Title of Invention

A HIGH MOLECULAR WEIGHT WATER-SOLUBLE POLYMER COMPRISING PENDANT SALICYLIC ACID GROUPS

Abstract A polymer comprising pendant salicylic acid groups and having a weight average molecular weight or at least 2,000.000 daltons, wherein said polymer is prepared by free radical polymerization of one or more salicylic acid containing monomers, one or more acrylate monomers selected from the group consisting of (meth)acrylic acid and salts thereof and one or more polymerizable anionic monomers, characterized in that said polymer is selected from the group consisting of emulsion polymers and inverse emulsion polymers and comprises 50 to 98 mole percent sodium or ammonium acrylate, 1 to 20 mole percent 4- methacrylamidosalicylic acid or a salt thereof, 4-methacrylamidosalicylic acid phenyl ester or a salt thereof, O-acetyl-4-methacrylamidosalicylic acid or a salt thereof or O-acetyl-4-methacrylamidosalicylic acid phenyl ester and 1-30 mole percent 2-acrylamido-2-methyl propanesulfonic acid or a salt thereof.
Full Text HIGH MOLECULAR WEIGHT POLYMERS CONTAINING FINDANT
SALICYLIC ACID GROUPS FOR CLARIFYING BAYER PROCESS
LIQUORS
TECHNICAL FIELD
This invention is directed to high molecular weight polymers comprising
pendant salicylic acid groups and a method of using the polymers for clarifying red
mud-containing liquors generated in the Bayer process for the recovery of alumina
from bauxite.
BACKGROUND OF THE INVENTION
The Bayer process is almost universally used for the production of alumina
from bauxite ore. The process involves pulverizing a bauxite ore, sharing it in caustic
soda solution and digesting it at elevated temperatures and pressures. The caustic soda
solution dissolves oxides of aluminum to form an aqueous sodium aJuminate solution.
The caustic-insoluble constituents of bauxite ore (referred to as "red mud") are then
separated from the aqueous phase containing the dissolved sodium aluminate. This
separation typically occurs through sedimentation, which is often aided by a flocculant,
and filtration. Once separated, alumina trihydrate is precipitated from the aqueous
sodium hydroxide and collected as product.
In more detail, the pulverized bauxite ore is fed to a slurry mixer where a
caustic slurry is prepared. The slurry makeup caustic soda solution is typically spent
liquor (described below) and additional caustic soda. The bauxite ore slurry is diluted
and passed through a digester or a series of digesters where, under high pressure and
temperature, about 98% of the total available alumina is released from the ore as
caustic-soluble sodium aluminate. After digestion, the slurry passes through several
flash tanks wherein the pressure of the digested slurry is reduced from several
atmospheres to one atmosphere and the temperature of the slurry is reduced from about
200°C to about 105°C.

The aluminate slurry leaving the flashing operation contains about 1 to 20
weight percent solids, which solid consists of the insoluble residue that remains after,
or is precipitated during, digestion. The coarser solids may be removed from the
aluminate liquor with "sand trap" cyclones. The finer solids are generally separated
from the liquor first by gravity settling aided by a flocculant and then filtration, if
necessary. In some cases, the slurry of aluminate liquor leaving the flash tanks is
diluted by a stream of recycled washer overflow liquor. Any Bayer process slurry
taken from the digesters through a subsequent dilution of the slurry, including the flash
tanks, but before the primary settler, is referred to hereinafter as the primary settler
feed.
Normally, the primary settler feed is thereafter fed to the primary settler (or
decanter) where it is treated with a flocculant As the mud settles, the clarified sodium
aluminate solution (referred to as "green" or "pregnant" liquor) overflows to a weir at
the top of the vessel and is collected. This overflow from the primary settling tank is
then passed to subsequent process steps.
The clarity of the primary settler overflow is crucial to efficient processing of
alumina trihydrate. If the aluminate liquor overflowing the settler contains an
unacceptable concentration of suspended solids (at tiroes from about 10 to about 500
mg suspended solids per liter), it must be further clarifled by filtration to give a filtrate
with no more than 10 mg suspended solids per liter of liquor. The treatment of the
liquor collected after the primary settlement to remove any residual suspended solids
before alumina trihydrate is recovered is referred to as a secondary clarification stage.
The clarified sodium aluminate liquor is cooled and seeded with alumina
trihydrate crystals to induce precipitation of alumina in the form of alumina trihydrate,
Al(OH)3. The alumina trihydrate particles or crystals are then classified by particle
size and separated from the concentrated caustic liquor. A flocculant is used to aid in
this classification and separation process. The very fine particles of alumina trihydrate
are returned as the seed crystals and the coarser particles are collected as product. The
remaining liquid phase, referred to as "spent liquor," is then returned to the initial
bauxite slurry make up and digestion step and employed as a digestant after
reconstitution with caustic.
The settled solids of the primary settler are withdrawn from the bottom of the

settler or decanter (and referred to as "underflow') and then passed through a
countercurrent washing circuit for the recovery of sodium aluminate and soda.
Overflow liquor from the first washing vessel (or "thickener") is recycled either as
primary settler feed, diluting the slurry as it leaves the flash tanks, and/or it may be
passed to filtration along with the overflow from the primary settler.
The partial separation of the red mud solids from the pregnant liquor in the
primary settler (or decanter) is expedited by the use of a flocculant. This initial
clarification of the pregnant liquor is referred to as the primary settler stage.
Flocculating agents, such as liquid emulsion polymers, dry polymers and
polysaccharides including starch, are commonly used to improve the separation of the
insoluble red mud solids by increasing the rate at which these solids settle, by reducing
the amount of residual solids suspended in the liquor, and by decreasing the amount of
liquor in the settled solids phase, or underflow. Flocculation performance is critically
important in the primary settling stages. Red mud solids comprised mostly of iron
oxides (typically at least about SO weight percent of the red mud solids), together with
silicon oxides, calcium titanates, calcium phosphate, aluminum hydroxide, sodium
alumino-silicates and other materials, commonly represent from about 5 to about 50
weight percent of the materials of the bauxite ore. Generally, these red mods are
composed of very fine particles, which hinder the desired rapid and clean separation of
the red mud particles from the solubilized alumina liquor. Improving the rate of
separation improves the overall process efficiency and increases the output of alumina
production. Improving the clarification of the process liquors reduces the need for
filtration and further purification and can also increase alumina production. If the
separation of the red mud particles is not clean, the resultant solubilized aluminate
liquor will require a more extensive treatment to remove residual solids, and/or the
alumina trihydrate recovered will contain levels of impurities that are undesirably high
for many end-uses of the alumina.
Relatively low molecular weight polymers containing pendant O-acetyisahrylic
acid groups for use in biomedical devices arc disclosed in U.S. Patent No. 5,693.; 10.
An acrylamide/4-acrylamidosalicylic acid solution polymer is disclosed in Jnten. J
Polymeric Mater., 1992, 18, 165-177.

SUMMARY OF THE INVENTION
This invention is a high molecular weight, water-soluble polymer comprising
pendant salicylic acid groups and having a weight average molecular weight of at least
about 3,000,000 daltons.
The polymers of this invention effectively flocculate suspended solids in Bayer
process liquors. In particular, use of these polymers in Bayer process caustic
aluminate streams reduces the suspended red mud solids and significantly reduces the
need for filtration of the pregnant liquor. Lower solids in the overflow liquor also
reduce the amount of impurities such as iron oxide and other minerals, thus improving
the purity of the alumina produced during precipitation.
The polymers of this invention also effectively clarify alumina trihydrate from
Bayer process streams. During continuous or batch precipitation of the alumina
trihydrate, coarse particles are separated from fine crystals primarily by gravity
settling. A slurry of fine particles is sent to a series of secondary and tertiary clarifiers
to concentrate the particles according to size. Flocculation and settling of the very fine
particles is significantly improved by the addition of the polymers of this invention,
resulting in reduced aluminum tri-hydrate solids in the spent liquor when compared
with conventional processes, including the use of polysaccharides such as starch and
dextran and/or combinations with polymers of acrylic acid and salts thereof
The polymers of this invention show excellent affinity towards alumina
trihydrate particles, flocculating such particles, and increasing the rate at which these
particles settle. The very fine particles of alumina trihydrate can then be returned as
seed crystals in the primary crystallization step. Use of the polymers of this inveaaon
reduces the suspended fine aluminum tri-hydrate in the tertiary classifier overflow,
thereby improving the recovery of the alumina, ensuring that less alumina is recyled
to digestion with the spent liquor.

DETAILED DESCRIPTION OF THE INVENTION
Definitions of Terms
"Acyl" means a group of formula -C(O)R where R is alkyl or aryl. A preferred
acyi is acetyl (R=CH3).
"AIBN" means 2,2'-azobis(2-methylpropionitrile), available from E.I. DuPont
de Nemours and Co., Wilmington, DE under the tradename Vazo ● 64.
"ATVN" means 2,2'-azobis(2,4-dimethylvaleronitrile), available from E.I.
DuPont de Nemours and Co., Wilmington, DE under the tradename Vazo● 52.
"Alkyl" means a monovalent group derived from a straight or branched chain
saturated C1-C4 hydrocarbon by the removal of a single hydrogen atom.
Representative alkyl groups include methyl, ethyl, n- and iso-propyl, n-, sec-, iso- and
terf-butyl, and the like. A preferred alkyl is methyl.
"Alkyl (meth)acrylate" means the alkyl ester of acrylic acid or methacrylic
acid.
"Anionic monomer" means a monomer as defined herein which possesses a net
negative charge above a certain pH value. Representative anionic monomers include
base addition salts of acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-
methyl propane sulfonate, sulfopropyl acrylate or methacrylate or other water-solute
forms of these or other polymerizablc carboxylic or sulfonic acids, sulphomethylated
acrylamide, allyl sulphonate, sodium vinyl sulphonate, and the like.
"Aryl" means an aromatic monocyclic or multicyclic ring system of about 6 to
about 14 carbon atoms. Representative aryl groups include phenyl, naphthyl and
anthracenyl. A preferred aryl is phenyl
"Base addition salt" means the salt resulting from reaction of a carbovxlic and
(-CO2H) group with a suitable base such as the hydroxide, carbonate, or bicarbonate of
a metal cation or tetraalkylammonium cation, or with ammonia, or an organic primary,
secondary, or tertiary amine of sufficient basicity to form a salt with the carboxylic
acid group. Representative alkali or alkaline earth metal salts include sodium, lithium,
potassium, calcium, magnesium, and the like. Representative organic amines useful
for the formation of base addition salts include, ethylamine, diethylamine,

cthylcncdiamine, ethanolamine, diethanolamme, pipcrazine, and the like. Preferred
base addition salts include the sodium and ammonium salts.
"Cationic Monomer" means a monomer as defined herein which possesses a
net positive charge. Representative cationic monomers include the quaternary or acid
salts of dialkylaminoalkyl acrylates and methacrylates, the quaternary or acid salts of
dialkyiaminoalkyiacrylamides and methacrybunides, N,N-diallyldialkyl ammonium
halides, Mannich products, and the like. Alkyl groups are generally C1-4 alkyl.
Representative cationic monomers include
N,N-dimethylaminoethylacrylate methyl chloride quaternary salt (DMAEA.MCQ),
diallyldimethylammonium chloride (DADMAC), and the like.
"EDTA" means ethylenediaminetetraacetic acid and the base addition salts
thereof, available from Aldrich Chemical Company, Milwaukee, WI.
"High molecular weight polymer" means a water soluble polymer having a
weight average molecular weight (Mw) greater than about 2,000,000 dalton. The
polymers preferably have a molecular weight greater than about 3,000,000 dalton and
a RSV greater than about 14 dL/g, more preferably greater than about 20 dL/g when
measured at 400 ppm (based on non-ionized acid mer units) in 2M NaNO3 as
described herein.
"IV" means intrinsic viscosity, which is RSV in the limit of infinite polymer
dilution (i.e. the polymer concentration approaching zero). The IV is obtained by
extrapolating the plot of RSV versus polymer concentration in the range of 0.015-
0.045 weight percent polymer to the intercept of the y axis.
"(Meth)acrylic acid" means acrylic acid or methacrylic acid and the base
addition salts thereof.
"Monomer" means a polymerizable allylic, vinylic or acrylic compound. The
monomer may be anionic, cationic, nonionic or zwitterionic. Vinyl monomers are
preferred, acrylic monomers are more preferred.
"Nonionic monomer" means a monomer as defined herein which is electrically
neutral. Representative nonionic monomers include acrylamide, methacrylamide,
alkyl esters of acrylic and methacrylic acid such as methyl acrylate, acrylonitrile,
methacrylonitrile,

N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamidc, N-
isopropyl(meth)acrylamide,
N-{2-hydroxypropyl)(meth)acrylamide, N-methylolacrylamide, N-vinyiformamide,
N-vinylacetamidc, N-vinyl-N-methylacetamide, poly(ethyleae glycol)(meth)acrylate,
polyethylene glycol) monomethyl ether mono(meth)acryate, N-vinyl-2-pyrrolidone,
glycerol mono((meth)acrylate), 2-hydroxyethyI(meth)acrylate, vinyl methylsulfone,
vinyl acetate, and the like. Preferred nouionic monomers include methyl acrylate,
acrylamide and methacrylamide.
"Reduced Specific Viscosity" (RSV) is an indication of polymer chain length
and average molecular weight The RSV is measured at a given polymer concentration
and temperature and calculated as follows:

wherein 77 = viscosity of polymer solution;
ŋ0 = viscosity of solvent at the same temperature; and
c = concentration of polymer in solution.
The units of concentration "c" are (grams/100 mL or g/deciliter). Therefore,
the units of RSV are dL/g. The RSV is measured at 30 °C. The viscosities ŋ and ŊO
are measured using a Cannon-Ubbelohde semimicro dilution viscometer, size 75. The
viscometer is mounted in a perfectly vertical position in a constant temperature bath
adjusted to 30 ± 0.02 °C. The error inherent in the calculation of RSV is about + or - 2
dL/g. Similar RSVs measured for two linear polymers of identical or very similar
composition is one indication that the polymers have similar molecular weights,
provided that the polymer samples are treated identically and that the RSVs are
measured under identical conditions.
In the case of the inverse emulsion polymers described herein, the inversion is
conducted in 1% sodium hydroxide solution at an emulsion concentration of 1% by
weight (based on the emulsion).

In the case of the water continuous emulsion polymers described herein, the
polymer is hydrolyzed in 1% sodium hydroxide solution at an emulsion concentration
of 1 % by weight.
"Salicylic acid containing monomer" means a monomer unit having pendant
salicylic acid group(s) as defined herein. Representative salicylic acid containing
monomers include
3-acrylamidosalicylic acid and its base addition salts, 3-metnacrylamidosalicylic acid
and its base addition salts, 4-acrylamidosalicylic acid and its base addition salts, 4-
methacrylamidosalicylic acid and its base addition salts, 5-acrylamidosalicybc acid
and its base addition salts, S-methacrylamidosalicylic acid and its base addition salts,
4-acrylamidosalicylk acid phenyl ester,
4-methacrylamidosalicyiic acid phenyl ester, O-acetyl-4-acryianiidosalicylic acid, O-
acetyl-4-methacrylamidosah'cylic acid, 3-hydroxystyrene-4-carboxylic acid, 4-
hydroxystyrene-3-carboxylic acid, and the like.
Preferred salicylic acid containing monomers are 4-methacrylamidosalicylic
acid,
4-methacrylamidosalicylic acid phenyl ester, O-acetyl-4-methacrylamidosabcylic acid
and
O-acetyl-4-methacrylamidosalicylic acid phenyl ester.
"Polymer comprising pendant salicylic acid groups" means a water soluble or
water insoluble polymer containing salicylic acid groups pendant to the polymer
backbone. The polymers are prepared by polymerizing one or more salicylic acid
containing monomers with one or more nonionic, anionic monomers or zwittcrionic
monomers, or by grafting one or more salicylic acid groups onto a preformed natural
or synthetic polymer backbone. The polymers preferably comprise from about 1 to
about 90, more preferably from about 1 to about 20 and still more preferably from
about 3 to about 10 mole percent of pendant salicylic acid groups.
"Salicylic acid group" means a group of formula


where M is hydrogen, alkyl, aryl or a base addition salt; X is hydrogen or acyl; and the
group
represents an aryl group as defined herein, where is optionally substituted
with -NO2,
-OH, -SO3H. Representative salicylic acid groups include salicylic acid, salicylic acid
methyl and phenyl ester, O-acetylsalicylic acid, O-acetylsalicylic acid methyl and
phenyl ester, 2-hydroxy-5-nitrobenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-
dihydroxybcnzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 5-
sulfosalicylic acid, 1-hydroxy-2-napthoic acid, 3-hydroxyanthracene-2-carboxylic
acid, 3- and 5-formylsalicylic acid, and the like. Preferred salicylic acid groups are
salicylic acid, salicylic acid phenyl ester, O-acetylsalicylic acid and O-acetytsalicylic
aeid phenyl ester.
"Zwitterionic monomer" means a polymerizable molecule containing cationic
and anionic (charged) functionality in equal proportions, so that the molecule is net
neutral overall. "Zwitterionic monomer" means a polymerizable molecule containing
cationic and anionic (charged) functionality in equal proportions, so that the molecule
is net neutral overall. Representative zwitterionic monomers include N,N-dimethyl-N-
acryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine,
N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-
dimethyl-N-acrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-N-
acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, 2-(methylthio)ethyl
methacryloyl-S-(sulfopropyl)-sulfonium betaine, 2-[(2-
acryloylethyl)dimethylammoniojethyl 2-methyl phosphate, 2-{acryloyloxyethyl)-2'-
(trimethylammonium)ethyl phosphate, 1(2-acryloylethyl)dunethylammonio]methyl
phosphonic acid,
2-methacryloyloxyethyl pbosphorylcholinc (MPC), 2-[(3-
acrylamidopropyl)dimethylammonio]ethyl 2'-isopropyl phosphate (AAPI), 1 -vinyl-3-
(3-sulfopropy])imidazolium hydroxide, (2-acryloxyethyl) carboxymethyl
methylsulfonium chloride, l-(3-sulfopropyl)-2-vinylpyridinium betaine, N-(4-
sulfobutyl)-N-methyl-N,N-diallylamine ammonium betaine (MDABS), N,N-diallyl-N-
methyl-N-(2-sulfoethyl) ammonium betaine, and the like.

Preferred Embodients
The high molecular weight, water soluble polymer of this invention is
preferably prepared by free radical polymerization of one or more salicylic acid
containing monomers, one or more acrylate monomers selected from the group
consisting of (meth)acrylic acid and salts thereof and alkyl esters of (meth)acrylic acid
and optionally one or more polymerizable monomers selected from the group
consisting of nonionic, anionic, cationic and zwitterionic monomers.
In another preferred aspect, the polymer is selected from the group consisting
of dispersion polymers, emulsion polymers, inverse emulsion polymers, dry polymers
and solution polymers.
"Dispersion polymer" means a water-soluble polymer dispersed in an aqueous
continuous phase containing one or more inorganic salts. Representative examples of
dispersion polymerization of water-soluble polymers in an aqueous continuous phase
can be found in U.S. Patent Nos. 4,929,655; 5,006,590; 5,597,859; and 5,597,858: and
in European Patent Nos. 657,478; and 630,909.
Dispersion polymers are prepared by combining water, one or more inorganic
salts, one or more water-soluble monomers, any polymerization additives such as
chelants, pH buffers or chain transfer agents, and a water-soluble stabilizer polymer.
This mixture is charged to a reactor equipped with a mixer, a thermocouple, a nitrogen
purging tube, and a water condenser. The monomer solution is mixed vigorously,
heated to the desired temperature, and then a water-soluble initiator is added. The
solution is purged with nitrogen whilst maintaining temperature and mixing for several
hours. During the course of the reaction, a discontinuous phase containing the water-
soluble polymer is formed. After this time, the products are cooled to room
temperature, and any post-polymerization additives are charged to the reactor. Water
continuous dispersions of water-soluble polymers are free flowing liquids with product
viscosities generally 100-10,000 cP, as measured at low shear rates. The advantages of
preparing water-soluble polymers as water continuous dispersions are similar to lk.se
mentioned below in association with the inverse emulsion polymers. The wzter
continuous dispersion polymers have the further advantages that they contain no
hydrocarbon oil or surfactants, and require no surfactant for "inversion" or activation.

"Inverse emulsion polymer" and "latex polymer" mean an invertible water-in-
oil emulsion polymer consisting of an aqueous polymer phase dispersed as micron size
particles in a hydrocarbon oil continuous phase, various emulsifying agents, and,
potentially, an inverting surfactant. The advantages of polymerizing water-soluble
monomers as inverse emulsions include 1) low fluid viscosity can be maintauaed
throughout the polymerization, permitting effective mixing and heat removal, 2) the
products can be pumped, stored, and used easily since the products remain liquids, and
3) the polymer "actives" or "solids" level can be increased dramatically over simple
solution polymers, which, for the high molecular weight flocculants, are linaited to
lower actives because of viscosity considerations. The inverse emulsion polymers are
then "inverted" or activated for use by releasing the polymer from the particles using
shear, dilution, and, generally, another surfactant, which may or may not be a
component of the inverse emulsion.
Inverse emulsion polymers are prepared by dissolving the desired monomers in
the aqueous phase, dissolving the emulsifying agent(s) in the oil phase, emulsifying the
water phase in the oil phase to prepare a water-in-oil emulsion, in some cases,
homogenizing the water-in-oil emulsion and polymerizing the monomers dissolved in
the water phase of the water-in-oil emulsion to obtain the polymer as a water-in-oil
emulsion. If so desired, a self-inverting surfactant can be added after the
polymerization is complete in order to obtain the water-in-oil self-inverting emulsion.
The oil phase comprises any inert hydrophobic liquid. Preferred hydrophobic
liquids include aliphatic and aromatic hydrocarbon liquids including benzene, xylene,
toluene, paraffin oil, mineral spirits, kerosene, naphtha, and the like. Paraffin oil is
preferred.
Free radical yielding initiators such as benzoyl peroxide, lauroyl peroxide,
Vazo ® 64, Vazo® 52, potassium persulfate and the like are useful in polymerizing
vinyl and acrylic monomers. Vazo® 64 and Vazo® 52 are preferred The initiator is
utilized in amounts ranging between about 0.002 and about 0.2 percent by weight of
the monomers, depending upon the solubility of the initiator.
Water-in-oil emulsifying agents useful for preparing the inverse emulsion
polymers of this invention include sorbitan esters of fatty acids, ethoxylated sorbitan
esters of fatty acids, and the like or mixtures thereof. Preferred emulsifying agents

include sorbitan monooleate, polyoxyethylene sorbitan monostearaie, and the like.
Additional details on these agents may be found in McCutchcon's Detergents and
Emulsifers. North American Edition, 1980. Any inverting surfactant or inverting
surfactant mixture described in the prior art may be used. Representative inverting
surfactants include ethoxylated nonylphenol, ethoxylated linear alcohols, and the like.
Preferred inverting surfactants are ethoxylated linear alcohols.
The polymer is prepared by polymerizing the appropriate monomers at from
about 1 °C to about 85 °C over about 1 to about 24 hours, preferably at a temperature
of from about 40 °C to about 70 °C over about 3 to about 6 hours.
"Emulsion polymer" means a water-continuous dispersion of a water-insoluble
polymer. The preparation of high molecular weight emulsion polymers such as
poly(methyl acrylate) is described in U.S. 6,036,869. The polymer is rendered water
soluble when activated with caustic solution to hydrolyze the ester groups and generate
poly(sodium acrylate). Among the advantages of polymerizing in the water
continuous format are that no hydrocarbon oil is present in the product (as is the case
with the inverse emulsion systems), low viscosity fluids are obtained as products ( 100 cP is typical), and spills are easily cleaned up since the polymer is not water
soluble until activated.
In the preparation of a water continuous dispersion, an aqueous mixture of one
or more water soluble or water misciblc surfactants is prepared such that a
homogeneous solution results. Thereafter, one or more water insoluble monomers are
added to this mixture with shear such thai a water continuous emulsion is formed.
After the emulsion has formed, the reaction vessel is cooled to below ambient
temperature and purged with a nitrogen stream. After this, a stream of redox initiators
are fed to the polymerization over time. Typical initiators include iron salts, peroxides
and hydroperoxides, persulfates, bisulfites, and the like.
A typical polymerization may last three to four hours, after which time the
emulsion is allowed to warm to ambient temperature, filtered and transferred to
storage. Once the polymers are hydrolyzed in caustic solution, they may be
characterized by the measurement of a RSV in a fashion similar to the inverse
emulsion polymers.
"Dry polymer" means a polymer prepared by drying a polymer prepared by

"gel" polymerization. The preparation of high molecular weight water-soluble
polymers as dry powders using a gel polymerization is generally performed as follows:
an aqueous solution of water-soluble monomers, generally 20-60 percent concentration
by weight, along with any polymerization or process additives such as chain transfer
agents, chelants, pH buffers, or surfactants, is placed in an insulated reaction vessel
equipped with a nitrogen purging tube. A polymerization initiator is added, the
solution is purged with nitrogen, and the temperature of the reaction is allowed to rise
uncontrolled. When the polymerized mass is cooled, the resultant gel is removed from
the reactor, shredded, dried, and ground to the desired particle size.
Alternatively, dry polymers are prepared by spray drying emulsion, solution or
dispersion polymers of this invention prepared as described herein.
Although it is not possible to prepare concentrated solutions of the same high
molecular weight polymers prepared as inverse emulsions, water continuous
dispersions, or gel polymers owing to the extremely high viscosities which are
encountered, it is sometimes desirable to prepare lower molecular weight polymers of
similar composition as solutions in water. To conduct a solution polymerization of
water soluble monomers, the desired monomers are dissolved in water, generally at
concentrations between 5 and 40%, along with any buffers, acid or caustic, chelants,
chain transfer agents. The solution is purged with nitrogen and heated to the
polymerization temperature. After the polymerization temperature is reached, one or
more water soluble initiators is added. These initiators may be either of the azo type or
of the redox type. Then, depending on the desired polymer characteristics, the
temperature is either allowed to rise uncontrolled (adiabatic) or is controlled with
cooling to remove the heat generated (isothermal). After the polymerization is
complete, the solution of polymer can be removed from the reaction vessel, transferred
to storage and characterized.
In a preferred aspect of this invention, the salicylic acid containing monomers
are selected from the group consisting of 4-methacrylamidosalicylic acid or a salt
thereof, 4-mcthacrylamidosalicylic acid phenyl ester or a salt thereof, O-acetyl-4-
methacrylamidosalicylic acid or a salt thereof and O-acetyl-4-methacrylamidosalicylic
acid phenyl ester.

In another preferred aspect, the polyrocrizable nonionic monomers are selected
from acrylamide and methacrylamide.
In another preferred aspect, the polymerizable anionic monomer is 2-
acryiamido-2-methyl propanesulfonic acid.
In another preferred aspect, the polymer is selected from the group consisting
of emulsion polymers and inverse emulsion polymers.
In another preferred aspect, the polymer comprises about 80 to about 99 mole
percent sodium or ammonium acrylate and about 1 to about 20 mole percent 4-
methacrylamidosalicyiic acid or a salt thereof, 4-methacrylamidosalicylic acid phenyl
ester or a salt thereof, O-acetyl-4-methacrylamidosalicylic acid or a salt thereof or O-
acetyl-4-methacrylamidoealicylic acid phenyl ester.
In another preferred aspect, the polymer comprises about 88 to about 98 mole
percent methyl acrylate, about 1 to about 6 mole percent sodium acrylate and about 1
to about 10 mole percent 4-methacrylamidosalicylic acid or a salt thereof, 4-
methacrylamidosalicylic acid phenyl ester or a salt thereof, Oacetyl-4-
methacrylamidosalicylic acid or a salt thereof or O-acetyl-4-methacrylamidosalicylic
acid phenyl ester.
In another preferred aspect, the polymer comprises about 50 to about 98 mole
percent sodium or ammonium acrylate, about 1 to about 20 mole percent 4-
mcthacrylamidosalicylic acid or a salt thereof, 4-methacrylamidosalicylic acid phenyl
ester or a salt thereof, O-acetyl-4-methacrylamidosalicylic acid or a salt thereof or O-
acetyl-4-methacrylamidosalicylic acid phenyl ester and about 1 to about 30 mole
percent acrylamide or methacrylamide.
In another preferred aspect, the polymer comprises about 98 mole percent
sodium or ammonium acrylate, about 1 to about 20 mole percent 4-
mcthacrylamidosalicylic acid or a salt thereof, 4-methacrylamidosalicylic acid phenyl
ester or a salt thereof, O-acetyl-4-methacrylamidosalicylic acid or a salt thereof or O-
acetyl-4-methacrylamidosalicylic acid phenyl ester and about 1 to about 30 mole
percent 2-acrylamido-2-methyl propanesulfonic acid or a salt thereof.
The polymer of this invention is also prepared by functionalizing natural or
synthetic polymer with salicylic acid groups. For example, poly(acrylamide)
containing pendant salicylic acid groups is prepared by Mannich reaction

(formaldehyde, HCl) of poly(acrylamide). Similarly, naturally occurring polymers
such as proteins can be functionalized with salicylic acid groups under Mannich
conditions as described above. Alternatively, proteins and carbohydrates can be
reacted with salicylic acid derivatives such as chlororoethylated salicylic acid to
incorporate pendant salicylic acid groups into the polymer.
Accordingly, in a preferred aspect, the polymer is prepared by functionalizing a
natural or synthetic polymer with salicylic acid groups.
In another preferred aspect, the synthetic polymer is polyacrylamide.
In another preferred aspect, the natural polymer is a protein or carbohydrate.
In another preferred aspect, the polymer is prepared by reacting a natural or
synthetic polymer with chloromethyl salicylic acid under Mannich conditions.
Bayer process liquors generally are aqueous media containing dissolved
sodium aluminate and red mud solids at various concentrations. Such liquors include
the primary settler slurry or feed, which contains high concentration levels of both red
mud and dissolved sodium aluminate, the red mud washing slurries, which have high
red mud concentrations but lesser concentrations of sodium aluminate and total
alkalinity, and the secondary clarification liquors, which are rich in dissolved sodium
aluminate but contain much less red mud than the other types of liquors. Additional
liquors include red mud slurries which are dewatered in centrifuges or on vacuum
drum or disc filters, as well as red mud slurries which are flocculated to improve their
mud stacking properties or to improve the tendency to release water from the mod
slurry. As discussed above, the separation of the red mud from the sodium aluminate
and its aqueous phase is continued from the primary settlement stage until
concentrated red mud is eliminated from the process circuit, and from the primary
settlement stage until the clarified liquor is subjected to the alumina trihydrate
crystallization.
The flocculation of red mud, which routinely precedes or follows either seeling
or filtration, is most difficult in the primary settlement stage because of the high
concentration of fine particles, and the high concentration of total alkalinity.
Improvement of the flocculation effectiveness in the primary settlement stage is
extremely important to the entire Bayer process. By reducing the level of suspence"
solids that remain in the supernatant above the settled mud solids formed in the

primary settler liquor, the solids to be removed during secondary clarification stages
are reduced.
In the Bayer process, the bauxite ore is digested under highly alkaline
conditions, and the typical primary settler liquors are routinely highly alkaline,
containing sodium hydroxide, sodium aluminate, and commonly sodium carbonate.
The total alkalinity of the primary settler feed, that is the liquor charged to the
primary settlement stage, is typically from about 100 to 300 grams per liter of settler
feed, as sodium carbonate equivalent The solids contents of typical primary settler
feeds vary from about 25 to about 85 grams per liter of settler feed.
Primary settler feed means the Bayer process digested slurry as charged to the
flash tanks or other vessels emptying into the primary settler. Such feed may be an
admixture of the digested slurry plus dilution liquor, and the dilvtkn liquor is routinely
the counter current technique wash water from the red mud washing stages discussed
above. The primary settler feed differs from the liquors or shinies subjected to
clarification and/or separation in the secondary clarification stage or the red mud
washing stages by composition as to the solids content, dissolved sodium aluminate
content, and total alkalinity. The primary settler feed also differs from the liquors or
slurries in that no insoluble fraction thereof has received an earlier flocculation
treatment.
Accordingly, improved clarification of Bayer process primary settler liquors is
one aspect of this invention. Nonetheless in its broadest sense, this invention is
directed to the clarification and settling of red mud-containing liquors in any aspect of
mineral processing wherein such red mud is found. For example, the polymers of this
invention may be used in the counter-current wash liquors, primary settler liquors of
the Bayer process, as well as in red mud which is dewatered in centrifuges or by
vacuum filtration (drum filters, and disc filters among others) or in the settler overflow
to improve filtration in the polishing filters (either pressure or sand filters) or in red
mud which is flocculated after the last mud washing stage to improve the mod stacking
properties in the mud disposal area, or in red mud which must be made useful for other
purposes.
Upon flocculation of a primary settler feed, using the polymers of this
invention, a liquor/mud interface will form upon settling of the mud solids. The

supernatant liquor is low in suspended solids (generally ranging from about 10 to about
500 mg/l) and overlies a mod layer. The lower mud layer contains the flocculated
material, and as discussed above, is comprised of both red mud solids (generally
ranging from about 10 to about 70% mud solids by weight) and some amount of
pregnant liquor. The overlying supernatant is the liquor that is separated for secondary
clarification, again as discussed above. The interface between the supernatant mud
liquor and the mud layer is clearly seen in some cases, but the supernatant is not
entirely free of suspended solids, appearing instead as a translucent liquid. The present
invention diminishes the amount of suspended solids in such supernatant, and hence
decreases the extent of secondary clarification required to obtain a given purity of
sodium aluminate solution. Use of the polymers of this invention also reduces or
eliminates the need for starch by improved supernatant liquor clarity and improved red
mud stability, and the rheological properties of the concentrated red mud shiny.
The digested slurry is typically discharged from the flash tanks at elevated
temperatures. The primary settler feed is generally not further cooled before charging
to the primary settlement stage other than the cooling which may occur when a
digested slurry is optionally admixed with the liquor from the first red mud wash stage
to form a primary settler feed. The flocculation of the primary settler feed is
conducted at atmospheric pressures and at elevated temperatures of from about 80 °C
to about 110 °C. The flocculation of the primary settled feed can also be conducted at
elevated pressures and temperatures as high as 200 °C.
The following applies to any aspect of this invention. High and/or lower
molecular weight salicylic acid containing polymers may be used in combination with
any conventional nonionic polysaccharide flocculant such as starch, dextran, alginate
and flour, and anionic flocculants such as homopolymers of acrylic acid or acrylates,
co-ploymers of acrylic acid or acrylates containing at least 50 molar percent acrylic
acid or acrylate monomers, alkali metal, alkaline earth metal or ammonium salts of
said acids, or a polyacrylate alkyl ester of acrylate copolymer with 60 to about 90
percent of the alkyl ester groups hydrolyzed. Any of the above anionic flocculants
may be further functionalized with pendant hydroxamic acid groups. The salicylic
acid containing polymer may be added before, after or simultaneously with any of the
foregoing.

The polymers may also be utilized to treat the last stage washer underflow at
the mud disposal site to improve mud stacking, or more rapid release of liquor from
the mud. Moreover, the polymers may also be utilized for the treatment of mud filters,
including but not limited to drum and vacuum filters.
Water soluble polymers of this invention are used as follows: A solution of the
polymer is prepared in an appropriate dilution water stream typically as an about 0.1 to
about 1 weight percent polymer active solution. This solution is added to the digested
bauxite sodium aluminate process stream containing suspended solids in an amount
sufficient to settle said solids. For example, the polymer is injected into the feed-line
upstream of the settling vessel and/or added to the center-well of the settling vessel.
Alternatively, water-continuous polymers of this invention are added neat or as
a dilute solution to the primary liquor feed of a Bayer process. The water continuous
polymers hydrolyze in situ in the Bayer process liquor itself. In more detail, co-
polymers and or terpolymers formed from acrylic acid and/or acrylic acid esters and
salicylic esters may not be active as red mud flocculants until the ester groups are
hydrolyzed. When placed in the Bayer process liquor in the presence of red mud, the
high alkalinity and the high temperatures convert the polymers to effective red mud
flocculants by hydrolyzing the various ester groups to ionized acrylic acid and salicylic
acid groups. Furthermore, the polymer does not hydrolyze instantly, but rather over
time. Therefore, the poly (acrylic acid/acrylic acid ester/salicylic acid ester) essentially
is being activated continuously.
The salicylic acid containing polymers are injected upstream from the primary
settler, such as in one of the flash tanks or between the flash tanks and the primary
settler feed well where there is sufficient temperature and residence time to allow the
hydrolysis of the polymer. The hydrolysis will progress as the polymer and mud make
their way from the flash tanks down the various piping and into the primary settler.
The red mud containing liquor may be a primary settler feed, a mud washer
feed, a centrifuge feed or the polishing filter feed (pressure or sand filter). The feed
may be from a digester blow-off, diluted digester blow-off, primary settler underflow,
washer underflow, or a combination of settler and washer underflows with other
process streams including but not limited to settler overflow, washer overflows, lake

return water or raw water. The polymers described herein, when utilized to treat Bayer
process red-mud containing liquor, result in an increase in both clarity and settling rate.
The water-continuous polymers of this invention may be hydrolyzed in a
caustic solution, using various plant liquor streams alone or combinations thereof such
as spent liquor, pregnant liquor, any washing circuit overflow liquor containing some
caustic, lake return water, and/or condensate waters with addition of caustic, prior to
being added to the primary liquor feed of a Bayer process as details above.
In another preferred aspect, the polymer is hydrolyzed prior to addition to the
Bayer process liquor.
In another preferred aspect, the Bayer process liquor is selected from settler
feed, settler overflow, digestion blow-off, mud washer in the washer train, feed to the
primary polishing filters, feed to a mud settler, feed to the primary alumina
crystallization tanks, feed to the secondary and tertiary alumina classifers or trays, feed
to hydrate filters or feed to a centrifuge.
In another preferred aspect, one or more anionic or nonionic flocculan(s) are
added to the liquor.
In another preferred aspect, the nonionic flocculant is starch, dextran or flour.
In another preferred aspect, the anionic flocculant comprises poly (meth)acrylic
acid.
In another preferred aspect, the poly (meth)acrylic acid is selected from the
group consisting of poly(meth)acrylic acid, poly(meth)acrylic acid containing pendant
hydroxamic acid groups,
poly (alkyl (meth)acrylate), (meth)acrylic acid/alkyl (meth)acrylate copolymers,
(meth)acrylic acid/acrylamide copolymers, (tneth)acrylic acid/acrylamide copolymers
containing pendant hydroxamic acid groups, (meth)acrylic acid/acryiamide/alkyl
(meth)acrylate terpolymers, and
(methjacrylic acid/acrylamide/AMPS terpolymers.
In another preferred aspect, the anionic flocculant is added prior to the salicylic
acid containing polymer.
In another preferred aspect, the anionic flocculant is added after the salicylic
acid containing polymer.

In another preferred aspect, the anionic flocculant is added together with the
salicylic acid containing polymer.
In another preferred aspect, the potyomer comprising pendant salicylic acid
groups has an RSV of at least about 14 dL/g and the anionic flocculant has an RSV of
at least about 21 dL/g.
The foregoing may be better understood by reference to the following
examples, which are presented for illustration and are not intended to limit the scope of
the invention.
Example 1
Preparation of 4-methacrylamidosalicylic acid (4-MASA).
In a 5 L flask, 250 g of 4-aminosalicylic acid (Aldrich Chemical Co.,
Milwaukee, WI) is dissolved in 2.0 L of acetone under a nitrogen atmosphere with the
aid of mechanical stirring. To this is added, at room temperature, 375 g of methacrylic
anhydride (Aldrich) dropwisc over 1 hour. After stirring for 16 hours, the volume of
acetone is reduced to 1.0 L by vacuum distillation. The crude solid product which
precipitates from solution is collected by vacuum filtration. The product is washed
with 500 mL of 5:1 water methanol and purified further by stirring the solid for 30
minutes in 1 L of 5:1 watenmethanol. The solid is isolated by vacuum filtration and
air-dried overnight to yield 295 g of a tan solid. This product is used without further
purification.
Example 2
Preparation of 4-methacrylamidosalicylic acid phenyl ester (4-MASAPE).
A solution of 29.6 g of phenyl 4-aminosalicylate (Aldrich) in 175 mL of
acetone is cooled to 0 °C. To this is added dropwisc with stirring 29 mL of
methacrylic anhydride (Aldrich) dissolved in 20 mL of acetone. The solution is
allowed to warm to room temperature and is then heated at reflux for 20 hours. The
reaction mixture is then cooled to room temperature and added to 400 mL of ice water.
The resulting light yellow solid is isolated and dried under vacuum. The product is
used without further purification.

Example 3
Preparation of O-acctyl-4-methacrylamidosalicylic acid (A-4-MASA).
A few drops of concentrated sulfuric acid is added to a stirring solution of 35.0
g of 4-methacrylamidosalicy)ic acid (prepared according to Example 1) in 350 mL of
acetic anhydride at 0 °C. The solution is stirred for 60 minutes at 0 °C and then for an
additional 6 hours at room temperature. The reaction mixture is then poured into 800 g
of cold deionized water. The solid product precipitates from solution, and is collected
by filtration. The product is then air dried at room temperature to afford A-4-MASA
in quantitative yield.
Example 4
Preparation of O-Acetyl-4-mcthacrylamidosalicylic acid phenyl ester (A-4-MASAPE).
Triethylamine (9.7 g) is added under nitrogen to a solution of 20.0 g of 4-
methacrylamidosalicylic acid phenyl ester in 120 mL of acetone at 0 °C. Acetyl
chloride (7.52 g, Aldrich) in 40 mL of acetone is then added dropwise to the stirred
reaction mixture. The mixture is stirred for 6 hours at room temperature. The reaction
mixture is filtered and then concentrated in vacuo. The resulting solid is dissolved in
acetone and the acetone mixture is slowly added to water. The resulting solid is
filtered and dried under vacuum.
Example 5
Preparation of a 3 mole percent 4-mcthacrylamidosalicylic acid (4-MASA) / 97 mole
percent sodium acrylate inverse emulsion copolymer by batch polymerization.
A 500 mL reaction flask equipped with a mechanical stirrer, reflux condenser,
dropping funnel, gas inlet tube and a thermometer is charged with 33 g of acrylic acid
and 45 g of deionized water. This solution is neutralized with sodium hydroxide (50%
aqueous solution), such that the final pH is about 8.5. The neutralization is conducted
in an ice bath and care is taken to ensure that the temperature of the monomer solution
does not exceed 25 °C. To the resulting neutralized solution is added 0.013 g of
ethylenediaminetetraacetic acid, tetrasodium salt (EDTA, Aldrich). Separately, 3.67 g
of 4-MASA is dissolved in 10.0 g of deionized water by adjusting the pH of this

solution to about 12.5 with sodium hydroxide (50 % aqueous solution). The two
monomer solutions are combined and the pH of the resulting mixture is adjusted to
about 10.5 with sodium hydroxide or sulfuric acid, as required.
An oil phase is prepared by heating a mixture of 45.2 g of a paraffinic solvent
(Escaid® 110, Exxon, Houston, TX), 3.15 g of a sorbitan monooleate (Span® 80, ICI
Americas, Wilmington, DE), 1.37 g of a polyoxyethylene sorbitan monostereate
(Tween® 61, ICI), 0.94 g of a polyoxyethylene sorbitan tristearate (Tween® 65, ICI),
and 2.89 g of oleic acid (J. T. Baker, Phillipsburg, NJ) until the surfactants are
dissolved (54-57 °C). The oil phase is transferred into the reactor described above and
heated to 45 °C.
With stirring at 1000 rpm, the aqueous monomer phase is added over two
minutes. The resulting water-in-oil emulsion is stirred for thirty minutes while it is
purged with nitrogen. After this time, 0.0525 g of Vazo® 64 and 0.0075 g of Vazo® 52
is added to the water-in-oil emulsion. The polymerization is carried out under a
nitrogen atmosphere at 45 °C for 4 hours, then at 55 °C for one hour. The finished
emulsion product is then cooled to 25 °C. The polymer has a reduced specific
viscosity of 18.8 dL/g (measured as a 400 ppm solution in 2N sodium nitrate solution
at 30 °C) and a Brookfield viscosity of 1050 cps (#3 spindle at 12 rpm).
Example 6
Semi-batch polymerization to produce a 6 mole percent 4-methacrylamidosalicylic
acid (4-MASA) / 94 mole percent sodium acrylate inverse emulsion copolymer.
The reaction apparatus employed in this example is the same as that described
in Example 4. Acrylic acid, 33 g and 0.013 g of EDTA is dissolved in 30 g of
deionized water and neutralized with sodium hydroxide (50% aqueous solution) such
that the final pH of the solution is about 8.5. The neutralization is conducted in an ice
bath and care is taken to ensure that the temperature ot the monomer solution does not
exceed 25 °C.
Separately, 6.65 g of 4-MASA is dissolved in 10.0 g of deionized water by
adjusting the pH of the water to about 12.5 with sodium hydroxide (50% aqueous
solution), and this solution is set aside.

An oil phase is prepared by beating (54-57 °C) 3.15 g of Span® 80,1.37 g
Tween® 61,0.94 g of Tween® 65, and 2.89 g of oleic acid in 45.20 g of Escaid® 110
until the surfactants are dissolved.
The oil phase is charged to the reactor and the contents of the reactor are stirred at
1000 rpm. The aqueous monomer phase is then added to the reactor over two minutes
so that a water-in-oil emulsion is formed. The emulsion is purged with nitrogen and
heated to 45 °C. Polymerization is initiated by adding 0.0525 g of Vazo#64 aad
0.0075 g of Vazo ® 52. After sixty minutes, the solution of 4-methacrylamidosalicylic
acid is fed to the reactor over a few minutes. The polymerization is continued for
another two hours at 45 °C, and then for one hour at 55 °C. After this time, the
emulsion is cooled to room temperature. The polymer has a reduced specific viscosity
of 17.4 dlVg (measured as a 400 ppm solution in 2N sodium nitrate solution at 30 ºC)
and a Brookfield viscosity of 3260 cps (#3 spindle at 12 rpm).
Example 7
Continuous Feed Polymerization (CFP) to produce a 6 mole percent 4-
methacrylamidosalicylic acid (4-MASA) / 94 mole percent sodium acrylate inverse
emulsion copolymer.
The reaction apparatus employed in this example is the same as that described
in Example 4. Acrylic acid (33 g) and 0.013 g of EDTA is dissolved in 30 g of
deionized water and neutralized with sodium hydroxide (50% aqueous solution) such
that the final pH of the solution is about 8.5. The neutralization is conducted in an ice
bath and care is taken to ensure that the temperature of the monomer solution does not
exceed 25 °C.
Separately, 6.65 g of 4-MASA is dissolved in 10.0 g of deionized water by
adjusting the pH of the water to about 12.5 with sodium hydroxide (50% aqueous
solution), and this solution is set aside.
An oil phase is prepared by heating (54-57 °C) 3.15 g of Span® 80, 1 -37 g
Tween® 61, 0.94 g of Tween® 65, and 2.89 g of oleic acid in 45.20 g of Escaid® 110
until the surfactants are dissolved.

The oil phase is charged to the reactor and the contents of the reactor are stirred at
1000 rpm. The aqueous monomer phase is then added to the reactor over two minutes
so that a water-in-oil emulsion is formed. The emulsion is purged with nitrogen and
heated to 45 °C. Polymerization is initiated by adding 0.0525 g of Vazo ® 64 and
0.0075 g of Vazo® 52. After fifteen minutes, the solution of 4-MASA is fed to the
reactor over sixty minutes. The polymerization is continued for a total of three hours
at 45 °C, and then for one hour at 55 °C. After this time, the emulsion is cooled to
room temperature. The polymer has a reduced specific viscosity of 31.0 dL/g
(measured as a 400 ppm solution in 2N sodium nitrate solution at 30 °C) and a
Brookfield viscosity of 4300 cps (#3 spindle at 12 rpm).
Example 8
Continuous Feed Polymerization (CFP) to produce a 3 mole percent 4-
methacrylamidosalicylic acid (4-MASA) / 97 mole percent sodium acrylate inverse
emulsion copolymer at higher polymer solids.
The reaction apparatus employed in this example is the same as that described
in Example 4. Acrylic acid (55.2 g) and 0.015 g of EDTA is dissolved in 66 g of
deionized water and neutralized with sodium hydroxide (50% aqueous solution) such
that the final pH of the solution is about 8.5. The neutralization is conducted in an ice
bath and care is taken to ensure that the temperature of the monomer solution does not
exceed 25 °C.
Separately, 5.79 g of 4-MASA is dissolved in 10.00 g of deionized water by
adjusting the pH of the water to about 12.5 with sodium hydroxide (50% aqueous
solution), and this solution is set aside.
An oil phase is prepared by heating (54-57 °C) 3.15 g of Span® 80, 1.37 g of
Tween® 61, 0.94 g of Tween® 65, and 2.89 g of oleic acid in 45.20 g Escaid® 110 until
the surfactants are dissolved.
The oil phase is charged to the reactor and the contents of the reactor are stirred
at 1000 rpm. The aqueous monomer phase is then added to the reactor over two
minutes so that a water in oil emulsion is formed. The emulsion is purged with
nitrogen and heated to 45 °C. Polymerization is initiated by adding 0.0525 g of Vazo®

64 and 0.0075 g of Vazo®52. After fifteen minutes, the solution of 4-MASA is fed to
the reactor over the course of sixty minutes. The polymerization is continued for a
total of three hours at 45 °C, and then for one hour at 55 °C. After this time, the
emulsion is cooled to room temperature and transferred to storage. The polymer has a
reduced specific viscosity of 36.7 dL/g (measured as a 400 ppm solution in 2N sodium
nitrate solution at 30 °C) and a Brookfield viscosity of 7300 cps (#3 spindle at 12 rpm).
The representative high molecular weight inverse emulsion polymers listed in
Table 1 are prepared according to the method of Examples 5-8. In Table 1, Na (or
NH4) AA = sodium or ammonium acrylate and Na 4-MASA = 4-
methacrylamidosalicylic acid, sodium salt.


Example 9
Preparation of a 6 mole percent O-acetyl-4-mcthacrylamidosalicylic acid (A-4-MASA)
/ 6 mole percent acrylic acid / 88 mole percent methyl acrylatc water continuous
emulsion polymerization.
The apparatus employed for carrying out this example comprised a 250 mL
reaction flask equipped with mechanical stirrer, reflux condenser, additional funnel,
syringe pump, nitrogen gas inlet/outlet tube and thermometer. The temperature is
controlled by using an acetone-dry ice bath.
Deionized water, 95.96 g, is charged to the reaction vessel, along with 0.9 g of
SAG2001 (Witco, Oai Specialties Group, Friendly,West Virginia), 6.6 g of 58%
Rhodapex® CO-436 (Rhone-Poulenc, Cranbury, New Jersey), 0.6 g of 70% IGEPAL-
CA-89 (Rhone-Poulenc, Cranbury, New Jersey), 0.6 g of Pluronic® F-68 (BASF,
Parsippany, New Jersey) and 0.03 g of EDTA, and the mixture is stirred until a clear
solution is obtained. Thereafter, a mixture of 21.31 g of methyl acrylate, 1.06 g of
acrylic acid, 0.047 g of formic acid and 7.84 g of A-4-MASA, (prepared according to
Example 3) is added in one portion. The system is cooled to 10 °C and then purged
with nitrogen thoroughly for 30 minutes. After this, 10.0 g of 0.0175% aqueous
solution of ferrous sulfate and 10.0 g of 0.0175% aqueous solution of tertiary butyl
hydroperoxide are introduced into the reaction mixture over one hour, during which
time the temperature of the polymerization is maintained between 10-14 °C. After the
addition of the initiator solutions is complete, the polymerization is allowed to
continue for another two hours. After this time, the temperature is raised to 25 °C and
the system is stirred for 30 minutes. The resulting latex is filtered through a sieve to
afford a milky white low viscosity product.
A polymer sample can be separated from the latex by precipitating a portion of
the latex in an acetone-water mixture. The polymer sample is washed with deionized
water and dried under vacuum at room temperature. Then, 0.6 g of the dried polymer,
4.0 g of NaOH (50 % aqueous solution) and 195.4 g of deionized water is stirred for 5
hours at 85 °C. The polymer has a RSV of 40.0 dL/g (measured under the conditions
described in the previous examples).

Example 10
Preparation of a 2 mole percent O-acetyl-4-methacrylamidosalicylic acid, phenyl ester
(A-4-MASAPE) / 1 mole percent acrylic acid / 97 mote percent methyl acrylate water
continuous emulsion polymer.
To a 0.25 L reaction flask equipped with mechanical stirrer, reflux condenser,
additional funnel, syringe pump, nitrogen gas inlet and outlet tube, and thermometer is
added 120.0 g of deionized water, 6.75 g of 58% Rhodapex® CO-436,0.75 g of 70%
IGEPAL-CA-89,0.75 g of Pluronic® F-68 and 0.03 g of EDTA and the mixture is
stirred until a clear solution is obtained. To the clear solution is added 0.9 g of SAG
2001, an antifoam, and nitrogen is purged through the solution for 15 minutes while
the solution is cooled to 10 ºC.
Methyl acrylate, 40 g, A-4-MASAPE (prepared according to Example 4) 3.27
g, acrylic acid 0.7 g and formic acid 0.0375 g are mixed in an addition funnel and
added to the emulsifier solution in the reactor and the nitrogen purge is continued for
additional 10 minutes.
Then, 7.64 g of 0.0175% aqueous solution of ferrous sulfate heptahydrate and
7.64 g of 0.0175% aqueous solution of tertiary butyl hydroperoxide are pumped in at a
rate so as to maintain a temperature of about 10-14 °C over one hour. After the
addition of the initiator solutions is complete, the polymerization is allowed to
continue for an additional two. hours. After this time, the temperature is raised to room
temperature and the system is stirred for 30 minutes. The resulting emulsion is filtered
through a sieve to afford a milky white low viscosity product.
The emulsion polymer is hydrolyzed in 1% caustic solution at 1% emulsion
concentration to determine the residual monomer by liquid chromatography (acrylic
acid) and the reduced specific viscosity.
The representative high molecular weight emulsion polymers listed in Table 2
are prepared according to the method of Examples 9 and 10. In Table 2, MA = methyl
acrylate, AA = acrylic acid and 4-MASA = 4-methacrylamidosalicylic acid.


Example 11
Preparation of N-acrylamido-4-aminosalicylic acid sodium salt.
In a reactor fitted with an addition funnel fitted with a drying tube, mechanical
stirrer and a condenser are placed 4-amino salicylic acid sodium salt (21 g, 1.2 eq) and
deionized water (400 g). This mixture is cooled to 10 °C and the pH is adjusted to
about 12 by adding aqueous sodium hydroxide. A mixture of chloroform (200 mL)
and acryloyl chloride (Aldrich, 9 g, 1 eq) are added dropwise via the addition funnel
over a period of 15 minutes while vigorously stirring the sodium amino salicylate/
water mixture. The temperature of the-reaction mixture is maintained at 10 ºC using an
ice-bath. After two hours, the chloroform layer is separated. NMR studies indicate the
aqueous phase contains N-acrytoyl-4-amino salicylic acid as the major component.
The aqueous phase is then neutralized with acetic acid to pH 8 and tbe resulting
precipitate is filtered, air-dried to constant weight (19.0 g) and used in the
polymerization with sodium acrylate without further purification.
Example 12
Preparation of sodium acrylate/sodium N-acrylamido-4-aminosalicylate (93.7 mole
%) copolymer inverse emulsion.
A mixture of acrylic acid (80.9 g) and deionized water (114 g) in a 500 mL
beaker equipped with a magnetic stirrer is cooled to 7-10 ºC and a 50% solution of

sodium hydroxide in water (92 g) is added dropwise over 30 minutes while
maintaining the reaction mixture temperature below 15 ºC. After the addition of
sodium hydroxide, powdered N-acryloyl-4-amino salicylic acid (19 g, prepared as
described in Example 11) is added and the mixture is stirred to form a homogenous
solution.
In a polymerization reactor fitted with nitrogen inlet, condenser, mechanical
stirrer and addition funnel is placed a mixture of Escaid® 110 (130 g), Ethomeen® T12
(9.24 g, Akzo America, Inc., Dobbs Ferry, NY) and Brij® (ICI) 93 (4 g). The contents
of the beaker from the previous step is added to this mixture. The beaker is then
washed with deionized water (50 mL) and the washings are added to the reactor. The
reaction mixture is stirred at 1000 rpra and heated to 38 °C. After stirring for 30
minutes at 38 °C, the reaction temperature is increased to 45 °C. A mixture of Vazo*
64 (0.2 g) and Vazo® 52 (0.05 g) is added and the nitrogen purge started. The reaction
mixture is kept at 45 ºC for 7 hours and then at 60 "C for one hour. The reactor is then
cooled and the product transferred to a container. The product has a RSV of 17.2 dl/g
(400 ppm solution in 2N NaNO3).
Example 13
Preparation of a 6 mole percent 4-methacrylamidosalicylic acid (4-MASA) / 6 mole
percent 2-acrylamido-2-methyl-l-propanesulfonic acid sodium salt (AMPS)/ 88 mole
percent sodium acrylate inverse emulsion copolymer by batch polymerization.
A 1500 mL reaction flask equipped with a mechanical stirrer, reflux condenser,
dropping funnel, gas inlet tube, and a thermometer is charged with 250.0 g of
deionized water, 204.8 g of acrylic acid, and 76.6 g of AMPS (58 % aqueous solution).
The solution is neutralized with sodium hydroxide (50% aqueous solution), to a pH of
7.0 and 51.6 g of 4-MASA (83.1%) is added to the reaction mixture. The
neutralization was then continued until the solution has a pH of 8.5. The temperature
is maintained below about 25 °C using an ice bath during the course of the
neutralization. To the resulting neutralized solution is added 0.12 g of
ethylenediaminetetraacetic acid, tetrasodium salt (EDTA, Aldrich).
An oil phase is prepared by heating a mixture of 235.0 g of a paraffinic solvent
(Escaid® 110, Exxon, Houston, TX), 20.0 g of a sorbitan monooleate (Span® 80, ICI

Americas, Wilmington, DE), and 11.7 g of a polyoxyethylene sorbitan monostereate
(Tween® 61, ICI) until the surfactants are dissolved (45-47 ºC). The oil phase is
transferred into the reactor described above and heated to 45 °C.
With stirring at 1000 rpm, the aqueous monomer phase is added over two
minutes. The resulting water in oil emulsion is stirred for thirty minutes. After this
time, 0.68 g of Vazo® 64 and 0.03 g of Vazo® 52 is added to the water in oil emulsion.
The polymerization is carried out under a nitrogen atmosphere at 45 °C for 5 hours,
then at 58 °C for one hour. The finished emulsion product is cooled to 25 °C. The
polymer has a reduced specific viscosity of 22.9 dL/g (measured as a 400 ppm solution
in 2N sodium nitrate solution at 30 °C).
Example 14
Preparation of a 6 mole percent 4-methacrylamidosalicylic acid (4-MASA) / 6 mole
percent acrylamide / 88 mole percent sodium acrylate inverse emulsion copolymer by
batch polymerization.
A 1500 mL reaction flask equipped with a mechanical stirrer, reflux condenser,
dropping funnel, gas inlet tube, and a thermometer is charged with 283.2 g of
deionized water, 32.8 g of acrylamide (47.6% aqueous solution), and 232 g of acrylic
acid. The solution is neutralized with sodium hydroxide (50% aqueous solution), to a
pH of 7.0 and 57.0 g of 4-MASA (85.2%) is added to the reaction mixture. The
neutralization was then continued until the solution has a pH of 8.5. The temperature
is maintained below about 25 °C using an ice bath during the course of the
neutralization. To the resulting neutralized solution is added 0.12 g of
ethylenediaminetetraacetic acid, tetrasodium salt (EDTA, Aldrich).
An oil phase is prepared by heating a mixture of 237.9 g of a paraffinic solvent
(Escaid® 110, Exxon, Houston, TX), 19.3 g of a sorbitan monooleate (Span® 80, ICI
Americas, Wilmington, DE), and 11.3 g of a polyoxyethylene sorbitan monostereate
(Tween® 61, ICI) until the surfactants are dissolved (45-47 °C). The oil phase is
transferred into the reactor described above and heated to 45 °C.
With stirring at 1000 rpm, the aqueous monomer phase is added over two
minutes. The resulting water in oil emulsion is stirred for thirty minutes. After this
time, 0.49 g of Vazo® 64 and 0.071 g of Vazo® 52 is added to the water in oil

emulsion. The polymerization is carried out under a nitrogen atmosphere at 45 °C for
5 hours, then at 58 °C for one hour. The finished emulsion product is cooled to 25 ºC.
The polymer has a reduced specific viscosity of 23.1 dL/g (measured as a 400 ppm
solution in 2N sodium nitrate solution at 30 °C) and a Brookfield viscosity of 900 cps
(#3 spindle at 12 rpm).
Representative high molecular weight inverse emulsion polymers prepared
according to the method of Examples 13 and 14 are listed in Table 3. In Table 3, Na or
(NH4) AA = sodium or ammonium acrylate, 4-MASA = 4-methacrylamidosalicylic
acid sodium salt, NaAMPS = 2-acrylamido-2-methylpropanesulfonate sodium salt, and
AcAm = acrylamide.

Example 15
Hydrolysis of 96/1/3 poly(methyl acrylate/acrylic acid/4-methacrylamidosalicylic acid)
emulsion polymer.
Activity tests reported herein are performed using the poly (sodium
acrylate/sodium

4-methacrylamidosalicylic acid) resulting from hydrolysis of the polymers prepared
above and shown in Table 2. Hydrolysis is effected using 1% of the emulsion in 1%
NaOH at 85°C for 20 minutes.
The rate at which the poly(methyl acrylate/acrylic acid/4-
methacrylamidosalicylic acid) polymers are hydrolyzed can be controlled by the
caustic soda concentration and by the reaction temperature. As hydrolysis occurs, the
polymers become more water soluble. For example, the percent hydrolysis of Polymer
2 at 1% of the emulsion in 1% NaOH at 85°C for 15, 30,45 60 90 and 120 minutes is
measured and summarized in Table 4. Colloid titration is used to determine the
anionic charge and the degree of hydrolysis.

Example 16
Settling and Clarity Performance of Representative Salicylic Acid Containing
Flocculants versus Conventional Polymer Treatments
The settling and clarity performance of representative salicylic acid containing
polymers of this invention is compared to conventional polymer treatments. The
results are summarized in Tables 5-24. The data summarized in Tables 5-24 are
obtained as described below.
The following general test procedure is utilized to obtain settling rate
information. A well mixed sample of settler feed slurry (red mud obtained from a
mineral processing facility) is portioned out into eighteen to twenty 1000-mL
Nalgene® graduated cylinders by filling all the cylinders to the 500-mL graduation.
The remaining 500-mL is then added to the cylinders in the opposite order. These

cylinders are immediately placed in a clear-sided glass or plastic hot water bath
maintained to 98-100°C. An alternative method involved performing the tests on a
smaller scale using 0.1 or 0.25 L cylinders.
Cylinders containing the feed slurry are allowed to equilibrate to the bath
temperature over a 20-30 min period.
While remaining in the water bath, the cylinder is immediately mixed by two
plunges. The plunger is a 1/8" metal rod with a #10 rubber stopper attached to the
bottom end. The plunger is allowed to fall freely on the downward stroke aad lifted at
the same speed on the upward stroke. To test a polymer, that polymer is added to the
1000 mL graduated cylinder and mixed with a constant number of plunges (typically
four or six).
To determine settling rate, the time for the solid/liquid interface to travel
between the 900 and 700 mL marks on the cylinder is recorded. After measuring the
distance between the two marks, the settling rate can be calculated in (ft/hr) or (m/hr)
units.
Based on this information, a replacement ratio (RR) may be calculated by
plotting a graph with settling rate on the Y-axis and dose on the X-axis for each
product tested. The dosage required to produce the desired plant settling rate is
determined from the above graph. The replacement ratio is the dose of new polymer
divided by the dose of conventional treatment needed to obtain the plant settling rate.
If the RR value is below one, the experimental polymer is superior, if it is one, it is
equivalent, and if it is above one it is poorer in activity relative to the conventional
treatment polymer.
For all settling test, the Conventional Treatment Polymer A (CTP A. a co-
polymer of methyl acrylate/acrylic acid, available from Nalco Chemical Company.
Naperville, IL) is hydrolyzed as 1% emulsion in a 10 g/L NaOH solution at 80-85 C
for the optimum period of time (typically, 20-30 min) then diluted in de-ionized water
to 0.1-0.2 weight percent (based on emulsion). Representative emulsion pohymers 1-4
are hydrolyzed at 80-85°C in a 10 g/L NaOH solution at 1.0-1.5 % for 30 minutes then
further diluted, with de-ionized water to 0.2 weight percent (based on emulsion). The
Conventional Treatment Polymer B (CTP B, poly(ammonium acrylate), available from
Nalco Chemical Company, Naperville, IL) is inverted as a 1% emulsion in a 10 gL

NaOH solution, then diluted, with de-ionized water to 0.05-0.1 weight percent (based
on emulsion). Representative inverse emulsion polymers 5-18 are inverted as a 1.0 or
a 2.0 % emulsion in a 10 g/L NaOH solution, then diluted, with de-ionized water to
0.1-0.2 weight percent (based on emulsion).
The clarity of the settler overflow is determined in a sample of the liquor taken
from the top of the 1000 mL graduated cylinder after a specific time after settling,
(e.g., typically 10 min, or 30 min). The overflow solids may be determined
gravimetrically by filtering a specific volume of liquor, washing the solids with hot
water and drying the solids in an oven at 100 °C for 2-4 hours. Alternatively, the
turbidity of the overflow liquor is considered to be an indirect measure of the overflow
solids. The turbidity (as NTU) is determined using a Hach Co. turbidimeter. If the
turbidity of the overflow sample is over the range of the meter, then all the samples
may be diluted to a specific volume using a hot 30 wt. % NaOH solution (e.g., 5 mL of
overflow combined with 10 mL of 30 wt % NaOH solution).
A clarity ratio is evaluated as a measure of the performance of the new polymer
compared to conventional polymers. This is determined as the ratio of the overflow
turbidity (or residual solids) using the new polymer divided by the turbidity (or
residual solids) of the overflow for the conventional fJocculant at the same specific
settling rate (i.e., the plant settling rate).
Laboratory settling tests are performed at 95-100 °C on a variety of red mud
slurries using the standard method described above. An aliquot (100 mL) of liquor is
removed via syringe from the top of the cylinder after a specific time after settling,
(e.g., typically 10 min, or 30 min). The filtration rate of this aliquot through a pre-
weighed filter paper is measured in seconds. A vacuum pump with a control gauge is
used to maintain a constant vacuum for/during all tests. The timer is started
immediately upon pouring the liquor on the filter paper, and then stopped at the first
sign of dry surfaces on the filter. The overflow clarity of the aliquot is also determined
gravimetrically (mg/L) after washing and drying the filter paper. To assess clarity and
filtration times appropriate doses of each floccuiant are used such that approximately
the same settling rates for all cylinders is obtained.
Filtration times can be effectively compared for different polymers which
produce approximately the same settling rate. A shorter filtration time value mease,

that the flocculant is aiding filtration more efficiently. Residual flocculant (both
synthetic and natural red mud flocculants) in the supernatant liquor have been shown
to severely reduce filtration rate in the secondary clarification stage.
A filtration ratio is determined by dividing the filtration time of the
experimental polymer by the filtration time of the CTP.
Tests are performed on a variety of red mud slurries using different Jamaican
bauxite ores. The results of the foregoing tests for representative polymers of this
invention are shown in Tables 5-24, below.
In Tables 5-24, Mud Slurries A-K are red mud slurries prepared from the low
temperature digestion of a Jamaican bauxite having the following total soda and solids
content.
Mud Slurry A: total soda = 245 g/L as Na2CO3 and 45.7 g/L solids;
Mud Slurry B: total soda = 270 g/L as Na2CO3 and 56.8 g/L solids;
Mud Slurry C: total soda = 235 g/L as Na2CO3 and 52.4 g/L solids;
Mud Slurry D: total soda = 305 g/L as Na2CO3 a*d 32.9 g/L solids;
Mud Slurry E: total soda = 248 g/L as Na2CO3 and 28.5 g/L solids;
Mud Slurry F: total soda = 300 g/L as Na2CO3 and 39.5 g/L solids;
Mud Slurry G: total soda = 304 g/L as Na2CO3 and 33.6 g/L solids;
Mud slurry H: total soda = 240 ± 10 g/L as Na2CO3 and 40.7 g/L solids;
Mud slurry J: total soda = 240 ± 10 g/L as Na2CO3 and 51.6 g/L solids;
Mud slurry K: total soda = 240 ± 10 g/L as Na2CO3 and 42.8 g/L solids;
Mud slurry L is a typical Bayer red mud slurry collected at a refinery with soda
= 232 g/L as Na2CO3 and 77.8 g/L solids.


As shown in Table 5, representative salicylic acid containing emulsion
polymers give comparable settling rates to those of the conventional treatment, as
evidenced by a replacement ratio of about 1.6 to 2.4 (based on polymer actives).

The relative performance of the polymers of this invention compared to CTP A
is shown in Table 6.
Table 6
Average Settling, Clarity and Filtration Performance of Representative Salicylic Acid
Containing Flocculants versus Conventional Treatment Polymer A (CTP A)

As shown in Table 6, the polymers of this invention afford a 25 - 55 %
improvement in the overflow clarity as evidenced by clarity ratios of about 0.75 to
0.45 respectively. The polymers also improve the fiiterability of the overflow liquor
by about 10 to 35%.










As shown in Tables 7-11, representative salicylic acid containing polymers
give good settling rate results relative to a conventional treatment, as evidenced by
replacement ratios (based on polymer actives) generally of about 1.6 to 5. In some
cases, the replacement ratio is higher than 4, for example from about 5 to 9. This can
be explained in part by the significantly lower RSV for the new polymer relative to the
conventional treatment polymer. In general, the replacement ratios for the inverse
emulsion polymers of this invention are higher than those of the emulsion polymers of
this invention, because on average they have lower polymer RSV.
The new inverse emulsion polymers afford significant improvements from
about 10 to 75 % in the overflow clarity relative to the conventional treatments as
evidenced by clarity ratios of about 0.75 to 0.25, respectively. The improvement in
overflow clarity is affected by the mole ratio of salicylic acid goups present in the
polymer, for example compare the results in Table 9, above. Increasing the amount of
salicylic acid groups in the copolymer increased the clarification performance of the
resulting polymer relative to the poly(acrylic acid) homopolymer.

The polymers of this invention also improve the filterability of the overflow
liquor by about 10 to 35 %. Filterability data for a representative polymer is shown in
Table 12.
Table 12
Filterability Data for a Representative Salicylic Acid Containing Polymer Flocculant
versus Conventional Treatment Polymer B

Statistical analysis of the foregoing data shows (at a 95 % confidence level): a
38% decrease in the overflow turbidity; a 42% decrease in overflow solids; and a 6%
faster filtration time for polymer 14 vs. CTP B.
Settling and clarity performance of representative polymers of this invention in
combination with conventional treatment polymers is shown in Tables 13 - 15.




As shown in Tables 13 and 14, when a salicylic acid containing polymer with
RSV of 14-21 dL/g is applied first to the mud slurry followed by the addition of a
small amount of a high molecular weight poly(methyl acrylate/acrylic acid) or
poly(ammonium acrylate) polymer having a RSV of > 31-49 dL/g, overflow clarities
can be improved by 40 to 70% over the conventional treatment alone. Furthermore,

adding the low molecular weight polymer before the high molecular weight polymer is
more effective at reducing the amount of residual overflow solids during clarification
of the feed solids than multiple additions of a pre-blended mixture of the two
polymers.
Table 15
Average Settling, Clarity, and Filtration Rate Performance of Representative Salicylic
Acid Containing Polymers versus Conventional Treatment Polymer A

As shown in Table 15, improved clarity is also obtained using combinations of
the low and high molecular weight polymers containing pendant salicylic acid groups.
Tests with addition of only the low molecular weight polymers of this invention (i.e.,
RSV ft/hr.
Table 14 further shows that upon comparison to conventional treatment
Polymer B, the polymers of this invention improve filtration rates on average. Better
clarity, lower NTU or lower suspended solids are preferred as the resulting liquor will
effectively allow a refinery to filter a larger amount of liquor before regenerating the
filter aid.
As a note, in the absence of any polymer treatment, mud settling rates would be
less than 1 ft/hr and clarity would be >4000 NTU for reference to Tables 3 to 13.
The polymers of this invention, alone and in combination with starch and/or
dextran effectively clarify Bayer process red mud thickener feed. The data is shown in

Table 16. The data shows a marked reduction in residual overflow solids and
improved filtration rate relative to a conventional polymer treatment.
Table 16
Settling and Clarity Performance of Representative Salicylic Acid Containing
Polymers versus Conventional Treatment Polymer B on Bayer Process Red Mud
Thickener Feed

The polymers of this invention are also effective in removing precipitated
alumina (bright hydrate) solids from Bayer process liquors. The data for a
representative poly(sodium acrylate /sodium 4-methacrylamidosalicylic acid)polymer
of this invention is shown in Tables 17 and 18. In Tables 17 and 18, CTP C is dextran.


As shown in Table 17, the polymers of this invention provide about 40-55
percent lower overflow solids in the liquor compared to the conventional treatment
program.
Table 18
Settling and Clarity Performance of Representative Salicylic Acid Containing
Polymers versus Conventional Treatment Polymer C in Bayer Process Secondary
Hydrate Thickeners

As shown in Table 18, the polymers of this invention provide overflow clarities
similar to the conventional treatment program and significantly improved underflow
densities.




As shown in Tables 19-22, representative salicylic acid containing terpolymers
demonstrate good settling rate results relative to conventional treatment at NaAMPS
levels less than or equal to 15 %. At NaAMPS levels above 15 % settling rates
decrease markedly, however clarity ratios exhibit a 40 % increase. The new polymers
afford a slightly better than 50 % increase in solution clarities as evidenced by the
clarity ratios. Again clarity performance is influenced by the amount of salicylic acid
incorporated into the polymer. For example compare the results of polymer 21 and 22.


As shown in Tables 23 and 24, representative salicylic acid containing
polymers incorporating acrylamide gave good settling rate results relative to
conventional treatment, as evidenced by replacement ratios (based on polymer actives)
generally 2.9 to 5.

The new inverse emulsion polymers afford significant improvements in the
overflow clarity of about 5 to 60 % relative to the conventional treatment as evidenced
by clarity ratios of 0.96 to 0.38, respectively. The improvement in overflow clarity is
affected by the mole ratio of salicylic acid groups m the polymer, for example compare
polymers 26 and 27 in Table 24 above. Increasing the amount of salicylic acid in the
copolymer increases the clarification performance of the resulting polymer relative to
conventional treatment polymer B.



As shown in Table 25, the salicylic acid containing flocculants of this invention
can be used alone or in combination with a traditional acrylate and or
acrylate/acrylamide polymer without the need for starch.
It is understood that mixtures of polymers of this invention, or mixtures of one
or more polymers of this invention with conventional treatment polymer(s) (for
example, polysaccharides, acrylate homopolymers, copolymers and or terpolymers
with acrylamide, hydroxamic acid groups, AMPS, etc ) or reagents are contemplated as
falling within the scope of this invention.
Changes can be made in the composition, operation and arrangement of the
method of the present invention described herein without departing from the concept
and scope of the invention as defined in the following claims:

We claim
1. A polymer comprising pendent salicylic acid groups and having a weight average
molecular weight of at east 2,000,000 daltons, wherein said polymer is prepared
by free radical polymerization of one or more salicylic acid containing monomers,
one or more acrylate monomers selected from the group consisting of
(meth)acrylic acid and salts thereof and one or more polymerizable anionic
monomers, characterized in that said polymer is selected from the group
consisting of emulsion polymers and inverse emulsion polymers and comprises 50
to 98 mole percent sodium or ammonium acrylate, 1 to 20 mole percent 4-
methacrylamidosalicylic acid or a salt thereof, 4-methacrylamidosalicylic acid
phenyl ester or a salt thereof, O-acetyl-4-methacrylamidosalicylic acid or a salt
thereof or O-acetyl-4-methacrylamidosalicylic acid phenyl ester and 1 to 30 mole
percent 2-acrylamido-2-methyl propanesulfonic acid or a salt thereof.
2. A method of flocculating suspended solids in a Bayer process liquor comprising
adding to the liquor an effective amount of one or more polymers according to
claim 1 comprising pendant salicylic acid groups.
3. The method of claim 2 characterized by further comprising hydrolyzing the
polymer comprising pendant salicylic acid groups prior to addition to the Bayer
process liquor and adding one or more anionic or nonionic flocculant(s) to the
process stream, wherein the nonionic flocculant is starch, dextran or flour.
4. The method of claim 3 characterized in that the anionic flocculant comprises
poly(meth)acrylic acid or poly(meth) acrylates.
5. The method of claim 4 characterized in that the poly(meth)acrylic acid or
poly(meth)acrylate is selected from the group consisting of poly(meth)acrylic
acid, poly(meth)acrylic acid containing pendant hydroxamic acid groups.

poly(alkyl(meth)acrylate), (meth)acrylic acid/alkyl(meth)acrylate copolymers,
(meth)acrylic acid/acrylamide copolymers, (meth)acrylic acid/acrylamide
copolymers containing pendant hydroxamic acid groups, (meth)acrylic acid/
acrylamide/alkyl (meth)acrylate terpolymers. and (meth)acrylic acid/acrylamide/
AMPS terpolymers.
6. The method of claim 3, 4 or 5 characterized in that the anionic flocculant is added
prior to or after the polymer comprising pendant salicylic acid groups.
7. The method of claim 3, 4 or 5 characterized in that the anionic flocculant is added
together with the polymer comprising pendant salicylic acid groups.
8. The method of any one of claims 4 to 7 wherein the polymer comprising pendant
salicylic acid groups has an RSV of at least 14 dUg and the anionic flocculant has
an RSV of at least 21 dUg.
9. The method of any one of claims 2 to 8 characterized in that the Bayer process
liquor is selected from settler feed, settler overflow, digestion blow-off, mud
washer in the washer train, feed to the primary polishing filters, feed to a mud
settler, feed to the primary alumina crystallization tanks, feed to the secondary
and tertiary alumina classifiers or trays, feed to hydrate filters or feed to a
centrifuge.

A polymer comprising pendant salicylic acid groups and having a weight average
molecular weight or at least 2,000.000 daltons, wherein said polymer is prepared
by free radical polymerization of one or more salicylic acid containing monomers,
one or more acrylate monomers selected from the group consisting of
(meth)acrylic acid and salts thereof and one or more polymerizable anionic
monomers, characterized in that said polymer is selected from the group
consisting of emulsion polymers and inverse emulsion polymers and comprises 50
to 98 mole percent sodium or ammonium acrylate, 1 to 20 mole percent 4-
methacrylamidosalicylic acid or a salt thereof, 4-methacrylamidosalicylic acid
phenyl ester or a salt thereof, O-acetyl-4-methacrylamidosalicylic acid or a salt
thereof or O-acetyl-4-methacrylamidosalicylic acid phenyl ester and 1-30 mole
percent 2-acrylamido-2-methyl propanesulfonic acid or a salt thereof.

Documents:

1526-KOLNP-2005-FORM-27.pdf

1526-kolnp-2005-granted-abstract.pdf

1526-kolnp-2005-granted-claims.pdf

1526-kolnp-2005-granted-correspondence.pdf

1526-kolnp-2005-granted-description (complete).pdf

1526-kolnp-2005-granted-examination report.pdf

1526-kolnp-2005-granted-form 1.pdf

1526-kolnp-2005-granted-form 18.pdf

1526-kolnp-2005-granted-form 2.pdf

1526-kolnp-2005-granted-form 26.pdf

1526-kolnp-2005-granted-form 3.pdf

1526-kolnp-2005-granted-form 5.pdf

1526-kolnp-2005-granted-reply to examination report.pdf

1526-kolnp-2005-granted-specification.pdf


Patent Number 226737
Indian Patent Application Number 1526/KOLNP/2005
PG Journal Number 52/2008
Publication Date 26-Dec-2008
Grant Date 24-Dec-2008
Date of Filing 03-Aug-2005
Name of Patentee NALCO COMPANY
Applicant Address 1601 W. DIEHL ROAD, NAPERVILLE. IL
Inventors:
# Inventor's Name Inventor's Address
1 MURAT ZUADIR 113 SPRUCE MILL LANE, SCOTCH PLAINS, NEW JERSEY 07076
2 EVERETT C. PHILLIPS 1201 N. BRANDYWINE CIRCLE BATAVIA, LLLINOIS 60510
3 JARRY E. BRAMMER, JR. 1110 WINDEMERE LANE, AURORA, LLLINOIS 60504
4 ROBERT P MAHONEY 2 AUSTIN LANE, NEWBURY, MASSACHUSETTS 01922
5 JOHN D KILDEA 40 WATERSON DRIVE, MANDURAH, W.A.
6 MANIAN RAMESH 5 LITTLE BEND ROAD, BARRINGTON HILLS, LLLINOIS 60010
7 JOHN T MALITO 241 ISLEVIEW DRIVE, OSWEGO, LLLINOIS 60532
PCT International Classification Number C08G
PCT International Application Number PCT/US2004/004004
PCT International Filing date 2004-02-11
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/373,132 2003-02-24 U.S.A.