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PEER REVIEWED

Deinking flexographic newsprint: Conventional flotation deinking tech-

using ultrafiltration to close nology is widely used for deinking sec-


ondary fiber furnish that has been
printed by the letterpress or litho-
the water loop graphic (offset) processes. This tech-
nology is not effective for removing
BRADLEY H. UPTON, GOPAL A. KRISHNAGOPALAN, AND SAID ABUBAKR water-based flexographic inks due to
the hydrophilic nature of thier pig-
ment particles. Washing effectively
removes flexographic ink dispersions

T
HE MOST COMMON PRINTING for removal of flexographic inks, fol-
from pulped secondary fiber, however,
techniques for the produc- lowed by alkaline flotation for oil-
the resulting wash effluent contains
tion of newspapers are let- based ink removal, has been pro-
significant quantities of pigment. The
terpress and lithography posed (2). There is also interest in
wash effluent must be clarified of pig-
(offset). Flexographic printing has developing flocculation aids (poly-
ment before it can be recycled within
recently been applied to newsprint mers) capable of rendering flexo-
the mill without reducing pulp bright-
publication and holds several advan- graphic pigment particles hydropho-
ness. The difficulty in clarifying flexo-
tages over letterpress and litho- bic (7), which would result in an
graphic pigment dispersions from
graphic printing (1, 2). The primary increased tendency for the flexo-
wash filtrate represents a significant
disadvantages of flexographic news- graphic inks to be removed by con-
ventional alkaline flotation deinking. barrier to closing the water loop of a
print publication are the difficulties
associated with recycling due to the Membrane separation technology is newsprint deinking operation.
water-dispersible flexographic inks. a potentially attractive method for Ultrafiltration was investigated as
Conventional flotation technology is the removal of flexographic ink a means to remove dispersed water-
widely used for deinking secondary residues from wash filtrate without based ink pigments from wash efflu-
fiber furnish that has been printed further addition of chemicals (11). ent. Ultrafiltration of high-concentra-
by the letterpress or lithographic Deinking a mixed old newsprint fur- tion ink dispersions resulted in stable,
(offset) processes, but it is ineffec- nish would rely on both froth flota- high production rates of pigment-free
tive in removing flexographic ink tion and washing, with the wash fil- permeate. The use of high-concentra-
residues (3-6), which form fine dis- trate clarified by ultrafiltration before tion feeds prevented irreversible
persions of pigment particles upon being recycled to the process. membrane fouling and actually
alkaline pulping (7). The same prop- Ultrafiltration removes contami- demonstrated membrane regenera-
erties of flexographic ink disper- nants based on size. Most modem tive properties. Inclusion of cellulose
sions that render them difficult to membrane separation processes are fines in the feed had variable effects
remove by flotation deinking, specif- operated under cross-flow condi- on permeation rates.
ically colloidal dimensions and tions. The membrane is configured in Application:
hydrophilic surfaces, lend them to a tubular or hollow fiber geometry, in This research investigates the applica-
efficient removal by washing tech- which the liquid to be clarified flows bility of ultrafiltration to clarify water-
niques (8-10). The wash filtrate axially through the interior of the based pigments from process water
from deinking newspapers printed tube under pressure. The pressure of an old-newsprint deinking facility.
with flexographic ink is estimated to forces any permeable materials to Clarification of the wash water will
contain between 0.05% and 0.1% pass through the membrane. This maximize wash water recycling in the
pigment. These pigments must be permeate consists primarily of sol- process without affecting pulp color.
removed before this stream can be vent and contains some dissolved or
recycled to the process without suspended materials. depending on
decreasing pulp brightness. the membrane pore size. Larger
Operating under acidic, or at solutes and solids are retained in the flow of fluid through the tube cre-
least nonalkaline conditions, im- feed stream. The permeation rate of ates a shear stress field parallel to the
proves the efficiency of froth flota- fluid through the membrane is membrane surface. retarding the
tion in removing water-based flexo- reported as flux, with units of vol- accumulation of a thick filter cake.
graphic inks. A two-stage process ume per unit of membrane surface This study focuses on the feasi-
consisting of nonalkaline flotation area per unit time (L/m2 h). The axial bility of ultrafiltration techniques to

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remove hydrophilic pigments from


aqueous dispersions. An ultrafiltra-
tion apparatus was assembled and
used to characterize the clarification
of dispersions prepared from two
commercially available water-based
flexographic inks. The efficiency of
the ultrafiltration separation process
is characterized by parameters such
as permeate flux, fouling rate, and
cleaning requirements.

EXPERIMENTAL
The ultrafiltration apparatus was
equipped with adequate instrumen-
tation and controls to manipulate
pressure tip across the membrane
surface (transmembrane pressure,
P tm, temperature, and flow rate stock, and the fraction between 65 Immediately following an ultrafil-
through the membrane module) and 200 mesh was added to the ink tration experiment the membrane
(Fig. 1). Two identical polysulfone dispersions. module and entire flow path were
hollow-fiber ultrafiltration mem- The feed solution was main- rinsed with tap water. A solution of a
branes were used. Each membrane tained at a constant ink concentra- commercial detergent in tap water
module was in a shell and tube con- tion during most of the experiments (with pH adjusted to 10) was then
figuration with 68 hollow fibers of by recycling the pigment-free per- pumped through the membrane
0.043 in. (0.109 cm) ID, for a total meate back to the feed tank. The per- module and associated piping for
surface area of 1 ft2 (0.0283 m2). The meate was removed from the ultrafil- several minutes. The dirty cleaning
molecular weight cut off (MWCO) is tration loop as it was produced dur- liquid was drained from the system,
a measure of pore size, or retention ing other experiments, resulting in and a fresh cleaning solution was
ability, and is the approximate mole- the ink dispersion becoming more recirculated for at least 30 minutes.
cular weight of the smallest com- concentrated as ultrafiltration pro- The final cleaning was performed
pound retained by the ultrafiltration ceeded (the total volume of feed using a fresh solution for several
membrane. The MWCO of the mem- decreased during these experi- hours. At this time the flux was mea-
branes used in this study was ments). The ink dispersions were sured at 25 psi P tm , 20C, and 1
500,000. kept well mixed by the action of the gal/min using a fresh cleaning solu-
Feed solutions were prepared recirculation pump. In most experi- tion as the feed stream. The resulting
using tap water, flexographic ink, sur- ments. the temperature was main- value is the water flux. which was
factant, and NaOH to adjust the pH tained constant by passing the feed used to evaluate the effectiveness of
to 10. Two formulations of flexo- through a constant-temperature wa- the cleaning procedure on restoring
graphic ink were used. one from a ter bath. An electric heater was used membrane performance.
regional newspaper publisher (ink to heat the feed when performing
no. 1), and another obtained from an experiments at elevated tempera- RESULTS
ink manufacturer (ink no. 2). Ink con- tures. During these experiments, the Flux vs. transmembrane pressure
centrations (CB) ranged from 0.04% water bath was used for fine control Plots of permeate flux vs. P tm for
to 22%, as determined by visible light of temperature. Flux was measured five dispersions of ink no. 1 are
spectroscopy (12). A commercially by the timed collection of permeate shown in Fig.2. Ultrafiltration
available anionic and nonionic sur- in a tared beaker, which rested on a achieved complete retention of the
factant mixture was used in an balance. The specific gravity of the flexographic pigment, producing
amount necessary to form a 0.01% permeate was determined to be 1.0. clear permeate. All dispersions
solution. In some of the experi- After the flux measurement, the col- demonstrated linear flux vs. P tm
ments, cellulose fines were added to lected permeate was returned to the relationships, indicating that the sys-
the feed. The fines were generated feed tank. tem behaved as predicted by the
by beating unprinted newsprint Hagen-Poiseuille law for streamline

156 TAPPI JOURNAL FEBRUARY 1997


low through channels, which is (those at 0.9% ink and above, Fig. 5). with fluid flow across the membrane
believed to best describe the pres- Flux was proportional to Ptm at low surface control the thickness of this
sure controlled flow of fluid through pressure and pressure independent layer, and, at steady state. convective
microporous membranes (13). The at high pressure. The shift to pres- transport and shear force dispersion
data demonstrate no correlation sure independence occurred at balance each other (17). This is
between ink content of the feed and lower P tm as ink concentration mass-transfer controlled ultrafiltra-
permeate flux rates. Flux vs. time increased, signifying that flux was tion, in which flux is pressure inde-
data for batch ultrafiltration of a strongly dependent on solids con- pendent. Increasing Ptm will cause
0.05% dispersion of ink no. 1 (25 psi) tent. Comparison of the data pre- the flux to rise initially, but this will
are shown in Fig. 3. Flux stabilized at sented in Figs. 4 and 5 demonstrates increase the amount of material
48 L/m2 h during the six-hour exper- that higher flux values were attained transported to the membrane sur-
iment, while the ink concentration while clarifying the high-concentra- face and thus the gel layer thickness.
steadily increased from 0.05% to tion flexographic ink dispersions The flux will then be reduced
0.12%, again indicating that flux was than when clarifyng the low-con- because of the increased resistance
independent of solids concentration. centration dispersions. A discussion to permeate flow, restoring the equi-
Flux vs. Ptm data of low-concentra- of this important finding will follow librium between pigment transport
tion dispersions of ink no. 2 (0.4% in later sections. by convective flow and by shear dis-
and less) also demonstrated pressure During ultrafiltration of colloidal persion. At these conditions, flux is
controlled permeation; however, at dispersions, particles are brought to predicted to decrease exponentially
25 psi flux became less sensitive to the membrane surface by convective with increasing feed concentration
further increases in Ptm (Fig.4). The transport as fluid passes through the (13, 14).
solids content of the feed stream membrane. This effect is known as The flux vs. feed composition
appeared to have a greater influence concentration polarization. At high curve (Fig. 6) demonstrates the log-
on flux, which decreased with flux levels, the nonpermeable mater- arithmic relationship between flux
increasing solids content of the feed ial (ink pigment in this case) will and ink content observed for disper-
stream. consolidate into a gel layer on the sions containing 0.9% ink and above
There were two distinct operat- membrane surface. imparting addi- (the high-concentration ink disper-
ing regions observed when process- tional resistance to permeate flow sions). Porter observed this same
ing higher-ink-content dispersions {14-16). Shear forces associated trend when ultrafiltering colloidal

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suspensions (electro deposition follow the same relationship. This centration dispersions, indicative of
primer and styrene butadiene latex), data show that flux was strongly operating under conditions in which
including the tendency for the flux affected by feed concentration when the gel layer was not the limiting
vs. ln(CB) line to be concave up, processing high-concentration dis- resistance to permeate flux (14).
which he attributed to variations in persions, indicating that the gel layer Extrapolating the data in Fig. 6 to
shear forces due to viscosity increas- was the limiting resistance to per- zero flux predicts that the gel con-
ing as the feed was concentrated meate flux. Relative independence centration (CG) was approximately
(14). The flux values for dispersions of flux on feed concentration was 30% solids. Porters data for ultgrafil-
containing less than 0.9% ink do not observed when processing low-con- tration of colloidal systems pre-

158 TAPPI JOURNAL FEBRUARY 1997


layer will be retarded. This effect
was investigated by processing a
4.6% flexographic ink dispersion at
three flow rates (0.5, 1.0, and 1.5
gal/min). The experiment was per-
formed in a random manner to pre-
clude any time effects (such as mem-
brane fouling) from entering into the
analysis. The desired operating con-
ditions (flow rate and P tm) were
tabulated and numbered, and the
order in which the data were
obtained was determined by a ran-
dom number generator. The data in
Fig. 7 illustrate that better ultrafiltra-
tion performance (higher flux) was
achieved when operating at high
feed flow rates and that mass-trans-
fer controlled ultrafiltration
occurred at lower Ptm when operat-
ing at low flow rates. However, since
dieted CG between 60% and 70%; The effect of flow rate on perme- the data were collected in a random
however, the operating conditions ate flux during cross-flow ultrafiltra- order, complete steady-state opera-
during his experiments were not tion is due to the shear forces tion (including formation of stable
specified (14). Desaulniers and exerted by flowing fluid at the wall pigment layers on the membrane
Hausslein attained a maximum solids of the membrane, which is instru- surface) may not have been
content of 3l% when ultrafiltering mental in preventing or controlling achieved. Therefore, the effect of
an aqueous dispersion of activated the size of a layer of retained pig- flow rate may be greater than that
carbon particles (median size 11 m) ment on the membrane surface (14, indicated by these results.
in a batch cell using an ultrafiltration 16, 18). Any pigment layer that Effectiveness of cleaning
membrane with MWCO of 250,000 forms on the membrane surface will The ultrafiltration membrane was
(18). They also determined that the act as a barrier to permeate flow, cleaned between experiments to
carbon falter cake on the membrane thus affecting flux negatively. At high ensure that a similar baseline perfor-
surface controlled the filtration rate. flow rates, the formation of a gel mance was realized prior to process-

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ing the next ink dispersion and to after the membrane had been (0.1% and 0.4%), and as the ink con-
evaluate the severity of any perfor- allowed to soak in a cleaning solu- tent of the feed stream increased, the
mance degradation that may have tion for one month. post-cleaning water flux followed,
occurred. Membrane performance Higher-concentration ink disper- indicating that the membrane was
was characterized by the water flux, sions prepared from ink no. 2 were becoming easier to clean (Fig. 8, bars
which is the flux when processing a then processed. The water flux after 12-14). The final water flux after
0.01% surfactant solution with pH processing a 0.9% ink dispersion and processing the 0.4% dispersion was
2
adjusted to 10, at 25 psi, 20C, and 1 cleaning the membrane was 430 213 L/m h.
2
gal/min feed flow rate. The following L/m h, which is higher than that A dispersion containing between
is a sequential summary of ultrafiltra- measured with the new membrane. 0.2% and 1.0% ink was processed
tion experiments and the effective- Processing this ink dispersion through the ultrafiltration membrane
ness of the cleaning procedure per- restored membrane performance for approximately 30 minutes. The
formed after each experiment. Fig- better than cleaning with soapy membrane was then cleaned and
ure 8 shows the post-cleaning water water. Subsequent processing, of allowed to soak in a cleaning solu-
flux after processing each of the ink other dispersions (1.8%, 3.6%, 6.6%, tion for approximately two months.
dispersions. and 9.8%) also resulted in high water The resulting water flux was 672
When new the ultrafiltration flux values after cleaning (Fig. 8, bars L/m 2 h, which was the highest yet
membrane demonstrated a water 7-11). The final water flux after pro- measured (Fig. 8, bar 15). At this
flux of 400 L/m2 h. After processing cessing the highest-concentration point, a series of experiments was
the first ink dispersion (0.05%, ink ink dispersion (9.8%) was 415 performed using a 0.2% ink disper-
no. 1), the water flux after cleaning L/m2h. sion in which the feed temperature
had decreased to 90 L/m2 h. This rep- Low-concentration dispersions was varied. The results of the tem-
resents significant membrane foul- prepared from ink no. 2 were then perature study will not be ptesented;
ing, which was not reversible upon processed. The water flux after pro- however, the impact on membrane
membrane cleaning. This trend con- cessing a 0.05% dispersion and cleaning effectiveness was marked.
tinued (Fig. 8, bars 2-6), and, after cleaning the membrane was 111 The experiments were performed at
processing the other low-concentra- L/m2 h, indicating that irreversible 20C, 35C, 50C, and 65C. Figure 8
tion dispersions of ink no. 1 (0.09%, membrane fouling had again (bars 16-19) shows the water flux
0.18%, 0.195%, and 0.37%), the final occurred. Two more low-concentra- values after each of these experi-
water flux was 104 L/m2 h, measured tion dispersions were processed ments, which demonstrate that high-

160 TAPPI JOURNAL FEBRUARY 1997


temperature processing was respon- which had been fouled by process- most noticeable for the 0.05% ink
sible for extensive membrane foul- ing low-concentration ink disper- dispersion (the lowest concentration
ing. sions at 65C (the water flux of the processed).
Apparently there was some prop membrane was 48 L/m2 h). Flux The flux vs. Ptm data from pro-
erty of the high-ink-content disper- increased from 12 L/m2h to 45L/m2h cessing high-concentration ink dis-
sions that promoted membrane after 160 minutes. This is almost persions show different trends.
cleaning and restored the water flux, identical to the performance ob- Higher flux was attained during the
whereas low-concentration disper- served during the previous experi- second pressure cycle than during
sions tended to foul the membrane. ment. Afterwards the membrane was the first pressure cycle for each dis-
To investigate this, we processed a cleaned, resulting in a water flux of persion that contained 0.9% ink or
3.5% ink dispersion at 25 psi and 1 315 L/m2 h, an increase of 556%. more. This effect was less noticeable
gal/min (Fig. 9). Flux increased from These results demonstrate that ultra- for the 6.6% and 9.8% ink disper-
10 L/m2 h to 56 L/m2 h during the filtration of high-concentration ink sions, but was quite pronounced for
first four hours of the experiment. dispersions has beneficial effects on the 0.9% and 1.8% dispersions. The
When the temperature was returned membrane cleaning. 0.9% dispersion was processed
to 26C, the flux decreased to 45 Stable flux during high-concen- through three pressure cycles, with
L/m2 h (demonstrating the effect of tration ink processing maximum fluxes observed of 72
temperature on flux) (17, 17). After In the course of a flux vs. Ptm exper- L/m2 h, 110 L/m2 h, and 130 L/m2 h
cleaning, the water flux was mea- iment, data were collected during at during the first, second, and third
sured at 350 L/m2 h, an increase of least two complete pressure cycles. pressure cycles, respectively. This
514% from the value prior to this Typically, during the first pressure indicates that flux increased with
experiment (Fig. 8, bar 20). This is an cycle a great degree of hysteresis time.
important finding; it indicates that was observed as the membrane sys- Figure 11 shows a plot of flux
processing this ink dispersion tem stabilized. When processing low- vs. time for ultrafiltration of a 0.05%
restored the membrane's perfor- concentration ink dispersions, lower dispersion of ink no. 1 at constant
mance. A similar experiment was flux was observed during the second pressure (25 psi) and temperature
performed at 20C (Fig. 10) using a pressure cycle than during the first (22C), with the permeate recycled
3.9% ink dispersion and an identical pressure cycle, indicating that flux back to the feed tank so that the ink
ultrafiltration membrane (UF2), decreased with time. This effect was concentration remained constant.

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The initial flux was 91 L/m2 h and shown in Fig. 11. The final flux was The stable high flux values
decreased to 41 L/m2 h over a five- 41 L/m2 h. Ultrafiltration of a 3.5% observed when processing high-
hour period. Over the next 60 min- dispersion with the same membrane concentration ink dispersions could
utes the flux changed only slightly. under identical conditions for one be due to a filtering action of the gel
During ultrafiltration of a 3.5% ink hour resulted in a stable flux value layer of pigment formed during
dispersion, the flux decreased from of 56 L/m2 h, over 36% higher than mass-transfer controlled ultrafiltra-
71 L/m2 h to 58 L/m2 h in the first 30 that achieved when processing the tion. The carbon black pigment par-
minutes, and then changed very little 0.05% dispersion. ticles in flexographic inks are very
during the next 30 minutes with a Effective clarification of flexo- small, with 90% of the particles less
final flux of 56 L/m2 h after one hour graphic ink dispersions entails con- than 5 m in size and a considerable
of operation (Fig. 12). When a 3.9% centrating the pigment to as high a fraction below 0.2 m (20). The
ink dispersion was processed, the level as possible as permeate (water smallest of these particles could
flux decreased from 78 L/m2 h to 58 and other dissolved species) is enter or partially block some of the
L/m2 h after only 20 minutes of oper- removed, while maintaining high pores in the ultrafiltration mem-
ation (Fig. 12). Continued processing flux rates. To evaluate the capabili- brane, reducing flux irreversibly.
resulted in the flux decreasing to 56 ties of ultrafiltration to achieve this However, the gel layer could act as a
L/m 2 h after 70 minutes of opera- goal. an experiment was performed falter aid, preventing even the small-
tion. These data demonstrate that in which permeate was removed est pigment particles from reaching
stable flux can be achieved when from the system as it was produced. the membrane surface. Closely
processing high-concentration ink causing the ink concentration of the packed cakes of micron or submi-
dispersions. Not only is flux more feed to increase as ultrafiltration pro- cron particles have high hydraulic
stable with time, but higher flux lev- gressed (Fig. 13). The initial ink con- permeabilities (21), facilitating high
els were attained when processing centration was 4.4%, and increased flux levels while promoting long-
the high-ink-content dispersions to 22.2% after 755 minutes of opera- term stability of flux by preventing
than when processing the low-ink- tion. After an initial rapid drop, flux membrane fouling.
content dispersions. After one hour decreased gradually as the ink con- Addition of cellulose fines
of ultrafiltering a 0.05% ink disper- centration increased. At an ink con- To evaluate the potential effects of
sion, the flux had decreased to 65 centration of 22.2% the flux had cellulose frees on ultrafiltration of
L/m2 h and was still decreasing, as decreased to 18 L/m2 h. flexographic ink dispersions, a series

162 TAPPI JOURNAL FEBRUARY 1997


of experiments was performed in 17. These results indicate that the centrations (greater than 0.9%) at
which fines were added to the ink presence of low amounts of cellu- low operating pressure. This is
dispersion. Constant-pressure ultra- lose tines did not significantly affect indicative of operating under condi-
filtration (25 psi at 1 gal/min) for one ultrafiltration performance, in con- tions in which the membrane, and
hour was followed by a pressure trast to the previous results. The not a gel layer of pigment, presents
cycle in which the flux vs. Ptm rela- presence of 0.025% frees had virtu- the limiting resistance to permeate
tionship was investigated. Cellulose ally no effect on ultrafiltration per- flux.
fines were then added and the exper- formance, and the presence of At ink concentrations of 0.9%
iment repeated. The membrane was 0.05% frees had only a minimal and above, flux decreased exponen-
cleaned between each step to evalu- effect. The effectiveness of mem- tially with increasing concentration.
ate the effect of fines on cleaning brane cleaning was not affected by Flux was relatively independent of
effectiveness. fines, in agreement with the previ- ink concentration at lower concen-
The data for processing a 3.5% ous results. The after-cleaning water trations.
ink dispersion with and without fluxes after processing these disper- Ultrafiltration of low-concentra-
fines are presented in Figs. 14 and sions were 276 L/m2 h (no fines), tion flexographic ink dispersions
15. The results indicate that inclu- 262 L/m2 h (0.025% fines), and 285 resulted in irreversible membrane
sion of low amounts of cellulose L/m2 h (0.05% fines). fouling. Performance could not be
frees decreased the ultrafiltration restored by cleaning after process-
performance (flux levels); however, CONCLUSIONS ing these dispersions. The cleaning
the effectiveness of membrane During ultrafiltration of flexo- procedures appeared to be quite
cleaning did not appear to be signifi- graphic ink dispersions the perme- effective after processing high-con-
cantly affected. The after-cleaning ate was free of ink pigments, demon- centration flexographic ink disper-
water fluxes after processing these strating the capability of ultrafiltra- sions. In fact, processing high-con-
feeds were 290 L/m2 h (no fines), tion to completely remove flexo- centration ink dispersions had bene-
302 L/m2 h (0.025% fines), and 306 graphic residues from wash effluent. ficial effects on performance and
L/m2 h (0.05% fines), Flux was directly proportional to restored high flux levels to ultrafil-
Results for the ultrafiltration of a P tm during ultrafiltration of low tration membranes that had previ-
3.9% ink dispersion with and with- concentrations of flexographic ink ously been fouled by processing
out frees are shown in Figs. 16 and (less than 0.4%) and high ink con- low-concentration dispersions.

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Aniline printing, cleaning, deinking,


effluent treatment, filtration, flexogra-
phy, flow, fouling, ink, letter press print-
ing, newsprint, printing, printing ink,
printing papers, separation, technology,
ultrafiltration.

164 TAPPI JOURNAL FEBRUARY 1997