Brewing Physical Chemistry: Beta
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Transcript Brewing Physical Chemistry: Beta
Flow and Filtration: The
Physics of Brewing
Dr. Alex Speers
Department of Food Science and Technology
<[email protected]>
Outline
Introduction
– Brewing gums
– shearing
Methods
– Rheometry
– Filtration
Summary
Why study -glucans?
Cause processing problems in brewing:
•
Under-modification of barley endosperm
•
High viscosity of wort and beer
•
Slow runoff of wort and beer
•
Haze formation in packaged beer
•
Clogging of membranes
•
Increased production cost
Localization of barley -glucans
Structure of a barley kernel
Scutellum
Acrospire
Aleurone layer
Husk
Embryo axis
Rootlets
Pericarp/testa
Endosperm
Beta-Glucan and Arabinoxylan Content
of Selected Beers (ug / ml)
Brew er
Product Type
B-Glucan
A/USA
Popular Priced L ager
(PPL)
29.4
1968
23.6
20.4
24.2
23.6
32.7
0.4
149.7
79.9
247.7
145.1
0.3
29.3
21.4
57.2
4.5
1031
1684
1657
2094
1292
1386
2368
3347
2598
3131
514
3103
4211
3174
524
B/US A
C/USA
A/USA
B/US A
B/US A
D/USA
E/US A
F/US A
G/Ge rmany
H/Ge rmany
B/US A
F/US A
H/Ge rmany
G/Ge rmany
LSD
Premium La ge r (PL)
Light
Whe at
Arabinoxyla n
Chemical structure of barley glucans
Unbranched chains of -D-glucopyranose
residues
O
O
O
O
-(14)- linkage
O
-(13)- linkage
O
Chemical structure of arabinoxylans
Localization of gums
•
Deposited mainly in in endosperm cell walls
•
Barley endosperm cell walls contain
20% arabinoxylans
70% -glucans
•
Barley aleurone cell walls contain
65-67% arabinoxylans
26-29% -glucans
•
Beta-glucan content
barley: 0.14 - 8.9 %
wort/beer: 12 - 940 mg/L
Non-Fermentable Brewing
Gums
Defined as Non Starch Polysaccharides
Gums - warm water extractable
Tend to viscosify wort and beer
Thus, add body/foam stability
In the distant past - not ‘a problem’
With advent of membrane filters, tight
production schedules & lighter beer
Pose problems in some breweries some
times
Beta-Glucan fringed micelles
C
A
B
20°C
>70°C
D
Micelle-like Aggregation
Methods
Rheological Definitions
Science of deformation and flow
Three important terms are shear rate (), shear
stress () and viscosity () - note different symbols
used.
h={
V/h,
= F/A
V, F
Calculation Example
Shear rate if dV= 1 cm/s and h = 1 cm?
Shear rate = 1cm/s ÷ 1 cm =1 /s
-1
Shear rate units /s or s
2
Shear stress if F= 0.001 N and A= 1 m ?
2
Shear stress = 0.001 N/ m = 1 mPa
Viscosity = 1 mPa s
Shear stress/shear rate
measurement: rotational
RPM -> shear rate
Torque -> shear stress
Viscosity = shear stress/shear rate
Rheometry
Cone and plate and coaxial fixtures
Shear stress/shear rate
measurement: pipe flow
Flow rate -> shear rate
Pressure loss -> shear stress
Viscosity = shear stress/shear rate
Best suited for measuring Newtonian
flow behaviour.
Rheometry
Capillary viscometer
Rheometry
Viscomat
Viscosity Dependence
Temperature = A e DE/RT
Concentration (gums,oP, Etoh)
Shear rate
Shear history
Shear effects
Shear Stress (mPa)
Newtonian Flow
2500
2000
1500
1000
500
0
0
500
1000
Shear Rate (/s)
1500
Shear effects
Viscosity (mPa.s)
Newtonian Flow
2.5
2
1.5
1
0.5
0
0
500
1000
Shear Rate (/s)
1500
Non-Newtonian Flow
Found
at high gum concentrations
Viscosity (mPa.s)
Pseudoplastic Flow
120
100
80
60
40
20
0
0
500
1000
Shear Rate (/s)
1500
Rheological Notes
Normally viscosity properly defined as apparent
viscosity - mPa s (= cP),
Kinematic viscosity is apparent viscosity divided by
density (Stokes)
– (Misleading terms in literature),
1 mPa s is = 1 cP ~ viscosity of water at 20oC,
Apparent viscosty depends on density, temperature,
shear rate and shear history.
Rheological Notes
Intrinsic Viscosity []
Based on extrapolated Specific viscosity (/ s -1)/c ->0
Can be used to determine shape of polymer based on
molecular weight:
[]KMa
Effect of Concentration
3
1/ log ( rel )
2.5
2
1.5
1
0.5
C*= 3.11 g/L
0
0
2
4
6
8
-glucan concentration (g/L)
10
Determination of C* with 327 kDa -glucan in a control buffer
Early Results
Using 327 kDa -glucan at 50 g/L,
ethanol (0-7%), maltose (0-15%) and
pH (3.6-5.2)
Viscosities were significantly
different (P<0.05).
Variation of [] and C* of -glucan
solutions
TreatmentpH
maltose ethanol []
C*
(%)
(%)
(mL/g) (g/L)
High ethanol 4.1
0.5
6.0
464
6.47
Low ethanol 4.1
0.5 4.0
812
2.72
Control
4.1
0.5 5.0
815
3.11
High maltose 4.1
0.8 5.0
806
2.13
Low maltose 4.1
0.1 5.0
862
3.05
Low pH
3.6
0.5 5.0
741
3.95
High pH
4.5
0.5 5.0
827
3.05
Why Sporadic?
Depends on crop year
Stressed plant tends to more -glucan
(Kendall)
Why Some Breweries?
Depends plant equipment
Depends on process
Possibly due to differences in shearing
of wort & beer
Brewing Shear Rates?
Turbulent or laminar?
NRE =V L/
= density, V = velocity L= diameter = viscosity
Average shear rate in turbulence
= [(/)3 / ]1/4
= average power dissipation per unit mass
Brewing Shear Rates?
Turbulent or laminar?
Turbulent flow cascades to laminar flow at
small distance scales
Brewing Shear Rates
Defined by Reynolds number of 20003000
Note Re= DV/
Also note V is the average pipe velocity
Generally get turbulent flow
Brewing Shear Rates
Shear in Kettle
8600 s-1
– (Speers et al. 2002)
Shear in Fermenter
20-60 s-1
(Speers & Ritcey, 1995)
Shear in Yeast brink tank
<15 s-1
(Kawamura et al. 1999)
Average shear rate in pipe flow
– High
– Mean
– Low
915 s-1
500 s -1
175 s -1
Membrane filtration
Theory developed in 30’s
Based on capillary plugging due to
gradual restriction in diameter
Surdarmana et al. 1996 Tech Quarterly
t/V = t/Vmax + 1/Qinit
Vmax maximum filtrate volume
Qinit intial flow rate
Membrane filtration
Theory developed in 30’s
Based on capillary plugging due to
gradual restriction in diameter
Surdarmana et al. 1996 Tech Quarterly
t/V = t/Vmax + 1/Qinit
Vmax maximum filtrate volume
Qinit intial flow rate
Filtration
Apparatus
Example Sudarmana Transform
Medium viscosity arabinoxlyan in model
beer
Relation of Intrinsic Viscosity
and Filtration
1/Vmax a [] for membrane test
Filterability negatively correlated with
[] for commercial (DE) filtration
Membrane filtration more suited for
detection of -glucan problems
Conclusions
Ethanol, pH and maltose effect viscosity
Shear strong effect on filtration
Shear within brewery typically turbulent
average 40-1250 s-1
Sudarmana fit ‘works’ (Tech. Quart 33:63)
Acknowledgments
Students !
NSERC
Labatt Brewing R&D
NSDAM
Westcan Malting
Canada Malting
Pfeuffer GmbH and Profamo Inc
(Viscomat automated capillary rheometer)