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Pervaporation of High Boiling Point Organic Compoundswith Composite PDMS MembraneChunyan Chen a , Zeyi Xiao a , Kewang Deng a , Weijia Li a , Haidi Cui a & Junqing Zhang aa School of Chemical Engineering , Sichuan University , Chengdu , ChinaAccepted author version posted online: 07 Jan 2013.Published online: 24 Apr 2013.

To cite this article: Chunyan Chen , Zeyi Xiao , Kewang Deng , Weijia Li , Haidi Cui & Junqing Zhang (2013) Pervaporation ofHigh Boiling Point Organic Compounds with Composite PDMS Membrane, Separation Science and Technology, 48:8, 1252-1260,DOI: 10.1080/01496395.2012.736049

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Pervaporation of High Boiling Point Organic Compoundswith Composite PDMS Membrane

Chunyan Chen, Zeyi Xiao, Kewang Deng, Weijia Li, Haidi Cui, and Junqing ZhangSchool of Chemical Engineering, Sichuan University, Chengdu, China

High Boiling Point Organic Compounds (HBOCs1) are definedas those organic compounds with boiling point over water (100�C).It is a challenging problem to separate HBOCs from their mixtureswith water. Three HBOCs, propargyl alcohol, butanol, and pyri-dine, were selected as the experimental samples for observing theirseparation behaviors from water mixtures by PDMS membranepervaporation. These HBOCs could preferentially permeate thePDMS membrane and were selectively extracted from the mixturesthrough the membrane. The experimental tests showed that the per-meation flux of propargyl alcohol, butanol, and pyridine was 243.24,976.5, and 904.70 gm�2h�1, with the corresponding selectivity of3.78, 29.65, and 26.09, respectively. The effects of the feed flowrate, feed concentration, and temperature on the separation beha-viors were examined. By comparison with distillation that separatesdifferent components in a mixture on the basis of boiling point, themembrane pervaporation seems to behave a ‘‘reverse direction’’selective separation for the HBOCs. For those aqueous mixtureswith tiny content of HBOCs, the ‘‘reverse selective separation’’ bymembrane pervaporation should be considered as a promising andeffective technology.

Keywords high boiling point organic compounds; PDMSmembrane; pervaporation

INTRODUCTION

The organic compounds with higher boiling points thanwater, such as propargyl alcohol, butanol, pyridine, andacetic acid, are defined as high boiling point organic com-pounds (HBOCs). HBOCs are generally important indus-trial chemicals and widely used in industry. For example,propargyl alcohol is extensively used in the oil industry(1,2) and electroplating industry (3). Butanol has beenregarded as an ideal fuel to relieve the depletion of pet-roleum fuel, due to its many superior properties over otherfuels (4). Besides, pyridine is also an important solventpresent in effluents from rubber and plastics, petrochem-icals and some other organic chemical industries (5).

In HBOCs industries, the process streams for productextraction were generally aqueous mixtures with tinycontent of HBOCs. For example, in propargyl alcoholindustry, the process stream was an aqueous mixture con-taining 3–5wt% propargyl alcohol and 4–9wt% butyne-diol. In the fermentation process for butanol production,the process stream was a broth containing butanol up to2wt%, and in the pyridine industry the process streamwas an aqueous mixture usually containing pyridine of3–5wt%. It was obviously not a good method to removethe bulk of water to separate or concentrate HBOCs byusual evaporation technology, although we had to do soin current practical industries.

To avoid tedious distillation process and annoyingbulky water evaporation, several separation technologieshave been developed to recover HBOCs from aqueous mix-tures, such as adsorption, extraction, gas stripping, andpervaporation (6,7). Pervaporation has been regarded asa promising technology owing to its energy saving andefficiency, as well as no product contamination. Mandalet al. studied pervaporation of pyridine in aqueous solu-tion and showed the feasibility of the technology withhigh separation factor from 14 to 20 (5). Likewise, anotherbutanol pervaporation research was reported with a hightotal flux of 1065 gm�2h�1and butanol separation factorof 18.4 (8).

As reported, polydimethylsiloxane (PDMS) membranehas shown good behaviors on the separation of organiccompounds from aqueous solutions, such as alcohols, acids,aldehydes, esters, ketones, and aroma compounds (9–16).In this work, experiments on pervaporation separation ofthree HBOCs, propargyl alcohol, butanol, and pyridine,from their water mixtures were carried out by means of acomposite PDMS membrane, to explore some commonfeatures on pervaporation separation of HBOCs-watermixture system.

MATERIALS AND METHODS

Experimental Materials

The pervaporation membrane used here was a self-prepared composite PDMS membrane, with the module

1HBOCs: High Boiling Point Organic CompoundsReceived 9 June 2012; accepted 29 September 2012.Address correspondence to Zeyi Xiao, Sichuan University,

No.24 South Section 1, Yihuan Road, Chengdu, China, 610065.Tel.: 86-028-85401057. E-mail: mgch@scu.edu.cn

Separation Science and Technology, 48: 1252–1260, 2013

Copyright # Taylor & Francis Group, LLC

ISSN: 0149-6395 print=1520-5754 online

DOI: 10.1080/01496395.2012.736049

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providing an effective membrane area of 0.024m2. Thepreparation procedure of the membrane and the structureof the module had been fully described in the previouswork (11,17).

Propargyl alcohol-butynediol-water mixture was aliquid mixture from the practical industry, offered by theTianyu Chemical Industry Corporation (Shandong, China).According to our analysis and measurement, the mixturecontained 2.7wt% propargyl alcohol, 5.08wt% butynediol,and about 92wt% water.

Aqueous butanol mixture was prepared directly usingn-butanol of reagent grade and distilled water. For model-ing the broth of butanol fermentation process, butanolconcentration varied in the range of 0.6–4wt%. Similarly,aqueous pyridine mixture was self-prepared for modelingthe practical stream in industry, with the pyridine concen-tration varying from 1wt% to 5wt%.

Experimental Apparatus and Process

A schematic diagram of the apparatus for pervaporationexperiments is shown in Fig. 1. The mixture liquid of2.5 L was circulating between the feed reservoir and up-stream of the membrane module by a pump. The feed flowrate was regulated by a rotameter and the temperature wascontrolled by a thermostat. The absolute pressure at thedownstream of the membrane was maintained at 2 KPaby a vacuum pump. The permeate vapor through themembrane was condensed and collected in the cold trapimmersed in a �30�C refrigerator. Samples were with-drawn every one hour to measure the concentrations of

the concerned components in the feed reservoir and coldtrap, respectively.

Analysis

The concerned organic components in this experimentwere propargyl alcohol, butynediol, butanol, and pyridine.The detailed analysis methods were described as follows:

1. Propargyl alcohol: propargyl alcohol reacts with silvernitrate, and forms a soluble compound, releasingequivalent Hþ simultaneously. The formed compoundsolution is titrated with sodium hydroxide standard sol-ution and then the concentration of propargyl alcoholcould be determined by the following formula (1):

W ¼ðC � VÞ � M

1000

m� 100 ð1Þ

where W is the mass fraction of propargyl alcohol(wt%), C is the concentration of sodium hydroxide stan-dard solution (mol �L�1), V is the volume of consumedsodium hydroxide solution (ml), M is the molar mass ofpropargyl alcohol (g �mol�1), and m is the mass of thesample (g).

2. Butynediol: butynediol reacts with acetic anhydride,and forms equivalent acetic acid. After the remainingacetic anhydride is hydrolyzed by adding water, thebutynediol concentration could be determined by titrat-ing the formed acid with sodium hydroxide standardsolution. The concentration of butynediol could becalculated by the following formula (2):

W ¼ðC�VÞblank�ðC�VÞsample½ �

2 � M1000

m� 100 ð2Þ

where W is the mass fraction of butynediol (wt%), C isthe concentration of sodium hydroxide standard sol-ution (mol �L�1), V is the volume of consumed sodiumhydroxide solution (mL), M is the molar mass of buty-nediol (g �mol�1), and m is the mass of the sample (g).

3. Butanol was directly determined with a density meterDMA 4500 (Anton Paar, Austria). If the permeate sepa-rated into two phases, the permeate sample was dilutedwith distilled water prior to injection.

4. Pyridine was determined by a gas chromatographyGC112A (Shanghai, China) equipped with a flame ioni-zation detector and a FFAP capillary column (30m x0.32mm). The carrier gas was nitrogen, and isobutanolwas used as the internal standard. The temperature con-ditions were as following: Injector temperature 200�C,detector temperature 200�C, column temperature line-arly ramping from 60�C to 180�C at 20�C per min.

FIG. 1. Schematic diagram of apparatus for pervaporation experiment

1. thermostat; 2. magnetic stirrer; 3 feed reservoir; 4 thermometer; 5.

circulation pump; 6. rotameter; 7. membrane module; 8. cold trap; 9.

refrigerator; 10. vacuum reservoir; 11. vacuum gauge; 12. desiccator; 13.

vacuum pump.

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Membrane Behaviors

Membrane behaviors were evaluated with twoparameters—selectivity and the permeation flux.

1. Selectivity:

ao=w ¼ Yo=Yw

Xo=Xwð3Þ

where X and Y is the mass fraction of components in thefeed and permeate (wt%), respectively. Subscript ‘‘o’’denotes organic compound and ‘‘w’’ water.

2. Permeation flux:

J ¼ Mp=At ð4Þ

whereMp is the weight of the collected permeate (g), t is thesampling time interval for the pervaporation (h) and Ais the effective membrane surface area (m2).

RESULTS AND DISCUSSION

Characteristics of the PDMS-PA Membrane

Figure 2 shows the cross-section structure of the PDMS-PA membrane investigated by SEM. The top layer was thedense PDMS active layer with the thickness of about 5 mm.The support layer was the porous PA with average diam-eter of around 0.5 mm. The binding interface between thetop layer and support layer was clear and well cross linked.

Effects of Feed Flow Rate on the PervaporationPerformance of HBOCs

In the pervaporation experiment of propargyl alcohol-butynediol-water mixture, the butynediol concentrationwas 0.1wt% or less in the permeate of the membrane

downstream, which means butynediol was not able to beselectively separated by the PDMS membrane. The influ-ence of feed flow rate on flux and selectivity of propargylalcohol, butanol, and pyridine was evaluated. As seen inFig. 3, the HBOCs fluxes all increased with the feed flowrate. According to the serial resistance model of membrane

FIG. 2. SEM image of the PDMS-PA membrane (�5000).

FIG. 3. Effects of feed flow rate on HBOCs flux and selectivity (A)

Propargyl alcohol (B) Butanol (C) Pyridine.

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transport (18), higher feed flow rates produced faster flowvelocities on the membrane surface, and then caused smal-ler boundary layer resistance for mass transfer through themembrane, finally resulting in increased fluxes. However,the increased degrees of HBOCs fluxes were different. Withthe feed flow rate increasing from 40 to 120 Lh�1, the fluxof propargyl alcohol, butanol, and pyridine was varying inthe range of 170–240, 260–290, 200–210 gm�2h�1, respect-ively. The difference may be attributed to the differentadsorption characteristics of propargyl alcohol, butanol,and pyridine. Besides, no obvious difference of the propar-gyl alcohol flux was observed from the flow rate of 90 Lh�1

to 150Lh�1, which may indicate the optimal feed flowrate for pervaporation of propargyl alcohol in this specificsystem.

Meanwhile, selectivities of the three HBOCs alsoincreased with feed flow rate. Nevertheless, with the feedflow rate increasing, the ranges of selectivity for propargylalcohol, butanol, and pyridine were 3.4–3.8, 20–22, 27–31,respectively. Obviously, the increased degrees of selectivityfor the three HBOCs were opposite to those of HBOCsfluxes, which demonstrated a trade-off between the vari-ation degrees of flux and selectivity.

Effects of Feed Concentration on the PervaporationPerformance of HBOCs

The pervaporation behaviors of HBOCs at differentfeed concentrations were investigated. Figure 4a showspropargyl alcohol flux and selectivity in the course of tem-perature at two different feed concentrations, while Fig. 4band 4c show the pervaporation behaviors of butanol andpyridine in the course of feed concentration, respectively.As the feed concentration increased so did the threeHBOCs fluxes. Higher feed concentration means strongerdiffusion driving force, which could reduce the resistanceof mass transfer and then result in higher flux. Therefore,increasing the feed concentration properly is also analternative method for improving the pervaporationperformance.

On the other hand, as observed in many membrane per-vaporation researches, selectivities of butanol and pyridinedecreased with the increase of feed concentration, since athigh feed concentrations the denominator term in the selec-tivity relationship becomes large (19). But selectivity ofpropargyl alcohol at 2.7wt% feed concentration was somehigher than that at 2.2wt%. The unexpected result may beexplained by the minor increase of the feed concentration,which needs to be confirmed in the further work.

Effects of Temperature on the PervaporationPerformance of HBOCs

The effects of temperature on the pervaporation perfor-mance of propargyl alcohol, butanol and pyridine werepresented in Fig. 5. As expected, the three HBOCs fluxes

increased almost linearly with temperature. As the feedtemperature rises, the vapor pressure in the feed compart-ment also increases, but the vapor pressure at the permeateside is not affected, which caused an increase of drivingforce, and then enhanced HBOCs fluxes with temperature.Besides, according to the free volume theory, an increase intemperature enhances the thermal mobility of the mem-brane polymer chains, which will create extra free volumeswithin the membrane matrix. This will further increase thesorption and diffusion rates of the permeating molecules,

FIG. 4. Effects of feed concentration on HBOCs flux and selectivity (A)

Propargyl alcohol, solid lines for flux, dashed lines for selectivity (B) Buta-

nol (C)Pyridine.

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thus result in an easy transport of organic component fromthe feed mixture (20). For example, propargyl alcohol fluxwas just 51.42 gm�2h�1 at the temperature of 25�C, theflux jumped to 243.94 gm�2h�1 when the temperature wentup to 60�C. It is reasonable to assume that with furthertemperature increase, a much higher flux of propargyl

alcohol could be obtained by using PDMS membranepervaporation.

The temperature dependency of permeation rates can beexpressed using the Arrhenius type equation (21):

J ¼ A expð� Ep

RTÞ ð5Þ

where J represents the organic permeation flux (gm�2h�1),A is the pre-exponential factor, Ep represents the apparentactivation energy of pervaporation (KJmol�1), R is molargas constant (Jmol�1K�1), and T is the thermodynamicabsolute temperature (K).

Arrhenius plots of lnJ versus 1=T are linear as displayedin Fig. 6, suggesting that the temperature dependency of allthe three HBOCs fluxes follow the Arrhenius. The calcu-lated Ep value for propargyl alcohol, butanol and pyridinewas 36.26, 47.05, and 23.99KJ mol�1, respectively. Theactivation energy values are all positive, which is a directevidence for the result of enhanced fluxes with higher tem-perature (20). Besides, the Ep value showed differences inthe order of pyridine< propargyl alcohol< butanol, whichmeans butanol is more temperature sensitive than the othertwo HBOCs.

On the other side, as seen in Fig. 5, the selectivities of thethree HBOCs behaved differently. For propargyl alcohol,the selectivity was just fluctuating in the range of 3.2–3.8as the temperature increases, which may be considered tobe temperature independent. For butanol, the selectivityincreased with temperature, which was contrary to thecommon trade-off phenomenon existing between flux andselectivity in pervaporation process. However, a similartrend was observed by Qureshi et al. (19). Their results

FIG. 5. Effects of temperature on HBOCs flux and selectivity (A )Pro-

pargyl alcohol (B) Butanol (C) Pyridine.

FIG. 6. Arrhenius plots of ln Jp versus 1000=T at 2.7wt% of propargyl

alcohol, 3wt% of butanol and 2wt% of pyridine in the feed with flow rate

of 110Lh�1.

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showed that higher temperatures were required to desorbbutanol on the basis of adsorption characteristic, whichexplains increased butanol selectivity at higher tempera-tures. For pyridine, the selectivity decreased with tempera-ture, which was in accordance with the trade-off betweenflux and selectivity. It is known that pyridine has largermolecular size (0.60 nm) than water (0.26 nm); therefore,the permeability of pyridine increases slowly than waterwith temperature, resulting in decrease of selectivity. Thedifferences among the three HBOCs selectivity tendenciescould be attributed to the different affinities of the PDMSmembrane for propargyl alcohol, butanol and pyridine.

Pervaporation Characteristics of HBOCs

The pervaporation performance of the three HBOCsunder optimal experimental parameters was summarizedin Table 1. Temperature and feed concentration are keyfactors for pervaporation, the highest pervaporation fluxof propargyl alcohol, butanol and pyridine was 243.24,976.5, and 904.7 gm�2h�1 respectively, with the corre-sponding selectivity of 3.78, 29.65, and 26.09.

With regard to the separation of the HBOCs from watermixtures, the difference between pervaporation and distil-lation is significant. In distillation system, the separationmechanism is based on the boiling point of the compo-nents, which means the light component (water in mostcases) is separated preferentially. While in the pervapora-tion system, the separation mechanism is based on the dif-fusivity and solubility of the components, thus the HBOCscould be separated preferentially through hydrophobicorganic membrane. For this reason, distillation could onlyobtain the low boiling point component first, but perva-poration is able to behave in a ‘‘reverse direction’’ selectiveseparation for the mixtures by obtaining the high boilingpoint component preferentially. Besides, distillation needsto be accomplished under high temperature with bulkyfacility and then causes intensive energy cost, while theoperation condition of pervaporation is relatively moder-ate, which saves not only the cost of heating, but also thecost of the subsequent cooling process.

Especially, the solubility of butanol in water is 7.7 wt%at the temperature of 20�C. In the butanol-water perva-poration experiment, the concentration of butanol in the

permeate was in the range of 22.3–48.4wt%, which farexceeded its solubility limit, and thus the permeate wasphase separated: the upper phase was substantiallyenriched in butanol (about 80wt%), and the lower aqueousphase contained about 92wt% water. The specific phe-nomenon is especially beneficial to butanol recovery.After the phase separation, the aqueous phase could berecycled to the feed stream to further increase the butanolconcentration.

Pervaporation Performance of Different Membranes forSeveral HBOCs Mixtures

Pervaporation behaviors of different membranes for sev-eral HBOCs mixtures are displayed in Table 2. Althoughdifferent membranes showed different separation perfor-mance, all the research indicated the promising prospectof this technology in the recovery of the HBOCs fromaqueous mixtures.

For propargyl alcohol recovery, a total flux of2570 gm�2h�1 with a selectivity of 3.78 was obtained in thiswork, at the feed concentration of 2.7wt% and temperatureof 60�C. To the authors’ knowledge, no such report onpropargyl alcohol recovery by pervaporation has beenpublished, and the results in this work indicate the greatpotential application of the reverse selective separationon propargyl alcohol recovery.

For butanol recovery, the pervaporation behaviors ofvarious membranes were shown in Table 2. The highestselectivity was up to 444, which demonstrated a very highreverse direction separation ability of the silicate mem-brane. Meanwhile, a relative low selectivity of 6 wasobtained by the surface modified PVDF membrane; how-ever, the flux of 4126 gm�2h�1 was high enough to compen-sate for the pervaporation performance. Both the flux andselectivity are important parameters to evaluate the mem-brane behaviors, therefore those membranes with high fluxand reasonable selectivity, such as PDMS=ceramic com-posite membrane and PDMS-PA composite membrane,are especially promising for butanol recovery.

Similarly, several hydrophobic membranes were appliedon pyridine recovery. A high selectivity of 110.3 with a cor-responding flux of 34.6 gm�2h�1 was obtained in the workof Zhang et al. (27), which also indicated a good reverse

TABLE 1Pervaporation performance of three HBOCs under optimal experimental parameters

ComponentFeed flow rate

(L h�1)Feed concentration

(wt%)Temperature

(�C)Component flux

(gm�2h�1) Selectivity

Propargyl alcohol 130 2.7 60 243.24 3.78Butanol 110 3 50 976.5 29.65Pyridine 120 5 35 904.7 26.09

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selective separation ability of the PDMS membrane. In thiswork, the PDMS-PA composite membrane exhibited ahigh flux of 2612.5 gm�2h�1 and reasonable selectivity of19.2. All the results showed that pervaporation, the reversedirection selective separation technology, would be effec-tive for pyridine recovery from aqueous mixtures.

In addition to propargyl alcohol, butanol and pyridine,pervaporation separations of several other HBOCs, includ-ing acetic acid, toluene, ethylbenzene and xylene, were alsoshown in Table 2. The selectivities were especially high forthose aqueous mixtures with tiny content of HBOCs. For

example, the toluene selectivity was up to 882 in thePolypropylene hollow fiber composite membrane perva-poration when the feed concentration was 25 ppm. Allthe results indicate that the ‘‘reverse selective separation’’by membrane pervaporation should be considered as apromising and effective technology.

CONCLUSIONS

Pervaporation separations of three typical high boilingpoint organic compounds (HBOCs) mixtures were carriedout with a composite PDMS membrane. These HBOCs

TABLE 2Pervaporation performance of different membranes for several HBOCs mixtures

Organiccomponent Membrane

Boilingpoint

Organic feedconcentration

(wt%)T

(�C)

Totalflux

(g �m�2 � h�1) Selectivity Ref

Propargylalcohol

PDMS-PA composite membrane 115 2.7 60 2570 3.8 This work

Butanol PDMS=PE=Brass supportcomposite membrane

118 2 37 132 32 (22)

Butanol Silicon membrane 118 3.3 43 69–105 25–58 (19)Butanol Silicate membrane coated with

silicone rubber118 1.01 45 35.6 444 (24)

Butanol PDMS=ceramic compositemembrane

118 1.3 37 1065 18 (8)

Butanol Surface modified PVDFmembrane

118 7.5 50 4126 6 (25)

Butanol Silicone rubber-coated silicalitemembrane

118 1 45 31 149 (26)

Butanol PDMS-PA composite membrane 118 3 50 2253 29.65 This workPyridine PDMS membrane 115 1 25 34.6 110.3 (27)Pyridine Poly(ether-block-amide)

membrane115 3 60 46 16.2 (5)

Pyridine PDMS-PA composite membrane 115 2 65 2612.5 19.2 This workAcetic acid Sn-ZSM-5 zeolite membrane 118 5 90 490 7.7 (6)Acetic acid PDMS-AMEO=OMMT=PES

composite membrane118 10 40 98.36 2.23 (28)

Acetic acid PDMS membrane 118 40 25 92 1.9 (29)Acetic acid Carbon molecular sieve-filled

PDMS membrane118 18 45 170 2.65 (14)

Toluene Dense SBS 111 150 ppm 25 1070 7196 (30)Toluene Porous SBS 111 150 ppm 25 5250 1571 (30)Toluene PDMS composite membrane

filled with carbon black111 200 ppm 25 300 210 (31)

Toluene PDMS composite membrane 111 200 ppm 25 700 85 (31)Toluene Polypropylene hollow fiber

composite membrane111 25 ppm 30 44.9 882 (32)

Ethylbenzene Polypropylene hollow fibercomposite membrane

136 14.8 ppm 30 18.5 604 (32)

Xylene Polypropylene hollow fibercomposite membrane

138 13.4 ppm 30 15.9 575 (32)

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could preferentially permeate the PDMS membrane and beselectively extracted from the mixtures through the mem-brane. To the authors’ knowledge, this is the first reportto present the conception of HBOCs and focus on therecovery of HBOCs by membrane pervaporation. Theeffects of feed flow rate, feed concentration, and tempera-ture on the pervaporation performance of the membranewere examined. The three HBOCs fluxes were all tempera-ture sensitive and followed the Arrhenius equation. Thehighest permeation flux of propargyl alcohol, butanol,and pyridine was 243.24, 976.5 and 904.70 gm�2h�1,respectively, with the corresponding selectivity of 3.78,29.65, and 26.09. Compared with the traditional distillationthat separates different components in a mixture on thebasis of boiling point, membrane pervaporation behavesin a ‘‘reverse direction’’ selective separation for HBOCs,which should be considered as the principal feature ofHBOCs pervaporation.

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