Note: Descriptions are shown in the official language in which they were submitted.
1()5~1870
INTRODUCTION
Mechanics of Pitch Formation
Pitch, as it is first introduced into the papermaking system,
is found adsorbed on the fiber (2%) and contained within the part of the
fiber termed ray cells (98%). Even when it is within the ray cells, it is
in a small particle state, attempting to achieve the greatest surface area
v.s. volume possible. When viewed under a microscope, the pitch in the ray
cell appears similar to eggs in a ~ish's egg sac-.
The pitch is forced from the fiber surface and from the ray cells
during the harsh process of digesting and during periods of high shear
(pumps, refiners, etc.).
When the oil-loving pitch particles are released from the fiber,
they enter the water system in the form of an unstable, crude dispersion. In
form and activity, they are very similar to micelles or a colloidal systems,
forming an unsta~le dispersion in suspension in the stock and ~ater system
used to process paper and pulp. This unstable dispersion completely destab-
; ilizes or breaks and the particles agglomerate when sub~ected to:
; 1. Shear
2. Temperature shock
3. pH shockInsoluble mineral salts such as calcium carbonate aggravate the problem by
,~ 20 providing sites for the pitch particles to adsorb and the pitch eventually
~j
acts as a binder, cementing the crystals together into a deposit. Technical-
ly, they offer liquid-solid interfaces which intensify the dispersion destab-
.
;: ilization forces, adding greatly to the bulk of the deposit.
~'
" ~
:,..
:.,. ,~
.,
,.,
~J
- 2 -
.,. ~
1~1870
Filler materials, fines and fibers can become trapped within
the organic matrix formed by the pitch coalesence and compound the
problem. Oil carriers from wash aids and defoamers are oleophilic
and tend to be attached to the oleophilic, crudely dispersed, pitch
particles causine further destabilization of the dispersion and
adding to the gross deposits.
Fa_t _ s That Influence Pitch Formation:
The composition of pitch and the amolmt of deposltable
materials are influenced by:
1. Type of wood
2. Seasoning of wood
3. Type of pulping process
. Process water
5. Pulp washing
6. Pulp bleaching
7. System additives
8. System desi B
1) TYpe of Wood and Its Com~onant~:
Softwood rs Hardwood
contain more fatty acids contains more neutral
contain more rosin acids organics (unsaponifiables
', and steroids)
; 2) Effect of Seasoning and Storage:
~,i
'~i The total amount of pitch forming organics that will
. .;~ ,
~ be released during the pulping operation is strongly
~;'
affected by its seasoning and storage. Wood stored as
chips, above freezing, will "season" more quickly and
completely than logs due to the greater surface area
available for oxidation. The oxidation of the resinous
:
~ materials tends to make the resins more soluble and easier
-- to remove by washing.
,;,
~.-
: .
. . .
", _ _
.,
, ~
1(~9~870
A chemical reaction, such as oxidation, takes place
more slowly during cold weather than during warm weather.
It thus follows that wood seasoned in the winter will have
a higher pitch forming tendency, this being the reason for
the traditional late winter and spring pitch outbreaks.
3) Pulping Process:
The presence and the relative amount of fatty/rosin
acids and neutral organics depend upon the type of wood and
the method of pulping. These materials are responsible for
most of the pitch deposition.
Kraft Cooks
Saponify natural fats completely into fatty acids
and glycerine.
Sulfite Cooks
~ot as severe as Kraft and may leave unsaponified
.~
~s fats
Groundwood
Contain great amounts of unsaponified fats as wood
:,~
is cooked.
;
~ 20 Neutral organics are found mostly in sulfite and
,,
groundwood systems because the acidic pulping systemsconditions causes any fatty acid, which do form, to be in
the free acid state.
".
Free fatty acids are almost insoluble in water, however
the sodium salts of fatty acids (present at higher pH) are
-;i
true surfactants and act to form the unstable dispersion of
',.'s
. .;
. .~;
.. ,j.~, ~
:
,
:~,
:~'
- 4 -
i~. ~.,;, .
1Q91870
neutral organics into a more stable natural dispersion
suspended in the pulp/waste system. If the pH is lowered,
they revert and the fatty acids deposit as pitch.
Kraft Cooks of hardwood pulps are more troublesome
than softwood due to the higher percentage of neutral
organics. Usually hardwood krafts have insufficient fatty
acid salts to stabilize theneutral organic dispersion.
4) Process Water/Washing System:
The process water is very important in controlline
pitch because it can aid in aggravating pitch problems or be
used to help prevent pitch outbreaks by providing a dynamic
system in which to suspend pitch in the form of a stable
emulsion.
i Water hardness, indigenous to the incoming mill water
~ or created by system chemistry, is very important to pitch
'r' formation, especially in kraft pitch. Kraft pulp, when it
leaves the digester is quite aIkaline and has a very high
~: sodium (salt cake) content.
When it enters a countercurrent brown stock washer
line, the pulp is washed with cooler and cleaner water, with
,, .
progressively lower solids content. At the high pH's, in the
first stages of washing, all of the fatty acids are present
as sodium salts, which are soluble and emulsify and non-polar
organics, any calcium present in the liquor or the wood
during the cook would be found as precipitated calcium
,.,
` carbonate. If the process water used in washing is soft
$
(naturally soft, chemically softened or boiler condensate),
no pitch outbreaks could be expected in the washer system.
;~:
~ 5 ~
.,
` ~.
- 1091870
However, the wash water added at most deckers or the
last stages of washing usually contains a fair amount of
calcium hardness. The calcium is detrimental to washing
and encourages pitch formation by two different mechanisms:
A. The calcium exchanges with the sodium in the
sodium soaps Or the fatty acids and forms insoluble calcium
soap.
No fatty acid + Ca ~___ Ca Fatty Acid 1 + Na
The insoluble soap (like a hard water soap
- 10 scum) no longer has the ability to act as a natural surfact-
ant (it once helped keep the pitch emulsified). The natural
pitch dispersion then becomes destabilized and forms a crude
dispersion, susceptible to depositing when faced with any
form of shear.
L. The calcium and bicarbonate alkalinity of the
:. wash water add to the carbonate and hydroxide alkalinity gen-
' erated during the caustic cook, forcing the precipitation of
', calcium carbonate.
Process Water Ca + HC03
Pulp + Liquor C03 + OH
x' HC03 + OH > C03 + H20
CA + C03 ~ > CaC03
The calcium carbonate crystals are then avail-
~,,
~, able as additional liquid-solid interfaces which
destabilizes the natural dispersion of pitch
forming organics. The destabilized dispersion...or
. .
: .
'~
,
:"
-- 6 --
~'
1091870
crude dispersion...then plates out at the decker
or screen room with typical kraft pitch.
Pitch usually doesn't occur before the decker or the
last stage of washing because, in countercurrent washing,
the earliest stages have the highest amount of natural
surfactants (sodium fatty acid salts) in the wash water and
this enables a natural stable dispersion of the pitch forming
materials.
In conJunction with this phenomenon, the earliest wash-
: 10 ing stages provide a higher concentration of sodium (soda)
, .. . .
and higher pH in the wash water, allowing the sodium todisplace the calcium in the fatty acid sales formed in the
last stages of the washer, the fatty acid salts act much like
the zeolites used in ~ater softening in their respon~e to
concentrations of sodium and calcium ions.
Na fatty acid + Ca ( ~ Na + Ca fatty acid
,~
The freed calcium then ties up with the available
carbonate but causes no problems due to the higher levels of
, natural surfactants. The CaC03 and sodium soaps then pass
progressively and innocuously through to the earliest stage
.:,
of washing and then to liquor recovery.
5) Pulp Bleaching System: -
Pulp bleaching is important to pitch control because it
provides an additional opportunity to remove resinous material
from the pulp which has not been removed in washing. The
naturally occuring resins are mostly unsaturated, making them
somewhat prone to attack by oxidizing agents:
~.
':~
:~,
,. .
,ii
-- 7 --
';' ~
: .
1091870
A. Chlorine
B . Chlorine Dioxide
C. Peroxides
D. Oxygen
The oxidation of the resins yield compounds which are more soluble
in water than the original resins and are more easily removed during caustic
extraction.
' .:
Calcium Hypochlorite bleaching causes problems because of calcium
fatty acid formation and the possibility of CaC03 formation.
6) System Additives:
Systems additives are very important to pitch control programs.
~- 10 Fatty Acid Defoamers - If applied incorrectly or in heavy dosages
add pitch forming material to the system.
Paraffin Oil Carriers - Found in most defoamers are usu~lly non-polar
and very hydrophobic and acts to destabilize natural pitch emulsions.
Light Hydrocarbons - Petrochemicals containing kerosene or xylene are
not quite as hydrophobic as the paraffin oils and tend to act as solvating
aeents to couple with the natural surfactants and increase the stability of
the resin emulsion.
Talc - Controls pitch by providing a hydrophobic surface for the pitch
,, .
' particle to adsorb and thus either de-stabilizing the natural emulsion or
`1 20 accumulating crudely dispersed pitch particles on its surface. It attempts
to bring the pitch particles together -- while the Nalco system's goal is to
keep them apart.
., .i
:,
:'~
v
~ -- 8 --
~Og~70
Talc provides a liquid-solid interface ~similar to calcium
crystals) on which the natural pitch dispersion can deposit without causing
deposits on the machinery, providing the proper amount is applied. The pitch
coated talc is large enough so that it tends to stay with the pulp.
System design plays an extremely important roll in pitch control.
A ~asher designed to wash 300 TPD of pulp obviously will not be as efficient
when 500 TPD are put across it. Minimizing the air-water interfaces in the s
washers, by proper machine designs and application of good defoamers, will
; help to stabilize the natural resinous emulsions.
Plastic materials in the machinery are more hydrophobic than metal
parts and provide a greater de-stabilizing effect on the natural pitch
emulsions than do metal parts.
. The invention seeks to provide a chemical additive capable of act-
ii ing on a variety of paper mill stocks to prevent pitch formation.
This invention also seeks to provide a pitch control composition
,:~
~hich is capable of dispersing and emulsifying pitch particles to an
exceptionally fine state of subdivision and allowing such finely dispersed
particles to be uniformly distributed throughout the finished paper in par-
ticles of microscopic size.
Thus in outline this invention seeks to provide a pitch dispersant
chemical composition which is capable of operating to prevent pitch buildup
in paper mill systems at low economical dosages.
.,
In accordance with the invention, it has been found that pitch
~j formation in paper mill pulp systems may be inhibited by adding to such sys-
`~ tems at a point prior to where pitch deposits normally occur at least 0.5
3 parts per million based on the weight of the pulp -of a 3-component formula-
,~ . .
,i, tion. This 3-component formulation is capable of acting upon the pitch
-~i contained ~ithin the pulp system to maintain it as a finely divided disper-
: sion or emulsion of pitch particles which frequently have a particle size
1 30 less than 10 microns, ~ith the majority of the particles being in the sub-
~ micron range.
.
'',! lPulp is total fiber/water suspension
:,
' ~ _ 9 _
.. .
. . .
gl870
The 3-component composition used in the practice of
the invention has the further advantage of being effective in
dispersing or emulsifying pitch which commonly occurs in a wide
variety of pulp systems. More importantly, the compositions
of the invention are capable of operating on the paper m.ill pulp
systems in amounts ranging from as little as 0.5 ppm up to
about 20 ppm. In certain instances, large amounts may be required,
e.g., 100 or 200 ppm, but the lower dosage ranges give good
~ results in most cases.
-~ 10 According to the process there is provided a method of
~ inhibiting pitch formation in paper mill pulp systems which
-- comprises adding to such systems at a point prior to where pitch
deposits normally occur at least 0.5 ppm based on the weight of
the pulp of a composition comprising:
Ingredients % by weight
A. Non-ionic surfactant 50 - 20
; B. Anionic Dispersant 40 - 15
C. Anionic Polymer having
molecular weight less
than 100,000 40 - 15
The compositionsof the invention are primarily designed
to prevent pitch buildup in the paper mill systems. It is well
known that pitch has favourite places for accumulating on the
various apparatus and equipment associated with the processing
~ of pulp. To be effective, the compositions of the invention
^~ should be added at a point in the mill system ahead of these
~ so-called problem areas.
';" ~ -10-
~?, r~
1091870
In certain inst~nces, the compositions may be added at multiple
points throughout the system to insure prevention of pulp buildup at
several points throughout the wet end of the paper-making process.
Since the compositions of the invention are primarily adapted
to disperse pitch already contained in pulp rather than remove heavy
accumulations thereof from equipment, the best results are obtained
in the practice of the invention when themill system has been
thoroughly cleaned by the use o~ a cleaning and/or sanitizing agent -~
such as chlorine. -
Prior art dispersing compositions which oftentimes contain
., :
one of the ingredients of the compositions of this invention, while
,; capable of maintaining pitch in a dispersed condition throughout a
, .j,
paper mill system, are incapable of producine micron to sub-micron
` particles of pitch which will attach themselves to the fibers in the
pulp system, thereby allowing the pitch to be incorporated into the -`
,
finished product in a finely divided state of subdivision. Prior
~ art compositions tend to allow the pitch to remain with the white
-~ water which is reused after sheet formation, thus producing a
,1
..:.
paper mill by-product which has an undesirable contaminant. When
~- 20 such pitch-containing white waters are re-dispersed back into the
pulp, the pitch buildup steadily increases, thus aggravating the
pitch deposit problem.
.
.. Compositions of the Invention
As indicated generically above, the compositions of the
invention contain 3 components. These components are listed below:
; ~
`~i
:~ ,
~ .
.
. .
~,. - 11 -
"
Generic Formula I
Ingredients % by weight
A. Non-ionic surfactant 50 - 20
B. Anionic Dispersant 45 - 15
C. Anionic Polymer having
molecular weight less
than lO0,000. 45 - 15
A more preferred composition falling within the scope of the
invention is set forth below:
, . .
Generic Formula II
Ingredients % by weight
- A. Non ionic surfactant50 - 30
B. Anionic Dispersant 40 - 20
~` C. Anionic Polymer having
molecular weight, less
than 100,000. 40 - 20
The Non-Ionic Surfactant
, ,~, .
~his portion of the composition may be selected from a wide
variety of non-ionic surfactants. Examples of such non-ionic
20surfactants are condensation products of higher fatty alcohols with
ethylene oxide, such as the reaction product of oleyl alcohol with
,
~ 0 ethylene oxide units; condensation products of alkylphenols and
. .
s~ ethylene oxide, such as the reaction products of isooctylphenol with
.'v
12 ethylene oxide units; condensation products of higher fatty acid
amides with five, or more, ethylene oxide units, polyethylene glycol
,.,
il
~A
.'
, .
~ - ~2 -
. ~z
870
esters of long chain fatty acids, such as tetraethylene glycol
monopalmitate, hexaethyleneglycol monolaurate, nonaethyleneglycol
; monostearate, nonaethyleneglycol dioleate, tridecaethyleneglycol
monoarchidate, tricosaethylene glycol monobehenate, tricosaethylene-
glycol dibehenate, polyhydrid alcohol partial higher fatty acid
esters such as sorbitan tristearate, ethylene oxide condensation
products of polyhydric alcohol partial higher fatty esters, and tbeir
inner anhydrides (mannitolanhydride, called Mannitan, and sorbitol-
anhydride, called Sorbitan), such as the emulsion even reacted they
10 molecules of ethylene oxide, pentaerythritolmonooleate reacted
. .
with 12 molecules of ethylene oxide, sorbitan monostearate reacted
;, with 10 to 15 molecules of ethylene oxide; long chain polyglycols in
which one hydroxyl group is esterified with a higher fatty acid and
the other hydroxyl group is etherified with a low molecular alcohol,
such as methoxypolyethylene glycol 550 monostearate (550 meaning the
averàge molecular weight of the polyglycol ether). A combination of
two or more of these surfactants may be used.
~ preferred group of non-ionic surfactants are the alkyl
phenols containing 4 to 12 carbon atoms which have been reacted with
from 4 to 10 moles of ethylene oxide. A typical material of this
type is nonyl phenol which has been reacted with 6 moles of ethylene
oxide.
,. ,
, The Anionic Surfactants
~i Typical anionic surfactants are sodium and potassium
i myristate, laurate, palmitate, oleate, stearate, resinate, and hydro-
`. abietate, the alkali metal alkyl or alkylene sulfates, such as
rt sodium lauryl sulfate, potassium stearyl sulfate, the alkali metal
~ alkyl or alkylene sulfonates, such as sodium lauryl sulfonate,
j ,
.,
~ ~ - 13 -
,`~ ' ' ,
.
potassium stearyl sulfonate, and sodium cetyl sulfonate, sulfonated
mineral oil, as well as the ammonium salts thereof; and salts of
higher means like lauryl amine hydrochloride, and stearyl amine
hydrobromide.
Other examples of suitable anionic surfactants are alkali
metal salts of alkyl-aryl sulfonic acids, sodium dialkyl sul-
- fosuccinate, sulfated or sulfonated oils, e.g., sulfated castor oil
sulfonated tallow, and alkali salts of short chain petroleum
sulfonic acids.
A particularly preferred group of anionic dispersants are
the alkali metal salts of sulfonated naphthalenes and alkyl substi-
tuted naphthalenes.
: A particularly preferred material of this type would be an
ethyl substituted naphthalene sodium sulfonate.
The Low Molecular Weight Anionic Polymers
These polymer~ are anionic and usually contain at least
5% by weight of alkali metal, amine or = onium carboxylate salt
groups. To be effective in the practice of the invention, they must
~`. have a molecular weight that does not exceed 100,000. In a preferred
embodiment of the invention, these materials contain at least 50% or
more carboxylate salt groups and have molecular weight ranges within
the range of 5 - 40,000 by weight.
~ypically, polymers of this type are either homo or co-
^ polymers of acrylic and/or methacrylic acid. A typical polymer
representing a preferred material is a co-polymer of acrylic acid
23% by weight of methyl acrylate which has a molecular weight of
.
~ about 12 - 15,000.
. .
~,:
-- 1~ --
~ ,~
, .
These polymers may be prepared as co-polymers with other monomers
such as acrylamide styrene sulfonates, maleic anhydride, acrylonitrile or
other vinyl monomers in amounts sufficient to maintain the polymers with
sufficient polar groupings to maintain a substantial degree of water solu-
bility or dispersancy.
The polymers containing acrylic acid may be prepared from low
molecular weight homo or co-polymers of acrylonitrile which is subsequently
subjected to an aqueous caustic hydrolysis step which converts a substantial
portion of the nitrile groups to sodium carboxylate groups. Alternatively,
homo or co-polymers of acrylamide may be subjected to alkaline hydrolysis to
convert the amide groups to alkaline carboxylate groups.
A typical method for preparing polymers of the above type by nit-
rile hydrolysis is disclosed in Example I of U.S. 3,419,502.
Using the techniques of the above patent, it is but a simple matter
`~ to prepare the polymers useful in the practice of this invention.
,, ,
', ~ptional Ingredients
' The above ingredients are conveniently prepared as an aqueous emul-
sion by dispersing them in uater. These concentrates may contain as little
as 5 up to about 45 or 50% by ueight of the active ingredients.
Such concentrates may also contain additional ingredients as anti-
foams, emulsifying agents, pH adjusting agents for maintaining formulation
.:
stability and the like.
. .
~,
` - 15 -
,
.,
1C)91870
A typical composition of the invention would be the ~ollowing
co]nposition:
Generic Formula III
Ingredients % by weight
Co-polymer of acrylic acid
and 23% methyl acrylate
(12,000-15,000 ~W) 15
Ethyl naphthalene sodium -
sulfonate 6.2
Nonyl phenol reacted with
6 moles of ethylene oxide 10
Polydimethyl siloxane anti- -
foam
.: .
Water balance
EXAMPLE I
To illustrate the invention, the following are presented by weight
of example:
; A composition corresponding to Formula 3 was tested in the southern
Craft Mill. ~he ma~or pitch problem that was experienced in this mill was
; pitch buildup in the bleach chest. Also, large pitch particles were being
~j 10 entrained in the finished product and were noticeable.
-~ Prior to the tests, the bleach chest which was o~ concrete con-
:
.:
struction was mechanically cleaned of pitch deposits. During the first day
of the test, Formula 3 was continuously fed at a dosage of 0.5 lbs. per ton
to the high density dilution line which fed into the bleach chest.
During the second day of the tests, the dosage was increased to
o.8 lbs. per ton. By mid-afternoon it was established that none of the
.~,
, paper produced was being rejected for dirt or pitch. Microscopic inspection
of the paper indicated that the pitch particles introduced therein were of a
much smaller size than those found at the beginning of the tests.
:
~ - 16 -
~' .~ ;.
On the third day of the tests, the dosage was increased to 1.5
lbs. per ton. The amount of dirt and pitch in the system was greatly im-
~i
proved. Particle size of the pitch in the paper was extremely small. At
the end of the fifth day, with the dosage bein8 continued at 1.5 lbs. per
,. . .
, ton, it was observed that the pitch in the paper was extremely small in
particle size and uniformly distributed throughout the sheet. As an ancil-
lary benefit, the dirt in the entire system was reduced by about 75% over
the tests.
It was also observed throughout the tests that existing pitch -
10deposits on the qquipment were gradually reduced indicating that the com-
positions of the invention are capable of reducing existing pitch deposits.
":~
..
. ........................................................................ .
. . i, .
,,
, .
,.,
~'
~,
: -
~
,
Ç~j
'~
".
,,:ç
:`
: .
; - 17 -
~.
