Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
llU7414
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This application is related to copending Canadian
application Serial No. 302,158, filed April 27, 1978.
The invention relates to an improved process for clarify-
ing waste waters arising from washing coal. More particularly, this
process relates to such a process in which there is used as clarify-
ing agent a polyacrylamide of certain molecular weight range chemical-
ly modified to provide quaternized dimethylaminomethyl groups on the
amide groups.
Recent developments in the field of water-soluble polymers
have led to materials that are effective in water treatment to
i remove undesirable materials suspended therein. The separation of
suspended particles from aqueous suspensions thereof is generally
referred to as "flocculation". Such general term can include a wide
range of aqueous systems varying from a minor amount of inorganic
solids in aqueous suspension, such as raw water, to high concentrations
of organic wastes, such as sewage sludges. Because of this widely
diverse nature of the solids-water systems, the agents provided for
such utility are generally provided in a form that offers versatile
performance, i.e. suitable for use with a wide variety of solids-
water systems.
For certain solids-water systems, such as raw waters,
these polymeric agents are used to clarify the water by removal of
inorganic solids suspended therein. For other solids-water systems,
such as sewage sludges, the polymeric agents are used primarily to
dewater the sludge so that the solids may be readily disposed of
without prohibitive amounts of water being associated therewith.
These distinct applications of the polymeric agents give rise to
different requirements as to the nature of the agents employed.
One prior art teaching with respect to certain prior
art flocculants is that, in general, increased effectiveness
arises with increased molecular weight of the
-- 1 --
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1~074~
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26,712 polymeric agent employed, see U. S. Patent 3,738,945 for
example. Another prior art teaching with respect to another
type of prior art flocculants is that there is a certain
high molecular weight value at which maximum effectiveness
; 5 occurs and above which effectiveness remains essentially
unchanged, see U. S. Patent 3,897,333 for example. Accord-
ingly, one seeking an effective flocculant for the various
solids-water systems contemplated by such application of
polymeric agents would provide such agent in high molecular
weight range.
Typically, polymeric agents that are used in
flocculation applications have molecular weights in excess
of about 200,000, usually in the range of about 500,000 to
several million, and in difficult solids-water systems,
such as sewage sludges, frequently higher, depending upon
the chemical nature of the polymeric agent. Most products
that have been available for commercial use have been in
the high molecular weight range so as to provide versatile
utility in the wide variety of applications in which they
are useful. Although the commercial products possess some
degree of versatility as to usage, they do not necessarily
provide the optimum performance in any given application.
Certain polymeric flocculants can be made airectly
from suitable reactants, such as reaction products of epi-
chlorohydrin and dimethylamine or free-radical polymerization
products of such monomers as diallyldimethylammonium chloride.
Other polymeric flocculants may be made by preparing a
polymer from a reactive monomer not containing certain desired
functionalities and subsequently modifying the pre-formed
polymer to provide the functionalities desired. In this
procedure the functionality of the pre-formed polymer can
2 --
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~ 1107414
26,712 be varied in a number of respects but the degree of poly-
merization as it affects molecular weight of the modified
; polymer is determined by the polymer pre-formed.
Acrylamide is a highly reactive monomer that is
~ 5 widely used to provide pre-formed polymers that can be
;~ readily modified chemically to provide alternative or
additional functionality for specific end-uses. Thus,
acrylamide polymers may be controllably hydrolyzed to
provide acrylic acid functions on the polymer structure
and provide an anionic polymer. Alternatively, formaldehyde
and dimethylamine can be reacted with the amide groups of
.. ~ ; ,
the polymer to provide substituent dimethylamlnomethyl
functionality thereon and provide a cationic polymer. Be-
cause of the high reactivity of acrylamide monomer, however,
; ~ 15 the pre-formed polyacrylamide used for subsequent chemical
modification is usually in the molecular weight range of
about 200,000 to 5,000,000, since such is the degree of
~ polymerization normally obtained. To obtain polyacrylamide
; of molecular weights outside this range, special preparative
2~0 procedures are necessary. For higher molecular weight poly-
acrylamides, for example, highly purified monomer is required.
Although procedures for obtaining lower molecular weight
polyacrylamides are available, use of such techniques is not
generally considered with respect to flocculation applications
because of the preference for high molecular weight polymers.
The intrinsic viscosity of a polymer is obtained
; by measuring the viscosity of varying concentrations of
the polymer in a specific solvent and extrapolating to a
value at zero concentration, which is the value designated
as "intrinsic viscosity". The viscosity is the resistance
of liquid forms of the polymer to f~ow and is a characteristic
-- 3 --
1107414
; 26,712 property measuring the combined effects of adhesion and co-
hesion. From the intrinsic viscosity can be calculated the
molecular weight of a polymer by use of appropriate equations.
As is apparent, the intrinsic viscosity molecular weight re-
lationship of one polymer type will differ from that of ano-
ther polymer type. Accordingly, the intrinsic viscosity of a
polyacrylamide of a specific degree of polymerization will
differ from that of a chemically-modified polyacrylamide of
the same degree of polymeriæation. The fact remains, however,
that as the molecular weight or the degree of polymerization of
a polymer increases, the intrinsic viscosity thereof also in-
creases in any particular series.
A quaternized dimethylaminomethyl-polyacrylamide
has been previously disclosed for the treatment of sewage
sludges, see U. S. Patent 3,897,333. The useful polymer
disclosed is one stated to have an intrin~ic viscosity of
at least O.S deciliters per gram and the examples used to
illu~trate the invention employ polymers having intrinsic
viscosities of 1.0 and 2.5 deciliters per gram. For a
quaternized dimethylaminomethyl-polyacrylamide containing
at least 50 mol percent of such quaternized groups to have
an intrinsic viscosity of at least 0.5 deciliters per gram,
; ~ the pre-formed polyacrylamide must have a molecular weight
of about 130,000 as a minimum and to conform to exemplified
species must have a molecular weight of about 350,000 to
1,500,000. The degree of polymerization for such polymers
would be at least 1,800 and, as ~xemplified, from about
5,000 to 20,000. At this range of degrees of polymerization,
the polymers of the reference are said to exhibit equivalent
performance in dewatering of sewage sludges, regardless of
the actual degree of polymerization in such range. Absent
any further teaching by the reference, one would be led to
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26,712 believe that the same range of intrinsic viscosities would
be the most effective range for other flocculation applica-
tions.
In accordance with the present invention, th~re
is provided a process for settling suspended solids in coal
washing waste water which comprises mixing with said water
an effective amount of a polymer consisting essentially of
repeating units of the structure
1 2 ~ ~ ; H2 l3 ~ t
C~3 x Y n
wherein A~ is an anion, R is alkyl of 1-3 carbons or hydroxy-
alkyl of 2-3 carbons, x is a mol fraction of at least about
50 percent, y is a mol fraction of up to about 50 percent and
represents unmodified acrylamide units, and n is an integer
in the range of about 100 to about 1,600 to provide the
chemically-modified polyacrylamide with an intrinsic viscos-
ity in the range of about 1.0 to 0.45 deciliters per gram
when measured in 3M NaCl at 30C. and thereafter settling
the solids to provide a clarified supernatant liqui.d.
.. ... . . _ . . ,
The process provides an improved process for
clarifying coal washing waste waters which offers the
following advantages:
1. The polymers used in the proce~s of the
present invention develop maximum effectiveness in coal
washing waste waters at low molecular weight, thus elimina-
ting disadvantages associated with pro~iding high molecular
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26,712 weight polymers.
2. Because preparation of low molecular weight
polymers takes less time than does preparation of high
molecular weight polymers, greater productivity is obtained
for a reactor of given capacity in a specified time period.
3. Because low molecular weight polymers provide
low solution viscosity, chemical modification can be achieved
at higher polymer concentrations than in the case of high
molecular weight polymers.
4. Because chemical modification can be achieved
at high polymer concentration, chemical modification is
more readily and completely effected.
5. Because the polymer used in the process of
, the present invention is provided at high polymer concentra-
tion, shipping cost per unit weight of polymer are reduced.
6. The low molecular weight polymers of the
present inventlon provide small absorbent flocs which can
absorb additional suspended solids of the coal washing waste
water and provide greater clarification than do high molecular
.:
~20 weight polymers which provide large non-absorbent flocs.
7. The polymers used in the process of the present
~ invention offer cost-performance advantages over other
; polymeric flocculants because of their processing advantages.
,.~
;'~;; In order to prepare polymers for use in the process
~ 25 of the present invention, it is first necessary to prepare
;~,
a low molecular weight polyacrylamide in a~ueous solution.
By "polyacrylamide" is meant a polymer which consists
essentially of repeating units of acrylamide. Although it
- is generally preferred to provide a homopolymer of acrylamide
for optimum results in use, it is also possible to replace
part of the acrylamide units with another monomer in amounts
- 6 -
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26,712 which do not interfere with the advantageous performance of
the polymer in coal washing waste water cl~rification.
Other monomers that may replace part of the acrylamide
monomer include acrylonitrile, methyl methacrylate, styrene,
diallyldimethylammonium chloride, methacrylamide, N,N-di-
methylacrylamide, and acrylic acid. If an acidic monomer
is used, it should constitute less than 10 mol percent of
,, .
the polymer. It is generally preferable to introduce a
high degree of chemical modification in the polyacrylamide
and, therefore, the amount of comonomer should be minimized
in order to achieve such preference. The polyacrylamide,
accordingly, will consist essentially of at least 50 mol
percent of acrylamide groups that have been chemically
modified to provide quaternized dimethylaminomethyl groups
lS thereon and, preferably, the balance of unmodified acrylamide
groups or of comonomer units that do not adversely affect
the performance of the polymer in the clarification of coal
washing waste waters. Both unmodified acrylamide units and
.
;l units derived from another comonomer may be present with
the required content of quaternized dimethylaminomethyl
acrylamide groups.
In preparing the polyacrylamide, an aqueous ~olution
of about 10 to 50, preferably!15 to 30, more preferably 20
to 25 weight percent of acrylamide or monomer mixture, i8
employed. A number of techniques are known which can be
employed to provide the desired low molecular weight polymer.
Use of initiator contents of at least about 0.1 weight
; percent are effective. The use of high reaction temperatures
such as at least 50C., preferably about 70C. to 100C., is
also effective u~ing the initiator concentration stated. A
chain transfer agent, such as isopropanol, is also effective
but is not necessary. The instances wherein an impurity,
-- 7
11~7414
26,712 such as ionic copper,-is present, a chelating agent, such
as ethylenediamine tetraacetic acid may be used to combine
with this impurity. However, the presence of an impurity
and the use of a chelating agent is not necessary to prepare
the low molecular weight polymer.
Free radical initiators useful at the concentration
specified include, for example, ammonium persulfate, potassium
persulfate, benzoyl peroxide, bromobenzoyl peroxide, t-butyl
hydroperoxide, and hydrogen peroxide in the presence of
ferrous ion.
As indicated, ~he initiated polymer solution is
heated to 50C. or higher and held at the selected temperature
until the polyacrylamide of desired molecular weight is
; obtained. The polyacrylamide should have a degree of poly-
, .
;15 merization in the range of about 100 to 1,600. In the case
of a homopolymer of acrylamide, this will correspond to a
molecular weight of about 7,000 to 110,000. After the
desired polyacrylamide is provided, the reaction solution is
cooled to about 40C. to effect chemical modification with
;~20 - formaldehyde and dimethylamine.
: . ,
; Formaldehyde may be used as a 20-60 weight percent
aqueous solution and dimethylamine is used as a 20-6~
weight percent aqueous solution. The molar amount of
.:
formaldehyde employed must be sufficient to chemically
modify enough acrylamide groups to provide at least 50 mol
; percent of modified acrylamide groups in the final polymer
but the amount of formaldehyde may be sufficient to provide
a polymer consisting essentially of modified acrylamide groups,
preferably a polymer containing 60-90 mol percent of modified
acrylamide groups. The amount of dimethylamine employed
in the chemical modification of the acrylamide groups will
constitute the molar equivalent amount of dimethylamine
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11~7~14
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26,712 plus about 1 to 10 mol percent excess, preferably about 5
; mol percent excess. The reaction to provide chemical modi-
fication is preferably conducted at about 40C. for sufficient
time to complete the reaction, generally in about two hours.
Temperature and appropriate time modifications may be made
in accordance with conventional procedures for providing
this chemical modification, which is also called Mannich
base formation.
After the reaction with formaldehyde and dimethyl-
` 10 amine is complete, the reaction product is quaternized with
an alkylating agent to a pH in the range of about 4 to 7.
Preferred alkylating agents are dimethyl sulfate and methyl
chloride but other alkylating agents may be used. The
quaternization is preferably carried out to involve essentially
all of the dimethylaminomethyl groups provided but complete
- reaction is not required so long as the minimum quantity
of quaternized groups is provided. In the event that all
of the dimethylaminomethyl acrylamide groups are not qua-
ternized, the unquaternized dimethylaminomethyl acrylamide
groups will represent a part of the polymer composition.
With respect to the individual steps of polymer
preparation, chemical modification of the polyacrylamide to
, provide Mannich base modification, and quaternization of
the reaction product, the conditions of reaction and useful
reactants are known. The process of preparation involves
a specific combination of the individual steps involving a
low molecular weight polyacrylamide as the polvmer under-
going chemical modification which results in a novel polymer
possessing unexpected properties when used in clarification
~0 of coal washing waste waters and provides unexpected pro-
cessing advantages not possible when the conventional high
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26,712 molecular weight polyacryl~mides are suitably processed.
The product obtained by the process of preparation
described is a stable product which contains from about 50
to 100 mol percent of quaternized dimethylaminomethyl acryl-
amide groups. The degree of-polymerization of the chemically
modified polyacr~lamide will be substantially the same as
that of the starting polyacrylamide since no increase in
backbone polymer molecular weight is known to arise as a result
of the chemical modification effected. Accordingly, the
degree of polymerization of the product polymer will range
; from about 100 to 1,600. As a result of the chemical modi-
fication of the polyacrylamide, the molecular weight of the
repeating units will be increased depending upon the extent
, to which chemical modification is effected and, accordingly,
the product polymer will have a higher molecular weight than
the starting polyacrylamide although the degree of polymeri-
zation is unchanged. Also, as a result of the chemical
modification of the polyacrylamide, the resulting product
., ~ , ,
~ ~ will have different rheological properties from those of the
^~ 20 ~ starting polyacrylamide and consequently the intrinsic visco--
: .
~~ ~ sity values of the starting and product polymers will differ.
:
The intrinsic viscosity of the polymer used in the process
of the invention will be in the range of about 0.1 and 0.45,
~ preferably 0.3 to 0.5, deciliters per gram when measured in
;25 3 molar sodium chloride at 30C.
The coal washing waste waters for which the process
of the invention is useful are those which generally contain
up to about 100,000 parts per million of inorganic solids
. .,
of particle size up to about 2 microns, generally about 500
to 50,000 parts per million o such solids. To carry out
the proces of the present invention, into such a water is
mixed an effective amount of the useful polymer described
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~' ' ' ' , .
.o~4~
26,712 above. An effective amount i5 that amount which provides
the desired level of clarification of the waste water.
Generally, such amount will range from about 0.1 to 1,000
parts per million parts of suspended solids, perferably
about 0.5 to 100 ppm.
` After the polymer has been mixed with the waste
water, the solids are settled to provide a clarified super-
natant liquid which may be separated from the settled solids
by suitable means, such as by decantation, filtration,
centrifugation and the like. The particular method of re-
covering the clarified supernatant liquid is not critical
since the process of the pre~ent invention effectively
settles the suspended solids.
The invention is more fully illustrated in the
lS examples which follow wherein all parts and percentages
are by weight unless otherwise specified.
,~
EXAMPLE 1
The following example illustrates a process for
manufacturing a polymer-containing aminomethylated acrylamide
groups quaternized with dimethylsulfate.
226 pounds of deionized water, 0.087 pounds of
ethylene diamine tetraacetic acid, disodium dihydrate salt
and 0.87 pounds of isopropyl alcohol are charged to a clean
reactor which is then sealed. Agitation is started and
; 25 the charge is heated to 70 + 2C under a stream of nitrogen.
At 70 C, a 5.16 weight percent aqueous solution of ammonium
persulfate (i.e., 15,000 ppm based on acrylamide) is added as
- rapidly as possible, the temperature is readjusted to 70C
if necessary, and then a 50 weight percent aqueous acrylamide
solution is metered in during 2 hours, while maintaining
the temperature at 70 + 2C. The amount of acrylamide
charged is calculated to give a 20 weight percent aqueous
~; -`` iil~7~
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26,712 polymer solution. After all the acrylamide has been added,
the batch is held at 70C fox anothex hour in order to
complete the polymerization, then the nitrogen flow is
stopped and isopropyl alcohol is distilled off at a batch
temperature of 70-75C and a pressure of 225 mm. Hg. Dis-
tilling off 0.8 to 0.9 weight percent of the batch load
removes 90-95 weight percent of the isopropyl alcohol as a
.~
22 weight percent aqueous solution (Sp. Gr. 0.967). After
,; ~ reducing the batch to a temperature below 50 C, the batch
weight is adjusted by adding an amount of deionized water
equal to the weight of isopropyl alcohol solution removed
J ~ during stripping. Then a premixed solution of 100 mole
percent each of formaldehyde and dimethylamine based on the
amount of acrylamide containing 5 mole percent excess di-
methylamine is added as rapidly as possible. The dimethyl-
amine-formaldehyde solution should be premixed and cooled
below 40C. After holding for two hours, the batch
, temperature is readjusted to 35 C and then 100 mole percent
of dimethylsulfate based on the amount of dimethylamine is
- 20 - ~pumped in as rapidly as possible while maintaining the batch
at 35 to 40 C to a final pH of 6.0 + 0.2. After the di-
methylsulfate has been added and the pH is stable at pH
,
~ 6.0 + 0~2, the batch is drummed off.
",~
EXAMPLE 2
~25 The following example illustrates another process
for manufacturing a polymer of this invention without the
use of a chain transfer agent and without purging the reactor
with nitrogen.
A. Preparation of the Polyacrylamide Backbone
738 lb. deionized water and 0.38 lb. EDTA (disodium
dihydrate, 1000 ppm on monomer) are charged to a clean
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llV7~
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26,712 reactor and the pH is adjusted to 4.5 with 10% sulfuric acid
solution. The reactor is sealed and the batch is heated to
reflux during 1 hr. After 1 hr., 0.22 lb. of ammonium
persulfate initiator is added and then 2.02 lb. of the
initiator and 941 lb. of 39.7% acrylamide monomer solution
(at pH 4.3) are metered in simultaneously during 90 mins.
while maintaining steady reflux. After the monomer and
initiator solutions have been added the batch is held at
reflux for 30 minutes to complete the polymerization and
- lO then the batch temperature is ~educed to 35-40C.
B. Preparation of the Aminomethylated
Polyacrylamide Quaternized Polymer
At 35C., a premixed solution of 532.75 lb. of a
37 weight percent formaldehyde solution and 779.88 lb. of a
40 weight percent dimethylamine solution (l:l:l.05 mole
ratio of amide: formaldehyde : amine) is added as rapidly
as possible with no cooling. The batch is held 3 hrs. Then
the batch temperature is reduced to 20C and 698 lb. of
dimethylsulfate is metered in at a temperature of 35C until
the pH is reduced to S + 0.5. After the dimethylsulfate
has been added and the pH is stable the batch may be drummed
off~
EXAMPLE 3
In this example a coal washing waste water con-
taining 40,000 to 50,000 parts per million of suspended
solids as silica and clay was employed to illustrate the
ability of various polymers to clarify such water. To one
liter portions of the waste water were mixed varying dosages
of the polymer under test in separate runs and the s~lids
were allowed to settle. After settling was complete, the
turbidity of the supernatant liquid was then determined.
From these runs was determined the polymer dosage necessary
A
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741~
26,712 to achieve a gi~en turbidity value in the supernatant.
; ~ Two samples of quaternized dimethylaminomethyl
polyacrylamide in accordance with the present invention and
-( prepared following the procedure of Example 1 were evaluated,the first having an intrinsic viscosity of 0.27 dl./g. and
, the second having an intrinsic viscosity of 0.34 dl./g.
For comparison purposes, two polymers obtained by
reàcting epichlorohydrin with dimethylamine to the same
,: ~
molecular weights as the backbone polyacrylamides of the
~ ~ 10 polymers of the invention were evaluated in the same manner.
- Results are given in Table I.
Table I
Clarification Of Coal Washing Waste Waters
Dosage~to Achieve Turbidity of
Polymer Intrinsic Vis!cosity 300 J.T.U. 100 J.T.U.
~ Example 1 0.27 23 35
!'~ ' Example 1 0.34 35 47
Molecular Weight
Comparative 1 45,000 - 50,000 73 88
Comparative 2 75,000 57 105
-Oppm
~; These results show that polymers o~ the present
invention require significantly lower dosages to aahieve a
given residual turbidity than do the prior art polymers.
It should be noted that the polymer of the invention of lower
intrinsic viscosity is effective at lower dosage than is the
polymer of the invention of higher intrinsic viscosity.
~;
EXAMPLE 4
The procedure of Example 3 was again followed
except that the solids in the coal washing waste water was
mostly mica and clay minerals. The polymer dosage required
for a specific value of optical transmission of the supernatant
was determined.
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74~4
26,712 Results are given in Table II.
Table II
Transmission Of Clarified Coal W~sh ~aste Waters
~ , ~
Dosa~e` ~ To Achieve
~ransmission of
Polymer Intrinsic Viscosity 50~ 80%
Example l 0.27 66 90
Example 1 0.34 82 98
Molecular Wei~ht
Comparative l 45,000 - 50,000 150 188
Comparative 2 75,000 108 144
lO ~ppm
These results again show that polymers of the
present invention require significantly lower dosages to
achieve a given transmission of the treated water than do
the prior art polymers. It should again be noted that the
polymer of the present invention of lower intrinsic viscosity
is effective at lower do age than is the polymer of the
invention of higher intrinsic viscosity. Contrary to this,
the prior art polymer is more effective at higher molecular
weight.
.
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