Vapor permeation systems processes

The most common membrane systems are driven by pressure. The essence of a pressure-driven membrane process is to selectively permeate one or more species through the membrane. The stream retained at the high pressure side is called the retentate while that transported to the low pressure side is denoted by the permeate (Fig. 11.1). Pressure-driven membrane systems include microfiltration, ultrafiltration, reverse osmosis, pervaporation and gas/vapor permeation. Table ll.l summarizes the main features and applications of these systems. 

On-line pervaporation, 18 518 On-line probes, for fermentation, 11 39 On-line vapor permeation, 18 518 On/off feedback controllers, 20 691 Onstream analyzers, 20 682 On-tank leak detection systems, 24 311 Onyx thermal printing process, 19 321 Oocytes, retroviral infection of, 12 457 Oolitic limestone, 15 28 Opacification, colorants for ceramics, 7 344-345... 

Indeed, in many cases the membrane system cannot be used directly and often pretreatment is necessary to facilitate the membrane process. Pretreatment is important and necessary in micro-, ultra-, and nanofiltration, while it is not that important for pervaporation (PV), vapor permeation (VP), or gas separation for which feed streams are usually much cleaner and do not contain many impurities. The cost of pretreatments can contribute appreciably to the overall costs. However, due to the intrinsic... 

As the membrane-based absorption process is usually efficient if the VQC concentration in the feed is ranging between 300 and 100 ppmv, whereas the membrane-based vapor permeation process is more effective at higher VQC concentrations, Poddar and Sirkar [34] studied the potentialities of a hybrid system where the two processes are coupled. The vapor permeation... 

According to a recent conference given by Prof. Kita [162], the classical synthesis method currently used by Mitsui allows to produce about 250 zeolite membranes per day. Both the LTA and T types (Na K) membranes are now commercial and more than 80 pervaporation and vapor permeation plants are operating in Japan for the dehydration of organic liquids [163]. A typical pervaporation system, similar to the one described in [8], is shown in Fig. 11. One of the most recent applications concerns the production of fuel ethanol from cellulosic biomass by a vapour permeation/ pervaporation combined process. The required heat is only 1 200 kcal per liter of product, i.e. half of that of the classical process. Mitsui has recently installed a bio-ethanol pilot plant based on tubular LTA membranes in Brazil (3 000 liters/day) and a plant with 30 000 liters/day has been erected in India. The operating temperature is 130 °C, the feed is 93 % ethanol, the permeate is water and the membrane selectivity is 10 000. 

Hyperfiltration (reverse osmosis), pervaporation, and gas/vapor permeation have been proposed for producing anhydrous ethanol. Several companies such as GFT Membrane Systems GmbH, Kalsep, and Lurgi have constructed membrane separation plants which utilize the pervaporation process or the vapor permeation process where flat membranes are used. 

Membranes can also be used to purify a mixmre and attain composition beyond the azeotropic composition. The pervaporation process features a liquid feed, a liquid retentate, and a vapor permeate. While gas-phase membrane processes are essentially isothermal, the phase change in the pervaporation process produces a temperature decrease as the retentate flows through the unit. Since flux rates decrease with decreasing temperature, the conventional pervaporation unit consists of several membrane modules in series with interstage heating. The vapor permeate must be condensed for recovery and recycle, and refrigeration is usually required. Hybrid systems of distillation columns and pervaporation units are frequently used in situations where distillation alone is impossible or very expensive. An important application is the removal of water from the ethanol-water azeotrope. Chapter 14 will discuss the details of design and control of such processes. 

Typical specirications for pipeline gas are CO2 less than 2%, H2S less than 4 ppmv. and water less than 7 Ib/MMscf. Water vapor is a very fast gas and, therefore, dehydration to pipeline specifications can be achieved by membrane systems while also removing the slower CO2 or H2S acid gases. Membrane permeation systems can remove CO2 to the required 2% level however, at low CO2 concentrations, the CO2 partial pressure driving force is reduced and a significant amount of hydrocarbon (primarily methane) is lost with the CO2-rich piermeate. The problem becomes even more severe when trying to remove substantial quantities of H2S to meet a 4 ppmv specification. Normally, with membranes only modest adjustments to H2S concentration in the ppm range are economically feasible. However, subsequent treatment with other processes to meet the H2S specification is possible. 

A hybrid process that combines membrane separation and distillation for bioethanol and biobutanol production is being worked on by MTR [88, 89]. The membrane units use either vapor permeation or PV. The BioSep processes offer more than 50% energy savings and are cost competitive with respect to conventional distillation-molecular sieve technology. They are attractive when the ethanol concentration in the fermentation step is low, such as in cellulose-to-ethanol and algae-to-ethanol. In the case of biobutanol production, the membrane systems concentrate and dehydrate the acetone, butanol and ethanol mixture, saving up to 87% of the energy required to recover biobutanol by conventional separation techniques. 

Membrane Pervaporation Since 1987, membrane pei vapora-tion has become widely accepted in the CPI as an effective means of separation and recovery of liquid-phase process streams. It is most commonly used to dehydrate hquid hydrocarbons to yield a high-purity ethanol, isopropanol, and ethylene glycol product. The method basically consists of a selec tively-permeable membrane layer separating a liquid feed stream and a gas phase permeate stream as shown in Fig. 25-19. The permeation rate and selectivity is governed bv the physicochemical composition of the membrane. Pei vaporation differs From reverse osmosis systems in that the permeate rate is not a function of osmotic pressure, since the permeate is maintained at saturation pressure (Ref. 24). 

If simple sample pretreatment procedures are insufficient to simplify the complex matrix often observed in process mixtures, multidimensional chromatography may be required. Manual fraction collection from one separation mode and re-injection into a second mode are impractical, so automatic collection and reinjection techniques are preferred. For example, a programmed temperature vaporizer has been used to transfer fractions of sterols such as cholesterol and stigmasterol from a reversed phase HPLC system to a gas chromatographic system.11 Interfacing gel permeation HPLC and supercritical fluid chromatography is useful for nonvolatile or thermally unstable analytes and was demonstrated to be extremely useful for separation of compounds such as pentaerythritol tetrastearate and a C36 hydrocarbon standard.12... 

So far, the separation of azeotropic systems has been restricted to the use of pressure shift and the use of entrainers. The third method is to use a membrane to alter the vapor-liquid equilibrium behavior. Pervaporation differs from other membrane processes in that the phase-state on one side of the membrane is different from the other side. The feed to the membrane is a liquid mixture at a high-enough pressure to maintain it in the liquid phase. The other side of the membrane is maintained at a pressure at or below the dew point of the permeate, maintaining it in the vapor phase. Dense membranes are used for pervaporation, and selectivity results from chemical affinity (see Chapter 10). Most pervaporation membranes in commercial use are hydrophyllic19. This means that they preferentially allow... 

Pervaporation is a membrane separation process where the liquid feed mixture is in contact with the membrane in the upstream under atmospheric pressure and permeate is removed from the downstream as vapor by vacuum or a swept inert gas. Most of the research efforts of the pervaporation have concentrated on the separation of alcohol-water system [1-20] but the separation of acetic acid-water mixtures has received relatively little attention [21-34]. Acetic acid is an important basic chemical in the industry ranking among the top 20 organic intermediates. Because of the small differences in the volatility s of water and acetic acid in dilute aqueous solutions, azeotropic distillation is used instead of normal binary distillation so that the process is an energy intensive process. From this point of view, the pervaporation separation of acetic acid-water mixtures can be one of the alternate processes for saving energy. 

The pervaporation process to separate liquid mixtures is shown schematically in Figure 9.1. A feed liquid mixture contacts one side of a membrane the permeate is removed as a vapor from the other side. Transport through the membrane is induced by the vapor pressure difference between the feed solution and the permeate vapor. This vapor pressure difference can be maintained in several ways. In the laboratory, a vacuum pump is usually used to draw a vacuum on the permeate side of the system. Industrially, the permeate vacuum is most economically generated by cooling the permeate vapor, causing it to condense condensation spontaneously creates a partial vacuum. 

In an attempt to overcome the significant difficulties that the presence of water vapor poses to the analysis of very volatile compounds, purge-and-membrane extraction techniques have been developed that largely prevent the introduction of water into the analytical system. Typical implementations of this form of sample introduction have been called by its developers membrane extraction with a sorbent interface (MESI),97 or membrane introduction mass spectrometry (MIMS).98 " They are based on a silicone hollow-fiber membrane that is inserted into the sample to be monitored, and the passing of a certain volume of inert gas through the membrane. Volatile compounds permeate the membrane and are swept to the adsorbent trap from which they are desorbed into the GC. This method of sample introduction is particularly suited for field and process monitoring and for dirty samples, since it prevents any nonvolatile compounds from entering the analytical system.100... 

A process referred to as vapor-arbitrated pervaporation addresses these issues by manipulating the transmembrane activity gradients of water and ethanol in a pervaporation system. Using a permeate side sweep stream that contains water vapor at a partial pressure corresponding to the activity of water on the feed side, permeation of water is halted while ethanol continues to diffuse through the membrane into the sweep stream and is removed. In this way, the native permselectivity of the membrane system can be altered in a controlled fashion to extract one or more volatile components from a solution. 

The models most frequently used to describe the concentration dependence of diffusion and permeability coefficients of gases and vapors, including hydrocarbons, are transport model of dual-mode sorption (which is usually used to describe diffusion and permeation in polymer glasses) as well as its various modifications molecular models analyzing the relation of diffusion coefficients to the movement of penetrant molecules and the effect of intermolecular forces on these processes and free volume models describing the relation of diffusion coefficients and fractional free volume of the system. Molecular models and free volume models are commonly used to describe diffusion in rubbery polymers. However, some versions of these models that fall into both classification groups have been used for both mbbery and glassy polymers. These are the models by Pace-Datyner and Duda-Vrentas [7,29,30]. 

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