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Original article
a Dairy Science Laboratory, A.R.O., The Volcani Center, P.O. Box 6, Bet Dagan 50250, Israel
b Laboratoire de Recherches de Technologie Laitière, INRA, 65 rue de Saint-Brieuc,
35042 Rennes, France
Abstract – Cleaning-in-place NaOH solutions from a milk standardisation dairy plant are reused for
several days before being discharged to the purification station. During reuse the surface tension of
the industrial cleaning solutions was reduced from ~70 mJ.m–2 for newly prepared NaOH down to
~30 mJ.m–2 during the week. The decrease was rapid during the first few reuse cycles and stabilised
thereafter, while the polluting load and suspended solids increased inversely. The cleaning efficiency
test consisted of an ultrafiltration membrane fouled with whey proteins, which was cleaned using
these cleaning solutions, either without any treatment, or following crossflow micro- and
nanofiltration. It was found that microfiltrates and nanofiltrates with both low surface tension and
suspended solids resulted in higher efficiency and cleanliness, and a much faster cleaning rate. The ef-
fects of suspended solids and low surface tension will have to be further studied to determine the role
of each parameter and confirmed on stainless steel surfaces and in a milk processing plant.
Résumé – Le nettoyage en place dans l’industrie laitière : critères pour la régénération des solu-
tions de soude. Les solutions de soude caustique de nettoyage en place d’un atelier de réception et
standardisation de lait sont réutilisées pendant une semaine (soit environ 400 cycles de nettoyage)
avant d’être rejetées vers la station d’épuration. Pendant cette période, la tension superficielle décroît
de 70 mJ.m–2 pour une solution fraîche à environ 30 mJ.m–2. La diminution est rapide pendant les pre-
mières dizaines de cycles puis se stabilise ensuite, tandis que la charge polluante et les matières en
suspension augmentent. L’efficacité et la vitesse de nettoyage par ces solutions industrielles, sans
traitement ou après épuration par microfiltration ou nanofiltration tangentielle, ont été quantifiées à
l’aide d’une méthode utilisant une membrane d’ultrafiltration colmatée par des protéines de lactosé-
rum. Les microfiltrats et les nanofiltrats sont plus efficaces que la solution industrielle réutilisée dont
ils proviennent et même que la solution de soude caustique fraîche.
Ainsi, l’absence de matières en suspension et une faible tension superficielle sont favorables à un net-
toyage efficace et rapide. Ces résultats doivent été confirmés pour des surfaces et équipements en
acier inoxydable. L’expérimentation à entreprendre visera à dissocier les effets des matières en
suspension et de la tension superficielle et à les quantifier.
France). After a standard cleaning cycle, As a result of a rough analysis it was as-
the clean UF membrane hydraulic resis- sumed that the very first part of the curve
tance, Rm, was recorded using 0.2 µm fil- Rf (t) was the only part which reflected the
tered water [16]. Fouling of the UF cleaning phenomenon, then that part was
membrane was achieved using reconsti- analysed according to a second order kinet-
tuted whey proteins in deionised water ics reaction. Thus, in order to calculate the
from a whey protein concentrate powder, rate constant, each Rf curve was printed and
WPC, PS-90 (Armor Protéines, 35 St. Brice the first 5 min or less relevant experimental
en Coglès, France) at a concentration of data points were assigned and graphed as
27.8 g.L–1 β-lactoglobulin and 3.2 g.L–1 1
vs. time, and the rate constant for each
α-lactalbumin, as determined by HPLC Rf
[24]. Sodium azide at 0.02% was added to cleaning test was determined. It should be
prevent bacterial growth. noted that by working that way, a few data
points that are already influenced by the re-
The UF membranes were fouled using
fouling phenomenon were taken into ac-
the WPC solution at the following operat-
count, which resulted in both a calculated
ing conditions: T = 50 oC; v = 4.0 m.s–1;
value smaller than the true cleaning rate
∆P = 1.5 × 105 Pa for 1 h. After a water rinse constant and an error depending on the ac-
the irreversible fouled membrane resis- tual experimental points. This error was in
tance, Rif WPC, was calculated from the pure the range 19–370% with one very high
water flux measurement [15]. The cleaning value of 1800%.
cycle of the fouled UF membrane was per-
formed at: T = 50 oC; v = 4.0 m.s–1; The cleaning efficiency (error . 6%)
∆P = 1.0 × 105 Pa for 1 h. The development which represented the relative part of the
of membrane fouling resistance, Rf, with fouling removed from the membrane by the
time during the cleaning test was calculated cleaning process was expressed as follows:
according to Darcy’s law [16]. After rinsing
with water, the cleaned membrane water R if c
flux was measured to calculate the residual Cleaning efficiency = 1 – .
R if WPC
irreversible fouling after the test cleaning
solution, Rif c. The residual fouling (if any)
after the cleaning test was removed using a The UF membrane hydraulic cleanli-
standard cleaning cycle (Ultrasil 13 fol- ness (error . 20%), which represented the
lowed by HNO3) as described for the clean relative contribution of residual fouling re-
membrane [9], and the cleaned membrane sistance to clean membrane resistance was
resistance, Rm, was calculated. Our data ac- calculated as follows:
quisition system provided the mean value Rm
of each parameter (T, v, ∆P, J) during the ex- Membrane cleanliness = .
periment every 15 s. R m + R if c
The kinetics of the cleaning process was The criterion is much more discriminat-
assumed to obey a second-order reaction as ing than that for efficiency. In order to better
presented by Daufin et al. [7] for cleaning illustrate cleanliness and to show how thin
of membranes after milk UF. The calcula- the residual fouling layer was after clean-
tion of the rate constant, k, was performed ing, pore narrowing (error . 2%) was esti-
according to the following equation: mated according to Poiseuille’s equation as
dR f the ratio between the diameter of a mem-
1
= − k R 2f , giving = kt + constant. brane pore after the cleaning test, dcf, to that
dt Rf of the pore of a clean membrane, dc.
362 U. Merin et al.
1/ 4
d Rm
Pore narrowing = cf = . 70
* 10
d c R m + R if c 60
CODtot (g.L-1)
tion is an accepted approximation for the 40 6
Cleaning efficiency
(1 - R if c / Rif WPC)
tension of expensive surfactants containing 0.95
detergents formulated for the dairy indus-
try.
The measure of soluble COD, although 0.90
seeming to include all the above constitu-
ents, did not correlate well to the value of
the surface tension, and neither did the solu- 0.85
ble nitrogen (results not presented). The
5
O
-0
41
5
25
N
-2
H
aO
F-
phenomenon of the reduction of the surface
to
H
+
M
aO
N
12
3
l1
tension and the species responsible for it,
F-
si
N
tra
proteins and fat, are now under further
U
investigation. Figure 2. Cleaning efficiency of new and reused
CIP solutions.
NaOH-0: newly prepared NaOH;
3.2. Impact of suspended solids NaOH-250: industrial solution after 250 clean-
and surface tension on ing cycles;
cleaning efficiency MF-250: microfiltered industrial solution after
250 cleaning cycles;
The composition of newly prepared NF-12 to 415: nanofiltered industrial solutions
NaOH solution, and reused solutions after after 12 to 415 cleaning cycles.
no treatment or total removal of the sus- Number after MF/NF (i.e., NaOH-250) denotes
the number of cleaning cycles the solution had
pended solids by MF and NF membranes is
performed.
presented in Table I. The cleaning effi-
ciency of microfiltrates (0.97 ± 0.01) and
nanofiltrates (0.97 ± 0.02) was higher than The contribution of the thickness of the
that of the reference “clean” caustic solu- residual fouling was roughly assessed by
tion, which did not yield complete cleaning calculating pore narrowing; it was between
of the membrane (0.93 ± 0.02), while the 0.80 and 0.86 for pure caustic solutions and
standard cleaning cycle (Ultrasil 13 + 0.88 and 0.97 for reused solutions. Despite
HNO3) is presented for comparison (Fig. 2). cleanliness of 0.57–0.88 for the reused so-
The poor cleaning efficiency of NaOH lutions, pore narrowing for the lowest effi-
alone (0.91 – 0.95) has also been reported ciency solution was around 1/20 of the pore
for membranes after milk UF [7]. The least diameter, which corresponds to a residual
satisfactory efficiency was with the reused fouling layer of less than 0.3 nm
solution, NaOH-250: 0.88 ± 0.02. [(1 – 0.88) × 3.5] in the 7 nm pore diameter
The cleanliness of the UF membrane af- of the UF membrane used for the test
ter the cleaning performed with the differ- (Tab. I). The latter emphasised the strict-
ent solutions confirmed and amplified the ness of membrane cleanliness as a cleaning
conclusion: it ranged from 0.57 to 0.88 for criterion for comparing filtrates of reused
the regenerated (MF, NF) solutions, com- CIP solutions.
pared to 0.44 and 0.24 with clean and re- The nature of the soluble components of
used caustic solutions, comparable to the micro- and nanofiltrates, that is, their
inefficient detergents found in other work lowered surface tension (30–35 mJ.m–2)
using UF and MF membranes fouled by was likely to explain their higher efficiency
milk and whey [7, 8, 16]. (0.94–0.99) and the improved cleanliness
364 U. Merin et al.
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