Polyquaternary flocculants of average molecular weight, in excess of 10,000 are prepared by reacting a secondary amine with an epihalohydrin or diepoxide for use in flocculation of aqueous systems where ordinary cationic flocculants cannot be used.
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1. A water-dispersible polyquaternary polymer of essentially linear structure consisting essentially of the difunctional reaction product of a lower dialkylamine and a difunctional epoxy compound selected from the group consisting of epihalohydrins, diepoxides, percursors of epihalohydrins and diepoxides which under alkaline conditions are readily converted into the corresponding epoxy compounds, and mixtures thereof, said polyquaternary polymer containing repeating units of ##EQU10## wherein R and R2 are individually selected from the group consisting of alkyl of 1 to 3 carbon atoms; E is a residue obtained from said epoxy compound; the total amounts of reactants being substantially equimolar, the combination of which is such as to provide a polyquaternary compound which as a 37% aqueous solution, by weight, based on the cationic portion of said polyquaternary compound has a viscosity at 25°C of at least 100 centistokes; and X- represents an ion forming the anionic
portion of said polyquaternary. 2. The polymer of claim 1 21 wherein said E is the residue obtained from epichlorohydrin. 3. The polymer of 4. A water-dispersible polyquaternary polymer consisting essentially of the reaction product of a lower dialkylamine, a polyfunctional amine, and a difunctional epoxy compound selected from the group consisting of epihalohydrins, diepoxides, percusors of epihalohydrins and diepoxides which under alkaline conditions are readily converted into the corresponding epoxy compounds, and mixtures thereof, said polyquaternary polymer containing repeating units of the structures ##EQU11## as the cationic portion, and X- as the anionic portion wherein R and R2 are individually selected from the group consisting of alkyls of 1 to 3 carbon atoms; E is a residue obtained from said epoxy compound; A is a residue obtained after at least bifunctional epoxy reaction from a polyfunctional amine selected from the group consisting of ammonia; primary amines; alkylene diamines of 2 to 6 carbon atoms; polyalkylenepolyamines of the structure ##EQU12## wherein y represents an integer of about 1 to 5, R3 is an alkylene radical of about 2 to 6 carbon atoms, and R4 is selected from the group consisting of hydrogen, alkyl of about 1 to 3 carbon atoms, and ω-aminoalkyl of about 2 to 6 carbon atoms; a polyglycolamine of a structure such as: ##EQU13## wherein a is an integer of about 1 to 5; piperazine; heteroaromatic diamines of the structure ##SPC7##
wherein q is zero or an integer of about 1 to 3; and aromatic diamines of the structure ##SPC8## wherein p and q are individually zero or an integer of about 1 to 3; X- is an anion forming the anionic portion of said polyquaternary compound; the amount of said polyfunctional amine being up to about 15 mole percent of the total moles of said dialkylamine and said polyfunctional amine, the amount of said E is from at least that amount which is equimolar to the molar quantities of said amines up to the full functional equivalency of said amines, so as to provide a polyquaternary compound which as a 37% aqueous solution based on the cationic portion of said polyquaternary compound has a viscosity at 25°C of at least 10 centistokes; and the amount of said ion present is such as to satisfy anion requirements of the cationic portion of said polyquaternary compound. 5. The polymer of
6. The polymer of
7. The polymer of
8. The polymer of
1,4-butanediol-diglycidyl ether. 9. The polymer of claim 1 21 wherein said viscosity is 235 centistokes. 10. The polymer of
11. The polymer of
12. A process for preparing a polyquaternary compound from a secondary amine selected from dialkylamines wherein the alkyl groups are individually selected from those containing about 1 to 3 carbon atoms and an epoxy compound selected from the group consisting of epihalohydrins, diepoxides, precursors for epihalohydrins and diepoxides which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof; which process comprises the steps of (1) preparing an aqueous reaction mixture of one of said reactants, the amount of water therein being from about 10% to about 55%, by weight, based on the total weight of reactants and water; (2) adding the other of said reactants to the reaction mixture at a rate which maintains the reaction mixture at a temperature in the range of about 20 to 70°C, the total amounts of said reactants employed being substantially equimolar; (3) heating the reaction mixture at a temperature in the range of about 40 to 70°C for a time period sufficient to obtain a polyquaternary compound which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary has a viscosity at 25°C of at least 100 centipoises; and thereafter recovering the polyquaternary compound thus
formed. 13. The process of claim 12 29 wherein said reactants are diamethylamine and epichlorohydrin. 14. The process of 16. A process for preparing a polyquaternary compound from a first reactant selected from the group consisting of dialkylamines wherein the alkyl groups are individually selected from those containing 1 to 3 carbon atoms; a second reactant selected from the group consisting of ammonia, primary amines, alkylenediamines of about 2 to 6 carbon atoms, polyamines of the structure: ##EQU14## wherein y represents an integer of about 1 to 5, R3 is an alkylene of about 2 to 6 carbon atoms, and R4 is selected from the group consisting of hydrogen, alkyl of about 1 to 3 carbon atoms, and ω-aminoalkyls of about 2 to 6 carbon atoms, piperazine, heteroaromatic diamines of the structure ##SPC9##
wherein q is zero or an integer of about 1 to 3, and aromatic diamines of the structure ##SPC10## wherein p and q are individually zero or an integer of about 1 to 3; and a third reactant selected from the group consisting of epihalohydrins, diepoxides, precursors which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof, the molar quantity of said second reactant being up to 15% of the total molar quantity of said first and said second reactants, and the molar quantity of said third reactant, being an amount which ranges from substantially equimolar to the total molar quantity of amines employed to substantially equal to the total functionality requirements of the amines: which process comprises (a) forming an aqueous reaction mixture of said reactants while maintaining the reaction mixture at a temperature in the range of about 20°C to about 100°C, the amount of water in said mixture being from about 10% to 55%, by weight, based on the total weight of reactants and water; (b) maintaining said reaction mixture at a temperature in the range of about 50 to 100°C until a polyquaternary compound is obtained which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary compound has a viscosity of at least 10 centistokes; and thereafter recovering said polyquaternary compound. 17. The process of
18. The process of
19. The process of
20. The process of
said polyquaternary. 22. The polymer of claim 21 wherein said viscosity is 250 centistokes. 23. The polymer of
portion of said polyquaternary. 28. A process for preparing a polyquaternary compound from a secondary amine selected from dialkylamines wherein the alkyl groups are individually selected from those containing about 1 to 3 carbon atoms and an epoxy compound selected from the group consisting of diepoxides and precursors for diepoxides which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof; which process comprises the steps of (1) preparing an aqueous reaction mixture of one of said reactants, the amount of water therein being from about 10% to 55%, by weight, based on the total weight of reactants and water; (2) adding the other of said reactants to the reaction mixture at a rate which maintains the reaction mixture at a temperature in the range of about 20 to 70°C., the total amounts of said reactants employed being substantially eqimolar; (3) heating the reaction mixture at a temperature in the range of about 40 to 70°C. for a time sufficient to obtain a polyquaternary compound which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary has a viscosity at 25°C. of at least 100 centipoises; and thereafter recovering the polyquaternary compound thus formed.29. A process for preparing a polyquaternary compound from dimethylamine and an epoxy compound selected from the group consisting of epihalohydrins and precursors for epihalohydrins which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof; which process comprises the steps of (1) preparing an aqueous reaction mixture of one of said reactants, the amount of water therein being from about 10% to about 55%, by weight, based on the total weight of reactants and water; (2) adding the other of said reactants to the reaction mixture at a rate which maintains the reaction mixture at a temperature in the range of about 20 to 70°C., the total amounts of said reactants employed being substantially equimolar; (3) heating the reaction mixture at a temperature in the range of about 40 to 70°C. for a time period sufficient to obtain a polyquaternary compound which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary has a viscosity at 25°C. of at least 100 centipoises; and thereafter recovering the polyquaternary compound thus formed. |
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To a flask equipped as above were added 76.28 g. deionized water and 92.53 g. epichlorohydrin (1.0 mole) to give an emulsion on stirring. To the addition funnel were added 107.09 g. 40% aqueous dimethylamine (42.84 g., 0.95 mole) of 5.16 g. diethylenetriamine (0.05 mole). The amine solution was added to the epichlorohydrin emulsion over one hour, keeping the temperature between 20°C and 31°C After 30 minutes the clear solution was heated to 50°C for 11/2 hours.
The solution was then heated to 90°C and 20 ml. of 50% potassium carbonate solution was added. The viscosity of the solution was increased by incremental additions of epichlorohydrin. Initially, 5 ml. of epichlorohydrin was added, followed by 2 ml. after 20 minutes, 1.5 ml. after an additional 15 minutes, 1.0 ml. after another 18 minutes and finally, 0.5 ml. after 27 minutes. To the viscous yellow solution was added 50 g. deionized water. The product has a viscosity of 800 centistokes at a dilution of 30% solids of the cationic portion of the polymer.
In this example the addition of reagents is reversed. 78.25 parts of water, 107.09 parts of 42% dimethylamine, and 3.0 parts of ethylenediamine were introduced into a stirred reactor provided with a cooling jacket. 92.53 parts of epichlorohydrin were then gradually added over a period of three hours at a rate keeping the temperature below 50°C After all of the epichlorohydrin had been added, the clear solution was heated up to 90°C for 30 minutes, and 6 parts of 50% aqueous sodium hydroxide solution gradually added.
The viscosity of the solution was advanced by incremental additions of epichlorohydrin. Initially, 2 ml. of epichlorhydrin were added, followed by 2 ml. more after 20 minutes and 1 ml. after a further 30 minutes. The reaction mixture was kept at 90°C for one more hour.
Viscosity readings were taken as the reaction proceeded, and each sample was tested for flocculating efficiency by the method described above. The results are shown by the curve in the drawing, the points being circles, which showed that the efficiency increased with increasing viscosity.
The final product has a viscosity of 285 centistokes at 25°C and at 37% solids, based on the cationic portion of the polyquaternary compound.
197 pounds of water are introduced into a 100-gallon glass-lined reactor with a variable speed agitator and a reflux condenser. The charge port is then closed and the agitator turned on and the reflux condenser supplied with cooling water. 239 pounds of epichlorohydrin were introduced, using an additional 30 pounds of water to flush the epichlorohydrin in the lines into the reactor. 290 pounds of 42% aqueous dimethylamine and 8.1 pounds of ethylenediamine were mixed. 284 pounds of the mixed amines were then added gradually to the reactor containing the epichlorhydrin at the initial rate of about one pound per minute. The addition takes 6 hours. The feed rate is controlled so that the reaction temperature is in the range of 30° to 35°C
After all the amine has been added, temperature is raised to 50°C and maintained for 2 hours. Then the reactor is heated to 90°C with atmospheric steam, using tempered water as the top temperature is reached. When the temperature reaches 80°C, 15.4 pounds of 50% aqueous sodium hydroxide is introduced. After thorough mixing, about 5 minutes, the agitator is shut off and viscosity determined periodically with a No. 4 Ford cup viscosimeter. 7.7 pounds of epichlorohydrin is then added, followed by an additional 7.7 pounds after 40 minutes, 6.2 pounds at 65 minutes, 6.2 pounds at 125 minutes, 6 pounds at 160 minutes and 5 pounds at 195 minutes. After the viscosity is stable the batch is cooled to 25°-30°C The viscosity at 37% solids of the cationic portion of the polymer was 100 centistokes.
The product of the German Auslegeschrift 1,111,114 was prepared as follows: 45 gm. of dimethylamine in the form of a 40% aqueous solution was introduced dropwise at a temperature of 0° to 5°C into an emulsion of 92.5 gr. epichlorohydrin in 150 cc. of water, vigorous agitation was maintained. The reaction solution containing 38.8% total polymer solids was stirred for 6 hours at 15°-20°C The reaction mixture, which then was still alkaline, was heated for 2 hours at 30°-35°C, and then 3 hours at 55°-60°C, and finally, 3.5 hours at 80°-85°C The clear solution then showed a neutral pH. The viscosity at 37% solids of the cationic portion of the polymer was 70 centistokes.
The product was tested and the flocculation efficiency is shown by the square on the drawing. This represented about 106% of the standard compound as compared with 135% for the product of Example 1, while products of the present invention with increasing viscosity reach an efficiency of 156%, as shown in Example 3.
To a 500 ml. flask equipped as before were added 101.98 g. of 42% dimethylamine (42.83 g., 0.95 mole), and 10.77 g. of the oligomers of hexamethylene diamine obtained from the still bottoms of the purification of this product and sold by the Dupont Company under the designation Dupont Amine 248 (0.05 mole) and 82.35 g. deionized water. The addition funnel was charged with 87.90 g. epichlorohydrin (0.95 mole). The epichlorohydrin was added over 2.7 hours, keeping the temperature in the range of 40°-52°C After two hours the brown solution was then heated to 90°C and 6.0 g. of a 50% by weight aqueous sodium hydroxide solution was added together with 2 ml. epichlorohydrin. The viscosity was increased further by addition of 2 mole ml. epichlorohydrin after 15 minutes and, finally, 1 ml. after an additional 30 minutes. After heating at 90°C for 45 minutes more, 75 g. water was added to the product. The viscosity at 30.5% solids of the cationic portion of the polymer was 235 centistokes.
To a 500 ml. flask equipped as before were added 107.1 g. 42% dimethylamine (44.98 g., 1.00 mole), 10.0 g. ethylenediamine still bottoms, sold by the Jefferson Chemical Company under their trade name "Polyamine PA-500" (0.05 mole), and 78.25 g. water. To the addition funnel was charged 92.5 g. epichlorohydrin (1.0 mole). The epichlorohydrin was added over 3 hours, keeping the temperature in the range of 20°-50°C The brown solution was heated to 90°C and 6.0 g. of a 50% by weight aqueous sodium hydroxide solution was added. After 30 minutes, 0.5 ml. of epichlorohydrin was added, followed by another 0.5 ml. after 45 minutes and another 0.5 ml. of epichlorohydrin was added, followed by 0.5 ml. after 30 minutes. The product became very thick and was diluted with 200 g. water. The viscosity at 20% solids of the cationic portion of the polyquaternary compound was 125 centistokes..] .
To a 500 ml. flask equipped as before were added 50.9 g. 42% dimethylamine (21.38 g., 0.475 mole), 1.50 g. ethylenediamine (0.025 mole) and 39.6 g. deionized water. To the addition funnel was added 101 g. of 1,4-butanediol-diglycidylether (0.5 mole), the diepoxide was added over 3 hours keeping the temperature in the range of 30°-55°C The solution was heated to 90°C and 1 ml. of the diepoxide was added. The viscosity was further increased by adding successive 1 ml. increments after 45, 75, 95, 165, 210 and 240 minutes. The viscosity at 65.4% solids of the cationic portion of the polymer was 800 centistokes. At 37% solids based on the cationic portion of polyquaternary compound the viscosity was 63 centistokes.
To a 500 ml. flask equipped as before was added 138.53 g. epichlorohydrin (1.5 moles). To the addition funnel was added 112.73 g. 60% aqueous dimethylamine (67.64 g., 1.5 mole). The dimethylamine solution was added over 14 hours keeping the temperature at 20°-30°C The viscous product containing 82.2% total polymer solids was then heated to 50°C for 6 hours. On dilution to 37% solids of the cationic portion of the polymer, the product had a viscosity of 235 centistokes. A comparison of Example 1 and 8 with Comparative Example B indicates the increased viscosity obtainable with increased solids of the reaction mixture.
To a 500 ml. flask equipped as before were added 107.1 g. 42% dimethylamine (44.98 g., 0.998 mole), 7.86 g. imino-bis-propylamine (0.06 mole) and 78.25 g. water. To the addition funnel was added 92.53 g. epichlorohydrin (1.0 mole). The epichlorohydrin was added over 2.7 hours keeping the temperature 30°-55°C The solution was heated to 90°C and 6 g. 50% by weight of a sodium hydroxide solution was added. The solution became very viscous and 150 ml. water was added. Epichlorohydrin, 0.2 ml., was added and the product became even more viscous. More water, 634 g., was added to give a product of 140 centistokes at 10.2% solids of the cationic portion of the polymer.
To a 500 ml. flask equipped as before is added 50.9 g. of 42% dimethylamine (21.38 grams real, 0.475 mole) and 39.6 g. deionized water. To the addition funnel is added 101 grams of 1,4-butanediol-diglycidyl ether (0.5 mole). The diepoxide is added over 3 hours maintaining the temperature in the range of 30°-55°C After completion of the addition the reaction mixture is heated to 90°C and analysis indicates reaction to be about 75% complete. 1.50 grams (0.025 mole) of ethylenediamine is added and the reaction temperature is maintained for an additional 2 hours. A polyquaternary compound is obtained which as a 37% aqueous solution, by weight, based on the weight of the cationic portion of the polyquaternary compound has a viscosity of 125 centistokes at 25°C
To a 500 ml. flask equipped as before were added 207.5 grams of a prepolymer of adipic acid and triethylenetetramine as a 37.4% aqueous solution (77.6 grams real, about 0.04 mole) and 27.4 grams aqueous dimethylamine solution (59.15%, 16.2 grams real, 0.36 mole). To the addition funnel was added 34.4 grams of epichlorohydrin (0.372 mole). The addition was carried out while maintaining the temperature of the reaction mixture in the range of 20°-40°C over a period of 3 hours. The solution was then heated to 90°C and maintained thereat until no further increased in viscosity was noted. Over a period of about one hour there was then added 0.9 ml. of epichlorohydrin and reaction continued until no further increase in viscosity was noted. There was then added 1.2 grams of 50% aqueous NaOH and an additional increment of 0.9 ml. of epichlorohydrin was added over a 5 hour time period. The reaction mixture was then diluted to 35% solids and the reaction advanced with an additional increment of 0.2 ml. of epichlorhydrin over a period of about one hour. The solution was diluted to 27% solids and advanced with an additional 0.1 ml. of epichlorohydrin over about one hour. The pH was then adjusted with 86% aqueous phosphoric acid to 3.7. The final viscosity at 25°C was 710 centistokes at a concentration of 24.2% based on the weight of the cationic portion of the polyquaternary compound.
In order to demonstrate the improved efficiency in settling iron ore slimes, the following test procedure was employed:
One liter samples of the test slime are placed in a six-place laboratory stirrer and stirred at 100 r.p.m. for 1 minutes. A predetermined amount of flocculant to be tested in 25 milliliters of deionized water is then added to a sample. The sample is then stirred for 4 minutes at 100 r.p.m. As soon as the stirrer is turned off the times of the floc interface to settle 3 inches and 4 inches are recorded. After 15 minutes from cessation of stirring, turbidity of the supernatant liquid is determined by use of a Hellige Turbidimeter. The six-place stirrer enables six flocculants to be simultaneously tested.
Using this procedure, three flocculants were tested, each at two concentrations. Two of the flocculants were commercial products and represent comparative performances. Comparative Sample C is a cationic flocculant and is a polymer derived from diallyl dimethyl ammonium chloride. Comparative Sample A is that of Comparative Example A above. The product of the present invention evaluated is that of Example 2. Results are as follows: ______________________________________ Tur- Setting Flocculant and bidity time concentration (p.p.m.) (p.p.m.) (seconds) ______________________________________ Comparative C: 0.3 275 53 0.5 165 36 Comparative A: 0.3 225 53 0.5 145 45 Example 2: 0.3 215 54 0.5 125 37 ______________________________________
The results show that the product of the present invention results in less turbidity and therefore produces improved flocculation compared to the prior art flocculants.
In order to demonstrate the advanctage of products of the present invention as filter aids advantage treating coal washings associated with processing bituminuous coal, the following procedure was used:
To a 2-liter pail is added 1500 cc. of the coal washings under test, which comprise the effluent from initially flocculated washings. The effluent from the initial flocculation produces washings containing from 5% to 25% solids, which solids consist of about 40% fine bituminous coal and about 60% non-combustible inorganic matter such as clay and various silicates. An anionic flocculant, a copolymer of 70% acrylamide and 30% acrylic acid, is added as a 0.3% aqueous solution to provide 80 parts per million in the effluent under test. The effluent is then mixed for 1 minute to distribute the anionic flocculant therein and then filtered using a Dorr type 0.1 square foot filter leaf using a polypropylene cloth filter medium. Filtration time was for 35 seconds and drying of the cake was for 60 seconds. In conjunction with the filtration, the volume of filtrate was measured, as well as cake thickness and weight.
The above procedure was repeated except that after the anionic flocculant was mixed in the effluent under test, there was added in separate runs sufficient of the product of Example 2 as a 1% aqueous solution, by weight, based on the total weight of the polymer, to provide 100 and 150 parts per million in the effluent under test. Stirring to mix the polyquaternary flocculant is for an additional 30 seconds.
The results of the various tests are as follows: ______________________________________ Poly- quater- Filter Anionic nary cake floccu- floccu- Filtrate thick- lant, lant, volume, ness, Weight Run No. p.p.m. p.p.m. c.c. inch grams ______________________________________ 1 80 0 105 1/8 31.4 2 80 100 185 5/16 58.6 3 80 150 208 1/4 63.5 ______________________________________
The results indicate the beneficial effects obtained by use of the products of the present invention as filter aids, resulting in larger cake formation and greater filtrate volume in a specified time period as compared to the normal use of anionic flocculant alone.
This example illustrates the advantages of the products of the present invention in raw water clarification.
Using a standard sludge contact clarifier raw water was treated with 50 parts per million of ferric chloride and 0.1 part per million of the anionic flocculant described in Example 13. The resulting effluent had a turbidity in excess of 10 parts per million expressed in Jackson turbidity units.
Replacing both the ferric chloride and the anionic flocculant by 5 parts per million of the product of Example 2 produced effluent having a turbidity less than 5 parts per million expressed in Jackson turbidity units.
Thus, the product of the present invention produced reduced turbidity at greatly reduced usage of additives. In addition, the clarifier was able to operate at an increase of 20% in flow rate while providing the above advantages.
This example illustrates the effectiveness of the products of the present invention as demulsifiers.
Using an American Petroleum Institute separator, an aqueous stream containing emulsified and suspended oil and suspended iron-containing solids was processed in the normal manner.
A similar trail was then made wherein prior to entry into the separator there was mixed sufficient of the product of Example 2 as a 1% aqueous solution to provide 5 parts per million in the stream being processed. Results of the runs are as follows: ______________________________________ Influent, p.p.m. Effluent, p.p.m. Product of Example 2, p.p.m. pH Oils Solids Oils Solids ______________________________________ 0 4.3 560 427 510 427 4.2 271 1.291 112 50 5 6.2 61 538 2 35 8.2 88 650 15 45 ______________________________________
In the above table, influent represents the stream prior to entering the separator and effluent represents the stream after exit from the separator. The results indicate the beneficial results in separation obtained with the product of the present invention. The results also show that the product of the present invention is beneficial at a wide range of pH values.
This example illustrates the advantages of products of the present invention in sludge dewatering.
In a standard sewage treatment plant operating at a flow rate of 205 gallons per minute, sludges containing a mixture of primary digested and waste activated solids were treated in separate runs with no additive and with various amounts of the products of Example 2. Results are as follows: ______________________________________ Product Suspended solids of Ex. 2 Solids in Solids in sludge added effluent captured (percent) (percent)1 (percent) (percent) ______________________________________ 7.59 0 3.13 59 6.18 0.2 1.22 80 6.16 0.565 0.38 95 5.06 1.4 0.08 98 ______________________________________ 1 Percent total polymer solids on weight of solids in sludge.
The results indicate the high increase in solids captured by use of the product of the present invention.
This example illustrates use of the products of this invention in air flotation sludge concentration.
Using standard air flotation units to concentrate activated sludge in sewage treatment, the following trials were made. In one run, the product of Comparative Example A was added as processing aid. In a second run the product of Example 2 was added as a processing aid.
The results and additive usage is given in the table which follows: ______________________________________ Product of com- parative Product Ex. A of Ex. 2 ______________________________________ Tons sludge processed 57 55 Pounds polymer added 1,830 1,686 Percent solids floated 4.62 4.79 ______________________________________
The above results show that the product of the present invention was more effective at lower polymer usage. The sludge was processed as 0.8% solids slurry and was concentrated during the air flotation.
Panzer, Hans Peter, Dixon, Kenneth Wayne
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| Mar 06 1974 | American Cyanamid Company | (assignment on the face of the patent) | / |
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