Aqueous silicon-containing composition and paper making process

FIELD: polymer materials and papermaking industry.

SUBSTANCE: invention relates to aqueous silicon-containing composition containing anionic organic polymer comprising at least one aromatic group and silica-based anionic particles in aggregated form or microgel form. Anionic organic polymer, in particular, contains at least one aromatic group and silica-based anionic particles in amount at least 0.01% of the total mass of composition. Composition contains essentially no sizing substance capable of reacting with cellulose, whereas anionic organic polymer containing at least one aromatic group is not naphthalenesulfonate-formaldehyde condensate. Invention also relates to methods for preparing the composition and to utilization thereof as a substance providing dehydration and retention in paper making process. Invention further relates to a paper making process using aqueous suspension containing cellulose fibers and optionally filler, wherein aqueous silicon-containing composition and at least one charged organic polymer are added to pulp.

EFFECT: improved dehydration and/or retention in paper making process and increased storage stability.

20 cl, 4 tbl, 4 ex

 

The present invention relates to aqueous silica-containing composition containing the anionic organic polymer containing at least one aromatic group, and particles on the basis of anionic silica. The invention also relates to a method for obtaining aqueous silica-containing composition, to the use of aqueous silica-containing composition and method of manufacture of paper.

PREREQUISITES TO the CREATION of INVENTIONS

In paper production aqueous suspension containing cellulosic fibres, and optional fillers and additives, called paper pulp, served in the headbox from which it putting on molding the mesh (wire cloth). Water from paper pulp drain through the mesh fabric, resulting in a grid cloth is formed wet paper web. Formed paper web is subjected to dehydration and drying in the dryer section of the papermaking machine. Usually in paper weight enter excipients that facilitate dewatering and retention to facilitate the process of dehydration and increase the adsorption of small particles and cellulose fibers so that the fibers are kept small particles on a grid conveyor.

In U.S. patent No. 4388150 described binder used in paper production, containing Sands is with cationic starch and colloidal silicic acid, for making paper with improved strength and improved levels of retention of the added minerals and fine particles used in the manufacture of paper.

In U.S. patent No. 4750974 described koatservatnyh binder designed for use in paper production, containing a combination of three components: cationic starch, anionic high molecular weight polymer and dispersed silica.

In U.S. patent No. 5368833 described silica sols containing silica particles modified with aluminum, with a large specific surface area and with a high content of microgel.

In U.S. patent No. 5567277 described composition containing aqueous pulp composition, high molecular weight cationic polymer and anionic polymer containing a modified lignin.

In U.S. patent No. 6022449 described the use of water-dispersible polyisocyanates with anionic and/or potentially anionic groups and cationic and/or potentially cationic compounds in paper composition.

In EP No. 0418015 A1 describes an active sizing (glue) a composition comprising a water emulsion in combination with an anionic dispersant or emulsifier. States that through the use of anionic polyacrylamide, anionic starch or colloidal silica can increase the density of the anion is on charge in the sizing composition.

U.S. patent No. 5670021 relates to a method of making paper by forming and dewatering a suspension of cellulose in which the dehydration is conducted in the presence of alkali metal silicate and phenolaldehyde polymer added at the same time in suspension.

In U.S. patent No. 6033524 described a method of improving characteristics of retention and dewatering of fillers in the composition for paper manufacturing in the method of manufacturing paper containing added into the composition of the suspension of fillers, which also contains phenolic amplifier.

U.S. patent No. 6315824 relates to a dispersion composition containing a hydrophobic phase and the aqueous phase, and the composition is stable cationic colloidal koatservatnyh stabilizing agent, where koatservatnyh stabilizing agent contains an anionic component and a cationic component.

In EP No. 0953680 A1 describes a method of making paper from a suspension, comprising adding to the suspension a cationic organic polymer.

In U.S. patent No. 5185062 described method of making paper comprising adding to the pulp of high molecular weight cationic polymer and then adding an anionic polymer average molecular weight.

In U.S. patent No. 4313790 described method of making paper which comprises adding to the composition for izgotovleniem Kraft lignin or modified Kraft lignin and polyethylene oxide.

U.S. patent No. 6165259 relates to a water dispersion containing a dispersant and a disperse phase comprising a hydrophobic material, and a dispersant contains an anionic compound and the cationic compound.

It is advisable to provide substances that contribute to dehydration and retention with improved characteristics. It is also advisable to increase the storage stability of the substances that contribute to dehydration and retention. It is also advisable to provide a method for the production of paper with improved dewatering and retention characteristics.

Description of the INVENTION

According to the present invention it has been unexpectedly found that improved the effect of dehydration and/or retention of the pulp suspension on a grid conveyor can be achieved by the use of aqueous silica-containing composition containing at least one anionic organic polymer containing at least one aromatic group and anionic particles based on silica in aggregate form or in the form of a microgel. The aqueous silica-containing composition suitable for the manufacture of paper of all types of paper pulp, in particular of paper mass with high salt content (high conductivity) and colloidal substances. The aqueous silica-containing composition is also suitable in the pic is Bach manufacture of paper, in which with a high degree of use circulation of cooling water, i.e. extensive recycling recycled water by the limited supply of fresh water. Thus, application of the present invention provides the possibility of increasing the speed of the paper machine and the use of smaller doses of additives to achieve the respective characteristics of dehydration and/or retention, thus leading to an improved method of making paper and achievement of economic benefit.

The term "substance, contributing to dehydration and retention" refers to one or more components, which when added to the aqueous pulp suspension to provide the best dehydration and/or retention than reach, if not add the mentioned one or more components. All types of paper pulp, particularly paper pulp with high salt content (high conductivity) and colloidal substances, will have the best characteristics of dehydration and keep adding the composition according to the present invention. This is important in the process of making paper, which to a high degree using the circulation of cooling water, i.e. extensive recycling recycled water by the limited supply of fresh water.

According to the present invention offer the W aqueous silica-containing composition, containing anionic organic polymer containing at least one aromatic group and anionic particles based on silica containing particles of silica in aggregate form or in the form of a microgel. The aqueous silica-containing composition contains anionic organic polymer containing at least one aromatic group and anionic particles based on silica, based on SiO2,in the amount of at least 0.01 wt.% from the total mass of the aqueous silica-containing composition. The composition essentially contains no sizing substance that reacts with cellulose, and the above-mentioned anionic organic polymer is anionic naphthaleneformaldehyde condensate.

It is also proposed aqueous silica-containing composition obtained by mixing anionic organic polymer containing at least one aromatic group, with water stabilized alkali-Sol silica having an S-parameter in the range from about 5 to about 50%, including anionic particles based on silica in aggregate form or in the form of a microgel. The resulting aqueous silica-containing composition contains anionic organic polymer containing at least one aromatic group and particles based on silica, the C based on SiO 2,in the amount of at least 0.01 wt.% from the total mass of the aqueous silica-containing composition. The composition essentially contains no sizing substance that reacts with cellulose, and the above-mentioned anionic organic polymer is anionic naphthaleneformaldehyde condensate.

It is also proposed a method of obtaining the aqueous silica-containing composition, comprising mixing essentially in the absence of a sizing agent that reacts with cellulose, anionic organic polymer containing at least one aromatic group, with particles of silica containing anionic particles based on silica in aggregate form or in the form of a microgel, to obtain the aqueous silica-containing composition containing the anionic organic polymer containing at least one aromatic group and particles based on silica, based on SiO2,in the amount of at least 0.01 wt.% from the total mass of the aqueous silica-containing composition, provided that the anionic organic polymer containing at least one aromatic group is not naphthaleneformaldehyde condensate.

It is also proposed a method of obtaining the aqueous silica-containing composition, comprising mixing an the traditional organic polymer, containing at least one aromatic group, and having a charge density of at least 0.1 mEq/g of dry polymer particles based on silica, containing anionic particles based on silica in aggregate form or in the form of a microgel, for the formation of aqueous silica-containing composition containing the anionic organic polymer containing at least one aromatic group and particles based on silica, based on SiO2,in the amount of at least 0.01 wt.% from the total mass of the aqueous silica-containing composition, provided that the anionic organic polymer containing at least one aromatic group is not naphthaleneformaldehyde condensate.

Also proposed is a method of obtaining the aqueous silica-containing composition, comprising: desalination of an aqueous solution of the anionic organic polymer containing at least one aromatic group; blending desalinated anionic organic polymer containing at least one aromatic group, with particles of silica containing anionic particles based on silica in aggregate form or in the form of a microgel, for the formation of aqueous silica-containing composition containing the anionic organic polymer containing, on ENISA least one aromatic group and particles based on silica in aggregate form or in the form of a microgel, based on SiO2,in the amount of at least 0.01 wt.% from the total mass of the aqueous silica-containing composition, provided that the anionic organic polymer containing at least one aromatic group is not naphthaleneformaldehyde condensate.

Also available aqueous silica-containing composition produced according to the methods in accordance with the invention.

The invention additionally relates to the use of aqueous silica-containing composition according to the invention as a flocculant in combination with at least one cationic organic polymer in the manufacture of paper pulp (pulp and paper and water treatment.

According to the invention it is also proposed a method of manufacturing paper from a suspension containing cellulosic fibres, and optional fillers, comprising adding to the suspension at least one cationic organic polymer and aqueous silica-containing composition according to the invention.

The aqueous silica-containing composition contains at least one anionic organic polymer with at least one aromatic group that is anionic naphthalenesulfonate legitim condensate. The aromatic group of the anionic polymer can be represented in the main polymer chain or in the replacement group, attached to the main polymer chain (the main goal). Examples of suitable aromatic groups include aryl, aralkyl and alkaline groups and their derivatives, such as phenyl, tolyl, naphthyl, phenylene, xylylene, benzyl, phenylethyl, and derivatives of these groups. Anionic charged groups can be represented either in anionic polymer or monomers used to obtain the anionic polymer. Anionic charged groups can be groups bearing an anionic charge, or acid groups, bearing an anionic charge when dissolved or dispersed in water. These groups in this description, together referred to anionic groups such as phosphate, phosphonate, sulfate, sulfonic acid, sulfonate, carboxylic acid, carboxylate, metalloelastase and phenolic groups, i.e. the replacement family and nattily. Group carrying anionic charge, usually are salts of alkali, alkaline earth metals or ammonia.

Anionic polymers containing one or more aromatic groups, according to the invention can appropriately be selected from the group consisting of speed of living polymers, polymers with a living chain, polysaccharides and natural aromatic polymers. The term "STU is enato living polymer" as used here, refers to a polymer obtained by stepwise polymerization, and also belongs to the polymer of step polymerization" and "step polymerization", respectively. Preferably the anionic polymer is a step living polymer. Anionic polymers according to the invention can be linear, branched or crosslinked polymers. Preferably the anionic polymer is a water-soluble or water-dispersible.

Examples of suitable anionic step living polymers according to the present invention include condensation polymers, i.e. polymers obtained by stepwise polycondensation, for example condensates of an aldehyde such as formaldehyde with one or more aromatic compounds containing one or more anionic groups, and optionally other comonomers, suitable polycondensation, such as urea and melamine. Examples of suitable aromatic compounds containing anionic groups include compounds containing anionic groups, such as phenolic compounds, such as phenol, resorcinol and their derivatives, aromatic acids and their salts.

Examples of suitable anionic step living polymers according to the present invention include an additive polymers, i.e. polymers obtained by stepwise polymerization accession, i.e. the measures of anionic polyurethanes, obtained from a mixture of monomers containing aromatic isocyanates and/or aromatic alcohols. Examples of suitable aromatic isocyanates include diisocyanates such as toluene-2,4 - and 2,6-diisocyanate and difenilmetana-4,4′-diisocyanate. Examples of suitable aromatic alcohols include dibasic alcohols, i.e. diols, such as bisphenol a, phenyldiethanolamine, glycerylmonostearate and trimethylolpropane. You can also use monohydroxy aromatic alcohols such as phenol and its derivatives. The mixture of monomers may also contain non-aromatic isocyanates and/or alcohols, usually diisocyanates and diols, for example, any of those of whom it is known that they are used in the manufacture of polyurethanes. Examples of suitable monomers containing anionic groups include monoamine the reaction products of triolo, such as trimethanolamine, trimethylolpropane and glycerol, with dicarboxylic acids or their anhydrides, such as succinic acid and anhydride, terephthalic acid and anhydride, such as glycerylmonostearate, glycerylmonostearate, trimethylolpropane, trimethylolpropane, N,N-bis(hydroxyethyl)glycine, di(hydroxymethyl)propionic acid, N,N-bis(hydroxyethyl)-2-aminoetansulfonovaya acid and the like, optional and usually in combination with a base, e.g. the p-hydroxides of alkali and alkaline earth metals, for example, sodium hydroxide, ammonia or an amine, such as triethylamine, thus forming counterion alkali, alkaline earth metal or ammonium.

Examples of suitable anionic polymers with living chain according to the invention include anionic vinyl additive polymers obtained from a mixture of vinyl - or Ethylenediamine monomers. The mixture of vinyl - or Ethylenediamine monomers contains at least one monomer containing an aromatic group and at least one monomer containing an anionic group. Typically, the monomers are subjected to copolymerization with non-ionic monomers, such as monomers on the basis of acrylate and acrylamide. Examples of suitable anionic monomers include (meth)acrylic acid and parameningeal (hydroxytrol).

Examples of suitable anionic polysaccharide with at least one aromatic group include starches, guar gums, cellulose derivatives, chitina, chitosans, glikana, galactanes, glucans, xanthan gums, pectins, mannans, dextrins, preferably starches and guar gums, and suitable starches include potato, corn, wheat, tanikely, rice, maize (waxy) and barley starch, preferably potato starch. Anionic groups in the polysaccharide can be native and/or introduced Potemkina processing. Aromatic groups in the polysaccharide can be introduced by chemical methods known in this field.

Examples of suitable (modified) natural aromatic anionic polymers according to the present invention include lignosulfonates, Kraft lignins, oxylysine and extracts tannin, i.e. natural polyphenolic substances that get in the process of obtaining sulfite or sulfate pulp or extracts of the bark.

Srednevekovaja molecular weight anionic polymer may vary within wide limits, among other things, depending on the type of polymer and is typically at least about 500, suitably above about 800 and preferably above about 1000. The upper limit is not critical; it can be about 10000000, usually 1000000, eligible 500000, preferably 200,000, and most preferably 100000.

The anionic polymer may have a degree of anionic substitution (DSA), varying within wide limits, among other things, depending on the type of polymer. DSAusually is 0.01 to 2.0; eligible 0,02-1,8; preferably of 0.025 to 1.5; and the degree of substitution in the aromatic ring (DSQ) may be about 0.001 to 1.0; usually 0.01 to 0.8; eligible 0.02 to 0.7 and preferably 0,025-0,5. In that case, if the anionic polymer contains cationic groups, tostapane cationic substitution (DS With) may be, for example, 0-0,2; eligible 0-0,1, and preferably 0-0,05; and the anionic polymer has a total anionic charge. Usually anionic charge of the anionic polymer is 0.1-10.0 mEq/g dry polymer; suitably 0.2 to 6.0 mEq/g, and preferably 0.5 to 4.0 mEq/g

The aqueous silica-containing composition according to the invention also contains anionic particles based on silica in aggregate form or in the form of a microgel, i.e. particles based on SiO2preferably formed by polymerization of silicic acid, covering both the homopolymers and copolymers. Optional particles of silica can be modified and can contain other elements, such as amine, aluminum and/or boron, which can be represented in the aqueous phase and/or in the particles based on silica.

Examples of suitable particles based on silica in aggregate form or in the form of a microgel include colloidal silica; colloidal silica modified with aluminum, or aluminum silicate; and various types of polysilicon acid and mixtures thereof, either separately or in combination with other types of anionic particles based on silica. In the art polysilicon acid is also called polymeric silicic acid, microgel polysilicon acid polysilicate and policelike the NYM microgel, all names are covered by the term "polysilicon acid that is used in this application. Aluminium-containing compounds of this type are usually called polyaluminosilicate and polyaluminosilicate the microgels, including modified colloidal aluminum silica and aluminosilicate.

Anionic particles of silica have dimensions in the range corresponding to the colloidal form. This form contains particles of sufficiently small size that they do not show the negative effects of gravitational forces, but a large enough size not to be noticeable deviations from the typical properties of the solutions, i.e. the average particle size substantially smaller than 1 μm. Anionic particles of silica have an average size of, respectively, less than approximately 50 nm, preferably less than about 20 nm, more preferably from about 1 to about 50 nm, most preferably from about 1 to about 10 nm. Usually in the chemistry of silica under the particle size understand the average size of the primary particles, which can be aggregated or neogregarine. Suitably the particles based on silica present in the aqueous silica-containing composition according to the invention include particles of silica in aggregate form is whether in the form of a microgel, optional and usually in combination with non-aggregated, or beads, particles based on silica.

Suitably the particles of silica have a specific surface area of more than 50 m2/g, more preferably 100 m2/g Specific surface area can be up to 1700 m2/g, preferably up to 1300 m2/g, and typically is in the range of 300-1300 m2/g, preferably 500-1050 m2/g Specific surface area can be measured by titration with NaOH according to the procedure described Sears, "Analytical Chemistry 28 (1956), 12, 1981-1983; or in U.S. patent No. 5176891. A given area, therefore, represents an average specific surface area of particles.

The total mass of the anionic organic polymer containing at least one aromatic group, and anionic particles based on silica, based on SiO2contained in the aqueous silica-containing composition is at least 0.01 wt.% calculated on the total weight of the aqueous silica-containing composition, preferably at least 0,05 wt.%, more preferably, at least 0.1 wt.%. Suitably the concentration of the anionic organic polymer containing at least one aromatic group, and anionic particles based on silica, based on SiO2on titsa within 1-45 wt.%, preferably 2-35 wt.% and most preferably 5-30 wt.%.

The aqueous silica-containing composition may have a density of anionic charge at least 0.1 mEq/g; usually the charge is 0.1-10 mEq/g; suitably in the range of 0.1 to 8 mEq/g, preferably in the range of 0.1 to 6 mEq/g and most preferably in the range of 0.2 to 4 mEq/g

The aqueous silica-containing composition according to the invention essentially does not contain a sizing substance that reacts with cellulose. The term "substantially" is meant that the aqueous silica-containing composition is present sizing substance that reacts with cellulose in the amount of less than or equal to 10 wt.%, suitably less than 5 wt.%, preferably less than 1 wt.%. Most preferably, in an aqueous silica-containing composition sizing substance that reacts with cellulose, was not present. Even more preferably the aqueous silica-containing composition according to the invention essentially does not contain a sizing substance, suitably does not contain a sizing agent.

The present invention additionally relates to a method for obtaining aqueous silica-containing composition. The two components are preferably mixed with each other. Anionic organic polymer containing at least one arene is political group, can be added to an aqueous Sol containing particles of silica, or particles of silica can be added to an aqueous solution of the anionic organic polymer containing at least one aromatic group. An aqueous solution of the anionic organic polymer containing at least one aromatic group, can be desalinated or deionized. Demineralization or deionization can be produced by dialysis, membrane filtration, ultrafiltration, reverse osmosis or ion exchange, or similar means. Preferably, the desalination or the de-ionization was performed by using ultrafiltration or dialysis. The pH value of an aqueous solution of the anionic organic polymer can be adjusted to the pH value of the particles based on silica, before or after mixing the aqueous solution with particles of silica. The pH value can be increased to at least an 8.0; suitably, at least, 9,0; preferably, at least 9,5; more preferably within 9,0-11,0.

Anionic organic polymer containing at least one aromatic group, which should be mixed with particles of silica may have a density of anionic charge at least 0.1 mEq/g; typically in the range of 0.1 to 10.0 mEq/g, suitably in the range of 0.2 to 6.0 mEq/g; before occhialino within 0.5 to 4.0 mEq/g

Particles based on silica, preferably anionic, to be mixed with anionic organic polymer may possess the above properties. Suitably the particles based on silica contained in the ash. The Sol may have S-parameter in the range of 5-80%; eligible 5-50%; preferably 8-45%, and most preferably 10-30%. Calculation and measurement of S-parameter can be performed in accordance with the methodology described Iler and Dalton in J.Phys. Chem. 60 (1956), pp. 955-957. S-parameter determine the degree of aggregation or the formation of microgel, and a lower value of S-parameter indicates a greater degree of aggregation.

Suitably the particles based on silica contain particles based on silica in aggregate form or in the form of a microgel, optional and usually in combination with non-aggregated, or beads, particles based on silica.

Suitably the particles of silica have a molar ratio of SiO2:Na2Of which is less than 60, usually within 5-60, preferably in the range 8-55.

The aqueous silica-containing composition obtained by any of the methods according to the invention, contains, respectively, the total weight of anionic organic polymer containing at least one aromatic group, and anionic particles based on silica, which, IU the greater extent, 0.01 wt.% from the total mass of the aqueous silica-containing composition; preferably, at least, of 0.05 wt.%; more preferably, at least 0.1 wt.%. Suitably the concentration of the anionic organic polymer containing at least one aromatic group, and anionic particles based on silica is from 1 to 45 wt.%; preferably 2-35 wt.%; most preferably 5-30 wt.%.

The products obtained by any of these methods, have improved characteristics dewatering and retention, and greater storage stability and, thus, improved dewatering and retention during storage, as it has a longer shelf life.

A blending operation in the above-mentioned methods, as appropriate carry out essentially in the absence of a sizing agent that reacts with cellulose. The term "essentially in the absence of" means that a sizing substance that reacts with cellulose, is present in a quantity less than or equal to 10 wt.%, suitably less than 5 wt.%, preferably less than 1 wt.%. Most preferably, a sizing substance that reacts with cellulose, was not present. The blending operation may also be carried out essentially in the absence of a sizing substances is a, or in the absence of a sizing agent.

The present invention additionally relates to a method of making paper from an aqueous suspension containing pulp fibers. The method comprises adding to the suspension a cationic organic polymer and aqueous silica-containing composition according to the invention. Cationic organic polymer according to the invention can be linear, branched or crosslinked. Preferably the cationic polymer is a water-soluble or water-dispersible.

Examples of suitable cationic polymers include synthetic organic polymers, for example, jagged living polymers and polymers with a living chain, and polymers derived from natural sources, such as polysaccharides.

Examples of suitable cationic synthetic organic polymers include polymers with the addition of the vinyl groups, for example polymers based on acrylate and acrylamide, and cationic poly(diallyldimethylammoniumchloride), cationic polyethylenimine, cationic polyamine, polyamidoamine and polymers on the basis of vinylamide, melamineformaldehyde and urea-formaldehyde polymers.

Examples of suitable polysaccharides include starches, guar gums, cellulose derivatives, chitina, chitosans, glikana, galactanes, glucans, xanthan gums, pectins, Mann is s, dextrins; preferably starches and guar gums. Examples of suitable starches include potato, corn, wheat, tapioca, rice, maize (waxy), barley etc.

Cationic starch and cationic polymers based on acrylamide are preferred polymers according to the invention, and can be used separately, together with each other or with other polymers, especially preferred are cationic starches and cationic polymers based on acrylamide containing at least one aromatic group.

Cationic organic polymers can contain one or more hydrophobic groups attached to them. Hydrophobic groups can be aromatic groups, groups containing an aromatic group or non-aromatic group; preferably hydrophobic groups contain aromatic groups. The hydrophobic group can be attached to a heteroatom, such as nitrogen or oxygen, the nitrogen is optionally charged, and the heteroatom may be attached to the main polymer chain, for example, through the chain of atoms. The hydrophobic group may contain at least 2, and usually at least 3 carbon atoms, suitably from 3 to 12, preferably 4 to 8 carbon atoms. A hydrophobic group are eligible are the two who is the hydrocarbon chain.

Suitable dosage, calculated on the dry substance, based on dry paper pulp (pulp) and optional filler, cationic polymer in the system, comprise from 0.01 to 50 kg/t kg/t - "metric ton"), preferably 0.1 to 30 kg/t and most preferably 1.0 to 15 kg/so

Suitable dosage, calculated on the dry substance, based on dry paper pulp (pulp), and optional fillers, aqueous silica-containing composition, as defined above, in the system comprise from 0.01 to 15 kg/ton, preferably from 0.01 to 10 kg/t, based on anionic organic polymer containing at least one aromatic group and anionic particles based on silica, and most preferably 0.05 to 5 kg/so

In the aqueous pulp suspension according to the invention may be added a suitable mineral fillers of conventional type. Examples of suitable fillers include kaolin, China clay (kaolin), titanium dioxide, gypsum, talc and natural synthetic calcium carbonates such as chalk, natural marble and precipitated calcium carbonate (PCC).

Can be, of course, used and other additives that are typically used in the manufacture of paper, in combination with the substances according to the present invention, for example, traps anionic weed (interfering) impurities, substances, giving strength in the wet state; ve is esta, giving strength in the dry state; fluorescent brightening agents; dyes; aluminium-containing compounds, etc. are Examples of suitable aluminium-containing compounds include alum, aluminates, aluminium chloride, aluminum nitrate and semi-aluminum compounds, for example the semi-aluminum chlorides, semi-aluminum sulfate, poly-aluminum alloys compounds containing chloride ions and/or sulfate, polyaluminosilicate sulfates and mixtures thereof. Semi-aluminum compounds can also contain other anions other than chloride ions, for example, anions of sulfuric acid, phosphoric acid or organic acids such as citric acid and oxalic acid. When using aluminum compounds in the present method, it is generally preferable to add it in the feedstock prior to introduction of the polymer component and material in the form of micro - or nanoparticles. Appropriate levels of addition of compounds containing aluminum, comprise at least 0.001 kg/ton, preferably from 0.01 to 5 kg/ton, more preferably 0.05 to 1 kg/t, based on Al2O3on the basis of dry paper pulp and optional filler.

Examples of suitable traps anionic trash include cationic polyamine, polymers or copolymers of Quaternary amines or compounds containing aluminum.

The method according to the present from which briteney used for the manufacture of paper. The term "paper" here includes not only paper and articles thereof, but also other products sheet type, such as paper plates, cardboard and products from it. The invention is particularly useful in the manufacture of paper with a density of 150 g/m2, preferably 100 g/m2such as thin paper, newsprint paper, lightweight coated paper, SC paper and silk paper.

The method can be used in the manufacture of paper from all types of raw materials, containing and not containing wood. Different types of fiber suspensions containing cellulose, and suspensions with the mentioned raw materials should suitably contain at least 25 wt.%, preferably, at least 50 wt.% such fibers, based on dry substance. Suspension containing fiber from chemically prepared pulp, for example, sulfate, sulfite, organic slurries containing wood pulp or mechanical pulp, such as thermomechanical pulp, chemi-thermomechanical pulp, refiner wood pulp and wood pulp as from hard and soft wood; and it can also be based on fibres from recycled materials, not necessarily free from dyes, paper pulp, and mixtures thereof. Preferably the feedstock is the raw material containing wood with a high content with what she (high conductivity).

The chemicals according to the present invention can be added to the aqueous pulp slurry or pulp, in the usual manner and in any order. It is generally preferable to add the cationic polymer in the pulp before adding the aqueous silica-containing composition, even if can be used in the opposite order. It is also preferable to add the cationic polymer to the stage shear effects that you can choose from discharge, mixing, cleaning, etc. and add the aqueous silica-containing composition after this stage, the shear effects.

The aqueous silica-containing composition can be used as a flocculant in water treatment for drinking water or as an agent for water treatment, environmental objects, such as lake water. The composition can also be used as a flocculant in the treatment of waste water or remove excess sludge.

The invention is additionally illustrated by the following examples that are not intended to limit the scope of the present invention. Parts and percentages are expressed in mass units and mass percent, respectively; all solutions are aqueous unless otherwise stated. The unit of measurement is metric.

EXAMPLE 1

Dehydrating effects were assessed by applying On nomicheski analyzer dehydration (DDA), the company supplied "Akribi, Sweden. The duration of the dehydration process was measured using a paper weight or a fixed amount through the wire when removing the tube and the vacuum side of the wire mesh, the opposite side, on which there was a paper weight.

The retaining effect was assessed by using a turbidity meter by measuring the turbidity of the effluent (recycled water)resulting from dewatering of paper pulp. The turbidity of the filtrate was measured in the values turbidity units (NTU).

The raw materials that were tested contained wood with a pH of 7.2, conductivity materials to 5.0 MS/cm and consistency of 1.42 g/l pulp was mixed in a vessel with baffles with a speed of 1500 rpm throughout the test.

In the example in the pulp prior to the introduction of the aqueous compositions according to the invention was added to the cationic polymer or anionic sample comparison. As the cationic polymer used cationic starch (C1)obtained by quaternization of native potato starch with 3-chloro-2-hydroxypropyltrimethylammonium to 0.5% n, and added, after which it was stirred for 45 s, and then added anionic aqueous composition, and then mixed for 15 s before dehydration.

Was determined by drying and keep the surrounding action of aqueous compositions according to the invention, containing anionic polyurethane and colloidal silica. All samples were diluted to solids content of 0.5% before evaluation of the characteristics of dehydration. Anionic polyurethane (P1) was an anionic polyurethane with a solids content of 15%, and it has received from glycerylmonostearate (GMS) and toluenediisocyanate (TDI), which forms a prepolymer, which was introduced in the reaction with dimethylolpropionic acid (DMPA), where 30 mol.% glycerylmonostearate (GMS) was replaced dimethylolpropionic acid (DMPA)/N-methyldiethanolamine (N-MDEA). The Sol of colloidal silica (S1) was a Sol of this type, which is described in U.S. patent No. 5447604, and had a molar ratio (SiO2:Na2O)equal to 10; specific surface area is 870 m2/g, S-parameter, 35% and silica content - 10.0 wt.%. Duration of dehydration process using paper pulp with the addition of 20 kg/t of C1 was 29, and the turbidity was 44 NTU. All additives were calculated on the dry substance, based on dry paper stock. Duration of dehydration process, obtained using different additives, introduced in the aqueous composition according to the invention, are shown in table 1.

Table 1
SampleRespect to the tion The duration of the dehydration process (C)/Turbidity of the filtrate (NTU) at dosage
4 kg/t6 kg/t8 kg/t10 kg/t
S119,7/3516,9/3115,6/3016,0/29
P117,7/3415,3/3314,0/3213,9/32
S1/P14:117,3/3314,0/3013,5/2814,0/27
S1/P11:116,4/3413,6/3013,0/2813,1/28
S1/P11:416,5/3313,9/3113,3/2912,9/29

The duration of the dehydration process and turbidity for the composition S1/P1 show that adding the two components (S1 and P1) in the form of a composition they have a synergistic improvement of the characteristics of dewatering and retention.

EXAMPLE 2

Aqueous compositions according to the invention containing anionic polyurethane (P2), based on the anionic polyurethane with 19% solids, obtained from toluenediisocyanate (TDI) and feildel is Salamina (PDEA), which forms a prepolymer, which was introduced into the reaction mixture with dimethylolpropionic acid (DMPA) and N-methyldiethanolamine (N-MDEA), where 30 mol.% PDEA was replaced DMPA/N-MDEA, and assessed the dewatering and retention effect of colloidal silica (S2)with respect to SiO2:Na2About equal to 20, the specific surface area of 700 m2/g, S-parameter is 32% and the content of the silica - 15.0 wt.%. All samples were diluted to 0.5% solids before drying and retaining properties, all performed exactly the same as in example 1, and using the same cationic starch in the same feedstock. Duration of dehydration process using paper pulp with the addition of 20 kg/t of C1 was 27, and the turbidity was 45 NTU. All additives were calculated on the dry substance, based on dry paper stock. Duration of dehydration process, obtained using different additives, introduced in the aqueous composition according to the invention, are summarized in table 2.

Table 2
SampleRatioThe duration of the dehydration process (C)/Turbidity of the filtrate (NTU) at dosage
2 kg/t4 kg/t6 kg/t 8 kg/t
S221,0/-15,7/-12,4/-12,9/-
P221,8/4418,0/3912,9/3112,0/29
S2/P24:121,0/4015,5/3112,0/2810,4/27
S2/P21:1-13,8/3011,0/279,8/27
S2/P21:4-13,3/3211,0/2910,3/27

EXAMPLE 3

In this example, the test paper pulp was the composition of the SC (composition for SC paper), which had a pH of 7.6, conductivity pulp of 0.5 MS/cm, consistency 1,49 g/l pulp was mixed in a vessel with baffles with a speed of 1500 rpm throughout the test. C1 was added to the pulp in the amount of 20 kg/t in each trial. Duration of dehydration process using paper pulp without any additives was 30 s and the turbidity was 98 NTU; duration of dehydration process using paper pulp adding only C1 was 14,8 with and turbidity was 52 NTU. Anionic polyurethane used in this example was an anionic polyurethane (P3) with 15% solids, obtained from glycerylmonostearate (GMS) and toluenediisocyanate (TDI), which forms a prepolymer, which was introduced in the reaction with dimethylolpropionic acid (DMPA)and colloidal silica (S3), described in U.S. patent No. 5368833 was a silica Sol having a molar ratio of SiO2:Na2About equal to 45, the specific surface area is 850 m2/g, S-parameter is 20% and the content of the silica - 8.0 wt.%, and was modified with aluminium to 0.3% of the content of Al2O3.

The action of aqueous compositions according to the invention was compared with the action of the components that were added separately. In all trials C1 was added to the pulp, after which it was stirred for 45 s, then added a composition S3/P3, then was stirred for 15 sec. When the components are added separately, it is first added to the first component, followed by stirring for 30 s, and then the second components, followed by stirring for 15 C. All additives was calculated based on dry matter, based on dry paper stock. Duration of dehydration process, obtained using different additives, introduced in the aqueous composition according to the invention, are summarized in table 3.

Table 3
SampleRatioThe duration of the dehydration process (C)/Turbidity of the filtrate (NTU)

when dosage
1 kg/t2 kg/t3 kg/t4 kg/t
S1+S3---10,2/56
C1+P313,9/5413,0/5512,0/5613,0/55
S1+S3/P31:112,6/5211,4/5110,0/5810,0/55
S1+S3/P33:112,2/5211,1/5410,7/5510,4/55
S1+S3/P31:312,9/5212,1/5511,6/54-
S1+S3+P31:1---12,4/53
C1+P3+S31:1---12,4/55

EXAMPLE 4

Aqueous compositions according to the invention containing 10% solution of anionic lignosulfonate (LS1), which depict avsl a sodium salt from sulphonated and carboxylating Kraft lignin, retrieved from soft wood, with a dry matter content of 89,0 wt.%, pH of 10.5, the sodium content of 9.5%, the total sulfur content of 5.4%, and the sulfur content is limited to 4.2%; or 10% solution of anionic lignosulfonate (LS2), which was oxilion sodium obtained from fermented sulfite solution coniferous wood, with a dry matter content of 93,0 wt.%, pH 8.5; the sodium content of 8% and a sulfur content of 3%, and colloidal silica S1, were tested to determine the characteristics of the dewatering and retention. All samples were diluted to 0.5% solids before defining characteristics of dehydration. Duration of dehydration process using paper pulp with the addition of 20 kg/t of C1 was 29, and the turbidity was 44 NTU. All additives were calculated on the dry substance, based on dry paper stock. Duration of dehydration process, obtained using different additives, introduced in the aqueous composition according to the invention, are summarized in table 4.

Table 4
SampleShall

solution
The duration of the process

dehydration(s)/Turbidity of the filtrate (NTU)

when dosage
2 kg/t 4 kg/t6 kg/t8 kg/t10 kg/t12 kg/t
S123,5/3819,7/3516,9/3115,6/3016,0/29-
LS1-21,9/3518,8/3417,5/3317,2/32-
LS2-22,5/-19,9/3617,9/3517,8/3418,5/-
S1/

LS1
4:1-18,5/-15,3/2914.4V/2614,5/25-
S1/

LS1
1:1-18,8/-15,5/3013,1/30of 12.8/31-
S1/

LS2
4:1-18,4/-15,1/3113,2/2812,5/2712,4/25
S1/

LS2
1:1 -19,2/-15,8/3313,8/2812,8/2512,1/26

1. The aqueous silica-containing composition containing the anionic organic polymer containing at least one aromatic group, and anionic particles based on silica containing particles of silica in aggregate form or in the form of a microgel, where the aqueous silica-containing composition contains anionic organic polymer containing at least one aromatic group, and anionic particles based on silica, based on SiO2in the amount of at least 0.01 wt.% from the total mass of the aqueous silica-containing composition, provided that the composition essentially contains no sizing substance that reacts with cellulose, and anionic organic polymer containing at least one aromatic group is anionic naphthaleneformaldehyde condensate.

2. The aqueous silica-containing composition according to claim 1, where the particles of silica have a specific surface area in the range 300-1300 m2/year

3. The aqueous silica-containing composition according to claim 1, where the particles based on silica have an average particle size ranging from about 1 nm to about 50 nm.

4. The aqueous silica-containing composition according to claim 1, where the particle is and silica have an average particle size ranging from about 1 nm to about 10 nm.

5. The aqueous silica-containing composition according to claim 1 where the anionic organic polymer containing at least one aromatic group is a polyurethane, a lignosulfonate, Kraft lignin or auxiliries.

6. The aqueous silica-containing composition according to claim 1, where the aqueous silica-containing composition has a density of negative charge in the range of 0.1 to 6 mEq/g

7. The aqueous silica-containing composition obtained by mixing anionic organic polymer containing at least one aromatic group, with water stabilized alkali-Sol silica having an S-parameter in the range from about 5 to about 50%, containing anionic particles based on silica in aggregate form or in the form of a microgel, to obtain the aqueous silica-containing composition containing the anionic organic polymer containing at least one aromatic group, and particles based on silica, based on SiO2in the amount of at least 0.01 wt.% from the total mass of the aqueous silica-containing composition, provided that the composition essentially contains no sizing substance that reacts with cellulose, and anionic organic polymer containing at least one aromatic group is anionic naphthaleneformaldehyde the first condensate.

8. The aqueous silica-containing composition according to claim 7, where the particles of silica have a specific surface area in the range 300-1300 m2/year

9. The aqueous silica-containing composition according to claim 7, where the particles based on silica have an average particle size ranging from about 1 nm to about 50 nm.

10. The aqueous silica-containing composition according to claim 7, where the particles based on silica have an average particle size ranging from about 1 nm to about 10 nm.

11. The aqueous silica-containing composition according to claim 7, where the anionic organic polymer containing at least one aromatic group is a polyurethane, a lignosulfonate, Kraft lignin or auxiliries.

12. The aqueous silica-containing composition according to claim 7, where the aqueous silica-containing composition has a density of negative charge in the range of 0.1 to 6 mEq/g

13. The use of aqueous silica-containing composition according to any one of claims 1 to 12 as a flocculant in combination with at least one organic polymer in the manufacture of paper pulp and paper and water treatment.

14. Method of making paper from a suspension containing cellulosic fibres, and optional fillers, comprising adding to the suspension at least one cationic organic polymer and aqueous silica-containing composition according to any one of p is.1-12.

15. The method according to 14, in which the cationic organic polymer is cationic starch or cationic polyacrylamide.

16. The method according to 14, in which the cationic organic polymer contains at least one aromatic group.

17. The method according to item 15, in which the cationic organic polymer contains at least one aromatic group.

18. The method according to 14, further comprising adding a suspension containing aluminum compounds.

19. The method according to 14, in which the aqueous silica-containing composition is added in an amount of from 0.01 to 10 kg/ton, calculated on the dry substance, based on dry paper stock, and an optional filler.

20. The method according to 14, in which the cationic organic polymer is added in an amount of from 0.1 to 30 kg/ton, calculated on the dry substance, based on dry paper stock, and an optional filler.



 

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