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 Cleaning

DEGRADATION PROGRESSION: The three samples show degradation from fresh caustic (left), caustic sampled from a fermentor at the start of CIP
(center), and caustic sampled from the caustic tank (right).
PHOTO: PHIBRO ETHANOL PERFORMANCE GROUP

CAUSTIC CIP
OPTIMIZATION
CIP brings unique challenges to ethanol, but they can be overcome.
By Dennis Bayrock

CONTRIBUTION: The claims and statements made in this article belong exclusively to the author(s) and do not necessarily reflect the views of Ethanol Producer
Magazine or its advertisers. All questions pertaining to this article should be directed to the author(s).

48 | ETHANOL PRODUCER MAGAZINE | FEBRUARY 2020

 Fuel ethanol plants utilize
cleaning-in-place (CIP) proce-
dures to prevent bacterial con-
tamination and optimize plant
performance. Most unit operations at
a plant use CIP as part of a standard oper-
ating procedures (SOP) program. Typically,
plants depend on using 2.5 to 5 percent
weight by volume (w/v) caustic solutions
and the CIP guidelines related to time, tem-
perature, titer (solution concentration) and
solution turbidity to properly clean multiple
locations within the plant.
Caustic not only has excellent cleaning
capabilities, but also has unique disinfec-
tion properties not found in other clean-
ers. Saponification, for example, hydrolyzes
fats and oils to free fatty acids and glycerol.
Caustic also causes saponification in the lip-
id membranes of yeasts and bacteria. This
destroys the cell’s integrity and is fatal. The
higher pH of caustic solutions also directly
impacts the cell’s ability to uptake nutri-
ents such as amino acids and sugars. These
transport mechanisms in the cell membrane
rely on a pH gradient across the cell mem-
brane in order to properly operate. By rais-
ing the pH, this pH gradient is removed and
can cause nutrient starvation.
In most CIP SOPs, an acid wash is also
implemented to remove mineral deposits
that caustic solutions typically do not re-
move.
A few measures can optimize pre-rinse
and caustic CIP practices.
CIP Challenges
Significant challenges exist for fuel
ethanol plants to effectively use caustic as
part of their CIP programs. Unlike CIP
procedures in other industries, the corn
used to create mash in dry-grind fuel etha-
nol plants contains significant amounts of
carbohydrates, proteins, oils and insoluble
CELL SAPONIFICATION: Destruction of the yeast cell membrane by caustic.
PHOTO: PHIBRO ETHANOL PERFORMANCE GROUP
fiber. CIP challenges specific to fuel etha-
nol plants include: thorough and effective
primary rinsing; limiting exposure of caus-
tic solutions to carbon dioxide; accurately
analyzing caustic concentration of CIP; and
monitoring solids contamination in CIP so-
lutions.
The primary rinse of pipes and vessels
with process water must be thorough and
extensive to be effective. The addition of
a surfactant detergent cleaner, such as Phi-
broClean, to the rinse cycle will improve the
overall effectiveness of the CIP process by
removing more material before the caustic
CIP cycle.
Without effective rinsing, the remain-
ing deposits can form an excellent scaffold
for bacteria to colonize as a result of the
increased surface area created. Research
on fouling and bacterial contamination
has shown that, depending on the particle
size of deposits, the potential surface area
for colonization can increase by over 400
percent compared to a clean, deposit-free
surface. Insufficient rinsing also allows or-
ganic material in mash to chemically neu-
tralize caustic, reducing and compromising
its strength and effectiveness. In addition,
multiple studies show chemical byproducts
can be generated from Maillard reactions
that form furfural, n-substituted glycosyl-
amines, acetaldehyde, and dioxins, which
are known to be inhibitory when recycled
back to yeast.
Improper rinsing will also lead to insol-
uble particle accumulation in the recycled
caustic solution. Not only will these par-
ticles displace the volume of caustic (which
requires more frequent additions of fresh
caustic to the system), but they will also be
recycled in subsequent CIP cycles and in-
crease the risk of bacterial contamination.
In addition, the Maillard reaction byprod-
ucts from the cleaning process and unre-
acted components of the mash (a result of
carryover to the caustic tank) will also re-
cycle, providing nutrients for contaminating
bacteria at other locations in the plant.
Carbonates—insoluble hard crystals—
form when caustic is exposed to carbon
dioxide. In distillation, carbonates can be
dissolved and removed with the addition of
an acid-based cleaning system, but it is ad-
vantageous to reduce or eliminate their for-
ETHANOLPRODUCER.COM | 49
Cleaning
POINTING OUT PROBLEMS: Issues associated with mash and caustic overlap in modified CIP
sequences.
PHOTO: PHIBRO ETHANOL PERFORMANCE GROUP
mation through better caustic CIP manage-
ment. Typically, the strength of this caustic
solution is periodically refortified with fresh
caustic, but any carbonates within the tank
are not usually removed until the plant de-
cides to purge the caustic tank.
Formation of carbonates also neu-
tralizes the strength of caustic solutions.
Therefore, the reuse of caustic solutions
containing carbonates will ultimately re-
duce the actual strength of the caustic solu-
tion, provide increased colonization power
of bacteria when crystals are deposited in
pipes and vessels, and decrease the overall
effectiveness of CIP within the plant.
To prevent these effects from occurring
and to enhance CIP effectiveness, periodic
purging and full turnover of the content of
the caustic tank with fresh caustic solution
should be implemented as a regular part of
any CIP program. The frequency of these
purges varies between fuel ethanol plants
depending on their overall CIP program.
It is also critical to accurately monitor
caustic strength to ensure it is maintained at
its target concentration. Most ethanol plants
check the concentration of their caustic so-
lution with pH and with a titration using a
single indicator (usually phenolpthalein in a
50 | ETHANOL PRODUCER MAGAZINE | FEBRUARY 2020
one-point titration procedure). The advan-
tages of a one-point titration procedure are
that it is inexpensive, convenient, rapid and
provides reasonable accuracy when deter-
mining the concentration of pure uncon-
taminated caustic solutions.
However, a one-point titration proce-
dure will overestimate the concentration of
a caustic solution if there are any carbon-
ates or any organic carryover from mash in
the CIP solution. To overcome this limita-
tion, the Warder titration method can be
used.
The Warder procedure expands the
one-point phenolphtalein titration to a
two-point titration using methyl orange.
The phenolpthalein end-point is titrated
first (determines caustic concentration)
followed by titration in the same flask to
the methyl orange end-point (determines
carbonate concentration). Simple calcula-
tions can then be performed to determine
the concentrations of each and thus the
true concentration of caustic in CIP. The
Warder procedure is simple to perform, and
only introduces one additional titration in
the same flask to the base one-point titra-
tion procedure.
Monitoring the amount of solids (car-
bonates and insoluble materials) in CIP
caustic solutions is important to indicate
how quickly the sediment level increases
over time. Close monitoring of solids
buildup can give an indication of whether
sufficient flushing was performed in the
initial rinse cycle of the CIP process and
will also give the plant another metric that
can be used to gauge when the recycled
caustic needs to be purged and refreshed.
This monitoring can be as simple as draw-
ing samples from the spent caustic tank, al-
lowing them to cool in a graduated cylinder,
and recording the amount of settled bulk
precipitate.
The addition of a detergent cleaner
such as PhibroClean to the pre-rinse and
caustic CIP solution improves CIP effec-
tiveness while providing potential savings
in caustic usage. When applied during the
pre-rinse cycle, PhibroClean removes or-
ganic material that would otherwise remain
in place, reducing the potential for caustic
solution degradation. PhibroClean addition
to the caustic CIP solution will lead to bet-
ter cleaning results through its detergent ac-
tion, facilitating the use of lower-strength
caustic CIP solutions, resulting in potential
net savings in overall CIP costs.
Proper and effective CIP practices can
reduce the severity and frequency of bac-
terial contamination at ethanol plants, im-
prove ethanol yields, optimize heat transfer
and energy inputs and reduce the need for
hydroblasting. Addressing the challenges
inherent in using CIP to clean and sanitize
mash-based fermentations reduces issues
with bacterial contamination and improves
plant operational efficiency.
Author: Dennis Bayrock
Global Director, Fermentation Research
Phibro Ethanol Performance Group
651.641.2826
dennis.bayrock@pahc.com