Thermodynamic analysis of synthesis of cyclopentanol from cyclopentene and comparison with experimental data

Abstract

Cyclopentanol is a very important chemical intermediate, which has been widely used in the chemical industry, and could be prepared from cyclopentene by two steps: an initial addition-esterification reaction of cyclopentene with acetic acid and the subsequent transesterification reaction with methanol. However, so far, no direct theoretical or experimental work has been reported on this process. In this work, we have carried out the thermodynamic calculation of the indirect process and also validated the thermodynamic prediction through experimental work. The liquid heat capacities of cyclopentanol and cyclopentyl acetate were estimated using the Ruzicka-Domalski group contribution method, the standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate by the Yoneda group contribution method, the standard vaporization enthalpy of cyclopentyl acetate by the Ducros group contribution method. The enthalpy changes, free energy changes, equilibrium constant and equilibrium conversion of the addition-esterification and transesterification reactions were calculated according to the principles of chemical thermodynamics in the temperature range from 273.15 to 373.15 K. The results showed that both the addition-esterification reaction and transesterification reaction were exothermic, the free energy changes increased with a rise on temperature, which indicated that low temperature was favorable for the reactions in the temperature range from 273.15 to 373.15 K. The optimal addition-esterification reaction conditions were a temperature range from 333.15 to 353.15 K, molar ratios of acetic acid to cyclopentene in the range from 2:1 to 3:1. For the transesterification reaction, the ideal temperature ranges from 323.15 to 343.15 K, with a molar ratio of methanol to cyclopentyl acetate in the range from 3:1 to 4:1. These thermodynamic calculation results for the addition-esterification reaction of cyclopentene and acetic acid experiments results are in good agreement with the experimental results.

http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = Appl Petrochem Res (2015) 5:135142 DOI 10.1007/s13203-015-0102-5

http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = ORIGINAL ARTICLE

http://crossmark.crossref.org/dialog/?doi=10.1007/s13203-015-0102-5&domain=pdf

Web End = Thermodynamic analysis of synthesis of cyclopentanol from cyclopentene and comparison with experimental data

Benzhen Yao1,2 Zhiqing Wang1 Tiancun Xiao2 Fahai Cao3 Peter P. Edwards2

Wangjing Ma2

Received: 4 November 2014 / Accepted: 24 February 2015 / Published online: 18 April 2015 The Author(s) 2015. This article is published with open access at Springerlink.com

Abstract Cyclopentanol is a very important chemical intermediate, which has been widely used in the chemical industry, and could be prepared from cyclopentene by two steps: an initial addition-esterication reaction of cyclopentene with acetic acid and the subsequent transesterication reaction with methanol. However, so far, no direct theoretical or experimental work has been reported on this process. In this work, we have carried out the thermodynamic calculation of the indirect process and also validated the thermodynamic prediction through experimental work. The liquid heat capacities of cyclopentanol and cyclopentyl acetate were estimated using the RuzickaDomalski group contribution method, the standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate by the Yoneda group contribution method, the standard vaporization enthalpy of cyclopentyl acetate by the Ducros group contribution method. The enthalpy changes, free energy changes, equilibrium constant and equilibrium conversion of the addition-esterication and transesterication reactions were calculated according to the principles of chemical thermodynamics in the temperature range from 273.15 to 373.15 K. The results

showed that both the addition-esterication reaction and transesterication reaction were exothermic, the free energy changes increased with a rise on temperature, which indicated that low temperature was favorable for the reactions in the temperature range from 273.15 to 373.15 K. The optimal addition-esterication reaction conditions were a temperature range from 333.15 to 353.15 K, molar ratios of acetic acid to cyclopentene in the range from 2:1 to 3:1. For the transesterication reaction, the ideal temperature ranges from 323.15 to 343.15 K, with a molar ratio of methanol to cyclopentyl acetate in the range from 3:1 to 4:1. These thermodynamic calculation results for the addition-esterication reaction of cyclopentene and acetic acid experiments results are in good agreement with the experimental results.

Keywords Cyclopentene Acetic acid Methanol

Cyclopentanol Cyclopentyl acetate Group contribution

method Thermodynamic analysis

Nomenclature

List of symbols Cp Heat capacity

G Gibbs energyH EnthalpyS EntropyK Equilibrium constantT TemperatureR Universal gas constant x Equilibrium conversion r Molar ratio

4 Value of change Superscripts and subscripts h Standard state

& Zhiqing Wang [email protected]

& Tiancun Xiao [email protected]

1 SINOPEC Shanghai Petrochemical Company Limited,48 Jinyi Road, Shanghai 200540, China

2 Inorganic Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QR, UK

3 College of Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China

123

136 Appl Petrochem Res (2015) 5:135142

P ProductionR Reactantf Formationr Reactiong Gas phasel Liquid phase1 Addition-esterication reaction2 Transesterication reaction

Introduction

Cyclopentanol is an important ne chemical intermediate, which has been used in the production of perfumes, medicines and dyes, and as a solvent for medicines and perfumes [1]. The main production process for cyclopentanol was cyclopentanone hydro-conversion, and the cyclopentanone was produced by decarboxylation of adipic acid at high temperature; however, the development of this process was limited due to the formation of a great deal of pollutant [2, 3]. Cyclopentanol can also be produced from furfural using the Noble-metal catalysts (such as Pt/C and Ru/C); however, the selectivity of cyclopentanol is quite low, and future development of high efcient, stable and economical catalysts will be highly desired [4, 5].

The dicyclopentadiene could be separated from the cracked C5 fraction available as a by-product of ethylene production, and the cyclopentadiene was produced by dicyclopentadiene cracking; cyclopentene was the hydrogenation product of cyclopentadiene, and the cyclopentanol could be produced from the direct hydration or indirect hydration of cyclopentene. Theoretically, cyclopentanol could be synthesized using a two-step process from cyclopentene, e.g., the addition-esterication reaction of cyclopentene with acetic acid, the transesterication of cyclopentyl acetate and methanol, the process of hydration of cyclopentene was one environment friendly technology with less pollution [6]. The ow charts of the main

production process for cyclopentanol and indirect synthesis of cyclopentanol from cyclopentene are shown in Fig. 1. However, so far, no literatures have been published for this indirect process either from the theoretical or experimental study. In this work, the thermodynamic analysis of the two reaction steps was carried out in the paper, which could provide theoretical principle for the experimental research and industrial production, and preliminary experimental work has been carried out and the results are in good agreement with the thermodynamic calculation results.

Thermodynamic calculation

Reaction equations

The two reactions have been considered in the system, the addition-esterication reaction of cyclopentene and acetic acid:

+ CH3COOH OOCCH3

cyclopentene acetic acid cyclopentyl acetate

1

The transesterication of cyclopentyl acetate and methanol:

OOCCH3 + CH3OH OH + CH3COOCH3

cyclopentyl acetate methanol cyclopentanol methyl acetate

2

Physical properties data of thermodynamic analysis

The standard enthalpy of formation and standard entropy of liquid cyclopentene, acetic acid, methanol, methyl acetate

Fig. 1 Flow chart of the main production process for cyclopentanol and indirect sythesis of cyclopentanol from cyclopentene

Adipic acid

Decarboxylation

Cyclopentanone

Hydrogenation

Cyclopentanol

The main production process for cyclopentanol

Acetic acid

Methanol

Cyclopentene

Addition-esterification

Cyclopentyl acetate

Transesterification

Cyclopentanol

The indirect synthesis of cyclopentanol from cyclopentene

123

Appl Petrochem Res (2015) 5:135142 137

Table 1 Contribution values of group of RuzickaDomalski and the group numbers in the each substance

Group ai bi/K-1 di/K-2 Group number

Cyclopentyl acetate Cyclopentanol

C(H)3(C) 3.8452 -0.33997 0.19489 1 CO(C)(O) 29.246 3.4261 -2.8962 1

O(C)(CO) -21.434 -4.0164 3.0531 1

C(H)(C)2(O)(alcohol) 2.2209 -1.435 0.69508 1 1 C(H)2(C)2 2.7972 -0.05497 0.10679 4 4 Substituted cyclopentane 0.29183 -1.5118 0.23172 1 1

O(C)(H) 12.952 -10.145 2.6261 1

Table 2 The functional correlations between Cp,t of materials and temperature

Constituents Cp,t * T

Cyclopentene 112.71-0.8864 T ? 6.2634 9 10-3 T2-

1.4632 9 10-5 T3 ? 1.3021 9 10-8 T4

Acetic acid 183.43-0.6817 T ? 2.9953 9 10-3 T2-

5.4815 9 10-6 T3 ? 4.1430 9 10-9 T4

Methanol -1373.10 ? 17.5230 T-7.9812 9 10-2

T2 ? 1.6112 9 10-4 T3-1.1979 9 10-7 T4

Methyl acetate -413.28 ? 6.3422 T-2.7999 9 10-2

T2 ? 5.5006 9 10-5 T3-3.9106 9 10-8 T4

Cyclopentyl acetate

210.8325-0.3406 T ? 1.4182 9 10-3 T2 Cyclopentanol 221.5974-1.1293 T ? 3.3645 9 10-3 T2

Table 3 Contribution values of group of Ducros

Constituents Group Number DH/

(KJ mol-1)

Cyclopentyl acetate

C(H)3(C) 1 5.65 CO(C)(O) 1 9.83

O(C)(CO) 1 8.37

C(H)(C)2(O)(alcohol) 1 1.97 C(H)2(C)2 4 4.98 Cyclopentaneadjustment

1 2.76

Cp;t R A B

T 100

2

" # 3

In the Eq. 3 A P

niai, B P

nibi, D P

nidi, the

contribution values of group are shown in Table 1 and the calculation results in Table 2.The standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate at the temperature of 298.15 K were estimated using Yoneda method (ABWY) [17, 20], and the effect of substitutions was covered with data from Ref. [20], and the calculation formula being

Df Hhg;298:15 XniDHi 4

Shm;g X

niDSi 5

The standard enthalpy of formation and standard entropy of liquid cyclopentyl acetate at the temperature of 298.15 K were estimated by Eqs. 6 and 7:

Df Hhl;298:15 Df Hhg;298:15 DvHh298:15 6

Shm;l Shm;g

T100 D

and cyclopentanol were adopted from the data handbooks [7, 8], the results are shown in the Table 4. The liquid heat capacities of cyclopentene, acetic acid, methanol and methyl acetate at the temperature range from 273.15 to 373.15 K were taken from the data handbook [9, 10], and the expression of liquid heat capacities was tted as multinomial; the results are shown in Table 2.

However, not all the physical properties of the chemicals could be obtained from handbook, the group contribution methods were investigated to estimate the physico chemical properties of organic compounds, such as Joback method [11], ConstantinouGani method [12], Benson method [13] and so on [14, 15]. In this paper, the liquid heat capacities of cyclopentanol and cyclopentyl acetate, the standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate at the temperature of 298.15 K, and the standard vaporization enthalpy of cyclopentyl acetate were estimated by RuzickaDomalski method [16], Yoneda method (ABWY) [17] and Ducros method [18, 19], respectively [20].

The liquid heat capacities of cyclopentanol and cyclopentyl acetate were estimated by RuzickaDomalski group contribution method [16, 20], the calculation formula was:

DvHh298:15

298:15 7

The standard vaporization enthalpy of cyclopentyl acetate was estimated by the Ducros method [1820], and the contribution values of group are shown in Table 3. The

123

138 Appl Petrochem Res (2015) 5:135142

Table 4 The Df Hhl;298:15 and Shm;l of each substance at 298.15 K

Constituents Df Hhl;298:15/(KJ mol-1) Shm;l/(J mol-1 K-1)

Cyclopentene 4.27 201.25

Acetic acid -484.5 159.8

Methanol -239.1 126.8

Methyl acetate -445.8 210.7

Cyclopentyl acetate -505.88 294.99

Cyclopentanol -300.1 206.3

30

25

20

1

15

10

5

0

-25.0

0

-25.5

Temperature/K

Fig. 3 Changes of the addition-esterication reaction equilibrium constant (Kh1) with temperature

-2

-1

m/kJmol

r1 G

m / kJmol

-1

-4

-26.0

Addition-esterication reaction of cyclopentene and acetic acid

The enthalpy changes and free energy changes of the addition-esterication reaction

The enthalpy changes (Dr1Hhm) and free energy changes (Dr1Ghm) of addition-esterication reaction were calculated at different temperature, the results are shown in Fig. 2.

As seen from Fig. 2, the Dr1Hhm was less than 0 in the temperature range from 273.15 to 373.15 K, the addition-esterication reaction was exothermic, and the Dr1Hhm decreased with increasing temperature in the range 273.15 to 373.15 K.

The Dr1Ghm value was less than 0 in the 273.15 to 373.15 K, which showed that the addition-esterication reaction could occur spontaneously. Dr1Ghm increased with the temperature rise, which indicated that lower temperatures were more favorable for the reactions in the temperature range from 273.15 to 373.15 K.

Equilibrium constant and equilibrium conversion of the addition-esterication reaction

The molar ratio of acetic acid to cyclopentene was set as r1,

the conversion of cyclopentene was set as x1,so:

Kh1

r1H

-6

-26.5

-8

-27.0 260 280 300 320 340 360 380

Temperature/K

Fig. 2 The Dr1Hhm and Dr1Ghm for the addition-esterication reaction as functions of temperature

260 280 300 320 340 360 380

standard enthalpy of formation and standard entropy of liquid cyclopentyl acetate appear in Table 4.

Calculation results and discussion

The enthalpy changes, free energy changes of each reaction were calculated by Eqs. 812 [21]:

DrHh298:15 X

Df Hhl;298:15 p X

Df Hhl;298:15 R

8

DrHhm DrHh298:15 Z

T

298:15

dT

9

X

Cp

P

X

Cp

R

DrShm;298:15 XShm

p

X

Shm

R

10

dT 11

DrGhm DrHhm TDrShm 12 The equilibrium constant of each reactions was calculated by Eq. 13 [21, 22]:

Kh exp DrGhm=RT 13

DrShm DrShm;298:15 Z

T

298:15

Cp T

x1

14

The equilibrium constant (Kh1) of the addition-esterication reaction at different temperature was calculated from

Eq. 13, and the conversion of cyclopentene as x1 at different temperature with different r1 was calculated from

Eq. 14 and the results appear in Figs. 3 and 4.

1 x1r1 x1

123

Appl Petrochem Res (2015) 5:135142 139

Fig. 4 Changes of the cyclopentene equilibrium conversion (x1) with temperature

1.00

0.95

0.90

0.85

0.80

0.75

x 1

r=1:2

r=1:1

r=2:1

r=3:1

r=4:1

0.70

0.65

0.60

0.55

0.50

0.45

0.40

0.35

0.30

0.25

260 280 300 320 340 360 380

Temperature/K

Figures 3 and 4 show that Kh1 and x1 decreased at higher temperature and that the x1 increased at higher values, r1, at the same temperature. The conversion of cyclopentene was higher at lower temperature and a greater molar ratio of acetic acid to cyclopentene. However, very low temperatures reduced the reaction rate, and the acetic acid spent increased with increasing of r1, and the cost of separation of acetic acid and cyclopentyl acetate increased.

The most suitable reaction conditions were temperature in the range from 333.15 to 353.15 K with an r1 value between 2:1 and 3:1.

Transesterication reaction of cyclopentyl acetate and methanol

The enthalpy changes and free energy changes of transesterication reaction

The enthalpy changes (Dr1Hhm) and free energy changes (Dr1Ghm) of transesterication reaction were calculated at different temperature and the results are plotted in

Fig. 5.

Figure 5 shows that Dr2Hhm was negative in the temperature range from 273.15 to 373.15 K, the addition-esterication reaction was exothermic, and the Dr2Hhm decreased at higher temperatures from 273.15 to 373.15 K.

The Dr2Ghm was greater than 0 in the temperature range from 273.15 to 373.15 K, which showed that the addition-esterication reaction couldnt carry through spontaneously. And theDr2Ghm increased with the raising of the temperature, which indicated that temperature increased was unfavorable for the reactions at the temperature range from 273.15 to 373.15 K.

Equilibrium constant and equilibrium conversion of the transesterication reaction

The molar ratio of methanol to cyclopentyl acetate was set as r2, the conversion of cyclopentyl acetate was set as x2, so:

Kh2

0.0

1.1

-0.5

1.0

0.9

-1 -1.0

m/kJmol

0.8

r2 G

m / kJmol

-1

-1.5

0.7

r2H

-2.0

0.6

-2.5

0.5

0.4

-3.0 260 280 300 320 340 360 380

Temperature/K

Fig. 5 The Dr2Hhm and Dr2Ghm of transesterication reaction as functions of the temperature

x22

15

In the same way, the equilibrium constant (Kh2) of the transesterication reaction at different temperature was calculated from Eq. 13, and the conversion of cyclopentene as x1 at different temperature with different r1 was calculated from Eq. 15, and the results are shown in Figs. 6 and 7.

Similarly, as seen from Figs. 6 and 7, the Kh2 and x2 decreased with the raising of the temperature, the x2 increased with the raising of the r2 at the same temperature. The conversion of cyclopentyl acetate was higher with

1 x2r2 x2

123

140 Appl Petrochem Res (2015) 5:135142

0.84

0.82

0.80

0.78

2

0.76

0.74

0.72

mCyclopentene; rawmaterials m

0.70 260 280 300 320 340 360 380

Cyclopentene; products

mCyclopentene; rawmaterials 100

16

Selectivity of cyclopentyl acetate %

Sel

Cyclopentyl acetate

Temperature/K

Fig. 6 Changes of the transesterication reaction equilibrium constant (Kh2) with temperature

mCyclopentyl acetate

mCyclopentene; rawmaterials m

Cyclopentene; products

100

17

lower temperature and greater molar ratio of methanol to cyclopentyl acetate. However, the extremely lower temperature reduced the reaction rate which was unfavorable for the transesterication reaction, and the methanol spent increased with increasing of r2, and the cost of separation increased. The suitable reaction conditions were temperature of range from 323.15 to 343.15 K, r2 of range from 3:1 to 4:1.

Experimental validation, results and discussion

Chemical and catalysts

Cyclopentene [AR [ 98.0 % (wt)] was purchased from Changzhou Sinly Pharmchem Co., Ltd. Acetic acid [AR [ 99.5 % (wt)] was purchased from Reagent No. 1

Factory of Shanghai Chemical Reagent Co., Ltd. Methanol [CP [ 99.9 % (wt)] was purchased from Shanghai Coking

Co., Ltd. Amberlyst-35 strong acidic cation-exchange resin catalysts were obtained from Rohm and Haas Shanghai Chemical Industry Co., Ltd. QRE-01 strong acidic cation-exchange resin catalysts were obtained from Research Institute of Qilu Petrochemical Co., SINOPEC.

Analysis and calculations

Chemical composition of products was analyzed using a gas chromatography (Agilent GC-6890) with a HP-FFAP silica capillary column (30 m 9 0.32 mm 9 0.25 lm). Nitrogen was used as the carrier gas at a ow rate of 0.7 mL/min. The temperature of column oven was programmed from 60 C increased at 5 C/min to 80 C, and held with an isothermal for 4 min, then increased at 10 C/min to 220 C, and held with an isothermal for 15 min. The temperature of injector

and detector was set at 220 and 250 C, respectively. The split ratio was 1:100; the sample injection volume was0.4 lL. Calibration normalization method was performed on the GC to ensure accuracy of the measurements.

The conversions of cyclopentene and cyclopentyl acetate, the selectivity of cyclopentyl acetate and cyclopentanol can be determined with the Eqs. (1620).

Conversion of cyclopentene %

Con

Cyclopentene

Conversion of cyclopentyl acetate %

Con

cyclopentyl acetate

mcyclopentylacetate;raw materials m

cyclopentylacetate; products

mcyclopentyl acetate;raw materials 100

18

Selectivity of cyclopentanol %

Sel

cyclopentanol

mcyclopentanol

mcyclopentyl acetate; rawmaterials m

cyclopentyl acetate; products

100

19

Yield of cyclopentanol %

Yie

Cyclopentene

Concyclopentyl acetate Sel

cyclopentanol

100

20

Experiment

The addition-esterication reaction of cyclopentene with acetic acid was operated in a glass tube xed bed reactor (u25 mm 9 500 mm) over Amberlyst-35 strong acidic cation-exchange resin catalysts, the reaction temperature was adjusted by the temperature control system, the reactants mass ow rate was controlled by the feeding pump. The addition-esterication reaction of cyclopentene and acetic acid with different reaction conditions was carried out under normal pressure, the mass space velocity of2.0 h-1. The analysis results showed that the selectivity of cyclopentyl acetate was around 98 %. The cyclopentyl acetate product (mass fraction of 99 %) was obtained by distillation, the unreacted cyclopentene and superuous acetic acid could be reused by distillation recovery. The conversion of cyclopentene from experimental results and the equilibrium conversion of cyclopentene from

123

Appl Petrochem Res (2015) 5:135142 141

0.80

Fig. 7 Change of the cyclopentyl acetate equilibrium conversion (x2) with temperature

0.75

0.70

0.65

0.60

r=1:2

r=1:1

r=2:1

r=3:1

r=4:1

0.55

x 2

0.50

0.45

0.40

0.35

0.30 260 280 300 320 340 360 380

Temperature/K

Table 5 Comparisons between experiments results and calculation data of the addition-esterication reaction

Experiment no. Reaction temperature (C) r1 Conversion of cyclopentene (%) Absolute errors (%) Relative errors (%)

Experiments results Calculation data

1 65 1.5 75.43 71.51 -0.0392 -5.49

2 65 2 77.00 79.41 0.0241 3.03

3 65 2.5 81.46 84.13 0.0267 3.18

4 65 3 84.38 87.19 0.0281 3.22

5 65 3.5 85.63 89.29 0.0366 4.10

6 50 3 75.94 91.14 0.1520 16.68

7 55 3 79.82 89.93 0.1011 11.24

8 60 3 82.81 88.61 0.0580 6.54

9 65 3 84.38 87.19 0.0281 3.22

10 70 3 80.52 85.67 0.0515 6.01

r1 molar ratio of acetic acid to cyclopentene

thermodynamics calculation in the addition-esterication reaction are compared in Table 5.

From Table 5, we can see that, the cyclopentene conversion relative errors of experiment nos. 6 and 7 were more than 10 %. Since the reaction rate I was slower in the lower temperature, it was difcult to achieve equilibrium at a lower reaction temperature during a short reaction time, the relative errors in the lower reaction temperature were larger than that in higher reaction temperature. The relative error of other experiments was lower than 7.0 %, and the average relative error was 2.98 % (experiment nos. 6 and 7 are not included); the thermodynamic calculation was in good agreement with the experiment results.

The transesterication of cyclopentyl acetate and methanol was operated in a glass tube xed bed reactor (u25 mm 9 500 mm) over QRE-01 strong acidic cation-exchange resin catalysts, the reaction temperature was adjusted by the temperature control system, the reactants

mass ow rate was controlled by the feeding pump. The transesterication of cyclopentyl acetate and methanol was carried out under normal pressure, the reaction temperature of 50 C, the molar ratio of methanol to cyclopentyl acetate of 3:1, the mass space velocity of 2.0 h-1, the conversion of cyclopentyl acetate was 55.3 %, the selectivity of cyclopentanol was 99.5 %, the yield of cyclopentanol was55.0 %. The cyclopentanol product was obtained by distillation, the unreacted cyclopentyl acetate and superuous methanol could be reused by distillation recovery.

Conclusions

Thermodynamic analysis for reactions of indirect synthesis of cyclopentanol from cyclopentene has been carried out based on partial physical properties data of cyclopentyl acetate and cyclopentanol estimated by group contribution

123

142 Appl Petrochem Res (2015) 5:135142

methods. The enthalpy changes, free energy changes, equilibrium constant and equilibrium conversion of the addition-esterication reaction and transesterication reaction were calculated.

The addition-esterication reaction of cyclopentene and acetic acid was exothermic reaction at the temperature range from 273.15 to 373.15 K, the optimal reaction condition was temperature of range from 333.15 to 353.15 K, molar ratio of acetic acid to cyclopentene of 2:13:1.

The transesterication reaction of cyclopentyl acetate and methanol is exothermic reaction at the temperature range from 273.15 to 373.15 K, the optimal reaction condition was temperature of range from 323.15 to 343.15 K, molar ratio of methanol to cyclopentyl acetate of 3:1 to 4:1.

The addition-esterication of cyclopentene and acetic acid experiments were carried out in a glass tube xed bed reactor, and the experiments results showed that the thermodynamic calculation was in good agreement with the experiment results.

Open Access This article is distributed under the terms of the Creative Commons Attribution License which permits any use, distribution, and reproduction in any medium, provided the original author(s) and the source are credited.

References

1. Ordomsky VV, Schouten JC, Van der Schaaf J et al (2013) Biphasic single-reactor process for dehydration of xylose and hydrogenation of produced furfural. Appl Catal A 451:613

2. Guo ShZh, Huang YR, Xu ZH, Huang HS, Fang L, Fang DY (2004) Preparation of cyclopantanol by hydration of cyclopentene. J East China Univ Sci Technol 30(6):618

3. Meng XY, Chen XR, Chen XY (2011) Study on catalytic hydration of cyclopentene to cyclopantanol. J Hebei Univ Technol 40(2):46

4. Yan K, Wu G, Laeur T et al (2014) Production, properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals. Renew Sustain Energy Rev 38:663676

5. Yan K, Liao J, Wu X et al (2013) A noble-metal free Cu-catalyst derived from hydrotalcite for highly efcient hydrogenation of biomass-derived furfural and levulinic acid. RSC Adv 3(12):38533856

6. Xu ZH, Chang H, Xia RH, Ye JM, Zh YJ (2012) CN 102399132A

7. Dean JA (1999) Langes handbook of chemistry, 15th edn. McGraw-Hill Book Co, New York

8. Li ML (2003) Concise handbook of chemical data. Chem Ind Press, Beijing

9. Liu GQ, Ma LX, Liu J (2002) Chemistry and chemical engineering physical properties databook. Chem Ind Press, Beijing

10. Fu B (1997) Common chemistry handbook. Geological Press, Beijing

11. Joback KG, Reid RC (1987) Estimation of pure-component properties from group-contributions. Chem Eng Commun 57(16):233243

12. Constantinou L, Gani R (1994) New group contribution method for estimating properties of pure compounds. AICHE J 40(10):16971710

13. Benson SW, Cruickshank FR, Golden DM et al (1969) Additivity rules for the estimation of thermochemical properties. Chem Rev 69(3):279324

14. Kolsk Z, Ruzick V, Gani R (2005) Estimation of the enthalpy of vaporization and the entropy of vaporization for pure organic compounds at 298.15 K and at normal boiling temperature by a group contribution method. Ind Eng Chem Res 44(22): 84368454

15. Kolsk Z, Kukal J, Zbransk M et al (2008) Estimation of the heat capacity of organic liquids as a function of temperature by a three-level group contribution method[J]. Ind Eng Chem Res 47(6):20752085

16. Rika V Jr, Domalski ES (1993) Estimation of the heat capacities of organic liquids as a function of temperature using group additivity. II. Compounds of carbon, hydrogen, halogens, nitrogen, oxygen, and sulfur. J Phys Chem Ref Data 22(3):619657

17. Yoneda Y (1979) An estimation of the thermodynamic properties of organic compounds in the ideal gas state. I. Acyclic compounds and cyclic compounds with a ring of cyclopentane, cyclohexane, benzene, or naphthalene. Bull Chem Soc Jpn 52(5):12971314

18. Ducros M, Gruson JF, Sannier H (1980) Estimation of the enthalpy of vaporization of organic compounds in the liquid phase. Part 1. Alkanes, cycloalkanes, alkenes, aromatic hydrocarbons, alcohols, thiols, chloro-and bromoalkenes, nitriles, esters, acids and aldehydes. Thermochim Acta 36:3965

19. Ducros M, Gruson JF, Sannier H et al (1981) Estimation des enthalpies de vaporisation des composes organiques liquides. Partie 2. Applications aux ethersoxydes, thioalcanes, cetones et amines[J]. Thermochim Acta 44(2):131140

20. Ma PSh (2003) Chemical engineering data, 1st edn. China petrochemical Press, Beijing

21. Hu Y, Lv RD, Liu GJ, Ye RW (1999) Physical chemistry, 4th edn. Higher Education Press, Beijing

22. Cao FH, Liu DH, Hou QSh, Fang DY (2001) Thermodynamic analysis of CO2 direct hydrogenation reactions. J Nat Gas Chem 10(1):24

123