WO2000034581A1 - Coagulant polyampholyte utilise pour la fabrication du papier - Google Patents

Coagulant polyampholyte utilise pour la fabrication du papier Download PDF

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Publication number
WO2000034581A1
WO2000034581A1 PCT/US1999/029135 US9929135W WO0034581A1 WO 2000034581 A1 WO2000034581 A1 WO 2000034581A1 US 9929135 W US9929135 W US 9929135W WO 0034581 A1 WO0034581 A1 WO 0034581A1
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WO
WIPO (PCT)
Prior art keywords
polyampholyte
coagulant
furnish
acid
paper
Prior art date
Application number
PCT/US1999/029135
Other languages
English (en)
Inventor
Kenneth F. Henderson
Original Assignee
CALGON CORPORATION a corporation of the State of Delaware
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CALGON CORPORATION a corporation of the State of Delaware filed Critical CALGON CORPORATION a corporation of the State of Delaware
Priority to AU31149/00A priority Critical patent/AU3114900A/en
Publication of WO2000034581A1 publication Critical patent/WO2000034581A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/01—Waste products, e.g. sludge
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D21H23/06—Controlling the addition
    • D21H23/14—Controlling the addition by selecting point of addition or time of contact between components

Definitions

  • the present invention relates to the use of polyampholyte coagulant polymers in several areas of the papermaking process: 1) as a retention/dramage/formation aid; 2) to treat coated broke wnere the white pitch or sticKies and pigments are affixed to the long fibers and finer fines; and 3) in process water clarification to settle or float the solids from the white water for removal of the solids from the water.
  • Retention is believed to be a function of different mechanisms, such as filtration by mechanical entramment, electrostatic attraction, and bridging between tne fibers and the fillers in the furnish. Because both the cellulosic fibers and many common filler materials are negatively charged, they are mutually repellent. Generally, the only factor tending to enhance retention is mechanical entramment. Therefore, a retention aid is generally used to improve retention of the fibers and fillers on the wire.
  • Drainage relates to the rate of removal of water from the furnish as the paper sheet is formed. Drainage usually refers to only water removal whicn takes place m the "drainage zone" (gravity and vacuum sections) of the Fourdrinier or twin wire paper machine primarily before any pressing of the wet paper web subsequent to formation of the web. Thus, drainage aids are used to improve the overall efficiency of dewatenng in the production of paper or paperboard.
  • Formation relates to the uniformity of the paper or paperboard sneet produced from the papermaking process. Formation is generally evaluated by the variance of light transmission through a paper sheet. A high variance is indicative of "poor” formation and low variance is generally indicative of "good” formation. Generally, as the retention level increases, the level of formation generally decreases from good formation to poor formation.
  • retention and drainage aids are generally added to the furnish as the furnish approaches the headbox of the paper machine and may comprise a coagulant/flocculant system used in conjunction with one or more shearing stages.
  • the coagulant is a low molecular weight cationic syntnetic polymer that reduces the negative surface charges on the fiber, fines, and/or filler particles to accomplish a degree of agglomeration of such particles.
  • the flocculant which generally is a high molecular weight cationic, nonionic, or anionic synthetic polymer, bridges the particles and/or agglomerates, from one surface to another, thereby binding the particles into larger floes .
  • the larger floes increase retention of the particles; however, as they are filtered out of the water onto the fiber web, the pores of the floes are covered, thereby reducing the drainage efficiency of the fiber web.
  • the larger floes can be broken ⁇ own by shearing whicn is provided by one or more of the cleaning, mixing and pumping stages of the papermaking process .
  • Coated broke may be used a portion of the furnish m certain grades of paper.
  • Coated broke is the name given to coated paper which has been repulped.
  • the coated paper generally contains natural or synthetic pigments, binders, dispersants, water and other agents.
  • the natural pigments may oe titanium dioxide, clay, talc, or calcium carbonate.
  • the binders act to adhere the pigment, particles to eacn otner and to the fiber and fines in the paper web.
  • the primary components of the coated broke are pigments and binders.
  • the binders such as starch, polyvinyl acetate (PVA) , latex, styrene butadiene rubber (SBR), polyvinyl alcohol (PVOH), and other synthetic organic binders, are liberated from the coating.
  • PVA polyvinyl acetate
  • SBR styrene butadiene rubber
  • PVOH polyvinyl alcohol
  • the binders can agglomerate at shear points or precipitate out of solution due to pH or temperature shock n tne furnish, depositing on tank walls, wires, boil olades, rolls, felts, dryer cans, or piping shear points. These deposits can break loose causing defects or breaks in the paper web.
  • the deposition of binder agglomerates at the shear points is referred to as "white pitch" or "stickles”.
  • the white water (process water) n the paper machine is generally piped to tanks for recycling purposes, which is referred to as a "saveall".
  • a vehicle Several methods or types of equipment can be used for removal of the solids and/or additives from this white water in the saveall so that the water can be recycled ana returned in the papermaking process in as pure a form as possible.
  • a polyampholyte coagulant is use ⁇ in the papermaking process to improve retention of pigments and fiber fines and/or to improve drainage and formation of the sheet being formed.
  • a water soluble flocculant polymer is used with this polyampholyte coagulant.
  • the paper may be produced by forming an aqueous cellulosic slurry comprising recycled deinked newsprint, bleached or unbleached chemical pulps (hardwood or softwood), pulp fibers, recycled fiber 'bleache ⁇ or unbleached), coated broke, and ground or mechanical pulp whicn may or may not contain a mineral filler or pigment; passing the suspension through one or more shear stages; draining the suspension to form a wet web; pressing and drying the wet web to produce the final sheet.
  • an aqueous cellulosic slurry comprising recycled deinked newsprint, bleached or unbleached chemical pulps (hardwood or softwood), pulp fibers, recycled fiber 'bleache ⁇ or unbleached), coated broke, and ground or mechanical pulp whicn may or may not contain a mineral filler or pigment
  • the polyampholyte coagulant preferably, is added to the slurry prior to the first or after the last shearing stage, and the flocculant may be added either before the addition of the coagulant or before the first or after the last shearing stage before the headbox.
  • the polyampholyte coagulant may also be added after the flocculant or can be combined with the flocculant and added to the aqueous cellulosic slurry ahead of the headbox.
  • the polyampholyte may be added to the aqueous cellulose slurry without the flocculant.
  • the polyampholyte coagulant may be supplied as a true solution in water, or as an emulsion where it is dispersed in a carrier oil, and is dissolved in water and added as a dilute aqueous solution to the furnish slurry during the papermaking process.
  • a polyampholyte polymer is used to treat coated broke prior to or after the coated broke is added to the paper furnish. After the coated paper is repulpe ⁇ , the polyampholyte polymer is added to the coated broke in order to attach the "white pitch" and the pigments to the longer fibers, thereby lessening the amount of "white pitch” being deposited onto sites throughout the papermaking process.
  • This treated coated broke can then be used as pulp m a papermaking process where a polyampholyte polymer may be used as a retention/drainage/formation aid m accordance with the teachings of a first aspect of the invention.
  • a polyampholyte polymer is used in saveall applications whereby the polyampholyte polymer is added to tne white water to cause the fiber and filler to settle out of the water or to float m air flotation type savealls for their easy removal therefrom.
  • the clarified water can then be reused.
  • the polyampholyte polymer has a molecular weight ranging from about 10 thousand to 20 million.
  • the polyampholyte polymer may comprise two, three or more monomers with a total ratio of a:b ranging from about
  • a) is the anionic monomer and (b) is the cationic monomer.
  • the weight percent ratio of these monomers in a polymer containing two or more monomers (a:b:c) may range from about 1:1:98 to 1:98:1 or 98:1:1 where a) is the nonionic monomer, b) is the anionic monomer and c) is the cationic monomer based on the dry weight of the polyampholyte.
  • the flocculant is a high molecular weight anionic, nonionic, or cationic polymer with a molecular average molecular weight ranging from about 1 million to about 30 million.
  • the preferred dosage for the coagulant may range from about 0.0025% to about 3.0%, and more preferably, from about 0.005% to about 1.5%, based on the dry weight of the solids.
  • the preferred dosage for the flocculant would range from about 0.0025% to about 3.0%, and more preferably from about 0.005% to about 1.5%, based on the dry weight of the solids in the furnish.
  • Figure 1 is a graph illustrating press solids (%) and brightness results for certain copolymer coagulants and cationic coagulants and includes a terpolymer polyampholyte of the invention (Product B) in a fine paper furnish.
  • Figures 2 - 4 are graphs illustrating brightness results for certain copolymer coagulants and cationic coagulants and includes several polyampholytes (terpolymers and copolymers) of the invention in a newsprint or super calendered (SC) grade furnish.
  • paper includes products comprising a cellulosic sheet material including paper sheet, paperboard, and the like.
  • polyampholyte is any polymer comprising at least a cationic charge and an anionic charge and can include a copolymer, a terpolymer, or a polymer containing three or more monomers .
  • a first aspect of the invention pertains to the use of a polyampholyte coagulant polymer and, optionally, a high molecular weight flocculant as a retention/dramage/formation aid for particular use in the wet end of a paper machine in the papermaking process for both acid, neutral, and alkaline paper grades.
  • the components of the coagulant/flocculant system of the invention may be added simultaneously or sequentially to the furnisn at the same or different points of addition but, preferably, are added n the manner and order described herembelow.
  • a conventional papermaking process contains one or several shearing stages, .e., mixing and cleaning of the furnish or stock as it passes from the stock preparation area through the papermaking process.
  • Thick stock generally comprises filler, fiber, strengthening agent and/or other additives and water.
  • the thick stock generally is diluted with white water to form "thin stock" by passing the thick stock and dilution water through a mixing pump.
  • the stock can be cleaned by passing it through vortex cleaners or a centri-screen and/or it may be pumped to the paper machine by one or more centrifugal pumps (transfer or fan pumps) .
  • the thin stock may be pumped to centrifugal cleaners by a first fan pump.
  • the thin stock may be cleaned further by passing it through a cent ⁇ screen or pressure screen prior to it being passed into a headbox m preparation for the sheet forming process.
  • the polyampholyte coagulant polymer is added to the thin stock before the fan pump or after the centriscreen and tne flocculant is added to the thin stock either as the thin stock exits the fan pump or prior to the thin stock being passed through the centriscreen before, after, or simultaneously with the addition of the polyampholyte coagulant polymer.
  • the polyampholyte coagulant is any polymer comprising at least a cationic charge and an anionic charge.
  • This polyampholyte may be a copolymer having anionic and cationic monomers or a terpolymer naving nonionic, anionic and cationic monomers.
  • This polyampholyte may also comprise more than three monomers which could be one or more anionic, cationic, and/or nonionic monomers .
  • the anionic monomer may be selected from the group consisting of acrylic acid, methacrylic acid, 2- acrylam ⁇ do-2-methylpropane sulfonic acid, sodium vinyl sulfonate, ⁇ taconic acid, 2-acrylam ⁇ do-2 methyl-butanoic acid ana acrylamidoglycolic acid or their corresponding salts.
  • the acrylic acid and the methacrylic acid may be introduced into the polyampholyte polymer by hydrolysis of acrylamide and methacrylamide, respectively.
  • the cationic monomer may be selected from the group consisting of diallyl dimethyl ammonium chloride, (DADMAC), acryloyloxyethyl t ⁇ methyl ammonium chloride (AETAC) , methacryloxyethyl trimethyl ammonium chloride, acrylamidopropyl trimethylammonium chloride, and methacrylamido propyl trimethyl ammonium chloride.
  • DMAC diallyl dimethyl ammonium chloride
  • AETAC acryloyloxyethyl t ⁇ methyl ammonium chloride
  • methacryloxyethyl trimethyl ammonium chloride acrylamidopropyl trimethylammonium chloride
  • methacrylamido propyl trimethyl ammonium chloride methacrylamido propyl trimethyl ammonium chloride.
  • the anionic monomer may be selected from the group consisting of acrylic acid (AA) or its homologues, sodium acrylate, vinyl sulfo ic acid, methacrylic acid, 2-acrylam ⁇ do-2-methylpropane sulfonic acid (AMPS), sodium vinyl sulfonate, ltaconic acid, sodium itaconate, acrylamidoglycolic acid, 2-acrylam ⁇ do- 2-methyl butanoic acid, 2-acrylam ⁇ do-2-methyl propane phosphonic acid, , sodium salt, sodium vinyl phosphonate, allyl phosphonic acid, and/or mixtures thereof.
  • acrylic acid AA
  • AMPS 2-acrylam ⁇ do-2-methylpropane sulfonic acid
  • AMPS 2-acrylam ⁇ do-2-methylpropane sulfonic acid
  • ltaconic acid sodium itaconate
  • 2-acrylamidoglycolic acid 2-acrylam ⁇ do- 2-methyl butanoic acid
  • the acrylic acid and the methacrylic acid may be introduced into the terpolymer by hydrolysis of acrylamide and methacrylamide, respectively, or the acrylic acid may be introduced into the terpolymer by adding acrylic acid prior to polymerization.
  • the cationic monomer may be selected from the group consisting of diallyl dimethyl ammonium chloride (DADMAC), dialkyl diallyl ammonium monomer, quarternary dialkyl diallyl ammonium, methacryloxyethyl trimethyl ammonium chloride, acrylamido propyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride (AETAC) , methacrylamido propyl trimetnyl ammonium cnlonoe, quatermze ⁇ derivatives of N,N-d ⁇ methyl ammo ethyl metnacrylate, dimethyl am o ethyl acrylate, and dibutyl ammo ethyl me
  • the nonionic monomer may be selected from the group consisting of acrylamide (AM) , N-vmylamide, N- alkylacrylamide, vinyl acetate, acrylate esters, diacetone acrylamide, and N, N-dialkylacrylamide, vinyl pyrrolidone, and vinyl alcohol.
  • AM acrylamide
  • N-vmylamide N- alkylacrylamide
  • vinyl acetate vinyl acetate
  • acrylate esters diacetone acrylamide
  • diacetone acrylamide and N, N-dialkylacrylamide
  • vinyl pyrrolidone vinyl alcohol
  • the copolymer polyampholyte of the invention has a weight percent ratio, i.e., a) anionic monomer to b) cationic monomer, ranging from about 1:99 to about 99:1, and preferably, 2:98 to 98:2 for monomers a:b, and has a molecular weight in excess of about 50,000.
  • the weight percent ratio of the terpolymer polyampholyte of the invention i.e., a) nonionic moiety to b) anionic monomer to c) cationic monomer, ranges from about 1:1:98 to about 1:98:1 to about 98:1:1, preferably, about 18:2:80 to about 25:50:25, and most preferably about 48:2:50 to about 25:25:50, or about 41:13:46 for monomers a:b:c.
  • the molecular weight is less than about 10 x 10 6 .
  • Preferred terpolymer compositions are: 1) acrylamide/acrylic acid/diallyl dimethyl ammonium chloride (AM/AA/DADMAC) in the weight ratio range of 48:2:50 to 25:25:50, and 2) AM/AMPS/DADMAC ⁇ acrylam ⁇ de/2- acrylam ⁇ do-2-methyl propane sulfonic acid/diallyl dimethyl ammonium chloride) in a weight ratio 41:13:46.
  • the nonionic moiety of the terpolymer polyampholyte has a molecular weight of about 5 x 10 5 and preferably less than 10 x 10 ⁇ , i.e., about 7 x 10 5 .
  • the cationic moiety of the polyampholyte coagulant draws the negatively charged pulp fines and fillers into small uniformly spaced agglomerates.
  • the anionic cnarge nelps maintain the uniform spacing, thus enhancing brightness through a good distribution of the filler in the paper web.
  • the molecular weight and charge of the ampholyte enhances drainage by uniform spacing of the agglomerates which allows the water to pass between the agglomerates, but which does not create large openings or void spaces which would give "good” free drainage but result m “poor” vacuum drainage.
  • the high molecular weight polymer of the invention comprises an agent for aggregating the fines and fibers in the papermaking furnish, thereby giving better drainage and retention.
  • an effective amount of a polyampholyte coagulant /flocculant system of the invention should be employed.
  • the effective amount for a given cellulosic furnish being treated generally depends on the source and type of pulp, the water chemistry, and the amount of pulp fines and fillers.
  • the effective coagulant dosage will be in an amount of at least about 0.01 (active) pounds per ton (0.0005% by weight) based on the dry weight of the solids in the aqueous cellulosic furnish.
  • the effective amount of flocculant dosage will be an amount of at least adout 0.01 (active) pounds per ton (0.0005% by weight) of dry solids m the aqueous cellulosic furnish.
  • the dosage of the coagulant is about 0.01 (active) pounds per ton, or about 0.0005 weight % to about 3 weight % of the total weight of the dry weight of solids in the aqueous cellulosic furnish and, most preferably, 0.005 weight % to 1.5 weight %.
  • the dosage of the flocculant ranges from about 0.05 to about 30.0 (active) pounds per ton based on the dry weight of the solids in the aqueous cellulosic furnish, or 0.0025 weight % to 1.5 weight % of the total weight of tne dry solids, and, preferably, 0.0025 weight % to 1.0 weight %.
  • the coagulant/flocculant system of the invention can generally be successfully added to aqueous cellulosic furnishes over the entire pH range customarily employed in the papermaking process.
  • the coagulant/flocculant system of the invention is added to aqueous cellulosic furnishes having a pH from about 3 to 10. Therefore, it will be appreciated by those skilled in the art that the system of tne invention may be added to paper furnishes that are acid, alkaline, or neutral in character.
  • an acid furnish has a pH range from about 3.8 to 6.5
  • an alkaline furnish has a pH range of about 7.2 to greater than about 10
  • a neutral furnish has a pH range of from about 6.5 to 7.2.
  • the polyampholyte coagulant polymer of the invention is added to the paper furnish before the final shearing stage and the nigh molecular weight flocculant polymer is added before or after the coagulant and, which may or may not be before the last shearing stage so "good mixing" of the polymers occurs before the thin stock enters the headbox of the paper machine.
  • nigh molecular weight polymer fiocculants suitable for use herein are those having a weight average molecular weight of about 100,000 or more, especially 500,000 or more. Preferably, the molecular weight is about 1 million and often above about 5 million, for instance m the range 10 to 30 million or more.
  • These polymers may be linear, branched, cationic, anionic, nonionic, amphoteric, or hydrophobically modified polymers of acrylamide or other nonionic monomers .
  • the polymer may contain at least one cationic monomer se ecte ⁇ from tne group of a quaternary dialkydiallyl ammonium, methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxeythyl trimethyl ammonium methosulfate, acrylamido propyl triethyl ammonium chloride, methacrylamido propyl triethyl ammonium chloride, acrylayloxethyl trimethyl ammonium chloride, quatermzed derivatives of N, N-dimethyl ammo ethyl methacrylate, dimethyl am o ethyl acrylate, diethyl ammo ethyl acrylate, dibutyl ammo ethyl methacrylate, dimethyl ammo methyl acrylate, demethyl ammo methyl methacrylate, dieth
  • dialkyldially ammonium monomer refers to any water soluble monomer of the formula [DADAAX], which represents dialkyldiallyl ammonium X, wherein each alkyl group is independently selected from an alkyl group of form about 1 to 18 carbon atoms, and preferably from about 1 to 4 carbon atoms, and wherein X is any suitable counte ⁇ on.
  • the counterions are selected from the group consisting of conjugate bases of acids having an lomzation greater than 10 13 , and more preferably selected from the group consisting of a halide, hydroxide, nitrate, acetate, hydrogen sulfate, methyl sulfate, and primary phosphate.
  • the halide may be any halide, and more preferably is selected from the group consisting of fluoride, bromide and chloride.
  • the quaternary dialkyldiallyl ammonium halide monomer is selected from the group consisting of dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, dimethyl diallyl ammonium bromide, and diethyl diallyl ammonium bromide.
  • the cationic flocculant polymer may contain at least one anionic monomer selected from the group of acrylic acid, methacrylic acid, 2-acrylam ⁇ o-2- methylpropanesulfonic acid, crotomc acid, sodium vinyl sulfonate, acrylamidoglycolic acid, 2-acrylam ⁇ do-2- methylbutanoic acid, 2-acrylam ⁇ do-2- methylpropanephosphonic acid, sodium vinyl phosphonate, allyl phosphonic acid.
  • anionic monomers selected from the group of acrylic acid, methacrylic acid, 2-acrylam ⁇ o-2- methylpropanesulfonic acid, crotomc acid, sodium vinyl sulfonate, acrylamidoglycolic acid, 2-acrylam ⁇ do-2- methylbutanoic acid, 2-acrylam ⁇ do-2- methylpropanephosphonic acid, sodium vinyl phosphonate, allyl phosphonic acid.
  • anionic monomers selected from the group of acrylic acid, methacrylic acid, 2-
  • the polymer may contain nonionic portions and may contain at least one nonionic monomer from the group of N-vmylamide, N-alkylacrylamide, vinyl acetate, vinyl alcohol, acrylate esters, diacetone acrylamide, N, N-dimethyl acrylamide.
  • the cationic flocculant polymer may have a weight average molecular weight ranging from about 500,000 to about 20 million.
  • the polymer is derived from monomers from the group of acrylic acid or its homologues, sodium acrylate, vmyl sulfonic acid, sodium vmyl sulfonate, ltaaconic acid, sodium itaconate, 2- acrylam ⁇ do-2-methylpropanesulfon ⁇ c acid sodium salt, acrylamidoglycolic acid, 2-acrylam ⁇ do-2-methylbutano ⁇ c acid, 2-acrylam ⁇ do-2-methylpropanephosphon ⁇ c acid, sodium vmyl phosphonate, allyl phosphonic acid and/or admixtures thereof.
  • the polymer may also be either nydrolyze ⁇ acrylamide polymers or copolymers of its homologues, such as methacrylamide.
  • the polymer may contain nonionic portions and may contain at least one nonionic monomer from the group of acrylamide, N-vmylamide, N- alkylacrylamide, vmyl acetate, vmyl alcohol, acrylate esters, diacetone acrylamide, N, N-dialkylacrylamide .
  • Acrylic acid and methacrylic acid may conveniently be introduced into the polymer by hydrolysis of acrylamide and methacrylamide, respectively.
  • the anionic polymer may be homopolymers, copolymers, or terpolymer.
  • the most preferred high molecular weight homopolymer is polyacrylic acid or its salts .
  • the most preferred high molecular weight copolymers are acrylic acid/acrylamide copolymer; and sulfonate containing polymers such as 2 - acrylam ⁇ do-2-methylpropane sulfonate/acrylamide; acrylamido methane sulfonate/acrylamide; 2-acrylam ⁇ do ethane sulfonate/acrylamide; 2-hydroxy-3-acrylam ⁇ de propane sulfonate/acrylamide .
  • the most preferred high molecular weight terpolymers are acrylic ac ⁇ d/acrylam ⁇ de/2-acrylam ⁇ do-2-methylpropane sulfonate; acrylic acid/acrylamide/acrylamido methane sulfonate; acrylic ac ⁇ d/acrylam ⁇ de/2acrylam ⁇ do ethane sulfonate; acrylic ac ⁇ d/acrylam ⁇ de/2-hydroxy-3-acrylam ⁇ de propane sulfonate.
  • Commonly accepted counter ions may be used for the salts such as sodium ion, potassium ion, etc.
  • the anionic flocculant polymer may have a weight average molecular weight ranging from about 1 million to about 30 million.
  • the high molecular weight flocculant is comprised of a nonionic polymer, preferably it would be a polyacrylamide having a weight average molecular weight of about 500,000 to about 20 million.
  • the polyampholyte coagulant polymer consists of three or more monomers comprising nonionic, anionic and cationic monomers which preferably in emulsion form or solution form has a weight % ratio based on the total dry weight of the polyampholyte coagulant ranging from 48:2:50 to 25:25:50 for AM/AA/DADMAC and AM/AMP/DADMAC having a weight ratio of about 41:13:46.
  • the polyampholyte coagulant is about 25-50% active
  • the polyampnolyte coagulant is about 4-20% active.
  • the initial stock can be made from any conventional papermaking stock such as traditional chemical pulps, for instance bleached and unbleached sulphate or sulphite pulp, mechanical pulps, such as groundwood, thermochemical or chemi-thermochemical pulp, or recycled pulp such as demked waste fiber filler composites, including coated broke and broke from aggregating or recycling processes and any mixtures thereof.
  • traditional chemical pulps for instance bleached and unbleached sulphate or sulphite pulp
  • mechanical pulps such as groundwood, thermochemical or chemi-thermochemical pulp
  • recycled pulp such as demked waste fiber filler composites, including coated broke and broke from aggregating or recycling processes and any mixtures thereof.
  • the furnish employed in tne final paper can be substantially unfilled, e.g., containing less than 10% and generally less than 5% by weight filler in the final paper, or the filler can be provided in an amount of up to 50% based on the dry weight of the solids of the stock or up to 40% based on the dry weight of the paper.
  • any conventional white pigment filler such as calcium carbonate, kaolin clay, calcined kaolin, titanium dioxide, chalk or talc or a combination thereof may be present.
  • the filler is preferably incorporated into the stock in a conventional manner, prior to the addition of the coagulant/flocculant system of the invention.
  • an acid tolerant calcium carbonate filler of the prior art could be used such as that discussed m U.S. Patent Nos. 5,593,489; 5,599,388; 5,647,902; 5,685,900; and 5,711,799 which are owned by the same assignee of the present invention.
  • U.S. Patent No. 5,711,799 discloses a calcium carbonate treated with sodium aluminate m order to make the carbonate acid resistant or tolerant to the acidic pulp.
  • the furnish employed in the invention may include other known optional additives, such as rosin, alum, neutral sizing agents, optical brightening agents, or a strengthening or binding agent which for example may comprise a starch, often a cationic starch or a guar gum.
  • rosin rosin
  • alum neutral sizing agents
  • optical brightening agents optical brightening agents
  • a strengthening or binding agent which for example may comprise a starch, often a cationic starch or a guar gum.
  • the amounts of fiber, filler or pigment, and other additives such as strengthening agents or alum can all be conventional.
  • the thin stock has a solids content from 0.1% to 1.5% by weight which consists mostly of fiber.
  • the total amount of the water soluble polyampholyte coagulant polymer in the furnish may be m the range of about 0.0005 to 3.0 weight %, and more preferably in the range of about 0.005 weight % to about 1.5 weight % (dry weight based on the dry weight of the solids m the stock or furnish) .
  • the total amount of the water soluble high molecular weight flocculant polymer the furnish may be in the range of about 0.0025 to 3.0 weight %, and more preferably, m the range of about 0.0025 weight % to about 1.5 weight % (dry weight based on the dry weight of the solids in the stock or furnish) .
  • a low molecular weight polyampholyte coagulant which may be a copolymer or three (terpolymer) or more monomers when used in conjunction with a high molecular weight flocculant polymer can increase drainage and retention in the papermaking process and improve sheet formation and brightness characteristics of the paper.
  • Products A, B, C, D, E, F, G, I, J, K, N, and Nl are available from Calgon Corporation, Pittsburgh, PA. and/or ECC International Inc., Atlanta, GA.
  • Product 01 is available from Nalco Chemical Company.
  • Products Dl and KI are available from ECC International Inc.
  • Product H is available from BASF Corporation Dispersions and Paper Chemicals .
  • Products A, B, and C are preferred terpolymer polyampholyte coagulants of the invention with Product L being the preferred flocculant.
  • Other terpolymers such as HI, PI, Ql, Rl, SI, Tl, Ul, VI, Wl, Yl, Zl, A2 and E2 are additional terpolymer polyampholytes of the invention, while the chemistries for B2, C2 and D2 are preferred copolymer polampholytes of the invention. Note: All dosages herein relating to the invention and m the following examples are expressed as active based on lb. /ton of dry pulp.
  • Example 1 A laboratory vacuum drainage test was conducted on newsprint stock to compare the polyampholyte coagulants of the invention with other coagulant products, some of which are available from ECC International Inc.
  • the furnish was obtained from a paper mill and comprised 75 to 80% fine TMP (thermomechanical pulp) , 5% kraft, 5% PCW (Post Consumer Waste), and 10 to 15% broke.
  • the paper machine was running at 4100 to 4300 feet per mmute, and the conditions were as follows: 35.1% First Pass Retention (FPR)
  • FPR First Pass Retention
  • the vacuum drainage test was conducted using the Buchner Funnel, a vacuum pump, 24.5" Hg, and a 500 ml glass vacuum flask.
  • the Vac. 400 which represents time (seconds) m which 400 ml of stock is drained from the flask, was recorded.
  • the flocculant (Products L and M) was used at 0.25 (active) lb./t., and the coagulants were used at 1.0 (active) lbs. /ton.
  • FPR First pass retention
  • Products A, B, and C (coagulants) of the invention when combined with Product T (flocculant), show high ash retention at 37.7%, 44.6% and 38.5% FPR with the highest for all dual polymer system being for Products B and T at 44.6% FPR.
  • These retention and drainage results indicate that in the invention, filler retention should be realized along with increased drainage.
  • Example 3 A retention aid study was performed for a high conductivity -.lnerpoarc. furnish. The furnish consisted of 100% unbleached hardwood kraft pulp. Britt ]ar testing was used to screen furnish for the best flocculant/coagulant system starting with an initial conductivity of 2800 ⁇ mhos, and increasing to 3800 and 4500 ⁇ mhos by adding sodium sulfate solution.
  • Procedure Headbox stock with a consistency of 1.0% was heated to 120°F, and the pH was adjusted to 5.0 with alum.
  • the initial conductivity measured 2800 umnos .
  • Each 500 ml aliquot of stock was poured into a vaned Britt jar with 70 mesh screen.
  • First the stock was mixed with 10% clay filler followed by the coagulant. After mixing the stock with the clay filler and coagulant for 15 seconds at 600 rpm, the mixer speed was increased to 1200 rpm for 10 seconds .
  • the flocculant was added to the stock and the mixer speed was reduced to 600 rpm and mixed for an additional 10 seconds. After 35 seconds total mixing, the pinch clamp was removed and 100 ml of filtrate was collected in a graduate cylinder.
  • the filtrate was flocked with a coagulant (Pro ⁇ uct B) to help retain the fines and the clay filler and to aid m the speed filtration.
  • a coagulant Pro ⁇ uct B
  • the filter pads were ashed at 900°C for 30 minutes.
  • the dry and ash weights of the filtrate solids were recorded and used to calculate fines, ash, and total first pass retention.
  • the results are shown in Table 5. Based on this study, at a high conductivity of 4500 ⁇ mhos, Product Z gave the best total first pass retention percentage, i.e. 79.1 for Product B (Item 28) and 79.0 for Product HI (Item 29), which are the coagulants of the invention. Products B and HI combined with Product Z as the flocculant also gave the best fines retention (Items 2i and 29) .
  • cationic coagulants with high charge density (> 4 meq charge/gram) are mixed with anionic particles (aqueous cellulosic furnish) to form a positive patch charge on the surface of the anionic particles.
  • anionic particles aqueous cellulosic furnish
  • collision of the positive patch with a negatively charged surface on another particle leads to agglomeration .
  • Polyampholyte As An Attachment Aid In Coated Broke And A Retention/Drainage Aid
  • Example 4 A second aspect of the invention pertains to the use of a polyampholyte coagulant of the invention for treating coated broke and then using the treated coated broke as a portion of the furnish in making paper and adding the polyampholyte coagulant of the invention as a retention and/or drainage aid m the papermaking process.
  • Coated broke is used in many fine or other paper furnishes.
  • the coating applied to the base sheet may contain this coated broke comprising pigments and binders, both of which can cause problems m the sheet forming process. As explained heremabove, the binders can agglomerate to form sheet defects or deposits on the machine.
  • the coating pigments m the coated broke are more difficult to retain than wet end pigments m view of their small size.
  • the polyampholyte coagulant of the invention as disclosed heremabove for treating coated broke has been found to be an effective way for significantly reducing white pitch deposits and poor coating pigment retention problems whereby the pigments and the binders are attached to the fiber n the pulp.
  • the polyampholyte of the invention was used as an attachment aid for the white pitch or stickles and the mineral pigments from coated broke where the white pitch or stickles and the pigments are attached to the longer fibers instead of depositing on sites in the paper machine .
  • the dosages for the coagulant was either 2.75 (active) pounds per ton (dry weight of solids in furnish), or 3.75 (active) poun ⁇ s per ton (dry wei ⁇ ht of solids in the furnish) .
  • the results of the turbidity (retention) tests are shown m Table 6. The "lowest" turbidity level is produced by the product and the dosage which attached the most colloidal and fine material onto the fiber. TABLE 6
  • Table 6 shows that the lowest filtered turbidity was for Product C (36 NTU) at a dosage of 3.7 (active) lbs. /ton, which Product C is one of the preferred polyampholytes of the present invention.
  • This Product C is a solution terpolymer with an 8% active AM/AA/DMDAAC at 45:5:50 weight % polymer composition.
  • the cationic demand for the furnish containing Products B and C (Items 11 and 10) of the invention in Table 6 Is -590 and -580 (meq./l), respectively which reduced the furnish charge to less than some of the standard coagulants presently used in the paper mills.
  • the polyampholyte coagulant of the invention was then used as a retention/drainage aid m the papermaking process .
  • the test procedure was similar to that used in Example 1, except that the coagulant was added during high shear mixing (simulated screening or shearing stage) and the flocculant was added during low shear mixing.
  • the ⁇ osage of the coagulant was 1.0 (active) lb. /ton based on tne dry solids in the aqueous cellulosic furnish and the dosage of the flocculant was 0.25 (active) lb. /ton based on the dry solids in the aqueous cellulosic furnish .
  • coated broke treated with the polyampholyte of the invention prior to its being added to the paper furnish can decrease the turbidity and increase the drainage rate of the fiber mat on the wire in the paper forming process.
  • a third aspect of the invention pertains to the use of a poiyampnoiyte coagulant of the invention in a saveall application. It has been found by the inventors that polyampholyte coagulants of the invention are very effective clarifying white water for reuse either in the paper machine or in the pulp mill. The white water is treated with the polyampholyte coagulant of the invention to aid in settling the solids or if air flotation is used in floating the solids for removal from the saveall .
  • Example 5 The polyampholyte coagulant of Example 5 was added to the saveall influent to settle the fibers and fines out of the recycled white water.
  • Example 5 The polyampholyte coagulant of Example 5 was added to the saveall influent to settle the fibers and fines out of the recycled white water.
  • the 1.0 % consistency stock was mixed with flocculant and coagulant using a Britt Jar type (variable speed mixer) according to the procedure below.
  • Handsheets were run m sets of five. The weight of each sheet was measured before the first press and after pressing through each nip. Oven dry weight was determined to calculate press solids. Brightness was measured on a Technidyne Color One Touch brightness meter according to Tappi Test Method T-452.
  • Amphoteric coagulants provide a brightness increase in furnishes containing either recycle fiber and or coated broke and virgin filler possibly by two different mechanisms.
  • the first mechanism is for furnishes containing recycled fiber and the second mechanism concerns the degree of agglomeration and distribution of filler within the sheet.
  • Polyampholyte coagulants of the invention on the other hand, using a combination of molecular weight and lower overall cationic charge, retain the recycled and virgin filler without retaining the mk so the brightness of the sheet remains higher.
  • the second part of the theory regarding higher sheet brightness deals with the agglomeration and distribution of the filler n the sheet.
  • Filler agglomeration is significantly less in handsheets containing a polyampholyte coagulant compared to sheets containing an equal dosage of a cationic coagulant.
  • SEM photomicrographs showing the distribution of filler in the x-y plane show much larger agglomerates of filler for sheets containing DADMAC, polyamme or PEI coagulants than for a polyampholyte coagulant.
  • the polyampholyte of course must be of sufficient molecular weight to retain the filler or poor filler retention will result.
  • the preferred polyampholyte chemistry consists of a terpolymer containing acrylamide to help build molecular weight providing good filler retention.
  • Figure 4 shows the data for a number of copolymer polyampholytes that do not show a drop in brightness as the dosage of the coagulant was increased, however, the sheet brightness is also low denoting poor filler retention.
  • Chemimechanical Pulp 1 Make handsheets using Britt Jar mixer to mix stock and polymer. Use 0.3, 0.6, and 0.9 #/t active for the coagulants and 0.3 #/ton active for the polymer
  • Brightness will be the most important criteria for measuring the performance of tne polyampholyte polymers. Brightness was measured on a Technidyne Color One Touch brightness meter according to Tappi Test Method T-452.
  • Dram sheet mold Press handsheet with new press felt. Dry handsheets with screen toward dryer drum (210 deg. F; 4 mm . /revolution) .
  • the brightness decrease of the handsheets containing Products N and K was possibly the result of two factors. First, as the dose of Products N and K was increased, the amount of mk retained from the recycle fiber was also increased. Secondly, increasing the dose of Products N and K excessively agglomerated the filler in the handsheets to the extent that the optical efficiency of the filler (light scattering) was reduced and thus the brightness level was decreased.
  • the polyampholytes of the invention fall into two groups in terms of performance, i.e handsheet brightness and filler retention.
  • the terpolymers shown m Figures 2 and 3 had higher brightness (above 57.0) than the copolymers shown in Figure 4.
  • the mam difference m polymer chemistry between the copolymers and the terpolymers is the presence of acrylamide m the terpolymers which tends to boost the molecular weight of the polymer.
  • the brightness of the paper containing the polyampholyte of the invention will not drop with increasing polymer dosage.
  • the filler retention with the acrylamide containing polyampholytes will remain high.
  • the brightness of handsheets containing the copolymer polyampholytes show the same trend of maintaining brightness as the polyampholyte copolymer dose is increased out the copolymers do not retain the filler nearly as well.

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Abstract

Au cours du processus de fabrication du papier, on utilise un coagulant polyampholyte comme agent de rétention/drainage/formation pour traiter les cassés de fabrication enduits, la où la poix blanche ou les adhésifs et les pigments sont fixés sur les fibres longues et sur les fibres fines, et pour purifier l'eau de traitement là où les solides présents dans l'eau blanches sont éliminés soit par dépôt, soit par flottage. En tant qu'auxiliaire de rétention/drainage/formation, le coagulant polyampholyte est ajouté à la suspension cellulosique avant la première ou après la dernière opération de cisaillement. De plus, on peut ajouter éventuellement un floculant soit avant l'adjonction du coagulant polyampholyte, soit avant la première ou la dernière opération de cisaillement. Le coagulant polyampholyte a un poids moléculaire moyen compris entre 10 mille et 20 millions, se présente sous forme d'émulsion ou de solution, et peut refermer un copolymère ou un acide acrylique (anionique) et un chlorure d'ammonium diallyl diméthyle (cationique) selon un pourcentage de poids compris entre environ 1:999 et environ 99:1 sur la base du poids à sec du polyampholyte, ou bien peut renfermer un terpolymère d'acrylamide (non ionique), un acide acrylique (anionique), et un chlorure d'ammonium diallyl diméthyle (cationique).
PCT/US1999/029135 1998-12-10 1999-12-08 Coagulant polyampholyte utilise pour la fabrication du papier WO2000034581A1 (fr)

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PCT/US1999/029228 WO2000034582A1 (fr) 1998-12-10 1999-12-09 Coagulant de copolymeres pour la fabrication du papier

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Cited By (9)

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WO2002002870A2 (fr) * 2000-06-20 2002-01-10 Grain Processing Corporation Procede de production d'une bande de papier
US6835282B2 (en) 1998-10-16 2004-12-28 Grain Processing Corporation Paper web with pre-flocculated filler incorporated therein
WO2006003122A1 (fr) * 2004-07-02 2006-01-12 Ciba Specialty Chemicals Water Treatments Limited Polymeres amphoteres permettant de commander le depot de poix et d'adhesifs dans la fabrication de papier
US7407561B2 (en) 2003-05-13 2008-08-05 Ciba Specialty Chemicals Water Treatments Ltd. Use of water-soluble crosslinked cationic polymers for controlling deposition of pitch and stickies in papermaking
WO2016114919A1 (fr) * 2015-01-12 2016-07-21 Ecolab Usa Inc. Polymères stables thermiquement pour une récupération améliorée du pétrole
WO2017007614A1 (fr) 2015-07-07 2017-01-12 Solenis Technologies, L.P. Procédés d'inhibition du dépôt de contaminants organiques dans des systèmes de fabrication de de pâte à papier et de papier
JP2017214669A (ja) * 2016-05-30 2017-12-07 ハリマ化成株式会社 ピッチコントロール剤およびピッチコントロール方法
CN108623128A (zh) * 2018-05-04 2018-10-09 武汉理工大学 一种污泥处理用两性型聚丙烯酰胺絮凝剂的制备方法
US10280565B2 (en) 2016-02-26 2019-05-07 Ecolab Usa Inc. Drainage management in multi-ply papermaking

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AU2014346569A1 (en) 2013-11-08 2016-05-05 Solenis Technologies, L.P. Surfactant based brown stock wash aid treatment for papermachine drainage and dry strength agents
WO2017214616A1 (fr) 2016-06-10 2017-12-14 Ecolab Usa Inc. Polymère en poudre sèche de faible poids moléculaire utilisable comme agent d'amélioration de la résistance à l'état sec dans la fabrication du papier
CA3071402A1 (fr) 2017-07-31 2019-02-07 Ecolab Usa Inc. Procede d'application de polymere sec
US11535985B2 (en) 2019-07-01 2022-12-27 Kemira Oyj Method for manufacture of paper or board and paper or board obtained by the method
US11976418B2 (en) 2021-10-12 2024-05-07 Kemira Oyj Starch fixation and retention in recycled fiber systems

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US4505828A (en) * 1979-10-15 1985-03-19 Diamond Shamrock Chemicals Company Amphoteric water-in-oil self-inverting polymer emulsion
EP0058622A1 (fr) * 1981-02-17 1982-08-25 Calgon Corporation Diminution de la formation de dépôt de résines poisseuses lors de la production de papier
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Cited By (18)

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Publication number Priority date Publication date Assignee Title
US6835282B2 (en) 1998-10-16 2004-12-28 Grain Processing Corporation Paper web with pre-flocculated filler incorporated therein
WO2002002870A2 (fr) * 2000-06-20 2002-01-10 Grain Processing Corporation Procede de production d'une bande de papier
WO2002002870A3 (fr) * 2000-06-20 2002-05-16 Grain Processing Corp Procede de production d'une bande de papier
US7407561B2 (en) 2003-05-13 2008-08-05 Ciba Specialty Chemicals Water Treatments Ltd. Use of water-soluble crosslinked cationic polymers for controlling deposition of pitch and stickies in papermaking
WO2006003122A1 (fr) * 2004-07-02 2006-01-12 Ciba Specialty Chemicals Water Treatments Limited Polymeres amphoteres permettant de commander le depot de poix et d'adhesifs dans la fabrication de papier
AU2005259257B2 (en) * 2004-07-02 2010-11-18 Ciba Specialty Chemicals Water Treatments Limited Amphoteric polymers for controlling deposition of pitches and stickies in papermaking
CN107108290A (zh) * 2015-01-12 2017-08-29 艺康美国股份有限公司 用于强化采油的热稳定聚合物
WO2016114919A1 (fr) * 2015-01-12 2016-07-21 Ecolab Usa Inc. Polymères stables thermiquement pour une récupération améliorée du pétrole
EP3245164A4 (fr) * 2015-01-12 2018-06-20 Ecolab USA Inc. Polymères stables thermiquement pour une récupération améliorée du pétrole
US10450500B2 (en) 2015-01-12 2019-10-22 Ecolab Usa Inc. Thermally stable polymers for enhanced oil recovery
CN107108290B (zh) * 2015-01-12 2021-02-02 艺康美国股份有限公司 用于强化采油的热稳定聚合物
WO2017007614A1 (fr) 2015-07-07 2017-01-12 Solenis Technologies, L.P. Procédés d'inhibition du dépôt de contaminants organiques dans des systèmes de fabrication de de pâte à papier et de papier
US10253214B2 (en) 2015-07-07 2019-04-09 Solenis Technologies, L.P. Methods for inhibiting the deposition of organic contaminates in pulp and papermaking systems
US10280565B2 (en) 2016-02-26 2019-05-07 Ecolab Usa Inc. Drainage management in multi-ply papermaking
JP2017214669A (ja) * 2016-05-30 2017-12-07 ハリマ化成株式会社 ピッチコントロール剤およびピッチコントロール方法
WO2017209037A1 (fr) * 2016-05-30 2017-12-07 ハリマ化成株式会社 Agent de commande de brai et procédé de commande de brai
US10240295B2 (en) 2016-05-30 2019-03-26 Harima Chemicals, Inc. Pitch-controlling agent and pitch-controlling method
CN108623128A (zh) * 2018-05-04 2018-10-09 武汉理工大学 一种污泥处理用两性型聚丙烯酰胺絮凝剂的制备方法

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WO2000014331A1 (fr) Procedes permettant d'ameliorer la retention et l'egouttage dans la fabrication du papier

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