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Article history: The present study explores the equilibrium and kinetics for the reactive extraction of mor-
Received 9 September 2017 pholine, an important industrial reagent from its aqueous stream using capric acid, CA
Received in revised form 12 March (extractant) in toluene (diluent). An equilibrium model that employs the mass action law
2018 was also developed to evaluate the optimum apparent equilibrium constants (KE ), stoichio-
Accepted 16 March 2018 metric ratio (m) and physical constant (S). Equilibrium model was valid in representing the
Available online 26 March 2018 mechanism of morpholine extraction. Moreover, for the first time the study availed the
simultaneous optimization of two significant response characteristics; extraction efficiency
Keywords: (%E) and loading ratio (Z) using Box–Behnken design (33 ) employing multivariate desirabil-
Reactive extraction ity function. The statistical models predicted %E of 80.2 and Z of 0.64 for the optimum
Loading ratio combination of process parameters as follows: CMO = 5%, CCAO = 5% and T = 303.15 K with the
Box–Behnken design desirability of 0.947. Further, the intrinsic kinetics of the extraction model demonstrated
Desirability function that the reactions between morpholine and CA fall in regime 3 (fast chemical reaction in
Extraction model diffusion film), follows first order kinetics with respect to morpholine and displays exother-
Kinetic study micity of the process as revealed from thermodynamic studies. The equilibrium and kinetic
data is useful for the development, design and reliable scale-up of the extraction process.
© 2018 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.
1. Introduction in fruit waxing (Behr et al., 2008; Lee et al., 2014; Kumari et al., 2017).
It is also used as separating agent and implemented as a building
4-Methyl-1,3-dioxolan-2-one or morpholine has emerged as a com- block in the preparation of antibiotics and, anti-cancer agents (Lee
mercially competent product having widespread applications in et al., 2014; McGuire and Dimitrios, 1999). In this context, the sep-
petrochemical plants, rubber industries, dye and resin industries, cok- aration of morpholine from aqueous waste streams is a statutory
ing as well as in many other organic chemical industries. It has often obligation. In the preparation of morpholine by the dehydration of
been selected for temperature-dependent multi-component solvent diethanolamine with sulphuric acid or hydrochloric acid a reaction
system applications such as in hydroformylation reaction and used mixture is obtained which contains the morpholine as an acid salt
∗
Corresponding author at: Process Development and Design Group, Chemical Engineering Division, CSIR – Indian Institute of Chemical
Technology, Hyderabad, Telangana 500007, India.
E-mail addresses: alka@iict.res.in (A. Kumari), satya@iict.res.in (B. Satyavathi).
https://doi.org/10.1016/j.cherd.2018.03.027
0263-8762/© 2018 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.
244 Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254
3.4. Box–Behnken experimental design coupled to RSM The experiments have been carried out to investigate the
physical (pure toluene) and chemical (CA in toluene) equilib-
Box–Behnken design is an efficient technique for process rium studies for extraction of morpholine.
optimization and designing a model, wherein the extreme
combinations of factor are excluded (Islam et al., 2009; 4.1. Physical extraction
Varala et al., 2016b). In the present research, a Box–Behnken
design coupled to response surface methodology (RSM) was The physical equilibrium studies were carried out for
employed wherein; initial morpholine concentration, temper- the extraction of morpholine with toluene alone for 1:1
ature and extractant concentration were identified as the most volume ratio of phases varying the morpholine concentra-
significant process variables in the extraction studies. The pro- tion (0.06–0.57) kmol m−3 at different operating temperatures
cess variables were designated with A, B and C in the design (303.15–323.15) K. The physical equilibrium isotherms were
matrix and the levels of the variables considered (low −1, cen- illustrated in Fig. 2 at different temperatures described a cor-
ter 0 and high +1) were shown in Table 1. relation between morpholine concentrations in aqueous and
Statistical design software (Design expert: version 10) was organic phase. The isotherm followed Henry’s law type model
utilized to generate the (33 ) BBD design matrix and is pre- at 303.15 K whereas at higher temperature, it displayed non-
sented in Table S2. According to a randomized experimental ideal behavior due to deviation from Henry’s law (Wasewar
design, a total of 17 experiments with 5 center points need et al., 2002). It was observed that as initial morpholine concen-
to be carried out to draw a complete picture of the effect of tration increases from (0.06 to 0.57) kmol m−3 , the distribution
factors (A, B and C) and reported along with experimental and coefficients (Kdiluent ) decreases from (0.19 to 0.10) at a constant
D
predicted responses for %E and Z. temperature 303.15 K. And also the distribution coefficients
246 Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254
Fig. 2 – Physical equilibrium isotherms for extraction of Fig. 3 – Chemical equilibrium isotherms for extraction of
morpholine in toluene at temperatures 303.15 K , 313.15 K morpholine with various concentrations of CA in toluene at
䊉, 323.15 K . 303.15 K. pure toluene , 5% CA 䊉, 10% CA , 15% CA .
(Kdiluent
D ) decreased from (0.19 to 0.12) with an increase in tem- high viscosity of CA to avoid mass transfer resistance as well
perature at a constant feed concentration of 0.06 kmol m−3 . to restrict the three-phase formation in layer separation.
Higher temperature facilitates the more back extraction of A plot of chemical equilibrium isotherms was shown in
solute molecules from organic to an aqueous phase. The Fig. 3, which shows aqueous and organic phase equilibrium
Kdiluent
D < 1, which is not much significant for extraction of concentrations at 303.15 K.
morpholine, accounted the morpholine affinity towards water The effect of extractant (CA) is evident on extraction of
than organic solvent, renders the difficulty of separation of morpholine. It can be observed that at a fixed concentration
physical extraction (Wasewar et al., 2011). of morpholine, the distribution coefficient increases with an
Also, it was concluded that the morpholine concentra- increase in CA concentrations, whereas upon varying the acid
tion in the organic phase increases with that of aqueous concentration for a fixed extractant concentration, KD value
phase at equilibrium. A statistical analysis was performed to decreases. It was concluded that chemical extraction is far
obtain the parameters signifying partition (P) and dimeriza- better than physical extraction. As ascribed in the above the-
tion coefficient (D) in regression equation Eq. (6) (supporting). oretical section, the reactive extraction of morpholine was
It was observed that P varies from 0.16 to 0.12 in the tem- mainly dominated by the hydrogen bond formation between
perature range of (303.15–323.15) K and negligible contribution solute-extractant because most of the morpholine is in the
to Kdiluent
D by the dimerization of solute–solute interaction in undissociated form in aqueous phase. This fact was certified
the organic phase. The P and Kdiluent
D were almost identical for by the pH measurement of the initial aqueous solution. The
the morpholine displaying the existence of only one chemical pH value plays a vital role in the existing form of solute in the
form of solute in physical extraction (Rewatkar et al., 2016). aqueous phase, when the equilibrium pH value in the aque-
As toluene is aprotic solvent, the solubilisation of mor- ous solution is larger than the pKa , dominates the existing
pholine is dominated by the formation of -bonded complex form of morpholine M which undermine the ion-pair com-
attributed to the morpholine imino hydrogen bonding with plex mechanism whereas, smaller pH than pKa dominates
the -electrons of toluene. Aroney et al. (1964) have reported the MH+ form of morpholine (Chai et al., 2016). In the present
in their study that molecules of morpholine interact in the study the higher pH of aqueous solution (∼10) > pKa (8.63) of
inert diluents, nevertheless weak, come into view to increase morpholine, quantify the negligible morpholine dissociation.
in the order as N-H < N-lone-pair. They have also established Thereby, hydrogen bonding dominates the mechanism. Mor-
the dominance of -hydrogen bonding between solute- pholine being a secondary amine have a lone pair of electrons
solvent rather than solute-solute association, evidenced by on the nitrogen atom attached to the heterocyclic ring co-
the infrared and nuclear magnetic resonance spectra. The ordinated with the CA in toluene, the extractants bind the
partition coefficient, P and distribution coefficient Kdiluent D amine molecules with a dipole–dipole or dipole-ion type of
decreases with temperature, which is an indicative of the intermolecular hydrogen bonding. The bond strength depends
exothermicity of solvation process of morpholine in toluene on the stability of the partially charged proton acceptor (mor-
(Rewatkar et al., 2016). The increase in temperature increases pholine) and donor (CA) atoms. The electronegativity of the
excess molar volumes manifested by weakening of interac- atoms decides the stability of its charges which is a measure
tions between molecules of toluene and morpholine through of the tendency of an atom to pull a shared pair of electrons
breaking off -hydrogen bonding. toward it. The higher electronegativity difference between
hydrogen (2.1) and nitrogen (3.0) creates stronger hydrogen
4.2. Chemical equilibrium bonding (Rewatkar et al., 2016).
This study includes the utilization of diluents in reactive
The chemical (reactive extraction) equilibrium data was extraction to improve the physical properties (viscosity, den-
obtained for extraction of morpholine from aqueous sity, surface tension at the interface) of the extractants and
solution (0.06–0.57) kmol m−3 using CA as extractant solvation of the acid–extractant complexes formed. The dilu-
(0.29–0.87) kmol m−3 dissolved in toluene at 303.15 K. The ent (toluene) chosen play a decisive role with regard to the
concentration of extractant was limited upto 15% due to the bonding with solute–extractant complex formed in the reac-
Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254 247
tive extraction. Generally, the bonding can be categorized into Substituting the values of C̄m1 and CM from Eqs. (2) and (5),
specific interaction and the general solvation (Wasewar et al., respectively in Eq. (8) is derived as:
2011). Toluene being aromatic and aprotic diluent provides a
better distribution because of the solvation occurred through qKE CM,total m−1 CCA s
KD = + (9)
the interaction of the aromatic -electrons of toluene with the CH+ CH+
1+ Ka 1+ Ka
complex. The increase in extraction efficiency is due to the
increase in acidic extractant concentration. As the concentra-
The free extractant concentration, C̄CA in the organic phase
tion of acidic extractant CA increases in the organic phase,
at equilibrium is represented as
enhancement in %E was observed, as the higher concentration
fulfils the stoichiometric obligation of the extractant.
C̄CA = C̄0CA − C̄m1 (10)
4.3. Modeling and optimization of stoichiometric Using Eq. (10), the equation is deduced as follows:
parameters (KE , m and S)
C̄0CA
An equilibrium model was developed to evaluate the optimum C̄CA = (11)
(1 + KE CM m )
apparent equilibrium constants (KE ), stoichiometric ratio of
morpholine to CA in toluene (m) and physical constant (S).
The value of C̄CA from Eq. (11) is substituted in Eq. (9), which
The mechanism of the reactive extraction process may be pro-
results in Eq. (12):
posed based on the following assumptions: (i) morpholine is
extracted into the organic phase through the physical solubil- mKE C̄0CA Cm−1 s
ity of the solute in the diluent of the organic phase (physical KD = M,total
m + (12)
Ka
constant, S) (ii) poor solubility of extractant and diluents in 1+ Ka
+ KE Cm 1+ [H+ ]
[H+ ] M
water, (iii) For simplicity, it was assumed that the solute (mor-
pholine) carries negligible amount of water in the organic To estimate the optimized values of KE , m and S for the reac-
phase, and (iv) negligible change in the volume of each phase tive extraction of morpholine, an objective function based on
at equilibrium (Kumar et al., 2011; Chai et al., 2016; Thakre least-squares method (know as root mean-square deviation,
et al., 2016). The extraction of morpholine (undissociated part, rmsd) was minimized for predicting
the stoichiometry of the
n
M) with extractant (CA) is an interfacial reaction described by (K −KD,pred )
2
1 D,exp
the following equation. complexation reaction. rmsd = n , where n is
the number of data points. By fitting the experimental data to
KE Eq. (12), the obtained optimized parameters such as KE , m and S
mM + CA↔Mm (CA) (1)
were reported in Table 2 and subsequently used for predicting
the KD values (Uslu et al., 2014).
With an expression of equilibrium constant as follows: The kE were found to be almost constant with increase
in concentration of morpholine (0.06–0.57) kmol m−3 due to
C̄m1 an appropriate concentration of CA (0.29–0.87) kmol m−3 . The
KE = (2)
CM m C̄CA kE values decreased with increasing CA concentration due to
availability of free extractant at higher concentration of CA
Morpholine dissociates at equilibrium in the aqueous (Kumar et al., 2011). The kE show dependency on the acid-
phase as mentioned in Eq. (1) and the dissociation constant ity of the CA and the specific basicity of morpholine (Zhou
(Ka ) is given by Eq. (3): et al., 2013). The stoichiometry coefficient m depends on the
dielectric constant of the diluent, which might be considered
CM CH+ for solute-solvent interaction considering the restrictions of
Ka = (3)
CMH+ solute solubilisation either by solvent or extractant attributed
to the existence of ionisable group in the solute chemical
Therefore, the total morpholine concentration in the aque- structure (Kumar et al., 2011). The values of S reveal that
ous phase, CM can be expressed in terms of undissociated physical extraction can be considered for extraction of mor-
solute concentration CM , Ka, and proton concentration CH+ . pholine in toluene and decreases with the increase in initial
morpholine concentration, support the outcome observed in
CM,total = CM + CMH+ (4) physical extraction. As shown in Fig. 4, the calculated val-
ues of KD , are in very good resemblance to the experimental
Ka
values. Standard deviation (SD) was calculated to test the
CM,total = CM 1 + (5)
[H+ ] consistency of the model with the experimental values. The
computed R2 values of fit of the model were obtained ≥0.99 for
Physical extraction is expressed as: reactive extraction using extractant in toluene. Therefore, the
developed model is adequate in representing the equilibrium
S mechanism of morpholine extraction.
Maq ↔Morg (6)
The stoichiometry of the overall extraction reaction gen-
erally depends on the loading ratio in the organic phase, Z
CMorg
S= (7) given in supporting Eq. (9). In the present study, in most of the
CMaq
cases the organic phase is not highly concentrated i.e. loading
ratios (Z < 0.5), it is expected that the 1:1 complex is formed.
CMorg qCm1 sCM It is apparent that 1:1 amine–acid complex is formed in the
KD = = + (8)
CM + CMH+ CM + CMH+ CM + CMH+ organic phase, as the loading ratio decreases with increas-
248 Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254
Table 2 – Values of equilibrium complexation constants (kE ), reacting molecules (m) and physical extraction constant (S)
with CA as extractant in toluene with different concentrations of morpholine.
CA (kmol m−3 ) kE m S SD CMO (kmol m−3 ) kE m S SD
o
0.29 7.96 1.13 0.13 0.26 0.057 3.64 1.00 0.19 0.14
0.41 3.04 0.90 0.13 0.25 0.143 3.96 1.11 0.14 0.27
0.58 2.24 1.02 0.13 0.27 0.316 3.92 1.18 0.12 0.25
0.75 2.07 0.96 0.13 0.24 0.459 4.11 0.94 0.10 0.26
0.87 2.06 0.97 0.13 0.18 0.574 4.17 1.03 0.10 0.29
R2 = 0.993, Pred R2 = 0.888, Adj R2 = 0.984, adequate precision = 35.37, C.V% = 3.64, std. dev = 1.42.
significant. It was observed that the first order terms TPCi complex at the interface of aqueous and organic phases. The
manifested the highest significance with a total contribution disturbed interaction of CA and morpholine exhibits lesser %E
of 94.1%, followed by quadratic terms TPCii with a total con- (Kumar et al., 2011). The extraction decreases with increase
tribution of 3.31% and then the interaction terms indicative in feed concentration at a constant extractant concentration
of the least level of significance with a total contribution of (CA) of 0.29 kmol m−3 . It was illustrated in Fig. 7b that at a
2.58. % to the extraction efficiency. It is evident from bar graph fixed temperature 303.15 K, with an increase in extractant
that the initial feed (B) showed the highest level of significance concentration (CA) %E increases, however it decreases with
with a contribution of 39.05%, making temperature being the increase in feed concentration. For a constant feed concentra-
second factor with 29.29% followed by extractant concentra- tion 0.06 kmol m−3 , %E decreases with increase in temperature
tion with 25.74% in first order terms as compared to other and increases with increase in extractant concentration (CA)
components for %E. as shown in Fig. 7c.
4.4.1. Interaction effect of process parameters: response 4.5. Multi-response optimization using desirability
surface plots function
The 3-D plots illustrated in Fig. 7 facilitate an examination
of interactive effects of parameters on response, which pro- The lower and upper limit values concerning all the
vides valuable information about the behavior of the system responses in the multivariate optimization employing desir-
within the experimental design. From surface plots, it can be ability approach were considered and given in supporting
observed that the interactions of AC, BC have a significant Table S4. The larger-the-better (LTB) funtions of the stan-
effect towards response (%E), whereas the interaction AB is dard desirability was used for the optimization of extraction
undermined concerning the statistical significance. The max- of morpholine. To achieve this, the importance of each goal
imum separation of morpholine is indicated by the surface was adjusted with respect to other goals (Islam et al., 2009).
confined in the smallest curve of the plot with the other vari- As the initial feed concentration contributes significantly to
ables maintained at zero levels. From Fig. 7a it can be found the responses, the goal was assigned as “maximum” with
that as temperature increases, the %E decreased from 56 to the respective importance of 5, as the higher concentration
38.9%. The increase in temperature results in an increase in is mainly favored in the extraction system. Under these set-
the thermal energy which interrupts the probable interac- tings and boundary condition, multivariate optimization was
tions between morpholine and CA to form a stable acid–amine conducted.
250 Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254
Fig. 7 – 3 D response surface plots (a) AB with %E (b) BC with %E (c) ACwith %E.
By seeking from 54 starting points in the response surface Since the solubility of extractant (the reactive component in
changes, the best optimum condition with overall maximum organic phase) is negligible in the aqueous phase, whereas
desirability was shown in Fig. 8. The best optimum conditions morpholine (the reactive component in the aqueous phase)
were achieved at a temperature (A) of 313.15 K, initial feed con- has a significant solubility in the organic phase (in diluent),
centration (B) of 5%, and an extractant concentration (C) 5% resistance to mass transfer is determined by interfacial chem-
with desirability of 0.947. ical kinetics and molecular diffusion of components towards
The experiment was perfomed for the confirmatory run at and away from the interface.
optimized conditions and the results obtained were %E: 35.5,
Z: 0.80 which were in reasonable agreement with the predicted
ones %E: 38.15 Z: 0.65. 4.6.1. Physical mass transfer coefficient (kL )
Physical mass transfer coefficient, kL is essential for con-
firming the extraction regime. Because of high distribution
4.6. Kinetics investigation coefficient between morpholine and water system, the aque-
ous diffusion film resistance was neglected, and only the
Reactive extraction of morpholine using CA involves the prin- resistance of organic diffusion film was considered. The trans-
ciple of mass transfer accompanied by a chemical reaction. fer of morpholine molecules from the aqueous phase to the
Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254 251
organic phase, the mass transfer rate (molar flux) was given
by:
Vorg dCorg
= kL C∗org − Corg (13)
A dt
4.6.2. Effect of process parameters on the initial rate of Fig. 11 – Effect of phase volume ratio (Vorg /Vaq ) on initial
extraction, RA rate of extraction, RA . N = 1 rev.s−1 , CMO = 0.06 kmol·m−3 ,
As explained by Doraiswamy and Sharma (1984), the effects CCAO = 0.29 kmol m−3 , T = 303.15 K.
of the volume ratio of the phases (Vorg /Vaq ), the speed of
agitation, initial feed concentration and extractant concentra- As shown in Fig. 10, there is no effect of agitation speed on
tion (CA) on the specific rate of extraction must be examined RA concluded that the extraction of morpholine is governed by
to determine the reaction regime. Therefore, the experi- the kinetic control regime in the stirring speed range investi-
mental data were collected to calculate the specific rate gated. And the chemical reaction between morphine and CA
of extraction in a stirred reactor with varying parameters in toluene in stirred cell reactor falls under either regime 1
viz. speed of agitation for 1.0–1.5 rev.s−1 , initial feed con- (very slow) or regime 3 (fast). In this range of agitation speed
centration of 0.06–0.57 kmol m−3 , initial CA concentration of the liquid–liquid interface was flat and the interfacial area is
0.29–0.87 kmol m−3 in toluene and volume ratio of the phases equal to cross sectional area of the stirred cell (Rani et al.,
at Vorg /Vaq of 1:0.8–1:2. The reaction regime was established by 2010).
discerning mechanism proposed by Doraiswamy and Sharma
(1984) as described in Table S1. 4.6.2.2. Effect of phase volume ratio (Vorg /Vaq ). The effect of
phase volume ratio on RA for reactive extraction of morpholine
4.6.2.1. Effect of agitation speed (N). Effect of stirring speed with CA in toluene was evaluated to differentiate between the
was verified to identify the contribution of mass transfer regime 1 and 3. The volume ratio of organic to aqueous phase
to the overall extraction regime. If the rate enhances with was varied in the range of 1:0.8–1:2 at a constant stirring of
stirring speed, diffusion governs the extraction process and 1 rev.s−1 .
the boundary layer thickness on each side of the interface The plot illustrated in Fig. 11 showed the independency of
decreases. Whilst, if the mass transfer rate is independent the phase volume ratio on the specific rate of extraction RA ,
of the stirring speed, the extraction process is under kinetic since the bulk of the volume does not involve in the rate of
control regime. To examine the hydrodynamic effects, the agi- extraction as the reaction mostly happens in a narrow region
tation speed varied from 1.0 to 1.5 rev.s−1 , while keeping in close to the interface (Marti et al., 2011). This demonstrates
view of accomplishing the absolute renewal of surface (Tang that the reaction between morpholine and CA falls in regime 3
et al., 2012). While, the agitation speed less than 1.0 rev.s−1 , i.e., extraction accompanied by a fast chemical reaction occur-
RA values were very low, which is probably due to the partial ring in the diffusion film. Very slow reaction regime, regime 1
renewal of the surface, resulting in a mass transfer resistance- is mass transfer independent and thus regime 1 is improbable
controlled regime (Marti et al., 2011). in the present case (Gadgil et al., 2014).
252 Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254
The first order reaction rate constant was calculated from The effect of temperature is an important study in the view
Fig. 12, for m = 1 and n = 0 the governing rate equation for the of operating temperature in the regeneration step, which is
initial rate of extraction reduced to: attributed to the consequence of different parameters like
the pKa value, the amine-acid interaction, the solubility of
RA = [C]∗Morg DAB k1 (14) the solute in phases, the extractant properties, and water co-
extraction (Eda et al., 2017). If it is assumed that the entropy
The experimental data were fitted to the above equa- and enthalpy of the reaction between morpholine and CA are
tion to obtain the value of the first order rate constant, k1 constant, the KE is related to temperature using Vantoff’s equa-
and found to be 6.30 s−1 . Diffusion coefficient (DAB ) was esti- tion (Thella et al., 2011).
mated using Hayduk and Minhas equation and found to be
DAB = 1.92 × 10−9 m2 s−1 (Reid et√al., 1987). For m = 1 and n = 0, H S
lnKE = − + (15)
DAB k1 RT R
Hatta number reduces to MH = kL
for non-aqueous (non-
electrolyte) system, where physical mass transfer coefficient A plot lnKE between and T−1 gave a straight line in
−6 m s−1 .
kL value is obtained from Fig. 9 with a value of 4.4 × 10√ Fig. 14, the slope and intercept represent the enthalpy and
D k
In order to confirm the reaction regime 3, the value of kAB 1 > entropy of extraction of morpholine. The results indicate that
L
3 as per the guidelines provided by Doraiswamy and Sharma amine–acid complex formed at the interface of phases is
(1984). The condition was satisfied for regime 3 i.e. the extrac- exothermic in nature since H found to be −58.21 kJ mol−1 .
tion accompanied by a fast chemical reaction taking place This is in agreement with the fact that hydrogen bond for-
in the diffusion film. The morpholine solubility in toluene is mation in complex is an exothermic reaction (Bokhove et al.,
quite high, whereas the DA solubility in water is not much 2012).
significant. This confirms that the reaction occurred in the The more exothermicity of the reaction, most sensitive of
organic diffusion film and RA is independent of staring speed the equilibrium to changes in the temperature. And, S was
Chemical Engineering Research and Design 1 3 3 ( 2 0 1 8 ) 243–254 253
found to be −187.8 J mol−1 K−1 . From a thermodynamic point Bokhove, J., Schuur, B., de Haan, A.B., 2012. Equilibrium study on
of view, the decrease in entropy with temperature pronounces the reactive liquid–liquid extraction of 4-cyanopyridine with
4-nonylphenol. Chem. Eng. Sci. 82, 215–222.
that the formation of the acid–amine complex makes the reac-
Chai, W., Zhu, X., Liu, W., Zhang, W., Zhou, Z., Ren, Z., 2016.
tive extraction system more ordered and thus reduces the
Extraction of aniline from wastewater: equilibria, model, and
system’s entropy and randomness (Robin et al., 2016). fitting of apparent extraction equilibrium constants. RSC Adv.
6, 6125–6132.
6. Conclusions Eda, S., Kumari, A., Thella, P.K., Satyavathi, B., Rajarathinam, P.,
2017. Recovery of volatile fatty acids by reactive extraction
using tri-N-octylamine and tri-butyl phosphate in different
A comprehensive study of extraction equilibrium of morpho-
solvents: equilibrium studies, pH and temperature effect, and
line in aqueous phase along with modeling and optimization
optimization using multivariate Taguchi approach. Can. J.
of the reactive extraction process was carried out. Further, Chem. Eng. 95, 1373–1387.
kinetic studies were explored in the present study. The extrac- Datta, D., Kumar, S., 2013. Equilibrium and kinetic studies of the
tions of morpholine (0.06–0.57) kmol m−3 from the aqueous reactive extraction of nicotinic acid with tri-n-octylamine
phase using capric acid, CA (0.29–0.87) kmol m−3 diluted in dissolved in MIBK. Ind. Eng. Chem. Res. 52, 14680–14686.
toluene have been carried out. Physical extraction revealed Datta, D., Kumar, S., Uslu, H., 2014. Status of the reactive
extraction as a method of separation. J. Chem. 2014, 1–16.
that the extraction mainly happened through the parti-
Doraiswamy, L.K., Sharma, M.M., 1984. Heterogeneous Reaction:
tion of undissociated morpholine to the organic phase and Analysis, Examples, and Reactor Design, vol. 2:
decrease with increase in temperature due to weakening of Fluid-Fluid-Solid-Reactions., 1st ed. John Wiley & Sons, New
–H complex. While, the chemical extraction is dominated by York, pp. 17–41.
complex formation due to H-bonding of undissociated amine Gadgil, O.D., Dalvi, V.H., Shenoy, K.T., Rao, H., Ghosh, S.K., Joshi,
molecules with CA attributed to the fact pH > pKa . A reac- J.B., 2014. Kinetics of extraction of uranium from phosphoric
acid by D2EHPA–TBP and D2EHPA–TOPO systems using
tive extraction model signifies that the physical extraction
constant interfacial area stirred cell. Chem. Eng. Sci. 110,
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employing desirability approach. It showed good correla- the removal of organo phosphorus pesticide from aqueous
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temperature 30 ◦ C and extractant concentration 5% with Kumar, S., Datta, D., Babu, B.V., 2011. Estimation of equilibrium
38.15% (extraction efficiency) and 0.64 (loading ratio) with a parameters using differential evolution in reactive extraction
desirability value of 0.947. Kinetic studies revealed that reac- of propionic acid by tri-n-butyl phosphate. Chem. Eng.
tion between morpholine and capric acid in toluene falls in Process. 50, 614–622.
Thella, P.K., Vishwanadham, B., Rani, K.N.P., Mallikarjun, M., Rao,
regime 3 (fast chemical reaction occurring in the organic dif-
V.V.B., 2011. Reactive extraction of levulinic acid from aqueous
fusion film). Thermodynamic study has demonstrated that solutions with tri-n-octylamine (TOA) in 1-octanol: equilibria,
amine–acid complex formed at the interface of phases is kinetics, and model development. Chem. Eng. Commun. 198,
exothermic and makes the extraction process more ordered. 572–589.
From the above results, it can be concluded that extractant; Kumari, A., Aniya, V., Rane, N.V., Thella, P.K., Satyavathi, B., 2017.
CA dissolved in toluene was efficient for the extraction of a Isobaric phase equilibrium of morpholine + 1-decanol,
volumetric properties and molar refractivity from 293.15 to
basic compound in aqueous waste stream based processes
333.15 K of morpholine + 1-decanol and 1-octanol + toluene
and the equilibrium and kinetic data might be useful for the
system with applications of Prigogine–Flory–Patterson theory.
development, design and reliable scale-up of the acid extrac- Thermochim. Acta 649, 41–53.
tion process. Also, a novel optimization technique for design Lee, T.G., Lim, S.Y., Song, K.H., Choe, J., 2014. Liquid–liquid
variables in the reactive extraction process introduces the equilibria for the ternary systems of
new era of multi-response optimization based on desirability 4-methyl-1,3-dioxolan-2-one + 1,4-dimethylbenzene + octane,
approach. decane, or dodecane and the ternary systems of
acetonitrile + morpholine + octane, decane, or dodecane at
313.15 K or 298.15 K. J. Chem. Eng. Data 59, 890–895.
Appendix A. Supplementary data Marti, M.E., Gurkan, T., Doraiswamy, L.K., 2011. Equilibrium and
kinetic studies on reactive extraction of pyruvic acidwith
Supplementary data associated with this article can be trioctylamine in 1-octanol. Ind. Eng. Chem. Res. 50,
found, in the online version, at https://doi.org/10.1016/ 13518–13525.
McGuire, R.G., Dimitrios, D.A., 1999. Evaluation of shellac and
j.cherd.2018.03.027.
sucrose ester fruit coating formulations that support
biological control of post-harvest grapefruit decay. Biocontrol
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