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ABSTRACT
INTRODUCTION
EXPERIMENTAL PROCEDURE
The liquors and sugars used in this study have been taken from the
Thames Refinery of Tate & Lyle Ltd. In some cases, lie luors were taken directly
from the melter; in other cases, washed raw sugar was collected from the affina-
tion machines and dried at room temperature for storage. Experimental details
for each of the techniques used are presented more appropriately in each of the
sub-sections in Results and Discussion. AI\ color measurements were made at
420 nm after adjustment of the undiluted, sample to pH 7.5. Colors are reported
as the attenuation index a *420 in milliabsorbancy units (mau). Cationic surfac-
tant concentrations were determined by partition titration with the anionic
surfactant, sodium dioctylsulphosuccinate, using the competitive dye, bromo-
cresol blue, after the method of Barr, Oliver and Stubbings (1).
M. C. BENNETT, F. J. GARDINER, J. C. ABRAM, J. T. RUNDELL 1571
'1200
0
COLOR
1·2
800
~
~
.s,'"
", ..
0
0'8
J.!!
s'"0 , ~
!J
400
.'/.
I
9
\
\
I
I
.
,S
III
,...
u
P \
p
/ • \
\ CTAB precipitated
\
0'4
,,
\
\
\
,If \
\
~
~
0. ......
-2 -1 0 2
10910 added C'TAB concentration (~eq/9)
Fig. 1. Precipitation of colorant from.65%Natal liquor with GrAB. Left-hand scale: filtrate
color. Right-hand scale: CTAB concentration in filtrate.
1572 s. MANUFACTURIN(;-,-PROCESSINC
removed from each sample are shown .asr:a function of the original CTAB con-
centration. It is seen that the filtrate color reaches a minimum at 1.2 p,eqjg (440
ppm), where the quantity of CTAB precipitated and removed by filtration is
at a maximum. Up to this point, all added CTAB is precipitated, the filtrate
content being effectively zero. For CTAB additions above 1.2 p,eqjg, CTAB
begins to appear in the filtrate and the color returns to its former value. The
result shown in Fig. I can be readily explained as follows. The precipitation of
colorant anions by CTAB is due to the attachment of the hydrophobic alkyl
(hexadecyl) chains as shown in Fig. 2, sketch (b). The colorant polyanion-
~$
e ---e
impurity polyanion
polyanlon/CTAB
complex
soluble polyanion/CTAB
complex
insoluble
soluble
Fig. 2. Diagrams representing the interaction between anionic' colorant and a cationic mono-
alkyl surfactant. Maximum precipitation is observed at stage (b), redissolution at stage (c).
1400
- - • Australian
- - - DBWII
1200 --OBWIII
- - ~ Mauritius
1000- i
- - eBWI m
800-
.'"
:;;:
oS
a:
9
8 600-
400
200
FLOC, where the decolorization lies in the range 40-70%, it is clear that with
this cationic surfactant there can be no risk of adding too much.
of the medium, and the electrokinetic or ~ (zeta) potential of the particle. The
electrophoretic mobility (ft) is given by the following equation:
.KD~
ft =-.--
7r7]
where K = a constant which is determined by the shape and size of the particles,
and the thickness of the electrical double layer; D _= dielectric constant of the
medium; 7] = viscosity of the medium; and ~. = zeta or electrokinetic potential,
The relationship between particle charge and zeta potential is very com-
plex, especially in this system. As the main interest in this work lies in the obser-
vation of change in zeta potential with addition of surfactant and, in particular,
in the concentration of surfactant necessary to produce zero zeta potential, no
attempt has been made to equate zeta potential with particle charge. In fact, as,
K, D, and 7] are effectively constant, all the results have been expressed in terms
of the electrophoretic mobility; ft.
In such a complex bio-colloidal system as this, the observed electrophoretic
mobility is determined by the nature of the particle surface rather than by the
composition of the particle itself. Since the suspension of particles observed in
the cell appears to be reasonably homogeneous, that is, most particles move with
the same mobility, it is reasonable to suppose that all particles present are cov-
ered by the same blanket of impurities adsorbed from solution in the liquor. Any
change in the electrical nature and solubility of anionic impurity, therefore,
affects all particles to a similar extent. .
Most of the work has been undertaken at room temperature, using 20%
solids melter liquor filtered through a BS 150 mesh screen. Electrophoresis mea-
surements were made using a Mattson cell (5) . The conclusions have been con-
firmed at higher sucrose concentrations in a thermostated capillary cell (Rank
Bros., Bottesham, Cambridge, England) .
Experiments were carried out in the following way: 65% solids washed
raw liquor was heated for 10 min at 75 C with the appropriate volume of sur-'
factant solution or the required concentration to give a final solution of 20%
solids concentration; after cooling to room temperature, this mixture was sep-
arated into 2 fractions; the Ist was filtered through kieselguhr and the percentage
color removed measured at pH 7.5 and 420 nm; the 2nd fraction was agitated in
a food blender for 30 sec to break up the large> floes and then placed in the
electrophoresis cell; measurements were made by observing a minimum of 5
particles moving through a distance of 40 microns under a maximum potential
of 5 volts/em; after each pass the current was reversed and the particle turned
in the reverse direction, following standard practice. Typical results are shown
in Fig. 4, 5 and 6.
Fig. 4 shows the effect of CTAB concentration on the mobility of the par-
ticles in a liquor of Jamaican origin. Because of the dilution, the CTAB concen-
tration is expressed in mM. Initially the impurity has a negative charge (an-
ionic), but as the concentration of CTAB added is increased, the magnitude of
the negative potential decreases to zero and then becomes increasingly positive.
This pattern has been observed subsequently for all cationic surfactants on all
cane melter liquors tested.
The relationship between color removal, CTAB concentration and electro-
M. C. BENNETT, F. ]. GARDINER,]. C. ABRAM, ]. T. RUNDELL 1575
+0·2
E 0
~
~~
-0,2
1e
u
'E
~ -0'4
:D
0
~
-2 -1 o
I0910CTAB conc~mM)
Fig. 4. The effect of added CTAB on electrophoretic mobility in Jamaican liquor diluted to
20% solids.
1576 MANUFACTURING-PROCESSING
20
"C
QI
>.
o
E
~ 40
...
.2
o
o
#
60
80
I
I
I
I
Negative I Positive
I
1 2 3
CTAB cone. (mM)
Fig. 5. Color precipitation by addition of CTAB to ]amaicanliquor, indicating the point of
zero electrophoretic mobiltiy.
between anionic centre on the impurity and cantionic centre on the surfactant. All
3 surfactants referred to in Fig. 6 have the same quaternary nitrogen as the
cationic centre.
M. C. BENNETI, F. J. GARDINER, J. C. ABRAM, J. T. RUNDELL 1577
o
. I
9
I
\\ I
20 \\ I
\\ I
~ diC 12/
..... \
I
-0
Q)
..... \ I
>
0 40 .•.. \
E /
e ".\ I
:;
'0 .....\ /
u
'.. \
,$2 /
0
\\ /
60 /
I
I
,/
/
/
/
80 /
'"
\, _ ~)f~·" ..• ~~~1(l.~.~~~.?~~?~_.
"
Negative Positive
Fig. 6. The relation between color precipitation and electrophoretic mobility in Jamaican liquor
for 3 cationic surfactants, hexadecyl, didodecyl and dioctadecyl quaternaries.
1578 MANUFACTURING-PROCESSING
en
c:
o
~
.!:
c
.9
~c
Q)
u
e
o
u
c
'"(;
"8
Q)
>
:;:;
'"
Qj
0::
til
c:
.Q
tJ
£ 4
.s
c
0
~c
Q)
u
c
0
u
c:
III
(;
"0
o
Q)
~
'"
Qj
0::
l
0 0-45
Concentiation of Sodium Chloride in Eluate(M)
(increasing net anionic charge of eluted cclorants c-s-)
Fig. 8. Ion exchange cellulose fractionation of colorant remaining after TALOFLOG treatment.
M. C. BENNETT, F. J .. GARDINER, J. C. ABRAM, J. T. RUNDELL 1579
. C" ~ 'NO
and the benzyl dimethylammoninm derivative C"N<Me, . CH'O. Results
are shown in Fig, 10, where it is seen that, although the 3 surfactants are similar
1580 MANUFACTURING-PROCESSING
500
C16
C12
~o
*.s~
l>:
o
o-'
u
4
en
.......
s
3.3- .
100
2 .S
~
U
t:
o
U
2 3 4
Added. surfactant~eq/g)
(Eto) n
I
e t8 - N+-Et Et.S0 4-
I .
(Eto) n
500
Trimethyl
400
Benzyldimethyl
0
300
II
'0
N
*.,.
I1J
0::
0
-'
0
u
200
3 ~
0-
'"
:1.
100
2
1i
~
;;:
S
U
c
0
u
2 3 4
Added surfactant (~eq/g)
Fig. 10. Precipitation of colorant with 3 hexaclecyl cationics, showing the surfactant leakage
concentration.
The results shown by Series 1, 2 and 3 all point to the requirement for
the molecule to he as hydrophobic as possible; this can be achieved by increasing
the number of alkyl chains in the molecule. Results for 2 dialkyl quaternaries
have been presented in earlier sections. Series 4 comprises 4 members of the
dialkyl series, while Series 5 comprises a number of tri- and tetra-alkyl derivatives.
In these experiments, the color-surfactant precipitate was separated by filtration
on a Millipore membrane (pore diameter 0.22 [.tm) , in absence of any phosphate
scavenger system.
Series 4. Dialkyldimethyl quaternaries. The surfactants were all of the
general formula
1582 MANUFACTURING-PROCESSING
400
n=5
300
'0
"..,.
C'l
'"0::
a
a-'
u
200 I
~~ () ()
()
'4
3~
100
I tr
O>
:>.
Q;
n;
2 §
.s
U
c
0
u
2
Added sUrfactant(~eq/g)
3
J
4
Fig. II. Precipitation of colorant with ethoxylated octadecyl quaternaries. The number of
ethoxy groups in each chain is indicated by n, and in the series shown n = 2, 5, 9 and 15.
R
I
N+-Me
R CI
I
Me
and in this series, R= C 1 0 ' C12> C 1 G and C 1 8 (TALOFLOq. Results are given
for 3 concentrations of each surfactant in Table 1. The results for both the di
C1 0 and the di C 1 2 derivatives show less decolorization at 0.1 % addition than at
0.05%. This indicates redissolution of the precipitate in higher concentrations
of the surfactant, as found for CTAB and all mono-alkyl derivatives. The di CHI
and di C 1 8 derivatives do not show any redissolution and the performance of the
di C 1 8 is superior to that of the di C w
Series 5. Trialkyl and tetra-alkyl quaternaries. In this series, each sur-
factant was used at a concentration of 0.05% on solids. The results are shown in
Table 2. In runs 1-3, the activity of the mono- di- and, tri-octadecyl derivatives
M. C. BENNETT, F. J. GARDINER, J. C. ABRAM, J. T. RUNDELL ]583
Table 1. The decolorization effect of dialkyldimethylammo-
nium chlorides. Untreated filtrate liquor colour : 1098 mau.
Surfactant
1 0.02 759 31
2 R=Ci0 0.05 481 56
3 0.10 548 50
4 0.02 756 31
5 R=C12 0.05 473 57
6 0.10 558 49
7 0.02 719 35
8 R=C16 0.05 469 57
9 0.10 ,415 62
10 0.02 694 37
11 R=C18 0.05 463 58
12 0.10 354 68
1 C18 N (Me) 3 Br 56
2 (C18) 2 N (Me) 2 Cl 62
3 (C18) 3 N Me Cl 55
4 (C8) 2 N (Me) 2 Br 37
5 (C8) 3 N Me Cl 40
6 (C 2) 4 N I 7
7 (C 4) 4 N Br 11
8 (4)4 N Br 27
9 (C 6) 4 N Br 34
are compared. It is seen 'that the dialkyl quaternary (TALOFLOC) shows the
best effect. The activity of the di- and tri-octylammonium surfactants, shown in
runs 4 and 5, is seen to be markedly inferior to that of the longer alkyl chain
derivatives. In runs 6-9, 4 tetra-alkylammonium compounds are compared. The
activity as a color precipitant increases strikingly with alkyl chain length, but it is
noted in Table 2 that 4 C 6 alkyl chains are considerably less effective than 1 C 1 8
chain.
Series 6. Other cationic centres. The color precipitation effect can be
demonstrated with many other types of cationic surfactants, but the really effec-
tive agents are all characterized byhaving 1 or more alkyl chains containing 16
or more carbon atoms. Some octadecyl primary and secondary amines have been
1584 MANUFACTURING-PROCESSING
found to be active, particularly when used as the acetate salts. However, the
activity is less than that of the corresponding quaternary dialkyl derivative.
(Eto) x H
A range of ethoxylated tertiary amines, of the typ~ R - N (
(Eta) y H
has been found effective when R = C I 8 and x + y = 2 or 5. In this series, the
ethoxy groups confer adequate water solubility on the surfactant molecule and,
in this respect, fulfill one of the functions of the strongly hydrophilic quaternary
ammonium centre.
Some experiments have indicated that when a small quantity of 1 of these
compounds is used, together with the normal amount of a quaternary, the result-
ing decolorization is somewhat greater than expected. This synergistic effect is
well-known for certain pairs of surfactants used in mineral are flotation processes.
The effect is shown by the results in Table 3. Some cyclic tertiary amines have
Tertiary surfactant
I - - 77
2 2 0.02 84
3 2 0.05 83
4 2 0.07 83
5 2 0.10. 86
6 5 0.05 82
millipore filtration, the filtrate from one filtration being passed through the next
smaller pore diameter membrane. Another sample of the same original liquor
was treated with 360 ppm on .solids of TALOFLOC and the successive filtration
repeated. Results are shown in Fig. 12, where all filtrate colors are plotted as a
1500
1000
1··:···1
~ \···1; :,".
ti:""
rt:
.... -- ....
';;""-
/
....
9 / --- -r ~-,-
0
u ~~~..- ~-.. liquor + O' 036% Talofloc
500 1---1--. ",
___ ,....."..., +13ppm Floccuiant
liquor ...r'.\.. ,....Ct·····
+ 0·036% Talofloc
Special
.Speedflow .
Superai1 ~~ rpeedex.
-2 ,-1 0
I0910(pore diameter, urn)
Fig. 12. Successive millipore filtration of 60% washed raw Mauritius liquor. Filtrate colors are
plotted as a function of lOg10 pore diameter (,urn) for (a) untreated liquor, (b) liquor treated
with 360 ppm TALO'FLOC and liquor (b) further treated with 13 ppm of a polyacrylamide floc-
culant.
Table 4. Decolorization and flotation results for Mauritius liquor, colour 1162.
Phosphatation at 0.05% P205, flotation aid at 5 ppm, temperature 75 C.
Clarified liquor
TALOFLOC Flotation rate color Decolorization
(ppm) (% clear in 3 min) (a *420) (%)
200 67 505 57
400 70 429 63
600 74 374 68
800 80 338 71
opment during the last 2 years and an increasing amount of data from full-scale
refinery operations is becoming available. Jacobs clarifiers have been operated at
17 min retention time, while a new pilot clarifier designed specially for these
high flotation rates has been operated at Tate & Lyle's Thames Refinery at less
than 10 min retention time. At two other refineries, polish filtration of clarified
liquor was discontinued when it was shown that the liquor from the clarifier was
already brilliant.
In many cases, TALOFLOC is used jn conjunction with conventional
decolorization agents, such as bone char, granular carbon and powdered vegeta-
ble carbon. The savings achieved in these processes are roughly in proportion to
the decolorization provided by T ALOFLOC.
T ALOFLOC·Carbonatation Separation
Most cationic surfactants have a profound effect on the carbonatation reac-
tion and lead to extremely low filterabilities in the carbonatated liquor. With an
increasing hydrocarbon content and increasing hydrophobic character in the sur-
factant, the effect becomes less pronounced. It has now been shown that T ALO-
FLOC may be used in conjunction with carbonatation, provided it is dosed
directly into the 1st saturator rather than into the melter liquor.
Laboratory experiments have shown signi~cant gains in filterability, but
1588 MANUFACTURING-PROCESSING
this effect has not been shown at any of the 5 carbonatation refineries where the
process has been under development.
The decolorization effect is approximately the same as that found in phos-
phatation systems, but the gain in bone char or carbon decolorization perfor-
mance is rather less. In carbonatation refineries operating a preliming stage,
there is virtually no saving in bone char and, therefore, no point in using T ALO-
FLOC. The reasons for this anomalous behaviour are not known but undoubt-
edly concern the chemical effects of high alkalinity and high temperature on
colorant and color precursors.
REFERENCES
1. Barr, T., J. Oliver, andW.···:V. Stubbings. 1948. The determination of surface active agents
in solution. J. Soc; Chern. Ind., 67:45. . .
2. Bennett, M. C. 1967; Improvements in and relating to sugar refining. British Patent No.
1224990.
3. Bennett, M. C. 1971. Preliminary results on the use of T ALOFLOC in sugar refining, Sugar
y Azucar 66 (10) :90-94.
4. Cookson, D., K. J. Parker, and J. C. WiHiams. 1970. Properties of sugar colorants removable
by ion-exchange resins. Proc, Tech. Sess. on Cane Sugar Refining Research (In Press) .
5. Mattson, S. 1928. Cataphoresis and the electrical neutralization of colloidal material. J.
Phys. Chem., 32:1532. .
6. Tomlinson, R. V., and G. M. Tener. 1963. The effect of urea, formamide and glycols on
secondary binding forces in the ion exchange chromatography of polyneucleotides on
DEAE cellulose. Biochemistry, 2:697.