Membrane Separation Technology

Membrane Separation Processes
Neha Kathayat Rugved Pathare Daksh Pratap Singh
Overview
Introduction Ultrafiltration Reverse Osmosis Electrodialysis Summary
Overview
Overview
Overview
Overview
Overview
Introduction
interphase separating two phases and selectively controlling the transport of materials between those phases Since the 1960s a new technology using synthetic membranes for process separations has been rapidly developed
Strathmann defines a membrane as an
Introduction
interphase separating two phases and selectively controlling the transport of materials between those phases Since the 1960s a new technology using synthetic membranes for process separations has been rapidly developed
Strathmann defines a membrane as an
Advantages offered
Ambient temperature operation Relatively low capital and running costs Modular construction
Advantages offered
Advantages offered
General Classification
Most of the membrane processes are pressure driven barring a few like electro dialysis (ED). Pressure driven process includes micro filtration (MF), ultra-filtration (UF), reverse osmosis (OS) Micro filtration, Ultra filtration, ReverseOsmosis are different with respect to pore-size of membrane
Historical Perspective
Following the end of World War II , the US Govt. became concerned about the shortage of water before the end of century. The US Dept. set up the Office of Saline Waters (OSW), and committed substantial financial resources to the development of various separation processes for water desalination, a significant portion of which was dedicated to the development of membranes for desalination, continuing the work up to 2 decades. Result was development of RO and UF and its no co-incidence that US is the world leader on this front.
Ultra filtration
A Pressure Driven Membrane Separation Process
Membrane Structure and Fabrication

The thin skin on the surface: usually 0.1 to 1 in thickness. Permits high hydraulic permeability The more open porous substructure (typically 120 in thickness) provides good mechanical support. Virtually eliminates internal pore-fouling.
Today UF membranes are made from thermally and chemically stable synthetic polymers like PVC, PAN, polyimides(PI), polysulphone(PS) ,PVDF. In addition there are inorganic UF membranes made from zirconium and aluminium oxides. Plasticizers are necessary for some membranes, if they are to be dried, to prevent collapse of the pores during drying.
Modification
Additional strength is provided by casting the membrane on a spun-bonded poly-ethylene or polypropylene backing.
Pore Size Determination

UF membranes have diffuse cut-off characteristics. The retention R (in percent) may be defined as , R = 100 ( 1- ( Cuf / CR ) ) The convention states that the molecular
weight cut-off of the membrane is equal to the molecular weight of the globular proteins which are 90% retained by the membrane.
Retention Characteristics
1.
2. 3. 4. 5.
Size and shape considerations Adsorption losses Charged membranes Pressure effects Temperature effects
1. Size and Shape considerations
Retention differs with linear or spherical structure of molecules.
2. Adsorption losses
The polymer which makes the UF affects the retention if it adsorbs the species on the membrane surface. Retention of membranes are often measured in stirred cells. A mass balance on cell, integrated over time t. R = 100 * (ln( Cf / Co ) )/ln( Vo / Vf ))
3. Charged membrane
Charged UF membrane reject low conc. Of salts, because the fixed charged group on membrane skin reject ionic solutes via repulsion of co ions. Obviously, divalent, trivalent ions are rejected better than monovalent ions.
4. Effect of pressure
5. Effect of temperature
It has been found experimentally for a large no.of membranes systems and feed streams that the permeation rate is inversely proportional to fluid viscosity. Viscosity of water decreases by 2.5% for every C rise, researchers refer to 3% rule that flux increases 3% per 1 C as rule of thumb.
Evaluation of Mass Transfer Co-efficient
To evaluate m.t.c, laminar parabolic velocity profile is assumed to be established at the channel entrance Leveques solution gives, Sh = 1.62 ( Re Sc dh / L)0.33 (For 100< (Re Sc dh /L) <5000) Generally, K = .816 ( D2 /L )0.33 = the fluid shear rate at the membrane surface. = 6U/b for rectangular slits. = 8U/d for circular tubes.
UF Plant Design
Mode of operation
The arrangement of membrane module and their mode of operation can affect the economics as much as the module design.
Applications
Semi conductor industry Reclamation of waste lubricating oil Decontamination of crude oil Waste treatment
Applications
Applications
Applications
Summarizing U.F
Twenty-five years of invention. Reliable and economic. Eliminated severe pollution problems. Recovery of by-products adds to the profit. Grafting eliminates fouling problems. Stringent environmental controls may necessitate UF. Bio-reactors using UF, have tremendous potential for continuous enzyme reactors.
Reverse Osmosis
A Pressure Driven Membrane Separation Process
Osmosis
Reverse Osmosis
R.O membranes
High resolution electron microscopy cannot resolve the extensive pore in the separating layer of the R.O. membranes Therefore it is generally considered that they do not contain pores and that they operate mainly by solution diffusion mechanism
Solution diffusion mechanism

Introduced by SOLTANEIH and GILL. It states that the membrane is non porous, and that solvent and solutes can only be transported across the membranes by first dissolving in, and subsequently diffusing through, the membrane
HAASE and BELFORT model
The solvent flux through the membrane is proportional to pressure gradient:
J1 K1 ( P )
For the solute it is found that:
J 2 K2 C2
Thus, solvent (water) flow occurs only when |P| > ||, solute flow is independent of |P| Hence, increasing the operating pressure increases the effective separation Typically for brackish water (1.5-2 kg/m3 salts), || = 0.1- 0.7MPa and |P| = 3-8 MPa
Salt rejection
Rejection of ions at R.O membranes depends on valence

The rejection of organic molecules depends on molecular weights
Membrane modules
1. 2. 3. 4.
There are currently four generic configurations for membranes in industrial use : Tubular modules Hollow fiber modules Flat plate modules Spiral wound modules.
Tubular module
Hollow fiber modules
Flat- sheet module
Spiral wound modules
Plant configuration
Batch Recirculation Feed and Bleed configuration Continuous Single-pass
Plant configuration
Plant configuration
Batch Recirculation
Feed and Bleed Configuration
Single pass configuration
Applications
In some applications the product is the retentate, and the objective is to concentrate or purify the retained species and in others the product is permeate. Whereas, in some both retentate and filtrate are important. For example, if a valuable product or by-product is a pollutant in a waste stream, recovery and use of the product will often pay for pollution abatement.
R.O. in water treatment

R.O. is a well-established large scale industrial process for the desalination of brackish water More than 1000 units in operation, each capable of producing 105 m3/day of drinking water
Membranes employed
1. 2.
The two basic membranes employed in in the commercial R.O. systems are The Thin Film Composite (TFC) membranes Cellulose acetate blend (CAB) membranes
Membranes employed
1. 2.
Membranes employed
1. 2.
Case Study: R.O at MRL

Objective is to reuse sewage water as process water for MRL Spiral wound module employed. MRL uses advanced composite membrane (ACM) which is in TFC form. It is made by first casting the porous polysulfone film on fabric support. The thin (0.05- 0.2 ) polyamide membrane is then formed on the film surface by polymerization of an aromatic diamine and cycloaliphatic tricarbonyl chloride
Advantages of ACM
Excellent biological stability Excellent chemical stability except toward Cl. Resistant to membrane compaction Longer life as compared to CAB membranes.
Advantages of ACM
Advantages of ACM
Advantages of ACM
Thin Film Composites
Process block diagram
Pretreatment
1.
2.
3.
R.O almost always requires pretreatment to control fouling Pretreatment scheme Addition of HCl to control pH Addition of SHMP to avoid calcium sulfate scale Micron cartridge filter to remove particles greater than 10 size
Pretreatment
1.
2.
3.
Pretreatment
1.
2.
3.
Pretreatment
1.
2.
3.
Permeate water characteristics
pH = 7.5 TDS = 400 ppm Total Hardness as CaCO3= 100ppm Free ammonia = 0.1 ppm Nitrates = 1ppm Silica = 10 ppm BOD =2ppm COD= 5ppm total Phosphates = 0.1 ppm
ACM characteristics
Membrane configuration = spiral wound Material = polyamide Supplier = dupont Dimension= 8 dia x 40 long Rated operating pressure = 200-350 psig Temperature range = 0-45oC pH range = 4-11 Membrane SA = 37.2 m2 Cl tolerance = 0.25 ppm (pH>8) ; 0.1ppm (pH<8)
Permeate can be used as

Process water Landscaping, gardening Ground water discharge for controlling intrusion of sea water into the ground water table
Summarizing R.O
Can be widely used as captive waste water recycle plants in industries Used for the production of drinking water in European countries. Largest such plant produces 140000 m3/ day water for north Paris In temperate climates nanofiltration is more economical on this regard.
Electrodialysis
An electrically driven membrane separation process.
Flow-diagram for ED
The membranes
Thin films of polymeric chains containing electrically charged functional sites. Anion-exchange membrane (e.g. with quartenary ammonium groups) Cation-exchange membranes (i.e. with sulfonate groups) Various methods of producing Close to 98% efficiency
ED Stack

1: Polypropylene end plate 2: Electrode 3: Electrode chamber 4: spacer-sealing PVC 5: Spacer fabric 6: Screws 7: Steel frame 8: Inlet anode cell 9: Inlet concentrate cell 10: cation exchange membrane 11: AAM 12: Inlet diluate cell 13: Inlet cathode chamber
Process configurations
Typical process configuration
Typical Applications
Demineralization Concentration of electrolytes Ion-replacement reactions Metathesis reactions Separation of electrolysis products Fractionation of electrolytes
Electrodialysis reversal (EDR)
Cation-neutral ED
Limiting current density

Transference number is the fraction of current carried by an ion t+ for cations and t- for anions ts- for anion through solution (say .5) tm- for anion through anion exchange membrane (say 1.0) So at membrane there is a depletion layer set up
Contd
At a certain current the conc. becomes 0 This is called limiting current density Beyond this H+ and OHis transported across the membrane Loss of efficiency and ppt of salts due to pH changes
i lim DF zCi l (tm ts )

Ilim= limiting current density D= diffusion coefficient F= Faradays const. l=Equivalent film thickness
Typical process configuration
Typical Applications
Demineralization Concentration of electrolytes Ion-replacement reactions Metathesis reactions Separation of electrolysis products Fractionation of electrolytes
Electrodialysis reversal (EDR)

Deals with fouling of the membrane and scale formation Reversal of polarity several times an hour along with alternation of conc. and demin stream Useful with Ni, Zn, Fe salts etc
Variations of ED
Cation exchange and neutral membrane Elimination of anion membrane Greater flexibility in selecting flow rates and feed and o/p conc
Electrosorption Neutral inner layer between a cation ex membrane and anion ex membrane During normal operation the neutral gets loaded and in reverse gets unloaded
Compact water purification
electrodialysis units are connected directly to the main water supply system through a flexible hose. The pressure of 13 atm is quite sufficient, because their operating pressure is within 0.30.4 atm. Thus, in comparison with RO there is no need
of additional pump of high pressure;
as a result there is another main advantage:
turn of the tap; residual chlorine in water does not influence the desalination process, therefore there is no need of cartridges before treatment; simplicity and slight adjustment of the process, low power consumption and low cost of units promises a great advantage in the future; when using these units there is no need of
consumers have the opportunity to regulate themselves the taste of water by means of a simple
bottle water purchase.
Seawater desalination with ED
Comparison of RO and ED

Membrane Separation Technology

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Membrane Separation Technology

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Membrane Separation Processes

Neha Kathayat Rugved Pathare Daksh Pratap Singh

Introduction Ultrafiltration Reverse Osmosis Electrodialysis Summary

Introduction Ultrafiltration Reverse Osmosis Electrodialysis Summary

Introduction Ultrafiltration Reverse Osmosis Electrodialysis Summary

Introduction Ultrafiltration Reverse Osmosis Electrodialysis Summary

Introduction Ultrafiltration Reverse Osmosis Electrodialysis Summary

Introduction Ultrafiltration Reverse Osmosis Electrodialysis Summary

Strathmann defines a membrane as an

Strathmann defines a membrane as an

Membrane Structure and Fabrication

Pore Size Determination

1. Size and Shape considerations

Retention differs with linear or spherical structure of molecules.

Evaluation of Mass Transfer Co-efficient

Evaluation of Mass Transfer Co-efficient

Evaluation of Mass Transfer Co-efficient

Solution diffusion mechanism

HAASE and BELFORT model

The solvent flux through the membrane is proportional to pressure gradient:

For the solute it is found that:

Rejection of ions at R.O membranes depends on valence

Hollow fiber modules

Flat- sheet module

Spiral wound modules

Feed and Bleed Configuration

Single pass configuration

R.O. in water treatment

Case Study: R.O at MRL

Thin Film Composites

Process block diagram

Permeate water characteristics

Permeate can be used as

Typical process configuration

Electrodialysis reversal (EDR)

Limiting current density

i lim DF zCi l (tm ts )

Typical process configuration

Electrodialysis reversal (EDR)

Compact water purification

of additional pump of high pressure;

as a result there is another main advantage:

bottle water purchase.

Seawater desalination with ED

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