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and chelant to the FAS stage more effective than sodium hydrosul-
fite as a reducing agent for removing
dyes in the bleaching of recycled
to bleach recycled fibers fibers.When sodium silicate instead
of sodium hydroxide is used for pH
G. J. KANG, Y. NI, AND A. R. P. VAN HEININGEN control during treatment with FAS,
bleaching results are better. Sodium
silicate minimizes the influence of
T
HE QUALITY AND BRIGHTNESS OF shown to be effective (4–7). transition metal ions, including man-
the recycled fiber furnish The removal of transition metal ganese and iron ions, which induce
dictates how it will be used. ions from a TMP pulp is enhanced FAS to decompose. When both
Dyes, ink, and stickies have when a small amount of sodium chelant and sodium silicate are
to be removed for the mill to pro- hydrosulfite is added to a DTPA added to an FAS stage that is fol-
duce recycled pulp with good prop- chelation stage (8). This stage is the lowed by a peroxide stage, the final
erties, including good optical prop- so-called “reducing-agent-assisted” brightness of the pulp is higher than
erties. chelation, or the Qy process. Conse- it would be otherwise. Bleaching
Chemicals used in a totally chlo- quently, the subsequent peroxide improves in the peroxide stage since
rine-free process for bleaching recy- bleaching is improved. Implementa- less hydrogen peroxide is consumed
cled fibers include oxidative and tion of the Qy process has resulted in by transition metal ions and pig-
reductive chemicals. The oxidative significant savings in bleaching costs ments, some of which have already
chemicals commonly used are oxy- (9). been removed in the FAS stage.
gen, ozone, and hydrogen peroxide, In pulp fibers, at least some of Application:
and the reductive chemicals are the transition metal ions are present
Sodium silicate and chelant can
sodium hydrosulfite and formami- in their high oxidation states. Unfor-
improve both the bleaching of recy-
dine sulfinic acid (FAS) (1). Both tunately, transition metal ions with
cled fibers with formamidine sulfinic
oxidative and reductive chemicals high oxidation states form stable
acid and further bleaching in a sub-
are required for the recycled fibers complexes with pulp constituents,
sequent peroxide stage.
to reach a high brightness (2, 3). which hinders their removal during
Between the two reducing chem- chelation with DTPA. However, the
icals, formamidine sulfinic acid is complexes formed between the
more effective than sodium hydro- same pulp constituent and the same
sulfite in terms of color stripping (1, transition metal ion at a lower oxida- ual manganese and iron contents
4). However, FAS is much more tion state are much less stable.There- and on the pulp brightness of recy-
expensive, so it would be beneficial fore, by reducing transition metal cled pulp. The results are shown in
to be able to use it more effectively. ions from their higher to their lower Table I.
Therefore, we studied ways to im- oxidation states during chelation, we The three processes studied are
prove the effectiveness of FAS as the can improve the removal of transi- designated as the Q, F, and FQ proc-
reducing agent in bleaching recycled tion metal ions from pulp fibers. esses. The Q process consisted of
fibers. Here, we have adopted this con- 0.2% DTPA at 70°C for 30 min at pH
cept of reduction and chelation in 5 and at a pulp consistency of 5%.
BACKGROUND bleaching recycled fibers. Since FAS The F process consisted of 0.5% FAS
The use of FAS in bleaching recy- is more efficient for recycled fibers, and 0.25% NaOH at 90°C for 60 min.
cled fibers has been studied exten- we used FAS as the reducing agent The FQ process was the same as the
sively. The most important parame- instead of sodium hydrosulfite. F process but with 0.2% DTPA
ter is its pH profile, with the pH usu- added. The control pulp was not
ally starting at about 10 and ending RESULTS AND DISCUSSION treated with DTPA.
at a neutral pH (4, 5). Sodium FAS reduction and DTPA As Table I shows, the FQ process
hydroxide is commonly used as the chelation has the lowest content of residual
source of alkalinity for bringing the First we studied the effect of a simul- transition metal ions among the
pulp to the desired initial pH.A ratio taneous action of reduction by FAS three stages studied.The explanation
of FAS to NaOH of 2:1 has been and chelation by DTPA on the resid- follows that of the Qy process,
RESIDUAL FAS, %
IV. The (FP) and (PF) sequences
80
70
Residual
Bright- H2O2 of P
ness, b* stage, % 60
% ISO value on pulp
50
F 61.4 10.0 …
FQ 62.3 10.8 … 40 0 20 40 60 80 100 120
FQ+Si 62.7 10.6 …
TIME, min
FP 76.0 6.0 0.12
FQ P 78.1 5.3 0.32 1. Effect of Na2SiO3 addition on the FAS decomposition induced by manganese.
FQ+SiP 78.6 5.3 0.37
F*Q+Si P 79.4 5.1 0.42 much more efficient than the P stage Results in Table IV also show that
of the PF sequence. In support of the brightness of the (PF)-bleached
FQ+Si: 10% pulp cons., 0.2% DTPA, 1% Na2SiO3, this explanation, there was some pulp (73.8% ISO) is slightly better
0.5% FAS, initial pH 9.6, 90°C, 1 h.
F*Q+Si: Same except that the pulp slurry was residual H2O2 at the completion of than that of the PF-treated pulp
acidified to pH 5 before washing. the P stage for the FP sequence, (73.2% ISO, Table III). This outcome
V. Comparison of various bleaching whereas the charged peroxide was may be explained by the presence of
processes completely exhausted for the PF sodium silicate carryover in the FAS
sequence. stage for the (PF) sequence, which
Albertsson et al. (15) have com- would improve the reductive stage.
As Table III shows, substituting pared the performances of (PF) and These results support the following
sodium hydroxide with sodium sili- (FP) sequences on the bleaching of conclusions:
cate improves the bleaching perfor- recycled pulp, where the parenthe-
mances for the PF and FP sequences. ses indicate that stages were con- • The FP sequence—an FAS stage,
The FP sequence is superior to the ducted with no washing between washing, and then a peroxide
PF sequence under conditions that them (16 ). They concluded that the stage—will produce a bleached
are the same except for the order of (PF) sequence was superior to the pulp with a higher brightness
stages. (FP) sequence, based on results from than the PF sequence will pro-
These results are in agreement both lab and mill trials. duce at the same chemical
with those obtained by Kogan et al. To clear up the apparent discrep- charges and the same process
(14). Both sets of results show that ancy between our results and those conditions.
the sequences that consist of reduc- of Albertsson et al., we repeated • If no washing is performed, the
tive chemicals first (sodium hydro- their runs (i.e., without washing (PF) sequence is superior to the
sulfite or FAS) followed by oxidative between the two stages).The results (FP) sequence.
chemicals (including ozone and in Table IV confirm Albertsson’s con- • The PF and (PF) sequences yield
hydrogen peroxide) are able to pro- clusion that the (PF) sequence yields similar bleaching results.
duce recycled pulps with better opti- a better bleaching result than does
cal properties. the (FP) sequence. DTPA and Na2SiO3
Our explanation is that in the FP The explanation is quite simple. We next investigated whether or not
sequence, FAS treatment removes Although there was no residual FAS the simultaneous addition of DTPA
transition metal ions and organic and at the completion of the FAS treat- and sodium silicate to an FAS stage,
inorganic pigments that otherwise ment, the products from FAS reac- denoted as the FQ+Si stage in Table V,
consume a substantial amount of the tions, such as bisulfite, are still oxi- would have an additive effect in
hydrogen peroxide charged in the dizable. Thus, the reaction products improving the bleaching perfor-
subsequent P stage. Consequently, consume H2O2 in the P stage if they mance. For both the F stage itself and
the P stage of the FP sequence is are not removed by washing. the FP sequence, the table shows
that the presence of both DTPA and transition metal ions from the recy- DTPA was added to the pulp slurry,
Na2SiO3 improves the final brightness cled fibers. As a result, the occur- and its pH was adjusted to about 5.0.
of the bleached pulp. rence of the colored metallic com- The pulp slurry was transferred to a
The end pH of the FQ+Si stage was plexes is decreased, and the perox- polyethylene bag.
7.5, and it is known that the most ide decomposition induced by tran- Fresh water was used to rinse the
suitable pH for a chelation stage with sition metal ions is minimized. beaker and was then poured into the
DTPA is about 5. Therefore, we did Also, the replacement of sodium plastic bag for the pulp to reach the
another experiment in which the pH hydroxide with sodium silicate as targeted consistency for DTPA chela-
of the pulp slurry was adjusted to 5 the source of alkali improves the FAS tion. After the specified time, the
with the addition of sulfuric acid at bleaching of recycled fibers.This out- pulp sample was filtered in a Buch-
the completion of the FQ+Si stage but come is explained by the reduced ner funnel and was thoroughly
before the pulp was washed. This FAS decomposition induced by tran- washed with deionized water.
experimental stage was denoted as sition metal ions, arising from the FAS bleaching
F*Q+Si. fact that sodium silicate can effi- For the preparation of the bleach
We found that the brightness of ciently deactivate the transition liquors, the required amount of for-
the resulting pulp was increased to metal ions. An additive effect is mamidine sulfinic acid and sodium
79.4% ISO as a result of this slight observed when both chelant and hydroxide or sodium silicate was
change. This value is 3.4 units higher sodium silicate are added to the FAS added to a beaker containing puri-
than the brightness of the FP-treated treatment in an FP sequence. fied water. This mixture was added
pulp.The brightness of the pulp from to the pulp in a polyethylene bag,
the F*Q+SiP sequence is also signifi- EXPERIMENTAL PROCEDURES and its contents were thoroughly
cantly higher than that of the QP- Material mixed. After the required retention
treated pulp (75.1% ISO, in Table I). We used a mixed office waste paper time, the ending pH was determined.
F*Q+Si (P+O) sequence with an initial brightness of 55% ISO. In the case of the (FP) sequence,
Peroxide bleaching at high tempera- Its manganese and iron contents bleaching continued. The required
ture has been shown to be effective were 2.5 ppm and 85 ppm, respec- chemicals were added in the order
in the bleaching of deinked mixed tively. of magnesium sulfate, sodium sili-
office waste pulp (17, 18). Therefore, FAS decomposition cate, sodium hydroxide, and hydro-
we studied the possibility of includ- The experiments on FAS decomposi- gen peroxide. In other cases, the
ing a (P+O) stage after the F*Q+Si stage tion were conducted in the absence pulp slurry was diluted, filtered, and
to further increase the pulp bright- of pulp. An FAS stock solution was washed with deionized water.
ness. diluted in purified water. NaOH was Peroxide bleaching
The F*Q+Si was performed under added.The ratio of FAS to NaOH was The required amounts of magne-
the same conditions as before. The 2:1.The initial pH was 9.9.The solu- sium sulfate and sodium silicate
(P+O) stage was conducted under tion was heated at 70°C in a water were added to a polyethylene bag
the conditions of 2% H2O2 at 70 psig bath. that contained well-disintegrated
O2 pressure with a pulp consistency An aliquot of the solution was pulp slurry. The slurry was mixed
of 12% and with 0.2% MgSO4, 2% taken at various times for the deter- well by kneading. Sodium hydroxide
Na2SiO3, and 1% NaOH at 95°C for 2.5 mination of residual FAS concentra- and hydrogen peroxide were added.
h.The resulting pulp had a brightness tion by a method obtained from The polyethylene bag with its con-
of 81.5% ISO and a b* value of 3.52. Paprican. tents was placed in a temperature
The residual H2O2 at the completion For the runs with the addition of bath. After the required retention
of the (P+O) stage was 0.51% on Mn2+ (as MnSO4), the chemicals were time, we took a liquid sample to
pulp. charged in the order of Mn2+, FAS, determine the ending pH and the
and then NaOH. For the runs with residual peroxide.
CONCLUSIONS stabilizers present (Na2SiO3 or In the (PF) sequence, a mixture
A chelant added to the FAS stage in DTPA), the charging sequence was containing the required amounts of
an FP sequence for recycled fibers Mn2+, Na2SiO3 or DTPA, FAS, and FAS and NaOH or Na2SiO3 was added
improves the bleaching performance NaOH. to the polyethylene bag to continue
of the FAS stage and, more impor- Q stage the bleaching. In all other cases, the
tantly, that of the subsequent perox- The pulp sample was diluted in puri- pulp slurry was diluted, neutralized,
ide stage.This improvement is attrib- fied water and was disintegrated in a and washed with deionized water.
uted to the enhanced removal of beaker. The required amount of
LITERATURE CITED
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