CA2219868A1 - Hydrophilic dispersion polymers for the clarification of deinking process waters - Google Patents
Hydrophilic dispersion polymers for the clarification of deinking process waters Download PDFInfo
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- CA2219868A1 CA2219868A1 CA002219868A CA2219868A CA2219868A1 CA 2219868 A1 CA2219868 A1 CA 2219868A1 CA 002219868 A CA002219868 A CA 002219868A CA 2219868 A CA2219868 A CA 2219868A CA 2219868 A1 CA2219868 A1 CA 2219868A1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/917—Color
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/928—Paper mill waste, e.g. white water, black liquor treated
Abstract
The invention comprises a method for clarifying ink-laden water obtained from the recycling of paper stocks by treating said water with a conventional coagulant followed by treatment with a hydrophilic dispersion polymer. The hydrophilic dispersion flocculant of the invention is a copolymer of dimethylaminoethyl (meth)acrylate methyl chloride quat (DMAEA-MCQ) cationic monomer and (meth)acrylamide (AcAm).
Following dosing with the flocculant, a floc is formed. The floc contains ink and impurities which are removed from the water process stream by means of solid liquid separation; the solid liquid separation comprising a dissolved air flotation method.
Following dosing with the flocculant, a floc is formed. The floc contains ink and impurities which are removed from the water process stream by means of solid liquid separation; the solid liquid separation comprising a dissolved air flotation method.
Description
Back,~roulld of the Invention 1. Field of the ~nv~ntion The invention relates to the clarification of deinking process waters which result from the recycling of paper stocks. More specifically, the present invention relates to the use of hydrophilic dispersion copolymers of DMAEA-MCQ and acrylamide as water clarifying agents for deinking influents.
2. Description of the Prior Art Recycled paper is increasingly used as a pulp source. One of the major pulping steps involves removal of the ink from any source of printed recycled paper. Large volumes of water are required for the ink removal process and its clean-up is accomplished using a solids/liquid separation unit operation. Dissolved air flotation (DAF) is commonly used. Recycle mills are most frequently located in the metropolitan 1~ areas where an emphasis on closing the water cycle of the mill is great. Consequently, effective clean-up of the deinking wash waters becomes important because reuse of the water generated e.g. from a DAF, can lead to reduced sheet quality such as brightness.
Also, if these waters are used for other purposes, minimi7in~ the amounts of BOD/-COD
and suspended solids is desirable.
Clarification chemicals are typically utilized in conjunction with mechanical clarifiers for the removal of solids from the process water stream. The clarification chemicals coagulate and/or flocculate the suspended solids into larger particles. which can then be removed from the process stream by gravitational settling or flotation.
Depending upon the characteristics of the individual waters, differing chemical types and programs may be ~ltili7~-1 Clarification generally refers to the removal of nonsettleable material by coagulation, flocculation and sedimentation. Coagulation is the process of destabilization by charge neutralization. Once neutralized, particles no longer repel each other and can be brought together. Coagulation is necessary for removal of colloidal sized suspended matter. Flocculation is the process of bringing together the destabilized, "coagulated"
particles to form a larger agglomeration or floc.
Often a dual polymer program is the treatment of choice for clarification of deinking process waters by dissolved air flotation. Typically, this comprises a low molecular weight cationic coagulant followed by a high molecular weight flocculant.
The preferred flocculant of the invention is a hydrophilic dispersion copolymer of 1~ dimethylaminoethyl acrylate methylchloride q--~ten ~ry salt, DMAEA-MCQ and acrylamide. The use of these flocculants affords removal of particulate materials without the unwanted addition of oils and surfactants contained in conventional latex polymers.
Additionally, these flocculants require no inverter system and can be introduced to the paper process stream using simple feeding equipment.
It is customary to use coagulants prior to using flocculants in the deinking process waters to provide charge neutralization. This affords efficient solids removal. A
variety of polymeric coagulants may be employed depending upon the particular deinking waste water treated.
Summary of the Invention The invention comprises a method for clarifying ink-ladened water obtained from the recycling of paper stocks by treating said water with a coagulant followed by treatment with a hydrophilic dispersion polymer.
According to one aspect of the present invention, there is provided a method for clarifying ink-laden paper process water, comprising: dosing the water with a coagulant to produce a coagulated process stream; dosing solids from the coagulated process stream with a hydrophilic dispersion polymer, to form a floc containing ink and other impurities;
and effecting solid-liquid separation of the floc from the process stream, wherein the solid-liquid separation is carried out by dissolved air flotation.
In a preferred embodiment, the hydrophilic dispersion polymer comprises (a) a cationic monomer represented by the following general formula (I):
CH2=C Rl O=C A' - B' N - R4.X
wherein Rl is H or CH3; each of R2 and R3 is an alkyl group having 1 to 2 carbon atoms; R4 is H or an alkyl group of 1 to 2 carbon atoms; A' is an oxygen atom or NH; B' is an alkylene group of 2 to 4 carbon atoms or a hydroxypropylene group; and X is an anionic counterion; and (b) a second monomer represented by (meth)acrylamide (in an - 4a -aqueous solution of a polyvalent anionic salt), wherein the polymerization is carried out in the presence of either an organic high-molecular weight multivalent cation comprising a water-soluble polymer co~ g at least one monomer of formula (I) andlor poly diallyl dimethyl arnmonium chloride (DADMAC). Reslllt~nt from the addition of the polymers is a clarified process water stream and highly flocculated solids, the latter being readily handled by ~"dh,;~ y solid/liquid separation processes, such as a dissolved air flotation method.
Brief Dese~ tion of theDr~
FIG. 1 is a graph co~ hlg turbidity reduction of the 10% and 30% mol DMAEA MCQ
latex with dispersion polymers in the presence of 30 parts per million of Composition A.
FIG. 2 is a graph c~ pa hlg turbidity reduction ofthe 10% and 30% mol DMAEA MCQ
latex with dispersion polymers in the presence of 30 parts per million of Composition B.
FIG. 3 is a graph comparing turbidity reduction of the 10% and 30% mol DMAEA MCQl j latex with dispersion polymers in the presence of 30 parts per million of Composition C.
Description of the Preferred F.rnbo(li...~"l~
The invention comprises a method for clarifying ink-ladened water obtained from the recycling of paper stocks by treating said water with a conventional coagulant followed by treatment with a hydrophilic dispersion polymer.
Preferably, the hydrophilic dispersion polymer of the invention is a copolymer of dimethylaminoethyl (meth)acrylate methyl chloride quat (DMAEA-MCQ) cationic monomer and (meth)acrylamide (AcAm). It has been found that the polymer described above confers advantages for use in a paperrn~kin~ process. Specifically, the hydrophilic dispersion polymers of the invention show improved or equal activity with respect to deinking process water clarification as compared to the commercial standard DMAEA
methyl chloride qu~L~lll~y latex ofthe same charge. The use ofthese flocculants affords removal of particulate materials without the unwanted addition of oils and surf~ct~ntc contained in conventional latex polymers. Additionally, these flocculants require no inverter system and can be introduced to the paper process stream using simple feeding equipment. Latex is defined within this application as an inverse water-in-oil emulsion polymer.
Examples I and 2 below outline processes for plcl ~hlg the copolymer at various ratios of the monomer components. Preferably, the arnount of dimethylaminoethyl acrylate methyl chloride quaternary present in the copolymer is from about 3 mole percent to about 30 mole percent. Preferably, the hydrophilic dispersion polymer has a cationic charge of from about 1% mol to about 30% mol. Further, the range of intrinsic viscosities for the hydrophilic dispersion polymers of the invention is preferably from about 10.0 to about 22.0 dl/g, more preferably from about 11.9 to about Zl.2 dl/g. According to the preferred method of the invention, the dispersion polymer is added in an amount from about 0.1 to about 100 ppm on a products basis. Preferably, the dosage of the hydrophilic dispersion polymer is from about 0.1 to about 100 parts per million on a productsbasis and the dosage of the hydrophilic dispersion polymer is from about 0.5 to about 10 parts per million on an actives basis.
The recycled paper effluent is initially treated with a coagulant to produce a coagulated effluent. This step functions to generally aggregate ink impurities in the effluent together. However, the aggregation of the impurities does not form them into particulates which are amenable to removal by mechanical solids liquid separation processes. As stated above, it is customary to use coagulants prior to using flocculants in the deinking process waters to provide charge neutralization. A variety of polymeric coagulants may be employed depending upon the particular deinking waste water treated. For a more detailed description of conventional polymeric coagulants see the Nalco Water Handbook, Second Edition, 1988, McGraw-Hill, Inc., the disclosure of which is incorporated herein by reference. The use of coagulants is conventional and does not form a part of this invention.
In order to accomplish the solid/liquid separation, distinct bodies or flocs must be formed with the aid of a flocculant. The preferred flocculant of the invention is a copolymer of dimethylaminoethyl (meth)acrylate methyl chloride quat (DMAEA-MCQ) - 7a -cationic monomer and (meth)acrylamide (AcAm). Preferably, the flocculant has an intrinsic viscosity of from about 10.0 to about 22.0 deciliters per gram (dl/g).
The flocculant is believed to cause the aggregation of neutralized colloidal particles which are suspended in the paper process water stream. Aggregation is the S result of either el~dpphlg agents (i.e., inorganic flocc.ll~nt.c) or bonding agents (i.e., organic flocculants) bringing the neutralized particles together.
A dual polymer tre~tment generally comprises a low molecular weight cationic coagulant in combination with a high molecular weight flocculant. Typical cationic coagulants are poly(diallyldimethyl ammonium chloride), amphoteric diallyldimethyl ammonium chloride/acrylic acid co"l~i";,~g copolymers, con~ n~tion polymers of ethylene dichloride/ammonia or dimethylarnine/eplchlorohydrin. Conventional acrylamide-based flocculants have been utilized to assist in the solid/liquid separation.
Traditionally, coagulants are preferably added to the system in solution form prior to the DAF unit while the flocculants are added to the DAF unit following dissolved air injection. The flocculants are added in an effective amount, generally between about 0.5-1 0 ppm.
The following examples are presented to describe preferred embodiments and utilities of the invention and are not meant to limit the invention unless otherwise stated in the claims appended hereto.
FY~IeS
Example 1 - Process for Synlh~ , Dispersion Copolymers of Aclylamide and 3 mole % DMAEA-MCQ.
To a two-liter resin reactor equipped with strirrer, temperature controller~ andwater cooled condenser, was added 287.59 grarns of a 48.1 % solution of acrylamide (1.9461 moles), 7.24 grams of an 80.6% solution of DMAEA-MCQ (0.0301 moles), 250grarns of ammonium sulfate, 225.59 grams of deior.uzed water, 27 grarns of glycerol, 56.25 grarns of a 16% solution of polyDADMAC (poiy diallyl dimethyl ammonium chloride)(IV= 1.5 dl/gm), 18 grarns of a 20% solution of polyDMAEA-MCQ
(IV=2.0dl/gm), and 0.3 grarns of EDTA. The llli;~lUlC was heated to 48~C and 0.50 grams of a 4% solution of 2,2' Azobis(2 amidinoplo~ualle) dihydrochloride was added.
The resulting solution was sparged with 1000 cc/min. of nitrogen. After l ~ minutes, polymerization began and the solution became viscous. Over the next 4 hours the temperature was maintained at 48~C and a solution co~ g 95.86 grams (0.6487 moles) of 48.1 % acrylamide, 12.07 grams (0.0502 moles) of an 80.6% solution of DMAEA-MCQ, 9 grams of glycerol and 0.1 gram of EDTA was pumped into the reactor using a syringe pump. To the resulting polymer dispersion was added 0.50 grams of a 4% solution of 2,2' Azobis(2 amidinopropane) dihydrochloride. The dispersion was then further reacted for 2.5 hours at a temperature of 48~C to 55~C. The resulting polymer dispersion had a Brookfield viscosity of 5600cps. To the above dispersion was added 10 grams of 99% acetic acid and 20 grams of sodium sulfate. The resulting dispersion had a Brookfield viscosity of 1525 cps and contained 20% of a 97/3 copolymer of acrylamide and DMAEA-MCQ with an intrinsic viscosity of 12.1 dllgm in 0.125 molar NaNO3.
Example 2 - Process for Syntl~_i,i;cillg Dispersion Copolymers of Ac~ylamide and 10 mole ~/O Dl\IAEA-MCQ.
To a two-liter resin reactor equipped with stirre}, temperature controller. and water cooled condenser, was added 239.38 grams of a 48.1% solution of acrylamide(1.6199 moles), 21.63 grams of an 80.6% solution of DMAEA-MCQ (0.09001 moles), 260 grams of ammonium sulfate, 258.01 grams of deionized water, 18 grams of glycerol, 33.75 grams of a 16% solution of polyDADMAC (IV= 1.5 dl/gm), 36 grams of a 20%
solution of polyDMAEA-MCQ (IV=2.0dl/gm), and 0.3 grarns of EDTA. The mixture was heated to 48~C and 0.S0 grams of a 4% solution of 2,2' Azobis(2 amidinopropane) dihydrochloride was added. The resulting solution was sparged with 1000 cc/min. of I ~ nitrogen. After 15 minutes, polymerization began and the solution became viscous. Over the next 4 hours the temperature was maintained at 48~C and a solution containing 79.79 grams (0.5399 moles) of 48.1 % acrylamide, 36.04 grams (0.1500 moles) of an 80.6%
solution of DMAEA-MCQ, 6 grams of glycerol and 0.1 gram of EDTA was pumped into the reactor using a syringe pump. To the resulting polymer dispersion was added 0.50 grams of a 4% solution of 2,2' Azobis(2 amidinopropane) dihydrochloride. The dispersion was then further reacted for 2.5 hours at a t~.,lpel~ re of 48~C to 55~C. The resulting polymer dispersion had a Brookfield viscosity of 7600cps. To the abovedispersion was added l O grams of 99% acetic acid and 20 grams of sodiurn sulfate. The resulting dispersion had a Brookfield viscosity of 2100 cps and contained 20% of a 90/10 copolymer of acrylamide and DMAEA-MCQ with an intrinsic viscosity of 1 j.5 dl/gm in 0.125 molarNaNO3.
Dissolved Air Flotation Water Samples Synthetic samples were ~e~aled in the laboratory under the following conditions.A mixture of oil-based printed newsprint (70 wt%) and m~g~7ine (30 wt%) was repulped (4.5% consistency, 45~C, 30 min.) with sodium hydroxide (0.5% based on paper), sodiurn silicate (2.0%~, surfactant (0.5%, ethoxylated linear alcohol, HLB 14.5), chelant (0.25%, DTPA. diethylenetriaminepentaacetic acid), and hydrogen peroxide (1.0%). The deinking water was mechanically extracted, collected. and diluted ~3-fold.
A sample of DAF influent was obtained from a Midwestern tissue manufacturer wherein the furnish was a typical newsprint m~7ine composition. Total solids in this influent were 4500 ppm with a solution pH of 7. All samples were stored at 4~C and tested within five days.
Polymer Evaluation Polymers and their respective descriptions used in this invention are summarizedin Table I.
Typical jar testing methods were used to monitor polymer performance. Standard coagulants were prepared as 1% (actives) solutions and flocculants as ~0.1% (product) solutions in deionized water. Dosages reported are based on actives for coagulants and as product for flocculants. Samples of the deinking influent were stirred at 200 rpm (fast mix) for 3 rnin. wherein the coagulant was added at the beginning of the fast mix and the flocculant during the last 40 seconds of the fast mix. This was followed by a slow mix of 25 rpm for 2 minutes. The samples were allowed to settle for 5 minutes and an aliquot of the upper liquid layer was removed and diluted a~ululopliately when required. Turbidity measurements were acquired with a HACH DR-2000 at 450 mn.
F~ ~le 3 Initial screening of the proprietary dispersion DMAEA MCQ/AcAm flocculants were performed on a synthetic water sample prepared as described above. Table IIsurnrnarizes the data used to determine the optimal coagulant concentration for subsequent flocculant studies. The coagulants screened, Composition A (linear Epi/DMA), Composition B (polyDADMAC), and Composition C (90/10 DADMAC/AA), are commonly used in DAF systems. Optimal coagulant performance with the cationic flocculant Composition D (latex 10% DMAEA MCQ/AcAm) was obtained at 15 ppm for Composition A, 10 ppm for Composition B, and 15 ppm for Composition C. A dose of 15 ppm for each coagulant was subsequently used during the screening of the dispersion flocculants.
Tables III - V summarize the results of the DMAEA MCQ dispersion polymer screening studies in conjunction with Composition A, Composition B, and Composition C, respectively. It is ~altllt that for each coagulant, the charge on the flocculant minim~lly affected the reduction in turbidity. Also, there was little difference in the turbidity values obtained at ~ ppm versus 3 ppm flocculant for a given coagulant.
By in large, the dispersion flocc~ nt~ performed as well as their similarily charged latex twins.
Ex~nlple 4 The series of DMAEA MCQ/AcAm copolymers were also screened in a recycle mill sample. Table VI summarizes the data used to determine the optimal coagulant 1~ concentration for the ensuing flocculant studies. Not surprisingly, higher amounts of coagulant were required to clarify the mill water compared to the synthetic water. In subsequent studies, for each coagulant the concentration was held at 30 ppm.
Tables VII-IX display the results for the DMAEA MCQ/AcAm copolymers and their ability to aid in the clarification of the mill water. When the hydrophilic dispersion flocculants were used in conjunction with Composition A (Table VII) or Composition B
(Table VIII), an increase in the amount of DMAEA MCQ present in the copolymer slightly enhanced the reduction in turbidity. However, this was not the case with the polyampholyte, Composition C, wherein minim~l dir~elences were obtained in turbidity reductions as a function of the flocculant s cationic charge. In each series, increasing the concentration of flocculant from 3 to 5 ppm did not enhance turbidity reduction.Comparison of the 10% and 30% mol DMAEA-MCQ latex and dispersion polymers (at ~ ppm) are shown in Figures 1-3. For this mill sample, the dispersion flocculants performed as well as, or slightly better than, their latex twin.
TABLE I
POLYMER DESCRIPTION
Intrinsic Co~l~nts Viscosity (dl/g) Composition A Epi/DMA, linear solution polymer0 11 Composition B poly(DADMAC), solution polymer 0 45 Composition C 90/10 DADMAC/AA solution polymer1 2 ~ispersions CompositionD 1 mol% DMAEA-MCQ/AcAm 11 9 Composition E 3 mol% DMAEA-MCQ/AcAm 15 7 Composition F 5 mol% DMAEA-MCQ/AcAm 14 1 Composition G 10 mol% DMAEA-MCQ/AcAm 17 0 Composition H 20 mol% DMAEA-MCQ/AcAm 21 2 Composition I 30 mol% DMAEA-MCQ/AcAm 17 0 Latex Polymers Composition J 10 mol% DMAEA-MCQ/AcAm 18 0 Composition K 30 mol% DMAEA-MCQ/AcAm 20 0 Epi/DMA epichlorohydrin/dimethylamine DADMAC diallyldimethyl arnmonium chloride AA acrylic acid DMAEA-MCQ dimethylaminoethylacrylate methylchloride quaternary salt AcAm acrylamide Table II
Coagulant Dosage Optin~i7~tion ~Synthetic D~F Water) Coagulant DosageFlocculant DosageTurbidit~~/O Turbiditv (ppm) (ppm) (FTU) Reduction Control 415 Composition A 5Composition J 5 276 33.49 Composition A 10Composition J 5 31 92.53 Composition A 15Composition J 5 15 96.39 Composition A 20Composition J 5 20 95.18 Composition A 40Composition J 5 154 62.89 Composition B 5Composition J 5 244 41.20 Composition B 10Composition J 5 19 95.42 Composition B 15Composition J 5 27 93.49 Composition B 20Composition J 5 218 47.47 Composition C 5Composition J 5 282 32.05 Composition C 10Composition J 5 58 86.02 Composition C 15Composition J 5 39 90.60 Composition C 20Composition J 5 246 40.72 Table III
Screening of DMAEA-MCQ Dispersion Polvmers (Synthetic DAF Water) Coagulant Dosage Flocculant Mole % Dosage Turbiditv %
(ppm) DMAEA- (ppm) ~TU) Turbiditv MCQ Reduction Control 41 j Composition A15 Composition J 10 5 15 96.39 Composition A15 Composition J 10 3 13 96.87 Composition A15 Composition K 30 5 11 97.35 Composition A15 Composition K 30 3 10 97.59 Composition A15 Composition D 1 5 18 9~.66 Composition A15 Composition E 3 5 18 95.66 Composition A15 Composition F 5 5 21 94.94 Composition A15 Composition G 10 5 15 96.39 Composition A15 Composition H 20 5 16 96.14 Composition A15 Composition I 30 5 10 97.~9 Composition A15 Composition D 1 3 16 96.14 Composition A15 Composition E 3 3 17 95.90 Composition A15 Composition F 5 3 16 96.14 Composition A15 Composition G 10 3 12 97.11 Composition A15 Composition H 20 3 10 97.59 Composition A15 Composition 1 30 3 8 98.07 Table IV
Screening of DMAEA-MCQ Dispersion Polymers (Svnthetic DAF Water) Coagulant DosageFlocculantMole % Dosage Turbidity %
(ppm) DMAEA (ppm) (FTU)Turbidity MCQ Reduction Control 415 Composition B 15Composition J 10 5 27 93.49 Composition B 15Composition J 10 3 28 g3.25 Composition B 15Composition K 30 5 21 94.94 Composition B 15Composition K 30 3 21 94.94 Composition B 15Composition D 1 5 17 95.90 Composition B 15Composition E 3 5 22 94.70 Composition B 15Composition F 5 5 20 95.18 Composition B 15Composition G 10 5 17 95.90 Composition B 15Composition H 20 5 21 94.94 Composition B 15Composition I 30 5 23 94.46 Composition B 15Composition D 1 3 28 93.25 Composition B 15Composition E 3 3 27 93.49 Composition B 15Composition F 5 3 24 94.22 Composition B 15Composition G 10 3 19 95.42 Composition B 15Composition H 20 3 20 95.18 Composition B 15Composition I 30 3 20 95.18 Table V
Screening of DMAEA-MCQ Dispersion Polymers (Synthetic DAF Water) Coagulant Dosage Flocculant Mole ~/O Dosage Turbidity %
(ppm) DMAEA- (ppm) (~i TU) Turbidity MCQ Reduction Control 415 Composition C 15 Composition J 10 5 39 90.60 Composition C 15 Composition J 10 3 30 92.77 Composition C 15 Composition K 30 5 20 95.18 Composition C 15 Composition K 30 3 62 85.06 Composition C 15 Composition D 1 5 30 92.77 Composition C 15 Composition E 3 5 47 88.67 Composition C 15 Composition F 5 5 19 95.42 Composition C 15 Composition G 10 5 36 91.33 Composition C 15 Composition H 20 5 28 93.~5 Composition C 15 Composition I 30 5 20 95.18 Composition C 15 Composition D 1 3 34 91.81 Composition C 15 Composition E 3 3 46 88.92 Composition C 15 Composition F 5 3 28 93.25 Composition C 15 Composition G 10 3 23 94.46 Composition C 15 Composition H 20 3 58 86.02 Composition C 15 Composition I 30 3 31 92.53 Table VI
Coagu}ant Dosage Opti-ni7~tion (A Midwestern Tissue Mill DAF Water) Coagulant DosageFlocculant DosageTurbidity %
(ppm) (ppm) Units Turbidity (~i TU) Reduction Control 450 Composition A 5Composition J 5 157 65.11 Composition A 10Composition J 5 133 70.44 Composition A 20Composition J 5 108 76.00 Composition A 30Composition J 5 99 78.00 Composition A 40Composition J 5 101 77.56 Composition A 50Composition J 5 94 79.11 Composition B 5Composition J 5 119 73.56 Composition B 10Composition J 5 107 76.22 Composition B 20Compositio.n J 5 91 79.78 Composition B 30Composition J 5 91 79.78 Composition B 40Composition J 5 89 80.22 Composition C 5Composition J 5 114 74.67 Composition C 10Composition J 5 98 78.22 Composition C 20Composition J 5 85 81.11 Composition C 30Composition J 5 79 82.44 Composition C 40Composition J 5 106 76.44 Table VII
Screening of DMAEA-MCQ Dispersion Polymers (A Midwestern Tissue Mill DAF Water) CoagulantDosage Floccnl~ntMole % Dos~ge Turbidit~ %
(ppm) DMAEA (ppm)(~i TU)Turbidit~-~MCQ Reduction Control 450 Composition A30 Composition J 10 3 114 74.67 Composition A30 Composition J 10 5 99 78.00 Composition A30 Composition J 10 10 92 79.56 Composition A30 Composition J 10 15 92 79.56 Composition A30 Composition K 30 3 95 78.89 Composition A30 Composition K 30 5 88 80.44 Composition A30 Composition D 1 3 127 71.78 Composition A30 Composition E 3 3 127 71.78 Composition A30 Composition F 5 3 118 73.78 Composition A30 Composition G 10 3 103 77.11 Composition A30 Composition H 20 3 102 77.33 Composition A30 Composition I 30 3 98 78.22 Composition A30 Composition D 1 5 128 71.56 Composition A30 Composition E 3 5 135 70.00 Composition A30 Composition F 5 5 122 72.89 Composition A30 Composition G 10 5 101 77.56 Composition A30 Composition H 20 5 95 78.89 Composition A30 Composition I 30 5 93 79.33 Table VIII
Screening of DMAEA-MCQ Dispersion Polymers (A Midwestern Tissue Mill DAF Water) Coagulant Dosage Flocculant Mole % Dosage Turbidity %
(ppm) DMAEA (ppm) Units Turbidity MCQ (FTU) Reduction Control 450 Composition B 30 Composition J 10 3 130 71.11 Composition B 30 Composition J 10 5 91 79.78 Composition B 30 Composition K 30 3 82 81.78 Composition B 30 Composition K 30 5 81 82.00 Composition B 30 Composition D 1 3 106 76.44 Composition B 30 Composition E 3 3 112 75.11 Composition B 30 Composition F 5 3 113 74.89 Composition B 30 Composition G 10 3 87 80.67 Composition B 30 Composition H 20 3 81 82.00 Composition B 30 Composition I 30 3 85 81.11 Composition B 30 Composition D 1 5 112 7S.11 Composition B 30 Composition E 3 5 119 73.56 Composition B 30 Composition F S S 113 74.89 Composition B 30 Composition G 10 5 86 80.89 Composition B 30 Composition H 20 5 83 81.56 Composition B 30 Composition I 30 S 80 82.22 S
Table IX
Screening of DMAEA-MCQ l)ispersion Polymers ~A Midwestern Tissue Mill DA~ Water) Coagulant Dosage Flocc~ nt Mole % Dosage Turbidit~ %
(ppm) DMA~A (ppm) Units Turbidit~
MCQ (FTU) Reduction Control 450 Composition C30 Composition J 10 3 78 82.67 Composition C30 Composition J 10 5 79 82.44 Composition C30 Composition K 30 3 78 82.67 Composition C30 Composition K 30 S 74 83.56 Composition C30 Composition D 1 3 78 82.67 Composition C30 Composition E 3 3 80 82.22 Composition C30 CompositionF 5 3 78 82.67 Composition C30 Composition G 10 3 78 82.67 Composition C30 Composition H 20 3 77 82.89 Composition C30 CompositionI30 3 77 82.89 Composition C30 Composition D 1 5 77 82.89 Composition C30 Composition E 3 5 80 82.22 Composition C30 Composition F 5 5 77 82.89 Composition C30 Composition G 10 5 77 82.89 Composition C30 CompositionH20 5 74 83.56 Composition C30 Composition I 30 5 68 84.89 j Changes can be made in the composition, operation and arrangement of the method of the present invention described herein without departing from the concept and scope of the invention as defined in the following claims:
Also, if these waters are used for other purposes, minimi7in~ the amounts of BOD/-COD
and suspended solids is desirable.
Clarification chemicals are typically utilized in conjunction with mechanical clarifiers for the removal of solids from the process water stream. The clarification chemicals coagulate and/or flocculate the suspended solids into larger particles. which can then be removed from the process stream by gravitational settling or flotation.
Depending upon the characteristics of the individual waters, differing chemical types and programs may be ~ltili7~-1 Clarification generally refers to the removal of nonsettleable material by coagulation, flocculation and sedimentation. Coagulation is the process of destabilization by charge neutralization. Once neutralized, particles no longer repel each other and can be brought together. Coagulation is necessary for removal of colloidal sized suspended matter. Flocculation is the process of bringing together the destabilized, "coagulated"
particles to form a larger agglomeration or floc.
Often a dual polymer program is the treatment of choice for clarification of deinking process waters by dissolved air flotation. Typically, this comprises a low molecular weight cationic coagulant followed by a high molecular weight flocculant.
The preferred flocculant of the invention is a hydrophilic dispersion copolymer of 1~ dimethylaminoethyl acrylate methylchloride q--~ten ~ry salt, DMAEA-MCQ and acrylamide. The use of these flocculants affords removal of particulate materials without the unwanted addition of oils and surfactants contained in conventional latex polymers.
Additionally, these flocculants require no inverter system and can be introduced to the paper process stream using simple feeding equipment.
It is customary to use coagulants prior to using flocculants in the deinking process waters to provide charge neutralization. This affords efficient solids removal. A
variety of polymeric coagulants may be employed depending upon the particular deinking waste water treated.
Summary of the Invention The invention comprises a method for clarifying ink-ladened water obtained from the recycling of paper stocks by treating said water with a coagulant followed by treatment with a hydrophilic dispersion polymer.
According to one aspect of the present invention, there is provided a method for clarifying ink-laden paper process water, comprising: dosing the water with a coagulant to produce a coagulated process stream; dosing solids from the coagulated process stream with a hydrophilic dispersion polymer, to form a floc containing ink and other impurities;
and effecting solid-liquid separation of the floc from the process stream, wherein the solid-liquid separation is carried out by dissolved air flotation.
In a preferred embodiment, the hydrophilic dispersion polymer comprises (a) a cationic monomer represented by the following general formula (I):
CH2=C Rl O=C A' - B' N - R4.X
wherein Rl is H or CH3; each of R2 and R3 is an alkyl group having 1 to 2 carbon atoms; R4 is H or an alkyl group of 1 to 2 carbon atoms; A' is an oxygen atom or NH; B' is an alkylene group of 2 to 4 carbon atoms or a hydroxypropylene group; and X is an anionic counterion; and (b) a second monomer represented by (meth)acrylamide (in an - 4a -aqueous solution of a polyvalent anionic salt), wherein the polymerization is carried out in the presence of either an organic high-molecular weight multivalent cation comprising a water-soluble polymer co~ g at least one monomer of formula (I) andlor poly diallyl dimethyl arnmonium chloride (DADMAC). Reslllt~nt from the addition of the polymers is a clarified process water stream and highly flocculated solids, the latter being readily handled by ~"dh,;~ y solid/liquid separation processes, such as a dissolved air flotation method.
Brief Dese~ tion of theDr~
FIG. 1 is a graph co~ hlg turbidity reduction of the 10% and 30% mol DMAEA MCQ
latex with dispersion polymers in the presence of 30 parts per million of Composition A.
FIG. 2 is a graph c~ pa hlg turbidity reduction ofthe 10% and 30% mol DMAEA MCQ
latex with dispersion polymers in the presence of 30 parts per million of Composition B.
FIG. 3 is a graph comparing turbidity reduction of the 10% and 30% mol DMAEA MCQl j latex with dispersion polymers in the presence of 30 parts per million of Composition C.
Description of the Preferred F.rnbo(li...~"l~
The invention comprises a method for clarifying ink-ladened water obtained from the recycling of paper stocks by treating said water with a conventional coagulant followed by treatment with a hydrophilic dispersion polymer.
Preferably, the hydrophilic dispersion polymer of the invention is a copolymer of dimethylaminoethyl (meth)acrylate methyl chloride quat (DMAEA-MCQ) cationic monomer and (meth)acrylamide (AcAm). It has been found that the polymer described above confers advantages for use in a paperrn~kin~ process. Specifically, the hydrophilic dispersion polymers of the invention show improved or equal activity with respect to deinking process water clarification as compared to the commercial standard DMAEA
methyl chloride qu~L~lll~y latex ofthe same charge. The use ofthese flocculants affords removal of particulate materials without the unwanted addition of oils and surf~ct~ntc contained in conventional latex polymers. Additionally, these flocculants require no inverter system and can be introduced to the paper process stream using simple feeding equipment. Latex is defined within this application as an inverse water-in-oil emulsion polymer.
Examples I and 2 below outline processes for plcl ~hlg the copolymer at various ratios of the monomer components. Preferably, the arnount of dimethylaminoethyl acrylate methyl chloride quaternary present in the copolymer is from about 3 mole percent to about 30 mole percent. Preferably, the hydrophilic dispersion polymer has a cationic charge of from about 1% mol to about 30% mol. Further, the range of intrinsic viscosities for the hydrophilic dispersion polymers of the invention is preferably from about 10.0 to about 22.0 dl/g, more preferably from about 11.9 to about Zl.2 dl/g. According to the preferred method of the invention, the dispersion polymer is added in an amount from about 0.1 to about 100 ppm on a products basis. Preferably, the dosage of the hydrophilic dispersion polymer is from about 0.1 to about 100 parts per million on a productsbasis and the dosage of the hydrophilic dispersion polymer is from about 0.5 to about 10 parts per million on an actives basis.
The recycled paper effluent is initially treated with a coagulant to produce a coagulated effluent. This step functions to generally aggregate ink impurities in the effluent together. However, the aggregation of the impurities does not form them into particulates which are amenable to removal by mechanical solids liquid separation processes. As stated above, it is customary to use coagulants prior to using flocculants in the deinking process waters to provide charge neutralization. A variety of polymeric coagulants may be employed depending upon the particular deinking waste water treated. For a more detailed description of conventional polymeric coagulants see the Nalco Water Handbook, Second Edition, 1988, McGraw-Hill, Inc., the disclosure of which is incorporated herein by reference. The use of coagulants is conventional and does not form a part of this invention.
In order to accomplish the solid/liquid separation, distinct bodies or flocs must be formed with the aid of a flocculant. The preferred flocculant of the invention is a copolymer of dimethylaminoethyl (meth)acrylate methyl chloride quat (DMAEA-MCQ) - 7a -cationic monomer and (meth)acrylamide (AcAm). Preferably, the flocculant has an intrinsic viscosity of from about 10.0 to about 22.0 deciliters per gram (dl/g).
The flocculant is believed to cause the aggregation of neutralized colloidal particles which are suspended in the paper process water stream. Aggregation is the S result of either el~dpphlg agents (i.e., inorganic flocc.ll~nt.c) or bonding agents (i.e., organic flocculants) bringing the neutralized particles together.
A dual polymer tre~tment generally comprises a low molecular weight cationic coagulant in combination with a high molecular weight flocculant. Typical cationic coagulants are poly(diallyldimethyl ammonium chloride), amphoteric diallyldimethyl ammonium chloride/acrylic acid co"l~i";,~g copolymers, con~ n~tion polymers of ethylene dichloride/ammonia or dimethylarnine/eplchlorohydrin. Conventional acrylamide-based flocculants have been utilized to assist in the solid/liquid separation.
Traditionally, coagulants are preferably added to the system in solution form prior to the DAF unit while the flocculants are added to the DAF unit following dissolved air injection. The flocculants are added in an effective amount, generally between about 0.5-1 0 ppm.
The following examples are presented to describe preferred embodiments and utilities of the invention and are not meant to limit the invention unless otherwise stated in the claims appended hereto.
FY~IeS
Example 1 - Process for Synlh~ , Dispersion Copolymers of Aclylamide and 3 mole % DMAEA-MCQ.
To a two-liter resin reactor equipped with strirrer, temperature controller~ andwater cooled condenser, was added 287.59 grarns of a 48.1 % solution of acrylamide (1.9461 moles), 7.24 grams of an 80.6% solution of DMAEA-MCQ (0.0301 moles), 250grarns of ammonium sulfate, 225.59 grams of deior.uzed water, 27 grarns of glycerol, 56.25 grarns of a 16% solution of polyDADMAC (poiy diallyl dimethyl ammonium chloride)(IV= 1.5 dl/gm), 18 grarns of a 20% solution of polyDMAEA-MCQ
(IV=2.0dl/gm), and 0.3 grarns of EDTA. The llli;~lUlC was heated to 48~C and 0.50 grams of a 4% solution of 2,2' Azobis(2 amidinoplo~ualle) dihydrochloride was added.
The resulting solution was sparged with 1000 cc/min. of nitrogen. After l ~ minutes, polymerization began and the solution became viscous. Over the next 4 hours the temperature was maintained at 48~C and a solution co~ g 95.86 grams (0.6487 moles) of 48.1 % acrylamide, 12.07 grams (0.0502 moles) of an 80.6% solution of DMAEA-MCQ, 9 grams of glycerol and 0.1 gram of EDTA was pumped into the reactor using a syringe pump. To the resulting polymer dispersion was added 0.50 grams of a 4% solution of 2,2' Azobis(2 amidinopropane) dihydrochloride. The dispersion was then further reacted for 2.5 hours at a temperature of 48~C to 55~C. The resulting polymer dispersion had a Brookfield viscosity of 5600cps. To the above dispersion was added 10 grams of 99% acetic acid and 20 grams of sodium sulfate. The resulting dispersion had a Brookfield viscosity of 1525 cps and contained 20% of a 97/3 copolymer of acrylamide and DMAEA-MCQ with an intrinsic viscosity of 12.1 dllgm in 0.125 molar NaNO3.
Example 2 - Process for Syntl~_i,i;cillg Dispersion Copolymers of Ac~ylamide and 10 mole ~/O Dl\IAEA-MCQ.
To a two-liter resin reactor equipped with stirre}, temperature controller. and water cooled condenser, was added 239.38 grams of a 48.1% solution of acrylamide(1.6199 moles), 21.63 grams of an 80.6% solution of DMAEA-MCQ (0.09001 moles), 260 grams of ammonium sulfate, 258.01 grams of deionized water, 18 grams of glycerol, 33.75 grams of a 16% solution of polyDADMAC (IV= 1.5 dl/gm), 36 grams of a 20%
solution of polyDMAEA-MCQ (IV=2.0dl/gm), and 0.3 grarns of EDTA. The mixture was heated to 48~C and 0.S0 grams of a 4% solution of 2,2' Azobis(2 amidinopropane) dihydrochloride was added. The resulting solution was sparged with 1000 cc/min. of I ~ nitrogen. After 15 minutes, polymerization began and the solution became viscous. Over the next 4 hours the temperature was maintained at 48~C and a solution containing 79.79 grams (0.5399 moles) of 48.1 % acrylamide, 36.04 grams (0.1500 moles) of an 80.6%
solution of DMAEA-MCQ, 6 grams of glycerol and 0.1 gram of EDTA was pumped into the reactor using a syringe pump. To the resulting polymer dispersion was added 0.50 grams of a 4% solution of 2,2' Azobis(2 amidinopropane) dihydrochloride. The dispersion was then further reacted for 2.5 hours at a t~.,lpel~ re of 48~C to 55~C. The resulting polymer dispersion had a Brookfield viscosity of 7600cps. To the abovedispersion was added l O grams of 99% acetic acid and 20 grams of sodiurn sulfate. The resulting dispersion had a Brookfield viscosity of 2100 cps and contained 20% of a 90/10 copolymer of acrylamide and DMAEA-MCQ with an intrinsic viscosity of 1 j.5 dl/gm in 0.125 molarNaNO3.
Dissolved Air Flotation Water Samples Synthetic samples were ~e~aled in the laboratory under the following conditions.A mixture of oil-based printed newsprint (70 wt%) and m~g~7ine (30 wt%) was repulped (4.5% consistency, 45~C, 30 min.) with sodium hydroxide (0.5% based on paper), sodiurn silicate (2.0%~, surfactant (0.5%, ethoxylated linear alcohol, HLB 14.5), chelant (0.25%, DTPA. diethylenetriaminepentaacetic acid), and hydrogen peroxide (1.0%). The deinking water was mechanically extracted, collected. and diluted ~3-fold.
A sample of DAF influent was obtained from a Midwestern tissue manufacturer wherein the furnish was a typical newsprint m~7ine composition. Total solids in this influent were 4500 ppm with a solution pH of 7. All samples were stored at 4~C and tested within five days.
Polymer Evaluation Polymers and their respective descriptions used in this invention are summarizedin Table I.
Typical jar testing methods were used to monitor polymer performance. Standard coagulants were prepared as 1% (actives) solutions and flocculants as ~0.1% (product) solutions in deionized water. Dosages reported are based on actives for coagulants and as product for flocculants. Samples of the deinking influent were stirred at 200 rpm (fast mix) for 3 rnin. wherein the coagulant was added at the beginning of the fast mix and the flocculant during the last 40 seconds of the fast mix. This was followed by a slow mix of 25 rpm for 2 minutes. The samples were allowed to settle for 5 minutes and an aliquot of the upper liquid layer was removed and diluted a~ululopliately when required. Turbidity measurements were acquired with a HACH DR-2000 at 450 mn.
F~ ~le 3 Initial screening of the proprietary dispersion DMAEA MCQ/AcAm flocculants were performed on a synthetic water sample prepared as described above. Table IIsurnrnarizes the data used to determine the optimal coagulant concentration for subsequent flocculant studies. The coagulants screened, Composition A (linear Epi/DMA), Composition B (polyDADMAC), and Composition C (90/10 DADMAC/AA), are commonly used in DAF systems. Optimal coagulant performance with the cationic flocculant Composition D (latex 10% DMAEA MCQ/AcAm) was obtained at 15 ppm for Composition A, 10 ppm for Composition B, and 15 ppm for Composition C. A dose of 15 ppm for each coagulant was subsequently used during the screening of the dispersion flocculants.
Tables III - V summarize the results of the DMAEA MCQ dispersion polymer screening studies in conjunction with Composition A, Composition B, and Composition C, respectively. It is ~altllt that for each coagulant, the charge on the flocculant minim~lly affected the reduction in turbidity. Also, there was little difference in the turbidity values obtained at ~ ppm versus 3 ppm flocculant for a given coagulant.
By in large, the dispersion flocc~ nt~ performed as well as their similarily charged latex twins.
Ex~nlple 4 The series of DMAEA MCQ/AcAm copolymers were also screened in a recycle mill sample. Table VI summarizes the data used to determine the optimal coagulant 1~ concentration for the ensuing flocculant studies. Not surprisingly, higher amounts of coagulant were required to clarify the mill water compared to the synthetic water. In subsequent studies, for each coagulant the concentration was held at 30 ppm.
Tables VII-IX display the results for the DMAEA MCQ/AcAm copolymers and their ability to aid in the clarification of the mill water. When the hydrophilic dispersion flocculants were used in conjunction with Composition A (Table VII) or Composition B
(Table VIII), an increase in the amount of DMAEA MCQ present in the copolymer slightly enhanced the reduction in turbidity. However, this was not the case with the polyampholyte, Composition C, wherein minim~l dir~elences were obtained in turbidity reductions as a function of the flocculant s cationic charge. In each series, increasing the concentration of flocculant from 3 to 5 ppm did not enhance turbidity reduction.Comparison of the 10% and 30% mol DMAEA-MCQ latex and dispersion polymers (at ~ ppm) are shown in Figures 1-3. For this mill sample, the dispersion flocculants performed as well as, or slightly better than, their latex twin.
TABLE I
POLYMER DESCRIPTION
Intrinsic Co~l~nts Viscosity (dl/g) Composition A Epi/DMA, linear solution polymer0 11 Composition B poly(DADMAC), solution polymer 0 45 Composition C 90/10 DADMAC/AA solution polymer1 2 ~ispersions CompositionD 1 mol% DMAEA-MCQ/AcAm 11 9 Composition E 3 mol% DMAEA-MCQ/AcAm 15 7 Composition F 5 mol% DMAEA-MCQ/AcAm 14 1 Composition G 10 mol% DMAEA-MCQ/AcAm 17 0 Composition H 20 mol% DMAEA-MCQ/AcAm 21 2 Composition I 30 mol% DMAEA-MCQ/AcAm 17 0 Latex Polymers Composition J 10 mol% DMAEA-MCQ/AcAm 18 0 Composition K 30 mol% DMAEA-MCQ/AcAm 20 0 Epi/DMA epichlorohydrin/dimethylamine DADMAC diallyldimethyl arnmonium chloride AA acrylic acid DMAEA-MCQ dimethylaminoethylacrylate methylchloride quaternary salt AcAm acrylamide Table II
Coagulant Dosage Optin~i7~tion ~Synthetic D~F Water) Coagulant DosageFlocculant DosageTurbidit~~/O Turbiditv (ppm) (ppm) (FTU) Reduction Control 415 Composition A 5Composition J 5 276 33.49 Composition A 10Composition J 5 31 92.53 Composition A 15Composition J 5 15 96.39 Composition A 20Composition J 5 20 95.18 Composition A 40Composition J 5 154 62.89 Composition B 5Composition J 5 244 41.20 Composition B 10Composition J 5 19 95.42 Composition B 15Composition J 5 27 93.49 Composition B 20Composition J 5 218 47.47 Composition C 5Composition J 5 282 32.05 Composition C 10Composition J 5 58 86.02 Composition C 15Composition J 5 39 90.60 Composition C 20Composition J 5 246 40.72 Table III
Screening of DMAEA-MCQ Dispersion Polvmers (Synthetic DAF Water) Coagulant Dosage Flocculant Mole % Dosage Turbiditv %
(ppm) DMAEA- (ppm) ~TU) Turbiditv MCQ Reduction Control 41 j Composition A15 Composition J 10 5 15 96.39 Composition A15 Composition J 10 3 13 96.87 Composition A15 Composition K 30 5 11 97.35 Composition A15 Composition K 30 3 10 97.59 Composition A15 Composition D 1 5 18 9~.66 Composition A15 Composition E 3 5 18 95.66 Composition A15 Composition F 5 5 21 94.94 Composition A15 Composition G 10 5 15 96.39 Composition A15 Composition H 20 5 16 96.14 Composition A15 Composition I 30 5 10 97.~9 Composition A15 Composition D 1 3 16 96.14 Composition A15 Composition E 3 3 17 95.90 Composition A15 Composition F 5 3 16 96.14 Composition A15 Composition G 10 3 12 97.11 Composition A15 Composition H 20 3 10 97.59 Composition A15 Composition 1 30 3 8 98.07 Table IV
Screening of DMAEA-MCQ Dispersion Polymers (Svnthetic DAF Water) Coagulant DosageFlocculantMole % Dosage Turbidity %
(ppm) DMAEA (ppm) (FTU)Turbidity MCQ Reduction Control 415 Composition B 15Composition J 10 5 27 93.49 Composition B 15Composition J 10 3 28 g3.25 Composition B 15Composition K 30 5 21 94.94 Composition B 15Composition K 30 3 21 94.94 Composition B 15Composition D 1 5 17 95.90 Composition B 15Composition E 3 5 22 94.70 Composition B 15Composition F 5 5 20 95.18 Composition B 15Composition G 10 5 17 95.90 Composition B 15Composition H 20 5 21 94.94 Composition B 15Composition I 30 5 23 94.46 Composition B 15Composition D 1 3 28 93.25 Composition B 15Composition E 3 3 27 93.49 Composition B 15Composition F 5 3 24 94.22 Composition B 15Composition G 10 3 19 95.42 Composition B 15Composition H 20 3 20 95.18 Composition B 15Composition I 30 3 20 95.18 Table V
Screening of DMAEA-MCQ Dispersion Polymers (Synthetic DAF Water) Coagulant Dosage Flocculant Mole ~/O Dosage Turbidity %
(ppm) DMAEA- (ppm) (~i TU) Turbidity MCQ Reduction Control 415 Composition C 15 Composition J 10 5 39 90.60 Composition C 15 Composition J 10 3 30 92.77 Composition C 15 Composition K 30 5 20 95.18 Composition C 15 Composition K 30 3 62 85.06 Composition C 15 Composition D 1 5 30 92.77 Composition C 15 Composition E 3 5 47 88.67 Composition C 15 Composition F 5 5 19 95.42 Composition C 15 Composition G 10 5 36 91.33 Composition C 15 Composition H 20 5 28 93.~5 Composition C 15 Composition I 30 5 20 95.18 Composition C 15 Composition D 1 3 34 91.81 Composition C 15 Composition E 3 3 46 88.92 Composition C 15 Composition F 5 3 28 93.25 Composition C 15 Composition G 10 3 23 94.46 Composition C 15 Composition H 20 3 58 86.02 Composition C 15 Composition I 30 3 31 92.53 Table VI
Coagu}ant Dosage Opti-ni7~tion (A Midwestern Tissue Mill DAF Water) Coagulant DosageFlocculant DosageTurbidity %
(ppm) (ppm) Units Turbidity (~i TU) Reduction Control 450 Composition A 5Composition J 5 157 65.11 Composition A 10Composition J 5 133 70.44 Composition A 20Composition J 5 108 76.00 Composition A 30Composition J 5 99 78.00 Composition A 40Composition J 5 101 77.56 Composition A 50Composition J 5 94 79.11 Composition B 5Composition J 5 119 73.56 Composition B 10Composition J 5 107 76.22 Composition B 20Compositio.n J 5 91 79.78 Composition B 30Composition J 5 91 79.78 Composition B 40Composition J 5 89 80.22 Composition C 5Composition J 5 114 74.67 Composition C 10Composition J 5 98 78.22 Composition C 20Composition J 5 85 81.11 Composition C 30Composition J 5 79 82.44 Composition C 40Composition J 5 106 76.44 Table VII
Screening of DMAEA-MCQ Dispersion Polymers (A Midwestern Tissue Mill DAF Water) CoagulantDosage Floccnl~ntMole % Dos~ge Turbidit~ %
(ppm) DMAEA (ppm)(~i TU)Turbidit~-~MCQ Reduction Control 450 Composition A30 Composition J 10 3 114 74.67 Composition A30 Composition J 10 5 99 78.00 Composition A30 Composition J 10 10 92 79.56 Composition A30 Composition J 10 15 92 79.56 Composition A30 Composition K 30 3 95 78.89 Composition A30 Composition K 30 5 88 80.44 Composition A30 Composition D 1 3 127 71.78 Composition A30 Composition E 3 3 127 71.78 Composition A30 Composition F 5 3 118 73.78 Composition A30 Composition G 10 3 103 77.11 Composition A30 Composition H 20 3 102 77.33 Composition A30 Composition I 30 3 98 78.22 Composition A30 Composition D 1 5 128 71.56 Composition A30 Composition E 3 5 135 70.00 Composition A30 Composition F 5 5 122 72.89 Composition A30 Composition G 10 5 101 77.56 Composition A30 Composition H 20 5 95 78.89 Composition A30 Composition I 30 5 93 79.33 Table VIII
Screening of DMAEA-MCQ Dispersion Polymers (A Midwestern Tissue Mill DAF Water) Coagulant Dosage Flocculant Mole % Dosage Turbidity %
(ppm) DMAEA (ppm) Units Turbidity MCQ (FTU) Reduction Control 450 Composition B 30 Composition J 10 3 130 71.11 Composition B 30 Composition J 10 5 91 79.78 Composition B 30 Composition K 30 3 82 81.78 Composition B 30 Composition K 30 5 81 82.00 Composition B 30 Composition D 1 3 106 76.44 Composition B 30 Composition E 3 3 112 75.11 Composition B 30 Composition F 5 3 113 74.89 Composition B 30 Composition G 10 3 87 80.67 Composition B 30 Composition H 20 3 81 82.00 Composition B 30 Composition I 30 3 85 81.11 Composition B 30 Composition D 1 5 112 7S.11 Composition B 30 Composition E 3 5 119 73.56 Composition B 30 Composition F S S 113 74.89 Composition B 30 Composition G 10 5 86 80.89 Composition B 30 Composition H 20 5 83 81.56 Composition B 30 Composition I 30 S 80 82.22 S
Table IX
Screening of DMAEA-MCQ l)ispersion Polymers ~A Midwestern Tissue Mill DA~ Water) Coagulant Dosage Flocc~ nt Mole % Dosage Turbidit~ %
(ppm) DMA~A (ppm) Units Turbidit~
MCQ (FTU) Reduction Control 450 Composition C30 Composition J 10 3 78 82.67 Composition C30 Composition J 10 5 79 82.44 Composition C30 Composition K 30 3 78 82.67 Composition C30 Composition K 30 S 74 83.56 Composition C30 Composition D 1 3 78 82.67 Composition C30 Composition E 3 3 80 82.22 Composition C30 CompositionF 5 3 78 82.67 Composition C30 Composition G 10 3 78 82.67 Composition C30 Composition H 20 3 77 82.89 Composition C30 CompositionI30 3 77 82.89 Composition C30 Composition D 1 5 77 82.89 Composition C30 Composition E 3 5 80 82.22 Composition C30 Composition F 5 5 77 82.89 Composition C30 Composition G 10 5 77 82.89 Composition C30 CompositionH20 5 74 83.56 Composition C30 Composition I 30 5 68 84.89 j Changes can be made in the composition, operation and arrangement of the method of the present invention described herein without departing from the concept and scope of the invention as defined in the following claims:
Claims (9)
1. A method for clarifying ink-laden paper process water, comprising:
dosing the water with a coagulant to produce a coagulated process stream;
dosing solids from the coagulated process stream with a hydrophilic dispersion polymer to form a floc containing ink and other impurities; and effecting solid-liquid separation of the floc from the process stream, wherein the solid-liquid separation is carried out by dissolved air flotation.
dosing the water with a coagulant to produce a coagulated process stream;
dosing solids from the coagulated process stream with a hydrophilic dispersion polymer to form a floc containing ink and other impurities; and effecting solid-liquid separation of the floc from the process stream, wherein the solid-liquid separation is carried out by dissolved air flotation.
2. The method of claim 1, wherein the hydrophilic dispersion polymer comprises:
(a) a cationic monomer represented by the following general formula (I):
wherein R1 is H or CH3; each of R2 and R3 ia an alkyl group having 1 to 2 carbon atoms; R4 is H or an alkyl group of 1 to 2 carbon atoms; A' is an oxygen atom or NH; B' is an alkylene group of 2 to 4 carbon atoms or a hydroxypropylene group; and X~ is an anionic counterion; and (b) a second monomer comprising (meth)acrylamide (in an aqueous solution of a polyvalent anionic salt), wherein the polymerization is carried out in the presence of a polymer selected from the group consisting of an organic high-molecular weight multivalent cationic water-soluble polymer containing at least one monomer of formula (I) and poly diallyl dimethyl ammonium chloride.
(a) a cationic monomer represented by the following general formula (I):
wherein R1 is H or CH3; each of R2 and R3 ia an alkyl group having 1 to 2 carbon atoms; R4 is H or an alkyl group of 1 to 2 carbon atoms; A' is an oxygen atom or NH; B' is an alkylene group of 2 to 4 carbon atoms or a hydroxypropylene group; and X~ is an anionic counterion; and (b) a second monomer comprising (meth)acrylamide (in an aqueous solution of a polyvalent anionic salt), wherein the polymerization is carried out in the presence of a polymer selected from the group consisting of an organic high-molecular weight multivalent cationic water-soluble polymer containing at least one monomer of formula (I) and poly diallyl dimethyl ammonium chloride.
3. The process of claim 2, wherein the hydrophilic dispersion polymer is a copolymer of acrylamide and dimethyl-aminoethylacrylate methylchloride quaternary.
4. The method of any one of claims 1 to 3, wherein the hydrophilic dispersion polymer has a cationic charge of from about 1% mol to about 30% mol.
5. The method of any one of claims 1 to 4, wherein the flocculant has an intrinsic viscosity of from about 10.0 to about 22.0 deciliters per gram.
6. The method of any one of claims 1 to 5, wherein the dosage of the hydrophilic dispersion polymer is from about 0.1 to about 100 parts per million on a products basis.
7. The method of any one of claims 1 to 5, wherein the dosage of the hydrophilic dispersion polymer is from about 0.5 to about 10 parts per million on an actives basis.
8. The method of any one of claims 1 to 7, wherein the coagulant is poly(diallyldimethyl ammonium chloride), amphoteric diallyldimethyl ammonium chloride/acrylic acid containing copolymers, condensation polymers of ethylene dichloride/ammonia or dimethylamine/epichlorohydrin.
9. The method of any one of claims 1 to 7, wherein the coagulant is selected from the group consisting of poly(diallyl dimethyl ammonium chloride), amphoteric diallyl dimethyl ammonium chloride containing copolymers and condensation polymers of dimethylamine/epichlorohydrin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/743,437 US5750034A (en) | 1996-11-01 | 1996-11-01 | Hydrophilic dispersion polymers for the clarification of deinking process waters |
| US08/743,437 | 1996-11-01 |
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| Publication Number | Publication Date |
|---|---|
| CA2219868A1 true CA2219868A1 (en) | 1998-05-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002219868A Abandoned CA2219868A1 (en) | 1996-11-01 | 1997-10-31 | Hydrophilic dispersion polymers for the clarification of deinking process waters |
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| Country | Link |
|---|---|
| US (1) | US5750034A (en) |
| EP (1) | EP0839767B1 (en) |
| JP (1) | JPH10192868A (en) |
| KR (1) | KR100468554B1 (en) |
| AU (1) | AU723643B2 (en) |
| BR (1) | BR9705405A (en) |
| CA (1) | CA2219868A1 (en) |
| DE (1) | DE69727030T2 (en) |
| ES (1) | ES2210446T3 (en) |
| ID (1) | ID18838A (en) |
| MY (1) | MY126364A (en) |
| NO (1) | NO313092B1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5938937A (en) * | 1995-08-16 | 1999-08-17 | Nalco Chemical Company | Hydrophilic dispersion polymers for treating wastewater |
| US6235205B1 (en) | 1996-10-03 | 2001-05-22 | Cytec Technology Corp. | Aqueous dispersions |
| US6310124B1 (en) | 1996-10-03 | 2001-10-30 | Cytec Technology, Corp. | Aqueous dispersions |
| US6262168B1 (en) | 1998-03-11 | 2001-07-17 | Cytec Technology Corp. | Aqueous dispersions |
| WO1999055625A1 (en) | 1998-04-24 | 1999-11-04 | Nalco Chemical Company | Use of polymer dispersions for paper mill color removal |
| US6036868A (en) * | 1998-07-23 | 2000-03-14 | Nalco Chemical Company | Use of hydrophilic dispersion polymers for oily wastewater clarification |
| KR100278507B1 (en) | 1998-08-24 | 2001-03-02 | 한성욱 | Water-soluble polymer dispersion for wastewater treatment containing inorganic coagulant and method for producing same |
| KR100278510B1 (en) | 1998-08-24 | 2001-03-02 | 한성욱 | Water-soluble polymer dispersion for fine particle retention containing colloidal silica and preparation method thereof |
| AU764315B2 (en) * | 1998-12-03 | 2003-08-14 | Nalco Chemical Company | Hydrophilic dispersion polymers of diallyldimethyl ammonium chloride and acrylamide for the clarification of deinking process waters |
| US6365052B1 (en) | 2000-03-21 | 2002-04-02 | Nalco Chemical Company | Very high molecular weight cationic dispersion polymers for dewatering animal farm wastewater |
| US6398967B2 (en) | 2000-04-20 | 2002-06-04 | Nalco Chemical Company | Method of clarifying water using low molecular weight cationic dispersion polymers |
| GB0018314D0 (en) * | 2000-07-27 | 2000-09-13 | Ciba Spec Chem Water Treat Ltd | Processes of reducing contamination from cellulosic suspensions |
| US6623658B1 (en) * | 2000-09-22 | 2003-09-23 | Industrial Chemical Consultants | Additive for controlling secondary contaminates |
| FR2815960B1 (en) * | 2000-10-30 | 2003-02-21 | Atofina | NOVEL ACRYLATES COMPRISING SEVERAL AMINO QUATERNARY GROUPS IN THE ALCOHOL PART, THEIR MANUFACTURING PROCESS AND THE (CO) POLYMERS OBTAINED FROM THESE MONOMERS |
| JP5159009B2 (en) * | 2001-08-31 | 2013-03-06 | ハイモ株式会社 | Water-soluble polymer dispersion and method for producing the same |
| JP5593791B2 (en) * | 2010-03-31 | 2014-09-24 | 栗田工業株式会社 | Foreign matter removing agent for floatator in deinking step, foreign matter removing method, and method for producing deinked pulp |
| US8764974B2 (en) * | 2010-04-16 | 2014-07-01 | Nalco Company | Processing aids to improve the bitumen recovery and froth quality in oil sands extraction processes |
| JP5961773B1 (en) * | 2016-02-25 | 2016-08-02 | オー・ジー株式会社 | Starch paste |
| WO2018075501A1 (en) | 2016-10-17 | 2018-04-26 | Ecolab USA, Inc. | Methods and compositions for clarifying produced waters for boiler feed waters |
| CN111268842B (en) * | 2020-02-25 | 2022-05-20 | 濮阳市盛源能源科技股份有限公司 | Sewage treatment method |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1267483A (en) * | 1984-11-19 | 1990-04-03 | Hisao Takeda | Process for the production of a water-soluble polymer dispersion |
| US4738750A (en) * | 1986-02-10 | 1988-04-19 | Stone Container Corp. | System and method for treating pulp and paper mill waste water |
| US4715962A (en) * | 1986-08-15 | 1987-12-29 | Nalco Chemical Company | Ampholytic diallyldimethyl ammonium chloride (DADMAC) copolymers and terpolymers for water clarification |
| CA1329283C (en) * | 1986-10-01 | 1994-05-03 | David Farrar | Water soluble polymeric compositions |
| JPH0651755B2 (en) * | 1988-10-14 | 1994-07-06 | ハイモ株式会社 | Method for producing water-soluble cationic polymer dispersion |
| US4874521A (en) * | 1988-10-18 | 1989-10-17 | Boise Cascade Corporation | Pulp mill effluent color removal process |
| US5032286A (en) * | 1988-10-18 | 1991-07-16 | Boise Cascade Corporation | Pulp mill effluent color removal process |
| EP0473653B1 (en) * | 1989-05-22 | 1995-11-08 | Commonwealth Scientific And Industrial Research Organisation | Effluent treatment |
| US5013456A (en) * | 1990-04-13 | 1991-05-07 | Nalco Chemical Company | Diallyldimethyl ammonium chloride polymers with anionic monomers for coagulating deinking process waters |
| US5178770A (en) * | 1991-07-12 | 1993-01-12 | Nalco Canada Inc. | Method of treating bctmp/ctmp wastewater |
| US5587415A (en) * | 1991-07-30 | 1996-12-24 | Hymo Corporation | Process for preparation of dispersion of water-soluble cationic polymer the dispersion produced thereby and its use |
| US5292793A (en) * | 1992-07-14 | 1994-03-08 | Nalco Chemical Company | Hydrophobic polyelectrolytes used in color removal |
| US5286806C1 (en) * | 1993-05-14 | 2001-01-30 | Cytec Tech Corp | Methods of making and using high molecular weight acrylamide polymers |
| DE4321819A1 (en) * | 1993-07-01 | 1995-01-12 | Henkel Kgaa | Process for reducing the content of finely dispersed solids in process water from papermaking |
| US5454988A (en) * | 1994-01-12 | 1995-10-03 | Mitsubishi Corporation | Packing to be used in substance and/or heat exchanging tower |
| US5708071A (en) * | 1994-12-15 | 1998-01-13 | Hymo Corporation | Aqueous dispersion of an amphoteric water-soluble polymer, a method of manufacturing the same, and a treating agent comprising the same |
-
1996
- 1996-11-01 US US08/743,437 patent/US5750034A/en not_active Expired - Fee Related
-
1997
- 1997-10-31 EP EP97119083A patent/EP0839767B1/en not_active Expired - Lifetime
- 1997-10-31 DE DE69727030T patent/DE69727030T2/en not_active Expired - Fee Related
- 1997-10-31 ID IDP973573A patent/ID18838A/en unknown
- 1997-10-31 ES ES97119083T patent/ES2210446T3/en not_active Expired - Lifetime
- 1997-10-31 NO NO19975027A patent/NO313092B1/en not_active IP Right Cessation
- 1997-10-31 CA CA002219868A patent/CA2219868A1/en not_active Abandoned
- 1997-11-01 MY MYPI97005185A patent/MY126364A/en unknown
- 1997-11-01 KR KR1019970057559A patent/KR100468554B1/en not_active IP Right Cessation
- 1997-11-03 AU AU43679/97A patent/AU723643B2/en not_active Ceased
- 1997-11-03 BR BR9705405-4A patent/BR9705405A/en not_active IP Right Cessation
- 1997-11-04 JP JP9301876A patent/JPH10192868A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NO313092B1 (en) | 2002-08-12 |
| MY126364A (en) | 2006-09-29 |
| ES2210446T3 (en) | 2004-07-01 |
| EP0839767B1 (en) | 2004-01-02 |
| KR100468554B1 (en) | 2005-03-16 |
| JPH10192868A (en) | 1998-07-28 |
| EP0839767A2 (en) | 1998-05-06 |
| US5750034A (en) | 1998-05-12 |
| NO975027L (en) | 1998-05-04 |
| DE69727030T2 (en) | 2004-06-09 |
| ID18838A (en) | 1998-05-14 |
| BR9705405A (en) | 1999-11-03 |
| DE69727030D1 (en) | 2004-02-05 |
| KR19980042020A (en) | 1998-08-17 |
| AU723643B2 (en) | 2000-08-31 |
| NO975027D0 (en) | 1997-10-31 |
| AU4367997A (en) | 1998-05-07 |
| EP0839767A3 (en) | 1998-07-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |