Stevia Sweetener Purification What Is Stevia Sweeteners? • Stevia sweeteners are natural...

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Transcript of Stevia Sweetener Purification What Is Stevia Sweeteners? • Stevia sweeteners are natural...

  • Stevia Sweetener Purification

    Mitsubishi Chemical Corporation Separation Materials Department

  • What Is Stevia Sweeteners?

    • Stevia sweeteners are natural sweeteners those are presented in the leaves Stevia rebaudiana Bertoni.

    • Steviosides, rebaudioside A, B, C, D, E and dulcoside A are representative compounds.

    • These compounds are 60 -300 times sweeter than sugar and contain significantly fewer calories.

    2

    Stevia leaves

    H

    H3C

    H3C H

    C OOO

    OH

    HOH2C

    HOHO

    CH2

    OO

    O

    HOH2C HO

    O

    O

    OH

    HOH2C

    HOHO

    O

    OH

    HOH2C

    HOHO

    Rebaudioside A C44H70O23, m.w.=967

    H

    H3C

    H3C H

    C OOO

    OH

    HOH2C

    HOHO

    CH2

    OO

    O

    HOH2C HO HO

    O

    OH

    HOH2C

    HOHO

    Stevioside C38H60O18, m.w.=804

  • Flow Chart of Stevia Sweeteners purification

    3

    Dried stevia leaves

    Extraction with hot water

    Pretreatment

    Filtration

    (Solvent evaporation)

    Cation exchange resins

    Anion exchange resins

    Finishing/decoloring

    Concentration

    Spray drying

    Aqueous alcohol

    solutions

    Eluate

    Product

    Waste water

    CaCl2, MgO, Ca(OH)2 etc.

    DIAION Manual p.304

    MeOH eluate

    Adsorption of stevia sweeteners

    Demineralization &

    Decolorization

    After treatment with IERs

    Synthetic adsorbents

  • Our products – Synthetic Adsorbents -

    We can provide synthetic adsorbents with various types of porosity.

    4

    SP825

    DIAION HP21, MCI GEL CHP50

    SP850

    peptide・protein Mw 1000~tens of thouthands

    β- lactam Mw~600 macrolide

    Mw 500~1500

    SP70

    SP700

    P o re

    v o lu m

    e (

    m L / g )

    HP20,CHP20 HP2MGL,CMG20

    SP207, CHP07

    Molecular Weight

    Stevioside Mw=804 RebaudiosideA Mw=967

  • Characteristic of SP700

    5

    HP20 SP700

    Chemical Structure

    Pore Volume(mL/g) 1.3 2.1

    Specific Surface Area(m2/g)

    590 1,200

    Pore Radius(Å) 290 90

    RebA Amount of adsorption (mg/mL-R)

    92 149

    ST Amount of adsorption (mg/mL-R)

    98 146

    CHCH2 CHCH2

    CH CH2

    CHCH2 CHCH2

    CH CH2 CH2CH3

    SP700 ・High specific surface area ・High stevia sweetener adsorption

  • Pore size distribution of synthetic adsorbents

    6

    SP700 has narrower pore size distribution and large surface area than HP20.

    0 0.2 0.4 0.6 0.8

    1 1.2 1.4 1.6 1.8

    2 2.2

    10 100 1000

    P O R E V

    O L U M

    E ( m L / g )

    PORE RADIUS (Å)

    HP20 細孔容積

    SP700 細孔容積

    HP20 dPV

    SP700 dPV

    Pore volume

    Pore volume

    Pore radius

    Pore radius

  • Loading profile

    7

    SP700 ・high capacity for stevia sweeteners adsorption ・long adsorption band →Multi column system is suitable for SP700.

    Condition column:φ30mm x L1000mm Resins 400mL Room temperature Flow rate SV4

    Short Adsorption

    band

    Long Adsorption

    band

    HP20

    0 10 20 30 40 50 60 70 80 90

    100

    0 20 40 60 80 100 120 140 160 180 200

    L e ak

    ag e C

    / C 0 (%

    )

    Stevia adsorpion amount(g/ L-R)

    SP700

  • Multi column system operation

    1 2 2 2 1 1

    Loading

    Eluent

    Elution (MeOH or EtOH)

    It is possible to effectively utilize the adsorption capacity of SP 700 with long adsorption zone.

    8

    Loading

  • Elution profile

    9

    0

    20

    40

    60

    80

    100

    120

    140

    0 1 2 3 4S te

    v ia

    s w

    e e te

    ne r

    c o nc

    . (m

    g / m

    L )

    Flow volume (mL/mL-resin)

    HP20 (5% BTP) SP700 (70% BTP) Condition Column:φ30mm x L1000mm Resins 400mL Room temperature 85% MeOH SV2 2BV Sweet off water SV2 2BV

    SP700 can concentrate higher stevia sweeteners than HP20. SP700 shows small tailing.

    HP20 elution (5% BTP)

    SP700 elution (70% BTP)

    Brix 8.7 9.7

    RA(mg/mL) 1.8 2.2

    ST(mg/mL) 20.0 32.1

    RA+ST recovery 100 % 100%

  • CER & Equipment

    10

    SK1B

    Appearance

    Type Strongly acidic cation (Gel)

    Salt splitting capacity (meq/mL) 2.0 min.

    Water content (%) 43–50 Shipping density* (g/L) 830

    Effective size (mm) 0.40 min. Maximum operating temperature (°C) 120 (H

    +, Na+)

    Pump

    C at

    io n

    e x ch

    an g e r

    e si

    n

    Sample solution

    Thermostatic circulator

    Jacketed column L 300 mm x 15 mm I.D.

    Electric conductivity

    meter

    pH meter

  • AER and Equipment

    11

    HPA512L

    Appearance

    Type Strongly basic anion

    Type I (trimethylammonium groups)

    Salt splitting capacity (meq/mL) 0.7 min.

    Water content (%) 63–73 Shipping density* (g/L) 670

    Effective size (mm) 0.45 min. Maximum operating temperature (°C) 80 (Cl

    –), 60 (OH–) Specific surface area* (m2/g) 9

    Pore volume* (mL/g) 0.11 Pore radius* (Å) 191

    Note: properties with a mark ‘*’ are reference data

    Pump

    A ni o n

    e x ch

    an g e r

    e si

    n

    Sample solution

    Thermostatic circulator

    Jacketed column L 300 mm x 15 mm I.D.

    Electric conductivity

    meter

    pH meter

  • Decolorization and Recovery

    12

    MeOH eluate

    After treatment with SK1B

    After treatment with HPA512L

    MeOH concentration 40% 40% 40% Absorbance (420 nm) 5.22 4.55 ≤ 0.3

    Rebaudioside A recovery – 100% 83%

    Stevioside recovery – 98% 77%

    0

    0.05

    0.1

    0.15

    0.2

    0.25

    0.3

    0.35

    0%

    20%

    40%

    60%

    80%

    100%

    R e c o v e ry

    4 2 0 nm

    A b s.

    BV

    HPA512L

    83%

    16%

    total recovery 99%

    MeOH

    HPA512L shows good performance for decolorization . Stevia sweeteners were Recovered in good yield.

    MeOH eluate

    After SK1B

    After HPA512L

  • MeOH consumption is key factor for total cost, rather

    than resin cost.

    SP700 is High capacity → Less resins → Less MeOH Cost reduction

    Running Cost Simulation

    13

    0

    10

    20

    30

    40

    50

    60

    70

    80

    90

    100

    HP20

    single column

    SP700

    single column

    SP700

    multi column

    %

    Cost Comparison

    Resin MeOH Waste/water

    Stevia adsorption

    (g/L-R) resin (m3)

    85% MeOH (m3)

    waste (m3)

    Process water (m3)

    HP20 (single column)

    65( 5%BTP) 15 30 375 180

    SP700 (single column)

    90( 5%BTP) 11 22 330 132

    SP700 (multi column)

    130(95%BTP) 7.5 15 285 90

    For 1000kg stevia sweetener production

    Stevia Sweetener Purification What Is Stevia Sweeteners? Flow Chart of Stevia Sweeteners purification Our products – Synthetic Adsorbents - Characteristic of SP700 Pore size distribution of synthetic adsorbents Loading profile Multi column system operation Elution profile CER & Equipment AER and Equipment Decolorization and Recovery Running Cost Simulation