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Korea 2012


     Process Intensification;
     a brief history of timing.

                 By
      Professor Malcolm Mackley

Department of Chemical Engineering and
            Biotechnology.
       University of Cambridge
                 UK

                                  1
Process Intensification
 Process; Route to manufacture
                  • Liquid processing
                  • Gas processing
                  • Solid processing
                  • Multiphase processing
Intensification
                  • Reduce footprint
                  • Reduce cost
                  • Reduce environmental impact
                  • Increase output
                  • Increase value and or quality of product
                  • Increase safety, reduce risk
                                             2
Process Intensification.
                    Time line
             Global                           Process Intensification

        Major Chemical Companies               “Product Invention”
1970s   Research Laboratories.               Polymers, PEEK, Pruteen,
        ICI, Shell, Bp, Courtaulds, Exxon.   PHB, Carbon Fibres.
                                             Processes; Fluidised beds.

          “Market forces”                     Heat Exchange Networks (HENS).
1980s   Mergers, sales and acquisitions.           Colin Ramshaw.
        Pharma.                                 “Process Intensification”
                                                  Spinning Disc reactor.

          Emergence of Asia and
                                                 Batch to Continuous.
1990s     Middle East as major players.
                                                 Membranes.
          Emergence of Biotechnology.
          Nanotechnology.

                                                          3
Process Intensification.
                 Time line
         Global                       Process Intensification
        CO2, Energy, Biofuels         Microfluidics
        Displays, Telecoms            Pharma, batch to continuous
2000s   Nanotechnology                Car catalyst exhaust


        “Economic pause”.             Pharma; continuous tablet.
2010s   Telecoms.                     Batteries.
        Electric cars.                Ink Jet Technologies
        Alternative energy sources.


2020s          ?                              ?



                                                  4
Examples of Process Intensification /Invention

• 1970-80s      High Modulus Polyethylene (HMP)

• 1980s onwards Oscillatory Flow Mixing (OFM)

• 1990s         Flexible Chocolate

• 2000s         Plastic Microcapillary Films (MCF)s
                  Time scales for;
             1. Invention / Innovation concept
             2. Development
             3. Commercialisation
                                            5
High Modulus Polyethylene (HMP)

         1970-2000




                         6
Bristol 1970- High Modulus Polyethylene;
                    the 1st inventive step
Sir Charles Frank                        Andrew Keller




                                           7
High Modulus Polyethylene (HMP)
                                                  The 2nd inventive steps 1970s

                                                              Zwijnenburg, A Pennings, AJ (1975)                         Paul Smith
Piet Lemstra



                                                                                                   Colloid and Polymer Science 1975


                               Piston




                                        1. Low entanglement UHMWPE polymer gel


                                             1% PE / Decalin solution
                                                         Solvent recovery
2. Unoriented Gel fibre



                                              4. Hot draw
             Quench bath



                                                           5. Oriented High Modulus Polyethylene


 3. Unoriented Low entanglement semi crystalline fibre


                                                                                                             8
P. Smith, and P.J.Lemstra, J. Material. Sci. 1980, 15,
High Modulus Polyethylene (HMP)
              Development and Commercialisation, late 1980s
                                                                           Solvent
                                                UHMWPE Polymer powde r
 Low entanglement polymer gel



                                                   Screw extruder
Spinnere t


                                                                        Solvent recovery
 Gel fibres



                                                             Hot draw


 Quench bath




                   Low entanglement semi crystalline fibre




             Schematic diagram of continuous High Modulus Polyethylene (HMP) process




               Dyneema®, the world’s strongest fiber™
                                                                                           9
Time scales



1.Invention /
  Innovation
      10 years
2. Development
     10 years
3. Commercialisation
       5 years
Oscillatory Flow Mixing ( OFM)
 Inertial flow. Tube diameters, mm - cms



          A question of scale!
         Tonnes/hr, Kg/hr, g/hr




                                   11
Oscillatory Flow Mixing (OFM) 1980s; process

         Inventive steps 1979- 1982




            Air turbine
            generates power




                                               12
Inventive steps. Plug flow residence time




                 Chem Eng Sci 1989   13
OFM Movie; poetry in motion




                              Adam Harvey
                              14
Heat transfer   Chen Eng Sci




                 15
Liquid Gas Mass transfer
    No oscillation                               With oscillation 8hz, 3mm




                      Go to OFM bubbles movies 1 and 2
Filipa Pereira and Nuno Reis
                                                             16
Mass transfer        Cheng Eng Sci




                17
Development Stage
Chem Eng Oscillatory Flow Reactor (OFR)


                - Oscillator Base Unit

                - Feed inlet section

                - Shell and baffled tube vessels


                - Product outlet section


                             Dr Paul Stonestreet
                                  18
Biodiesel Reaction Progress
along Reactor




                                   Net Flow
            Net Flow In            Out
                              19
Commercialisation




Prof Xiongwei Ni




                                   20
Further development OFM Meso Reactor
                                                         System configuration

                                                          Meso tube,
                                 Sc                       diameter d
                                    ale
                                       -     do
                                               wn


                                                                        Smooth constrictions:
                                                                            spacing 3d
                                                                        Minimum constriction
                                                                        diameter 0.4d


                            35 mm, V ≈ 4.5 mL




           a)


                                         L




                                             d      d0


                                    ≈ 45º
                            δ

                       b)




         Nuno Reis, Minghzi Zheng
2000s
                                                                       21
Meso Fluid Mechanics




Go to OFM PIV and LES movies           Minghzi Zheng
                                         22
Continuous Flow Oscillatory Mesoreactor


                                0.02
                                             b)                                 Exp-E(t)
                               0.018                                                       1
                                                                                Exp-E(t)
                                                                                           2
                               0.016                                            Exp-E(t)3
                               0.014                                            Fit-E(t) (1->2)
                                                                                       2
                                                                                Fit-E(t) (1->3)
                               0.012                                                   3
                                                                                Fit-E(t) (2->3)




                    E(t) (-)
                                                                                       3
                                0.01

                               0.008

                               0.006

                               0.004

                               0.002

                                  0
                                   0   100        200   300   400   500   600   700    800        900
                                                              Time (s)




                                                          Minghzi Zheng
                                                              23
Mesotube; Liquid drop dispersion




             a) f=6Hz                         a) xo=3 mm




            b) f=10Hz                          b) xo=4 mm

Silicon oil (4.6mPas,2.5%) mixing   Silicon oil (4.6mPas, 2.5%) mixing
    with water at xo=2 mm               with water at f=6Hz


                                                   24
Mesotube; Particle suspension




Instantaneous velocity vector maps of fluid phase at Reo = 625,
x0 = 2 mm, f = 10.0 Hz at vertical position in the presence of 3%
(v/v ) amount of ion-exchange particles                          25
Time scales



1.Invention / Innovation
       2 years
2. Development
    10 years
3. Commercialisation
  Ongoing


                           26
Flexible Chocolate
       1994




                     27
Flexible Chocolate 1994; invention

                         Extrusion processing

                          Cold                                    Melt
Polyethylene              Extrusion                               Processing
               ∆H




                    50                100                     150              200
                                                          0
                                            Temperature       C


Chocolate
                          Cold                                    Melt
                          Extrusion                               Processing
               ∆H
                                                                                     16 0



                                                                                     14 0



                                                                                     12 0                                                                  Piston/(ram)
                    10                20                      30               40
                                                                                                             A    Yield
                                                          0                          10 0
                                            Temperature       C                                                   pressure                                 Chocolate feed
                                                                                                                                          Pressure
                                                                                                                                         transducer
                                                                                      80                                                                   Die


                                                                                      60


                                                                                                                    B        Extrusion pressure
                                                                                      40



                                                                                      20
                                                                                            0      5         10         15          20           25   30         35

                                                                                                                                                              C
                                                                                                Compaction
                                                                                                 (no flow)

                                                                                                                                    t (s)
                                                 Review. Chen et al Soft Matter 2006
Cold Extrusion




Go to Flexible Chocolate extrusion movie
Knotting Chocolate




    Go knotting movie
Cold Moulding Chocolate




 Go to moulding movie
Chocolate Development
Time scales



1. Invention / Innovation
      1 day
2. Development
      5 years
3. Commercialisation
             ?
Plastic Microcapillary Films (MCFs)

           2004-2012




                          34
MicroCapillary Films (MCFs) 2000s; invention

           Polymer flow

                           Injector
Die land

MCF extrudate

            Quench bath   Extrudate to haul off




                             Bart Hallmark
                                                  35
Micro Capillary Film; invention
                            Die exit                        Direction of flow
Polymer
 melt             Entrainment
                                                                                          Chill rollers
                     body
                                                                   MCF




                                             Array of 19 entrainment
                                                     nozzles
                                                                 PLAN VIEW
                                                               Quenching length, L
  Air inlet

        Single screw extruder




                                                          MCF
                                                        extrusion
                                                            die
                                        P2          T5 T6
                                                                                      Chilled rollers
                                                                     MCF
                    T1 T2 T3 T4
                                                                                                             Spooling
                                       Gear pump




                                                                                 Guide rollers

              B. Hallmark, et al. Adv. Eng. Mat., (2005).
                                                                                                        36
MCF Development; Pressure Drop




 Christian Hornung         37
MCF Development RTD



                     50
                     45           length = 20 m                           inlet
                                  flow rate = 0.5 ml/min                  outlet
                     40
                     35
                     30




          c [mg/l]
                     25
                     20
                     15
                     10
                     5
                     0
                          0   5           10             15     20   25            30
                                                      t [min]




                                                      38
MCF Commercialisation
   2 flat silicon heaters (200 W each)
    PID control - Temperature monitoring at top and bottom heater
    plates
                                                             developed by
   Tmax = 150 °C                                            Lamina Dielectrics Ltd.
                                                             & Cambridge University




        Reactor disk tray


                                                         Temperature control
                                         Teflon coated
                                         hot plates




     Patrick Hestor Lamina Ltd
MCF Development; Microflow




Organic.
Kerosene, 1.8 mPas                              Video,
Oil,      27 mPas                               Methanol         Nuno Reis
Vegetable oil. 50 mPas                          into Veg oil




                         Water, 1 mPas, glycerol 10-50 mPas or methanol
MCF Development; Slug separation




         Scheiff et al. Lab on a Chip. 2011
Multi channel flow




            Go to MCF multi channel movie




Nuno Reis
MCF Development; Biodiesel Microreactor

   Input                                       Output


Vegetable oil                                    Biodiesel



  Methonal plus                            Glycerol
  catalyst



  Microcapillary
  Flow disc
MCF Microreactor; Biodiesel
          Methanol                                Glycerol
Veg oil

                                                             Biodiesel


   Methanol plus                       Glycerol
   catalyst
MCF Development. Microporous MCF membranes
              Bore fluid

                                  Die                   Haul-off
                                          Air-gap

Nitrogen                    External
  Gas                      Coagulant
Cylinder
                                       Glass Water
           Polymer                         Bath
           Solution                              Single Capillary,
                                                MCF membranes




                                                             Sina Bonyadi
Microporous MCFs
                2 µm




       100 µm

                                       1 µm




   2 µm




Bonyadi et al. Journal of Membrane Sci 2012
Time scales



1. Invention / Innovation
       3years
2. Development
      8 years
3. Commercialisation
     Ongoing
Lessons to be learnt


• Work  backwards.
Identify need and then “process intensify”.

• Get timing right.
Anticipate current and future
need for process intensification.

• Build an interdisciplinary team.

•Plan for a timescale of say 10 years
                                     48
Future Message

Process intensification can result in a
concentration of process leading to monopolies
and a single source provider.

Process Diversification can help prevent
“bottlenecks” and provide flexibility.

   We need a balance between Process
Intensification and Process Diversification.

   Process Intensification and Diversification
                                        49

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Process Intensification Korea-2012

  • 1. Korea 2012 Process Intensification; a brief history of timing. By Professor Malcolm Mackley Department of Chemical Engineering and Biotechnology. University of Cambridge UK 1
  • 2. Process Intensification Process; Route to manufacture • Liquid processing • Gas processing • Solid processing • Multiphase processing Intensification • Reduce footprint • Reduce cost • Reduce environmental impact • Increase output • Increase value and or quality of product • Increase safety, reduce risk 2
  • 3. Process Intensification. Time line Global Process Intensification Major Chemical Companies “Product Invention” 1970s Research Laboratories. Polymers, PEEK, Pruteen, ICI, Shell, Bp, Courtaulds, Exxon. PHB, Carbon Fibres. Processes; Fluidised beds. “Market forces” Heat Exchange Networks (HENS). 1980s Mergers, sales and acquisitions. Colin Ramshaw. Pharma. “Process Intensification” Spinning Disc reactor. Emergence of Asia and Batch to Continuous. 1990s Middle East as major players. Membranes. Emergence of Biotechnology. Nanotechnology. 3
  • 4. Process Intensification. Time line Global Process Intensification CO2, Energy, Biofuels Microfluidics Displays, Telecoms Pharma, batch to continuous 2000s Nanotechnology Car catalyst exhaust “Economic pause”. Pharma; continuous tablet. 2010s Telecoms. Batteries. Electric cars. Ink Jet Technologies Alternative energy sources. 2020s ? ? 4
  • 5. Examples of Process Intensification /Invention • 1970-80s High Modulus Polyethylene (HMP) • 1980s onwards Oscillatory Flow Mixing (OFM) • 1990s Flexible Chocolate • 2000s Plastic Microcapillary Films (MCF)s Time scales for; 1. Invention / Innovation concept 2. Development 3. Commercialisation 5
  • 6. High Modulus Polyethylene (HMP) 1970-2000 6
  • 7. Bristol 1970- High Modulus Polyethylene; the 1st inventive step Sir Charles Frank Andrew Keller 7
  • 8. High Modulus Polyethylene (HMP) The 2nd inventive steps 1970s Zwijnenburg, A Pennings, AJ (1975) Paul Smith Piet Lemstra Colloid and Polymer Science 1975 Piston 1. Low entanglement UHMWPE polymer gel 1% PE / Decalin solution Solvent recovery 2. Unoriented Gel fibre 4. Hot draw Quench bath 5. Oriented High Modulus Polyethylene 3. Unoriented Low entanglement semi crystalline fibre 8 P. Smith, and P.J.Lemstra, J. Material. Sci. 1980, 15,
  • 9. High Modulus Polyethylene (HMP) Development and Commercialisation, late 1980s Solvent UHMWPE Polymer powde r Low entanglement polymer gel Screw extruder Spinnere t Solvent recovery Gel fibres Hot draw Quench bath Low entanglement semi crystalline fibre Schematic diagram of continuous High Modulus Polyethylene (HMP) process Dyneema®, the world’s strongest fiber™ 9
  • 10. Time scales 1.Invention / Innovation 10 years 2. Development 10 years 3. Commercialisation 5 years
  • 11. Oscillatory Flow Mixing ( OFM) Inertial flow. Tube diameters, mm - cms A question of scale! Tonnes/hr, Kg/hr, g/hr 11
  • 12. Oscillatory Flow Mixing (OFM) 1980s; process Inventive steps 1979- 1982 Air turbine generates power 12
  • 13. Inventive steps. Plug flow residence time Chem Eng Sci 1989 13
  • 14. OFM Movie; poetry in motion Adam Harvey 14
  • 15. Heat transfer Chen Eng Sci 15
  • 16. Liquid Gas Mass transfer No oscillation With oscillation 8hz, 3mm Go to OFM bubbles movies 1 and 2 Filipa Pereira and Nuno Reis 16
  • 17. Mass transfer Cheng Eng Sci 17
  • 18. Development Stage Chem Eng Oscillatory Flow Reactor (OFR) - Oscillator Base Unit - Feed inlet section - Shell and baffled tube vessels - Product outlet section Dr Paul Stonestreet 18
  • 19. Biodiesel Reaction Progress along Reactor Net Flow Net Flow In Out 19
  • 21. Further development OFM Meso Reactor System configuration Meso tube, Sc diameter d ale - do wn Smooth constrictions: spacing 3d Minimum constriction diameter 0.4d 35 mm, V ≈ 4.5 mL a) L d d0 ≈ 45º δ b) Nuno Reis, Minghzi Zheng 2000s 21
  • 22. Meso Fluid Mechanics Go to OFM PIV and LES movies Minghzi Zheng 22
  • 23. Continuous Flow Oscillatory Mesoreactor 0.02 b) Exp-E(t) 0.018 1 Exp-E(t) 2 0.016 Exp-E(t)3 0.014 Fit-E(t) (1->2) 2 Fit-E(t) (1->3) 0.012 3 Fit-E(t) (2->3) E(t) (-) 3 0.01 0.008 0.006 0.004 0.002 0 0 100 200 300 400 500 600 700 800 900 Time (s) Minghzi Zheng 23
  • 24. Mesotube; Liquid drop dispersion a) f=6Hz a) xo=3 mm b) f=10Hz b) xo=4 mm Silicon oil (4.6mPas,2.5%) mixing Silicon oil (4.6mPas, 2.5%) mixing with water at xo=2 mm with water at f=6Hz 24
  • 25. Mesotube; Particle suspension Instantaneous velocity vector maps of fluid phase at Reo = 625, x0 = 2 mm, f = 10.0 Hz at vertical position in the presence of 3% (v/v ) amount of ion-exchange particles 25
  • 26. Time scales 1.Invention / Innovation 2 years 2. Development 10 years 3. Commercialisation Ongoing 26
  • 28. Flexible Chocolate 1994; invention Extrusion processing Cold Melt Polyethylene Extrusion Processing ∆H 50 100 150 200 0 Temperature C Chocolate Cold Melt Extrusion Processing ∆H 16 0 14 0 12 0 Piston/(ram) 10 20 30 40 A Yield 0 10 0 Temperature C pressure Chocolate feed Pressure transducer 80 Die 60 B Extrusion pressure 40 20 0 5 10 15 20 25 30 35 C Compaction (no flow) t (s) Review. Chen et al Soft Matter 2006
  • 29. Cold Extrusion Go to Flexible Chocolate extrusion movie
  • 30. Knotting Chocolate Go knotting movie
  • 31. Cold Moulding Chocolate Go to moulding movie
  • 33. Time scales 1. Invention / Innovation 1 day 2. Development 5 years 3. Commercialisation ?
  • 34. Plastic Microcapillary Films (MCFs) 2004-2012 34
  • 35. MicroCapillary Films (MCFs) 2000s; invention Polymer flow Injector Die land MCF extrudate Quench bath Extrudate to haul off Bart Hallmark 35
  • 36. Micro Capillary Film; invention Die exit Direction of flow Polymer melt Entrainment Chill rollers body MCF Array of 19 entrainment nozzles PLAN VIEW Quenching length, L Air inlet Single screw extruder MCF extrusion die P2 T5 T6 Chilled rollers MCF T1 T2 T3 T4 Spooling Gear pump Guide rollers B. Hallmark, et al. Adv. Eng. Mat., (2005). 36
  • 37. MCF Development; Pressure Drop Christian Hornung 37
  • 38. MCF Development RTD 50 45 length = 20 m inlet flow rate = 0.5 ml/min outlet 40 35 30 c [mg/l] 25 20 15 10 5 0 0 5 10 15 20 25 30 t [min] 38
  • 39. MCF Commercialisation  2 flat silicon heaters (200 W each)  PID control - Temperature monitoring at top and bottom heater plates developed by  Tmax = 150 °C Lamina Dielectrics Ltd. & Cambridge University Reactor disk tray Temperature control Teflon coated hot plates Patrick Hestor Lamina Ltd
  • 40. MCF Development; Microflow Organic. Kerosene, 1.8 mPas Video, Oil, 27 mPas Methanol Nuno Reis Vegetable oil. 50 mPas into Veg oil Water, 1 mPas, glycerol 10-50 mPas or methanol
  • 41. MCF Development; Slug separation Scheiff et al. Lab on a Chip. 2011
  • 42. Multi channel flow Go to MCF multi channel movie Nuno Reis
  • 43. MCF Development; Biodiesel Microreactor Input Output Vegetable oil Biodiesel Methonal plus Glycerol catalyst Microcapillary Flow disc
  • 44. MCF Microreactor; Biodiesel Methanol Glycerol Veg oil Biodiesel Methanol plus Glycerol catalyst
  • 45. MCF Development. Microporous MCF membranes Bore fluid Die Haul-off Air-gap Nitrogen External Gas Coagulant Cylinder Glass Water Polymer Bath Solution Single Capillary, MCF membranes Sina Bonyadi
  • 46. Microporous MCFs 2 µm 100 µm 1 µm 2 µm Bonyadi et al. Journal of Membrane Sci 2012
  • 47. Time scales 1. Invention / Innovation 3years 2. Development 8 years 3. Commercialisation Ongoing
  • 48. Lessons to be learnt • Work backwards. Identify need and then “process intensify”. • Get timing right. Anticipate current and future need for process intensification. • Build an interdisciplinary team. •Plan for a timescale of say 10 years 48
  • 49. Future Message Process intensification can result in a concentration of process leading to monopolies and a single source provider. Process Diversification can help prevent “bottlenecks” and provide flexibility. We need a balance between Process Intensification and Process Diversification. Process Intensification and Diversification 49