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Патент USA US3072531

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3,072,521
United States Patent
1
.
2
p The cooked and de?bered pulp is thendiluted to less
3,072,521
" than 1% ‘concentration and rif?ed and screened to re-'
,
NON-AQUEOUS DEINKING PROCESS
move oversized objectsand unde?bered pieces of paper,
Gilbert J. Samuelson, Webster Groves, and Kenneth J.
Lissant, St. Louis, Mo., assignors to Petrolite Corpora
This’mate'rial is then washed with voluminous amounts
of Water, an average of 20,000 gallons of water per ton
-' tiou, Wilmington, Del., a corporation of Delaware
‘ N0 Drawing. Filed July' 27,1959, Ser. No. 829,498
'
19 Claims.
‘ Patented Jan. 8, 1953
(Cl. 162—5)
of pulp, to separate the?ber from‘ other substances by
washing or screening or by a?otation process; The dis
_
posal of large amounts of water used inthe process poses
This invention relates to an essentially non-aqueous
a stream pollution problem which must be remedied in
process of deinking cellulosic materials, such as, paper 10 most areas of the country.‘ __ l . p
,
_ H
v
= p
products, which comprises treating imprinted cellulosic
The problem’ of deinking has been further‘ complicated
by certain recent changes in the paper industry which"
materials such as paper products with a surfactant-con
taining organic solvent.
1
have increased the dif?culty of deinking', among which
Paper manufacture does not damage or alter the char
acter of the essential ?ber from which the paper is orig
inally made; hence, such‘ ?ber may be recovered from
used paper and reused, time after time, in’ the manufac
ture of fresh‘ paper stock. The limitations in respect of
changes are the following:
(1) The increased use of groundwood containing
slivers of wood rubbed from pulp wood present, jagged
sawtooth‘ends which affordexcellent crevicesfor'trapping; '
the carbon particles of the printer’s ink, thus making'jit"
practical recovery of ?ber from used paper are to be
increasingly di?icult to produce a reuseable pulp of high
found in the di?iculty and consequent expense of thor 20 quality of whiteness, _
_
Y A’
,_
,,
oughly deinking printed paper stock to upgrade it to the
(2) ‘Many of the improved new inkscurrently in use
color and quality of the original paper stock.
are‘ non-saponi?able with caustic, and generally'require
Many processes have been used for ‘deinking cellulosic
more drastic cooking conditions during deinking, thus'
materials, such as waste paper to make the c'ellulosic
content thereof useful in a pulp for reuse informing pa‘
per or other cellulosic products. These processes, how
tending to further degrade‘ the cellulosic ?ber.
v
I n
' (3) ' Certain paper coatings such as casein andsoybean
proteins, hardened with formaldehyde require for their
ever, are expensive, laborious, time-consuming, complicat
ed, and present pollution problems in disposing of the
removal higher temperatures which also degrade the‘
wastes thereof.
(4) The increased ?ller content of paper, (now, ap
In general, in preparing used paper for deinking and 30 proaching an average of 25%, results in increased shrinki.
recovery of ?ber, the stock to be salvaged is ?rst thor
age during deinking which increases the cost of deinked
oughly cleansed’ of super?cial dirt and macerated by
means of any suitable system or apparatus;
stock.‘
Then‘ the
-
' Among the disadvantages of prior processes are the
maceratum is boiled, subjected to the cooking and de?ber
ing in a suitable aqueous alkali to soften ‘the paper ?bers,
following:
,
_
_
'
,
p
g
V
H (1) Longv cooking periods at‘ elevated temperatures re,
loosen and disintegrate atileast part of the ink and other ' _ quite large expenditures of energy with increased ex
matter adheringr'to the ?bers‘, and thoroughly agitated,
either while‘ in the‘ alkaline solution or‘ subsequently, to
(2) High‘temperatures and strong chemicals employed
disintegrate and de?ber the stock as thoroughly as“ possi'
in these processes tend to deleteriously affect the ?bers
ble. Thereafter, the pulp is rit?ed and screened and‘ sub
so' that they are not always of the same quality as those
pense.
sequently dewatered, preferably through suitable rolls,
from freshpaper pulp.
?lters, or the like, to remove a.considerable portion of
Thus,‘ all commercially successful processes for deink
ing waste paper involve thefollowing steps:
p
I
I
v
p
solutions thereof can be found, for example, in the fol~
lowing patents:
,
60
(3) Ri?iing and screening
(4) Washing
I
.
pollution problem" whichvrequires expensive pollution‘
control systems.
Arstatement of“ the deinking problems andproposed
many times as may be practical‘ and expedient;
(2)‘ Alkali cooking and de?bering V
v
,
(3) The use ‘of large amounts of water poses a'strearn
the loosened ink. Itis then washed and dewatered ‘for
removal of additionalv quantities ‘of the loosened ink as‘
' (l) Dusting and maceration
,
7 4
2,607,678
2,077,059;
23,580,161
,
.
2,112,561
2,673,798
2,005,742
2,219,781
‘1,993,362, etc:
In general, the sorted, dusted and macerated paper is
‘ We have now discovered an‘ essentially non-aqueous
cooked with an aqueous’ deinking agent at a temperature
55 process of deinkingcellulosic materials, suchQa's’impi-inti
of from 140° F. to its boiling point for 25-48. hours at
ed'paper products, which comprises treating ink-contain
concentrations of 4-25 %. by weight of paper in the al
ing celluolsic materials with a" surfactant-containing’or
kali solution. Heat consumption willvary
'
inversely with‘ '
ganic' solvent. Since this, process can be carried‘ out‘at
the concentration and viscosity of the stock. ‘ De?bering'
room temperature in a shortperiod’of time, no‘expedi
is generally accomplished during the cooking'operation. 60 .ture of heat energy nor long holding periods‘a‘re required:
’ In general, the deinking agent employed containsl‘an
Since no strong‘ chemicals,‘high temperatures no extended‘
aqueous alkali solution which may in addition contain
reaction‘ periods are required, little, if- any, degradation’
‘one or more of the following: a detergent,.for example
of the pulp occurs, with obvious advantages; Since no:
sodium. soaps of fatty acids orabietic'acid, sulfonated‘oil;
etc.; a dispersing agent to preyenta'gglom‘er'ation- of the‘
pigment after release and to emulsify any ‘unsaponi?a
ble material; a softening'age'nt suchasikerosine or mineral
water washes are required,“ or if they are. employed, they‘
65 are carried out at room temperatures,‘ little,"if any, stream
pollution results" from the aqueous“ e?‘luent: These andv
- , other advantages will‘ become evidentr-as'the» process?‘ is"
oil‘, etc} to" soften‘ the‘ vehicle of the ink‘sf'an' agent such
as clay,“ a silicate‘, etcl, for selective adsorption after re-_
The facility with‘ which‘ the“ ink isremoved from3 the?
lease from thej?ber. a; prevent reiiepositidn‘ on the ?ber; 70 paper by the present invention is‘ indeed unexpected in
a" basic exchange chemical to" prevent formation of ‘cal
the party since organic ‘solvents themselves, without‘the sur-‘
cium soaps, etc. i
i
' '
’
fac'tant, effect little, if any, separation of-the ink—-in fact;
~
described.
,
.
3,072,521
.
.
.
,
4
3
they tend to further darken the paper. Furthermore, to
tally or substantially totally non-aqueous systems of any
kind have never been successfully employed. In addi
tion, the present effect of a surfactant in a non-aqueous
I. Anionic
A. Carboxyllc acids:
(1) Carboxyl joined directly to the hydrophobic group (subcalssiil
cation on basis of the hydrophobic group, e.g., fatty acid
soaps, rosin soaps, etc.
(2) Oarboxyl joined through an intermediate linkage.
system is unexpected since one generally employs sur
factants to affect the properties of a dual aqueous-organic
system and not those in which the system is essentially
(a) Amide group as intermediate link.
(1)) Ester group as intermediate link.
(c) Sulfonan'iide group as intermediate link.
(11) Miscellaneous intermediate links, ether, —-S0a--, —S—-, etc.
organic.
THE SOLVENT
10
The non-aqueous solvent employed in the present proc
ess may vary widely although, in general, the more non
polar oraguic solvents are most advantageously employed.
This does not preclude the use of polar type solvents, par
ticularly where polarity is masked by an organic group, 15
or groups having a relatively large hydrocarbon group or
groups. A convenient test of suitable polarity of the sol
vent is its solubility in water. Those solvents which are
relatively insoluble, for example, will dissolve less than
about ?ve percent by volume, but preferably less than 20
about one percent by volume, of water are most advanta
B. Sulfuric esters (sulfates):
(l) Sulfate joined directly to hydrophobic group.
(a) Hydrophobic group contains no other polar structures (sul
fated alcohol and suliated ole?n type).
(b) Sulfuric esters with hydrophobic groups containing other
polar structures (suliated oil type).
(2) Sulfate group joined through intermediate linkage.
(a) Ester linkage (Artie Syntex M. type).
(b) Amide linkage (Xynomine type).
(c) Ether linkage (Triton 770 type).
_
(d) Miscellaneous linkages (e.g., oxyalkylirnidazole sulfates).
O. Alkane sulionic acids:
(1) Sulionic group directly linked.
(a) Hydrophobic group bears other polar substitutents (“highly
suliatcd oil” type). Chloro, hydroxy, acetoxy, and ole?n
suli‘onic acids (Nytron tvpe).
(b) Unsubstitutcd alkaue sulionic acids (MP 189 type; also ce
taue sulio acid type).
(0) Miscellaneous sulionic acids of uncertain structure, e._g.,
oxidation products of suliurized ole?ns, sull’onated rosin,
etc.
(2) Sulfonic groups joined through intermediate linkage.
(a) Ester linkage.
geously employed.
(l) RCOO—X—SO;H (Igepon AP type).
Based on commercial considerations, the solvent should
' _
(2) ROOC—X—SO3II (Aerosol and sulioacctate type).
(b) Amide linkage.
(1) RCONH——X—SO3H (Igeoon T type).
be inexpensive and relatively low boiling, for example,
boiling below about 200° C., but preferably below about 25
(2) RNHOC~'X_SO3H (suliosuccinamide type).
(c) Ether linkage (Triton 720 type).
.110’0 C. I However, this does not preclude the use of- high
(11) Miscellaneous linkages and two or more linkages.
boiling solvents since various methods can be used for
their recovery, such as by reduced pressure, steam distil
D. Alkyl aromatic sulionic acids:
,
(1) Hydrophobic group joined directly to sulionated aromatic nu
cleus (subclasses on basis of nature of hydrophobic group.
lation, etc.
' Examples of suitable solvents include straight and 30
branched chain alkanes, for example hexanes, heptanes,
octanes, nonanes, decanes, undecanes, etc.; cycloalkanes,
for example cycle-hexane, terpenes, etc., the reduced
Alkyl phenols, terpene, and rosin-aromatic condensates, alkyl
aromatic ketones, etc).
(2) Hydrophobic group joined to sulionated aromatic nucleus through
as intermediate linka e.
(a) Ester linkage (suliophthalates, suliobenzoates).
(b) Amide and imide linkages.
(i) R-CONH-ArSO?I type.
(2) Sult‘obenzamide type.
aromatic compounds such as those of benzene and naph
(c) Ether linkage (alkyl phenyl ether type).
thalene such as di-, tetra-, and hexahydrobenzene, tetra-, 35
(d) Heterocyelic linkage (Ultravon type, etc).
(e) Miscellaneous and two or more links.
and decahydronaphthalene; aromatic compounds, for ex
E. Miscellaneous anionic hydrophilicgroups:
ample benzene, toluene, ethylbenzene, xylene, etc. and
21) Phosphates and phosphonic acids.
2) Persuliates, thiosuliates, etc.
(3) Sulionamides.
(4) Suliamic acids, etc.
ample, petroleum ethers, gasoline, kerosine, naphtha sol
II. Cationic
vents, white spirits, etc. In addition, other water insoluble
A. Amine salts (primary, secondary, and tertiary amines):
(1)
Amino
group
joined
directly
to hydrophobic group.
or substantially water insoluble organic solvents can be
(a) Aliphatic and aromatic amino groups.
employed, for example halocarbons, alcohols, ethers,
(b) Amino group is part of a heteroeycle (olkaterge type).
(2) Amino group joined through an intermediate link.
ketones solvents having more than one of these groups, for
(a) Esther link.
example keto-alcohols, etc. Although the solvent em 45
(It) Amide link.
(c) Ether link.
ployed is a non-aqueous solvent, the presence of small
(d) Miscellaneous links.
amounts of water which do not interfere with the es
B. Quaternary ammonium compounds:
(1) Nitrogen joined directly to hydrophilic group.
sentially organic nature of the solvent is within the scope
(2) Nitrogen joined through an intermediate link.
of this invention.
(a) Ester link.
(b) Amide link.
50
(a) Ether link.
(d) Miscellaneous links.
THE SURFACTANTS
0. Other nitrogenous bases:
(1) N on-quaternary bases (classi?ed as guanldine, tbiuronium salts,
A wide variety of surfactants can be employed in this
mixtures thereof that occur naturally or result from in
dustrial processes or which are arti?cially mixed, for ex
40
etc.
(2) Quaternary bases.
invention. The chemical nature and structure of the sur
Non-nitrogenous bases:
factant are not important except as they relate to their 55 D. (1)
Pbosphonium compounds.
function in the present process.
In general, all classes of surfactants can be employed in
(2) Sulionium compounds, etc.
III. N 011-] onto
A. Ether linkage to solubilizing groups.
B. Ester linkage.
C. Amide linkage.
this'invention including anionic, cationic, non-ionic and
ampholytic surfactants, provided they are sui?ciently
soluble in the organic solvent to be e?ective.
As is evident, the subclasses and species under the above
D. Miscellaneous linkages.
E. Multiple linkages.
IV. Ampholytic
classes are legion. To enumerate all surfactants that can
A. Amino and carboxy:
be employed in this invention would be unnecessary and
would render the speci?cation too voluminous. Therefore,
we shall merely present the general types of surfactants
which can be employed in this invention and more fully
describe certain preferred types of surfactants which are
(l)
(2)
(1)
(2)
Non-quaternary.
Quaternary.
Non-quaternary.
Quaternary.
B. Amino and sulfuric ester:
C. Amine and alkane sulionie acid.
D. Amine and aromatic sulfonic acid.
E. Miscellaneous combinations of basic and acidic groups.
illustrated by speci?c examples.
An excellent discussion of surfactants can be found
Examples of speci?c commercial surfactants useful in
in the texts, “Surface ‘Active Agents and Detergents” by 70 the present invention include those disclosed in “Emulsions
Schwartz et al. (vol. I, 1949, vol. II, 1958), Interscience
Theory and Practice,” by Paul Becker, ACS Monograph
Publishers, New York, which volumes are by. reference
No. 135, Rhinhold Publishing Corp., 1957, pp. 337-371,
incorporated into the present application. In vol. I of
which are hereby incorporated by reference into the
present speci?cation.
these textbooks is a classi?cation scheme that is useful
in a general representation of useful surfactants.
75
One class of surfactant advantageously employed in
3,072,521
6
5
The nature of the oxyalkylatable starting material used
in the preparation of the emulsi?er is not critical. Any
species of such material can be employed. By proper
additions of alkylene oxides, this starting material can be
eludes the non-ionic surfactants. Because it is a preferred
class, we will discuss it in detail.
. The most typical representatives of this class are the
oxyalkylated surfactants or more speci?cally polyalkylene
ethers or polyoxyalkylene surfactants. Oxyalkyl-ated sur
factants as a class are well known.
rendered suitable as a surfactant in the present process.
The possible sub
TABLE I.-—-REPRESENTATIVE EXAMPLES OF Z
classes and speci?c species are legion. The methods em
ployed for the preparation of such oxyalkylated sur
No.
factants are also too well known to require much elabora
tion. Most of these surfactants'contain, in at least one 10
place in the molecule and often in several places, an
Z
0
ll
1 _________ __
RO—O-——
2 --------- —-
a,
3 _________ __
R—~O~—
4 _________ __
R-S
5 _________ _-
R—‘O--
alkanol or a polyglycolether chain. These are most com
monly derived by reacting a ‘starting molecule, possessing
one or more oxyalkylatable reactive groups, with an
alkylene oxide such as ethylene oxide, propylene oxide,
butylene oxide, or higher oxides, epichlor-ohydrin, etc.
o
15
However, they may be obtained by other methods such as
shown in U.S. Patents 2,588,771 and 2,596,091-3, or by
esteri?cation or amidi?cation with an oxyalkylated ma
terial, etc. Mixtures of oxides or successive additions 20
of the same or different oxides may be employed. Any
0
II
oxyalkylatable material may be employed. As typical
starting materials may be mentioned alkyl phenols, phenol
E
—'
O
/
6 _________ __ R—g-'-—N'
ic resins, alcohols, glycols, amines, organic acids, carbo
hydrates, mercaptans, and partial esters of polybasic acids.
\
In general, the art teaches that, if the startingmaterial is
water-soluble, it may be converted into an oil~solub1e sur~
i‘
7 _________ ._
factant by the addition of polypropoxy or polybu-toxy
chains. If the starting material is oil-soluble, it may be
converted into a water-soluble surfactant by the addition
of polyethoxy chains. Subsequent additions of ethoxy ,
units to the chains tend to increase the water solubility,
R-—N—
8_________ __ RN/
9; _______ _.
Phenol-aldehyde resins
10 ........ _. —O— (EX7 Alkylene oxide block polymers)
while subsequent additions of higher alkoxy chains tend to
increase the oil solubility. In general, the ?nal solubility
R
R
and surfactant properties are a result of a balance between 35
the oil-soluble and water-soluble portions of the molecule.
11 -------
Since the present invention relates to non-aqueous systems,
the oxyalkylated surfactant employed herein should be
organically soluble.
'1
'
In general, the compounds are oxyalkylated surfactants
of the general formulav
_
.
r
.
.
.
ll
..
x_o-, ~s~, -—CHz-'~, éonr??ete.
‘
O
>
'
wherein Z is the oxyalkylatable material, R is the radical
derived from the alkylene oxide which can be, for exj 45
ample, ethylene, propylene,.buty1ene, epichlorohydrin and
‘
ll’
1-2. _______ .-
R—S—CH2O—-O—
13.;...... _-
RPO4‘H
14,. ______ _- RPOA/
‘ the like, n is a number determined by the moles of alkyl
=_
ene oxide reacted, for example 1: to 2000 or more and ‘m
a whole number determined by the number of reactive
oxyalkylatable groups. Where only one group is oxy 50
15 ________ __ '
'\
04:
1s.- ....... _- . RF'Q-somL ‘
alkylatable as in the case of a monofunctional phenol or
alcohol, R’OH, then m=1. Where Z iswater, or a glycol,
171:2. Where Z is glycerol, m=3, etc.
'
17‘. _______ -_ \ RFC>so2N=
In. certain cases, it is advantageous to react alkylene
oxides with the oxyalkylatable material in a random fash 55
.‘ (I? H
‘
ion‘ so as to form a random copolyrner on the oxyalkylene
....... .. ace-MGM
chain, i.e. the‘ [ (OR) nOH] m chain such as
‘
19 ........ __ Polyohdcrived (‘Exz'glyceroh glucose‘, peritae'ritliytol)‘
AABAAABBABABBABBA+ _
In addition, the alkylenel oxides can be reacted. in an
alternate fashion to form block copolymers on the chain, 60
for example BBBAAABBBAAAABBBB~ or
20; _______ ..
Auhydrohexitan or anhydrohexide‘derived
2i ________ __ , Polycarboxylic derived
22.‘_._.-._.. lenienmL
\
1]
-BBBBAAACCCAAAA-BBBB—
where A is the unit‘ derived from one alkylene oxide, for
example ethylene oxide, and B is the unit derived from‘ a
Ha
amine
second alkylene oxide,.for example propylene oxide, and C
‘is the unit derived from’a third alkylene oxide, for.eX-‘
ample, butylene oxide, etc. Thus, these compounds in- '
elude terpolymers or higher copolymers polymerized
randomly or in: a block-wise fashion or in. many varia-
'
'
THE PROCESS
“ dusted. and. macerated, with the surfactantscontaining' or
ganic solvent. ' In practice, the waste papef to be treated1
is preferably subdivided in relatively small pieces .as‘ by
passing. the waste paper vthrough a» conventional shred-"
r575. ding machine. The exact» size of theipieces-is'rndt mater
—-A,,B1,C;,— or any variation thereof, wherein a, b and!
c are 0 or a number providedthat at leastone of‘ them- is
i
>
by treating used paper, which’ has preferably been sorted,.
tions of sequential additions.
Thus, (OR)-n in the above formula can‘ be Written‘
greater-than 0.
I
. In general, the process of this‘ invention is-carrie‘d out‘
3,072,521
rial, it being advisable merely to so subdivide the waste
8
paper as to avoid the presence of a thick bulky mass which
able in some instances to subject the recovered ?ber to
a bleaching operation in which case it is advantageous to
might damage the beater in which the waste paper is sub
pass the ?ber from the continuous ?lter to a chest where
sequently treated and to expose the inked paper to inti
mate contact with the surfactant-containing solvent.
the ?ber is subjected to the action of a bleaching agent,
for example 1% chlorine bleach, after which the bleached
?ber is thoroughly washed with water. This washing may
After the paper has been shredded, it is introduced into
the surfactant-containing solution in an operating beating
engine in su?icient quantity to provide a suspension which
also be advantageously conducted by the use of a con
tinuous ?lter of the Oliver type although other conven
the beater can satisfactorily handle. In practice, we em
tional means may be employed.
ploy a suspension of approximately from about one to 10
The process can also be carried out continuously such
ten percent by weight, or higher, solid content, but pref
as by removing the ink from the solvent-surfactant me
erably about two to ?ve percent, with an optimum of
dium, by any suitable means, for example, by ?ltration,
about 2.5 to 4 percent.
settling and decantation, distillation, etc., and combina
The ratio of surfactant to organic solvent will vary
tions thereof and thereupon reusing the solvent-surfac
depending on various factors: for example, the particular
tant medium to deink additional paper. In other words,
solvent employed, the particular surfactant employed, etc.
the solvent-surfactant medium is separated from the paper
However, in practice, we employ a concentration of sur
pulp, freed of ink or other undesirable matter, and reused
factant in organic solvent of about 2 to 20 volume percent,
to treat additional waste paper. The reuse of the solvent
or higher, for example about 4 to 12 percent with an
surfactant system can be carried out batchwise or con
optimum of about 6 to 10 percent. Of course, it should
tinuously.
be realized that the surfactant can be added to the solvent
prior to addition to the heater or any time thereafter,
provided the combination of surfactant and solvent is
placed in intimate contact with the paper.
The temperature of the reaction mass is not critical.
Other variations on the above process can also be em
ployed, for example, counter current extraction, etc.
As is quite evident, the ef?ciency of the present process
will vary with the speci?c solvent-surfactant system as
Any temperature can be employed which is convenient.
Well as the ratios of each employed. For example, a
speci?c class or species of solvent may be more effective
In practice, we carry out the treatment at room tempera~
as compared with other solvents employing the same sur
ture although there is no reason why higher or lower tem
factant while another solvent may be more effective with
peratures cannot be employed, if desired, for example,
one particular class or species of surfactant as compared
below room temperature or above the boiling point of the 30 to other surfactants. In addition, certain surfactants are
solvent if pressure equipment is employed, in certain
more effective as deinkers in an organic system which is
instances.
not followed by a water Wash, while others are more effec
The mass in the beater is circulated around the heater
tive when followed by a water wash. An advantage of
and subjected to the action of the beater wheel until
the present invention is the fact that the surfactant can
“shiners” have practically disappeared from the mass.
be “custom built” to perform whatever function one de
The time required for this operation will vary with the
sires as to the system employed where no water wash is
particular apparatus employed. Further beating promotes
employed or where a water wash is employed. In addi
an excess of ?ne ?bers which may not be desirable in
tion, the surfactant can be “custom built” for optimum
preparing paper. Beating time varies with the particular
system and apparatus employed, but ordinarily in the
laboratory the beating'of the mass is continued from
about one-half to three minutes, or longer, for example
about one to two minutes with an optimum of about one
to one and one-half minutes, or until the ?ber is com
pletely freed of ink and other extraneous material pres
ent. However, these times will vary in the plant, depend
ing on the effectiveness of the apparatus employed.
vAfter completion of the beating action the mass is
withdrawn from the heater and the excess liquid is sepa
rated from the ?ber content which is then washed, if de
sired, with an organic solvent. The separation and work
ing of the ?bers may, for example, be advantageously
accomplished by passing the mass from the beater di
rectly to a continuous ?lter of the Oliver type. In this
type of ?lter a perforated drum rotates in a tank con
taining the suspension and by the action of reduced pres
sure or suction the liquid is drawn through the perfora
tions leaving a mat of ?ber on the surface of the drum,
performance in any particular solvent.
As is quite evident, new surfactants will be constantly
developed which could be useful in our invention. It is,
therefore, not only impossible to attempt a comprehensive
catalogue of such compositions, but to attempt to describe
the invention in its broader aspects in terms of speci?c
chemical names of its components used would be too
voluminous and unnecessary since one skilled in the art
could by following the description of the invention herein
select a useful surfactant. This invention lies in the use
of suitable surfactants in conjunction with suitable organic
solvents in deinking paper and their individual composi
tions are important only in the sense that their properties
can a?ect this function. To precisely de?ne each speci?c
useful surfactant and solvent in light of the present dis
closure would merely call for chemical knowledge within
55 the skill of the art in a manner analogous to a mechani
cal engineer who prescribes in the construction of a ma
chine the proper materials and the proper dimensions
through which subsequent ?ltering takes place. During
thereof. From the description in this speci?cation and
Heat as well as reduced pressure can also be used to re
and solvents suitable for this invention by applying them
the rotation of the drum the mat of ?ber on the surface 60 with the knowledge of a chemist, one will know or deduce
with con?dence the applicability or speci?c surfactants
thereof can be subjected to sprays of organic solvent.
cover the solvent. Other types of apparatus can also be
in the process set forth herein. In analogy to the case
employed.
of a machine, wherein the use of certain materials of con
struction or dimensions of parts would lead to no prac
~
If desired, the mat can also be water washed. Whether
a water wash is desirable will depend on many factors,
for example, the nature of the surfactant employed,
tical useful result, various materials will be rejected as
inapplicable where others would be operative. We can
whether one wishes to remove water soluble material from
obviously assume that no one will wish to use a useless
the ?bers, etc. Alternatively the mat can be reslurried
surfactant or a useless surfactant-solvent system nor will
in water and then ?ltered and rematted on the Oliver ?lter. 70 be misled because it is possible to misapply the teachings
After separation and washing, the ?ber is conveyed to a
of the present disclosure to do so. Thus, any surfactant
storage chest for use in the manufacture of paper or it is
or surfactant-solvent system that can perform the func
suspended in water and passed over a drum or screen to
tion stated herein can be employed.
form laps or sheets of pulp. While the foregoing process
The following tests were devised to evaluate the process
results in the production of white pulp, it may be desir 75 of the present invention:
3,072,521
10"
‘Although newsprint has been used to illustrate our
process, any imprinted cellulosic material can be salvaged
_' Ten grams of newsprint cut into approximately one
for reuse by the process of the present invention, for
‘inch squares, the solvent and the surfactant were placed
example various kinds of imprinted paper, suchras im
1n a one pint Mason jar ?tted with a Hamilton Beach
cutter head and stirred on the Hamilton Beach blender 5 printe‘i newsprint’ Iotogravure newsprint’ bopkstocli’
from one to three minutes. The pulp was then ?ltered,
“Pagan” stock’ ledger Stock’ cardboard’ etc‘ In addl'
Process I
using a 500 ml. ?lter ?ask and a Biichner ?lter funnel,
non’ the PIPES? may.be used to d‘a‘wax paper apt-he
with a wire Screen in place of ?lter paper.
same time it demks, since the solvent-surfactant system
The pulp
was then washed twice with water by placing the ?ltered
alslo 1s ggil?ble (If rim??? waxlgugmi the grocgss' 1
for one minute_ After each wash’ the pulp was then
vents and surfactants aremerely exemplary _of a wide
?ltered to remove the water_ A clean pulp was obtained
variety of other surfactants and. solvents which can be
pulp in the blender with 300 ml. of water and stirring 10
-
-
-
~
v
‘
-
n a
1 Ion’ 1 s on
e rea-lze it at t e a We 5.01’
employed to yield a clean pulp.
Pmcess H
.
Deinked paper is a very important source of rawlma
Ten grams of newsprint cut into approximately one ‘15 terial for the manufacture of book and magazine papers,
inch squares, the solvent and the surfactant were placed
in‘ a one pint Mason jar ?tted with a Hamilton Beach
labels’ coated Papers’ etcf' was? Edger papeis’ bonds.’
etc" can be ‘Flaked makmapmslble this riaducnon 11.1. the
cutter'head and stirred on the Hamilton Beach blender
amount of Vlrgm Pulp reqmred m suchgrades as Patent
from one to three minutes. The pulp was then ?ltered,
F°ated'b°ards# Pnstols, envelope Papers’ etc" as' We,“ as
using a 500 ml. ?lter ?ask and a ‘Biichner ?lter funnel, 20 111 book’ magazme, and Cover Papem Delnked ground
with a wiere screen in place of ?lter paper. _ The pulp ' wood Papers can b‘? usFd'advantagewsly as Summits?“
was then washed twice-With Solvent by placing the pulp
patent-coated, r‘nulticyllnder boards and as a substantial
in the blender with 300 ml. of solvent and stirring for
one minute. After each wash, the'pulp was then ?ltered
Porno“ of Phe hnerfurnlsh, 1n maml'a'hmf'd b°ards~ They
are also’ bemg usifd 111' consldelzable quantlty for the Flam-1'
to remove ‘the solvent. A clean pulp was obtained.
25 facture of hangmgs, newspnm, 199st‘?r PQPQY, mlmeo"
It is to be noted that Process I and Process II are carsraphraper, catalog P?PerS,_t1SS,u¢S, and slmllar Papers
ried out in exactly. the same manner except for the ?nal
mFVhmh groundwoqd ‘5 ordmanlyv USed- Othe? uses of
wash. Thus, both Processes I and II are inessence nondemke?i Paper are “(Q11 known Po the_ art_
aqueous processes, differing only in the ?nal step after
Havmg thus flescnbed our mventlona What _We clalm
the completion of the non-aqueous treatment and as 30 as new and deslre to 3?“? bl’ Leiters Patent 151
much of the solvent as possible is removed for economic
reasons_
,
‘1- A Process‘ of delnklng _1mpf1nted Pallet Products
‘
without any prior contact with water consisting essen
In Process I a terminal aqueous wash is e?ected, whereas in Process II a solvent wash is effected, With some
tially of contacting said products with a waterless sur
factant-contammg organic solvent, said surfactant being
surfactants, Process I is preferred, with others Process II 35 substautlally S0111b1e in Sald Organic SOIVent
is preferred, and with still others Process I or Process II
2. The Process of Clalm 1 Whef?ln the SOIVeIlt is a
is equally e?ective.
liquid hydrocarbon.
The following examples were run according to the
3. The process of claim 2 wherein the surfactant is
above procedures and are presented for purposes of illus~
non-ionic.
tration and not of limitation.
40
'
TABLE II
Solvent
Surfactant
Ex.
No.
'
Pro
cedure
‘
Name
Amt,
ml.
1 ____ _- Kerosine ________
_-
Tradename
Chemical name
Amt.,
ml.
270 .............................. .. Dingnylphenoeplusethyleneoxide(weightratio 1.0 to 1.31)...
. _....do ____________________ ..
.
..
3(5)
1
I
30
I
Dincnylpnenol plus ethylcn
e(we
ati
Dinonyl phenol plus ethylene oxide (weight ratio 1.
Dinonyl phenol plus ethylene oxide (weiaht ratio 1.
Dinonyl phenol plus ethylene oxide (weight ratio 1.
Dinonyl phenol plus ethylene oxide (weight ratio 1.
Dinonyl phenol plus ethylene oxide (Weialit ratio 1.
Dinonyl phenol plus ethylene oxide (Weight ratio 1.
30
30
30
30
30
30
30
I
I
I
I
I
I
I
Dinonyl phenol plus ethylene oxide (weizht ratio 1.0
30
I
270
Triton X—171 (Rohm & Haas). Blend of alkyl aryl polycther alcohols with organic sull‘onates.
30
I
275
Victarnul20 (Victor Chem)..- Oxyethylated phosphoric ester ______________________________ ..
25
I
275
Span-85 (Atlas) _____________ ..
25
I
Sorbitan trioleate ___________________________________________ ._
275
Surfynol 'I‘G. (air reduction)-. Mixture of ditcrtiary acetylenic glycol, alkyl phenyl ether of
25
I
275
275
Span-20 (Atlas) ............. .. Sorbitan monolaurate _______________________________________ ._
.............................. __ Dinnoyl phenol (1.011.31) plus ethylene oxide _________ ._
...
25
25
I
I
275
Surfynol104E (air reduction). Ethylene glycol solution oiaditertiary acetylenic glycol ..... -_
25
II
275
Span-85 (Atlas) _____________ ..
Sorbitan trioleate
25
II
275
Span-20 (Atlas) _____________ -.
Sorbitan monolaurate _______________________________________ ..
25
II
275
Victamul 20 (Victor Chem)-.- Oxyalkylated phosphoric ester..-
25
II
275
Victamul 89
Oxyethylated phosphoric ester ________ ..
.
25
II
275
Arquad 16 (Armour)
n-Palmityl t‘rimethyl ammonium chloride
.
25
I
Gocoyl ammonium acetate ............ -.
.
25
I
.
25
I
l-hydroxyethyl, 2-heptadecenyl glyoxalidine ................ __
25
I
polyethylene glycol and ethylene glycol.
‘
‘
..
275
ArmacO (Armour)...
275
Arquad 2-0 (Armour) ______ -- di-Oocoyl dimethyl ammonium chloride“
275
Aglln? 220 (Carbide and Caron
.
'
‘
‘
.
.
Dinonylphenolplus Et0(1.0:1.31) .......................... ....__
30.._..
Xylene .......... .-
31.____ Tur entine/
xy ene 50:50 by
'
‘270
.
Deriphat
1700
(General
O_____
'
%
N-lauryl?-amlno propionicacid _________________________ __,..__
25
I
Nonyl phenol oxyethylated and suliated ____________________ _.
25
I
n-LaurylB-amino propionic acid ............................. --
30
I
Mills).
volume.
32"---
Cyclohexanone.__.
270
33 ________ __do .......... .-
270
.............................. __
Delirl‘liir?rstt
S
'44
_____do__
- 270
‘
.
1600
'
______ -.
Nonylphenoloxyethylated and sulfated ...... ._
.
30' I
(General Partialsodium salt oin-laurylB-iminodipropion
_
30
I
. . _ _ . .-
30
I
>
Dinonyl phenol plus ethylene oxide (1.021.31) _ _ . . .
.
3,072,521
11
' 4. The process of claim 2 wherein the surfactant is
cationic.
5. The process of claim 2 wherein the surfactant is
anionic.
6. The process of claim 2 wherein the surfactant is
ampholytic.
7. The process of claim 2 wherein the surfactant is an
oxyalkylated phenolic compound.
12
16. The process of claim 15 wherein the surfactant is
oxyalkylated alkyl phenol.
17. The process of claim 16 wherein the surfactant is
an oxyethylated dinonyl phenol.
18. The process of claim 14 wherein the surfactant is
an oxyalkylated phosphoric ester.
19. The process of claim 14 wherein the surfactant
is a sorbitan ester.
8. The process of claim 7 wherein the surfactant is an
oxyalkylated alkylphenol.
9. The process of claim 2 wherein the surfactant con
tains an organic sulfonate.
10. The process of claim 2 wherein the surfactant is
an oxyalkylated phosphoric ester.
11. The process of claim 2 wherein the surfactant is
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,833,804
2,390,695
Watanabe ___________ .... Nov. 24, 1931
Dean _______________ _._ Dec. 11, 1945
401,145
545,113
Germany ___________ __ Aug. 28, 1924
Canada ____________ _. Aug. 20, 1957
a sorbitan ester.
12. The process of claim 11 wherein the surfactant is
sorbitan trioleate.
13. The process of claim 11 wherein the surfactant is
sorbitan monolaurate.
14. A process of deinking imprinted paper products
without any prior contact with water consisting essential
1y of contacting said products with a waterless surfactant
containing low boiling petroleum hydrocarbon solvent,
said surfactant being substantially soluble in said solvent.
15. The process of claim 14 wherein the surfactant is
an oxyalkylated phenolic compound.
FOREIGN PATENTS
OTHER REFERENCES
CA41, #1103, 1947, Removal of Synthetic Finishes
From Papers To Be Recovered.
CA35, “4205, Regeneration of Pulp From Waste
5 Printed Papers,” Japanese Patent 133,421, Nov. 21, 1939.
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