6.

Membrane Separation Processes as Unit Operation

Summary In this chapter technically relevant membrane separation processes are treated as unit operation. Their basic principles and various commonly applied operation modes are described. The theoretical and practical limitations due to membrane properties or the design of the processes indifferent applications is discussed and their technical and economic advantages compared to other competing processes are pointed out. The possibility of combining processes which have different ranges of optimum efficiencies for a given separation tasks as so-called hybrid is discussed and typical hybrid processes of practical relevance are described.

6.1 General considerations As pointed out earlier, membrane separation processes can differ greatly in the membranes and driving forces used for separation, the process design, the area of application and their technical and economic relevance. Table II gives a summary of technically relevant membrane separation processes, the membrane type used in these processes, their operating principles and their main areas of application. The driving forces applied for the transport of the various components through the membrane are hydrostatic pressure differences, chemical and electrochemical potential gradients across the membrane which may be expressed in concentration differences, partial pressure differences or electrical potential differences between two solutions separated by a membrane. The effeciency of a separation in a given membrane process, however, is not only determined by the membrane properties and the applied driving force or forces. In membrane separation processes components are generally concentrated in the so-called retentate and depleted in the permeate. The maximum or minimum concentration that can be achieved in the retentate or the permeate, respectively depents not only on the membrane properties but is also effected by the process design especially by the recovery rate of the original feed mixture. The same is true for the loss of produce which shall be recovered in the retentate when the membrane is not strictly semipermeable. For economic reasons should the recovery rate in a membrane process always be as high as possible. However, for given membrane properties andmembrane process and its application can a certain maximum recovery rate not be exceeded. In treating the various membrane pocesses as unit operations a relation between various process parameters such as concentration of the different components in the feed, the retentate and the permeate and the recovery rate is developed.

Table II Technically relevant membrane separation processes, their operating principles, and their application
separation process microfiltration membrane type used symmetric porous structure, pore radius 0.05-5 m asymmetric porous structure,pore radius 2-10 nm asymmetric porous structure,pore radius 2-10 nm asymmetric skin-type solution-diffusion structure Symmetric porous or gel-type structure symmetric ionexchange membrane symmetric ionexchange membrane bipolar membrane homogeneous symmetric structure homogeneous symmetric structure homogeneous symmetric structure symmetric porous hydrophobic structure, symmetric porous structure, or liquid membrane applied driving force hydrostatic pressure 0.5-4 bar hydrostatic pressure 1-10 bar hydrostatic pressure 1-10 bar hydrostatic pressure 10-100 bar concentration gradient electrical potential concentration gradient of individual ions electrical potential vapor pressure gradient vapor pressure gradient vapor pressure gradient vapor pressure gradient chemical potential gradient mode of separation filtration (size exclusion) filtration (size exclusion) filtration & dialysation (size exclusion) solutiondiffusion mechanism diffusion applications water purification, sterilization Separation & fractionation of molecular mixtures purification of molecular mixtures artificial kidney sea & brackish water desalination artificial kidney

ultrafiltration

diafiltration

reverse osmosis

dialysis

electrodialysis donnan dialysis

migration Donnan-exclusion diffusion Donnan exclusion migration, Donnan-exclusion solutiondiffusion solutiondiffusion solutiondiffusion diffusion diffusion solution

water desalination water softening

electrodialytic water dissociation gas separation pervaporation vapor permeation

membrane distillation membrane contactores

acid & base production from salts oxygen/nitrogen separation separation of azeotropic mixtures recovering of organic vapors from air liquid/solid separation Solvent extraction

6.2 Pressure driven membrane processes Typical pressure-driven membrane processes are microfiltration, ultrafiltration, reverse osmosis, and gas separation which, however, will be treated seperatly. The principle of these processes is illustrated in Figure 1.

feed mixture

pfeed pperm

retentate permeate

concentrate filtrate

perm = papplied, ( pfeed > pperm) p feed - p

Fig. 1. Schematic diagram illustrating pressure-driven membrane separation processes

Microfiltration, ultrafiltration and reverse osmosis are basically identical processes and differ only in the sizes of the particles to be separated and the membranes used. In all three processes, a mixture of different size components is brought to the surface of a semipermeable membrane. Under the driving force of a hydrostatic pressure gradient, some components permeate through the membrane while others are more or less completely retained. Thus, in reverse osmosis or ultra- and microfiltration, a feed solution is separated into a filtrate depleted of particles or molecules and a retentate in which these components are concentrated. The term microfiltration is used when particles with diameters in the range of 0.1 to 10 m are separated from a solvent or other components of low molecular weight. The separation mechanism is based on a sieving

effect and particles are separated solely according to their dimensions. The membranes used for microfiltration are symmetric microporous structures with pore sizes in the range of 0.1 to 10 m. The hydrostatic pressure differences used are in the range of 0.5 to 4 bars. The separation process is called ultrafiltration when the components to be retained by the membrane are true molecules or small particles not larger than 0.1 m in diameter. This roughly corresponds to the limit of resolution obtainable in an optical microscope. In ultrafiltration, where generally the osmotic pressure of the feed solution is negligibly small, hydrostatic pressures of 2 to 10 bars are used. Ultrafiltration membranes are mostly asymmetrically structured with pores in a skin layer having a diameter of 4 to 50 nm.

In reverse osmosis low molecular weight compounds, such as salts, sugars etc. are separated from a solvent, usually water. Feed solutions, therefore, often have significant osmotic pressures. These have to be overcome by the hydrostatic pressure applied as driving force. As shown earlier, the transmembrane flux, according to Equation (2.161), is a function of the hydrodynamic permeability, and a net pressure difference, the hydrostatic pressure difference between feed- and filtrate solution minus the difference in osmotic pressure between the feed and filtrate solutions. The osmotic pressure of a solution containing low molecular weight solutes, such as salts or sugar etc., can be rather high, even at relatively low solute concentrations. The osmotic pressure for sea-water, for instance, is about 20 to 25 bars. The osmotic pressure of orange juice is between 25 and 30 bars. The osmotic pressure which has to be overcome by the applied hydrostatic pressure limits the practical application of reverse osmosis. Gas permeation is in many aspects similar to reverse osmosis. In both processes asymmetric solution diffusion-type membranes and a hydrostatic pressure driving force are used for the transport of different components through the membrane. The selectivity of which is also determined by the solubility and diffusivity of the different components in the membrane. In

contrast to reverse osmosis, where liquid mixtures are separated, in gas permeation, the feed mixture to be separated consists of gases or vapors. The terminology used in gas permeation to describe the separation properties of the membrane or the process is also different to those used in reverse osmosis and will be discussed separately.

6.2.1 Pressure driven membrane processes as unit operation The most relevant pressure driven processes today are ultra- and microfiltration, and reverse osmosis. Their basic operating principle is illustrated in Figure 1. It shows a membrane in converting a feed mixture under the driving force of a hydrostatic pressure gradient into a retentate and a filtrate. For simplicity, both the retentate and the filtrate are assumed to be well mixed and to have no concentration gradients. When the feed mixture of molecules and particles is brought to the surface of a semi-permeable membrane by convection the solvent and/or small solutes pass the membrane as filtrate under a hydrostatic pressure driving force, while larger particles and molecules are retained by the membrane and concentrated in the retentate. The performance of a membrane in a pressure driven separation process is determined by its filtration rate, i.e. the transmembrane flux at a certain hydrostatic pressure driving force and its mass separation properties, that is its capability to retain certain components of a mixture. The filtration rate or transmembrane fluxes in microfiltration, ultrafiltration and reverse osmosis can be described respectively by the equations (2.126), (2.131) and (2.161), as discussed in the previous section of this outline. In a more general relation the membrane flux properties in pressure driven membrane processes can also be expressed by a hydrodynamic resistance of the membrane matrix, i.e.:

Jv

1 RM

(1)

Here Jv is the filtration rate and RM is the hydrodynamic resistance of the membrane.

6.2.1. 1 Recovery rate, membrane retention, retentate and filtrate concentrations The separation capability of a membrane in reverse osmosis or ultra- and microfiltration can be expressed in terms of a membrane retention or rejection rejection coefficient, which is defined as:

Cf R =1 s r Cs

(2)

Here R is the rejection of the membrane for a given component, s under certain operating
f r conditions of hydrostatic pressure and feed solution concentration. Cs and Cs are the

concentrations of the rejected component, s in the filtrate and the retentate, respectively. Because of osmotic pressure, viscosity, etc., the concentration in the retentate in reverse osmosis or ultra- and microfiltration cannot exceed a certain maximum value. The solvent of feed solution can, therefore, never be completely recovered as filtrate. The part of the feed solution that can be recovered as filtrate, i.e. ratio of the filtrate volume to that of the feed solution volume is referred to as the recovery rate, :

Vf Vo

(3)

Here Vf and Vo are the volume of the filtrate and the feed solution, respectively. The recovery rate is a strictly operational variable, which is not directly linked to membrane properties. 7

The concentrations in the retentate and the filtrate are not only determined by the membrane rejection but they are also a function of the feed solution concentration and the recovery rate. The relation between concentration of retentate, filtrate, and feed solutions and the membrane rejection and recovery rate, can be obtained from a simple mass balance. If complete mixing of the retentate solution is assumed, the concentration of a component in the retentate is given by:

r Cs = Co (1 )R s

(4)

o Here Cs is the initial concentration of the feed solution.

The concentration in the filtrate is directly proportional to that in the retentate and given by: C f r = (1 R)Cs s (5)

Thus, for a given recovery rate, the filtrate concentration at any given time is found by introducing Equation (4) into equation (5):

f o Cs = Cs (1 R)(1 )R

(6)

o r f HereCs , Cs and Cs are the concentrations of the feed solution, the retentate and the filtrate,

respectively, at a given time during the filtration process. R is the rejection of the membrane and the recovery rate achieved during a given time. It should be noted that the filtrate concentration expressed in equation (6) is the concentration corresponding to a given recovery rate, i.e. during an infinitely small time interval. For most practical application, however, the filtrate concentration obtained at an infinitely small time interval, at a certain recovery rate, is of less interest than the so-called "mixing cup" concentration, which is obtained when the entire filtrate up to a given recovery rate, is collected and

mixed. The mixing cup filtrate concentration can be calculated by the following relation, which is obtained by integration of equation (6):

Co f Cs = s (1 )(1 )1 R

(7)

f Here Cs is the mixing-cup concentration.

The mixing cup concentration is always lower than the concentration obtained during an infinitely short time period at a certain recovery rate. The relation between the recovery rate, the membrane rejection, the retentate, the filtrate and the mixing cup concentration is illustrated in Figure 2, where the retentate, the filtrate, and the mixing cup concentrations are each shown as a function of the recovery rate for three different membrane rejection coefficients.
20 retentate concentration C rs / Cos

15

R = 0.99

10 R = 0.8 5

a)

R = 0.5

0.0

0.2

0.4

0.6

0.8

1.0

recov ery rate

3.0 f iltrate concentration (C f s / Cos )

R=0.99 2.0 R=0.8 b) 1.0 R=0.5

0.0

0.0

0.2

0.4

0.6

0.8

1.0

recov ery rate

mixing-cup f iltrate concentration (C fs /C os )

1.0 0.8 0.6 0.4 0.2 0.0 R=0.8 R=0.99

c)

R=0.5 0.0 0.2 0.4 0.6 0.8 1.0

recov ery rate

Fig. 2 a) Ratio of retentate to feed solution concentration, b) filtrate to feed solution concentration and c) "mixing cup" filtrate to feed solution concentration as a function of the recovery rate calculated by equations (4), (6) and (7), each for three different membrane solute rejections.

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In membrane evaluation or characterization tests, the rejection of a membrane is generally calculated from the mixing cup filtrate and the retentate concentration, two experimental values which can easily be measured by rearranging Equation 7:

R =1

Cf ln 1 s Co s ln(1 )

(8)

f Here R is the membrane rejection, Cs and are the mixing cup filtrate and the feed solution

concentrations, respectively, and is the recovery rate. The significance of the mixing cup and maximum retentate concentration can be illustrated in practical examples. For instance, in the production of potable water from sea or brackish water the concentration in the filtrate should not exceed 500 mg total dissolved solutes per liter. This concentration is the filtrate collected over a certain time and recovery rate, i.e. the mixing cup concentration. For economic reasons the recovery rate should always be as high as possible. Often, however, the recovery rate of a given feed solution is not only limited by the maximum value of the mixing cup concentration of the filtrate. If the feed solution contains solute with limited solubility, e.g. salts such as CaSO4 or CaCO3, the recovery rate is determined by the maximum retentate concentration achievable without solute precipitation and that is the maximum retentate concentration at a given recovery rate. 6.2.1.2. Solute losses in membrane filtration processes In a membrane filtration process the product may be either the filtrate (as in the production of ultra pure or sterile water) or the retentate (as in the concentration of proteins from whey). For membranes, which are not strictly semi-permeable, i.e. membranes which have a solute rejection of less than 100 %, some solutes will be found in the filtrate. This might effect the

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quality of the filtrate, which for example may be ultrapure water, or may lead to product losses, when say protein are recovered from whey by filtration. The fractional solute loss is usually expressed by the ratio of solute lost with the filtrate divided by the total amount of solutes in the feed solution. The fractional solute loss is calculated from Equation (2) and (7) and given by:

Vf C r 1 R o = 1 (1 ) VoC

(9)

Here is the fractional solute loss, Vf and Vo are the volumes of the filtrate and the feed solution, Cr and Co are the mixing cup filtrate and the initial feed solution concentrations. is the recovery rate, and R is the membrane rejection. The product loss may be significant even with membranes that have a relatively high solute rejection, when high retentate concentrations are desired, as indicated in Figure 3. Here fractional solute loss is shown as a function of the recovery rate for different membrane rejection.
0.8 f ractional solute loss 0.6 0.4 R=0.8 0.2 R=0.99 0.0 0.0 0.2 0.4 0.6 0.8 1.0 R=0.5

recov ery rate

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Fig. 3

Fractional solute loss in membrane filtration, calculated for different membrane

rejection by equation (9), shown as a function of the recovery rate.

6.2.1.3 The osmotic pressure and energy requirements in membrane filtration processes The minimum energy, i.e. the reversal energy required in any separation process is given by the Gibbs free energy of mixing of the filtrate and retentate solutions, which is given by:

a Gm = G G = ( dn = dn) RT ln i i i i i a
i i i

(10)

Here Gm is the Gibbs free energy of mixing two solutions indicated by and , m is the chemical potential, a the activity and n the number of moles, the subscript i refers to individual components. For dilute solutions the chemical potentials can to a first approximation be expressed by the osmotic pressures of the solution. Thus is:

Gm Vf ( ) = Vf

(11)

Here is osmotic pressure difference between the two solutions and separated by the membrane and Vf is the filtrate volume. The energy required in pressure driven filtration processes in a practical application for the separation of various components is always higher than the theoretical minimum due to irreversible friction energy which is consumed when the individual molecules move through the membrane matrix and when the pressurized retentate is brought back to atmospheric pressure by forcing it through a pressure relieve valve. Thus, the total energy consumed in a

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pressure driven filtration process is given by the applied hydrostatic pressure multiplied by the filtrate volume and if there is no energy recovery system by the volume of the retentate. E tot Vf (p ) + Vr p

(12)

The basic difference between reverse osmosis and ultra- or microfiltration, as pointed out before, is the size or molecular weight of the solutes which are separated from a solution. In reverse osmosis low molecular weight components, such as salts, sugars, etc. are separated from a solvent and the feed solution has a significant osmotic pressure, which has to be overcome by the hydrostatic pressure applied as driving force while in ultra- and especially in microfiltration macromolecular components or particles are retained by the membrane and the solutions have generally negligibly low osmotic pressures.

6.2.1.4 Diafiltration A variation of the ultrafiltration process, generally referred to as diafiltration, is often used when a more complete separation of micro- and macrosolutes from a mixture is required. This process, which competes directly with dialysis, is shown schematically in Figure 4 .

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rinse solution (V w)

feed solution (V o C o ) membrane

diafiltrate (V f,C f)

Fig. 4 Schematic diagram illustrating the operating mode of diafiltration

The schematic diagram shows a batch-type ultrafiltration system containing a mixture of various macro- and microsolutes. The membrane to be used in diafiltration should retain the macromolecular components more or less completely and should not reject the microsolutes. If the filtrate removed from the cell is replaced by pure solvent the low in molecular weight constituents will gradually be washed out of the feed mixture. The concentration of the various components in the diafiltration vessel at any time can be calculated by a simple mass balance. If the volume of the original solution is kept constant and identical to the volume of the diafiltration vessel, the concentration in the diafiltration vessel can then be calculated as a function of the membrane retention and the volume of the diafiltration washing solution, i.e. the pure solvent replacing the filtrate volume. The concentration change in time in the filtrate is given by:

dC Vf C f = Vo dt Furthermore is:

(13)

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 Vf = Vw and C f = (1 R )C r

(14)

(15)

Here Vf and Vw are the volume fluxes of the filtrate and the added wash solution, C f and C r are concentrations in the filtrate and the diafiltration vessel at a certain time t and R is the membrane retention. Introducing Equations (14) and (15) into Equation (13) and integrating with the boundary
r r conditions: t = 0,Cr = Co and t = t x ,C = Ct leads to:

Cr t C

= exp

V t x (1 R ) Vo

(16)

Introducing Vw t x = Vw into equation (16) and rearranging gives the concentration in the diafiltration vessel at a given time as an exponential function of the volume wash solution added and the membrane retention: V r o C t = C exp w (1 R) Vo (17)

r Here are C t and Co the concentrations in the diafiltration vessel at the time t and the feed

solution at the beginning of the filtration, respectively. Vo is the volume of the diafiltration vessel, Vw is the volume of solvent added at time t, and R is the rejection of the membrane for the component under consideration. If the component is completely retained by the membrane, i.e R = 1, its concentration in the batch cell will not change. If the component passes the membrane unaffected, i.e. R = 0, its concentration in the diafiltration vessel will decrease according to the exponential function expressed in equation (17). The wash-out effect obtained in diafiltration is illustrated in

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Figure 5, where the retentate concentration is shown as a function of the ratio of rinse to feed solution volume for various membrane rejections.

1 .0 Cr / C o

0 .8

R = 0 .99 R = 0.9

0 .6

0 .4 R = 0 .5 0 .2 R=0 0 ,0 0 2 4 6 8 Vw/ Vo 10 12

Fig. 5 Reduced retentate concentration in diafiltration as a function of the rinse water volume calculated by equation (17) for various solute rejections

If the a macromolecular component is only partially rejected by the membrane, a substantial loss of product will be encountered. If complete removal of a components the low in molecular weight without substantial loss of macromolecular material is desired, rejection of the membrane should be close to zero for the component low in molecular weight, and close to one for the macromolecular component as shown in Figure 5.

6.2.1.5 Product loss in diafiltration As in ultrafiltration, product losses in diafiltration may be significant when, e.g., in a process of desalting a macromolecular solution, the membrane does not reject the macromolecules completely. The product loss is then given by: 17

Vf Cf VoCo

(18)

Furthermore is at any time: Vf C f = Vo Co Vo Cr (19)

Introducing Equation (17) and (19) into Equation (18) and rearranging gives the product loss in diafiltration as function of the wash solution volume, the diafiltration vessel volume and the membrane retention.

V = 1 exp w (1 R) Vo

(20)

Here is the fractional product loss, Vo , Vf and Vw are the volumina of the diafiltration vessel, the filtrate and the wash solution, R is the membrane rejection. In Figure 6 the fractional product loss is shown as a function of the ratio of feed solution and wash solution volume for membranes with different rejection characteristics as calculated from Equation (20).

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1.0 R = 0.8 f ractional product loss 0.8

0.6 R = 0.90 0.4 R = 0.99 0.2

0.0 0 10 20 V w /Vo

Fig. 6 The fractional product loss in diafiltration calculated by equation (20) for various solute rejections

As can easily be seen from Figures 5 and 6, the concentration of a low molecular weight solute is reduced to less than 1 % of its original value by wash solution volume 5 times that of the feed solution volume, when the membrane passes the solute unhindered, i.e., R = 0. If the solute is partially rejected by the membrane correspondingly more wash solution is needed to reduce the concentration of the low molecular weight solute below a certain value. On the other hand when the membrane rejects the macro solute completely, no product is lost, but partial rejection leads to a significant product loss.

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