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Mass Transfer in anaerobic system

Mass Transfer in anaerobic system

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Published by Dessy A. Sari
Mass Transfer in anaerobic system
Mass Transfer in anaerobic system

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APPLIED
AND
ENVIRONMENTAL
MICROBIOLOGY,
June
1990,
p.
16361644
Vol.
56,
No.
6
0099-2240/90/061636-09$02.00/0Copyright
©
1990,
American
Society
for
Microbiology
Liquid-to-Gas
Mass
Transfer
in
Anaerobic
Processes:
Inevitable
Transfer
Limitations
of
Methane
and
Hydrogen
in
the
Biomethanation
Process
ANDRE
PAUSS,
GERALD
ANDRE,
MICHEL
PERRIER,
AND
SERGE
R.
GUIOT*
Biotechnology
Research
Institute,
National
Research
Council
Canada,
6100
Avenue
Royalmount,
Montreal,
Quebec
H4P
2R2,
Canada
Received
15
August
1989/Accepted
26
March
1990
Liquid-to-gas
mass
transfer
in
anaerobic
processes
was
investigated
theoretically
and
experimentally.
By
usingthe
classical
definition
of
kLa,the
global
volumetric
mass
transfer
coefficient,
theoretical
development
of
mass
balances
in
such
processes
demonstrates
that
the
mass
transfer
ofhighlysoluble
gases
is
not
limited
in
the
usual
conditions
occurring
in
anaerobic
fermentors
(low-intensity
mixing).
Conversely,
the
limitation
is
important
for
poorly
soluble
gases,
such
as
methaneand
hydrogen.
The
latter
could
beoverconcentrated
to
as
much
as
80
times
the
value
at
thermodynamic
equilibrium.
Such
overconcentrations
bring
into
question
thebiological
interpretations
that
havebeendeduced
solely
from
gaseous
measurements.Experimental
results
obtained
in
three
different
methanogenic
reactors
for
a
wide
range
of
conditions
of
mixing
and
gas
productionconfirmed
the
general
existence
of
lowmass
transfer
coefficients
and
consequently
oflarge
overconcentrations
of
dissolved
methaneand
hydrogen
(up
to
12
and
70
times
the
equilibrium
values,respectively).
Hydrogen
mass
transfer
coefficients
were
obtained
from
the
direct
measurements
of
dissolved
and
gaseous
concentrations,
while
carbon
dioxide
coefficients
were
calculated
from
gas
phasecomposition
and
calculation
of
related
dissolved
concentration.
Methane
transfer
coefficients
werebasedon
calculations
from
the
carbon
dioxide
coefficients.
From
mass
balances
performed
on
agas
bubble
during
its
simulated
growthand
ascent
to
thesurface
of
the
liquid,
the
methaneand
carbon
dioxide
contents
in
the
gas
bubble
appeared
to
be
controlled
by
the
bubble
growth
process,
while
the
bubble
ascent
was
largely
responsible
for
a
slight
enrichment
in
hydrogen.
The
theoryof
liquid-to-gas
or
gas-to-liquid
mass
transfer
in
biological
processeshas
been
developed
in
numerous
engineering
textbooks
(e.g.,
references
1
and
19).
Applica-
tions
havebeen,
however,
essentially
restricted
to
oxygen
transfer
in
aerobic
processes.
In
anaerobic
processes
in
which
many
different
gases(such
as
methane,
nitrogen,
hydrogen,
hydrogen
sulfide,
and
carbon
dioxide)
arepro-
duced
and/or
consumed,
the
problem
of
liquid-to-gas
trans-
fer
is
quite
poorly
documented.
Generally,
material
balances
on
these
species
assume
equilibrium
between
phases
as
dictated
by
Henry's
law.
In
the
biomethanation
process,
in
which
numerous
gases
are
produced,
liquid-to-gastransfer
is
crucial.
Methane,carbon
dioxide,
hydrogen,
and
hydrogen
sulfide
gases
result
from
the
activity
of
microorganisms
in
the
liquid
phase.
Thermodynamic
considerationsabout
dissolved
hydrogen
interspecies
transfer,
aswell
as
carbon
balances
around
a
reactor
basedon
methane
flow
rates
or
specific
microbial
production
and/or
consumption
rates,
aresubject
to
error
when
interphase
transferresistance
is
neglected.
On
the
other
hand,hydrogen,an
intermediate
metabolite
in
the
process,
must
be
present
at
avery
low
concentration
to
ensurethe
properoperationof
theprocess.
For
instance,
its
partial
pressure
at
equilibrium
must
be
no
more
than
10
Pa
to
allow
degradation
of
propionate
(13).
Because
of
technical
difficulties
involved
in
the
direct
measurement
of
dissolved
hydrogen,
most
hydrogen
techniques
have
been
developed
for
the
gas
phase
(10);
knowledge
ofpossible
hydrogen
transfer
limitations
is
then
crucialfor
estimating
the
dis-
solved
H2
concentration.
On-line
dissolved-hydrogen
sen-
*
Corresponding
author.
sors
are
now
available
(14a,
17,
20)
to
investigate
the
interphase
transfer
ofhydrogen.
Carbon
dioxide
was
shown
to
be
in
quasiequilibrium
undernormal
operating
conditions
(2),
while
no
data
havebeen
reported
about
methane
gas
transfer.
In
studying
batch
kinetics
of
consumption
of
gaseous
hydrogen
plus
carbon
dioxide,
Robinson
and
Tiedje
(16)
found
that
hydrogen
transfer
was
the
limiting
step
in
thecase
of
highly
concen-
trated
or
viscous
sludge.
These
conclusions
were
drawn
despite
an
experimental
design
favoring
gas
transfer
from
the
gas
to
the
liquid
phase,
i.e.,
a
gas-to-liquid
volume
ratio
of
3,
and
strong
mixing
of
the
sludge.
Fardeau
andco-workers
(8,
9)
have
studied
the
growth
of
Methanococcus
thermo-
lithotrophicus
andMethanobacteriumthermoautotrophicum
on
H2
and
CO2
under
batch
conditions
and
in
continuous
culture
in
fermentors
where
the
agitation
rate
was
lowandwhere
the
gas
transfer
was
not
optimal.
When
ahigh
agitation
speed
(up
to
1,300
rpm
with
an
impeller)
was
used
in
fermentors
operated
in
batch
mode,
the
methane
produc-
tivity
and
the
final
biomass
concentration
were
increased
17-
and
4-fold,
respectively,
compared
with
earlier
experiments.
Their
results
clearly
indicated
that
the
level
of
dissolved
hydrogen
was
the
growth-limiting
factor
in
this
fermentation
(15).
Other
preliminary
results,
recently
presented
byJud
et
al.
(FEMS
Symposium,
Marseille,
France,
12
to
14
Septem-
ber,
1989),also
indicated
hydrogenmass
transfer
limitations
in
a
culture
of
M.
thermoautotrophicumgrowingon
H2
and
CO2.
We
report
here
the
results
of
experiments
in
anaerobicfermentorsof
different
designs
and
operatedunder
various
conditions
for
which
the
liquid
and
gas
phase
concentrations
were
compared;
the
resulting
mass
transfer
limitations
are
discussed.
1636
 
LIQUID-TO-GAS
MASS
TRANSFER
IN
ANAEROBIC
PROCESSES
Before
the
experimental
results
arediscussed,
theoretical
material
balances
involving
mass
transfer
terms
are
pre-
sented
below
to
facilitate
understanding
of
the
phenomenon.
The
mathematical
approachused
is
not
restricted
to
the
biomethanation
process
and
could
be
easily
extended
to
othermultiphase
bioreactors.
THEORY
Nomenclature.
The
following
variables
and
abbreviations
will
beusedthroughout
this
paper:
biol.
rate,
net
volumetric
rate
ofproduction
due
to
biological
activity
(moles
liter-'
hour-');
D,
gas
diffusivity
coefficient
(centimeters2
second-');
D,
dilutionrate
(hour-');
HRT,
hydraulic
reten-tion
time
(days);
KH,
Henry's
law
constant(moles
liter-'
pascal-');
kLa,
global
volumetric
mass
transfer
coefficient
for
the
bioreactor
(hour-');
OLR,
organicloading
rate
(gramsCOD
liter-'
day-'
[COD,
chemical
oxygen
demand]);
Pgas,
gas
partial
pressure
(pascals);
phys.
rate,
net
volumet-
ric
rate
of
production
due
to
physicochemical
reaction,
i.e.,
pH
variation
(moles
liter-'
hour-');
Qg,
gasflow
rate
(liters
hour-');
QV,
volumetricgas
production
rate
(QgIVL);
R,
ideal
gasconstant
(8,314
Pa
mole-'
K-');
T,
temperature
(Kelvin);
VL,
volume
of
the
liquid
phase
(liters);
Vg,
volume
of
the
gas
phase
(liters);
[gasig,
concentration
of
gaseous
species
in
the
gas
phase
(moles
liter-');
[gas]L,in,
concentra-
tion
of
dissolved
gaseous
species
in
the
influent
(moles
liter-1);
[gaslL
ef,
concentrationof
dissolved
gaseous
species
in
the
effluent
(moles
liter-');
[gasiL,
concentrationof
dis-
solvedgaseous
species
in
thereactor
(normally
equal
to
the
concentration
in
the
effluent)
(moles
liter-');
[gas]L*,
con-
centration
of
dissolvedgaseous
species
in
thereactor
at
thermodynamic
equilibrium
(moles
liter-')
(equal
toPgas
X
KH);
[gas]L/[gas]L*,
overconcentration
factor.
Anaerobic
processes.
When
a
continuously
fed
fermentor
and
homogeneous
gas
and
liquid
phases
are
considered,
mass
balances
ofgaseous
metabolites
canbe
established
for
both
liquid
and
gas
phases:
fortheliquid
phase,
d[gas]L_
dt
-
D
([gas]L,in
-
[gas]Lkef)
+
(biological
rate)
+
(physicochemical
rate)
-
kLa
([gas]L
-
[gas]L*)
(1)
forthe
gas
phase,
dt
=
V
kLa
([gas]L
-
[gas]L*)
V
RT
(2)
dt
Vg
gR
In
equations
1
and
2,
the
driving
force
for
the
transfer
from
the
liquid
phase
to
the
gas
phase
is
expressed
as
thedifference
between
the
actual
concentration
of
dissolved
gas
and
the
concentration
that
would
be
in
equilibrium
with
the
partial
pressureof
the
given
species
in
the
gas
phase.
The
global
mass
transfer
coefficient,
kLa,
is
representative
of
the
rate
of
transfer
in
either
direction
(gas
to
liquid
or
liquid
to
gas)
for
the
whole
reactor.
Conceptually,
kLa
is
made
up
of
two
terms,
kL
(the
"film"
coefficient)
and
a
(the
specific
interfacial
area
per
unit
volume
of
liquid
in
the
reactor).
kLa
is
usually
determined
as
a
single
coefficient
fromexperimental
data
and
is
clearly
specific
to
a
given
reactor
and
mode
of
operation.
kL
is
a
function
of
the
nature
of
the
gas
and
of
the
physicochemical
properties
of
the
liquid
TABLE
1.
Physical
dataof
the
different
gasesofa
biomethanation
process
Diffusivity
coefficienta
Henry's
constantb
(KH)
Gas
(D)
(cm2/s-1)
(105)
(mol
liter-'
Pa-1)
H2
4.65
7.40
x
10-9
CH4
1.571.12
x
10-8
CO2
1.98
2.70
x
10-7
H2S
NAC
8.22
x
10-7
a
From
Sherwood
et
al.
(19).
b
From
Seidell
(18).
c
NA,
Not
available.
phase,
whereas
a
is
largely
dependent
on
the
hydrodynamic
conditions
existing
in
the
bioreactor
and
on
the
gas
produc-
tion
rate.
In
anaerobic
reactors
in
which
bubblesoccur
as
a
result
of
internal
biological
activities,
it
is
expected
that
a
(and
thuskLa)
will
be
greatly
influenced
by
the
bubble
formation
process
and
gas
production
rate.
Mixing
of
the
liquid
phase
will
be
less
important
as
long
as
the
concentra-
tions
of
the
various
species
are
keptuniform.
At
a
steady
state,
the
above
equationscan
be
easilysolved.
A
steady
state
corresponds
to
the
situation
where
the
observed
parameters
(namely,
composition
of
thegas
phase,
dissolved
metabolite
concentration,
and
dissolved
gas
con-
centration)
areconstant.
In
such
conditions,
the
time
deriv-
atives
are
set
to
zero,
and
by
introducing
the
volumetric
gas
production
rate,
QV
=
QgIVL
(liters
of
gas
liters
of
reactor-'
hour-1),
equation
2
becomes
kLa
=
QV
(
[gas]L
_
KgasTL*
(3)
1)
or
[gas]L
[gas]L*
Qv
KHRTkLa
(4)
A
steady
state
withnomass
transfer
limitation
is
charac-
terized
by
a
dissolved-gas
concentration
very
close
to
the
equilibrium
value,
i.e.,
[gas]L/[gas]L*
1.
In
this
case,
kLa
approaches
infinity,
which
means
that
the
controlling
resis-
tance
is
the
production
process
(in
practice,
the
actual
dissolved-gas
concentration
will
always
be
greater
than
the
value
at
equilibrium).
Equation
4
also
indicatesthat,for
a
given
volumetric
gas
production
rate
and
for
a
fixed
value
of
the
mass
transfer
coefficient,
the
[gas]L/[gas]L*
ratio
approaches
1
(i.e.,
ther-
modynamic
equilibrium)
in
the
case
of
more
soluble
gases,
i.e.,
high
KH
values
(Table
1).
Highly
soluble
gases,
such
as
C02,
H2S,
and
NH3,
are
more
likely
to
be
at
thermodynamic
equilibrium
even
for
a
low
kLa
value,
while
poorly
soluble
gases,
such
as
02,
N2,H2,
and
CH4,
are
predicted
to
be
further
away
from
thermodynamic
equilibrium.
The
varia-
tions
of
the
overconcentration
factor
([gas]L/[gas]L*)
offour
different
gases
as
a
function
of
the
mass
transfer
coefficient
are
shown
in
Fig.
1.
For
a
volumetric
gas
production
rate
of
1
liter
ofgasper
liter
of
reactor
per
day
(Qv)
at
35°C,
the
transfer
coefficientsfor
H2
and
CH4
lower
than22
and
14.5
h-V,
respectively,
will
result
in
an
overconcentration
of
thesegases
with
respect
to
thermodynamic
equilibrium.
On
the
other
hand,
the
kLa
coefficients
of
CO2
and
H2S
are
approximately
2
ordersof
magnitude
lower.
The
biomethanation
process.
Applying
the
above
analysis
VOL.
56,
19901637
 
1638
PAUSSET
AL.
10
0*
3-u,
W
ci
1
0
10
20
30
kL
a
(h1)
FIG.
1.
Overconcentration
of
gases
in
the
liquid
phase
asa
function
of
their
mass
transfercoefficient
(at
35°C;
Q,
=
1liter
of
gas
liter-'
day-').
Inset,
Magnification
of
the
gas
overconcentration
variationsfor
kLa
values
between
0
and
2h-1.
Symbols:
El,
H2;
*,
CH4;
0,
C02;
A,
H2S.
to
the
biomethanation
process,
in
which
methane,carbon
dioxide,
hydrogen,
andhydrogen
sulfide
gases
are
involved,
overconcentrations
of
methane
and
hydrogen
(both
poorly
soluble
gases)
in
the
liquid
phase
can
be
anticipated.
This
problem
deserves
consideration
for
the
followingfour
rea-
sons.
First,
as
the
mass
transfer
coefficient
of
gases
is
mostly
affected
by
design
and
operating
parameters
(such
as
mixing
efficiency,
reactor
design,
and
specific
total
gas
production
rate),
kLa's
should
be
of
the
same
orderof
magnitude
for
all
gases.
In
fact,
kLa
is
slightly
affected
by
theproperties
of
the
gaseous
species,
as
kL
varies
with
the
square
root
of
the
diffusivity
(6).
Second,mixing
intensity
in
methanogenic
reactors
is
generally
just
high
enough
to
homogenize
the
liquid
phase,
but
it
is
presumably
limited
to
preserve
the
syntrophicassociations
ofmicroorganisms.
Third,
mixing
problems
often
occur
infull-scale
reactors.
Demuynck
et
al.
(7),
for
example,
showed
that
20%
of
the
full-scale
methano-
genic
reactors
surveyed
in
the
European
Community
present
major
or
minormixing
problems.
Fourth,
as
shown
in
equation
4,
the
higherthe
volumetric
gas
rate,
i.e.,
as
in
almost
all
industrial-scale
reactors,
the
higher
the
expectedoverconcentrationof
dissolved
gas
in
the
liquid
for
a
given
kLa.
The
theoretical
developments
described
above
thus
clearly
demonstrate
that
anaerobic
processes,
and
more
particularly
the
biomethanation
process,
could
suffer
from
severe
liquid-to-gastransfer
limitations.
Inthe
next
section,
we
will
evaluate
the
importance
of
such
phenomena
in
real
methanogenic
reactors.
MATERIALS
AND
METHODS
Experimental
protocol.
To
evaluate
the
importance
of
mass
transfer
limitations
in
real
anaerobic
reactors,
the
dissolved
hydrogen
concentrations
were
compared
with
the
gaseous
hydrogen
measurements
in
threereactors
of
dif-
ferentdesigns:
a
completely
stirred
reactor,
an
upflow
sludge
bed
reactor,
and
an
upflow
sludge
bed
reactor
topped
with
a
filter
part
(UBF
reactor).
Different
steady-stateconditions
or
batchconditions
were
applied
to
these
reactorsto
obtain
the
widest
possible
range
of
hydraulic
and
biological
conditions:
mechanical
agitation
or
liquid
recycle,
lowand
high
hydrau-
lic
retention
times,
and
lowand
high
gas
production
rates
(Table
2).
Our
experimental
protocol
focused
on
hydrogen
and
meth-
ane,
as
they
were
expected
to
be
the
gases
most
sensitive
to
mass
transfer
limitations.
During
at
least
two
residencetimes
(from
2
to
38days,
depending
on
the
reactor),
the
hydrogenandmethane
fractions
of
the
gas
phase
and
the
total
gas
flow
rate
were
measured
daily,
whilethe
dissolved
hydrogen
level
was
continuouslyrecorded.
Average
values
were
used
to
calculatethe
transfer
coefficients,
namely,
the
H2
transferrate
and
the
H2
overconcentration
factor
(equation
3).
As-
suming
that
the
mass
transfer
coefficients
of
the
different
gases
in
the
medium
are
proportional
to
the
square
root
of
their
diffusivity
(equation
5),
the
kLa
value
and
then
the
overconcentration
factor
of
CH4
were
calculated
forthe
three
reactors
on
the
basis
of
hydrogen
data.
(kLa)CH4
=
(kLa)H,
(DCH4/DH2)1/2
(5)
Finally,
for
each
gas
species,
both
terms
which
describethe
removal
rate
from
the
reactor
(equation
1)
were
com-
pared.
These
terms
are
the
loss
in
the
effluent
(D
[gas]L)
and
the
interphase
transfer
rate
{kLa([gas]L
-
[gas]L*)}.
Reactors.
The
baffled,
Plexiglas-built,
completely
stirred
reactor
was
operated
in
a
fed-batch
mode.For
20
h
each
day,
the
reactor
was
continuously
fed
while
agitation
of
the
liquid
was
maintained,
thereby
increasingthe
liquid
volume
from
21
to
32.5
liters.
To
keep
the
biomass
in
the
reactor,
the
mixing
and
the
feed
addition
were
stopped
for
4
h
each
day.
A
total
of
11.5
liters
of
decanted
liquid
was
then
removed
for
the
next
cycle
(an
average
liquid
volume
of26.75
liters
was
used
for
thecalculations
of
volumetric
parameters).
A
con-
centratedsynthetic
medium
was
diluted
withbicarbonate-
buffered
tap
water
(NaHCO3
[8
g/liter],
KHCO3
[10
g/liter])in
a
1/40(vol/vol)
ratio.
One
liter
of
the
concentrated
medium
contained
sucrose
(198
g),
ammonium
acetate
(37
g),
potas-
sium
acetate
(47
g),
sodium
acetate
(39
g),
yeast
extract
(32
g),
KH2PO4
(6.8
g),
K2HPO4
(8.7
g),
NH4HCO3
(33
g),
(NH4)2SO4
(5
g),
KHCO3
(55
g),
NaHCO3
(46
g),
and
50
ml
of
a
trace
metal
solution,
of
which
1liter
contained
FeCl2
-
4H20
(2
g),
H3BO3
(50
mg),
ZnCl2
(50
mg),
TABLE
2.
Running
conditions
for
all
reactors
Reactor
type
and
OLR
(gCOD
D
(day')
±
SD
pH
+SD
Qv
(liters
of
gas
condition
liter-
day-')
Day-
+
liter-'
day-1)
Completely
stirred
5.70
0.43
±
0.02
7.77
±
0.052.39
±
0.18
Sludgebed
Steady
state
1
1.20
0.081
+
0.001
7.6
±
0.1
0.64
±
0.4
Steady
state
2
1.57
0.053
±
0.001
7.44
±
0.030.95
±
0.05
UBF
Steady
state
1
27.0
3.0
±
0.4
7.22
±
0.02
9.3
±
1.4
Steady
state
2
7.50
2.2
±
0.2
7.12
±
0.05
1.73
±
0.06
i-
APPL.ENVIRON.
MICROBIOL.

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