Note: Descriptions are shown in the official language in which they were submitted.
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COMPO8ITIONS AND PROCESS FOR REMOVING
TOXIC RESIN ACIDS AND THEIR DERIVATIVES FROM EFFLUENT
FIELD OF THE l~V~ lON
This invention relates to novel compositions and
a novel process for removing toxic resin acids and deriva-
tives from water and waste water effluent. In one specific
aspect, the invention pertains to novel compositions and a
novel process for removing toxic resin acids from effluent
of pulp and paper mills.
BAC~GROUND OF THE lNv~ lON
15 Toxic acids and harmful substances are contained
in effluent of many industries, for example, industrial
manufacturing plants, municipal sewage treatment plants,
petroleum, gas and metal producing processes. Anionic
organics and phosphates are contained in municipal efflu-
ents. To prevent or curtail damage to what has been
discovered to be a delicate environment, considerable
research and development activity has taken place with the
objective of discovering novel compositions and processes
for reducing or eliminating the toxic components of indus-
trial and municipal effluent streams.
Norwegian Patent No. 8,704,840, June 20, 1983,entitled "Retention or Cleaning Process for Waste Water and
Cellulose Fibre Suspensions", discloses the use of poly-
ethyleneoxide (PEO) with phenol formaldehyde resin (PF) andcationic starch as a retention aid and/or clarifier floccu-
lant.
Canadian Patent No. 1, 150, 913, August 2, 1983,
entitled "Separation of Unbleached Sulphate Fibres from
Aqueous Fibre Suspension by Adding High Molecular Weight
Polyalkylene Oxide as Flocculant", discloses the use of
polyethyleneoxide (PEO) as a selective flocculant for
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unbleached Kraft fibre in mixed secondary furnishes to
upgrade paperboard.
Canadian Patent No. 1,004,782, Hecktor et al.,
granted February 1, 1977, disclosed a process for separat-
ing solid and dissolved materials from waste water and in
particular a process for purifying waste water from indus-
tries dealing with "lignocellulose" fibres, for example,
the paper and board industries. Hecktor et al. purify
waste water container cont~m;n~nts by treating the water
with a sufficient amount of a phenolformaldehyde resin (PF)
to form flocs which contain the cont~m;n~nts and resin.
This is done in the presence of a water soluble non-ionic
polyalkylene ether containing lower alkyl groups in the
alkyl chain and having a molecular weight exceeding 50,000.
The flocs are then separated. In a specific embodiment,
polyethylene oxide of a molecular weight of about 300,000
having a solid content of 0.1~ by weight is used.
U.S. Patent No. 3,141,816 also discloses a method
of treating white water by using ethylene oxide polymers as
flocculants.
Because of the increasing awareness of damage and
potential damage to the environment by toxic resin acid
containing effluent, governmental regulatory bodies have
been passing regulations which place maximum permissible
levels on toxicity emitted in pulp and paper effluent
streams. If such toxin levels are exceeded, the pulp and
paper mills suffer economic hardship because the production
rates must be reduced to stay within the limits.
SUMMARY OF THE lNv~L.llON
Effective resin acid removal is achieved by
treatment of the resin acid containing effluent using a
coagulant such as a multivalent metal ion, (eg. aluminum),
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alone or in conjunction with another flocculant or by
treatment of the effluent with a natural, or chemically
modified organic colloid, such as cationized guar gum,
lignin, or lignosulfonate. This treatment is then followed
by flocculation and removal of the flocs by a liquid-solid
separation technique. Dissolved air flotation, decantation
and filtration are acceptable techniques.
The invention is directed to a composition for
treating effluent comprising: (a) a water soluble non-
ionic polyalkylene ether containing lower alkyl groups in
the alkyl chain and having a molecular weight exceeding
50,000; and (b) a non-phenolic ionic water-soluble polymer
having a molecular weight exceeding about 10,000. The
composition may include guar gum.
The polyalkylene ether can comprise between about
10% to 100% by weight of the composition, and the ionic
water-soluble polymer can comprise between about 0% to
about 90% by weight of the composition. The polyalkylene
ether can be polyethylene oxide having a molecular weight
of between about 100,00 to about 10,000,000. The ionic
water-soluble polymer can have a molecular weight of
between about 10,000, and 30,000,000.
The invention is also directed to a process for
purifying waste water containing contaminants which com-
prises treating the water with a sufficient amount of a
water-soluble non-ionic polyalkylene ether containing lower
alkyl groups in the alkyl chain and an ionic water-soluble
polymer.
In the process, the polyalkylene ether and the
ionic polymer can be added to the effluent at a concentra-
tion in a range of usually less than 10 parts per millionof the waste water effluent (the upper dosage limit being
established by resin acid concentration, efficacy and econ-
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omics). The effluent can also be treated with a composi-
tion containing polyaluminum chloride. The polyaluminum
chloride can be mixed with polyepiamine ( a copolymer of
epichlorohydrin, dimethyl amine and occasionally some other
organic amine). The composition can include polydiallyd-
imethylammonium chloride (polyDADMAC).
The invention is also directed to a composition
for treating effluent comprising:
Polyethylene oxide - 10-99.9
Ionic Polyacrylamide - 0.1-90
adding up to lO0~ of the formulation.
Alternatively, the composition for treating
effluent can comprise:
Polyethylene oxide - 5-99.9
Ionic Polyacrylamide - 0.1-90
Guar based polymer - 0-90
adding up to lO0~ of the formulation.
A further composition for treating effluent
comprises:
Com~onent A
Alum (Aluminum sulphate) - 0-50
Polyaluminum chloride (PAC) - 5-99.9
Polyepiamine (100,000 mol. wt.) - 0-50
Polyepiamine (300,000 mol. wt.) - 0-50
adding up to lO0~; and
Component B
Polyethylene oxide - 5-99.9
Cationic Polyacrylamide - 0.1-90
Guar based polymer - 0-90
adding up to lO0~ of the formulation.
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DETAILED DESCRIPTION OF SPECIFIC
EMBODIMENT8 OF THE lNv~.llON
We have invented a novel process for removing or
greatly reducing toxic resin acids and/or their derivatives
from water and waste water, particularly in pulp and paper
mills effluent and woodwaste leachate effluent. Effluent
toxicity is a waste water parameter that is subject to
strict government regulation. Offending sources are shut
down or curtailed.
In our process, waste waters containing up to
several hundred parts per million of resin acids, and their
derivatives, can be treated to remove such resin acids,
using a coagulant such as alum (aluminum sulphate), poly-
aluminum chloride, ferric chloride, and/or organic coagu-
lants such as polydiallyldimethylammonium chloride, and
polyepiamine.
Such coagulants may be used alone or in blended
combinations. The treatment can include coagulant addition
alone or can be in conjunction with a natural, or chemical-
ly modified organic colloid, such as guar or lignin. The
chemically modified organic colloid can also be used alone.
This treatment is then followed by the addition of a
flocculant blend consisting of polyethylene oxide with or
without an ionic water-soluble polymer. This overall
treatment, after allowing a floc to form which is separated
from the liquid phase, reduces the level of resin acid and
their derivatives in such aqueous systems.
Our treatment is very flexible and versatile
because it can be used with or without further biological
treatment of effluent (for example, aerobic or anaerobic),
and with and without other traditional waste treatments
such as primary sedimentation and filtration.
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Two ComPonent Composition
We have conducted experimental research into a
group of substances which have been found unexpectedly to
be highly useful in removing toxic resin acids from efflu-
ent streams. In particular, the inventors have discovered
that the following specific two component composition is
uniquely effective in removing resin acids from effluent:
Polyethyleneoxide - 10-99.9
Ionic Polyacrylamide - 0.1-90
adding up to lOO~ of the formulation.
We have discovered that if this combination is
added at a concentration of usually less than 10 parts per
million to an effluent containing toxic resin acids, toxic
resin acid levels in the effluent are reduced.
Three Component ComDosition
We have also discovered that the following three
component composition is effective in removing toxic resin
acids from effluent:
Polyethyleneoxide - 5-99.9
Cationic Polyacrylamide - 0.1-90
Guar based polymer - 0-90
adding up to lOO~ of the formulation
The polyethyleneoxide, the polyacrylamide and the
guar based polymer are mixed together.
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Multi-ComPonent comPosition
In addition to the foregoing, we have also
discovered unexpectedly that the following two component
composition is highly effective in removing or substan-
tially neutralizing the toxic resin acids in effluent:
ComPonent A
Alum (aluminum sulphate) - 0-50%
Polyaluminum chloride (PAC) - 5-99.9%
Polyepiamine - (100,000 mol. wt.) - 0-50
Polyepiamine - (300,000 mol. wt.) - 0-50%
adding up to 100% of the formulation.
comPonent B
Polyethyleneoxide - 5-99.9%
Cationic Polyacrylamide - 0.1-90%
Guar based polymer - 0-90%
adding up to 100% of the formulation.
PAC, polyepiamine 100,000 mol. wt. and
polyepiamine 300,000 mol. wt. are all available from
Diachem Industries Ltd. Polyepiamine 100,000 mol. wt. is
available under the trade-name DIAFLOCC 3490TM.
Polyepiamine 300,000 mol. wt. is available under the trade-
name DIAFLOCC 359 oTM .
The foregoing two-component formulation, we have
discovered, is effective in neutralizing or removing toxic
resin acids in effluent streams if about 50 or less parts
per million of component A is added to the effluent, fol-
lowed by usually less than 10 parts per million of compo-
nent B.
Resin acid Separation
For the following examples, Component A was a
mixture of 10% liquid alum, 80% PAC and 10% polyepiamine.
Component B was a mixture of 50% polyethylene oxide, 40%
cationic polyacrylamide and 10% cationic guar.
Example #1
A 1 litre sample of waste water in the form of
diluted black liquor taken from the spill lagoon of a Kraft
pulpmill at pH 10.9 containing 14.4ppm of resin acids was
placed in a 1 litre beaker. During agitation at lOOrpm
using a paddle stirrer, 4 ml of a 1% w/w solids solution of
lignosulfonate was added. After 30 seconds of agitation,
3 ml of a .029% solution of cationic polyacrylamide based
polymer, and 3 ml of a 0.1% solution of a 7 million molecu-
lar weight polyethylene oxide (PE0) were added to the
dilute black liquor. Agitation was continued for 75
seconds after which the agglomerated flocs were allowed to
settle. After 30 minutes of settling, 500 ml of treated
dilute black liquor was decanted from the beaker and
analysed for resin acid content. The resin acid concentra-
tion after treatment and settling was 9.1ppm, a 37% removal
rate.
Example #2
The same procedure and test liquid as in Example
#1 was repeated except for the omission of cationic poly-
acrylamide from the treatment. Resin acid concentration
after treatment and settling was 11.5ppm or a 20% removal
rate. This test demonstrated that treatment is much more
effective when cationic acrylamide is included.
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Example #3
The same procedure and test liquid as in Example
#2 was repeated, however 1 ml of a 1% solution of Component
A was added 15 seconds after the addition of the ligno-
sulfonate and 15 seconds prior to the addition of the
polyethylene oxide. Resin acid concentration after treat-
ment and settling was 10.5%, a 27% removal rate. This
example showed the high utility of a mixture of PAC, alum
and poly epiamine.
ExamPle #4
The same procedure, but a different test liquid
than used in Example #1, was repeated with the only treat-
ment being addition of 5 mls of a 0.1% solution of Compo-
nent B, followed by 75 seconds of agitation. The test
liquid was obtained from the same location as Example 1,
but at a time when resin acid concentration was 17.6ppm.
Resin acid concentration after treatment and settling was
13.5ppm, a 23% removal rate. This example demonstrated
that reasonable removal can be achieved using one blended
product of the invention.
ExamPle #S
The same procedure and test liquid as in Example
#4 was used but treatment consisted of the non-
polyethylene oxide components of Component B. Resin acid
concentration after treatment and settling was 16.3ppm, a
7% removal rate, showing the necessity of including PEO in
the treatment to be effective.
Example #6
One litre samples of waste water of combined
effluent streams from all sections of a Kraft pulp mill
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having a pH of 6.5 were treated using the same procedure,
but four different chemical treatments than in Example #1.
The resin acid concentration of the waste water was 7.8ppm.
Results of treatments 6A-6D are listed in Table 1 below.
Treatment A
4 ml of a 1% solution of lignosulfonate was
followed by 2 ml of a 1~ solution of Component A
which was followed by 2 ml of a 0.1% w/w solution
of PE0.
Treatment B
The same treatment as 6A was used except that 3
ml of a .029~ solution of a cationic polyacyl-
amide was added after component A and prior to
PE0 addition.
Treatment C
The same treatment as 6B, but omitting the PE0.
Treatment D
The same treatment as 6B, but omitting the ligno-
sulfonate.
Table 1
Treatment Resin acid conc. after treatment % Ren~l
6A 4.3 46
6B 3.8 51
6C 6.7 14
6D 3.2 59
Example 6 Discussion
Treatment 6C illustrates the need to include PE0
in the treatment, while treatment 6D shows that
lignosulfates are not always required.
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Example 7
The same test solution and procedure as in
Example #6 was used. However, chemical treatment consisted
of 4 ml of a 1% solution of Component A followed by 15
seconds of agitation, followed by 3 ml of a .035% solution
of a cationic polyacrylamide and 3 ml of a 0.1% solution of
PEO. After settling and decantation the resin acid concen-
tration was 2.4ppm, a removal rate of 69%.
Ionic Water-Soluble Polymer
By the term ionic water-soluble polymers in this
disclosure, we mean to include any non-phenolic water
soluble polymer which carries or is capable of carrying an
ionic charge when dissolved in water, whether or not that
charge-carrying capacity is dependent upon pH. Such
polymers include condensation polymers as well as polymers
derived from vinyl monomers. As an example of successful
use of these ionic polymers, the polymers obtained from the
condensation reaction of epichlorohydrin and ethylene-
diamine and/or dimethylamine may be successfully used.
Vinyl polymers having water solubility and ionic
characteristics, as described above, include modified
polyacrylamides, modification being made, for example, by
the typical Mannich reaction products or the quaternized
Mannich reaction products known to the artesan, or the
vinylic polymers, copolymers and terpolymers which use as
vinyl monomers those monomers containing functional groups
which have ionic character. As an example, but not limit-
ing to the scope of this invention, we include in these
vinyl monomers, monomers such as DMAEM, DMAEM QUAT, DACHA
HCl, DADMAC, DMAEA, DMAEA QUAT, MAPTAC, AMPIQ, DEAEA,
DEAEM, and ALA (see Table 2 below for definitions), the
quaternized compounds containing these monomers, acrylic
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acid or its salts, vinyl carboxylic acids or their salts,
acrylamide monomer, and the like.
Table 2
Monomer Abbreviation-Q
DMAEM = Dimethylaminoethylmethacrylate
and/or its acid salts.
DMAEM QUAT = Dimethylaminoethylmethacrylate
quaternized with dimethylsulfate,
methylchloride or methyl Bromide
DACHA HCl = Diallylcyclohexylamine Hydro-
chloride
DADMAC = Diallydimethyl ammonium chloride
DMAEA QUAT = Dimethyl amino ethyl acrylate
quaternized with Dimethyl sulfate,
methyl chloride or methyl Bromide
MAPTAC = Methacrylamidopropyl trimethyl
ammonium chloride
AMPIQ = l-acrylamido-4 methyl piperazine
(quaternized with MeC1, MeBr or
Dimethyl sulfate)
DEAEA = Diethyl aminoethyl acrylate and/or
its salts.
DEAEM = Diethyl aminoethyl methacrylate
and/or its salts
ALA = Allyl amine
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To be effective, these polymers, be they conden-
sation polymers or vinyl polymers must have a molecular
weight of at least 10,000 and may have molecular weights
exceeding l,OOO,oO0.
Polyacrylamide Based Polymer
By the term "poly acrylamide based polymer" we
mean to include any water soluble polymer which contains
acrylamide. Numerous representative comonomers are listed
under "Ionic Water Soluble Polymers".
Resin Acid
By the term Resin Acid, we mean to include
organic acids extracted from wood during milling or pulping
processes. Examples of resin acids include Pimaric,
Sandaracopimaric, Isopimaric, Levopimaric, Dehydroabietic,
Abietic, and Neoabietic acids.
As will be apparent to those skilled in the art
in the light of the foregoing disclosure, many alterations
and modifications are possible in the practice of this
invention without departing from the spirit or scope
thereof. Accordingly, the scope of the invention is to be
construed in accordance with the substance defined by the
following claims.
