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Date (Web): January 22, 2013 | doi: 10.1021/ie302267s Article pubs.acs.org/IECR Kinetics of Mixed Ethanol/ n ‑
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Article

Kinetics of Mixed Ethanol/ nButanol Esteri cation of Butyric Acid with Amberlyst 70 and pToluene Sulfonic Acid

Arati Santhanakrishnan, Abigail Shannon, Lars Peereboom, Carl T. Lira, and Dennis J. Miller *

Department of Chemical Engineering and Materials Science, Michigan State University, 2527 Engineering Building, East Lansing, Michigan 48824-1226, United States

ABSTRACT: Esteri cation of butyric acid with ethanol, n -butanol, and ethanol/ n-butanol mixtures was studied using Amberlyst 70 cation-exchange resin and homogeneous p -toluene sulfonic acid as catalysts. The kinetics of individual alcohol esteri cation were rst examined in batch reactions at dierent temperatures and catalyst loadings, and then esteri cation in ethanol/ n -butanol mixtures of varying concentration ratios was characterized. Both nonideal solution and ideal solution kinetic models were developed. These models accurately predict the esteri cation of butyric acid by the individual alcohols; a simple additive combination of the individual alcohol esteri cation kinetics properly describes mixed alcohol esteri cation, indicating that the alcohols do not compete with each other or inhibit esteri cation when present together. When solution density is included in the kinetic rate expression to account for the actual concentration of OH groups in ethanol and n-butanol, butyric acid esteri cation kinetics with the two alcohols are described by a common rate constant. This rate constant also predicts butyric acid esteri cation kinetics with other alcohol combinations, suggesting a generalized esteri cation rate constant for simple alcohol esteri cation of butyric acid over Amberlyst 70 catalyst. These results provide signi cant predictive capabilities for simulating processes such as reactive distillation processes for mixed alcohol esteri cation.

capabilities for simulating processes such as reactive distillation processes for mixed alcohol esteri fi cation.

1. INTRODUCTION

The growing need to reduce dependence on fossil sources for fuels and chemicals has led to exploration of pathways for their manufacture from renewable sources. Esters of higher alcohols (alcohols with more than two carbons) are one such industrially important class of compounds, and economically viable processes for making them need to be designed. Blends of esters are being considered as attractive solvents or additives to biofuels because of their high energy density and favorable fuel properties. The most common route for producing esters is direct esteri cation of carboxylic acids with alcohols 1 using either homogeneous acid catalysts such as sulfuric acid or p- toluene sulfonic acid ( p -TSA) or solid heterogeneous acid catalysts such as cationic exchange resins. Mixed alcohol streams from biomass can be obtained in several ways: from condensation of lower alcohols to higher alcohols via the Guerbet reaction, 2 4 via Fischer Tropsch synthesis of alcohols from synthesis gas, 5 8 or from fusel alcohols 9 produced in ethanol fermentation. Esteri cation for biofuel or solvent applications is an attractive use of these mixed alcohol streams, as it would lead to value-added products without the need for separation into individual components. Simultaneous esteri cation with multiple alcohols is described in the patent literature. 10 13 Since esteri cation reactions are thermodynamically limited, reactive distillation is a viable option for mixed alcohol processing. 14,15 In simulations of reactive distillation, ester- ication of a mixture of amyl alcohol and n -butanol with acetic acid has been examined to compare separation- rst and reaction- rst schemes. 16 Reaction- rst schemes were deter- mined to be more economical. Design of such reactive distillation schemes for mixed alcohols requires a good understanding of the kinetics of the reaction system, as it is generally not known whether the presence of one alcohol

is generally not known whether the presence of one alcohol © 2012 American Chemical Society accelerates

© 2012 American Chemical Society

accelerates or inhibits the rate of reaction of another, or if formation of mixed esters leads to transesteri cation that could overcomplicate the recovery process. Recent advances in producing butyric acid via fermentation of biomass carbohydrates has sparked interest in using butyric acid as a building block via esteri cation and other reactions. 17 Apart from their potential as biofuel components, ethyl butyrate and n -butyl butyrate serve as food avoring agents and green solvents. 18 The kinetics of n -butyl butyrate formation using Dowex 19 as an esteri cation catalyst has been previously studied and modeled using quasi-homogeneous, EleyRideal, and Langmuir Hinshelwood rate models. The kinetics of ethyl butyrate formation have not been previously reported. In this study, the kinetic behavior of butyric acid esteri cation with mixed ethanol and n -butanol (Scheme 1) is investigated using homogeneous (p -TSA) and heterogeneous (Amberlyst 70 ion-exchange re sin) catalysts. Kinetics of individual ethanol and n -butanol esteri cation reactions are rst presented, and the results are then used to predict kinetics of butyric acid esteri cation with ethanol/ n -butanol mixtures of varying compositions. The results provide the capability to predict butyric acid esteri cation reaction kinetics with any simple alcohol, a useful result for biore nery process design.

2. MATERIALS AND METHODS

2.1. Materials. Reagent-grade ethanol (200 Proof, Decon Laboratories, Inc., King of Prussia, PA), n-butanol (99.9%, Sigma Aldrich Corp., St. Louis, Missouri), n -butyl butyrate

1845

Received: August 23, 2012

Revised: November 15, 2012

Accepted: December 28, 2012

Published: December 28, 2012

dx.doi.org/10.1021/ie302267s | Ind. Eng. Chem. Res. 2013, 52, 1845 1853

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Scheme 1. Esteri cation of Butyric Acid with Ethanol and n-Butanol

fi cation of Butyric Acid with Ethanol and n -Butanol Table 1. Summary of Experiments and

Table 1. Summary of Experiments and Conditions

 

molar feed ratios

 

run

temp. ( ° C)

catalyst

ethanol:acid

n -butanol:acid

solution density ( ρ) (kmol m 3 )

catalyst loading (kg cat./kg soln)

1

60

A-70

4.3

14.9

0.0100

2

80

A-70

2.8

15.0

0.0101

3

100

A-70

8.7

15.0

0.0075

4

120

A-70

6.6

14.9

0.0099

5

60

A-70

3.7

10.9

0.0096

6

80

A-70

4.4

10.9

0.0101

7

100

A-70

4.5

10.9

0.0101

8

120

A-70

3.3

10.9

0.0115

9

60

A-70

0.5

4.7

14.9

0.0109

10

60

A-70

2.6

2.6

12.8

0.0085

11

60

A-70

0.9

4.2

11.5

0.0099

12

80

A-70

1.5

1.7

12.6

0.005

13

80

A-70

4.5

3.9

12.9

0.0105

14

80

A-70

2.0

1.9

12.6

0.0077

15

80

A-70

0.8

3.8

11.5

0.0093

16

80

A-70

1.9

2.2

12.6

0.0196

17

80

A-70

0.6

3.0

11.5

0.0097

18

60

p-TSA

2.9

14.8

0.0012

19

80

p-TSA

2.8

14.9

0.0013

20

100

p-TSA

3.7

15.0

0.0012

21

120

p-TSA

3.7

15.0

0.0013

22

60

p-TSA

2.0

10.9

0.0013

23

80

p-TSA

3.0

10.9

0.0013

24

100

p-TSA

2.8

10.9

0.0014

25

120

p-TSA

3.7

10.9

0.0013

26

60

p-TSA

0.4

1.8

11.4

0.0012

27

60

p-TSA

3.6

3.3

13.0

0.0013

28

60

p-TSA

5.0

1.0

14.4

0.0013

29

80

p-TSA

0.5

2.7

11.4

0.0013

30

80

p-TSA

1.9

1.9

12.6

0.0014

31

80

p-TSA

3.7

0.9

14.0

0.0014

(>98%, Sigma Aldrich Corp., St. Louis, MO), ethyl butyrate (>99%, Sigma Aldrich Corp., St. Louis, MO), water (HPLC solvent, JT Baker Reagent Chemicals. Phillipsburg, NJ), p- toluene sulfonic acid monohydrate (Spectrum Quality Prod- ucts, Inc., Gardena, CA), butyric acid (>99%, natural, Sigma Aldrich Corp., St. Louis, MO), acetonitrile (HPLC grade, Emanuel Merck Damstadt Chem icals, Philadelphia, PA), methanol (Sigma Aldrich Corp., St. Louis, MO), and ethyl octanoate (Sigma Aldrich Corp., St. Louis, MO) were used without further puri cation. Gas chromatographic (GC) analysis of the aforementioned chemicals showed no signi cant presence of impurities except trace amounts of water. Hydranal-

coulomat E solution (Riedel-de Haen,̈ Seelze, Germany) was used in Karl Fischer titrations. Helium (99.995%, AirGas, USA) was used as carrier gas for GC. The properties of the heterogeneous cation-exchange resin catalyst Amberlyst 70 (Dow Chemical Co., Midland, MI) are reported in the literature. 20 2.2. Heterogeneous Catalyst Conditioning. As-received Amberlyst 70 (A-70) was sieved in a series of US-standard sieves (Dual Manufacturing Co., Chicago, IL), and the 45 + 60 mesh (0.25 0.35 mm diameter) fraction was used in kinetic experiments. The resin was washed with methanol multiple times until the supernatant liquid was colorless and then ltered

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to remove excess methanol. The resin was then dried in an oven at 373 K for 2 days. The dried resin was stored in a sealed container in a desiccator and removed in required amounts for reactions. Fresh catalyst was used for each experiment. To nd the ion-exchange capacity of the catalyst, a known quantity of dry A-70 was submerged in ethanol for 4 5 h and then titrated with NaOH. The average ion-exchange capacity was found to be 2.35 ± 0.1 equiv of H + /kg, in reasonable agreement with the value reported by the manufacturer. 20 2.3. Kinetic Experiments. Isothermal kinetic experiments were carried out in 75 mL batch reactors in a Parr 5000 Multireactor system (Parr Instrument Co., Moline, IL). The reactor system is equipped with temperature and stirring speed control and with a dip tube on each reactor to collect liquid samples during reaction. The end of the dip tube is tted with a 2 μ m stainless steel lter to avoid withdrawing solid catalyst along with liquid sample. To begin an experiment, ethanol and n -butanol were weighed out alone or in predetermined molar ratios and added to the reactor with a known amount of catalyst (A-70 for heterogeneous catalysis and p -toluene sulfonic acid for homogeneous catalysis). The reactor was sealed and heated until it stabilized at the desired reaction temperature. Stirring was set to 800 rpm unless otherwise speci ed. Once the desired temperature was reached, a specied amount of butyric acid was added to the reactor through the sample port in a single shot; the moment of addition was taken as time zero of the reaction. Total reactant weight came up to approximately 0.040 kg per reaction. Samples of 0.5 1 mL were withdrawn at specied time intervals during the kinetic regime (06 h) using 3 mL Luer-Lok tip syringes (Becton Dickson and Co., Franklin Lakes, NJ) and stored in hermetically sealed vials in a standard refrigerator at 277 K. Samples to characterize reaction equilibrium were taken 24 48 h after the start of reaction. 2.4. Analysis. The initial water concentration in the reactants was determined by Karl Fischer titration in an Aquacounter coulometric titrator AQ-2100 (JM Science Inc., Grand Island, NY) and taken into account in calculations. Analysis of reaction samples was carried out in a Varian 450 gas chromatograph out tted with a thermal conductivity detector (Varian Medical Systems Inc., Palo Alto, CA). Reaction samples were diluted 10-fold in acetonitrile containing 11.11 wt % ethyl octanoate as an internal standard. Separation was done on a 0.53 mm i.d, Aquawax-DA 30 m capillary column with 1.0 μ m lm thickness. Helium carrier gas ow rate was set to 10 mL min 1 . The following temperature program was used: initial column temperature 313 K for 2 min, ramp at 10 K min 1 to 423 K, ramp at 30 K min 1 to 503 K, hold 2 min. Detector temperature was held at 513 K. Standards of known composition in the range of interest were prepared and run in the chromatograph before and after reaction samples to calibrate the response factor of each component of the reaction.

3. RESULTS

A list of all experiments conducted along with their conditions (temperature, initial reactant molar ratio, weight fraction of catalyst) is given in Table 1. Control experiments to investigate autocatalysis of the reaction showed negligible rates over the temperature range studied. Although etheri cation side reactions have been observed in other studies involving the esteri cation of n -butanol 7,13 and ethanol 8 at temperatures above 386 K, no ethers (di- n -butyl ether, diethyl ether, or ethyl n -butyl ether) were observed in the reaction samples in this

study. This is because low loadings of catalyst ( 0.1 wt % p - TSA and 1 wt % A-70), low ratios of alcohol to acid (3:1 6:1), and relatively low temperatures were used in the experiments. 3.1. Mass Transfer Considerations. Accurate character- ization of reaction kinetics requires that experiments be conducted in the kinetic regime, i.e., at conditions where

external and internal mass transfer resistances do not a ect the reaction rate. Preliminary experiments at varying stirring speeds showed that conversion rates were una ected above 600 rpm, implying that the external mas s transfer resistances are negligible at a stirring speed of 800 rpm. To estimate the in uence of intraparticular mass transfer resistance in the heterogeneous catalyst reaction, the Weisz Prater criterion was

used.

21

The observable modulus was rst calculated by eq 1

ϕ =

w

( r ) ρ

obs

*

d

6

CAT

p

D C

eff

BA

2

(1)

where r * obs is the observed rate of reaction per weight of

catalyst, ρ CAT is the density of catalyst (assumed to be 1000 kg

m 3 ), C BA is the liquid-phase concentration of butyric acid, the swelled diameter of catalyst at reaction conditions (eq 2)

is

d p

d p

= d

p,dry

×

V p,swollen 3 V p,dry
V
p,swollen
3
V
p,dry

(2)

where d p is 0.30 mm and V p,swollen /V p,dry is determined from a simple measurement to be 2.0 for both alcohols. The eective di usivity D eff of butyric acid in alcohol is estimated in eq 3, where pore tortuosity τ is assumed to be equal to the inverse of particle porosity ε, and D BA is bulk di usivity of butyric acid in alcohol estimated from the Wilke Chang equation

22

DD

eff

=

BA

ε

τ

=

D

BA

ε

2

(3)

The Thiele modulus ( φ) and e ectiveness factor ( η ) for butyric acid esteri cation are calculated from the observable modulus ϕ w = ηφ 2 assuming the reaction is pseudo- rst order in butyric acid (i.e., excess alcohol) and thus η = ((tanh( φ))/( φ)). Values of η were evaluated for butyric acid in each of the alcohols (Table 2) and found to be 0.93 and 0.96 for ethanol and n - butanol esteri cation, respectively. These values of η indicate that intraparticular resistances can be neglected. 3.2. Reaction Equilibrium Constants. The equilibrium constant for a given experiment was estimated by determining the unchanging composition of the reaction solution after 24

Table 2. Intraparticle E ectiveness Factors for A-70- Catalyzed Butyric Acid Esteri cation

 

molar feed ratio

 

run

temp. ( ° C)

ethanol:acid

n -butanol:acid

η

1

60

4.3

0.99

2

80

2.8

0.99

3

100

8.7

0.99

4

120

6.6

0.98

5

60

3.7

0.99

6

80

4.4

0.98

7

100

4.5

0.98

8

120

3.3

0.98

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Industrial & Engineering Chemistry Research Article Figure 1. van ’ t Ho ff plots for equilibrium

Figure 1. vant Ho plots for equilibrium constants of ethanol and n -butanol esterication of butyric acid: ( ) ethanol ideal solution; ( ) ethanol activity based; ( ) n -butanol ideal solution; ( ) n -butanol activity based. Error bars for each temperature represent one standard deviation.

48 h of reaction. The activity-based equilibrium constant K a,m for reaction m is given in eq 4.

K

a,

m

=

KK

xm ,

γ ,

m

=

N

C

i = 1

( x γ )

i

i

ν

i , m

E

Q

(4)

Here x i , γ i , and v i,m represent the equilibrium mole fraction, activity coe cient at equilibrium, and stoichiometric coecient, respectively, of component i in the reaction mixture. The mole- fraction-based equilibrium constants ( K x ,m ) were calculated directly from the equilibrium composition of the reaction mixture. The ratio of activity coe cients ( K γ ,m ) accounts for deviation from ideal behavior; values of activity coe cients were estimated using UNIFAC (universal functional activity coecient). 23 The experimental values of K x and K a for butyric acid esteri cation with ethanol and n -butanol with A-70 ion- exchange resin or p -TSA as catalyst are presented together in Figure 1. Consistent values of the equilibrium constants were observed with both catalysts. Scatter in the values of the equilibrium constant is a result of uncertainty arising from the necessity measuring the concentration of every species (including water) participating in the reaction at the equilibrium state. The enthalpy of reaction ( Δ H r ), obtained from the slope of the trend line in Figure 1, is +18 kJ for ethanol and +12 kJ for n -butanol esteri cation of butyric acid, indicating that the reactions are mildly endothermic. Although previous studies have reported temperature-independent values of equilibrium constants in kinetic models, 19 here the data in Figure 1 were used to calculate temperature-dependent equilibrium constants in the kinetic model described below. 3.3. Kinetic Model Description. In a batch reactor, the change in number of moles N i of component i participating in M reactions can be expressed as

d N

i

d t

=

N T

d x

i

d t

=

(

M

θ

r

imm ,

1

)

V

(5)

where N T is the total number of moles in the reactor, M is the number of reactions in the system, V is the reaction volume, r m

is the rate of reaction m per unit volume, and x i is the mole fraction of component i in the liquid mixture. The parameter θ i,m is the ratio of stoichiometric coe cients of component i

with respect to the reference component in reaction m .

For this esteri cation system, eq 5 can be expressed in terms of total molar density of the liquid phase ( ρ = N T /V ) because the total number of moles is conserved and the reaction volume is constant during reaction.

d x

i

1 (

ρ

d t

=

M

1

θ

r

imm

,

)

(6)

The rate of formation of ester in reaction m , r m , is based on the law of mass action (e.g., a power lawmodel) with the driving force for the reversible reaction described in terms of species activity ( a i = x i γ i ), re ecting the role of chemical potential in describing reaction equilibrium. For esteri cation in neat mixtures of reactants (e.g., no solvent) that constitute a nonideal liquid phase, the activity of each species is multiplied by solution density to account for the absolute concentration of each species (OH and COOH) in the reaction mixture. This inclusion of solution density is necessary to compare reaction rates for dierent alcohol acid combinations because the molar concentration of OH groups decreases as alcohol molecular weight increases (Table 1). This approach has been previously de ned and used for liquid-phase reactions. 24,25 The rate of formation ( r m ) of butyrate ester (BE) in reaction m can be expressed in terms of the activity of butyric acid (BA), alcohol (OH), butyrate ester (BE), and water (W), w CAT , the catalyst loading in the reaction mixture, ρ, the total molar density of the reacting uid, k 0,m , the pre-exponential factor, and E a,m , the activation energy of the rate constant for reaction m .

r

m

=

exp

w

CAT

ρ

0,

m

x

BE

γ

BE

x

W

γ

W

K

a, m

2 k

E

⎟ ⎡ ⎢ x γγ

BA

BA

x

OH

OH

a, m

RT ⎠ ⎢

(7)

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Table 3. Optimized Kinetic Parameters with 95% Con dence Limits and Equilibrium Constants from Experimental Data ( T in Kelvin)

 

ethanol

n -butanol

parameter

ideal

activity

ideal

activity

K a Amberlyst 70 k o ((kg soln ·m 3 )/ (kg cat. ·s ·kmol)) E a (kJ/kmol) p -toluenesulfonic acid k o ((kg soln ·m 3 )/(kg cat. ·s· kmol)) E a (kJ/kmol)

exp(8.18 2654/T)

exp(8.85 2207/T)

exp(7.50 2339/T)

exp(6.88 1365/T)

4.1 ± 0.5 × 10 3

6.2 ± 1.6 × 10 3

6.8 ± 1.4 × 10 3

11.9 ± 0.5 × 10 3

45 900 ± 3400

47 300 ±

6100

46 800

± 290

48 300 ± 155

22.9 ± 1.4 × 10 3

26.2 ± 1.7 × 10 3

21.3 ± 2.6 × 10 3

71.8 ± 6.8 × 10 3

44 900 ± 182

45 200 ± 192

44 900

± 375

48 300 ± 300

By inserting the appropriate rate expression (eq 7), eq 6 can be written for every species in the reaction mixture to give a set of ordinary di erential equations describing the esteri cation system. For the individual ethanol butyric acid system and the n -butanolbutyric acid system, these equations were integrated numerically and reaction parameters determined using the functions nlint and ode23 from the optimization toolbox in Matlab 7.12.0. Both the activity-based model described above and an ideal solution model with all activity coecients γ i set to unity were regressed to give rate parameters for the individual reactions. Optimization was done by minimizing F min , where F min 2 is de ned (eq 8) as the sum of squared di erences between calculated ( x icalcd ) and experimental ( x iexp ) species mole fractions for all species in all esteri cation reactions conducted.

2

min

F

=

1

n

samples

N

C

i

=

1

(

x

i

exp

x

i

calcd

)

2

(8)

In eq 8, n is the number of experimental samples withdrawn in all experiments regressed and N c is the number of reacting components in those experiments. Optimized kinetic parameters with 95% condence limits are reported in Table 3 for ethanol butyric acid and n -butanol butyric acid esteri cation with A-70 and p -TSA catalysts. The activation energies in Table 3 are in the expected range of values (45 ± 10 kJ mol 1 ) for esteri cation of small aliphatic carboxylic acids with aliphatic alcohols. The temperature- dependent expression for the thermodynamic equilibrium constant K a is reported for each reaction in Table 3. A comparison of the experimental and predicted mole fraction pro les for individual alcohol esteri cation is given in Figure 2 for A-70 heterogeneous catalyst and in Figure 3 for p- TSA homogeneous catalyst. It can be seen that the kinetic model ts the individual alcohol esteri cation reactions reasonably well. The kinetic parameters reported in Table 3 for individual ethanol butyric acid and n -butanol butyric acid esteri cation reactions were combined, without adjustment or additional regression, to model the mixed ethanol/ n -butanol esteri cation of butyric acid. Comparison of both ideal solution and nonideal activity-based model predictions of mixed alcohol esteri cation with experimental data for several experiments is shown in Figure 4 for A-70 catalyst and Figure 5 for p -TSA. These plots clearly show that the simple combined model ts the experimental data well. The average deviation of the kinetic model prediction from experimental data at a given data point is described in eq 9.

data at a given data point is described in eq 9. Figure 2. Experimental and predicted

Figure 2. Experimental and predicted concentration pro les of individual ethanol and n -butanol esteri cation in the presence of 1 wt % A-70: (a) run 2 (ethanol, T = 80 ° C); (b) run 5 ( n -butanol, T = 60 ° C). ( ) Ideal solution model prediction; (---) activity-based model predictions; ( ) butyric acid; ( ) ethanol; ( ) ethyl butyrate; ( × ) water; ( ) n -butanol; () n -butyl butyrate.

f

ABS

=

1

N n

c

N

C

|−

x

i

exp

samples

i

=

1

x

i

calcd

|

(9)

For ethanol butyric acid esteri cation, the average deviation per data point over all experiments with A-70 was 0.012 and

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Industrial & Engineering Chemistry Research Article Figure 3. Experimental and predicted concentration pro fi

Figure 3. Experimental and predicted concentration pro les of individual ethanol and n -butanol esterication in the presence of 0.1 wt % pTSA: (a) run 20 (ethanol, T = 100 ° C); (b) run 23 (n -butanol, T = 80 ° C). ( ) Ideal solution model predictions; (---) activity-based model predictions; ( ) butyric acid; ( ) ethanol; () ethyl butyrate; (× ) water; ( ) n -butanol; ( ) n-butyl butyrate.

with p -TSA was 0.015. For n -butanol butyric acid esteri ca- tion, the average deviation per data point over all experiments with A-70 was 0.016 and p -TSA was 0.020. These values indicate that the experimental data are indeed reasonably represented by the kinetic models. For the mixed alcohol esteri cation, the average deviation of the predicted values from experimental data was 0.011 for A-70 and 0.013 for p -TSA. The similarity of these deviations with those from the tted individual alcohol experiments is veri cation that the combined model is a good representation of mixed alcohol esteri cation. These deviations thus represent the scatter in the experimental data collection and analysis procedure, the largest contributor to which was measurement of water concentration using Karl Fischer analysis. The uncertainty in the rate constants at the 95% condence level (Table 3) are quite reasonable, given the relatively small number of data points (ranging from 32 to 60 depending on the data set) used in each regression and the relatively low

the data set) used in each regression and the relatively low Figure 4. Experimental and predicted

Figure 4. Experimental and predicted concentration pro les of mixed alcohol esterication in the presence of 1 wt % A-70: (a) run 13 (ethanol: n -butanol = 1.15:1, T = 80 ° C); (b) run 11 (ethanol: n - butanol = 0.21:1, T = 60 ° C); (c) run 9 (ethanol: n -butanol = 1:1, T = 60 ° C). ( ) Ideal solution model predictions; (---) activity-based model predictions; ( ) butyric acid; ( ) ethanol; ( ) ethyl butyrate; ( × ) water; ( ) n -butanol; ( ) n -butyl butyrate.

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Figure 5. Experimental and predicted concentration pro les of mixed alcohol esterication in the presence of 0.1 wt % p -TSA: (a) run 31 (ethanol: n -butanol = 4.1:1, T = 80 ° C); (b) run 29 (ethanol: n -butanol = 0.18:1, T = 80 ° C); (c) run 30 (ethanol: n -butanol = 1:1, T = 80 ° C). () Ideal solution model predictions; (---) activity-based model predictions; ( ) butyric acid; ( ) ethanol; ( ) ethyl butyrate; ( × ) water; ( ) n -butanol; ( ) n -butyl butyrate.

sensitivity of the objective function to values of the kinetic parameters. This low sensitivity arises from the well-known compensation e ect , wherein di erent combinations of pre- exponential factors and activation energies can give nearly the same values of rate constants over a narrow range of temperatures. The values of actual rate constants at a given temperature, however, are unique in their t and thus useful for design or comparison between systems. The rate of esteri cation with homogeneous p -TSA catalyst is substantially higher than with heterogeneous A-70 resin. Using catalyst loadings, the A-70 acid site density of 2.35 equiv of H + /kg, and initial species concentrations, the initial turn over number (TON, kmol BA/kmol H + /h) for ethanol on p -TSA is 70.8 and on A-70 is 16.8. For n -butanol, the initial TON is 40.7 on p-TSA and 11.3 on A-70. The ratio of TON for the two catalysts is approximately four for both alcohols. We attribute the lower TON in A-70 not to mass transport eects (see Table 2) but most likely to steric eects associated with limited access of acid and alcohol to an anchored acid site in the porous solid catalyst versus the unhindered access acid and alcohol have to free acid in solution. The similarity in activation energies over the two catalysts supports this postulate and suggests that the reaction mechanism is the same on homogeneous p -TSA and heterogeneous A-70. The ability of individual alcohol kinetic models to t mixed alcohol esteri cation over a wide range of alcohol molar ratios is strong evidence that the alcohols are not competing or inhibiting each other during esteri cation. It is consistent with the accepted mechanism of acid-catalyzed esteri cation in which the carboxylic acid is protonated by the acid site, followed by the slow, rate-limiting attack of nucleophilic alcohol on the electron-de cient carbonyl carbon. There is evidently a high enough concentration of protonated butyric acid in the present case to provide ample opportunity for either ethanol or n -butanol to attack without interference. The results described here are in accordance with a similar study examining mixed acid esteri cation, which reported that the additive combination of both esteri cation reactions also predicted the kinetics of the mixed acid system well. 26 3.4. Generalized Rate Constant for Butyric Acid Esteri cation. The absolute rate of butyric acid esteri cation (kmol/m 3 /s) in ethanol is higher than in n -butanol for both catalysts. This is expected because the absolute concentration (kmol/m 3 ) of ethanol in solution is higher than n -butanol, and thus, the hydroxyl group concentration is higher. 27 However, in the rate expression developed here for each catalyst, the rate constants for ethanol and n -butanol esteri cation at a given temperature, determined from the pre-exponential factors and activation energies for each reaction in Table 3, have the same values within experimental uncertainty. This result is true for both heterogeneous A-70 and homogeneous p -TSA catalysts. The activity kinetic model with solution density included (eq 7) thus unies esteri cation of butyric acid with ethanol and n - butanol. The generalization of esteri cation rate was extended by applying the rate expression (eq 7) to the initial rates of a set of C2 C8 alcohol esteri cation reactions with butyric acid conducted previously in our laboratory 27 over A-70 catalyst. The resulting rate constant at 60 °C for each of the alcohols examined is given in Table 4. It can be clearly seen that the values of the rate constant are strikingly similar for all alcohols examined. This results strongly supports the concept of a

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Table 4. Generalized Rate Constants for Butyric Acid Esteri cation Over A-70 for Dierent Alcohols

 

alcohol

ρ i , kmol ·m 3

k × 10 4 (60 ° C) kg soln·m 3 (kmol ·kg cat. ·s) 1

methanol

23.5

5.0

b

ethanol

16.4

2.3

a

ethanol

16.4

3.0

b

propanol

12.8

2.2

b

n

-butanol

10.4

3.0

a

n

-butanol

10.4

3.0

b

isobutanol

10.4

1.9

b

2-EHA

6.2

2.8

b

4-heptanol

6.8

2.5

b

1-heptanol

6.8

0.9

b

1-octanol

6.1

0.9

b

a This work. b Reference 27.

generalized rate constant for esteri cation of butyric acid over A-70 catalyst with any alcohol. As a further generalization of butyric acid esteri cation, we calculated the initial reaction rate for n-butyl butyrate formation over Dowex 50Wx8-400 resin 19 at 110 ° C and a 4:1 BA: n- BuOH initial feed ratio. Adjusting the value of the resulting rate constant to 60 ° C using an activation energy of 38 200 kJ/ kmol 19 and accounting for the dierences in acid site density between Dowex resin and Amberlyst 70, the rate constant for their system in a form equivalent to that presented in Table 4 is 1.98 × 10 4 m 3 soln·kg soln/(kg cat. ·kmol ·s), a remarkably similar value, given the dierences in the reaction system.

4. CONCLUSIONS

The kinetics of ethanol and n -butanol esteri cation of butyric acid in the presence of homogeneous p -toluene sulfonic acid and heterogeneous ion-exchange resin catalyst Amberlyst 70 have been accurately described by an activity-based kinetic model with solution density included. Mixed alcohol esteri cation kinetics are accurately predicted by an additive combination of esteri cation rates of the individual alcohols, indicating that alcohols do not compete with each other or inhibit each other in simultaneous esteri cation reactions. By including solution density to describe actual concentrations of OH and COOH in solutions of neat reactants, butyric acid esteri cation kinetics with simple C2 C8 alcohols are described by a single rate constant, which serves as a generalized rate constant for butyric acid esteri cation over Amberlyst 70. The additivity of rates and existence of a generalized rate constant greatly simpli es the simulation of actual biorenery esteri cation processes with single or multiple alcohols.

AUTHOR INFORMATION

Corresponding Author

*Tel.: (517) 353-3928. E-mail: millerd@egr.msu.edu.

Notes

The authors declare no competing nancial interest.

NOMENCLATURE AND UNITS

a i = activity of species i in reaction solution

C BA = concentration of butyric acid in liquid phase, kmol

m 3

D eff = e ective liquid-phase di usivity of butyric acid, m 2 s 1 D BA = bulk di usivity of butyric acid in alcohol, m 2 s 1

d p = swelled diameter of catalyst in reaction conditions, m

E a,m

= activation energy of the rate constant for reaction m ,

kJ kmol 1

F min = square root of mean of squared absolute residues f abs = average deviation of predicted vs experimental mole fraction in kinetic modeling K a ,m = activity-based equilibrium constant for reaction m

K x,m = mole-fraction-based equilibrium constant for reaction

m

K γ ,m

= ratio of activity coe cients of species in reaction m

= pre-exponential factor of reaction m , kg soln ·m 3 (kg

cat.) 1 s 1 kmol 1 N C = number of components in reaction N i = number of moles of species i in the reaction mixture, kmol N T = total number of moles in the reactor, kmol r m = rate of reaction m per unit volume of liquid phase, kmol

s 1 m 3

r * obs = observed rate of reaction per weight of catalyst, mol

s 1 kg 1

k 0,m

R

= ideal gas constant

V

= volume of reaction liquid phase, m 3

V p,swollen

V p,dry

= bulk volume of swollen catalyst, m 3

= dry bulk volume of catalyst, m 3

w CAT = catalyst loading in the reaction mixture, kg catalyst (kg solution) 1

x i = mole fraction of component i in the liquid mixture

Greek

γ i = activity coecient of component i in the reaction mixture ε = particle porosity η = intraparticle eectiveness factor Φ W = Weisz Prater observable modulus φ = Thiele modulus ρ = molar density of reacting liquid phase, kmol m 3 ρ CAT = density of catalyst particles, kg m 3 θ i,m = ratio of stoichiometric coe cient of component i with respect to the reference component in reaction m τ = pore tortuosity v i,m = stoichiometric coecient of component i in reaction m

Abbreviations

A-70 = Amberlyst 70 BA = butyric acid BE = butyrate ester BB = n -butyl butyrate But = n -butanol EB = ethyl butyrate EQ = equilibrium Eth = ethanol OH = alcohol p -TSA = p -toluene sulfonic acid

UNIFAC = universal functional activity coe cient

W = water

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