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Towards a new Brewing control chart for the 21st century John MELROSE, Borja ROMAN-CORROCHANO, Marcela MONTOYA-GUERRA, and Serafim BAKALIS J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b04848 • Publication Date (Web): 14 Apr 2018 Downloaded from http://pubs.acs.org on April 15, 2018
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Towards a new Brewing control chart for the 21st century.
2 3
John MELROSEa*, Borja ROMAN-CORROCHANOa, Marcela MONTOYA-GUERRAa,
4
Serafim BAKALISb.
5
a- Jacobs Douwe Egberts R&D GB Ltd. Ruscote Avenue, Banbury Oxon OX16 2QU, UK
6 7
b - Centre for Formulation Engineering, Department of Chemical Engineering, University of
8
Birmingham, Edgbaston Birmingham, B15 2TT, UK.
9
*Corresponding author:
[email protected] 10 11
ABSTRACT
12 13
This paper describes new results from a base model of brewing from a bed of
14
packed coffee grains. The model solves for the diffusion of soluble species out of a
15
distribution of particles into the flow through the bed pore space. It requires a limited
16
set of input parameters. It gives a simple picture of the basics physics of coffee
17
brewing and sets out a set of reduced variables for this process. The importance of
18
bed extraction efficiency is elucidated. A coffee brewing control chart has been
19
widely used to describe the region of ideal coffee brewing for some 50 years. A new
20
chart is needed, however, one that connects actual brewing conditions (weight, flow
21
rate, brew time, grind>.) to the yield and strength of brews. The paper shows a new
22
approach to brewing control charts, including brew time and bed extraction efficiency
23
as control parameters. Using the base model, an example chart will be given for a
24
particular grind ratio of coarse to fine particles, and an ‘espresso regime’ will be
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picked out. From such a chart yield, volume and strength of a brew can be read off
26
at will.
27 28
KEYWORDS
29
coffee, brewing, diffusion, modelling
30
31
INTRODUCTION
32
The brewing of coffee from a packed bed of particles is complex: it involves many
33
molecular and colloidal species released from a distribution of particle sizes. A
34
challenge is to provide brewers a guide to the effect of changing conditions (flow
35
rate, coffee grind, temperature etc) on brew performance. Modelling the process
36
offers a route to encapsulating experimental observations, but also to establish the
37
basic physics of the process. In general, it is best to start modelling at a simple
38
enough level to provide a base model with few input parameters, one which
39
demonstrates the basic physics with a fair level of accuracy and has a clear route to
40
development and improvement. This paper reports new results from what the
41
authors argue to be such a base model. The model was briefly reported in ASIC
42
conference posters 2-4 and a recent thesis5.
43
The main aim of the paper is to elucidate the basic physics of coffee brewing
44
through use of a simple base model of diffusive release from particles into a bed
45
pore space. It introduces reduced variables, and the concept of bed extraction
46
efficiency. Use of reduced variables, whilst a standard engineering practice, is
47
crucial to allow ease of comparison of different experiments and a comprehensive
48
set is not hitherto evident in the coffee literature. The paper presents a format for a
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new control chart which explicitly includes brew time; this is done for an espresso
50
brewing grind size. This example is consistent with, and predictive of, current
51
optimal espresso practice. Different regimes within the chart are physically
52
described.
53
time response.
54
The paper points out many open questions in particular on the early
Critique of other modelling strategies will be made. By explicitly solving the
55
diffusion equation within particles, the model captures the early time high fluxes of
56
the diffusion equation. It can, in principle, respect both the polydisperse distribution
57
of particle area and volume in the problem, thus allowing a direct interpretation of
58
fitted parameters, in particular diffusion constants.
59
the base model required from experiment are: the diffusion constants of species
60
inside particles, the particle size distribution (the volume averaged dimension and
61
the fraction of volume in fines), the bulk density of the bed, the coffee particle density
62
and the maximal yield - the last parameter is not commonly discussed in the
63
literature. The porosity of the dry bed can be estimated from bulk densities and
64
particle densities; however, it likely varies during brewing. Using particle-based
65
models such as that here, diffusion constants and composition weights can be fit to
66
experiment. Alternatively, predictive modelling of beds can be attempted by using
67
values of diffusion constants fitted to dilute slurry experiments or values estimated
68
from measured bulk values and grain structure. There are a number of effects
69
whose impact can be explored relative to the base model: variable flow rates,
70
partition coefficients and solubility, sphericities, dispersion coefficients, mass transfer
71
layers and boundary conditions, initial wetting of the bed, varying bed porosity and
72
surface composition of particles. In this paper and the base model these are
73
ignored. Directions for improvement of the model will be noted throughout the paper.
The key input parameters for
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The SCAA (Speciality Coffee Association of America) brewing control chart
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from the 1960’s is still used today as a guide to coffee brewing, it was produced
76
based on research by Lockhart1. The chart overlays various flavour regions on a
77
space of brew strength and brew yield. Sensory data suggests a region of optimal
78
coffee flavour: on the low yield side of this, the brew is said to be under-extracted,
79
generally described as sour or green and lacking in sweetness; on the high yield
80
side, it is over extracted with a bitter, smoky/burnt flavour and sometimes said to give
81
a dry mouthfeel. On the high strength side, these flavours are strong and on the low
82
strength side weak (although in practice desired strength will vary with culture). Note
83
the major flavour variation from under through balanced to over extraction is
84
indicated to just depend on the yield axis, the strength axis delineates weak to strong
85
flavours. The claimed dominant dependence of flavour on yield is not a given
86
feature, if correct it tells us there is something broadly generic about the relative time
87
scales for release of different flavour component families. As a map solely of the
88
outcome of the brewing process, the control chart has some shortfalls. It would be
89
preferable to have a set of charts that given a grind distribution, flow rate and brew
90
time, allows the brewer to look-up the resulting strength and yield. One that could
91
be applied, furthermore, not to just the total mass extracted but also for individual
92
extracting species. The ideal flavour zone found by sensory studies can then be
93
over-laid and related to actual parameters under the brewer’s control. This paper is
94
a step in that direction.
95
In earlier literature, measurement of the release kinetics of total mass and of
96
individual molecular species from coffee grains into dilute solution was reported by a
97
number of authors. 6-14 Spiro and co-workers 7-12 reported extensive work on the
98
release of caffeine and fit their data to models for diffusion out of spherical particles.
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One particular question debated was if the response of the system at early times
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was consistent or not with a diffusion model.13 Understanding of the early time
101
response is still however in-complete as will be discussed below. Lee et al.14
102
studied the release kinetics from flow through a coffee basket and reported the
103
release kinetics of wide range of molecular species, using half-lives they separated
104
the species into slow and fast extractors.
105
time of molecules from coffee particles and beds has been published. 15-25 These
106
involve the collection of aliquots and subsequent GCMS analysis, or dynamic
107
PTRMS measurement of volatiles in the vapour phase by Sánchez-López et al. 24,25
108
The reader is referred to Kuhn et al.25 for a summary and review of the recent
109
literature. Some papers fit the release profiles to equations. Mateus et al.17 fit both
110
the Weibull function and a single sphere diffusion model, they conclude that for
111
several species, the former equation indicates deviations from simple diffusive
112
release. Mestdagh et al.18 use hyperbolic equations to fit profiles, correlating polarity
113
with the initial release rates. Physical models have been developed based on first
114
order rate equations by Kuhn et al.25 and Moreney et al.26
More recent date on release profiles over
115
116
117
METHODS MODEL. The type of brewing modelled in this paper is a flow through a packed
118
bed of roast and ground coffee particles of dry weight W and involves transfer of
119
releasing species from the particles into the pore space of the bed and convection by
120
the flow through the bed and out into the beverage. An example would be brewing
121
of an espresso. If the volumetric flow rate Q(t) and mass concentration of an
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extracted species in the bed pore space at the exit of the bed C(t) are known at time
123
t, then the total mass extracted into the brew from the grains is given by
124
125
126
() = ( ∗ ) ( ∗ ) ∗
(1)
and the mass of the brew is given by
() = () ( ∗ ) ∗
(2)
127
where is the density of the brew. The strength S(t) and yield Y(t) of the brew
128
at time t are normally expressed as the following percentage values
129
S(t) =
∗ ( )
130
Y(t) =
∗ ( )
(3)
( )
.
(4)
131
Equation 3 and 4 are the common definition of brew strength and yield of the total
132
mass of all extracting species together. In the control chart1 , the regime of ideal
133
flavour lies between 18% to 22% total mass yield. For the strength and yield of a
134
particular species, the numerator in Eq. 3 is defined just with respect to the mass of
135
that species.
136
The full problem involves convective transport through the pore space of the
137
bed, a distribution of particles sizes, a wide variety of diffusing species and the
138
internal structure of coffee grains. These are discussed in turn as the base model
139
with its approximations are introduced.
140
The bed is divided into a set of particles and a bed pore space external to the
141
volume of the particles.
The flow is assumed not to penetrate the bulk of the
142
particles; however, the particles are assumed to wet rapidly by capillary action
143
(observations of gas bubbles on 500 μm grains wetting under a microscope suggest 6 ACS Paragon Plus Environment
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a time scale of a few secs, although complete water ingress into the grain matrix
145
may take longer). The initial wetting of the bed is not modelled, simulations start with
146
a wetted bed and grains at t = 0 and the release of species is assumed to start at
147
that time. In the simulations reported below, the flow is assumed a constant. The
148
transport of extracting species from within particles to their surface is assumed to be
149
due to diffusion driven by concentration gradients, activity, osmotic pressure and
150
solubility effects are ignored. The flow through the bed pore space removes species,
151
eventually into the external brew. The concentration in the pore space sets a
152
changing boundary condition on the diffusion within the particles. In the context of
153
gel chromatography, models for mass transport between particles and beds have
154
been applied27 ; Melrose et al.2-5 have adapted these for coffee brewing.
155
The particle size distribution (PSD) of coffee post grinding measured dry is
156
bimodal with a fine distribution and a coarse distribution. Some recent examples are
157
shown in Wang et al.22
158
these are fit well by a sum of a log-normal distribution for the fine particles, and a
159
log-normal distribution for the coarse particles.
160
approaching mm improved fits are found if a sum of log-normal for the fines and a
161
Weibull distribution for the coarse particles is used. Observation shows that the
162
peak of the fine distribution remains relatively constant in the range of dimensions
163
30-60 μm, but as the coarse size is reduced the volume of fines increases - see for
164
example the data in Wang et al.22
165
three parameters:
166
fraction of fines. The particles are assumed spherical. The coarse particle radius is
167
set at one half the volume averaged dimension, d4,3. This two-particle approximation
168
is the simplest way of both mimicking the longer length scale particles in the PSD but
For coarse size in the range below 0.5 mm, it is found that
For grinds with coarse sizes
The base model approximates the PSD to just
representative fine and coarse particle sizes and the volume
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also the shorter length scale (and fast release) of the fines, together they mimic the
170
dimensions of the surface area of the total grind and the volume averaged
171
dimension.
172
time release kinetics of the system.
173
particles and the use of many particles to represent the PSD is work in progress.
174
Coffee grains are in practice not spheres, sphericities are measured in the range 0.8-
175
0.75
176
unity for the results below. Swelling of grains is assumed absent.
177
5
The volume averaged dimension of the distribution captures the longer It is straightforward to generalise to many
; shape can in part be accounted for with this correction, but this was set to
The results in Figure 2 below are for the model solved for a single diffusing
178
species. Assuming that the species do not interact with each other, the single
179
species solution is not a limitation because multiple species can be handled by
180
rescaling time and superimposing the single species solution. In principle, multiple
181
particles cannot be handled this way as they are coupled together by the common
182
concentration in the bed pore space through the boundary condition - although in
183
dilute enough slurry conditions or fast enough flow through beds (see below) they
184
can be considered decoupled. One of the uses of modelling is to make estimates of
185
when these dilute or fast flow conditions hold.
186 187 188
The concentration of extracting species averaged over the coffee particle volume (that portion of mass extractable) is given by
= ( /100) #
(5)
189
where is the maximal possible yield and # is the density of a coffee particle.
190
In reduced units, the yield is defined by
191
$(̃) = (̃)⁄ .
(6)
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The maximal yield needs be measured, for example by bringing a dilute slurry
193
extraction to equilibrium over a long time.5 For the total mass it was found5 to vary
194
with grind size: at extraction temperatures circa 80 oC total yields are 32-30% for a
195
very fine grind (coarse peak < 200 μm) to values for 25-24% for a larger grind with
196
coarse peak circa 1 mm.
197
extractable may be due to several reasons: diffusing species inside the wet grain
198
may have a probability of being irreversibly trapped or absorbed in the coffee matrix
199
or of being transformed by chemical reaction with the matrix. The maximal yields do
200
vary with temperature; the kinetics of brewing also changes with temperature, but
201
beyond that expected by just the temperature scaling of diffusion constants.
202
The variation with particle size of the total mass
Roast and ground coffee particles have a heterogeneous internal structure28
203
consisting of a nano-porous matrix of structural carbohydrates and proteins
204
surrounding 30-60 μm macro-pores (the pockets in the matrix that held the biological
205
cells before roasting); the surface has exposed sections of macro-pores. It is likely
206
that the extractable material is similarly distributed heterogeneously - the roasted
207
and reacted contents of the original biological cells and oil bodies are most likely on
208
the surface of the macro-pores28 and probably are the majority component. Some
209
species may also release from the matrix, in particular oligomers of the structural
210
carbohydrates, but possibly also small molecules. The fines are fragments of the
211
nano-porous matrix on length scales comparable to that of the macro-pores. This
212
heterogeneity is on the whole ignored in the current model. The model particles,
213
both fines and coarse, are approximated as homogeneous although the impact of
214
heterogeneity on diffusion constants is included (see Eq. 8). The soluble
215
components are assumed to dissolve rapidly as the grain wets. Moroney et al.26 do
216
start with a formalism which separates the matrix and macro-pores, however they 9 ACS Paragon Plus Environment
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also eventually homogenise their model and also assume rapid dissolution of internal
218
species on wetting as is done here.
219
Partitioning may occur between the particles and external bulk. This is may be
220
accounted for by using partition coefficients K: the ratio of total mass concentration
221
averaged over the volume of the particles relative to that of the external bulk at
222
equilibrium in a slurry experiment (see Eq. 11 below). Interpretation of K for coarse
223
coffee particles is complex due to their heterogeneous structure; it is likely that within
224
the particle there is a species dependent partitioning between the particle matrix, oil
225
phase and the macro-pores - given their 30-60 μm scale it seems reasonable to
226
assume that at equilibrium the concentrations in the macro-pores are that of the bulk.
227
K can be found by a series of dilution experiments, Spiro12. Corrochano5 reports K =
228
0.6 on a very fine distribution with 70% of the volume in fines (< 100 μm ) which can
229
be assumed to contain few macro-pores and thus to be an estimate of the
230
partitioning between the matrix and bulk. At typical brewing flow rates, modelling
231
suggests that release kinetics of the total mass is weakly dependent on K. These
232
effects are ignored in the base model. Although, for individual molecular species
233
over typical brewing temperature ranges there may be a strong temperature effect
234
on partition coefficients.
235
Units of time, , length, r0 and concentration c0 are chosen and the model
236
constructed in dimensionless units ̃ = ⁄ , (̃ = ( ⁄( and )̃ = )⁄) ; ( is as
237
defined in Eq. 5. The choice of units of time and length will be discussed later.
238
Within the representative particles, the diffusion equation is solved for the time
239
varying radial grain concentration profile *+ , for the pth particle size fraction
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,-*. , *
240
2
*
*
1+ (, 2-. + 4 ,-.) , = −0 , ̃
(7)
̃ ,̃
241
1+ , is an average over the porous and heterogeneous where the diffusion constant, 0
242
structure of the coffee particle.
243
grain microstructure parameters and known diffusion constants Db. in bulk (water)31 :
1+ can be estimated from measured Values for 0
8
0+ = 56 (7) 9: 0 ,
244
(8a)
245
1+ = 5 ;2 : 0+ , 0
246
(8b)
;
247
where ε and < are averaged particle porosity and tortuosity and 7 is the ratio of pore
248
size to species size - together they set an overall hinderance factor rescaling the
249
bulk diffusion constant to a smaller particle diffusion constant. Equation 8b gives
250
the diffusion constant in the reduced units. The hinderance factor could vary with
251
particle size, in the base model it will be assumed constant for all particles. Spiro and
252
co-workers7-12 reported on the hinderance factor for caffeine. Corrochano5 made
253
estimates based on measurements of particle porosity. The following boundary
254
conditions are applied to Eq. 7:
255 256
= 0; 1+ 0
,-*. ,̃
*+ = *> ; ?0 ≤ )̃ ≤ A$+ B = 0 ; ()̃ = 0, ∀̃ )
(10)
257
where Rp denotes the radius of the pth particle size. Concentration boundary
258
conditions are applied:
259
*+ (A$+ , ̃ ) =
-* ( *) D
(9)
; (̃ > 0) .
(11)
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Equation 7 is hence subject to time varying boundary conditions, and in the
261
polydisperse, packed beds the different particle sizes are coupled together via the
262
common * (̃). As discussed above, K = 1 in the base model.
263
The particle transport equations, Eqs. 7-11, are imbedded in a coarse-grained
264
model of convection through the bed; this is given below in a finite difference form.
265
The bed is assumed axially symmetric and divided into N layers orthogonal to the
266
axis, such that each layer has equal volume and dimensions larger than that of the
267
individual particles. A set of particles are simulated in each layer with the PSD
268
assumed uniform across the bed. The concentration profiles with in each particle in
269
each layer evolve in time according to the boundary condition set by that layer’s pore
270
space concentration and Eqs. 7-11.
271
the ith layer, Cbi , evolves in time according to
272
273
L.
*F (̃ + ∆ ̃ ) = *F (̃) + H3J ∑+
M̃ .N ( *)
̃.
The concentration in the bed pore space of
+ J O PQ 5 *FR (̃)- *F (̃ ):T ∆ ̃ ,
(12)
where (R8U )
274
J=
275
PQ = (
8U
VW X( )
(13)
,
) ,
(14)
276 277
with YZ the bed porosity, W the weight of coffee in the bed, Q the volumetric fluid
278
flow rate through the bed, # the density of a coffee particle, [+F the flux out of the
279
surface of the pth particle class in layer i, \+ the fraction of grind volume in the pth
280
particle class and ∆ ] the computational time step.
281
(for each layer) in Eq. 12 is restricted to just two particles classes sizes: one fine,
In this paper, the of sum fluxes
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one coarse. The pore space concentration in each layer *F (̃) is assumed zero at t
283
= 0. The pore concentration in the final layer i = N is used in Eq. 1 to predict the
284
mass extracted into the brew. The parameter PQ will be termed here the bed
285
extraction efficiency and is discussed in section 2.3. (Eq. 12 is a discretised version
286
of bed transport equations27 with dispersion terms omitted. Dispersion effects can
287
be included in the formulation, the flow rates are typically in the regime where the
288
introduced coefficients will be order N d/L, where L is the bed axial length, and d is a
289
microscopic length of order the particle size. For the problems here, the
290
concentration gradients in the bed are such that these terms are found negligible.)
291 292 293
It remains to make a choice of length and time units. The unit of time is chosen as the diffusive relaxation time for fine particles: ) = A^F_
= ^F_ =
2 `aNb
c.
(15)
294
where A^F_ is the radius of the fine particles. Given that for coffee grinds A^F_ is a
295
relatively fixed length scale, Eq. 15 is a useful definition even if the grind of interest
296
has a low level of fines. The value A^F_ = 20 μm is used in the base model.
297
In general, analytic and trivial solutions are not available for polydisperse and
298
moving boundary condition problems and numerical techniques need be used. The
299
equations were implemented in the scripting language Scilab30 with be-spoke code
300
written by one of the authors. It was found that choosing N=10 layers gave
301
satisfactory convergence of the results vs computational expense. Using a
302
discretised version of Eq. 7 the code updates the concentration profiles for one fine
303
and one coarse particle in each layer according to the updated bed pore space
304
boundary condition. The particles are typically meshed at a scale circa 0.5-1 μm in
305
real units (50 mesh points for the fine particles). The time steps are determined by
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Eq. 12 and are chosen so that the volume flowed is a small fraction ( < 0.1 ) of the
307
layer volume. The time steps so set are such that an explicit scheme was used to
308
solve Eq. 7, and to iterate profiles inside particles. A typical run out to time of 40 in
309
reduced units (an individual curve of Figure 2 below) takes circa 1hr on a Dec-13
310
Pentium 7 laptop with 16GB of RAM. DISCUSSION ON MODELLING. In the models of Kuhn et al.25 and Moreney
311 312
et al.26 transport is modelled by fitting rate constants in first order expressions
313
between particle surfaces and the bed pore space, in contrast the diffusion equation
314
for concentration profiles inside the particles is solved in the model here. First order
315
expressions are a limitation when the overall mass transfer rate in coffee brewing is
316
controlled by diffusion inside the grains, in particular they do not represent the high
317
diffusion fluxes out of particles at early times13, relevant on brewing time scales.
318
Fitted rate constants also limit interpretation in terms of underlying parameters such
319
as diffusion constants and partition coefficients and thus moving from the conditions
320
of the fit to different brewing and grind conditions. The fitted coefficients are not
321
independently measurable, whereas fitted diffusion constants can in principle be
322
independently measured or estimated. As in the base model here and earlier work2-
323
5
324
problem.
325
, Moreney et al.26 do represent separately the coarse and fine length scales in the
The base model does not include brewing pressure as a directly relevant
326
variable. Given the hydrodynamic resistance of the bed, the pressure gradient sets
327
the flow rate but it is assumed in the base model not to directly influence release
328
other than through flow rate. Experiments26 showed that pressure applied to a slurry
329
brewing did not influence release. The grain volume, however, is circa 50% gas
330
(either air or CO2 depending on the level of CO2 degassing before use) and may 14 ACS Paragon Plus Environment
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331
contain an adsorbed load of CO2. This gas is released as the bed is wetted and does
332
effect coffee crema and organoleptic properties of brew, this process may directly be
333
influenced by the pressure gradient. Multi-phase effects of gas in the beds is
334
beyond the current model and gas release is ignored.
335
In the simulations of this paper, the flow rate is kept constant. The model can,
336
however, be directly coupled to a ‘brewer model’ in which pump behaviour, pressure
337
and flow rate are coupled by the time varying flow resistance of the system3.
338
also feasible to extend the model to include the heterogeneity of the particles: one
339
approach would be to approximate the internal structure of grains to be a series of
340
layers with appropriate thicknesses of matrix and macro-pores with different effective
341
D’s, and distribution of species, in each layer, this would preserve the radial
342
symmetry of Eq. 7.
343
It is
POROSITY AND BED EXTRACTION EFFICIENCY. Given measurements of
344
the density of individual particles5 (# = 550 − 600 kg/m3 ), for packed beds in
345
coffee brewing with dry bulk densities in the range 400-500 kg/m the porosity can
346
crudely be estimated to lie in the range 0.3 - 0.1. Porosity, however, varies during
347
wetting and brewing due to several effects: consolidation of the bed under pressure,
348
an increase in fines level due to those encrusted on the surface of the coarse
349
particles being released into the bed and possible swelling of the grains dependent
350
on water quality. The strategy used in the modelling is to keep it as a separate
351
parameter and to study the sensitivity of the model to it.
352
3
A bed relaxation time is defined as the time by which the volume of fluid flowed
353
through the bed equals the volume of the bed itself. Physically, the optimal
354
definition would be the time to match the pore volume of the bed, but this would
355
complicate the role that bed porosity plays in Eq. 12. Practically, it is just required 15 ACS Paragon Plus Environment
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356
that a definition of the bed relaxation time scales with the bed pore volume; porosity
357
is kept as a separate parameter. The choice in Eq. 14 is that the bed relaxation time
358
is defined relative to the volume of coffee grains:
359
360
361
Z =
/VW
(16)
X
and with the choice Eq. 15 for time units
PQ =
aNb U
.
(17)
362
The bed extraction efficiency, PQ , as defined above can be interpreted as follows. If
363
^F_ > Z species coming out into the pore space of the bed are removed at a
364
faster rate than they come out of the grain, the concentration in the pore space,
365
( , is very low and the rate of release from the grain is maximised (PQ is large,
366
efficient bed extraction). Alternatively, if Z > ^F_ relative to the release rate from
367
the grains, the removal from the bed is slow, concentration builds up in the bed pore
368
space and the release rate from the grain is slowed according to Eq. 11 (PQ is small,
369
inefficient bed extraction). Moreney et al.26 use a similar ratio of bed advection time
370
to grain diffusion time as one of their parameters in an asymptotic analysis of their
371
model.33
372
Extraction efficiency of the bed is a key concept. As beverages are generally
373
produced for fixed target volumes, a variation in brew time is coupled to efficiency:
374
longer brew times occur with lower extraction efficiency and vice-versa, hence yield
375
does not vary as significantly with brew time as might be expected (see below). In a
376
bed extracted at a given flow rate to a target volume, the faster a diffusing species
377
(larger D) the lower (in reduced units) is its bed extraction efficiency, however the 16 ACS Paragon Plus Environment
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Journal of Agricultural and Food Chemistry
378
real brew time will map onto a larger reduced time and hence a higher yield for the
379
faster species occurs overall.
380
EXPERIMENTAL RIG. A series of brewing experiments using a range of grinds
381
was done by Corrochano et al.4,5 in both dilute slurry conditions and in a custom-built
382
brewing rig32. The rig drives flow by applying a constant hydrodynamic pressure to a
383
cell and bed of dimensions comparable to that of typical brewing chambers - see
384
Corrochano et al.32 for a more complete description and diagram of the rig.
385
particular experiment from this series is reported below. A blend of Medium-dark
386
roasted arabica beans from Central America (30%) and Brazil (70%) (moisture
387
content 3.5%, medium roast colour) were ground in a Dalla Corte disc grinder
388
(Baranzate, Italy). PSD were measured by using light scattering on a Helos
389
Sympatec.
390
dry. The bed was cylindrical of diameter 3.7 cm; 9.5 g of coffee was packed to a bulk
391
density 480 kg/m (dry at start), resulting in a bed height of 1.8 cm. The rig operates
392
at a fixed applied over pressure; 3.75 bar and 1.75 bar were applied resulting in
393
average flow rates of 3.7 ml/s (HF) and 1.3 ml/s (LF) corresponding to extraction
394
efficiencies of gQ = 0.9, 0.3 respectively. Aliquots were taken over time and brew
395
concentrations measured by refractometer methods (RFM340, Bellingham Stanley
396
Ltd, UK), which had been previously calibrated against the standard drying oven
397
method (103°C during 16-24 hours until constant weight) to measure concentration
398
of soluble solids5; experiments were done in triplicate. Slurry experiments in dilute
399
conditions were used to find the maximal yield of the grind of = 28% and the
400
coffee particle density was estimated # = 580 kg/m3 , these values were used in Eq.
401
5 to set
.
One
The PSD had d4,3 = 325 μm and 20% of the volume in fines measured
3
402 17 ACS Paragon Plus Environment
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403
Page 18 of 38
RESULTS AND DISCUSSION COMPARISON WITH AN EXPERIMENT. Figure 1 shows comparison of the rig
404 405
experiment and model predictions. The experimental results plotted are the total
406
mass concentration (all species) in the brew; 3.75 and 1.75 bar were applied
407
resulting in average flow rates of 3.7 (HF) and 1.3 ml/s (LF) corresponding to
408
extraction efficiencies of PQ = 0.9 , 0.3 respectively. Concentrations were found using
409
the average flow rate to define brew volume. Data is averaged over three
410
experiments; errors of the mean are less than the symbol size. Models were run
411
with a single diffusing species and a weighted sum of two diffusing species.
412
Convection through the bed was modelled in this case, by dividing it into 10 layers.
413
The coarse particle radius is set at half d4,3 and a fine particles radius was set at 20
414
Jk.
C kg/m3
100.0 80.0 60.0 40.0 20.0 0.0 0
20
40
60
80
100
120
Time s
415 416
Figure 1. Expt. Data: Squares (LF) and diamonds(HF). Model predictions for a single
417
species of Dp =1.0X10
-10
m2/s representing the total mass are shown by the solid lines. 18 ACS Paragon Plus Environment
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Journal of Agricultural and Food Chemistry
418
Also shown by dashed lines is a model fit with two species one with Dp =2.6X 10-10 , and the
419
other with Dp =1.3X10-11 m2/s , with 60-65% of the mass in the larger D species
420
(representing small molecules).
421 422
In early experiments6 , the fitting of diffusion models to slurry/bulk brewing data gave
423
an effective particle diffusion constant for the total soluble solids in the range 0.8-
424
1.1X10 . Figure 1 shows that for a packed bed brewing, with adoption of the value
425
of Dp = 1.0X10
426
for the coarse particle and fines as discussed, the model makes a fair prediction for
427
the extraction of the total mass over early times 20-30 s; but it over predicts the yield
428
and concentrations at longer times.
429
Figure 1. Using two diffusion constants with 60-65% of the mass associated with
430
the larger diffusion constant, fits the data well out to longer times at both flow rates.
431
Two parameters were varied, a base value of D and one a factor 1/20 smaller,
432
motivated by estimates of the bulk values of carbohydrate oligomers (see below).
433
The mass distribution between the two species was then varied to minimise error.
434
The full problem involves a spectrum of relaxation times, due to multiple particle
435
sizes and multiple releasing species. In principle, the model just fits relaxation times,
436
such as that of Eq. 15. The degree to which the diffusion constants used are
437
comparable to that of the actual diffusion of species relies on the success of the
438
choice of length scales to mimic the real system PSD (in the base model here, using
439
just one coarse and one fine particle size). The fitting is also sensitive to the values
440
used for maximal yield, in this case that measured in dilute conditions, the level of
441
fines (in this case that given by the PSD measured on dry grains) and the
442
assumption of homogeneous flow across the bed.
-10
-10
m2/s from ref. 6 when combined with the PSD approximated to d4,3
The model was also used to fit the data of
19 ACS Paragon Plus Environment
Journal of Agricultural and Food Chemistry
443
Page 20 of 38
It is now discussed how consistent the values of the two diffusion constants and
444
fitted compositions used in Figure 1 are with separate observations and estimates.
445
The spectrum of releasing species is known to range from minerals, to small
446
molecules (e.g. caffeine), to oligomers of structural carbohydrates (mainly
447
galactomannans) to small colloids up to 100-200 nm in size (e.g. coffee large
448
melonoidins). An average degree of polymerisation of 20 is reported for the
449
galactomannan oligomers.34 This size range corresponds to a range of bulk
450
diffusion constants from l(10Rm ) m2 /s for minerals and small molecules thru to
451
l(10R ) m2 /s for the carbohydrate oligomers and l(10R4 ) m2 /s for the colloids.
452
It is, however, the hindered particle diffusion constants (c.f. Eq. 8a) that determine
453
the release rates rather than bulk diffusion; these can be measured or estimated
454
independently of fitting slurry and brew data. In a series of papers, Spiro and co-
455
workers7-12 measured the infusion of caffeine in slurry conditions. At 80 oC and for
456
particles in the 850-1200 Jk they report hindrance factors of 11 and a particle
457
diffusion constant of 1.7 n10R m2 /s for caffeine at 84 oC 10; Jaganyi and Madlala15
458
report hindrance factors for caffeine in the range 11-14. Values estimated from
459
structural data of coffee particles5 were in the range 6-10 and increased with grind
460
size. Rescaling the expected range of bulk diffusion constants by hindrance factors
461
of this order, suggests small molecules will have particle diffusion constants
462
l(1.0n10R ) m2 /s and the carbohydrates oligomers l(1.0n10R ) m2 /s . These
463
crude range estimates are used to set the values for the two-species fit of Figure 1.
464
There are few studies of the relative composition of species but the limited data
465
available29, suggests 60-70% of the mass extracted into a brew are small molecules
466
and the main mineral potassium. This is consistent with the fitted mass fraction of
467
the faster diffusion species. However, it is likely that the mass fraction resulting in
20 ACS Paragon Plus Environment
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Journal of Agricultural and Food Chemistry
468
the smaller diffusion constant of the fit is also in part due to small molecules which
469
are hindered by other interactions as discussed below.
470
Given the heterogeneous nature of the real coffee particles, a given species will
471
likely experience varying hindrance factors (c.f. Eq. 8a) as they diffuse through the
472
structure.
473
coarse particles could have diffusion constants closer to bulk values. It would be
474
straightforward to include these effects in a model. However, this outer layer of
475
exposed macro-pores is only 30-60 μm thick and extraction from this layer is over in
476
a few seconds, a time scale comparable to that of the release from the fines. Whilst
477
this is a likely feature, it need be recognised that the spectrum of species rather than
478
grain structure may be the dominant cause of multiple relaxations times evident in
479
the data for total mass release over longer timescales. In support of this, and in
480
contrast to multiple relaxations in the total mass, studies of a single molecule
481
(caffeine) from short to long times (150 min), reported a good fit to a single diffusion
482
constant, hindered from that of bulk values but constant over time.10
Species released from exposed macro-pores at the grain surface of
483
Hindrance may also arise due to interactions other than grain structure. As is
484
evident in recent published data17-21 some species deviate from a simple diffusion
485
release model and these may constitute part of the mass fit by the smaller diffusion
486
constant in Figure 1. Speculation on mechanisms for this includes: slow dissolution
487
due to low water solubility, partitioning with oil phases, adsorption and binding
488
interactions within the grain matrix and other species. A classification of a wide
489
range of molecular release profiles has been made23,24, with low polarity, weakly
490
soluble compounds releasing more slowly18. Species might also interact with each
491
other inside the grains, e.g. phenolic molecules such as chlorogenic acids are known
492
to bind to colloid melanoidin particles.29 Jaganyi and Madlala15 observe that the 21 ACS Paragon Plus Environment
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Page 22 of 38
493
mineral ion manganese shows diffusion constants order l(1.0n10R ) m2 /s
494
(comparable to the estimates above for oligomers). They argue this is due to co-
495
valent interactions due it being a transition metal. Guaiacols have been shown to
496
have relatively slow release for their molecular weight and have been argued to be
497
contributing to flavour in over-extraction21. As noted earlier, that maximal yield
498
decreases with grind size may also result from such interactions. Conversely, with
499
size exclusion of large species (light scattering shows the presence of colloidal
500
material in the range 100- 200 nm), it is possible that large and slow diffusing
501
species can only be released from the outer rim of coarse grains and fines, from
502
exposed cell-pockets – via this route such large species may appear to be fast
503
releasing. These many effects may offer routes to new technology and are a rich
504
area for further experimentation and modelling with suitable source/sink terms added
505
to the modelling.
506
A key feature seen in Figure 1 is that the concentration has a peak at early
507
times; this is evident in the model here and in that of Moreney et al.26 In the model
508
here the origin of this effect is simply a very large flux out of the coarse and fine
509
particles at early times. An initial high flux (the so called ‘wash off’) was well known
510
and a contentious issue in the earlier coffee literature. By mistakenly comparing
511
early time behaviour with the long-time (first order) behaviour of diffusion models it
512
was even claimed as evidence against a diffusion model at early times. This issue
513
was resolved by the work of Stapley13 who showed that the early time deviation from
514
first order kinetics was consistent with the early time behaviour also in the diffusion
515
model. Because in coffee systems the early time behaviour may have additional
516
complications, the issue is perhaps not closed.26 As noted by Moreney et al.26 the
517
surface includes both the fines and coarse particle surfaces. In addition to species 22 ACS Paragon Plus Environment
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Journal of Agricultural and Food Chemistry
518
at the surface having closer to bulk diffusion constants (as noted above), it is also
519
possible that the surface of grains holds an excess of extractable species over the
520
particle interior: e.g. the contents of cell pockets lost during grinding. Furthermore,
521
the initial flux out of a bed includes the complication of how the front wetting the bed
522
initially wets the grains and convects released species. Densified coffee has fines
523
incorporated into the surface macro-pores of coarse particles. Some of these
524
features can be directly incorporated in models but require detailed calibration
525
against short time data not yet available. Moreney et al.26 explicitly include a first
526
order rate term to model early time release from fines and surfaces, in the model
527
here2-4 fast release at early times is included via the fraction of fine particles.
528 529 530 531
CHARTS OF YIELD AND STRENGTH VS BREW TIME. Figure 2 shows a
532
chart of the model predictions in reduced units for a particular grind in which the
533
coarse particles are 8 times larger than the fine particle and with fines at 20% of the
534
grind volume. For coffee with fines of dimension (diameter) circa 40 μm this is a
535
coarse particle dimension d4,3 circa 320 μm - typical of an espresso grind and the
536
example in Figure 1.
537
bulk density circa 480 kg/m3. The yield is plotted against time (solid lines) for a
538
range of bed extraction efficiencies; overlaid are examples of contours of constant
539
strength (dashed lines) and constant ratio of brew volume to the volume of coffee
540
grind in the bed (dashed-dot lines).
The bed porosity was set at YZ = 0.2, appropriate for a dry
23 ACS Paragon Plus Environment
Journal of Agricultural and Food Chemistry
Page 24 of 38
541 542
Figure 2. The solid lines are extraction efficiencies, from the bottom to top : gQ = 0.001,
543
0.002, 0.004, 0.006, 0.008, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.1, 0.12,
544
0.14, 0.16, 0.18, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.8, 1.0, 2.0, 4.0. The dashed lines are
545
contours of constant strength, at times beyond the peak strength values and the dashed-dot
546
lines are contours of constant ratio of brew volume to grind volume.
547
figure tfine is the fine relaxation time defined in Eq. 15. The crosses show where the peaks
548
of the strength vs time plot occur (see text).
549
In the notation of the
Note that as PQ is increased, the yield vs time curves bunch to a limiting case.
550
This limit is when the flow through the bed is so fast (or equivalently the species
551
diffusion is so slow) that the concentration in the pore space approaches zero, the
552
bed extraction efficiency is high and extraction is just limited by diffusion through the
553
grains into the bed. Note in the high PQ limit with the bed concentration low,
24 ACS Paragon Plus Environment
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Journal of Agricultural and Food Chemistry
554
different particle sizes are weakly coupled and a polydisperse solution can be built
555
up by time rescaled and weighted sums of the mono-disperse solution. Conversely,
556
in the very low PQ limit, the bed pore space and particles are close to equilibrated on
557
the timescale of the bed relaxation time. The model then is truly trivial, diffusion can
558
be ignored and there is simply a first order decline in the concentration averaged
559
over the whole bed with decay constant given by (1 − YZ ) PQ . In between these
560
extremes (where for most species most brewing is in practice) the solution is more
561
complex.
562
influence. Along each PQ line the brew strength first increases to a maximum and
563
then declines (c.f. Figure 1); the crosses indicate the location of the peaks.
As this regime is approached, polydispersity has increasingly a weak
564
Note the interplay between flow rate and brew time acting along a contour of
565
fixed brew volume relative to grind volume (dashed-dot lines in Figure 1): a longer
566
brew time to a fixed target brew volume, implies a lower flow rate and lower
567
extraction efficiency and vice-versa; it is seen that after a reduced time of 10, the
568
yield along the contour shows a weak dependence on brew time. Overall, however,
569
plotting yield against brew volume does not collapse the data set further.
570
Given the brew weight, W, diffusion constant, Dp, maximal yield Ymax of the
571
species of interest, and the density of the particles, # ; a point ?PQ, ̃, $B of reduced
572
parameters can be mapped to real variables using definitions in Eqs. 6,15-17. and
573
the relationships:
574
= $
,
(18)
575
= ]^F_
,
(19)
576
o = PQ̃
VW
= ( )
(20)
,
25 ACS Paragon Plus Environment
Journal of Agricultural and Food Chemistry
577
=
p
q
=
pVW #Q *
Page 26 of 38
(21)
,
578 579
where o is the volume of the brew and is the concentration kg/m3 of
580
released coffee mass in the brew.
581
in the range 550-600 kg/m3 and maximal yields were given earlier. Conversely,
582
inversion of Eqs. 18-21 can be used to map absolute values onto the reduced
583
variables. The dashed-dot lines in Figure 2 are lines of constant PQ̃.
584 585
Typical values for the coffee particle density lie
Commonly, coffee concentration is measured and reported as a strength S as defined in Eq. 3. The relationship between to S is given by
586 587
S=
-
V
≅ 100 ∗
-
Vst (Ru-)
,
(22)
588 589
where is the density of water at the appropriate temperature. The experimental
590
problem is to infer a value of C from a measured S, the simulations have the inverse
591
problem. Up to practical concentrations S < 20%, measurements of vs C or S
592
show a weak linear variation, e.g. using the data for espresso brews reported by
593
Navarini et al.35 one finds v = 0.0002 m3/kg. Using v = 0 is a good approximation
594
and this was used to compute the strength contours in Figures 2 and 3 below.
595
THE ESPRESSO REGIME. In principle, Figure 2 is a control chart of the
596
model grind run for a single species. However, use of 0+ = 1.0n10R m2/s as a
597
proxy for total mass (see Figure 1 and Volliey and Simatos6 ) combined with a
598
measurement of maximal yield , the chart can be read as an predictive estimate of
599
the profile in time of the total mass yield - at least over the time scales of a typical
600
espresso brew. Adopting 0+ = 1.0n10R m2/s , ^F_ = 4s and using Ymax = 28%, 26 ACS Paragon Plus Environment
Page 27 of 38
Journal of Agricultural and Food Chemistry
601
for a system of d4,3 circa 320 μm,
602
chart, plotted in real units.
Figure 3 shows an “espresso region” of the
603 604 605
Figure 3. The ‘Espresso region’, reading from to left to right, the extraction
606
efficiencies (solid lines) are PQ = 4, 2, 1, 0.8, 0.6, 0.5, 0.4, 0.35, 0.3, 0.25, 0.2, 0.18,
607
0.16, 0.14, 0.12; the strength contours (dashed lines) are 3%, 5%, 7% 9%. Two
608
brew volume to grind volume contours (dashed-dot lines) are shown for 40 ml
609
brewed from a weight of 5.5 gm (L) and 9 gm (R). The region shown lies in the box
610
between coordinates (2, 0.6) and (10, 0.8) on the reduced units chart of Figure 2.
611 612 613
A typical café espresso system with a 9 g basket with 40 ml extracted in circa 25 s has PQ = 0.4. An on-demand coffee system, such as the NespressoTM system
27 ACS Paragon Plus Environment
Journal of Agricultural and Food Chemistry
Page 28 of 38
614
with capsules containing 5.5 g of coffee brewing to 40 ml in circa 20 s has PQ = 0.8.
615
These brewing systems are predicted to have comparable yields, circa 19% , within
616
the ideal flavour box (18-22%) of the original brew chart. The NespressoTM system
617
has a lower strength circa 3% vs 5%. The strengths (3-5%) are somewhat higher
618
than those in the 1960’s chart for US drip filter brews, but, are appropriate for a
619
modern espresso brew. Figure 3 is a reasonable prediction of actual espresso brew
620
performance and is able to differentiate between know brewing methods.
621
Regions typical of other brewing systems could be extracted from Figure 2 ,
622
e.g. a typical drip filter with 50 g, at 150 ml/min flow would have PQ = 0.14 and brew
623
times in reduced units circa 30; however, the actual flow regime drip filter beds can
624
be quite in-homogeneous, challenging the assumption of homogeneous flow in the
625
model. A drip filter grind size would typically be coarser that that used in Figure 2.
626
In practice, a series of charts are needed for different grind sizes. The prediction of
627
yields for longer times would also need to use a multiple diffusion constant model,
628
c.f. Figure 1.
629
Alternatively, if diffusion constants are known, the model and charts can be
630
used for making predictions and contrasting between individual releasing species. In
631
this case, the flow rate would be considered fixed, and using Eqs. 15 and 17
632
different species map onto different PQ , the larger the diffusion constant the smaller
633
PQ. The model predicts how strength in the brew (or species concentration measured
634
in aliquots over time) will decline post their peak value and this can be used to model
635
experimental data. The form of this decline varies across the chart with flow rate,
636
hence modelling is a vital aid to interpreting experiments.
637
species are independently diffusing, then for a contour of fixed brew volume to grind
638
volume ratio and a fixed flow rate, working out a PQ value for each species and
Assuming that multiple
28 ACS Paragon Plus Environment
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Journal of Agricultural and Food Chemistry
639
where it would intersect the contour will give its individual yield. The relative
640
composition of different species can thus be predicted. In the model, brews with the
641
same total mass yield achieved by different routes can have different compositions
642
and the degree of such variation can be predicted.
643 644
OUTLOOK
645
The format of charts such as that of Figure 2 and 3 is argued to be superior to the
646
current version1 because given weight, brew time and flow conditions, the modelling
647
and chart makes predictions of yield and strength. The base model used here was
648
found to be consistent with actual practice. Given the many approximations and
649
effects neglected in the base model, this is perhaps surprising. There are many other
650
complications in real systems as outlined throughout this paper: partitioning between
651
grind matrix, oil phase, grind macro-pores and bulk; interactions between species
652
and grind matrix; and early time effects such as wetting time scales, fast release
653
from fines and grind surface composition. On-going work is assessing how some of
654
these impact brewing relative to the prediction of the base model and improving the
655
modelling of the PSD and the spectrum of diffusion constants.
656
building models of individual species characteristic of different components of coffee
657
flavour, flavour significant compositional variations can be quantified. Algorithmic
658
improvements could be made to avoid the expensive solution of the diffusion
659
equations inside particles, alternatively interactions and the particle heterogeneity of
660
matrix and macro-pores could be modelled directly. The model can be combined
661
with a brewer and pump models3 to include realistic changing flow conditions and
662
more accurate predictions for real systems, although the modelling and
It is hoped that by
29 ACS Paragon Plus Environment
Journal of Agricultural and Food Chemistry
Page 30 of 38
663
measurement32 of dynamic bed flow resistance is required for this. Multi-phase gas-
664
liquid flow effects through beds which lead to coffee crema are a challenge.
665 666
AUTHOR INFORMATION
667
Corresponding Author
668
Email
[email protected] 669
ORCHID
670
John Melrose 0000-0003-4234-9000
671
Funding
672
The authors would like to acknowledge Mondelèz International for sponsorship and
673
the EPSRC (UK) for financial support via the Formulation Engineering Doctorate
674
program.
675
Acknowledgments
676
The authors acknowledge and are grateful too several referees who made significant
677
suggestions for improving and editing the original manuscript. Several questions by
678
the referees have lead to sections of the paper which address and clarify key
679
technical and literature details.
680
acknowledged for the oven-refractometer calibration.
Mr Etienne Arman (Jacobs Douwe Egberts) is
681 682 683
684
REFERENCES 30 ACS Paragon Plus Environment
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Journal of Agricultural and Food Chemistry
685
(1)
Lockhart, E.E. The soluble solids in beverage coffee as an index to cup
686
quality. Tea and Coffee Trade J., 1957, 113, (1) 12; Coffee and Tea Industries,
687
1957, 80,
688
Technology, Westport, Comm.: AVI Pub. Co.
689
US8495950.
690
(2)
691
Bakalis, S. Optimising Coffee Brewing using a Multiscale approach. In ASIC(ed.)
692
proceedings of the 24rd conference International conference on Coffee Science San
693
Jose, Costa-Rica 2012.
694
(3)
695
from packed beds in On-Demand coffee systems. In ASIC(ed.) proceedings of the
696
25th International conference on Coffee Science, Armenia, Colombia 2014.
697
(4)
698
particle microstructure: Numerical modelling and experimental validation in slurry
699
experiments. In ASIC(ed.) proceedings of the 25th International conference on Coffee
700
Science, Armenia, Columbia 2014.
701
(5)
702
Doctorate in Engineering Thesis, University of Birmingham 2017.
703
(6)
704
coffee brewing. J. Food Process Eng. 1979, 3, 185–198.
705
(7)
706
coffee: the temperature variation of the hindrance factor.
707
74, 416-420.
16 . See discussion in Sivetz, M.; Foote H.E. Coffee Processing 1963;
see further examples in
Melrose, J. R.; Corrochano, B.; Norton M.; Silanes-Kenny, J.; Fryer, Peter.;
Melrose, J. R.; Corrochano, B.; Bakalis, S. The principles of coffee extraction
Corrochano, B.; Melrose, J.R.; Bakalis, S. Kinetics of coffee extraction and
Corrochano, B. Advancing the engineering understanding of coffee extraction.
Voilley, A.; Simatos, D. (1979). Modeling the solubilization process during
Spiro, M.; Chong, Y. The kinetics and mechanism of caffeine infusion from J. Sci. Food Agric. 1977,
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(8)
Spiro, M.; Siddique, S. Kinetics and equilibria of tea infusion: Kinetics of
709
extraction of theaflavins, thearubigins and caffeine from Koonsong broken pekoe. J.
710
Sci. Food Agric. 1981, 32, 1135–1139.
711
(9)
712
coffee: Hydrodynamic aspects. J. Sci. Food Agric. 1984, 35, 925–930.
713
(10)
714
caffeine infusion from coffee: The effect of particle size. J. Sci. Food Agric. 1984, 35,
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