Kimia dan Teknik Membran

Overview
Introduction Membrane materials Preparation of membranes Characterisation of membrane Membrane processes Fouling Process design Applications of membrane

Introduction
Separation processes

Introduction
Separation processes based on physical/chemical properties Physical/chemical property Separation process
Size Vapour pressure Freezing point Affinity Charge Density Chemical nature Filtration, microfiltration, ultrafiltration, dialysis, gas separation Distillation, membrane distillation Crystallisation Extraction, adsorption, reverse osmosis, gas separation, pervaporation Ion-exchange, electrodialysis, electrophoresis, diffusion dialysis Centrifugation Complexation, carrier mediated transport

Introduction
Phase 1 Membrane Phase 2

Feed

Permeate

Driving force C, P, T, E

A two-phase system separated by a membrane

Introduction
General definition of a membrane:
A selective barrier between two phases, the term selective being inherent to a membrane or a membrane process

Membrane materials
Inorganic membranes
Membrane polymers

Membranes

Biological membranes

Liquid membranes

Membrane materials
Membrane polymers

Porous membranes
Polytetrafluoroethylene, polyvinylidenefluoride, polypropylene, polycarbonate, polyamide

Non porous membranes

Polymer type can range from an elastomer to a glassy material Poly(m-phenylene)-1,3,4oxadiazole; poly(mphenylene)-1,2,4-triazole

Membrane materials
Inorganic membranes
Alumina membranes Titania membranes

Membrane materials
Inorganic membranes Zirconia composite membranes

Membrane materials
Biological membranes
Contain a basic lipid bilayer structure Each lipid molecule possess a hydrophobic and a hydrophilic part
Hydrophilic region 70A
Hydrophobic region Hydrophilic region A lipid bilayer

Membrane materials
Liquid membranes

Carrier

Preparation of polymer membranes

Preparation for phase inversion membranes Phase inversion is a process whereby a polymer is
transformed from a liquid to a solid state. The process of solidification is initiated by the transition from one liquid state into two liquids (liquid-liquid demixing). At a certain stage during demixing, one of the liquid phases (the high polymer concentration phase) will solidify so that a solid matrix is formed. By controlling the initial stage of phase transition, the membrane morphology can be controlled

Preparation of polymer membranes

Solvent
Polymer

Precipitation Polymer solution

The polymer solution is cast on suitable support

Preparation techniques for phase inversion:

Precipitation by solvent evaporation Precipitation from the vapour phase Precipitation by controlled evaporation Thermal precipitation Immersion precipitation

Study of gas separation properties of ethylene vinyl acetate(EVA) copolymer membranes prepared via phase inversion method, Seyyed Abbas Mausavi, et al., Separation and purification technology, 62 (2008), 642-647

Preparation of polymer membranes

Precipitation by solvent evaporation
Precipitation is conducted by evaporating the solvent in an inert (nitrogen) atmosphere, in order to exclude water vapour.

Precipitation is done in a vapour atmosphere where the vapour phase consist of a non-solvent saturated with the same solvent. The high solvent concentration in the vapour phase prevent the evaporation of solvent from the cast film. Membrane formation occurs because of the penetration (diffusion) of non-solvent into the cast film. This lead to a porous membrane without top layer

Precipitation from the vapour phase

Preparation of polymer membranes

Precipitation by controlled evaporation

The polymer is dissolved in a mixture of solvent and nonsolvent (the mixture act as a solvent for the polymer). Since the solvent is more volatile than the non-solvent, the composition shift during evaporation to a higher non-solvent and polymer content. This lead to the formation of a skinned membrane

Thermal precipitation
A solution of polymer in a mixed or single solvent is cooled to enable phase separation to occur. Evaporation of the solvent often allows the formation of a skinned membrane.

Preparation of polymer membranes

Immersion precipitation
A polymer solution (polymer + solvent) is cast on a suitable support and immersed in a coagulation bath containing a non-solvent. Precipitation occurs because of the exchange of solvent and non-solvent. The membrane structure obtained results from a combination of mass transfer and phase separation Non solvent,
J2

solvent
Polymer

Coagulation bath Polymer solution Support

J1

Non solvent, solvent

Preparation of polymer membranes

Some factors that affect membrane structure: The choice of solvent and non solvent system The polymer concentration The Composition of the coagulation bath The composition of the polymer solution

Preparation of polymer membranes

Solvent for cellulose and polysulfone
Cellulose acetate
Dimethylformamide (DMF) Dimethylacetamide (DMAc) Acetone Dioxan Tetrahydrofuran (THF) Acetic acid (HAc_)

Polysulfone
Dimethylformamide (DMF) Dimethylacetamide (DMAc) Dimethylsulfoxide (DMSO) Formylpiperidine (FP) Morpholine (MP) N-methylpyrrolidone (NMP)

Dimethylsulfoxide (DMSO)

Preparation of polymer membranes

Classification of solvent/non solvent pairs
Solvent
DMSO DMF DMAc NMP DMAc DMAc DMAc

Non solvent
water water water water n-propanol i-propanol n-butanol

Type of membrane
porous porous porous porous nonporous nonporous nonporous

Preparation of polymer membranes

Choice of polymer and polymer concentration
Polymer:
Polysulfone Poly(ether sulfone) Poly(vinylidene fluoride) Polyacrylonitrile Cellulose acetate Polyimide Poly(ether imide) Polyamide (aromatic)

Pure water flux through polysulfone membranes

Polymer concentration (%) 12 15 17 35

Flux (l m-2 h-1) 200 80 20 0

Preparation of polymer membranes

Polymer solution Casting knife

Phase-inversion membrane Post treatment Coagulation bath

Support layer (non-woven)

Schematic drawing depicting the preparation of flat membranes

Preparation of polymer membranes

Tubular membranes
a. Hollow fiber membranes (diameter < 0.5 mm)

b. Capillary membranes (diameter: 0.5-5 mm)

c. Tubular membranes (diameter: > 5 mm) The dimension of the tubular membranes are so large that they have to be supported, whereas the hollow fibers and capillaries are self supporting. Hollow fibers and capillaries can be prepared via three different methods: Wet spinning (or dry spinning)

Melt spinning
Dry spinning

Preparation of polymer membranes

Polymer solution Bore liquid

Gear pump Air gap

Spinneret

Bore liquid

pump

Coagulation bath

Flushing bath

Schematic drawing of a dry-wet spinning process

Preparation of polymer membranes

Air pressure Reservoir

Polymer solution
Cast film Polymer solution

Porous tube

Coagulation bath

Casting bob

(a)

(b)

(c)

Pressure is applied to a reservoir filled with a polymer solution, so that the solution is forced through a hollow pipe. At the end of the pipe is a casting bob with small holes which the polymer solution is forced. The porous tube is moving vertically and a film is cast upon its inner wall. The pipe is then immersed in a coagulation bath where precipitation of the cast polymer solution leads to the formation of a tubular membrane

Preparation of polymer membranes

Microporous polypropylene tubular membranes via thermally induced phase separation using a novel solvent-champene,
M.C. Yang and J.S. Perng, Journal of membrane science, 187, (2001), 13-22

Proses pemisahan cair-cair

Berpori
t = komposisi pada lapisan atas,

Rapat
b = komposisi pada lapisan bawah

t hubungan kesetimbangan pada antarmuka film/non pelarut