|
Claims  |
|
|
What is claimed is:
1. In the flotation deinking of printed media in which at least about 7.5
wt % of the media was printed with a hydrophilic flexographic ink having a
particle size of less than about 5 .mu.m by performing the steps of: (1)
forming a pulp slurry comprising printed media and water having a hardness
of at least about 100 ppm Ca.sup.+2 ; (2) adding to the slurry a fatty
acid or salt thereof of the formula R.sup.1 COOM wherein R.sup.1 is a
linear or branched alkyl or alkenyl group having about 7 to about 24
carbon atoms and M is hydrogen or a counterion; and (3) subjecting the
slurry to flotation deinking in a flotation cell,
the improvement comprising further adding to the slurry prior to the
flotation deinking (a) a rosin acid of the formula R.sup.2 COO-M wherein
R.sup.2 is an unsaturated, alkylated, tricyclic, fused ring containing
about 20 carbon atoms and M is hydrogen or a counterion and (b) a
non-ionic or anionic surfactant which is capable of dispersing the rosin
acid in water, said rosin acid and surfactant being added in a weight
ratio of rosin acid to surfactant of about 12:1 to about 1:5 and in a
total amount sufficient to increase the brightness of a filter pad
prepared from the hydrophilic flexographic ink-containing media by at
least about 2%, wherein the rosin acid and the surfactant agglomerate
fleographic ink particles prior to the flotation deinking.
2. The method of claim 1, wherein the rosin acid comprises a mixture of
abietic and pimaric acids.
3. The method of claim 1, wherein the surfactant is a non-ionic surfactant.
4. The method of claim 3, wherein the non-ionic surfactant is derived from
mono-and diglycerides of a naturally occurring fatty acid which glycerides
have been alkoxylated.
5. The method of claim 1, wherein the fatty acid, rosin acid and surfactant
are used in a total amount of about 0.3 to about 1.5 wt % based upon the
weight of the printed media.
6. The method of claim 5, wherein the fatty acid will be about 60 to 90 wt
%, the rosin acid about 5 to 30 wt %, and the surfactant about 2 to about
25 wt %, each of the total amount.
7. The method of claim 5, wherein the fatty acid will be about 65 to 85 wt
%, the rosin acids about 10 to 25 wt %, and the surfactant about 3 to 20
wt %, each of the total amount.
8. The method of claim 1, wherein the rosin acid is derived from natural
source selected from the group consisting of wood rosin, gum rosin, and
tall oil.
9. The method of claim 1, wherein the fatty acid or salt thereof is a
mixture derived from a natural oil selected from the group consisting of
marine, rapeseed, tallow, tall oil, soy, cottonseed, and coconut oils.
10. The method of claim 1, wherein the flotation deinking is performed at a
water hardness of about 100 to about 400 ppm Ca.sup.+2.
11. In the deinking of printed media in which at least about 7.5 wt % of
the media was printed with a hydrophilic flexographic ink having a
particle size of less than about 5 .mu.m by performing the steps of: (1)
forming a pulping slurry of printed media and water; (2) adding tall oil
to the slurry; and (3) subjecting the slurry to flotation deinking in a
flotation cell;
the improvement comprising using partially derosinated tall oil having a
rosin acid content of about 5 to 30 wt % in combination with at least one
non-ionic or anionic surfactant, at a water hardness greater than about
100 ppm Ca.sup.+2, and performing the flotation deinking for a period of
less than about 10 minutes, wherein the tall oil and the anionic
surfactant agglomerate flexographic ink particles prior to the flotation
deinking.
12. A method of deinking printed media in which at least about 7.5 wt % of
the media has been printed with a hydrophilic flexographic ink having a
particle size of less than about 5 .mu.m comprising the steps of:
(i) forming a pulp slurry of printed media and water having a hardness
greater than about 80 ppm Ca.sup.+2 ;
(ii) adding to the slurry:
(a) a fatty acid or salt thereof of the formula R.sup.1 COO-M wherein
R.sup.1 is an alkyl or alkenyl group having about 7 to about 24 carbon
atoms and M is hydrogen or a counterion;
(b) a rosin acid or salt thereof of the formula R.sup.3 COO-M wherein
R.sup.3 is an alkylated, tricyclic, fused ring unsaturated group
containing about 20 carbon atoms, and M is H or a counterion;
(c) a non-ionic surfactant represented by the formula:
RO[(AO).sub.n --R.sup.o.sub.]m
wherein R is selected from the group consisting of: linear and branched
alkyl and alkenyl groups having about 7 to about 24 carbon atoms; R.sup.1
CO-- wherein R.sup.1 is a linear or branched alkyl or alkenyl group having
about 7 to about 24 carbon atoms; (R.sup.3).sub.a C.sub.6 H.sub.5-a --
wherein R.sup.3 is linear or branched C.sub.7 -C.sub.18 alkyl and alkenyl
and "a" is an integer from 1 to 3; a group derived from a linear,
branched, and cyclic aliphatic polyol having about 2 to 6 carbon atoms;
and a group derived from a linear, branched, and cyclic aliphatic diacid
having about 8 to 42 carbon atoms; AO is an oxyalkylene group having 2 to
about 4 carbon atoms or a mixture of such groups in random or block
configuration; R.sup.o is selected from the group consisting of H, R.sup.1
and R.sup.1 CO; n is a number from about 4 to 250; and m is an integer
from 1 to about 6 wherein the fatty acid or the salt, the rosin acid or
salt and the surfactant agglomerate the flexographic ink; and
(iii) subjecting the slurry to flotation deinking.
13. The method of claim 12, wherein the non-ionic surfactant is added to
the slurry prior to the commencement of an air flow for the flotation
deinking.
14. The method of claim 12, wherein the non-ionic surfactant is derived
from mono-and diglycerides of a naturally occurring fatty acid which have
been alkoxylated.
15. The method of claim 14, wherein the non-ionic surfactant comprises a
mixture of:
______________________________________
CH.sub.2 O--C(O)--R.sup.5
and CH.sub.2 O--C(O)--R.sup.5
CHO--(AO).sub.n --R.sup.6
CHO--C(O)--R.sup.5
CH.sub.2 O--(AO).sub.n --R.sup.6
CH.sub.2 O--(AO).sub.n --R.sup.6
______________________________________
wherein R.sup.5 is an alkyl group derived from the fat, e.g. tallow and
R.sup.6 is either H or R.sup.3 CO.
16. The method of claim 12, wherein the fatty acid or salt thereof is a
mixture derived from a natural oil selected from the group consisting of
marine, rapeseed, tallow, tall oil, soy, cottonseed, and coconut oils.
17. The method of claim 12, wherein the flotation deinking is performed at
a water hardness of about 100 to about 400 ppm Ca.sup.+2. |
|
|
|
|
Claims  |
|
|
Description  |
|
|
BACKGROUND OF THE INVENTION
The present invention is directed to the removal of inks, particularly very
fine particles of hydrophilic flexographic inks, from recycled paper
products, i.e. deinking. Flexographic (hydrophilic) inks are becoming of
greater and greater importance due to their greater environmental
friendliness and lower equipment investment costs than when using
conventional hydrophobic ink systems. However, limiting the growth in
flexographic ink usage has been the difficulty in recycling paper with
flexographic inks in flotation deinking systems.
"Deinking" is the process of removing ink and other contaminants from waste
paper and there are two main techniques in current use. "Flotation
deinking" entails forming an aqueous suspension of waste paper pulp
fibers, inks, and other non-cellulosic contaminants and then mixing air
into the suspension. In the presence of various additives, air bubbles
selectively attach to ink particles and carry those particles to the
surface of the aqueous suspension, thereby forming an ink rich froth. The
froth is then removed leaving behind a relatively ink-free fiber slurry.
Flotation deinking processes have heretofore been especially useful in
removing hydrophobic inks with particle sizes larger than about 10 .mu.m.
The additives used in such processes are generally specialty surfactants
or fatty acids which are intended to agglomerate the relatively large
hydrophobic ink particles to increase removal efficiency in the flotation
cells. The presence of additives which would disperse the ink particles
rather than agglomerate them is considered detrimental to the
effectiveness of the flotation stage.
"Wash deinking," on the other hand, is particularly useful when the ink and
other particles being removed are smaller than about 5 .mu.m. The process
requires the addition of dispersants so that when a dilute waste paper
pulp slurry is thickened, the very fine particles, including the
hydrophilic flexographic type inks, will tend to stay with the water being
removed to thereby produce a relatively clean pulp.
Newspapers, magazines and other printed media have been recycled for many
years. Recently the need to recycle paper has increased significantly and
will likely continue to increase in the future in view of environmental
concern and legislative action. To reclaim fibers from printed material, a
deinking process is required to remove the ink and other contaminants.
Deinking of waste paper has become increasingly more difficult, however,
because of changes in the printing techniques being used and the wide
variety of printing inks. As a result, a slurry of recycled waste paper
contain mixtures of hydrophilic and hydrophobic inks, resin binders,
fillers, and the like, the substantial majority of which must be removed
to produce a paper product having sufficient whiteness to be used in many
commercial applications. The materials being removed, in addition to
having a wide range of particle sizes, include polymeric binders such as
polystyrene, polyacrylates, and acrylic copolymers. This has made removal
of many of the newer inks more and more difficult. The industry response
has generally been to utilize deinking systems which combine both
flotation and washing processes.
However, the requirements for flotation and wash processes are different
and are in conflict with each other. In flotation processes, relatively
large ink particles are agglomerated to a size where they can be removed,
while in washing processes relatively fine ink particles are dispersed so
that they can be removed. This dichotomy has been further effected by
recent changes in printing techniques which have resulted in an
ever-increasing usage of hydrophilic flexographic inks. The very fine ink
particles (<5 .mu.m) associated with such flexographic inks can currently
be substantially removed only by means of washing processes. The
increasing usage of the very fine particle size hydrophilic flexographic
inks is causing increasing problems in attaining the brightness necessary
to permit the use of recycled paper products in many applications.
The difficulty in using flotation deinking for removal of hydrophilic
flexographic inks is compounded because flotation deinking is generally
operated under alkaline conditions, i.e. at a pH between about 8.5 and 10,
while the hydrophilic flexographic inks become insoluble at pH's below
about 7 so that neutral or acidic conditions are desired for their
removal.
The conventional industry chemical formulations for flotation deinking for
many years have entailed using a fatty acid or fatty acid soap. See, for
example, U.S. Pat. Nos. 4,964,949 and 4,483,741. Fatty acids and fatty
acid soaps have a number of problems associated with their use. They
require high dosage rates, typically at least about 16 pounds/ton of waste
paper (0.8 wt %) but often as high as 30 pounds/ton (1.5 wt %). Also,
despite their use, fatty acids and fatty acid soaps are relatively poor
foaming agents especially in the presence of hydrophilic flexographic inks
which has led to current flotation deinking processes doing a poor
performance of removing such inks.
In a Bulgarian laboratory study of flotation deinking in the early 1970's
(prior to the advent of hydrophilic flexographic inks), waste paper
containing hydrophobic inks dispersed in an asphalt binder was shredded,
soaked in water for for 2-3 hr, fiberized and mixed with reagents to cause
saponification of the asphalt binder and dissolution of the hydrophobic
ink. Flotation deinking was performed with: liquid soap, technical grade
oleic acid, stearic acid, tall oil fatty acids, and tall oil. Although few
details or results are provided, the article states that the best results
occurred when tall oil was used at an amount of 0.30%, with a flotation
time of 15-20 minutes, and with the water exhibiting a hardness of less
than about 3 mg eqv per liter (equivalent to 60 ppm Ca.sup.+2). In fact,
the article states: "the hardness of the water used in the process must
not exceed 3 mg eqv/liter." Mikhailova et al, "Deinking of Waste
Newspapers by the Flotation Process," Tseluloza Khartiya 4, No. 2, 22-24,
30 (March/April 1973).
Tall oil generally contains (a) about 55-60 wt % tall oil fatty acids which
have been reported to contain about 45 wt % oleic acid, about 40 wt %
linoleic acid and about 15 wt % resin acid and (b) about 40-45 wt % rosin
acids. Rosin acids (also known as resin acids) are alkylated, tricyclic,
unsaturated organic acids. The two main rosin acids of tall oil are
abietic acid and pimaric acid. Rosin acids and fatty acids are both
commonly referred to as being amphipathic because they have a small polar
carboxyl group attached to a large bulky hydrophobic hydrocarbon portion.
When such acids are adsorbed onto the surface of a material, the polar
hydrophilic end is oriented toward the surface of the material with the
hydrophobic portion directed toward the water. Rosin acids are
particularly useful as paper sizes. Commercial rosin acid products,
generally containing more than about 80 wt % rosin acids, are also
particularly useful as additives to provide tack (stickiness) for rubber
polymers, in ink resin formulations, and in adhesive resins, particularly
when color stability is not critical.
Recently, specific non-ionic surfactants such as are described in U.S. Pat.
Nos. 4,964,949 and 5,100,574 have been especially developed for use in
flotation deinking systems.
However, as the levels of hydrophilic flexographic ink continue to increase
in waste paper, the previous deinking compositions are being found less
and less effective in the removal of such ink particles in a flotation
deinking procedure, especially one which is operated for about 8 minutes
or less. As such, there is a continuing need to develop improved flotation
deinking additive compositions which will effectively and rapidly deal
with the changing compositions of waste recycled paper.
Accordingly, it is an object of the present invention to produce a deinked
printed media which media had previously contained very fine hydrophilic
ink particles, e.g. the flexographic inks present in increasing quantities
in waste paper, by means of a flotation deinking process.
It is a further object of the invention to remove hydrophilic flexographic
inks from printed media in a flotation deinking process while minimizing
scale deposition therein.
It is a further object of the invention to remove hydrophilic flexographic
inks from printed media in a flotation deinking process while limiting the
time required for completing the process.
These and still further objects will be apparent from the ensuing
description of the present invention.
SUMMARY OF THE INVENTION
The present invention is directed to a deinking method for removing
hydrophilic inks from recycled printed media, said inks being present
either alone or more commonly in combination with hydrophobic inks, in a
flotation deinking system either alone or in combination with a wash
deinking system. The deinking is accomplished by adding to an aqueous
waste paper pulp slurry (a) a fatty acid or salt thereof, (b) a rosin acid
or salt thereof, and (c) a non-ionic or anionic surfactant. The fatty acid
will represent at least about 60 wt % of the three components with the
balance being the rosin acid and the surfactant in a weight ratio ranging
from about 12:1 to about 1:5. Use of the deinking additive combination of
the present invention has been found to effectively and efficiently remove
hydrophilic inks in a flotation process or in the flotation stage of a
combined flotation/-wash process, especially when using water having a
hardness of from about 80 to 500 ppm Ca.sup.+2.
By using the three deinking additives at appropriate levels, release of
hydrophilic flexographic inks from the waste paper fibers is accomplished
without overdispersing the inks while simultaneously initiating
agglomeration of the fine hydrophilic ink particles and then completing
the agglomeration to a sufficient extent that the ink particles coalesce
and are of sufficient size to be effectively and efficiently removed in
the froth of conventional flotation deinking equipment. Compared to prior
deinking processes with fatty acids or their salts alone the present
combination yields significant increases in brightness and lower residual
ink contents in processed pulps which contain substantial amounts of
hydrophilic flexographic inks.
DETAILED DESCRIPTION OF THE INVENTION
The deinking procedure of the present invention entails the use of a
flotation stage to remove very fine hydrophilic (flexographic) inks from
printed media, particularly waste newspapers, in which up to 100% of the
ink may be flexographic. The benefits of this invention are clearly
evident when at least about 7.5 wt %, preferably at least about 20 wt %,
more preferably at least about 30 wt %, and even up to 100 wt %, of the
printed media being recycled was printed with a hydrophilic flexographic
ink having a particle size of less than about 5 .mu.m. The need for and
benefits from the invention are more evident as the flexographic ink
content of the printed media increases.
More particularly, the first component of the deinking formulation is a
fatty acid or salt thereof of the formula R.sup.1 COO-M wherein R.sup.1 is
a linear, branched, or cyclic alkyl or alkenyl group having about 7 to
about 48 carbon atoms and M is hydrogen or a counterion such as Na, K, Ca,
NH.sub.4, or NH.sub.x (CH.sub.2 CH.sub.2 OH).sub.y wherein x and y are
each integers from 0 to 4 and total 4. Most commonly, for economic reasons
the fatty acid or salt thereof is used in the form of a mixture of such
materials having about 12 to 24 carbon atoms and derived from natural oils
such as marine, rapeseed, tallow, tall oil, soy, cottonseed, coconut, and
the like. Such fatty acids, salts, and mixtures are either commercially
available or may be manufactured by known techniques. The fatty acid
functions primarily to agglomerate ink particles. The fatty acid or salt
is added either to an aqueous pulp slurry either during pulping or as the
slurry is introduced into the flotation stage. Fatty acid is used herein
to include a fatty acid which has been pre-reacted with, e.g., calcium to
form a salt and is used as an aqueous salt emulsion or dispersion.
The second component is a rosin acid or salt thereof of the formula R.sup.2
COO-M wherein R.sup.2 is an unsaturated, alkylated, tricyclic, fused ring
containing about 20 carbon atoms and M is hydrogen or a counterion. Rosin
acids are generally derived in mixtures from natural sources such as wood
rosin, gum rosin, tall oil, and the like. While the rosin acids may be
separated into individual acids for use herein, no benefit from so doing
has been noted. The two main rosin acids are abietic acid and pimaric
acid.
The third component is an anionic or non-ionic surfactant. Any anionic or
non-ionic surfactant may be used herein provided that it is capable of
dispersing the rosin acid in water. Preferably, the surfactant is a
non-ionic surfactant. Most preferably, the non-ionic surfactant is a
non-ionic alkoxylated surfactant which may be represented by the general
formula:
R--O--[(AO).sub.n --R.sup.o.sub.]m
wherein AO is an oxyalkylene group having 2 to about 4 carbon atoms or a
mixture of such groups in random or block configuration; R is selected
from the group consisting of (a) linear and branched alkyl and alkenyl
groups having about 7 to about 24 carbon atoms; (b) R.sup.3 CO-- wherein
R.sup.3 is a linear or branched alkyl or alkenyl group having about 7 to
about 24 carbon atoms; (c) (R.sup.4).sub.a C.sub.6 H.sub.5-2 -- wherein
R.sup.4 is linear or branched C.sub.7 -C.sub.18 alkyl and alkenyl and "a"
is an integer from 1 to 3; (d) a group derived from a linear, branched,
and cyclic aliphatic polyol having about 2 to 6 carbon atoms; and (e) a
group derived from a linear, branched, and cyclic aliphatic diacid having
about 8 to 42 carbon atoms; R.sup.0 is selected from the group consisting
of H, R.sup.3 and R.sup.3 CO; n is a number from about 4 to about 250; and
m is an integer from about 1 to 6.
Suitable polyols include, for example, ethylene glycol, propylene glycol,
trimethylene glycol, butylene glycol, glycerol, trimethylol propane,
trimethylol ethene, 1,2,4-butanetriol, 1,2,6-hexanetriol,
1,1,1-trimethylol hexane, pentaerythritol, diglycerol, and sorbitol.
Suitable diacids include, for example, octanedioic (suberic), nonanedioic
(azelaic), hexadecanedioic (thapsic), octadecanedioic, and
heneicosanedioic (japanic) acids.
The non-ionic surfactant component may comprise mixtures of two or more
ethoxylated and/or propoxylated materials. Presently preferred non-ionic
surfactants include surfactants based on mono- and diglycerides or a
naturally occurring fatty acid which have been ethoxylated and/or
propoxylated. A particularly preferred non-ionic surfactant is the mixture
derived from the reaction of a fat such as tallow tallow with potassium
hydroxide, glycerol, ethylene oxide and propylene oxide such as is
described in U.S. Pat. Nos. 4,964,949 and 5,100,574 which includes as
major components each of the following structures:
______________________________________
CH.sub.2 O--C(O)--R.sup.5
and CH.sub.2 O--C(O)--R.sup.5
CHO--(AO).sub.n --R.sup.6
CHO--C(O)--R.sup.5
CH.sub.2 O--(AO).sub.n --R.sup.6
CH.sub.2 O--(AO).sub.n --R.sup.6
______________________________________
wherein R.sup.5 is an alkyl group derived from the fat, e.g. tallow and
R.sup.6 is either H or R.sup.3 CO. The non-ionic surfactant generally
functions as a penetrant of the paper fiber in the slurry and stabilizes
the ink particles so that they do not redeposit on the pulp fibers.
Generally, the non-ionic surfactant component is either commercially
available or may be made by techniques well known in the art.
The total amount of deinking additives generally used in the present
invention is about 0.25 to about 1.5, preferably about 0.4 to 1 wt %. The
fatty acid or salt thereof will be about 60 to 90 wt %, the rosin acids
about 3 to 30 wt %, and the surfactant about 2 to about 35 wt %, all based
upon the total deinking additives used. The preferred weight ratio of the
rosin acid:surfactant is about 12:1 to about 1:5, more preferably about
8:1 to about 1:1. Still more preferably, the fatty acids are about 65 to
85 wt %, the rosin acids about 10 to 25 wt %, and the surfactant about 3
to 20 wt % of the deinking additives.
The combination of the rosin acid and the surfactant facilitate and
accelerate more effective agglomeration of the very fine hydrophilic
flexographic ink particles into particles amenable to effective removal in
a flotation process. The combination is used in a total amount sufficient
to either increase brightness of a filter pad prepared from media wherein
at least about 7.5% thereof was printed with a hydrophilic flexographic
ink by at least about 2% or to increase the rate of ink removal as a
function of time in the flotation cell, both as compared to a fatty acid
alone.
The deinking technology of the present invention may be used with water
hardness levels ranging from about 80 to about 500 ppm Ca.sup.+2.
Preferably the water hardness is from about 100 to about 400 ppm Ca.sup.+2
since, particularly at the lower end of the range, the additives are
generally sufficient to minimize the generation of undesirable deposits.
When a fatty acid is used in the form of an aqueous salt emulsion or
dispersion, the water need contain no hardness.
The deinking procedure of the present invention entails the use of a
flotation stage to remove very fine, i.e. a particle size of <about 5
.mu.m, hydrophilic flexographic inks from printed media. Generally, the
process begins with the addition of the deinking additives into a standard
pulping step in which printed waste paper, often in combination with
virgin wood pulp, is treated in an alkaline medium with water in a reactor
having an agitation system. The aqueous suspension so formed contains pulp
fiber, inks, coatings, inorganic fillers, and the like, in an amount of
from about 3 to 18 wt % and is maintained at a pH of about 7.5 to 11.
Typical pulping chemicals used in the pulper include such as NaOH and
hydrogen peroxide. Sodium silicate, a metal chelating agent such as
diethylenetriaminepentaacetic acid (DTPA), and calcium chloride may also
be added to the pulper. According to the process of this invention, the
additives are generally added directly to the pulper during the pulping
stage, although a portion of the deinking additives can be withheld and
added prior to flotation.
As a result of the addition of the combination of additives of this
invention, the hydrophilic ink particles are released from the recycled
printed media and agglomerated into larger particles. After the slurry
exits the pulper, it is diluted to about 1 wt % solids and transferred
into flotation deinking equipment. Thereafter, air is introduced into the
flotation equipment to cause vigorous mixing of the diluted pulp slurry.
The air bubbles then attach to the agglomerated fine hydrophilic ink
particles and carry the agglomerated particles to the surface of the
flotation equipment and form a froth thereon. This ink-rich froth is
removed from the surface in any of the conventional manners well known in
the art of deinking. The froth is a mixture of bubble sizes with rigidity
in the flotation equipment. Upon leaving the flotation cell and the
continuous air bubble supply, the froth collapses so that the resulting
inky liquid can be easily removed and sent to waste treatment prior to
disposal. It is a particular advantage of the present three component
deinking system that the flotation can be completed in less than about 10
minutes, commonly less than about 8 minutes, more commonly about 6
minutes or less, and when multiple (for example 3 or 4) flotation cells
are used in series the time per cell can be 3 minutes or less.
Following the flotation deinking procedure, the pulp slurry is thickened to
about 6 to 12 wt % solids and washed using conventional equipment readily
available and in widespread commercial use. The filtrate from the washing
is typically treated in a dissolved air flotation (DAF) clarifier to
remove inks, fillers, fiber fines, and other suspended solids so that the
filtrate water can be recycled for use in a subsequent deinking procedure.
Commonly, cationic and/or anionic polymers are added to the filtrate prior
to or in the dissolved air flotation clarifier so that the suspended
solids will be agglomerated and/or flocculated and removed.
Many modifications and variations of the basic deinking procedure explained
herein have been proposed and/or are in commercial use and the method of
the present invention may be applied to those procedures. The simple
system explained herein is used for illustration purposes only and is not
meant to be in limitation of the scope of this invention. The pulping
process may be carried out either in a continuous way or batchwise, with
excellent results with any type of printed media including newspaper,
magazines, printed cardboard and colored printed media. The recycled paper
is fed to the process so that it is present in an amount of about 10 to
100 wt % of the fiber undergoing pulping. The equipment used in this
process is conventional equipment which is readily available and in
widespread use.
The deinking composition of the present invention has several advantages
when compared to the prior deinking of printed media printed which
contains substantial amounts of water-soluble hydrophilic flexographic
inks. Specifically, a significant increase in brightness with lower
residual ink content in the pulp after flotation is realized when using
this method. The foam volume and height are also increased by the addition
of the rosin/surfactant combination.
It has also been found that the dosage rate of the fatty acid component of
the composition can be substantially reduced from the about 1-2 wt % for a
conventional process to about 0.35 to 0.7 wt % for the present invention.
This lower amount significantly reduces the potential for scale and
deposit problems normally associated with fatty acid components of
deinking formulations.
The advantages of the deinking composition of the present invention as
compared with conventional fatty acid deinking is illustrated in the
following Examples in which all parts and percents are by weight unless
otherwise specified. All filter pads for brightness were made using alum
as specified in TAPPI Test Method T 218 om-83. Where necessary the pulp
samples were first diluted to 1 wt % solids with tap water, 2 ml of 10%
alum solution added to each sample, and the slurry then thickened on a
Buchner funnel using Ahlstrom grade 631-25 filter paper. The filter pads
were air dried before taking brightness measurements. All brightness data
was obtained using an ACS Spectrosensor II spectrophotometer and reported
as TAPPI 452 brightness. The brightness data represents the percent of
light at wavelength 457 nanometers which is reflected off the filter pad
and recorded by the spectrophotometer.
EXAMPLE 1
A mixture of 20% OMG (old magazines), 80% ONP (old newspapers) (25% flexo
printed) are shredded dry and thoroughly mixed to form a master batch. 200
g of the mixture is added to a laboratory pulper along with 3,800 g water
(40.degree. C.) and conventional pulping additives (NaOH1%, Na.sub.2
SiO.sub.3 2%, and H.sub.2 O .sub.2 0.7%) to make a final consistency of
5%. Using a syringe, the deinking additives as shown in Table I below are
added at a total dosage rate of 0.7%, as calculated on a 100% active
basis, based upon the dry weight of the paper added to the pulper. The
fatty acid is a fatty acid soap (tallow fatty acid sodium salt) (DI-280
available from High Point Chemical Corporation). The rosin acid is a
commercially available mixture of such acids (Westvaco R-24 rosin from
Westvaco Chemicals) derived from tall oil and containing about 91.5% rosin
acids and about 4% tall oil fatty acids. The surfactant is a non-ionic
surfactant predominantly containing a mixture of mono- and di-glycerides
of tallow which has been alkoxylated (DI-600 available from High Point
Chemical Corporation). The compositions are each pulped for 10 minutes.
The contents are diluted to 1% solids by the addition of water and then a
filter pad (identified as "Fb" for "before flotation") is made for
measuring the brightness of the pulp prior to deinking.
5,000 g of the 1% stock slurry is then placed in a laboratory flotation
cell, 200 ppm of water hardness as Ca.sup.+2 is added, and the cell run
for 6 minutes with an air flow of 4.5 liters per minute. The froth that
collects on the surface is removed periodically and the foam height
measured. After 6 minutes the air flow to the flotation cell is stopped
and the operation ended. A second filter pad (identified as "Fa" for
"after flotation deinking") is made for measuring the brightness of the
deinked pulp.
The remaining 1% slurry is thickened to 10% on an 80 U.S. mesh sieve to
simulate a washing process and a third filter pad (identified as "Wa" for
"after washing") is made.
The deinking compositions which are evaluated, both comparative and within
the scope of this invention and the results obtained therewith are
provided in Table I.
TABLE I
______________________________________
Results of Example 1
Composition, % Brightness, %
FA ROS SURF Fb Fa Wa
______________________________________
100 -- -- 43.7 48.5 49.8
86.5 13.5 -- 44.1 48.8 50.2
73 27 -- 43.9 49.1 50.5
59.5 40.5 -- 44.2 49.2 50.7
82.2 12.8 5 44.1 51.3 53.2
69.3 25.7 5 43.9 51.5 54.4
56.5 38.5 5 44.1 50.6 51.2
______________________________________
FA = total fatty acid content
ROS = total rosin acid content
SURF = surfactant content
The results in Table I indicate that, with a 20% hydrophilic flexographic
ink printed media, there is little difference in flotation deinking
performance between the use of 100% fatty acid and when a portion of the
fatty acid is replaced by rosin acids. However, when a portion of the
fatty acid is replaced by a combination of rosin acids and surfactant, the
brightness of the resulting filter pads are substantially increased. It is
also evident that with all three additives, when the rosin acid content is
too high, i.e. increased to 40.5%, the deinking performance is not as good
as when it is at a lower level.
EXAMPLE 2
The basic procedure of Example 1 is repeated but varying the amount of
printed media which contains a hydrophilic flexographic ink while
comparing the performance of composition of this invention: 82% tallow
based fatty acid soap, 10% rosin acids, and 8% non-ionic surfactant
(DI-600) to that of a 100% tallow based fatty acid soap. The waste paper
is 100% ONP. The water hardness is 350 ppm Ca.sup.+2. The results of the
tests are shown in Table II in which differences in the filter pad
brightnesses (Fa-Fb) between the composition of this invention vs. that of
the fatty acid alone are seen to increase with increasing levels of
flexographic hydrophilic inks. Also as the flexographic ink content
increases, there is a large increase in the absolute brightness values
obtained with the present invention as compared to fatty acid only.
TABLE II
______________________________________
Results of Example 2
Fatty
Acid Only
Invention
% Flexo Ink
Fb Fa Fb Fa % Difference
______________________________________
0 44.1 49.9 44.7 50.4 -0.1
20 40.4 47.5 41.5 49.9 +1.3
40 37.2 44.3 40.2 48.6 +1.3
60 37.4 43.4 39.3 48.0 +1.7
80 31.4 34.9 38.9 47.0 +4.6
100 28.2 30.1 38.2 46.5 +6.4
______________________________________
EXAMPLE 3
Using the same basic procedure as in Example 2 with pulping followed by
flotation a comparison is made between the following deinking systems: a
fatty acid only vs. a composition containing 81.5% fatty acid, 12.5% rosin
acids, and 6% non-ionic surfactant (DI-600). The flotation deinking
process is performed at a water hardness of 150 ppm Ca.sup.+2 using
varying levels of flexographic hydrophilic ink containing printed media.
The results shown in Table III demonstrate the increasing benefit of the
deinking additive combination of this invention as the content of
hydrophilic ink in the waste paper increases.
TABLE III
______________________________________
Results of Example 3
Fatty Acid Only
Invention
% Flexo Ink
Fa Fa % Improvement
______________________________________
0 47.5 48.7 1.2
10 43.7 49.0 5.3
20 43.8 50.2 6.4
30 41.7 52.2 8.5
40 38.4 54.1 15.7
50 38.6 52.5 13.9
______________________________________
EXAMPLE 4
To compare the performance of a flotation deinking composition of the
present invention with a commercial composition which is reported as
giving reasonable results in the deinking of media containing flexographic
ink. The basic procedure of Example 1 is repeated with a mixture of 33.3%
magazines, 33.3% old newspapers, and 33.3% flexographic ink printed media.
The waste paper is shredded dry and added to a pilot plant pulper along
with water and NaOH 1.5%, Na.sub.2 SiO.sub.3 2%, diethylenetriamine
pentaacetic acid (DTPA) 0.3%, and H.sub.2 O.sub.2 1.0%). The deinking
additives of this invention are: 70.1% tallow based fatty acid soap, 25.9%
rosin acids, and 6% non-ionic surfactant (DI-600). The comparative
flotation deinking additive is Lionsorb 951 of Lion Chemicals Inc. which
is intended for use in flotation deinking with flexographic ink-containing
media. The results are shown in Table IV.
TABLE IV
______________________________________
Results of Example 4
Additive Dosage, % Fb Fa
______________________________________
Lionsorb 951
1.5 38.1 54.1
" 0.7 41.5 52.3
DI-600 only 0.5 43.1 51.8
Invention 0.7 41.6 59.1
_______ | | |