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PERVAPORATION

MT5009 Analyzing Hi-Tech Opportunities
          Semester 2, 2011/2012



        See Siew Hui     A0077625X
         Too Kim Hui     A0077025J
        Hubert Giam      A0082070R
        Chua Wei Sun     A0082022X
      Damien Poh Weiye   A0076856M
       Linda Wibisono    A0077098N
Overview
1) Intro
    Distillation and its disadvantage
    What is pervaporation?
    Applications of pervaporation

2) Pervaporation Performance Parameters
    Selectivity
    Flux
    Membrane Thickness
    Temperature
    Kinetic diameter

3) Improvements

4) Hybrid Process (Distillation and Pervaporation)

5) Potential Business Opportunities
Drawbacks of the Existing Method (Distillation)
 Distillation is a conventional liquid mixture separation technology
   based on their boiling points.

 Disadvantages of distillation
    Difficult to separate liquids mixtures which the components have similar boiling
      point (azeotropes).

 Advance in technology - Pervaporation can be used for breaking
   azeotropes.
Pervaporation
 Pervaporation is the separation of liquid mixtures by partial
   vaporization through a membrane.


                      Key component in
                       Pervaporation
                                                 Feed



                   membrane
Major Advantage of Pervaporation
Distillation has major disadvantage compared to the new method of Pervaporation.
Distillation is a very energy consuming process (heating process).




  Source: Trends in Research and Development of Nanoporous Ceramic Separation Membranes, 2009
Applications of Pervaporation
 Applications include:
   Environmental application: Removing organic solvents from industrial
      waste waters.
    Pollution control: Removal of small quantities of VOCs (Volatile organic
      compounds) from contaminated water
    Chemical Industry: removal of water from organic solvents and solvents
      mixtures – to obtain pure organic solvents

 Pervaporation is a very mild process and hence very effective for separation
   of those mixtures which can not survive the harsh conditions of distillation.
Overview
1) Intro
    Distillation and its disadvantage
    What is pervaporation?
    Applications of pervaporation

2) Pervaporation Performance Parameters
    Selectivity
    Flux
    Membrane Thickness
    Temperature
    Kinetic diameter

3) Improvements

4) Hybrid Process (Distillation and Pervaporation)

5) Potential Business Opportunities
Measured Performance Parameters

Some of the most important parameters used to assess the pervaporation process are:

1.   Membrane selectivity : what goes through and what gets rejected

2.   Flux: Denote the amount of output (measured in relation to membrane area , thickness and
     time).




           What will influence the performance?
1.   Feed temperature: Refers to temperature of the feed stock or any other representative between
     feed and retentate streams.

2.   Membrane thickness: Refers to dry thickness.

3.   Kinetic diameter: diameter of pore needed to let a specific molecule pass
Performance Parameters - Selectivity

 Membrane selectivity allows us to choose certain
  molecules to pass through the membrane
   Improved membrane selectivity will increase absorption
    rates
     more efficient and possible cost reduction
   This can be achieved by better understanding of the
    material selected for the membrane
Impact of Feed Temperature on Flux
 Feed Temperature
   Molecules movement increases exponentially with temperature
      improve flux rate
Impact of Membrane Thickness on Flux



                            The thinner the
                          membrane, the faster
                               the flux
Influencing Parameters – Kinetic Diameter (1)

Kinetic diameter can be understood as the diameter of a pore needed to let that
specific molecule pass




        Source: Fundamentals and applications of pervaporation through Zeolite membranes, 2004
Influencing Parameters – Kinetic Diameter (2)




     Source: Fundamentals and applications of pervaporation through Zeolite membranes, 2004
Overview
1) Intro
    Distillation and its disadvantage
    What is pervaporation?
    Applications of pervaporation

2) Pervaporation Performance Parameters
    Selectivity
    Flux
    Membrane Thickness
    Temperature
    Kinetic diameter

3) Improvements

4) Hybrid Process (Distillation and Pervaporation)

5) Potential Business Opportunities
Key Cost Components For Pervaporation




• The operating cost of pervaporation is heavily reliant on the cost of
  generating heat and the cost of the membrane used

• Current trend: decreasing heating cost and decreasing membrane cost




  Source: http://www.scielo.org.ar/scielo.php?pid=S0327-07932003000200018&script=sci_arttext&tlng=en
Decreasing Trend in Membrane Cost from 1989 to 2000




      Reasons of decreasing membrane cost:
      1. Membrane surface area per module increase  lesser membrane modules to produce the same
         amount of output
      2. Membrane mass production  production cost decrease
      3. More compact module  cost savings in civil works

Source: J.-M. Laine, D. Vial, Pierre Moulart, Status after 10 years of operation – overview of UF technology today, Desalination
  131 (2000) 17-25
Similar Decreasing Trend in Membrane Cost from 1970 to 2010




Source: American Membrane Technology Association (AMTA), www.amtaorg.com
Improvement in cost of heat generation




-Cost of Conserved Energy (CCE) summarizes annual costs associated
with saving a GJ (approximately 0.95 MBtu) of energy with a particular
measure.
-Table shows that energy efficient measures lead to energy savings that
have short payback periods from immediate to 2.7 years.
-Industry is looking towards reducing cost of heat generation
Improvements in membrane

1) Membrane preparation methods  more methods are developed to
   prepare membranes with different structures for different application
     Phase separation method developed in 1960
     Scanning Electron Microscope became available in 1960  helped in
       the detailed study of the membrane structure

2) Membrane selective layer is getting thinner over 30 years

   0.2 – 0.4 µm  <0.1 µm  0.05 µm (only in lab)

3) In 30 years membrane flux and selectivity improved by 10 times, e.g.
   selectivity factor from 8 to 80.
How to control pore size?
 Methods used to create pores on membrane surface:
     Sintering
     Stretching
     Casting
     Leaching
     Nucleation-track
     Gelation by water vapor

 Variables that affect pore size:
   Membrane materials
   Different solvents used and concentration in the casting
    solution
   Temperature of the casting solution
Overview
1) Intro
    Distillation and its disadvantage
    What is pervaporation?
    Applications of pervaporation

2) Pervaporation Performance Parameters
    Selectivity
    Flux
    Membrane Thickness
    Temperature
    Kinetic diameter

3) Improvements

4) Hybrid Process (Distillation and Pervaporation)

5) Potential Business Opportunities
Conventional Process – Distillation

Eliminate:
i) heating process
ii) use of benzene




                            Heater
Hybrid Process
(Distillation & Pervaporation)


Distillation          Pervaporation
Lower Cost of Hybrid Process

                                         140
                                                                       €130 / ton

                                         120

                                                                                                                    - 45%
                                         100
Total Cost (€/ton product)




                                          80
                                                                                                                                              €72 / ton

                                          60



                                          40



                                          20



                                              0
                                                                        Distillation                                           Distillation - Pervaporation
                             Maintenance Cost                              15.11                                                          12.45
                             Investment Cost                               78.28                                                          42.16
                             Operation Cost                                36.65                                                          17.25


                                  Source: Economic comparison between azeotropic distillation and different hybrid systems combining distillation with pervaporation
                                  for the dehydration of isopropanol, Elsevier, 2004
Overview
1) Intro
    Distillation and its disadvantage
    What is pervaporation?
    Applications of pervaporation

2) Pervaporation Performance Parameters
    Selectivity
    Flux
    Membrane Thickness
    Temperature
    Kinetic diameter

3) Improvements

4) Hybrid Process (Distillation and Pervaporation)

5) Potential Business Opportunities
Opportunity for Material Supplier
1) Chitosan membranes
 “Natural membrane”, i.e. without chemical /toxic cross-linkers
 Used in biotechnology applications, e.g. entrap drugs, bioactive
   ingredients, enzyme immobilization

2) Zeolite membranes
 Higher flux
 Higher output
Improvement with Zeolite membrane

                                                                                                       Higher flux with
                                                                                                       Zeolite Membrane



                                                                                                            Conventional
                                                                                                         Polymer Membrane




                                                                                                       Higher output with
Membrane Type                         Feed                             Output                          Zeolite Membrane
    Polymer                                                       99.59% IPA
                                  83% IPA                         0.41% Water
      Zeolite                    17% Water                        99.68% IPA
                                                                  0.32% Water
  Source: Economic comparison between azeotropic distillation and different hybrid systems combining distillation with pervaporation
  for the dehydration of isopropanol, Elsevier, 2004
Opportunities for IT

Diffusion of computer programs for selection of Zeolite
         membrane composition from databases
Opportunities for Pervaporation System
               Suppliers
           Huge market of the separation in the future
Huge business opportunity to introduce pervaporation to these plants
Others Opportunities


1) For companies dealing with green energy (can recover biofuels from
  fermentation broths)

2) For companies dealing with other membrane-property separations
     Gas separation
THANK YOU!
Appendix
Pervaporation



                 Advantages                                        Drawbacks

• Low energy consumption.                        • Scarce membrane market.
• Low investment cost.                           • Lack of information.
• Better selectivity without thermodynamic       • Low permeate flows.
limitations.                                     • Better selectivity without thermodynamic
• Clean and close operation.                     limitations.
• No process wastes.                             • Limited applications:
• Compact and scalable units.                           • Organic substances dehydration.
                                                        • Recovery of volatile compounds at low
                                                        concentrations.
                                                        • Separation of azeotropic mixtures.




   23
Summary (2)


     Membranes:              Composite membranes with an
                             elastomeric or glassy polymeric top layer.
     Thickness:               0.1 to few m (for top layer)
     Pore size:              Non-porous
     Driven force:           Partial vapor pressure or activity
                             difference.
     Separation principle:   Solution/Diffusion
     Membrane material:      Elastomeric and glassy.
     Applications:            Dehydration of organic solvents.

                              Removal of organic compounds from

                                water.
                              Polar/non-polar.

                              Saturated/unsaturated.

                              Separation of isomers.




24
Zeolite Synthesis – A Summary
Synthesis by Hydrothermal process involving

1) crystallization of a zeolite layer onto a
   porous support

2) from a gel that is usually composed of
   water, amorphous silica, a source for
   tetrahedral framework atoms other than
   Si, a structure directing organic template,
   and sometimes a mineralizing agent

3) Difference in synthesis time, temperature,
   gel composition for crystallization results
   in different types of Zeolite formation

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Membranes for Pervaporation

  • 1. PERVAPORATION MT5009 Analyzing Hi-Tech Opportunities Semester 2, 2011/2012 See Siew Hui A0077625X Too Kim Hui A0077025J Hubert Giam A0082070R Chua Wei Sun A0082022X Damien Poh Weiye A0076856M Linda Wibisono A0077098N
  • 2. Overview 1) Intro  Distillation and its disadvantage  What is pervaporation?  Applications of pervaporation 2) Pervaporation Performance Parameters  Selectivity  Flux  Membrane Thickness  Temperature  Kinetic diameter 3) Improvements 4) Hybrid Process (Distillation and Pervaporation) 5) Potential Business Opportunities
  • 3. Drawbacks of the Existing Method (Distillation)  Distillation is a conventional liquid mixture separation technology based on their boiling points.  Disadvantages of distillation  Difficult to separate liquids mixtures which the components have similar boiling point (azeotropes).  Advance in technology - Pervaporation can be used for breaking azeotropes.
  • 4. Pervaporation  Pervaporation is the separation of liquid mixtures by partial vaporization through a membrane. Key component in Pervaporation Feed membrane
  • 5. Major Advantage of Pervaporation Distillation has major disadvantage compared to the new method of Pervaporation. Distillation is a very energy consuming process (heating process). Source: Trends in Research and Development of Nanoporous Ceramic Separation Membranes, 2009
  • 6. Applications of Pervaporation  Applications include:  Environmental application: Removing organic solvents from industrial waste waters.  Pollution control: Removal of small quantities of VOCs (Volatile organic compounds) from contaminated water  Chemical Industry: removal of water from organic solvents and solvents mixtures – to obtain pure organic solvents  Pervaporation is a very mild process and hence very effective for separation of those mixtures which can not survive the harsh conditions of distillation.
  • 7. Overview 1) Intro  Distillation and its disadvantage  What is pervaporation?  Applications of pervaporation 2) Pervaporation Performance Parameters  Selectivity  Flux  Membrane Thickness  Temperature  Kinetic diameter 3) Improvements 4) Hybrid Process (Distillation and Pervaporation) 5) Potential Business Opportunities
  • 8. Measured Performance Parameters Some of the most important parameters used to assess the pervaporation process are: 1. Membrane selectivity : what goes through and what gets rejected 2. Flux: Denote the amount of output (measured in relation to membrane area , thickness and time). What will influence the performance? 1. Feed temperature: Refers to temperature of the feed stock or any other representative between feed and retentate streams. 2. Membrane thickness: Refers to dry thickness. 3. Kinetic diameter: diameter of pore needed to let a specific molecule pass
  • 9. Performance Parameters - Selectivity  Membrane selectivity allows us to choose certain molecules to pass through the membrane  Improved membrane selectivity will increase absorption rates  more efficient and possible cost reduction  This can be achieved by better understanding of the material selected for the membrane
  • 10. Impact of Feed Temperature on Flux  Feed Temperature  Molecules movement increases exponentially with temperature  improve flux rate
  • 11. Impact of Membrane Thickness on Flux The thinner the membrane, the faster the flux
  • 12. Influencing Parameters – Kinetic Diameter (1) Kinetic diameter can be understood as the diameter of a pore needed to let that specific molecule pass Source: Fundamentals and applications of pervaporation through Zeolite membranes, 2004
  • 13. Influencing Parameters – Kinetic Diameter (2) Source: Fundamentals and applications of pervaporation through Zeolite membranes, 2004
  • 14. Overview 1) Intro  Distillation and its disadvantage  What is pervaporation?  Applications of pervaporation 2) Pervaporation Performance Parameters  Selectivity  Flux  Membrane Thickness  Temperature  Kinetic diameter 3) Improvements 4) Hybrid Process (Distillation and Pervaporation) 5) Potential Business Opportunities
  • 15. Key Cost Components For Pervaporation • The operating cost of pervaporation is heavily reliant on the cost of generating heat and the cost of the membrane used • Current trend: decreasing heating cost and decreasing membrane cost Source: http://www.scielo.org.ar/scielo.php?pid=S0327-07932003000200018&script=sci_arttext&tlng=en
  • 16. Decreasing Trend in Membrane Cost from 1989 to 2000 Reasons of decreasing membrane cost: 1. Membrane surface area per module increase  lesser membrane modules to produce the same amount of output 2. Membrane mass production  production cost decrease 3. More compact module  cost savings in civil works Source: J.-M. Laine, D. Vial, Pierre Moulart, Status after 10 years of operation – overview of UF technology today, Desalination 131 (2000) 17-25
  • 17. Similar Decreasing Trend in Membrane Cost from 1970 to 2010 Source: American Membrane Technology Association (AMTA), www.amtaorg.com
  • 18. Improvement in cost of heat generation -Cost of Conserved Energy (CCE) summarizes annual costs associated with saving a GJ (approximately 0.95 MBtu) of energy with a particular measure. -Table shows that energy efficient measures lead to energy savings that have short payback periods from immediate to 2.7 years. -Industry is looking towards reducing cost of heat generation
  • 19. Improvements in membrane 1) Membrane preparation methods  more methods are developed to prepare membranes with different structures for different application  Phase separation method developed in 1960  Scanning Electron Microscope became available in 1960  helped in the detailed study of the membrane structure 2) Membrane selective layer is getting thinner over 30 years 0.2 – 0.4 µm  <0.1 µm  0.05 µm (only in lab) 3) In 30 years membrane flux and selectivity improved by 10 times, e.g. selectivity factor from 8 to 80.
  • 20. How to control pore size?  Methods used to create pores on membrane surface:  Sintering  Stretching  Casting  Leaching  Nucleation-track  Gelation by water vapor  Variables that affect pore size:  Membrane materials  Different solvents used and concentration in the casting solution  Temperature of the casting solution
  • 21. Overview 1) Intro  Distillation and its disadvantage  What is pervaporation?  Applications of pervaporation 2) Pervaporation Performance Parameters  Selectivity  Flux  Membrane Thickness  Temperature  Kinetic diameter 3) Improvements 4) Hybrid Process (Distillation and Pervaporation) 5) Potential Business Opportunities
  • 22. Conventional Process – Distillation Eliminate: i) heating process ii) use of benzene Heater
  • 23. Hybrid Process (Distillation & Pervaporation) Distillation Pervaporation
  • 24. Lower Cost of Hybrid Process 140 €130 / ton 120 - 45% 100 Total Cost (€/ton product) 80 €72 / ton 60 40 20 0 Distillation Distillation - Pervaporation Maintenance Cost 15.11 12.45 Investment Cost 78.28 42.16 Operation Cost 36.65 17.25 Source: Economic comparison between azeotropic distillation and different hybrid systems combining distillation with pervaporation for the dehydration of isopropanol, Elsevier, 2004
  • 25. Overview 1) Intro  Distillation and its disadvantage  What is pervaporation?  Applications of pervaporation 2) Pervaporation Performance Parameters  Selectivity  Flux  Membrane Thickness  Temperature  Kinetic diameter 3) Improvements 4) Hybrid Process (Distillation and Pervaporation) 5) Potential Business Opportunities
  • 26. Opportunity for Material Supplier 1) Chitosan membranes  “Natural membrane”, i.e. without chemical /toxic cross-linkers  Used in biotechnology applications, e.g. entrap drugs, bioactive ingredients, enzyme immobilization 2) Zeolite membranes  Higher flux  Higher output
  • 27. Improvement with Zeolite membrane Higher flux with Zeolite Membrane Conventional Polymer Membrane Higher output with Membrane Type Feed Output Zeolite Membrane Polymer 99.59% IPA 83% IPA 0.41% Water Zeolite 17% Water 99.68% IPA 0.32% Water Source: Economic comparison between azeotropic distillation and different hybrid systems combining distillation with pervaporation for the dehydration of isopropanol, Elsevier, 2004
  • 28. Opportunities for IT Diffusion of computer programs for selection of Zeolite membrane composition from databases
  • 29. Opportunities for Pervaporation System Suppliers Huge market of the separation in the future Huge business opportunity to introduce pervaporation to these plants
  • 30. Others Opportunities 1) For companies dealing with green energy (can recover biofuels from fermentation broths) 2) For companies dealing with other membrane-property separations  Gas separation
  • 33. Pervaporation Advantages Drawbacks • Low energy consumption. • Scarce membrane market. • Low investment cost. • Lack of information. • Better selectivity without thermodynamic • Low permeate flows. limitations. • Better selectivity without thermodynamic • Clean and close operation. limitations. • No process wastes. • Limited applications: • Compact and scalable units. • Organic substances dehydration. • Recovery of volatile compounds at low concentrations. • Separation of azeotropic mixtures. 23
  • 34. Summary (2) Membranes: Composite membranes with an elastomeric or glassy polymeric top layer. Thickness:  0.1 to few m (for top layer) Pore size: Non-porous Driven force: Partial vapor pressure or activity difference. Separation principle: Solution/Diffusion Membrane material: Elastomeric and glassy. Applications:  Dehydration of organic solvents.  Removal of organic compounds from water.  Polar/non-polar.  Saturated/unsaturated.  Separation of isomers. 24
  • 35. Zeolite Synthesis – A Summary Synthesis by Hydrothermal process involving 1) crystallization of a zeolite layer onto a porous support 2) from a gel that is usually composed of water, amorphous silica, a source for tetrahedral framework atoms other than Si, a structure directing organic template, and sometimes a mineralizing agent 3) Difference in synthesis time, temperature, gel composition for crystallization results in different types of Zeolite formation