CA2004549A1 - Separation process - Google Patents
Separation processInfo
- Publication number
- CA2004549A1 CA2004549A1 CA002004549A CA2004549A CA2004549A1 CA 2004549 A1 CA2004549 A1 CA 2004549A1 CA 002004549 A CA002004549 A CA 002004549A CA 2004549 A CA2004549 A CA 2004549A CA 2004549 A1 CA2004549 A1 CA 2004549A1
- Authority
- CA
- Canada
- Prior art keywords
- polyelectrolyte
- copolymer
- process according
- modified
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
Abstract
ABSTRACT
The present invention relates to modified polyelectrolytes which are useful as flocculents in separation processes, to processes for preparing the modified polyelectrolytes, flocculent compositlons incorporating the modified polyelectrolytes and to separatlon methods employing the modified polyelectrolytes and modified polyelectrolyte compositions of the invention.
The present invention relates to modified polyelectrolytes which are useful as flocculents in separation processes, to processes for preparing the modified polyelectrolytes, flocculent compositlons incorporating the modified polyelectrolytes and to separatlon methods employing the modified polyelectrolytes and modified polyelectrolyte compositions of the invention.
Description
5~3 SEPARATION PROCESS
TECHNICAL FIELD
The present invention relates to modified polyelectrolytes which are useful as flocculents in separation processes, to processes for preparing the modified polyelectrolytes, flocculent compositions incorporating the modifiecl polyelectrolytes and to separation methods employing the modified polyelectrolytes and modlfied polyelectrolyte compositions of the invention.
The modified polyelectrolytes of the invention perform better than the prior art polyelectrolytes in that they are capable of achieving the same level of flocculation at lower concentrations and are capable of retaining a higher percentage of super fines.
BACKGROUND ART
Introduction of synthetic water-soluble polymers to the mining industry in 1951 represented a major development in solid-liquid separation by chemical reagents. They were the first of a wide range of flocculents tailored to meet many needs such as clarification of water (municipal and industrial), treatment of municipal sewerage and industrial waste (food processing, oil refining, metal finishing, pulp and paper mills etc.), mineral processing (benefication, recycle-water clarification, effluent treatment), and manufacturing processes (paper production, sugar refining, phosphoric acid production etc.).
Although there are a large nurnber of commercially available synthetic flocculents the number of significantly different types of chemical structures is relatively limited. In the market place selection of a flocculant depends on optimizing the cost-to-perforrnance ratio, that is, achieving clesired performance at minimal cost. Although a systems point of view predominates (including flocculant availability, reproducibility, handling, storage~
tolerance to fluctuatiorls in treatment-plant loading while meeting outpu-t specifications, equipment-in-place and necessary modification etc), the delivered cost per unit weight of individual flocculants enter as one factor.
Consequently, a relatively few monomers suitable for incorporation into water-soluble polymers and produced on a sufficiently large scale to have low cost, are the major building blocks of commercially important synthetic polymeric flocculants.
Practical synthetic organic flocculants are water soluble polymeric substances with weight average molecular weights ranging from about 1000 to greater than 5 million (reported values as high as 20 million).
Polyelectrolytes used as flocculants include polymers and copolymers made from a number of monomers including maleic anhydride, maleic acid, acryl~c ac~d, acrylam~de, acrylonltrile, methacrylic acid, vlnyl sulfonic acld, p-styrene sulfonlc acid, styrene, vinyl methyl eth~r, metaphosphoric acid, vinylamine, ethyleneimine, vinyl pyr~dine and 4-vinyl-N-dodecylpyridinium chloride.
DISCLOSURE OF THE INVENTION
In a first embod~ment of the invention th2re is provided a modlfied polyelectrolyte characterized in that a polyelectrolyte is reacted with a copolymer of at least two ethylenically unsaturated monomers, at least one of which contains anhydride groups.
In a second embodiment of the invention there is provided a process for manufacturing a modified polyelectrolyte, which process comprises reacting a polyelectrolyte with a copolymer of at least 2 ethylenically unsaturated monomers, at least one of which contains acid anhydride groups. The reaction can be initiated by heat and/or by an inorganic accelerator such as a metallic base. A suitable accelerator is potassium carbonate.
The types of known polyelectrolytes suitable for use in this invention are extremely numerous and diversified. No unsuitable commercially available or laboratory synthesized polyelectrolyte has been found. Common trade names defining such polyelectrolytes include: SANYOFLOC; ALFLOC; SUPERFLOC;
MACROFLOC; MAGNAFLOC; MAXFLOC and ZETAG.
Other materials designed for the same or similar purposes to those described above may also be used.
Generally, the polyelectrolytes which can be modified according to the invention have molecular weights in the range 2xlO~ to lx108, especially lxlO5 to 7xl0h daltons. The preferred copolymers with which the polyelectrolytes are reacted have molecular weights in the range lxlO~ to lx106 daltons.
It is particularly preferrerl that a known polyelectrolyte flocculant is reacted with a copolymer o~ methyl vinyl ether and maleic anhydride.
A third embodilllent of the invention provides a further modified polyelectrolyte characterized in that the modified polymer according to the first embodiment of the invention is further modified by reaction with vinyl pyrrolidone or polyvinyl pyrrolidone followed by further reaction with the copolymer.
A fourth embodiment of the invention provides a process for manufacturing a further modified polyelectrolyte which process comprises terminating the process according to the second embodiment of the invention by reducing the temperature, dispersing the reaction mixture with vinyl pyrrollidone or polyvinyl pyrrolidone and allowing the reaction to proceed.
~."~0~ S ~3 The further reackion can also be ini-tiated by heat and/or by an inorganic accele~ator.
A fifth errbodiment of the invention provides a flocculating composition cornprising a modified polyelectrolyte or a fuIther modified polyelectrolyte according to the invention in association w~th the usual carriers and dlluents employed in conventional flocculating compositions.
A sixth embodiment of the invention provides a method of flocculation which method comprises adding to a material to be flocculated a modified polyelectrolyte, a further modified electrolyte and/or a flocculating composition according to the invention.
BEST MODES OF CARRYING OUT THE INVENTION
Polymer solids at an amount of between O and 200%, preferably 10/ (on the basis of polyelectrolyte solids) may effectively be employed in this in~ention.
Generally, the reaction is carried out by simple mixing or homogenization of the polyelectrolyte and copolymer. Reaction times and reaction temperatures will depend on the nature of the polyelectrolyte and the copolymer but generally the reaction can be carried out at temperature of between 0 and 120C for a time of between 5 minutes to 4 hours. It is preferred that the polyelectrolyte and copolymer be selected such that the reaction can be carried out at a temperature of bet~leen 40~ and 80C ior a time of up to 50 minutes. Preferably, the reaction is carried out in solution.
In order to further modify the polyelectrolyte, the reaction is stopped, preferably by reducing the temperature to below 30C, vir1yl pyrrolidorle or polyvinyl pyrrolidorle is added, l:he mixture is agil:ated or stirred to disperse the vinyl pyrro1i(lo~le or polyvinyl pyrrolidone and the mixtul-e is reheated torestart the reaction. I:E there is an excess of copolymer, the vinyl pyrrolidone or polyvinyl pyrrolidone reacts ~ith the anhydride moiety of either reacted or unreacted copolymer resulting in a mixture of further modified polyelectrolyte and mofified copo-lymer.
It is preferred that the r~tio of vinyl pyrrolidone or polyvinyl pyrrolidone to copolymer is in the range 1:1 to 1:10 by weight, more preferably l:S by weight.
* by weight - 3a -The following examples illustrate preferred embodiments of the invention and should not be construed as limiting on the scope thereof.
11 polyelectrolytes were reacted with various methyl vinyl ether/maleic anhydride copolymers. The types of base polymers are set out in Table 1.
Table 1 Example Tvpe ~ Approx MW
(daltons) O Polyacrylamide 5x106 1 Copolymer of Sodium Acrylate and Acrylamide 6X106 2 " 6X106 6xlo6 4 ~1 6xlO6 .. . . .. ..
~.,Q~ ''3 ., 5%,o6 6 " 1x106 7 Terpolymer of Acrylamide, Sodium Acrylate and Maleic Anhydride lx105 8 Terpolymer of Acrylamide, Sodium Acrylate and Vinyl Pyridine lx106 9 Copolymer of Sodium Acrylate and Acylamide 5X106 10 Polysodium Acrylate lx106 NOTE: It can be seen that samples O to 10 range from nonionic to 100% anionic.
The polymers ln Table 1 were reacted with poly methyl vinyl ether/maleic anhydride copolymers of the following molecular weights:
20,000; 67,000 and 80,000.
All reactions were carried out by dispersing the poly methyl vinyl ether/maleic anhydride copolymers in the finished base polymer. This blend was then placed in a water bath at 80C and the reaction occurred within 40 minutes. The end point of the reaction could be determined as a visible physical change in the base polymer.
lhe amounts of poly(methyl vinyl ether/maleic anhydride) were varied between O to 100% of the solids of base polyelectrolytes.
The results obtained demonstrated that maximum efficiency ~as determined by maximum performance for lowest amount of material) was at 10%
polymer solids (based on polyelectrolyte solids) wlth molecular weight of poly(methyl vinyl ether/maleic anhydride) at 67,000 daltons.
Example 2 is based on the above percentage and molecular welyht. The base polymer number refers to Table 1.
~XAMPLE 2 The polymers prepared in Example 1 were evaluated for efficiency by comparison with the polyelectrolytes from which they were derived. In all cases the performance of the new materials was superior to that of -the polyelectrolytes from which they were derived. Comparisons conducted at mine sites were advantageously done by selecting a polyelectrolyte with correct charge density for the materials being separated and comparing these with modified polyelectrolytes comprising the same base polyelectrolyte and possessing the same or similar charge density.
Whilst these examples are based on coal flocculation, the same and/or similar benefits can be attained wherever polyelectrolyte technology is ln use.
The following results ~Jere obtained in laboratory scale testing on site at the following coal washeries:
~ 3a)~S 4 ~3 1. Mount Thorley [R.~. M~ller]
2. ~est Cllff [Kembla Coal & Coke]
TECHNICAL FIELD
The present invention relates to modified polyelectrolytes which are useful as flocculents in separation processes, to processes for preparing the modified polyelectrolytes, flocculent compositions incorporating the modifiecl polyelectrolytes and to separation methods employing the modified polyelectrolytes and modlfied polyelectrolyte compositions of the invention.
The modified polyelectrolytes of the invention perform better than the prior art polyelectrolytes in that they are capable of achieving the same level of flocculation at lower concentrations and are capable of retaining a higher percentage of super fines.
BACKGROUND ART
Introduction of synthetic water-soluble polymers to the mining industry in 1951 represented a major development in solid-liquid separation by chemical reagents. They were the first of a wide range of flocculents tailored to meet many needs such as clarification of water (municipal and industrial), treatment of municipal sewerage and industrial waste (food processing, oil refining, metal finishing, pulp and paper mills etc.), mineral processing (benefication, recycle-water clarification, effluent treatment), and manufacturing processes (paper production, sugar refining, phosphoric acid production etc.).
Although there are a large nurnber of commercially available synthetic flocculents the number of significantly different types of chemical structures is relatively limited. In the market place selection of a flocculant depends on optimizing the cost-to-perforrnance ratio, that is, achieving clesired performance at minimal cost. Although a systems point of view predominates (including flocculant availability, reproducibility, handling, storage~
tolerance to fluctuatiorls in treatment-plant loading while meeting outpu-t specifications, equipment-in-place and necessary modification etc), the delivered cost per unit weight of individual flocculants enter as one factor.
Consequently, a relatively few monomers suitable for incorporation into water-soluble polymers and produced on a sufficiently large scale to have low cost, are the major building blocks of commercially important synthetic polymeric flocculants.
Practical synthetic organic flocculants are water soluble polymeric substances with weight average molecular weights ranging from about 1000 to greater than 5 million (reported values as high as 20 million).
Polyelectrolytes used as flocculants include polymers and copolymers made from a number of monomers including maleic anhydride, maleic acid, acryl~c ac~d, acrylam~de, acrylonltrile, methacrylic acid, vlnyl sulfonic acld, p-styrene sulfonlc acid, styrene, vinyl methyl eth~r, metaphosphoric acid, vinylamine, ethyleneimine, vinyl pyr~dine and 4-vinyl-N-dodecylpyridinium chloride.
DISCLOSURE OF THE INVENTION
In a first embod~ment of the invention th2re is provided a modlfied polyelectrolyte characterized in that a polyelectrolyte is reacted with a copolymer of at least two ethylenically unsaturated monomers, at least one of which contains anhydride groups.
In a second embodiment of the invention there is provided a process for manufacturing a modified polyelectrolyte, which process comprises reacting a polyelectrolyte with a copolymer of at least 2 ethylenically unsaturated monomers, at least one of which contains acid anhydride groups. The reaction can be initiated by heat and/or by an inorganic accelerator such as a metallic base. A suitable accelerator is potassium carbonate.
The types of known polyelectrolytes suitable for use in this invention are extremely numerous and diversified. No unsuitable commercially available or laboratory synthesized polyelectrolyte has been found. Common trade names defining such polyelectrolytes include: SANYOFLOC; ALFLOC; SUPERFLOC;
MACROFLOC; MAGNAFLOC; MAXFLOC and ZETAG.
Other materials designed for the same or similar purposes to those described above may also be used.
Generally, the polyelectrolytes which can be modified according to the invention have molecular weights in the range 2xlO~ to lx108, especially lxlO5 to 7xl0h daltons. The preferred copolymers with which the polyelectrolytes are reacted have molecular weights in the range lxlO~ to lx106 daltons.
It is particularly preferrerl that a known polyelectrolyte flocculant is reacted with a copolymer o~ methyl vinyl ether and maleic anhydride.
A third embodilllent of the invention provides a further modified polyelectrolyte characterized in that the modified polymer according to the first embodiment of the invention is further modified by reaction with vinyl pyrrolidone or polyvinyl pyrrolidone followed by further reaction with the copolymer.
A fourth embodiment of the invention provides a process for manufacturing a further modified polyelectrolyte which process comprises terminating the process according to the second embodiment of the invention by reducing the temperature, dispersing the reaction mixture with vinyl pyrrollidone or polyvinyl pyrrolidone and allowing the reaction to proceed.
~."~0~ S ~3 The further reackion can also be ini-tiated by heat and/or by an inorganic accele~ator.
A fifth errbodiment of the invention provides a flocculating composition cornprising a modified polyelectrolyte or a fuIther modified polyelectrolyte according to the invention in association w~th the usual carriers and dlluents employed in conventional flocculating compositions.
A sixth embodiment of the invention provides a method of flocculation which method comprises adding to a material to be flocculated a modified polyelectrolyte, a further modified electrolyte and/or a flocculating composition according to the invention.
BEST MODES OF CARRYING OUT THE INVENTION
Polymer solids at an amount of between O and 200%, preferably 10/ (on the basis of polyelectrolyte solids) may effectively be employed in this in~ention.
Generally, the reaction is carried out by simple mixing or homogenization of the polyelectrolyte and copolymer. Reaction times and reaction temperatures will depend on the nature of the polyelectrolyte and the copolymer but generally the reaction can be carried out at temperature of between 0 and 120C for a time of between 5 minutes to 4 hours. It is preferred that the polyelectrolyte and copolymer be selected such that the reaction can be carried out at a temperature of bet~leen 40~ and 80C ior a time of up to 50 minutes. Preferably, the reaction is carried out in solution.
In order to further modify the polyelectrolyte, the reaction is stopped, preferably by reducing the temperature to below 30C, vir1yl pyrrolidorle or polyvinyl pyrrolidorle is added, l:he mixture is agil:ated or stirred to disperse the vinyl pyrro1i(lo~le or polyvinyl pyrrolidone and the mixtul-e is reheated torestart the reaction. I:E there is an excess of copolymer, the vinyl pyrrolidone or polyvinyl pyrrolidone reacts ~ith the anhydride moiety of either reacted or unreacted copolymer resulting in a mixture of further modified polyelectrolyte and mofified copo-lymer.
It is preferred that the r~tio of vinyl pyrrolidone or polyvinyl pyrrolidone to copolymer is in the range 1:1 to 1:10 by weight, more preferably l:S by weight.
* by weight - 3a -The following examples illustrate preferred embodiments of the invention and should not be construed as limiting on the scope thereof.
11 polyelectrolytes were reacted with various methyl vinyl ether/maleic anhydride copolymers. The types of base polymers are set out in Table 1.
Table 1 Example Tvpe ~ Approx MW
(daltons) O Polyacrylamide 5x106 1 Copolymer of Sodium Acrylate and Acrylamide 6X106 2 " 6X106 6xlo6 4 ~1 6xlO6 .. . . .. ..
~.,Q~ ''3 ., 5%,o6 6 " 1x106 7 Terpolymer of Acrylamide, Sodium Acrylate and Maleic Anhydride lx105 8 Terpolymer of Acrylamide, Sodium Acrylate and Vinyl Pyridine lx106 9 Copolymer of Sodium Acrylate and Acylamide 5X106 10 Polysodium Acrylate lx106 NOTE: It can be seen that samples O to 10 range from nonionic to 100% anionic.
The polymers ln Table 1 were reacted with poly methyl vinyl ether/maleic anhydride copolymers of the following molecular weights:
20,000; 67,000 and 80,000.
All reactions were carried out by dispersing the poly methyl vinyl ether/maleic anhydride copolymers in the finished base polymer. This blend was then placed in a water bath at 80C and the reaction occurred within 40 minutes. The end point of the reaction could be determined as a visible physical change in the base polymer.
lhe amounts of poly(methyl vinyl ether/maleic anhydride) were varied between O to 100% of the solids of base polyelectrolytes.
The results obtained demonstrated that maximum efficiency ~as determined by maximum performance for lowest amount of material) was at 10%
polymer solids (based on polyelectrolyte solids) wlth molecular weight of poly(methyl vinyl ether/maleic anhydride) at 67,000 daltons.
Example 2 is based on the above percentage and molecular welyht. The base polymer number refers to Table 1.
~XAMPLE 2 The polymers prepared in Example 1 were evaluated for efficiency by comparison with the polyelectrolytes from which they were derived. In all cases the performance of the new materials was superior to that of -the polyelectrolytes from which they were derived. Comparisons conducted at mine sites were advantageously done by selecting a polyelectrolyte with correct charge density for the materials being separated and comparing these with modified polyelectrolytes comprising the same base polyelectrolyte and possessing the same or similar charge density.
Whilst these examples are based on coal flocculation, the same and/or similar benefits can be attained wherever polyelectrolyte technology is ln use.
The following results ~Jere obtained in laboratory scale testing on site at the following coal washeries:
~ 3a)~S 4 ~3 1. Mount Thorley [R.~. M~ller]
2. ~est Cllff [Kembla Coal & Coke]
3. Hunter Valley No.l [Coal & Allied]
1. Mount Thorley A. Base Polymer No.6*
Settling Velocity 8.2m/h Clarity Good B. New Polymer No.6R*
Settling Velocity 18.0 m/h Clarity Good 2. ~est Cliff A. Base Polymer No.2~ No.3*
Settling Velocity 1.0 m/h 0.8 m/hz Clarity Good Good 6. ~ew Polymer No.2R~ No.3R*
Settling Velocity 1.25 m/h 1.4 m/h Clarity Very Good Very Good 3. Hunter Valley No.l A. Base Polymer No.4 No.5 No.6 Settling Velocity 4.3 m/h 8.3 m/h 6.1 m/h Clarity Very Poor Very Poor Very Poor B. Base Polymer No.4R No.SR~ No.6R
Settling Velocity 9.9 m/h 20 m/h 20 m/h Clarity <Poor <Poor <Poor ~ Indicates tne correct charge de1lsi~y on the base polymer m/tl Metres/11oul^
R ~here a second reaction has been performed on the base polymer.
A Latex polymer of the following characteristics was prepared.
Organic solids 32.0X pH(1%) 6.0 Ratio Acrylamide:Dimethylaminoethyl Methacrylate 60:40 nominal mw 2X106 This polymer was cooled to below 30C then further reacted with l.5%
by weight poly(methyl vinyl ether/maleic anhydride) with a mw 80,000 (daltons). The reaction was carrled out by dispersing the powder through the latex and placing into a water bath at 50C for 50 minutes. On cooling the flocculent latex was packaged.
V,~ r11~
- G - .
The following results were obtained from testing work on a undigested sewerage sludge obtained from a sewerage -treatment pla~t.
A. Base Polymer dose 240 ppm Settling Velocity 2.6 m/h Shear resistance pass 8. New Polymer dose 240 ppm Settling Velocity 4.7 m/h Shear resistance pass m/h Metres/hour A solution polymer of the following characteristics ~as cooked.
Organic polymer solids 6/~ pH(neat) 8.0 Ratio Acrylamide:Acrylic Acid 60:100 nominal mw 6X106 This polymer was reacted with 0.5% polymer (methyl vinyl ether/maleic anhydride) with a mw of 67 000 daltons(ex GAF). The reaction was carried out by dispersing the powder through the solution and placing into a water bath at 60C for 4 hours. The resultant mixture was cooled to below 30C and 1.0% of polyvinyl pyrollidone was dispersed into the mixture. The mixture was replaced into the water bath for 2 hours. On cooling the flocculent solution was packaged.
A latex polymer oF the following characteristics was prepared.
Organic solids 28.5% pll(~VL) 3.0 Ratio Acrylamide:Acrylic Acid 3~:23 nolllinal mw l2xloG
This polyrller was cooled to below 30C then flJrthet- reacted with 2.5%
by weight of poly(methyl vinyl ethQr/maleic anhydride) mw 67 000 (daltons) dispersed in twice its weight of in aromatic solvent. This mixture was cooled to below 30C and 0.5% of polyvinyl pyrrolidone was dispersed in the mixture.
The mixture was replaced into the water bath for 30 min. On cooling the flocculent latex was packaged.
A solution polymer of the following characteristics was prepared.
Organic polymer solids 6X pH(neat) 8.0 Ratio of Acrylamide:Acrylic Acid 7:1 nominal mw 5X106 ~;J~
Th7s polymer was reacted wlth 0.5% poly(methyl v~nyl ether/male~c anhydr~de~ with a mw 80 000 daltons. ~he reactlon was carr~ed out by d7spers1ng the powder through the solution and plac~ng lnto a water bath at 60C for 4 hours. The resultant mixture was cooled to below 30C and 0.1% of polyvinyl pyrrolidone was dispersed in the mixture. The mixture ~Jas replaced into the water bath for 2 hours. On cooling the flocculent solution was packaged.
A solution polymer of the following characteristics was prepared.
Organic solids 6% pH~neat) 8.0 Ratio of Acrylamide:Acrylic Acid 50:50 This base polymer was reacted with 0.5% w/w poly~methyl vinyl ether/
maleic anhydride) with a mw of 67 000 daltons. The reaction was carried out by dispersing the powder throuyh the solution and placing into a sealed container in a water bath for 4 hours at 60C. The resultant mixture was cooled to below 30C and 0.1% of polyvinyl pyrrolidone was dispersed in the mixture. The mixture was replaced into the water bath for 2 hours. On cooling the flocculent solution was packaged.
EXA~PLE 8 A solution polymer of the following characteristics was prepared.
Organic solids (of acrylic acid) 6~1~ pHtneat) 8.0 This base polymer was reacted with 0.5% poly(methyl vinyl ether/maleic anhydride) with a mw of 67 000 daltons. The reaction was carried out by dispersing the powder through the solution and placiny i-t into a sealed conr~iner in a water bath for ~ hours at 60C. Ttle resultant mixture WdS
cooled to below 30C and 0.1% of polyvinyl pyrrolidone was dispersed in the mixture. The mixture was replaced into the water bath for 2 houls. On cooling the flocculent solution was packaged.
The following results were obtained i.n labora-tory scale testing on site at the following coal washeries:
I. Mount Thorley [R.W. Miller]
Hunter Valley CPP CCoal & Allled]
II. Ravensworth Colliery [Elcom]
III. West Cliff CKembla Coal & CokeJ
IV. Hunter Valley CPP [Coal & Allied]
I. Mount Thorley A. Base Polymer Settling Velocity 8.2m/h Clarity Good B. New Polymer Settling Velocity 29m/h Clarity Very Good I. Hunter Valley CPP
; A. Base Polymer Settling Velocity 6.lm/h Clarity Very Poor B. New Polymer Settling Velocity 18.4m/h Clarity poor II. Ravensworth A. Base Polymer Dose 5ppm Settling Velocity 4.0m/h Clarity 65% at 400nm B. New Polymer Dose 5pp~l1 Settling Velocity 12.8m/h Clarity >90% at 400nm III . West Cli~f A. Base Polymer Settling Velocity 0.8m/h Clarity Good B New Polymer Settling Velocity 2.9m/h Clarity Very Good IV. Hunter Valley CPP
A. Base Polymer Settling Velocity 8.3m/h fb,~ 3 . g Clarity Very Poc,r B. New Polymer Settllng Veloclty 27.1m/h Clarity Good m/h Metres/hour It can be seen from the test data that not only are these compounds a more cost efficient base (on the reaction being done on the compound of ideal charge density in order to coincide with the material being separated), but they also allow for a far greater latitude in charge density wllilst maintaining performance. This is of particular importance in the mining industry where frequent (and sometimes dramatic) changes in charge density requirementS are experienced throughout the mining process [e.g. change in orebody, change within a coal seam, or changes from coal seam to coal seam.
changes in climatic conditions affecting the treatment of sewerage. ~lany other examples can be quoted]
INDUSTRIAL APPLICATION
The present invention provides modified polyelectrolytes which are useful as flocculents and find use in separation processes from fields as diverse as ~later treatment, oil refining, metal finishing, food processing, paper milling, mineral processing and rnanufacturil-~g processes.
1. Mount Thorley A. Base Polymer No.6*
Settling Velocity 8.2m/h Clarity Good B. New Polymer No.6R*
Settling Velocity 18.0 m/h Clarity Good 2. ~est Cliff A. Base Polymer No.2~ No.3*
Settling Velocity 1.0 m/h 0.8 m/hz Clarity Good Good 6. ~ew Polymer No.2R~ No.3R*
Settling Velocity 1.25 m/h 1.4 m/h Clarity Very Good Very Good 3. Hunter Valley No.l A. Base Polymer No.4 No.5 No.6 Settling Velocity 4.3 m/h 8.3 m/h 6.1 m/h Clarity Very Poor Very Poor Very Poor B. Base Polymer No.4R No.SR~ No.6R
Settling Velocity 9.9 m/h 20 m/h 20 m/h Clarity <Poor <Poor <Poor ~ Indicates tne correct charge de1lsi~y on the base polymer m/tl Metres/11oul^
R ~here a second reaction has been performed on the base polymer.
A Latex polymer of the following characteristics was prepared.
Organic solids 32.0X pH(1%) 6.0 Ratio Acrylamide:Dimethylaminoethyl Methacrylate 60:40 nominal mw 2X106 This polymer was cooled to below 30C then further reacted with l.5%
by weight poly(methyl vinyl ether/maleic anhydride) with a mw 80,000 (daltons). The reaction was carrled out by dispersing the powder through the latex and placing into a water bath at 50C for 50 minutes. On cooling the flocculent latex was packaged.
V,~ r11~
- G - .
The following results were obtained from testing work on a undigested sewerage sludge obtained from a sewerage -treatment pla~t.
A. Base Polymer dose 240 ppm Settling Velocity 2.6 m/h Shear resistance pass 8. New Polymer dose 240 ppm Settling Velocity 4.7 m/h Shear resistance pass m/h Metres/hour A solution polymer of the following characteristics ~as cooked.
Organic polymer solids 6/~ pH(neat) 8.0 Ratio Acrylamide:Acrylic Acid 60:100 nominal mw 6X106 This polymer was reacted with 0.5% polymer (methyl vinyl ether/maleic anhydride) with a mw of 67 000 daltons(ex GAF). The reaction was carried out by dispersing the powder through the solution and placing into a water bath at 60C for 4 hours. The resultant mixture was cooled to below 30C and 1.0% of polyvinyl pyrollidone was dispersed into the mixture. The mixture was replaced into the water bath for 2 hours. On cooling the flocculent solution was packaged.
A latex polymer oF the following characteristics was prepared.
Organic solids 28.5% pll(~VL) 3.0 Ratio Acrylamide:Acrylic Acid 3~:23 nolllinal mw l2xloG
This polyrller was cooled to below 30C then flJrthet- reacted with 2.5%
by weight of poly(methyl vinyl ethQr/maleic anhydride) mw 67 000 (daltons) dispersed in twice its weight of in aromatic solvent. This mixture was cooled to below 30C and 0.5% of polyvinyl pyrrolidone was dispersed in the mixture.
The mixture was replaced into the water bath for 30 min. On cooling the flocculent latex was packaged.
A solution polymer of the following characteristics was prepared.
Organic polymer solids 6X pH(neat) 8.0 Ratio of Acrylamide:Acrylic Acid 7:1 nominal mw 5X106 ~;J~
Th7s polymer was reacted wlth 0.5% poly(methyl v~nyl ether/male~c anhydr~de~ with a mw 80 000 daltons. ~he reactlon was carr~ed out by d7spers1ng the powder through the solution and plac~ng lnto a water bath at 60C for 4 hours. The resultant mixture was cooled to below 30C and 0.1% of polyvinyl pyrrolidone was dispersed in the mixture. The mixture ~Jas replaced into the water bath for 2 hours. On cooling the flocculent solution was packaged.
A solution polymer of the following characteristics was prepared.
Organic solids 6% pH~neat) 8.0 Ratio of Acrylamide:Acrylic Acid 50:50 This base polymer was reacted with 0.5% w/w poly~methyl vinyl ether/
maleic anhydride) with a mw of 67 000 daltons. The reaction was carried out by dispersing the powder throuyh the solution and placing into a sealed container in a water bath for 4 hours at 60C. The resultant mixture was cooled to below 30C and 0.1% of polyvinyl pyrrolidone was dispersed in the mixture. The mixture was replaced into the water bath for 2 hours. On cooling the flocculent solution was packaged.
EXA~PLE 8 A solution polymer of the following characteristics was prepared.
Organic solids (of acrylic acid) 6~1~ pHtneat) 8.0 This base polymer was reacted with 0.5% poly(methyl vinyl ether/maleic anhydride) with a mw of 67 000 daltons. The reaction was carried out by dispersing the powder through the solution and placiny i-t into a sealed conr~iner in a water bath for ~ hours at 60C. Ttle resultant mixture WdS
cooled to below 30C and 0.1% of polyvinyl pyrrolidone was dispersed in the mixture. The mixture was replaced into the water bath for 2 houls. On cooling the flocculent solution was packaged.
The following results were obtained i.n labora-tory scale testing on site at the following coal washeries:
I. Mount Thorley [R.W. Miller]
Hunter Valley CPP CCoal & Allled]
II. Ravensworth Colliery [Elcom]
III. West Cliff CKembla Coal & CokeJ
IV. Hunter Valley CPP [Coal & Allied]
I. Mount Thorley A. Base Polymer Settling Velocity 8.2m/h Clarity Good B. New Polymer Settling Velocity 29m/h Clarity Very Good I. Hunter Valley CPP
; A. Base Polymer Settling Velocity 6.lm/h Clarity Very Poor B. New Polymer Settling Velocity 18.4m/h Clarity poor II. Ravensworth A. Base Polymer Dose 5ppm Settling Velocity 4.0m/h Clarity 65% at 400nm B. New Polymer Dose 5pp~l1 Settling Velocity 12.8m/h Clarity >90% at 400nm III . West Cli~f A. Base Polymer Settling Velocity 0.8m/h Clarity Good B New Polymer Settling Velocity 2.9m/h Clarity Very Good IV. Hunter Valley CPP
A. Base Polymer Settling Velocity 8.3m/h fb,~ 3 . g Clarity Very Poc,r B. New Polymer Settllng Veloclty 27.1m/h Clarity Good m/h Metres/hour It can be seen from the test data that not only are these compounds a more cost efficient base (on the reaction being done on the compound of ideal charge density in order to coincide with the material being separated), but they also allow for a far greater latitude in charge density wllilst maintaining performance. This is of particular importance in the mining industry where frequent (and sometimes dramatic) changes in charge density requirementS are experienced throughout the mining process [e.g. change in orebody, change within a coal seam, or changes from coal seam to coal seam.
changes in climatic conditions affecting the treatment of sewerage. ~lany other examples can be quoted]
INDUSTRIAL APPLICATION
The present invention provides modified polyelectrolytes which are useful as flocculents and find use in separation processes from fields as diverse as ~later treatment, oil refining, metal finishing, food processing, paper milling, mineral processing and rnanufacturil-~g processes.
Claims (20)
1. A modified polyelectrolyte characterized in that a polyelectrolyte is reacted with a copolymer of at least two ethylenically unsaturated monomers, at least one of which contains anhydride groups.
2. A process for the manufacture of a modified polyelectrolyte, which process comprises reacting a polyelectrolyte with a copolymer of at least 2 ethylenically unsaturated monomers, at least one of which contains acid anhydride groups.
3. A process according to claim 2 wherein the polyelectrolyte has a molecular weight in the range 2x104 to 1x108 daltons.
4. A process according to claim 3 wherein the polyelectrolyte has a molecular weight in the range 1x105 to 7x106 daltons.
5. A process according to any one of claims 2 to 4 wherein the polyelectrolyte is present at an amount of from 0 to 200% on the basis of polyelectrolyte solids.
6. A process according to claim 5 wherein the polyelectrolyte is present at an amount of 10% on the basis of polyelectrolyte solids.
7. A process according to any one of claims 2 to 6 wherein the copolymer has a molecular weight in the range 1x104 to 1x106 daltons.
8. A process according to any one of claims 2 to 7 wherein the copolymer is a copolymer of methyl vinyl ether and maleic anhydride.
9. A process according to any one of claims 2 to 8 wherein the polyelectrolyte is reacted with the copolymer at a temperature of between 0°
and 120°C for a time of between 5 minutes and 4 hours.
and 120°C for a time of between 5 minutes and 4 hours.
10. A process according to claim 9 wherein the reaction is carried out at a temperature of between 40° and 80°C for a time of up to 50 minutes.
11. A process according to any one of claims 2 to 10 wherein the polyelectrolyte and copolymer are reacted in solution.
12. A modified polyelectrolyte as defined in claim 1 manufactured according to a process as defined in any one of claims 2 to 11.
13. A further modified polyelectrolyte characterized in that the modified polyelectrolyte according to claim 1 is further modified by reaction with vinyl pyrrolidone or polyvinyl pyrrolidone followed by further reaction with the copolymer.
14. A process for the manufacture of a further modified polyelectrolyte which process comprises terminating the process according to claim 2 by reducing the temperature, dispersing the reaction mixture with vinyl pyrrolidone or polyvinyl pyrrolidone and allowing the reaction to proceed.
15. A process according to claim 14 wherein the temperature is reduced to below 30°C, the mixture Is agitated or stirred to disperse the vinyl pyrrolidone or polyvinyl pyrrolidone and the mixture is reheated to restart the reaction.
16. A process according to claim 14 or claim 15 wherein the ratio of vinyl pyrrolidone or polyvinyl pyrrolidone to copolymer is in the range 1:1 to 1:10 by weight.
17. A process according to claim 16 wherein the ratio of vinyl pyrollidone or polyvinyl pyrollidone to copolymer is 1:5 by weight.
18. A further modified polyelectrolyte as defined in claim 13 manufactured according to a process as defined in any one of claims 14 to 17.
19. A flocculating composition comprising a modified polyelectrolyte as defined in claim 1 or claim 12 or a further modified polyelectrolyte as defined in claim 13 or claim 18 in association with the usual carriers and diluents employed in conventional flocculating compositions.
20. A method of flocculation which method comprises adding to a material to be flocculated a modified polyelectrolyte as defined in claim 1 or claim 12, a further modifed polyelectrolyte as defined in claim 13 or claim 18 and/or a flocculating composition as defined in claim 19.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPJ1807 | 1988-12-05 | ||
| AUPJ1806 | 1988-12-05 | ||
| AUPJ180688 | 1988-12-05 | ||
| AUPJ180788 | 1988-12-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2004549A1 true CA2004549A1 (en) | 1990-06-05 |
Family
ID=25643589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004549A Abandoned CA2004549A1 (en) | 1988-12-05 | 1989-12-04 | Separation process |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0400129A4 (en) |
| JP (1) | JPH03503295A (en) |
| CN (2) | CN1043298A (en) |
| CA (1) | CA2004549A1 (en) |
| DK (1) | DK186090D0 (en) |
| IL (1) | IL92554A0 (en) |
| IN (1) | IN176443B (en) |
| MY (1) | MY105082A (en) |
| WO (1) | WO1990006336A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9068776B2 (en) | 2009-10-30 | 2015-06-30 | Suncor Energy Inc. | Depositing and farming methods for drying oil sand mature fine tailings |
| US9404686B2 (en) | 2009-09-15 | 2016-08-02 | Suncor Energy Inc. | Process for dying oil sand mature fine tailings |
| US9909070B2 (en) | 2009-09-15 | 2018-03-06 | Suncor Energy Inc. | Process for flocculating and dewatering oil sand mature fine tailings |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2693910B1 (en) * | 1992-07-23 | 1994-08-26 | Taema | Equipment and methods for delivering doses of at least one gas to the respiratory tract of a user. |
| CN111483654A (en) * | 2020-05-08 | 2020-08-04 | 胡艳锋 | Case sealing device for automatic fruit and vegetable packaging machine |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL131797C (en) * | 1964-01-27 | |||
| FR2030358A1 (en) * | 1969-02-07 | 1970-11-13 | Mobil Oil Corp | |
| JPS5611775B2 (en) * | 1972-09-11 | 1981-03-17 | ||
| US4255309A (en) * | 1979-08-16 | 1981-03-10 | Betz Laboratories, Inc. | Polyacrylic acids and methyl vinyl ether/maleic anhydride copolymers as soft scale inhibitors |
| JPS6383150A (en) * | 1986-09-29 | 1988-04-13 | Mitsubishi Petrochem Co Ltd | Water-absorbing resin composition and production thereof |
-
1989
- 1989-12-04 EP EP19900900031 patent/EP0400129A4/en not_active Withdrawn
- 1989-12-04 JP JP2500110A patent/JPH03503295A/en not_active Withdrawn
- 1989-12-04 CA CA002004549A patent/CA2004549A1/en not_active Abandoned
- 1989-12-04 MY MYPI89001693A patent/MY105082A/en unknown
- 1989-12-04 WO PCT/AU1989/000523 patent/WO1990006336A1/en not_active Application Discontinuation
- 1989-12-05 IL IL92554A patent/IL92554A0/en not_active IP Right Cessation
- 1989-12-05 IN IN1142DE1989 patent/IN176443B/en unknown
- 1989-12-05 CN CN89109764.3A patent/CN1043298A/en active Pending
-
1990
- 1990-08-03 DK DK186090A patent/DK186090D0/en not_active Application Discontinuation
-
1995
- 1995-03-17 CN CN95100572.3A patent/CN1112906A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9404686B2 (en) | 2009-09-15 | 2016-08-02 | Suncor Energy Inc. | Process for dying oil sand mature fine tailings |
| US9909070B2 (en) | 2009-09-15 | 2018-03-06 | Suncor Energy Inc. | Process for flocculating and dewatering oil sand mature fine tailings |
| US10590347B2 (en) | 2009-09-15 | 2020-03-17 | Suncor Energy Inc. | Process for flocculating and dewatering oil sand mature fine tailings |
| US9068776B2 (en) | 2009-10-30 | 2015-06-30 | Suncor Energy Inc. | Depositing and farming methods for drying oil sand mature fine tailings |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1043298A (en) | 1990-06-27 |
| JPH03503295A (en) | 1991-07-25 |
| IN176443B (en) | 1996-05-25 |
| DK186090A (en) | 1990-08-03 |
| EP0400129A1 (en) | 1990-12-05 |
| EP0400129A4 (en) | 1992-05-06 |
| DK186090D0 (en) | 1990-08-03 |
| CN1112906A (en) | 1995-12-06 |
| MY105082A (en) | 1994-08-30 |
| IL92554A0 (en) | 1990-08-31 |
| WO1990006336A1 (en) | 1990-06-14 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |