k1

k2

k3

Ea1

Ea2

Ea3

k1
k2
k3
Ea1
Ea2
Ea3

9.19E-07
7.04E-13
2.41E-07
1.11E 05
6.80E 04
2.00E 04

1.69E-06
1.80E-12
6.02E-07
4.16E 04
2.74E 05
2.62E 05

1
0.416
0.434
0.99
 0.16
 0.171

1
0.999
0.389
 0.96
 0.964

1
0.407
 0.954
 0.96

1
 0.133
 0.144

1
0.997

Units: k1, k2, k3-m /mol
min; Ea J/mol; Tmean 300 C.

3

Table 3d
The numerical values of the estimated kinetic parameters for reaction scheme 2.
Catalyst 2 wt% ZnCl2/Al2O3 Degree of explanation 99.12%

Correlation matrix

Parameter

value

/ 

k2

k3

k4

Ea2

Ea3

Ea4

k2
k3
k4
Ea2
Ea3
Ea4

5.62E-07
2.51E-15
9.97E-07
9.96E 04
8.18E 04
2.23E 04

2.22E-07
8.04E-16
2.88E-07
9.86E 03
3.04E 04
1.96E 04

1
0.479
0.716
0.794
 0.21
 0.238

1
0.912
0.272
 0.322
 0.282

1
0.49
 0.266
 0.317

1
0.065
0.058

1
0.807

Units: k3 (m3/mol)3
min; k2,k4,-m3/mol
min; Ea J/mol; Tmean 300 C.

r 4 k4s
C DEE
C HCl  C EtCl
C EtOH =K eq4 =D2

13

The reactor model equations for all compounds become now as

follows:

r5 k5s
C DEE
C H C EtOx
C HC =K eq5 =D2

14

dcEtOx =dt r 1  r 2 3
r 3 r 5
B

15

dcEtOH =dt  r 1 r 4
B

16

dcHCl =dt  r 2 r 3  r 4
B

17

where D is:
D 1 K EtOx
C EtOx K HCl
C HCl K EtCl
C EtCl K DEE
C DEE
K H2O
C H2O K EtOH
C EtOH

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N. Bukhanko et al. / Chemical Engineering Science 142 (2016) 310317

Fig. 2. Parity plot model prediction vs. experimental data (mol/min), for the kinetic
model 1. The experiments were carried out over Al2O3 catalyst.

Fig. 3. The reactants and products molar ows inside the catalyst bed, kinetic
model 1. The reaction conditions: T 200 C, p 6 bar, nEtOH: nHCl 1:1, catalyst
2 wt% ZnCl2/Al2O3.

dEtCl =dt r 2 r 3 r 4
B

18

dH2O =dt r 2 r 3
B

19

dcDEE =dt r 3  r 4  r 5
B

20

dcH =dt r 1 r 5
B

21

dcHC =dt r 5
B

22

5. Numerical methods, thermodynamic calculations and

software
The software Modest was used for the modeling of the reaction
kinetics (Haario, 2007). The software solves the reactor model
equations (system of ordinary differential equations) with the
backward difference method and optimizes the parameter values

Fig. 4. The reactants and products molar ows inside the catalyst bed, kinetic
model 1. The reaction conditions: T 325 C, p 6 bar, nEtOH: nHCl 1.05:1, catalyst
2 wt% ZnCl2/Al2O3.

Fig. 5. Parity plot model prediction vs. experimental data (mol/min), kinetic model
1. The experiments were carried out over Al2O3 catalyst.

using a hybrid method involving Simex and LevenbergMarquardt methods.

After some initial parameter estimation trials with all unknown
reaction kinetic parameters, it became clear that the reaction
equilibrium parameters could not be reliably estimated. Large
statistical errors were obtained so estimating them together with
frequency factors and activation energies was not reasonable.
However, for gas phase reactions, it is possible to calculate the
reaction equilibrium constants from thermodynamic theories. To
calculate the reaction equilibrium constants as function of temperature, the software Aspen Plus equipped with the Gibbs equilibrium reactor model for gas phase reactions was used (http://
www.aspentech.com). The equilibrium constants, calculated from
thermodynamic theories-reaction systems 1 and 2, are listed in
Tables 2a and 2b respectively.

N. Bukhanko et al. / Chemical Engineering Science 142 (2016) 310317

Fig. 6. The reactants and products molar ows inside the catalyst bed, kinetic
model 1. The reaction conditions: T 200 C, p 6 bar, nEtOH: nHCl 1:1, catalyst
Al2O3.

Fig. 7. The reactants and products molar ows inside the catalyst bed, kinetic
model 1. The reaction conditions: T 325 C, p 6 bar, nEtOH: nHCl 1.025:1, catalyst
Al2O3.

6. Estimation of the kinetic parameters

Parameter estimation for models 1 and 2, respectively, was
performed by estimating the frequency factors k2-4 and activation
energies Ea2-4. The desorption coefcients, (KEtOx, KHCl, KEtCl, KDEE,
KH2O and KEtOH but not KHC and KH in model 2)), were also estimated but even if including all the available experimental data,
they had a minor inuence on the t of the model to the. Since the
parameter values obtained had large statistical errors, they were
set to zero in the nal parameter estimation run. For model
2 reaction I was assumed instantaneous and reaction V was not
included in modeling since very low concentrations of H, HC
species.
The estimated parameter values are presented in Tables 3a3d
together with the parameter errors for 95% condence interval
and correlation matrix.

315

Fig. 8. Parity plot model prediction vs. experimental data (mol/min), kinetic model
2. The experiments were carried out over 2 wt% ZnCl2/Al2O3 catalyst.

Fig. 9. Parity plot model prediction vs. experimental data (mol/min), kinetic model
2. The experiments were carried out over Al2O3 catalyst.

It can be noted that the estimated activation energies for ethyl

chloride formation, i.e. the Ea2 values, are close to those reported
for methyl chloride synthesis process-108 kJ/mol (Schmidt et al.,
2013) and 98 kJ/mol (Ivanov and Makhlin, 1996) (model 1).
Both models give almost similar degrees of explanation for
both catalyst types. Nevertheless, the model 2 displays a bit lower
statistical errors and less correlation between parameters.
Regardless, it is not possible to determine whether one model
describes the experimental data better than the other one.

7. Fit of models to experimental data

The t of the kinetic models 1 and 2 to experimental data are
shown in Figs. 211. The parity plots, model vs. experimental data
determined for the model 1 that include all experiments are shown
on Figs. 2 and 5, respectively. Both of catalyst materials, pure alumina
and 2 wt% ZnCl2/Al2O3 catalyst are considered. The same data, but for

316

N. Bukhanko et al. / Chemical Engineering Science 142 (2016) 310317

10 -4

2%ZnCl 2 /Al 2 O3 Temp= 200 oC, Pressure= 6 atm

8
7

mol/min

6
5
4
3
2
1
0
Fig. 10. The reactants and products molar ows inside the catalyst bed, kinetic
model 2. The reaction conditions: T 325 C, p atm, nEtOH: nHCl 1.05:1, catalyst
2 wt%ZnCl2/Al2O3.

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

z
Fig. 12. The reactants and products molar ows inside the catalyst bed, kinetic
model 2. The reaction conditions: T 200 C, p 6 atm, nEtOH: nHCl 1.:1, catalyst
2 wt%ZnCl2/Al2O3.

Consequently, the data tting curves show good correspondence

with the experimental data. The alternative kinetic model (model
2), assuming intermediate states, including ethoxy-formation,
gives equally good description of the experimental data. The
activation energy values are close to that for similar reactions of
methyl chloride synthesis, listed in literature.
Nomenclature

Fig. 11. The reactants and products molar ows inside the catalyst bed, kinetic
model 2. The reaction conditions: T 275 C, p atm, nEtOH: nHCl 1:1, catalyst Al2O3.

the model 2, are presented in Figs. 8 and 9, respectively. Figs. 3, 4, 6,

7, 10, 11 and 12 depict the molar ow vs. length coordinate in the
packed bed reactor, i.e. the calculated molar ow prole inside the
reactor tube from inlet to outlet. The solid lines illustrate the calculated molar ows inside the reactor tube as a function of the length
coordinate; symbols are measured data at the outlet of the reactor.
Consequently, as can be seen, the models can predict the behavior of
the reaction in a packed bed reactor.

8. Conclusions
The kinetic regularities of ethyl chloride gas phase synthesis
from ethanol and HCl in a packed bed reactor over pure and ZnCl2impregnated alumina catalysts and at the temperature range of
200325 C were studied. The values of the rate constants, reaction equilibrium constants and activation energy were calculated
for both rival kinetic models. The model 1, based on two routes for
ethyl chloride formation from ethanol and diethyl ether, respectively, could be used to describe all experimental data well.

A
C
Di
Ea
k
K
mcat
.
ni
p
R
ri
z
T

frequency factor
concentration
diffusion coefcient
activation energy
rate constant
equilibrium constant
catalyst mass
molar ow of i-component
pressure
gas constant
component generation rates
dimensionless reactor length coordinate
temperature
coverage
effectiveness factor
catalyst bulk density
Thiele modulus
radius of pellet

List of symbols
EtCl
EtOH
DEE
EtOx
H
HC

ethyl chloride
ethanol
diethyl ether
ethoxy
proton
hydrocarbons

List of symbols
i

component index

N. Bukhanko et al. / Chemical Engineering Science 142 (2016) 310317

0
cat

inlet conditions
catalyst

Acknowledgments
Financial support from Kempe Foundations (Kempe Stiftelserna) and Bio4Energy Programme are gratefully acknowledged.
This work is also associated with the research programs by the
Academy of Finland.

Appendix A. Supplementary material

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.ces.2015.12.005.

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