EP1456468B1 - Wässrige silicium enthaltende zusammenstzung und verfahren zur herstellung von papier - Google Patents

Wässrige silicium enthaltende zusammenstzung und verfahren zur herstellung von papier Download PDF

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Publication number
EP1456468B1
EP1456468B1 EP02793740A EP02793740A EP1456468B1 EP 1456468 B1 EP1456468 B1 EP 1456468B1 EP 02793740 A EP02793740 A EP 02793740A EP 02793740 A EP02793740 A EP 02793740A EP 1456468 B1 EP1456468 B1 EP 1456468B1
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EP
European Patent Office
Prior art keywords
silica
containing composition
anionic
aqueous
based particles
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English (en)
French (fr)
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EP1456468A1 (de
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Hans Johansson-Vestin
Johan Nyander
Jan Nordin
Solhage Fredrik
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Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
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Akzo Nobel NV
Eka Chemicals AB
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    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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

Definitions

  • the present invention relates to an aqueous silica-containing composition comprising an anionic organic polymer having at least one aromatic group and anionic silica-based particles.
  • the invention further relates to a method for the preparation of the aqueous silica-containing composition, uses of the aqueous silica-containing composition and a papermaking process.
  • an aqueous suspension containing cellulosic fibres, and optionally fillers and additives, referred to as stock is fed into a headbox which ejects the stock onto a forming wire. Water is drained from the stock through the forming wire so that a wet web of paper is formed on the wire. The formed paper web is dewatered and dried in the drying section of the paper machine. Drainage and retention aids are conventionally introduced into the stock in order to facilitate drainage and to increase adsorption of fine particles onto the cellulosic fibres in such a way that the fine particles are "retrained with the fibres on the wire.
  • US 4,388,150 discloses a binder in papermaking comprising a complex of cationic starch and colloidal silicic acid to produce a paper having increased strength and improved levels of retention of added minerals and papermaking fines.
  • US 4,750,974 discloses a coarcervate binder for use in papermaking comprising a tertiary combination of a cationic starch, an anionic high molecular weight polymer and a dispersed silica.
  • US 5,368,833 discloses silica sols containing aluminium modified silica particles with high specific surface area and a high content of microgel.
  • US 5,567,277 discloses a composition comprising an aqueous cellulosic furnish, a high molecular weight cationic polymer and an anionic polymer comprising modified lignin.
  • EP 0 418 015 A1 discloses an active sizing composition containing an aqueous emulsion in combination with an anionic dispersant or emulsifier.
  • anionic polyacrylamide, anionic starch or colloidal silica the anionic charge density in the sizing composition can be extended.
  • US 5,670,021 refers to a process for the production of paper by forming and dewatering a suspension of cellulose, wherein the dewatering takes place in the presence of an alkali metal silicate and a phenolic resin added at the same point into the suspension.
  • US 6,033,524 discloses a method for Increasing retention and drainage of filling components in a paper making furnish in a paper making process comprising adding to the furnish a slurry of filling components, also containing a phenolic enhancer.
  • US 6,315,824 pertains to a dispersed composition comprising a hydrophobic phase and an aqueous phase, the composition being stabilised by a cationic colloidal coacervate stabilising agent, the coacervate stabilising agent comprising an anionic component and a cationic component.
  • EP 0,953,680 A1 refers to a process for the production of paper from s suspension comprising adding to the suspension a cationic organic polymer.
  • US 5,185,062 discloses a papermaking process including the steps of adding to the papermaking slurry a high molecular weight cationic polymer and then a medium molecular weight anionic polymer.
  • US 4,313,790 refers to a process for the production of paper which consists of the addition to the papermaking furnish of kraft lignin or modified kraft lignin and poly(oxyethylene).
  • US 6.165,259 relates to an aqueous dispersion containing a dispersant and a disperse phase containing a hydrophobic material, the dispersant comprising an anionic compound and a cationic compound.
  • an improved drainage and/or retention effect of a cellulosic suspension on a wire can be obtained by using an aqueous silica-containing composition comprising at least one anionic organic polymer with at least one aromatic group which is a polyurethane and anionic aggregated or microgel formed silica-based particles.
  • the aqueous silica-containing composition is useful in processes for production of paper from all types of stocks, in particular stocks having high contents of salts (high conductivity) and colloidal substances.
  • the aqueous silica-containing composition is also useful in papermaking processes with a high degree of white water closure, i.e. extensive white water recycling and limited fresh water supply.
  • the present invention makes it possible to increase the speed of the paper machine and to use a lower dosage of additives to give a corresponding drainage and/or retention effect, thereby leading to an improved papermaking process and economic benefits.
  • drainage and retention aid refer to one or more components, which when added to an aqueous cellulosic suspension, give better drainage and/or retention than is obtained when not adding the said one or more components. All types of stocks, in particular stocks having high contents of salts (high conductivity) and colloidal substances will obtain better drainage and retention performances by the addition of the composition according to the present invention. This is important in papermaking processes with a high degree of white water closure, i.e. extensive white water recycling and limited fresh water supply.
  • an aqueous silica-containing composition comprising an anionic organic polymer having at least one aromatic group which is a polyurethane and anionic silica-based particles comprising aggregated or microgel formed silica-based particles.
  • the aqueous silica-containing composition contains the anionic organic polymer having at least one aromatic group and the anionic silica-based particles, calculated as SiO 2 , in an amount of at least 0.01 % by weight based on the total weight of the aqueous silica-containing composition.
  • the composition contains substantially no cellulose-reactive sizing agent.
  • an aqueous silica-oontaining composition obtainable by mixing an anionic organic polymer having at least one aromatic group which is a polyurethane with an aqueous alkali stabilised silica-based sol having an S-value in the range of from about 5 up to about 50% containing-anionic aggregated or microgel formed sillca-based particles .
  • the obtained aqueous siiica-containing composition contains the anionic organic polymer having at least one aromatic group and the silica-based particles, calculated as SiO 2 , in an amount of at least 0.01 % by weight based on the total weight of the aqueous silica-containing composition.
  • the composition contains substantially no cellulose-reactive sizing agent and that said anionic organic polymer is not anionic naphthalene sulphonate formaldehyde condensate.
  • a method for preparation of an aqueous silica-containing composition which comprises mixing in the presence of substantially no cellulose-reactive sizing agent an anionic organic polymer having at least one aromatic group which is a polyurethane with silica-based particles comprising anionic aggregated or microgel formed silica-based paricles to provide an aqueous silica-containing composition containing the anionic organic polymer having at least one aromatic group and the silica-based particles, calculated as SiO 2 , in an amount of at least 0.01 % by weight, based on the total weight of the aqueous silica-containing composition with the proviso that the anionic organic polymer having at least one aromatic group is not an anionic naphthalene sulphonate formaldehyde condensate.
  • an aqueous silica-containing composition which comprises mixing an anionic organic polymer having at least one aromatic group being a polyurethane and a charge density of at least 0.1 meq/g of dry polymer, with silica-based particles comprisng anionic aggregated or microgel formed to provide an aqueous silica-containing composition containing the anionic organic polymer having at least one aromatic group and the silica-based particles, calculated as SiO 2 , in an amount of at least 0.01 % by weight, based on the total weight of the aqueous silica-containing composition, with the proviso that the anionic organic polymer having at least one aromatic group is not an anionic naphthalene sulphonate formaldehyde condensate.
  • an aqueous silica-containing composition which comprises desalinating an aqueous solution of an anionic organic polymer having at least one aromatic group, being a polyurethane mixing in the desalinated anionic organic polymer having at least one aromatic group with silica-based particles comprisng anionic aggregated or microgel formed siluca-based particles to provide an aqueous silica-containing composition containing the anionic organic polymer having at least one aromatic group and the aggregated or microgel formed silica-based particles, calculated as SiO 2 , in an amount of at least 0.01 % by weight, based on the total weight of the aqueous silica-containing composition with the proviso that the anionic organic polymer having at least one aromatic group is not an anionic naphthalene sulphonate formaldehyde condensate.
  • the invention further relates to the use of the aqueous silica-containing composition of the invention, as flocculating agent In combination with at least one cationic organic polymer in the production of pulp and paper and for water purification.
  • a process for the production of paper from a suspension containing cellulosic fibres, and optionally fillers comprising adding to the suspension at least one cationic organic polymer and an aqueous silica-containing composition according to the invention.
  • the aqueous silica-containing composition comprises at least one anionic organic polymer with at least one aromatic group, being a polyurethane.
  • the aromatic group of the anionic polymer can be present in the polymer backbone or in a substituent group that is attached to the polymer backbone (main chain).
  • suitable aromatic groups include aryl, aralkyl and alkaryl groups and derivatives thereof, e.g. phenyl, tolyl, naphthyl, phenylene, xylylene, benzyl, phenylethyl and derivatives of these groups.
  • the anionically charged groups can be present either In the anionic polymer or in the monomers used for preparing the anionic polymer.
  • the anionically charged groups can either be groups carrying an anionic charge or acid groups carrying an anionic charge when dissolved or dispersed in water. These groups are herein collectively being referred to as anionic groups, such as phosphate, phosphonate, sulphate, sulphonic acid, sulphonate, carboxylic acid, carboxylate, alkoxide and phenolic groups, i.e. hydroxy-substituted phenols and naphthyls. Groups carrying an anionic charge are usually salts of an alkali, alkaline earth metals or ammonia.
  • Anionic polymers containing one or more aromatic groups being polyurethanes according to the invention can suitably be selected from the group consisting of step-growth polymers,
  • step-growth polymer refers to a polymer obtained by step-growth polymerisation, also being referred to as step-reaction polymer and step-reaction polymerisation, respectively.
  • the anionic polymer is a step-growth polymer being a polyurethane.
  • the anionic polymers according to the invention can be linear, branched or cross-linked. Preferably the anionic polymer is water-soluhle or water-dispersible.
  • suitable anionic step-growth polymers include condensation polymers, i.e. polymers obtained by step-growth condensation polymerisation, e.g. condensates of an aldehyde such as formaldehyde with one or more aromatic compounds containing one or more anionic groups, and optional other comonomers useful in the condensation polymerisation such as urea and melamine.
  • suitable aromatic compounds containing anionic groups comprises compounds containing anionic groups such as phenolic compounds, e.g. phenol, resorcinol and derivatives thereof, aromatic acids and salts thereof.
  • suitable anionic step-growth polymers include addition polymers, i.e. polymers obtained by step-growth addition polymerisation, e.g. anionic polyurethanes prepared from a monomer mixture comprising aromatic isocyanates and/or aromatic alcohols.
  • suitable aromatic isocyanates include diisocyanates, e.g. toluene-2,4- and 2.6-diisocyanates and diphenylmethane-4,4'-diisocyanate.
  • suitable aromatic alcohols include dihydric alcohols, i.e. diols, e.g.
  • the monomer mixture can also contain non-aromatic isocyanates and/or alcohols, usually diisocyanates and diols, for example any of those known to be useful in the preparation of polyurethanes.
  • suitable monomers containing anionic groups include the monoester reaction products of triols, e.g. trimethylolethane, tri-methylolpropane and glycerol, with dicarboxylic acids or anhydrides thereof, e.g.
  • succinic acid and anhydride terephthalic acid and anhydride, such as glycerol monosuccinate, glycerol monoterephthalate, trimethylolpropane monosuccinate, trimethylolpropane monoterephthalate, N,N-bis-(hydroxyethyl)-glycine, di-(hydroxymethyl)proptonic acid, N,N-bis-(hydroxyethyl)-2-aminoethanesulfonic acid, and the like, optionally and usually in combination with reaction with a base, such as alkali and alkaline earth metal hydroxides, e.g. sodium hydroxide, ammonia or an amine, e.g. triethylamine, thereby forming an alkali, alkaline earth metals or ammonium counter-ion.
  • a base such as alkali and alkaline earth metal hydroxides, e.g. sodium hydroxide, ammonia or an amine, e.g. trie
  • the weight average molecular weight of the anionic polymer can vary within wide limits dependent on, inter alia, the type of polymer used, and usually it is at least about 500, suitably above about 800 and preferably above about 1,000.
  • the upper limit is not critical; It can be about 10,000,000, usually 1,000,000, suitably 500,000, preferably 200,000 and most preferably 100,000.
  • the anionic polymer can have a degree of anionic substitution (DS A ) varying over a wide range dependent on, Inter alia, the type of polymer used.
  • DS A is usually from 0.01 to 2.0, suitably from 0.02 to 1.8 and preferably from 0.025 to 1.5; and the degree of aromatic substitution (DS Q ) can be from 0.001 to 1.0, usually from 0.01 to 0.8, suitably from 0.02 to 0.7 and preferably from 0.025 to 0.5.
  • the degree of cationic substitution (DS c ) can be, for example, from 0 to 0.2, suitably from 0 to 0.1 and preferably from 0 to 0.05, the anionic polymer having an overall anionic charge.
  • the anionic charge of the anionic polymer is within the range of from 0.1 to 10.0 meq/g of dry polymer, suitably from 0.2 to 6.0 meq/g, and preferably from 0.5 to 4.0 meq/g.
  • the aqueous silica-containing composition according to the invention also comprises anionic aggregated or microgel formed silica-based particles i.e. particles based on SiO 2 , preferably formed by polymerising silicic acid, encompassing both homopolymers and copolymers.
  • silica-based particles can be modified and contain other elements, e.g. amine, aluminium and/or boron, which can be present in the aqueous phase and/or in the silica-based particles.
  • suitable aggregated or microgel formed silica-based particles include colloidal silica, colloidal aluminium-modified silica or aluminium silicate, and different types of polysilicic acid and mixtures thereof, either alone or in combination with other types of anionic silica-based particles.
  • polysilicic acid is also referred to was polymeric silicic acid, polysilicic acid microgel, polysilicate and polysilicate microgel, which are all encompassed by the term polysilicic acid used herein.
  • Aluminium-containing compounds of this type are commonly referred to as polyaluminosilicate and polyaluminosilicate microgel including colloidal aluminium-modified silica and aluminium silicate.
  • the anionic silica-based particles are in the colloidal range of particle size. This state comprises particles sufficiently small not to be affected by-gravitational forces but sufficiently large not to show marked deviation from the properties of typical solutions, i.e. average particle size significantly less than 1 ⁇ m.
  • the anionic silica-based particles have an average particle size suitably below about 50 nm, preferably below about 20 nm and more preferably in the range of from about 1 to about 50 nm, most preferably from about 1 up to about 10 nm.
  • the particle size refers to the average size of the primary particles, which may be aggregated or non-aggregated.
  • the silica-based particles present in the aqueous silica-containing composition of the invention comprise aggregated or microgel formed silica-based particles, optionally and usually in combination with non-aggregated, or monodisperse, silica-based particles.
  • the silica-based particles have a specific surface area larger than 50 m 2 /g, preferably larger than 100 m 2 /g.
  • the specific area can be up to 1700 m 2 /g, preferably up to 1300 m 2 /g and usually in the range from 300 to 1300 m 2 /g, preferably from 500 to 1050 m 2 /g.
  • the specific surface area can be measured by means of titration with NaOH according to the method described by Sears, Analytical Chemistry 28(1956), 12, 1981-1983 or in U.S. Patent No. 5,176,891 .
  • the given area thus represents the average specific surface area of the particles.
  • the total weight of the anionic organic polymer having at least one aromatic group and anionic silica-based particles, calculated as SiO 2 , contained in the aqueous silica-containing composition is at least 0.01% by weight, calculated on the total weight of the aqueous silica-containing composition, preferably at least 0.05 % by weight, more preferably at least 0.1 % by weight.
  • concentration of the anionic organic polymer having at least one aromatic group and the anionic silica-based particles, calculated as SiO 2 is within the range of 1 to 45% by weight, preferably within the range of 2 to 35 % by weight, most preferably 5 to 30% by weight.
  • the aqueous silica-containing composition can have an anionic charge density of at least 0.1 meq/g, usually the charge is within the range of from 0.1 to 10 meq/g, suitably within the range of from 0.1 to 8 meq/g, preferably within the range of from 0.1 to 6 meq/g, and most preferably within the range of from 0.2 to 4 meq/g.
  • the aqueous silica-containing composition according to the invention contains substantially no cellulose-reactive sizing agent.
  • substantially no means that less than or equal to 10% by weight, suitably less than 5%, preferably less than 1% by weight of cellulose-reactive sizing agent is present in the aqueous silica-containing composition.
  • the aqueous silica-containing composition according to the invention contains substantially no sizing agent, suitably, contains no sizing agent.
  • the present invention relates further to a method for preparation of an aqueous silica-containing composition.
  • the two components are preferably stirred together.
  • the anionic organic polymer having at least one aromatic group can be added to an aqueous sol containing the silica-based particles or the silica-based particles can be added to an aqueous solution of anionic organic polymer having at least one aromatic group.
  • the aqueous solution of anionic organic polymer having at least one aromatic group may be desalinated or deionisated. The desalination or deionisation can be carried out with dialysis, membrane filtration, ultrafiltration, reversed osmosis or ion exchange or the like.
  • the desalination or deionisation is carried out by the use of ultra-filtration or dialysis.
  • the pH of an aqueous solution of anionic organic polymer may be adjusted to the pH of the silica-based particles, prior to or after mixing the aqueous solution with the silica-based particles.
  • the pH can be adjusted to at least pH 8.0, suitably at least 9.0, preferably at least 9.5, preferably within the range of 9.0 to 11.0.
  • the anionic organic polymer having at least one aromatic group to be mixed with the silica-based particles can have an anionic charge density of at least 0.1 meq/g, usually within the range of from 0.1 to 10.0 meq/g of dry polymer, suitably within the range of from 0.2 to 6.0 and preferably within the range of from 0.5 to 4.0.
  • the silica-based particles, preferably anionic, to be mixed with the anionic organic polymer can have the previous mentioned properties.
  • the silica-based particles are contained in a sol.
  • the sol may have an S-value in the range of from 5 to 80%, suitably from 5 to 50%, preferably from 8 to 45%, and most preferably from 10 to 30%. Calculation and measuring of the S-value can be performed as described by Iler & Dalton in J. Phys. Chem. 60(1956), 955-957 .
  • the S-value indicates the degree of aggregate or microgel formation and a lower S-value is indicative of a higher degree of aggregation.
  • the silica-based particles comprise aggregated or microgel formed silica-based particles, optionally and usually in combination with non-aggregated, or monodispers, silica-based particles.
  • the silica-based particles have a molar ratio Si 2 O:Na 2 O less than 60, usually within the range 5 to 60, and preferably within the range from 8 to 55.
  • the aqueous silica-containing composition obtained by any of the methods according to the invention contains suitably a total weight of the anionic organic polymer having at least one aromatic group and anionic silica-based of at least 0.01% by weight, calculated on the total weight of the aqueous silica-containing composition, preferably at least 0.05 % by weight, more preferably at least 0.1 % by weight.
  • concentration of anionic organic polymer having at least one aromatic group and anionic silica-based particles is within the range of 1 to 45% by weight, preferably within the range of 2 to 35 % by weight, most preferably 5 to 30% by weight.
  • the products prepared by any of these methods shows improved drainage and retention properties, and also a better storage stability and therefore a better drainage and retention aid performance when stored because it has a longer shelf life.
  • the mixing procedure of above mention methods is suitably carried out in the presence of substantially no cellulose-reactive sizing agent.
  • substantially no means that less or equal to 10% by weight, suitably less than 5%, preferably less than 1% by weight of cellulose-reactive sizing agent is present. Most preferably there is no cellulose-reactive sizing agent present.
  • the mixing procedure may also be carried out in the presence of substantially no sizing agent, or in the presence of no sizing agent.
  • the present invention further relates to a process for the production of paper from an aqueous suspension containing cellulosic fibres.
  • the process comprises adding to the suspension a cationic organic polymer and the aqueous silica-containing composition of the invention.
  • the cationic organic polymer according to the invention can be linear, branched or cross-linked.
  • the cationic polymer is water-soluble or water-dispersible.
  • Suitable cationic polymers include synthetic organic polymers, e.g. step-growth polymers and chain-growth polymers, and polymers derived from natural sources, e.g. polysaccharides.
  • Suitable cationic synthetic organic polymers include vinyl addition polymers such as acrylate- and acrylamide-based polymers, as well as cationic poly(diallyl dimethyl ammonium chloride), cationic polyethylene imines, cationic polyamines, polyamidoamines and vinylamide-based polymers, melamine-formaldehyde and urea-formaldehyde resins.
  • suitable polysaccharides include starches, guar gums, cellulose derivatives, chitins, chitosans, glycans, galactans, glucans, xanthan gums, pectins, mannans, dextrins, preferably starches and guar gums.
  • suitable starches include potato, corn, wheat, tapioca, rice, waxy maize, barley, etc.
  • Cationic starches and cationic acrylamide-based polymers are preferred polymers according to the invention, and they can be used singly, together with each other or together with other polymers, particularly preferred are cationic starches and cationic acrylamide-based polymers having at least one aromatic group.
  • the cationic organic polymers can have one or more hydrophobic groups attached to them.
  • the hydrophobic groups can be aromatic groups, groups comprising aromatic groups or non-aromatic groups, preferably the hydrophobic groups comprise aromatic groups.
  • the hydrophobic group can be attached to a heteroatom, e.g. nitrogen or oxygen, the nitrogen optionally being charged, which heteroatom, it can be attached to the polymer backbone, for example via a chain of atoms.
  • the hydrophobic group may have at least 2 and usually at least 3 carbon atoms, suitably from 3 to 12 and preferably from 4 to 8 carbon atoms.
  • the hydrophobic group is suitably a hydrocarbon chain.
  • Suitable dosages counted as dry substance based on dry pulp and optional filler, of the cationic polymer in the system is from 0.01 to 50 kg/t (kg/tonne, "metric ton") of, preferably from 0.1 to 30 kg/t and most preferably from 1 to 15 kg/t.
  • Suitable dosages counted as dry substances based on dry pulp and optional filler, of the aqueous silica-containing composition defined above in the system are from 0.01 to 15 kg/t, preferably from 0.01 to 10 kg/t calculated as an anionic organic polymer having at least one aromatic group and anionic silica-based particles, and most preferably from 0.05 to 5 kg/t.
  • Suitable mineral fillers of conventional types may be added to the aqueous cellulosic suspension according to the invention.
  • suitable fillers include kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, ground marble and precipitated calcium carbonate (PCC).
  • Such aluminium compounds include alum, aluminates, aluminium chloride, aluminium nitrate, and polyaluminium compounds, such as polyaluminium chlorides, polyaluminium sulphates, polyaluminium compounds containing chloride and/or sulphate ions, polyaluminium silicate sulphates, and mixtures thereof.
  • the polyaluminium compounds may also contain other anions than chloride ions, for example anions from sulfuric acid, phosphoric acid, or organic acids such as citric acid and oxalic acid.
  • an aluminium compound in the present process it is usually preferably to add it to the stock prior to the polymer component and micro- or nano-particulate material.
  • Suitable addition levels of aluminium containing compounds is at least 0.001 kg/t, preferably from 0.01 to5 kg/t and more preferably from 0.05 to 1 kg/t, calculated as Al 2 O 3 based on dry pulp and optional filler.
  • anionic trash catchers examples include cationic polyamines, polymers or copolymers of quaternary amines, or aluminum containing compounds.
  • the process of this invention is used for the production of paper.
  • paper include not only paper and the production thereof, but also other web-like products, such as for example board and paperboard, and the production thereof.
  • the invention is particularly useful in the manufacture of paper having grammages below 150 g/m 2 , preferably below 100 g/m 2 , for example fine paper, newspaper, light weight coated paper, super calendered paper and tissue.
  • the process can be used in the production of paper from all types of stocks, both wood containing and woodfree.
  • the different types of suspensions of cellulose-containing fibres and the suspensions should suitably contain at least 25% by weight and preferably at least 50% of weight of such fibres, based on dry substance.
  • the suspensions comprise fibres from chemical pulp such as sulphate, sulphite and organosolv pulps wood-containing or mechanical pulp such as thermomechanical pulp, chemo-thermomechanical pulp, refiner pulp and groundwood pulp, from both hardwood and softwood, and can also be based on recycled fibres, optionally from de-inked pulps, and mixtures thereof.
  • the stock is a wood containing stock, which have high contents of salts (high conductivity).
  • the chemicals according to the present invention can be added to the aqueous cellulosic suspension, or stock, in conventional manner and in any order. It is usually preferably to add the cationic polymer to the stock before adding the aqueous silica-containing composition, even if the opposite order of addition may be used. It is further preferred to add the cationic polymer before a shear stage, which can be selected from pumping, mixing, cleaning, etc., and to add the aqueous silica-containing composition after that shear stage.
  • the aqueous silica-containing composition can be used as a flocculation agent in the treatment of water for the production of drinking water or as an environmental treatment of waters for instance in lakes.
  • the composition can also be used as flocculation agent in the treatment of wastewater or waste sludges.
  • Parts and % relate to parts by weight and % by weight, respectively, and all solutions are aqueous, unless otherwise stated.
  • the units are metric.
  • Retention performance was evaluated by means of a nephelometer by measuring the turbidity of the filtrate, the white water, obtained by draining the stock.
  • the trurbidity was measure in NTU (Nephelometric Turbidity Units).
  • test stock was wood containing with a pH 7.2, the conductivity of the stock was 5.0 mS/cm, and the consistency was 1.42 g/l.
  • the stock was stirred in a baffled jar at a speed of 1500 rpm throughout the test.
  • a cationic polymer was added to the stock before the aqueous compositions according to the invention or the anionic reference.
  • the cationic polymer was a cationic starch (C1) obtained by quarternisation of native potato starch with 3-chloro-2-hydroxypropyl dimethyl benzyl ammonium chloride to 0.5% N was added followed by 45 seconds of stirring, and then the anionic aqueous composition was added, followed by 15 seconds stirring before drainage.
  • Aqueous compositions according to the invention containing anionic polyurethane and colloidal silica were measured to evaluate their drainage and retention performance. All samples were diluted to 0.5% of solids before the evaluation of drainage properties.
  • the anionic polyurethane (P1) is based on an anionic polyurethane of 15% solids, produced from glyceryl monostearate (GMS) and toluolyl diisocyanate (TDI), which forms a pre-polymer, which is reacted with dimethylol propionic acid (DMPA), with 30 mol% of GMS is replaced by DPMA N-methyl diethanol amine (N-MDEA).
  • the colloidal silica sol (S1) is of the type described in US 5,447,604 having a molar ratio SiO 2 :Na 2 O of 10, specific surface area of 870 m 2 /g, S-value of 35% and silica content of 10.0% by weight.
  • the drainage time measured on the stock with addition of 20 kg/t of C1 was 29 seconds and the turbidity was measured to 44 NTU. All additions are calculated as dry on dry stock.
  • the drainage times derived from the different additions to the stock of the aqueous composition of the invention are summarised in Table 1.
  • anionic polyurethane (P2) based on an anionic polyurethane of 19% solids produced from TDI and phenyl diethanoi amine PDEA, which forms the pre-polymer, which is reacted with a mixture of DMPA and N-MDEA and of which 30 mol% of PDEA is replaced by
  • the anionic polyurethane used in this example was an anionic polyurethane (P3) of 15% solids, produced from GMS and TDI, which forms a pre-polymer, which is reacted DMPA and the colloidal silica (S3) described in US 5,368,833 was a silica sol having a molar ratio SiO 2 :Na 2 O of 45, specific surface area of 850 m 2 /g, S-value of 20% and a silica content of 8.0%, and was modified with aluminium to 0.3% Al 2 O 3 .
  • P3 anionic polyurethane
  • S3 colloidal silica
  • LS1 anionic lignosulphonate

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)

Claims (20)

  1. Eine wässrige Siliciumdioxid enthaltende Zusammensetzung, die ein anionisches organisches Polymer mit mindestens einem aromatischen Rest umfasst, wobei es sich um ein Polyurethan handelt, und anionische Teilchen auf Siliciumdioxid-Basis, umfassend aggregierte oder mikrogelgeformte Teilchen auf Siliciumdioxid-Basis, umfasst, wobei die wässrige Siliciumdioxid enthaltende Zusammensetzung das Polyurethan und die anionischen Teilchen auf Siliciumdioxid-Basis, berechnet als SiO2, in einer Menge von mindestens 0,01 Gew.-%, basierend auf dem Gesamtgewicht der wässrigen Siliciumdioxid enthaltenden Zusammensetzung enthält, wobei die Zusammensetzung weniger oder gleich 10 Gew.-% eines cellulosereaktiven Leimungsmittels enthält.
  2. Die wässrige Siliciumdioxid enthaltende Zusammensetzung gemäß Anspruch 1, wobei die Teilchen auf Siliciumdioxid-Basis eine spezifische Oberfläche in einem Bereich von 300 bis 1300 m2/g aufweisen.
  3. Die wässrige Siliciumdioxid enthaltende Zusammensetzung gemäß einem der Ansprüche 1-2, wobei die Teilchen auf Siliciumdioxid-Basis eine mittlere Teilchengröße im Bereich von etwa 1 nm bis zu etwa 50 nm aufweisen.
  4. Die wässrige Siliciumdioxid enthaltende Zusammensetzung gemäß einem der Ansprüche 1-3, wobei die Teilchen auf Siliciumdioxid-Basis eine mittlere Teilchengröße im Bereich von etwa 1 nm bis zu etwa 10 nm aufweisen.
  5. Die wässrige Siliciumdioxid enthaltende Zusammensetzung gemäß einem der Ansprüche 1-4, wobei die wässrige Siliciumdioxid enthaltende Zusammensetzung eine negative Ladungsdichte im Bereich von 0,1 bis 6 meq/g aufweist.
  6. Die wässrige Siliciumdioxid enthaltende Zusammensetzung gemäß einem der Ansprüche 1-5, wobei die Zusammensetzung kein Leimungsmittel enthält.
  7. Ein Verfahren zur Herstellung einer wässrigen Siliciumdioxid enthaltenden Zusammensetzung, welche das Mischen, in Gegenwart von weniger oder gleich 10 Gew.-%, eines mit cellulosereaktiven Leimungsmittels, eines anionischen organischen Polymers mit mindestens einem aromatischen Rest, wobei es sich um ein Polyurethan handelt mit Teilchen auf Siliciumdioxid-Basis, die anionische, aggregierte oder mikrogelgeformte Teilchen auf Siliciumdioxid-Basis umfassen, umfasst, um eine wässrige Siliciumdioxidenthaltende Zusammensetzung, die das Polyurethan und die Teilchen auf Siliciumdioxid-Basis, berechnet als SiO2, in einer Menge von mindestens 0,01 Gew.-%, basierend auf dem Gesamtgewicht der wässrigen Siliciumdioxidenthaltenden Zusammensetzung enthält, bereitzustellen.
  8. Das Verfahren gemäß Anspruch 7, wobei das Polyurethan eine Ladungsdichte von mindestens 0,1 meq/g des trockenen Polymers aufweist.
  9. Das Verfahren gemäß einem der Ansprüche 7-8, wobei die Teilchen auf Siliciumdioxid-Basis in einem Siliciumdioxid-Sol, das einen S-Wert in einem Bereich von etwa 5 bis zu etwa 50% vor dem Mischen mit dem Polyurethan aufweist, enthalten sind.
  10. Das Verfahren gemäß einem der Ansprüche 7-9, wobei das Polyurethan vor dem Mischen mit den Teilchen auf Siliciumdioxid-Basis entsalzt wird.
  11. Das Verfahren gemäß einem der Ansprüche 7-10, wobei die Teilchen auf Siliciumdioxid-Basis eine spezifische Oberfläche in einem Bereich von 300 bis 1300 m2/g aufweisen.
  12. Das Verfahren gemäß einem der Ansprüche 7-11, wobei die Teilchen auf Siliciumdioxid-Basis eine mittlere Teilchengröße im Bereich von etwa 1 nm bis zu etwa 50 nm aufweisen.
  13. Das Verfahren gemäß einem der Ansprüche 7-12, wobei die Teilchen auf Siliciumdioxid-Basis eine mittlere Teilchengröße im Bereich von etwa 1 nm bis zu etwa 10 nm aufweisen.
  14. Das Verfahren gemäß einem der Ansprüche 7-13, wobei der pH der wässrigen Lösung des Polyurethans auf einen pH von mindestens 8 vor dem Mischen mit den Teilchen auf Siliciumdioxid-Basis eingestellt wird.
  15. Das Verfahren gemäß einem der Ansprüche 7-14, wobei die wässrige Siliciumdioxid enthaltende Zusammensetzung eine negative Ladungsdichte im Bereich von 0,1 bis 6 meq/g aufweist.
  16. Eine wässrige Siliciumdioxid enthaltende Zusammensetzung, erhältlich durch das Verfahren gemäß einem der Ansprüche 7-15.
  17. Verwendung einer wässrigen Siliciumdioxid enthaltenden Verbindung gemäß einem der Ansprüche 1-6 oder 16 als Flockungsmittel in Kombination mit mindestens einem organischen Polymer zur Herstellung von Zellstoff und Papier und für die Wasseraufreinigung.
  18. Ein Verfahren zur Herstellung von Papier aus einer Suspension, die Cellulosefasern und gegebenenfalls Füllstoffe enthält, umfassend das Zugeben von mindestens einem kationischen organischen Polymer und einer wässrigen Siliciumdioxid enthaltenden Zusammensetzung gemäß einem der Ansprüche 1-6 oder 16 zu der Suspension.
  19. Das Verfahren gemäß Anspruch 18, wobei das kationische organische Polymer kationische Stärke oder kationisches Polyacrylamid ist.
  20. Das Verfahren gemäß einem der Ansprüche 18-19, wobei das kationische organische Polymer mindestens einen aromatischen Rest aufweist.
EP02793740A 2001-12-21 2002-12-20 Wässrige silicium enthaltende zusammenstzung und verfahren zur herstellung von papier Expired - Lifetime EP1456468B1 (de)

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EP01850224 2001-12-21
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PCT/SE2002/002444 WO2003056099A1 (en) 2001-12-21 2002-12-20 Aqueous silica-containing composition and process for production of paper
EP02793740A EP1456468B1 (de) 2001-12-21 2002-12-20 Wässrige silicium enthaltende zusammenstzung und verfahren zur herstellung von papier

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CA2504387A1 (en) 2002-10-30 2004-05-13 The Lubrizol Corporation Fiber dispersant-containing systems
US7323083B2 (en) 2002-10-30 2008-01-29 The Lubrizol Corporation Adhesion promoters for glass-containing systems
US7955473B2 (en) 2004-12-22 2011-06-07 Akzo Nobel N.V. Process for the production of paper
BRPI0614081B1 (pt) * 2005-05-16 2019-02-19 Akzo Nobel Chemicals International B.V. Composição auxiliar de drenagem e retenção, uso da composição e processo para produção de papel
US20060254464A1 (en) 2005-05-16 2006-11-16 Akzo Nobel N.V. Process for the production of paper
US9017649B2 (en) * 2006-03-27 2015-04-28 Nalco Company Method of stabilizing silica-containing anionic microparticles in hard water
DE102007059736A1 (de) * 2007-12-12 2009-06-18 Omya Development Ag Oberflächenmineralisierte organische Fasern
WO2012117763A1 (ja) * 2011-03-03 2012-09-07 富士フイルム株式会社 シリカ分散組成物
AR086593A1 (es) * 2011-06-08 2014-01-08 Akzo Nobel Chemicals Int Bv Proceso para la produccion de papel y carton
CN106349513A (zh) * 2016-08-26 2017-01-25 强新正品（苏州）环保材料科技有限公司 一种高粘度硅溶胶及其制备方法
FR3055896B1 (fr) 2016-09-09 2020-04-03 S.P.C.M. Sa Procede de traitement d'effluents aqueux
CN106833570B (zh) * 2017-01-06 2019-05-28 中国海洋石油集团有限公司 一种悬浮减轻剂及其制备方法和用途

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4313790A (en) 1980-03-31 1982-02-02 Pulp And Paper Research Institute Of Canada Additives for increased retention and pitch control in paper manufacture
US4795531A (en) * 1987-09-22 1989-01-03 Nalco Chemical Company Method for dewatering paper
GB8920456D0 (en) * 1989-09-11 1989-10-25 Albright & Wilson Active sizing compositions
US5185062A (en) 1991-01-25 1993-02-09 Nalco Chemical Company Papermaking process with improved retention and drainage
US5670021A (en) * 1992-01-29 1997-09-23 Kemira Kemi Aktiebolag Process for production of paper
SE9502522D0 (sv) * 1995-07-07 1995-07-07 Eka Nobel Ab A process for the production of paper
US6315824B1 (en) 1996-02-02 2001-11-13 Rodrigue V. Lauzon Coacervate stabilizer system
US6165259A (en) 1997-02-05 2000-12-26 Akzo Nobel N.V. Aqueous dispersions of hydrophobic material
US6033524A (en) * 1997-11-24 2000-03-07 Nalco Chemical Company Selective retention of filling components and improved control of sheet properties by enhancing additive pretreatment
EP0953680A1 (de) * 1998-04-27 1999-11-03 Akzo Nobel N.V. Verfahren zur Herstellung von Papier

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ES2381028T3 (es) 2012-05-22
EP1456468A1 (de) 2004-09-15
JP2005513300A (ja) 2005-05-12
KR20040068321A (ko) 2004-07-30
RU2004122419A (ru) 2005-03-27
BR0215227A (pt) 2004-11-16
CN1606647A (zh) 2005-04-13
NO20043139L (no) 2004-09-21
ZA200404079B (en) 2005-05-25
ATE544906T1 (de) 2012-02-15
CA2470803A1 (en) 2003-07-10
PT1456468E (pt) 2012-05-08
PL369967A1 (en) 2005-05-02
WO2003056099A1 (en) 2003-07-10
MXPA04005533A (es) 2004-09-13
CA2470803C (en) 2009-05-26
AU2002359218B2 (en) 2005-12-08

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