Pervaporation of Ethanol-Water Solutions

Matthew Graham, Tsung-Ming Yeh, Benjamin Hsiao and Devinder Mahajan

Chemical and Molecular Engineering, Stony Brook University, Stony Brook, New York 11794,

______________________________________________________________________________ Abstract
Ethanol can only be used as a fuel if over 99% anhydrous. Currently used distillation and molecular sieves methods are expensive and energy intensive. Pervaporation offers a viable alternative to ethanol dehydration. A pilot unit consisting of a 4L vessel and fitted with a 3 inch membrane holder was designed and assembled. The unit was used to test both commercial and novel polyvinyl alcohol (PVA) membranes for ethanol dehydration. In a typical run, ethanol/water mixtures of 70 to 90 wt.% ethanol were tested with a flow rate of 22 gallons per hour at temperatures ranging from 25C to 90C. In this study, commercially available Sulzer Chemtech Allschwil PERVAP 1210 membrane was used as a baseline to characterize the pilot-scale system within these parameters. The Sulzer 1210 membrane utilizes a micro porous polyacrylonitrile (PAN) support layer produced by phase inversion. The synthetic membranes, under development, utilize a PAN electrospun support layer which makes the support layer more porous. The goal is to increase the flux of these membranes while maintaining selectivity. The obtained results will be used to compare with the synthetically made PVA membranes.

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Introduction
The current energy crisis is affecting countries all over the world. Demand for energy has been growing at an alarming rate as many large countries become industrialized. This has caused substantial pressure on supply and resulted in rising energy prices and constant political tension internationally. Additionally, nearly the entire scientific community now agrees that the worlds current energy sources are having extremely damaging effects on the Earths climate. These political, economic, and environmental forces have sparked considerable interest in developing alternative energy sources [1]. In particular, renewable energy sources have attracted the largest amount of attention in the scientific community. Ethanol is one of these renewable sources receiving considerable attention. It is a very appealing alternative because of its high energy content and versatility in being used as either a mixture with

gasoline, or as a pure fuel, in internal combustion engines with little engine modifications. Currently, most gasoline sold in the United States contains10% ethanol blend (commonly referred to as E10) as no automobile modification is needed to run this mixture [2]. Ethanol fuel has considerably less environmental effect compared to traditional fossil fuels. As a renewable fuel, it is produced from harvested crops that take carbon dioxide out of the atmosphere and thus is often referred to as a carbon neutral energy source [3]. Ethanol is actually one of the oldest chemicals produced by man and thus the engineering of its production has long been established. Almost all the ethanol used for fuel in the United States is produced by fermentation of corn. Fermentation leads to a mixture of 10% to 15% mixture of ethanol and water. This mixture is then distilled until a 95.5% ethanolwater azeotropic mixture is achieved. Ethanol is not an affective fuel unless completely anhydrous. Several commercial techniques are employed to

produce anhydrous ethanol from azeotropic ethanol. The most common are azeotropic distillation methods which employ a third component that can shift the vapor-liquid equilibrium for enrichment and produce anhydrous ethanol. [4] The next most popular method is to dehydrate the wet ethanol with a molecular sieve. Passing the mixture over potassium or sodium zeolite will absorb water while allowing ethanol to percolate through unabsorbed. This separation is based on the size difference between water and ethanol. The ethanol molecular diameter of 4.4 angstroms is too large to be absorbed whereas waters smaller diameter of 2.8 angstroms is small enough to be absorbed. The molecular sieve becomes saturated after repeated use, and it must be heated to expel all the water it absorbed in order to reuse it. Azeotropic distillation is energy intensive and expensive while using molecular sieves are difficult to use on a large scale [5]. Developing a more economical dehydrating method to improve the economics of ethanol fuel production has sparked an exploration for different separation techniques. Pervaporation is one of the methods being explored in this study. Pervaporation utilizes a membrane that separates a specific chemical component from another by the difference in chemical potential and by implementing a pressure difference. The pressure is caused by placing the back side of the membrane under vacuum. The hydrophilicity or hydrophobicity (chemical potential)

is a characteristic of the chemical makeup and structure of the selectivity layer of the membrane results in changing the components permeability. Pervaporation leads to vaporization of the permeate as it travels through the membrane. This phase transition during transport is what uniquely distinguishes pervaporation from other membrane filtration techniques. Since its separation is not related to gas-liquid equilibrium, pervaporation eliminates the problems introduced by the ethanolwater azeotrope [6]. Investigations into pervaporation have proved that it is a viable solution that can reduce costs of producing anhydrous ethanol for fuel. Specifically, table 1 compares the costs of producing dehydrated ethanol (99.8 wt.%) for a 1580L/hour installation. This data shows pervaporation to be half as expensive as other methods[7][8]. Another study of a small scale system (100L/day) revealed that azeotropic distillation is twice as expensive as pervaporation, and molecular sieve absorption is 1.5 times more expensive. [9] The costs of pervaporation increase linearly as production increases whereas azetropic distillation become more cost effective when production reaches 5,000L/hour [10]. From table 2 we see that the pure energy consumption of azetropic distillation is 8 times greater than pervaporation of 95.5% to 99.5% [11]. For this reason pervaporation used in combination with distillation will result in significant energy savings and economic advantages [12].

Table 1. Costs of ethanol dehydration by different techniques in Dollars per Tonne (53L). [7][8]

interest recently because they possess advantages of both polymer and inorganic membranes. Poly vinyl alcohol (PVA) is probable one of the most commonly used membranes for dehydration of alcohols. It consists of 1-3 diglycol which allows for its numerous hydroxy groups to strongly interact with water. It is unique because it is one of the few polymers that is soluble in water, has a high molecular weight, and can be crossed linked either thermally or chemically easily. These characteristics have made PVA membranes the most rigorously studied membranes. A premier membrane company, Sulzer Chemtech, has developed several PVA membranes that are the best in the industry for pervaporation. Their PVA is laid over a micro-porous polyacrylonitrile (PAN) layer that is produced by phase inversion techniques. This mid layer is on top of a non-woven porous polyester (PET) support layer. Our goal is to make a PVA membrane with an electrospun PAN layer. The phase inversion PAN is not nearly as porous as an electrospun PAN layer. Phase inversion produces pockets (or dead ends) that hold liquid and lower the permeable surface area of the membrane and decreases the flux of the membrane. Our goal is to use electrospun PAN layer that will allow for higher fluxes but maintain the membranes selectivity. Unfortunately the electrospun layer produces a very uneven surface for the PVA to be applied. This lowers the structural integrity of the delicate selective layer and makes it more susceptible to damage. In addition, the method of producing the electrospun layer uses charges that attract dust that results in defects in the selective layer. These obstacles must be overcome. In this study, our focus was two-fold: 1) Design and construct a unit to study pervaporation membranes and 2) collect baseline data with a commercial membrane.

Figure 1. Energy consumptions by distillation and pervaporation. [11] Membranes can be organized into different groups based of their chemical affinity. Hydrophilic membranes are the oldest and most widely studied and employed commercially. Because of their hydrophilic properties, they allow dehydration of organics. Naturally the second grouping is the hydrophobic membranes. Though these were developed long after the hydrophilic membranes, there are already finding applications utilizing their characteristics to separate organic mixtures. Several types of membranes exist for pervaporation. Most are grouped into three board categories based on their composition. These include polymers, inorganics, and mixed matrix. Polymeric have been used for the longest period of time and consistent of polymer chains that contain varying degrees of crosslinking. They are the easiest and cheapest to manufacture. Inorganics are mainly made from ceramics and zeolites. They have several advantages in that they can withstand higher temperatures, harsher chemicals, and often have greater selectivity accompanied by greater flux. Unfortunately they are difficult on a large scale and thus very expensive. Mixed matrix membranes are a polymer with inorganics disbursed throughout the membrane structure. They have gained a significant amount of

Experimental
Materials The Sulzer Chemtech Allschwil PERVAP 1210 commercial membrane was used. Its diameter was 3

inches. The ethanol solution of concentration 95.5% by volume in distilled water was used as a feed. Ethanol of 99.9% purity was bought from SigmaAldrich. System A pervaporation system similar to the specifications in Sulzers MEMBRANTECHNIK was assembled though it was customized (Figure 2). The main parts included a 4L feed tank, heating tape & temperature control, 150 psi safety valve, 2 flow meters, vacuum pump, circulating pump, thermocouples, pressure

transmitter, and fume hood. The safety relief valve was added to the feed tank. Two additional pressure gauges were added; one above the feed tank, and the other after Flow meter 2 and before Valve 8. Shielding was added around system to prevent spills from hitting electrical equipment along with insulation for the pumps and feed tank. The system was properly grounded to prevent any possible sparks that could ignite ethanol vapors.

Figure 2. Flow diagram of the pervaporation apparatus.

Method The feed tank was filled with 3L of desired ethanolwater solution and initial samples were taken for analysis to establish accurate mixture composition. The heating tape was then set to 5C above the desired temperature (this is because there is 5C decrease in the temperature at the membrane from the feed tank) and set to 50% voltage as to not damage the heating tape. It is important to note that all vales were closed at this point. The vacuum pump was turned on and valve 1 was opened to allow the pressure to drop to between 200 and 300 millitorr. Once the desired temperature was reached the feed tank pressure was released from the system by opening valve 6 to bring the pressure down to approximately 40 psi. This was done to prevent damage to the membrane during start up. The membrane was installed into membrane holder and sealed tight with the O-ring. Valve 4 was opened and the vacuum was maintained at 800 millitorr. If the pressure did not reach the desired value, the membrane and O-ring were adjusted. Bubbles were released by opening valve 5 and valve 8. The circulating pump was then switched on and both valve 6 and valve 7 were opened to open flow to the membrane. The voltage of the circulation pump was set to produce a flow rate of 22 gallons per hour in all experiments. The system was allowed to equilibrate for 15 minutes and to ensure the absence of bubbles during circulation. Note that at this time the cold trap was not cooled with liquid nitrogen and thus no permeate was yet collected. After the equilibrium time, liquid nitrogen was then added to the cold trap. After 2 hours, the circulating pump and heating tape were switched off. Valve 5 was closed and valve 8 opened to allow the liquid in the membrane holder to drain out of the membrane section. Valve 6 and valve 7 were then closed. The membrane holder was then opened and any remaining liquid was gently soaked up and valve 4 was closed. The membrane was then removed, and cleaned. The vacuum pump was switched off and the vacuum in the cold trap released at valve 2. After the cold trap had warmed to room temperature, the permeate was collected. A small sample of the retentate was also taken. The system

was emptied by opening the valve to the gas cylinder and applying a small pressure to push the feed solution out of valve 8. Analysis Permeate samples were collected and weighed to two decimal places of accuracy. Gas chromatography (GC) was utilized to establish ethanol content in the ethanol/water mixtures run in The GC was an HP 5890 Series II fitted with a HPCarboWax 20M column. It was calibrated by using methanol as an internal standard The analysis method was set as follows. The initial temperature was set at 50C for 3 minutes. Then the temperature was raised at a rate of 40C/min until it reached 120C. It held this temperature for 1 minute.

Figure 3. Assembled apparatus.

Results and Discussion

The pervaporation apparatus built had many additions to its original design in order make it more efficient. One of the first things realized when testing was that our initial guess to add 2L of solution to the feed was not sufficient. We realized the systems piping actually took up about 1L. We thus added 3L of solution to our system for each test. It was also found that our thermometer in the feed tank was not inserted deep enough to the feed tank. It was adjusted to better measure the liquids temperature instead of the gass temperature. Not long after building the apparatus we added insulation to all the pipes and to the feed tank. Without the insulation, the feed tank had to be set much higher than the desired cell temperature. This caused additional pressure within the system that was unnecessary and problematic. With the insulation the feed tank would only have to be set approximately 5C than the desired membrane temperature. The safety relief valve was originally set at 200 psi but the feed tank had a pressure limit of 190psi. We thus replaced the 150 psi relief valve. After several tests the flow meter became damaged from the ethanol solution. It was replaced with a chemical resistant flow meter. Bubbles had plagued the system for the initial tests. With the feed set to high temperatures, the liquid would immediately vaporize and these bubbles would enter into the pump and halt the flow. It was decided that the system could use 15 minutes to equilibrate. After which bubble formation had ceased and the flow was steady at 22 gallons per hour. This is when we added the liquid nitrogen to the cold trap and began collecting permeate. Testing was done with both the bypass (valve 10) closed. Two additional pressure gauges were added; one above the feed tank, and the other after Flow meter 2 and before Valve 8. These gauges helped us observe the pressure drop from the membrane. Extreme pressure differences would indicate the membrane was leaking. Analysis was first done using Total Organic Carbon (TOC) analysis. After many weeks of testing we were unable to get consistent results via this method. Even after calibration results were inconsistent and at times unreasonable. After exhausting our efforts, a gas chromatography with HP-CarboWax 20M column

was used to analyze and quantify the ethanol concentration in our samples. The purpose of this system is to run pervaporation experiments with different membranes. The goal is to have the parameters of the pervaporation system optimized with the commercial membrane. The results of the commercial membrane were used as a standard in which will be used to compare against our synthetically made membranes. As stated above a large portion of the work was done to adjust the system physically to operate the pervaporation experiments more efficiently. Next, a significant portion of work was put into adjusting our operating procedure in order to get the reliable and accurate results. Once our system was able to achieve results similar to literature data for the sulzer 1210 membrane, we made certain that the system was properly optimized. The independent variables in the pervaporation experiments are temperature and ethanol concentration of the feed solution. Adjusting these variables would yield different membrane flux, and ethanol concentrations in the permeate. From the measured concentrations of feed and permeate we can calculate the separation factor. The separation factor is determined by the equation:

Where both y and x are weight fractions (of their component) in the permeate and feed respectively [20]. This factor helps us compare how well a particular membrane, or set of parameters, is affecting the separation. A higher value indicates better separation. The results for the permeate flux at different temperatures and feed concentrations are plotted in Figure 4. We can see that as temperature increases, the flux for each sample increases in a linear fashion. This is an expected result as the temperature is directly correlated with flux. The increased kinetic energy translated to greater kinetic activity at the membrane and thus greater flux. We could also see that as the feeds ethanol content increased, the flux decreased. This is also an expected result. Since the membrane is selective towards water, with the concentration of water decreasing, the flux will

naturally decrease. Figure 4 also includes a reference line from known literature data (REF). Their results for the Sulzer 1210 membrane at 80% ethanol feed solution over this temperature range overlap nicely with our 80% feed concentration. The results for flux for our current operation are right on target with other current experiments.

Figure 5. Permeate ethanol concentration vs. temperature at different ethanol feed concentrations.

Figure 4. Permeate flux vs. temperature at different ethanol feed concentrations. The results for separation factor and permeate concentration vs. temperature at different concentrations of feed solution are shown in figure 5 and 6. The data reveal that higher temperature results in the permeate containing more ethanol and decreasing separation factor. Higher temperatures mean more activity at the membrane and thus poor separation (despite increasing flux). We also see that a higher ethanol concentration in the feed results in higher separation factor. This can be expected by looking at the mathematic formula which shows the higher feed concentration will naturally result in the formula returning a higher separation factor. The higher the ethanol concentration in the feed, the less the ethanol in the permeate. Experiments done with 90% ethanol feed concentration were omitted as the results were unusual and must be repeated.

Figure 6. Separation factor vs. temperature at different ethanol feed concentrations. Though the results for our permeate flux line up perfectly with the literature, the results for the selectivity of our Sulzer 1210 membrane have not been as pleasing. The literature values with the Sulzers 1210 separation membrane should be higher. Some of the literature values refer to a precondition which requires the membrane to sit in contact with the solution for 12 hours. It is believed that this time allows the membrane become equilibrated and will yield the actual selectivity results. Future experiments will test this new method. The next set of tests will be done with synthetically produced membranes and accurately compared with the results now obtained with the commercial membrane. This information will help us gauge and analyze the effectiveness of the synthetic membranes as we continue developing better membranes for ethanol dehydration.

Error Analysis and Statistical Significance of Results

The data obtained is the first set of data. Therefore, no error analysis or statistical significance was conducted. A duplicate set needs to be conducted to conduct such analysis.

[6] B. Smitha, D. Suhanya, S. Sridhar,M. Ramakrishna, Separation of organic-organic mixtures by pervaporationa review Journal of. Membrane Science, 241 (2004) 121. [7] U. Sander, P.B. Soukup, Design and operation of pervaporation plant for ethanol dehydration Journal Membrane Science, 36 (1988) 463475. [8] U. Sander, P.B. Soukup, Practical experience with pervaporation systems for liquid and vapor separation Journal Membrane Science, 62 (1991) 6789. [9] H.E.A. Bruschke, G.F. Tusel, Economics of industrial pervaporation processes Proceedings of the Conference on Membranes and Membrane Processes, (1986) 581586. [10] R.W. Baker, Pervaporation, Membrane Separation SystemsRecent Developments and Future Directions William Andrew Publishing Noyes (1991) 161186. [11] K.R. ,Lee, J.Y. Lai, Pervaporation Journal of the Chinese Institute of Chemical Engineers, (1998) [12] C.H. Gooding, F.J. Bahouth, Membrane-aided distillation of azeotropic solution Chem. Eng. Com. 35 (1985) 267279. [20] Xiang-Yi Qiao, Pervaporation study of aqueous ethanol solution through zeolites-incorporated multilayer poly(vinly alcohol) membranes: Effect of zeolites Journal of Membrane Science, 276 (2005) 260-271.

Conclusion
The world is currently facing an energy crisis as demand is growing significantly faster than supply. Current sources are also leading to a worldwide climate shift that could have serious consequences. Ethanol fuel offers a viable solution to help elevate these problems. However, current purification technology causes manufacturing costs to be high. The development of the pervaporation as an alternative separation method could drastically reduce production costs. In the reported study, the Sulzer 1210 commercial membrane was evaluated in our customized pervaporation apparatus. These results are our baseline to develop PVA membranes with an electrospun PAN support layer that should have increased flux with similar selective properties.

References
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