EP2238294A1 - Procédé de modification d'amidon pour des performances accrues de rétention de et d'égouttage de machine à papier - Google Patents
Procédé de modification d'amidon pour des performances accrues de rétention de et d'égouttage de machine à papierInfo
- Publication number
- EP2238294A1 EP2238294A1 EP09705709A EP09705709A EP2238294A1 EP 2238294 A1 EP2238294 A1 EP 2238294A1 EP 09705709 A EP09705709 A EP 09705709A EP 09705709 A EP09705709 A EP 09705709A EP 2238294 A1 EP2238294 A1 EP 2238294A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starch
- silicate
- metal silicate
- cationic
- polysaccharide
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 169
- 235000019698 starch Nutrition 0.000 title claims abstract description 166
- 239000008107 starch Substances 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000014759 maintenance of location Effects 0.000 title description 24
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 97
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229920000881 Modified starch Polymers 0.000 claims abstract description 15
- 235000019426 modified starch Nutrition 0.000 claims abstract description 15
- 125000002091 cationic group Chemical group 0.000 claims description 66
- 229920001282 polysaccharide Polymers 0.000 claims description 47
- 239000005017 polysaccharide Substances 0.000 claims description 47
- 150000004804 polysaccharides Chemical class 0.000 claims description 47
- 239000004115 Sodium Silicate Substances 0.000 claims description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 11
- 229920002261 Corn starch Polymers 0.000 claims description 9
- 239000008120 corn starch Substances 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- 240000003183 Manihot esculenta Species 0.000 claims description 6
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 6
- 239000004111 Potassium silicate Substances 0.000 claims description 6
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
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- 150000004836 anionic polysaccharides Chemical class 0.000 claims description 2
- 229920006320 anionic starch Polymers 0.000 claims 1
- 239000000123 paper Substances 0.000 abstract description 16
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- 238000002360 preparation method Methods 0.000 abstract description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 239000000178 monomer Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 23
- 125000000129 anionic group Chemical group 0.000 description 21
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- 238000012360 testing method Methods 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
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
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- 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 modifying starch with metal silicates, and the use of the modified starch in the preparation of cellulosic fiber compositions.
- the present invention further relates to cellulosic fiber compositions, such as paper and paperboard, which incorporate the starch modified with metal silicates.
- the making of cellulosic fiber sheets includes the following: 1) producing an aqueous slurry of cellulosic fiber; which may also contain inorganic mineral extenders or pigments; 2) depositing this slurry on a moving papermaking wire or fabric; and 3) forming a sheet from the solid components of the slurry by draining the water.
- Improved dewatering can also result in a dryer sheet in the press and dryer sections, resulting in reduced energy or steam consumption. Yet further, this is the stage in the papermaking method that determines many sheet final properties.
- Papermaking retention aids are used to increase the retention of fine furnish solids in the web during the turbulent method of draining and forming the paper web. Without adequate retention of the fine solids, they are either lost to the method effluent or accumulate to high levels in the recirculating white water loop, potentially causing deposit buildup. Additionally, insufficient retention increases the papermakers 1 cost due to loss of additives intended to be adsorbed on the fiber to provide the respective paper opacity, strength, or sizing property.
- Cationic starch is utilized extensively in the paper industry. It is introduced into the pulp slurry to increase interfiber bonding and to obtain paper strength properties, to emulsify synthetic internal sizing agents, such as alkenyl succinic anhydride (ASA), or to provide drainage.
- ASA alkenyl succinic anhydride
- Metal silicates which include sodium silicate, potassium silicate, and sodium metasilicate, are commodity chemicals utilized widely in many industries, including paper and water treatment.
- Rushmere teaches an improved drainage aid and retention aid for papermaking which is added to an aqueous paper furnish containing pulp and which comprises a silicated cationic starch composition which is a dry solid which contains from about 1 to 25 wt % silica and consists essentially of granules of a cationized starch having the silica in the form of a water soluble polysilicate microgel deposited on the surfaces thereof and, optionally, the composition further containing discreet agglomerates of silica microgels in admixture with the silicated starch granules.
- the one-component product is a dry solid which offers convenience and economy over colloidal silica combinations because shipping large quantities of water can be avoided.
- This invention describes a method for improving the retention and drainage properties during the papermaking process by the addition of a cationic or amphoteric polysaccharide or polysaccharide derivative that has been modified with a metal silicate.
- the present method also provides for a method of modifying a cationic or amphoteric polysaccharide or polysaccharide derivative by the addition of a metal silicate.
- the present invention also provides for a cationic or amphoteric polysaccharide or polysaccharide derivative modified with a metal silicate
- the cationic or amphoteric polysaccharide or polysaccharide derivative is a cationic or amphoteric starch.
- a papermaking process comprising adding to a papermaking slurry, at least one polysaccharide or polysaccharide derivative, wherein the polysaccharide or polysaccharide derivative has been modified with at least one metal silicate, wherein the at least one polysaccharide or polysaccharide derivative is selected from the group consisting of polysaccharide derivatives containing a cationic nitrogen group, a blend of cationic and anionic polysaccharides and combinations thereof.
- metal silicate to cationic starch will provide a dramatic increase in the drainage. Best results are obtained when the metal silicate is added to the starch after the starch has been cooked.
- the metal silicate can be added while the starch is still at an elevated temperature or after the starch has been cooled to ambient temperatures. Improved retention and drainage performance has also been observed with adding the metal silicate to the water prior to adding the starch and cooking.
- the metal silicate is sodium silicate.
- the metal silicate may also be potassium silicate or sodium metasilicate.
- the materials utilized in the method of the invention include cellulosic pulp and at least one starch modified with a metal silicate. There can also be employed one or more additional materials, including, but not limited to, additional unmodified starch, filler, inorganic or organic coagulant, conventional flocculant, and at least one organic or inorganic drainage aid.
- additional materials including, but not limited to, additional unmodified starch, filler, inorganic or organic coagulant, conventional flocculant, and at least one organic or inorganic drainage aid.
- the cationic or amphoteric polysaccharide or polysaccharide derivative is a cationic or amphoteric starch.
- the order in which the different materials are introduced into the method of the invention is not limited to that set forth in the preceding discussion, but will generally be based on practicality and performance for each specific application.
- Suitable cellulosic fiber pulps for the method of the invention include conventional papermaking stock such as traditional chemical pulp. For instance, bleached and unbleached sulfate pulp and sulfite pulp, mechanical pulp such as groundwood, thermomechanical pulp, chemi-thermomechanical pulp, recycled pulp such as old corrugated containers, newsprint, office waste, magazine paper and other non-deinked waste, deinked waste, and mixtures thereof, may be used.
- Fillers are used in papermaking. Filler provides optical properties to the cellulosic product. It provides opacity and brightness to the finished sheet, and improves its printing properties. Fillers which are suitable include calcium carbonate (both naturally occurring ground carbonate and synthetically produced precipitated carbonate), titanium oxide, talc, clay, and gypsum. The amount of filler employed can be that which results in a cellulosic product of up to about 50 weight percent filler, based on the dry weight of the pulp.
- Coagulants are utilized to enhance retention and drainage.
- Coagulants may be either inorganic or organic.
- the most common inorganic coagulant is an alumina species. Suitable examples include, but are not limited to, technical grade aluminum sulfate (alum), polyaluminum chloride, polyhydroxy aluminum chloride, polyhydroxy aluminum sulfate, sodium aluminate, and the like.
- the organic coagulant is typically a synthetic, polymeric material. Suitable examples include, but are not limited to, polyamines, poly(amido amines), polyDADMAC (poly(diallyldimethylammonium chloride)), polyethyleneimine, hydrolyzates and quaternized hydrolyzates of N-vinyl formamide polymers and copolymers, and the like.
- Coagulants are generally employed in a proportion of from about 0.05 Ib. per ton to about 50 lbs. per ton of cellulosic pulp, based on the dry weight of the pulp.
- the coagulant concentration can be from about 0.5 lbs. per ton to about 20 lbs. per ton, and or from about 1 Ib. per ton to about 10 lbs. per ton, of the pulp.
- Ionic flocculants are conventionally used in the papermaking art.
- Polymers suitable as flocculants include, but are not limited to, homopolymers of a nonionic ethylenically unsaturated monomer.
- Copolymers of monomers comprising two or more nonionic ethylenically unsaturated monomers can also be used, as can copolymers of monomers comprising at least one nonionic ethylenically unsaturated monomer and at least one cationic ethylenically unsaturated monomer and/or at least one anionic ethylenically unsaturated monomer.
- Suitable nonionic ethylenically unsaturated monomers include, but are not limited to, acrylamide; methacrylamide; N-alkylacrylamides, such as N- methylacrylamide; N,N-dialkylacrylamides, such as N,N-dimethylacrylamide; methyl acrylate; methyl methacrylate; acrylonitrile; N-vinyl methylacetamide; N- vinyl methyl formamide; vinyl acetate; N-vinyl pyrrolidone; hydroxyalkyl(meth) acrylates such as hydroxyethyl(meth) acrylate or hydroxypropyl(meth) acrylate; mixtures of any of the foregoing and the like.
- acrylamide, methacrylamide, and the N-alkylacrylamides are preferred, with acrylamide being particularly preferred.
- the cationic ethylenically unsaturated monomers which may be used include, but are not limited to, diallylamine, the (meth)acrylates of dialkylaminoalkyl compounds, the (meth)acrylamides of dialkylaminoalkyl compounds, the N-vinylamine hydrolyzate of N-vinylformamide, and the salts and quaternaries thereof.
- the N,N-dialkylaminoalkyl acrylates and methacrylates, and their acid and quaternary salts are preferred, with the methyl chloride quaternary of N,N-dimethylaminoethylacrylate being particularly preferred.
- Suitable anionic ethylenically unsaturated monomers include, but are not limited to, acrylic acid, methylacrylic acid, and their salts; 2- acrylamido-2-methyl-propane sulfonate; sulfoethyl-(meth)acrylate; vinylsulfonic acid; styrene sulfonic acid; and maleic and other dibasic acids and their salts.
- Acrylic acid, methacrylic acid and their salts are preferred, with the sodium and ammonium salts of acrylic acid being particularly preferred.
- Cationic polymer flocculants will generally contain one or more of the cationic monomers described above.
- the level of total cationic monomer can range from about 1 to about 99%, preferably from about 2 to about 50%, and still more preferably from about 5 to about 40 mole % cationic monomer, with the remaining monomer being one of the previously described non-ionic monomers.
- Anionic polymer flocculants will generally contain one or more of the anionic monomers described above.
- the level of total anionic monomer based upon molar concentrations, will range from about 1 to about 99%, preferably from about 2 to about 50%, and still more preferably from about 5 to about 40 mole % anionic monomer, with the remaining monomer being one of the previously described non-ionic monomers.
- Amphoteric polymer flocculants will contain a combination of one or more of the described cationic and anionic monomers. Any combination of cationic and anionic monomer(s) can be used, provided at least one cationic and one anionic monomer are utilized.
- the polymer may contain an excess of cationic monomer, an excess of anionic monomer, or equivalent amounts of both cationic and anionic monomers.
- the level of total ionic monomer being the combined amount of both cationic and anionic monomers, based upon molar concentrations, will range from about 1 to about 99%, preferably from about 2 to about 80%, and still more preferably from about 5 to about 40 mole % ionic monomer, with the remaining monomer being one of the previously described non-ionic monomers.
- the flocculant can be employed, inja proportion of from about 0.01 Ib. per ton to about 10 lbs. per ton of cellulosic pulp, based upon active polymer weight and on the dry weight of the pulp.
- the concentration of flocculant is more preferably from about 0.05 Ib. per ton to about 5 lbs. per ton, and still more preferably from about 0.1 Ib. per ton to about 1 Ib. per ton, of the pulp.
- inorganic or organic drainage aids known in the art as microparticles, micropolymers, organic microbeads, or associative polymers, may also be employed.
- the inorganic microparticles employed include any of the materials selected from the group consisting of silica based particles, silica microgels, colloidal silica, silica sols, silica gels, polysilicates, polysilicate microgels, aluminosilicates, polyaluminosilicates, borosilicates, polyborosilicates and zeolites.
- the inorganic microparticle may also be a swellable clay, including, but not limited to, clays often referred to as hectorite, smectites, montmorillonites, nontronites, saponite, sauconite, hormites, attapulgites and sepiolites.
- micropolymers or organic microbeads are crosslinked, cationic or anionic, polymeric, organic microparticles having an unswollen number average particle size diameter of less than about 750 nanometers and a crosslinking agent content of above about 4 molar parts per million based on the monomeric units present in the polymer and are generally formed by the polymerization of at least one ethylenically unsaturated cationic or anionic monomer and, optionally, at least one non-ionic comonomer in the presence of said crosslinking agent.
- a micropolymer is Polyflex® (CIBA Corporation, Tarrytown, NY)
- the associative polymer useful in the present invention can be described as a water-soluble copolymer composition, wherein the associative properties of the inverse emulsion anionic copolymer are provided by an emulsification surfactant chosen from diblock and triblock polymeric surfactants.
- the associative inverse emulsion anionic copolymer contains at least one nonionic polymer segment and at least one anionic polymer segment, and has a Huggins 1 constant (k 1 ) determined in 0.01 M NaCI greater than 0.75 and a storage modulus (G 1 ) in a 1.5 wt. % actives polymer solution at 4.6 Hz greater than 175 Pa.
- Examples of associative polymers include, but are not limited, to PerForm®9232 and PerForm® 7200 (Hercules Incorporated, Wilmington, DE)
- Starch adds strength properties to the cellulose products, particularly dry strength by increasing inter-fiber bonding. Starch will also affect drainage properties.
- Starch is the common name for a polymer of glucose that contains alpha-1 ,4 linkages. Starch is a naturally occurring material; this carbohydrate can be found in the leaves, stems, roots and fruits of most land plants.
- the commercial sources of starch include, but are not limited to, the seeds of cereal grains (com, wheat, rice, etc.), and certain roots (potato, tapioca, etc.). Starch is described by its plant source; reference would be made to, for example, corn starch, potato starch, tapioca starch, rice starch, and wheat starch.. Starch can be considered to be a condensation polymer of glucose.
- starches consist of a mixture of two polysaccharide types: amylose, an essentially linear polymer, and amylopectin, a highly branched polymer.
- amylose an essentially linear polymer
- amylopectin a highly branched polymer.
- the relative amounts of amylose and amylopectin vary with the source, with the ratio of amylose to amylopectin typically being 17:83 for tapioca, 21 :79 for potato, 28:72 for corn and 0:100 for waxy maize corn. Although these are the typical starch ratios found the present invention contemplates that any ratio of amylose to amylopectin can be useful in the present invention.
- waxy maize is considered a type of corn starch.
- Starch is synthesized by plants and accumulates in granules that are distinctive for each plant. Starch granules are separated from the plant through a milling and grinding process. The granules are insoluble in cold water and must be heated above a critical temperature in order for the granules to swell and rupture, allowing the polymer to dissolve in solution.
- Starch can be modified to provide specific properties of value in selected applications. This includes modification to either or both the physical and chemical structure of the material. Physical modification includes reduction in molecular weight, which is most often achieved by hydrolysis. Such modified materials are often referred to as derivatized starch or starch derivatives.
- the present invention modifies a cationic or amphoteric polysaccharide or polysaccharide with a metal silicate.
- the cationic or amphoteric polysaccharide or polysaccharide derivative is preferably a cationic or amphoteric starch or starch derivative.
- Starches that may be used in the method of the invention include cationic and amphoteric starches. Suitable starches include those derived from corn, potato, wheat, rice, tapioca, and the like. Cationicity is imparted by the introduction of cationic groups, and amphotericity by the further introduction of anionic groups. For instance, cationic starches may be obtained by reacting starch with tertiary amines or with quaternary ammonium compounds, e.g., dimethylaminoethanol and 3-chloro-2- hydroxypropyltrimethylammonium chloride. Cationic starches preferably have a cationic degree of substitution (D. S.
- Amphoteric starches can be provided by adding anionic groups to cationic starches.
- Preferred amphoteric starches are those with a net cationicity.
- anionic phosphate groups can be introduced into cationic starches through reaction with phosphate salts or phosphate etherifying reagents.
- the amount of phosphate reagent employed in the modification preferably is that which will provide about 0.07-0.18 mole of anionic groups per mole of cationic groups.
- amphoteric starches that may be used are those made by introduction of sulfosuccinate groups into cationic starches. This modification is accomplished by adding maleic acid half-ester groups to a cationic starch and reacting the maleate double bond with sodium bisulfite.
- Cationic starch can also be etherified with 3-chloro-2- sulfopropionic acid, carboxyl groups can be introduced into starches by reaction with sodium chloroacetate or by hypochlorite oxidation, and propane sultone can be employed to treat cationic starches to provide amphotericity.
- Further useful amphoteric starches can be obtained by xanthation of diethylaminoethyl- and 2-(hydroxypropyl)trimethylammonium starch ethers.
- the modification can be extended by the introduction of nonionic or hydroxyalkyl groups from treatment with ethylene oxide or propylene oxide.
- Starches that require gelatinizing or "cooking" at the use location, or pre-gelatinized, cold-water dispersion starches can be used. Starch granules are insoluble in water. The gelatinization of starch at elevated temperatures results in water penetrating the starch granule, rupturing the granule and releasing the starch molecule into solution. The release of the starch molecule into solution results in an increase in the solution viscosity.
- aqueous solutions of starch are prepared at concentrations typically ranging from 1 to 5%.
- the Starch is added to cellulosic pulp, in a proportion of from about 1 Ib. per ton to about 100 lbs. per ton of cellulosic pulp, based on the dry weight of the pulp.
- the starch concentration is more preferably from about 2.5 lbs. per ton to about 50 lbs. per ton, and still more preferably from about 5 lbs. per ton to about 25 lbs. per ton, of the pulp. These weights do not include the weight of the metal silicate used to modify the starch.
- the starch or a portion of the starch will be modified by metal silicate prior to being added to the cellulosic pulp.
- Metal silicate is preferably employed, in the method of the invention, in a proportion of from about 0.1 Ib. per ton to about 10 lbs. per ton of cellulosic pulp, based on the dry weight of the pulp.
- the metal silicate concentration is more preferably from about 0.5 lbs. per ton to about 5 lbs. per ton, and still more preferably from about 1 Ib. per ton to about 2 lbs. per ton, of the pulp.
- the weight ratio of cationic starch to metal silicate (as SiO 2 ) can vary from 1 :10 to 100:1 or can vary for 1:1 to 50:1.
- the preferred weight ratio is from about 20:1 to about 2:1 , or from 15:1 to 2:1 , orfrom 10:1 to 2:1 or from 10:1 to 3:1.
- polysaccharides may also be employed for modification with metal silicates. These include, but are not limited to, guar, cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, chitin and the like.
- the other polysaccharides may be unsubstituted, or substituted with cationic, anionic, or combined cationic or anionic moieties.
- These polysaccharides are in a proportion of from about 1 Ib. per ton to about 100 lbs. per ton of cellulosic pulp, based on the dry weight of the pulp, preferably from about 2.5 lbs. per ton to about 50 lbs. per ton, and still more preferably from about 5 lbs. per ton to about 25 lbs. per ton, of the pulp. These weights do not include the weight of the metal silicate used to modify the polysaccharide.
- the metal silicate can be any of the alkali silicate commonly utilized, including, for example sodium silicate, aka "water glass", potassium silicate, and sodium metasilicate or. any combination of the metal silicates.
- Sodium silicate can vary in the Si ⁇ 2 :Na 2 ⁇ weight ratio, which is controlled during manufacture by the ratio of the two reactants.
- the ratio of SiO 2: Na 2 O for commercially available sodium silicates can vary from about 3.22 to about 2.0.
- the weight ratio of potassium silicate Si ⁇ 2: K 2 ⁇ can vary from about 1.65 to about 2.50.
- the metal silicates are available as an aqueous solution or a dry powder version.
- the preferred metal silicate is a sodium silicate solution with a SiO 2: Na 2 O ratio of 3.22:1.
- a polysaccharide or derivitized polysaccharide is modified by at least one metal silicate.
- the modified polysaccharide or derivitized polysaccharide modified with the at least one metal silicate is then added to a papermaking process.
- the polysaccharide or polysaccharide derivative is a cationic or amphoteric starch.
- the metal silicate can be added to the cationic or amphoteric starch after the starch has been cooked, while the starch is still warm (> 65° C), has moderately cooled (30 to 65° C) or has been cooled to ambient temperatures ( ⁇ 30° C).
- the addition of the metal silicate to the cooked starch results in slight increases in the turbidity and viscosity of the starch solution.
- the metal silicate can also be added to the aqueous starch slurry before the starch has been cooked such that the starch granules are gelatinized in the presence of the metal silicate. In this embodiment the starch is then cooked in the presence of the metal silicate. This process also produces a starch solution which is more turbid, but less viscous, than a starch solution cooked without the addition of metal silicate.
- the starch modified with metal silicate may be added to the thick stock, in the machine chest or blend chest. Alternatively the starch modified with metal silicate may be added to the thin stock, after or before any of the typical thin stock addition points, i.e. fan pump, cleaners, or screen. [0054] In the present invention, the metal silicate may be added to all of the starch, or may treat a side stream of the starch to modify a fraction of the starch. In a preferred embodiment the metal silicate is added to all of the starch. The starch modified with metal silicate may also be added simultaneously, before, or after any of the conventional wet-end additives, untreated starch, coagulants, flocculants, sizing agents, drainage aids, fillers, and the like.
- VDT vacuum drainage test
- the VDT test was conducted by first setting the vacuum to10 inches Hg, and placing the funnel properly on the cylinder. Next, 250 g of 0.5 wt. % paper stock was charged into a beaker and then the required additives according to treatment program (e.g., starch, alum, flocculants and drainage aids) were added to the stock under the agitation provided by an overhead mixer. The stock was then poured into the filter funnel and the vacuum pump was turned on while simultaneously starting a stopwatch. The drainage efficacy is reported as the time required to obtain 230 ml of filtrate.
- treatment program e.g., starch, alum, flocculants and drainage aids
- the Britt jar retention test a specific volume of furnish was mixed under dynamic conditions and an aliquot of the furnish was drained through the bottom screen of the jar, so that the level of fine materials which were retained can be quantified.
- the Britt jar utilized for the present tests was equipped with 3 vanes on the cylinder walls to induce turbulent mix, and a 76 ⁇ m screen in the bottom plate.
- the Britt jar retention tests were conducted with 500 ml of the synthetic furnish, having a total solids concentration of 0.5 %. The test was conducted at 1 ,200 rpm with the sequential addition of starch, followed by alum, followed by polymer flocculant, followed by drainage aid; the materials were all mixed for specified interval times. After the drainage aid had been introduced and mixed, the filtrate was collected.
- the retention values calculated are fines retention where the total fines content in the furnish is first determined by washing 500 ml of furnish with 10 liters of water under mixing conditions to remove all the fine particles, defined as particles smaller than the Britt jar 76 ⁇ m screen. The fines retention for each treatment was then determined by draining 100 ml of filtrate after the described addition sequence, then filtering the filtrate through a pre-weighed 1.5 ⁇ m filter paper. The fines retention are calculated according to the following equation:
- the furnish employed in the series of tests was a synthetic alkaline furnish. This furnish was prepared from hardwood and softwood dried market lap pulps, and from water and further materials. First the hardwood and softwood dried market lap pulp were separately refined in a laboratory Valley Beater (Voith, Appleton, Wis.). These pulps were then added to an aqueous medium.
- the aqueous medium utilized in preparing the furnish comprises a local tap water, and was further modified with inorganic salts added in amounts so as to provide this medium with a m-alkalinity of 75-100 ppm as NaHCO 3 and a total solution conductivity of 750 - 1000 ⁇ S/cm.
- the hardwood and softwood were dispersed into the aqueous medium at weight ratios of about 67% hardwood and 33% softwood Precipitated calcium carbonate (Albacar® 5970, Minerals Technologies, Bethlehem, PA) was introduced into the furnish at 25 weight percent, based on the combined dry weight of the pulps, so as to provide a final furnish comprising 80% fiber and 20% PCC filler.
- the furnish had a consistency of 0.5% (total solids of 0.5 lbs per 100 lbs of water).
- Stalok® 400 is a cationic potato starch (A. E. Staley, Decatur, III.).
- the metal silicate is Silicate O, a liquid sodium silicate possessing a SiO 2 : Na 2 O ratio of 3.22:1 (PQ Corporation, Valley Forge, PA); the dosage of metal silicate in all examples is based upon active SiO 2 .
- the alum is aluminum sulfate- octadecahydrate available as a 50% solution (Delta Chemical Corporation, Baltimore, Md.).
- Perform® PC 8138 is a cationic emulsion flocculant (Hercules Incorporated, Wilmington, DE).
- Perform® SP 7200 is an advanced structured organic microparticulate (Hercules Incorporated, Wilmington, DE).
- a 2% starch solution was prepared by heating adding 4 grams
- Stalok® 400 cationic starch to 196 grams deionized water and heating the starch to 95° C for 30 minutes until a clear, viscous solution was produced. The starch solution was allowed to cool to ambient temperatures.
- a blend of cationic starch and sodium silicate at the indicated ratio was prepared by adding the indicated amount of metal silicate to the cooked starch solution. For example, a 10:1 starchimetal silicate solution was prepared by adding 0.68 grams of Silicate O (29% active sodium silicate) to 100 grams of 2% starch cooked starch solution.
- a solution was also prepared by cooking the starch in the presence of the metal silicate.
- a 10:1 cooked solution was prepared by mixing 1.38 grams of Silicate O (29% active sodium silicate) with 198.62 grams of deionized water. 4 grams of Stalok® 400 cationic starch was added and the solution was heated to 95° C for 30 minutes until a turbid, viscous solution was produced. The starch solution was allowed to cool to ambient temperatures.
- the data in Table 1 illustrate the improved retention and drainage performance of the invention, where starch modified with a metal silicate provides better drainage compared to the unmodified starch.
- the data further iiiustrate the metal silicate can be blended with the starch after cooking, or added to the starch slurry prior to cooking.
- Stalok 400 10 Silicate O 10:1 cooked 16.5 together Stalok 400 10 Silicate O 10:1 15.4 89.3 Blend
- Starch was modified with metal silicate prior to addition to the pulp slurry.
- Dose # indicates individual qualities of starch and metal silicate prior to modification and subsequent addition to the pulp slurry.
- Total #/T of modified starch including metal silicate is found by adding starch dose and metal silicate dose.
- the Metal Silicate Dose is measured as Active metal silicate.
- Starch was modified with metal silicate prior to addition to the pulp slurry.
- Dose # indicates individual qualities of starch and metal silicate prior to modification and subsequent addition to the pulp slurry.
- Total #/T of modified starch including metal silicate is found by adding starch dose and metal silicate dose.
- the Metal Silicate Dose is measured as Active metal silicate.
- Starch was modified with metal silicate prior to addition to the pulp slurry. Dose # indicates individual qualities of starch and metal silicate prior to modification and subsequent addition to the pulp slurry. Total #/T of modified starch including metal silicate is found by adding starch dose and metal silicate dose.
- Starch was modified with metal silicate prior to addition to the pulp slurry. Dose # indicates individual qualities of starch and metal silicate prior to modification and subsequent addition to the pulp slurry. Total #/T of modified starch including metal silicate is found by adding starch dose and metal silicate dose.
- Another series of drainage tests was conducted with the VDT with the starch blended with the metal silicate at the indicated ratio utilizing starches with different degrees of substitution; the data are presented in Table 5.
- the materials, methods, and addition sequence are as specified in Table 1.
- the data in Table 5 illustrate the improved drainage provided by the inventive process compared to an unmodified starch, utilizing starches with varying degrees of substitution.
- Starch was modified with metal silicate prior to addition to the pulp slurry. Dose # indicates individual qualities of starch and metal silicate prior to modification and subsequent addition to the pulp slurry. Total #/T of modified starch including metal silicate is found by adding starch dose and metal silicate dose.
- N-Hance 3196 is a cationically modified guar gum (Ashland Aqualon, Wilmington, DE) The materials, methods, and addition sequence are as specified in Table 1. The data in Table 6 illustrate the improved drainage provided by the inventive process compared to an unmodified cationic guar. TABLE 6
- the polysaccharide was modified with metal silicate prior to addition to the pulp slurry.
- Dose # indicates individual qualities of starch and metal silicate prior to modification and subsequent addition to the pulp slurry.
- Total #/T of modified starch including metal silicate is found by adding polysaccharide dose and metal silicate dose.
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Abstract
L'invention concerne un procédé de modification d'amidon avec des silicates de métaux, et l'utilisation de l'amidon modifié dans la préparation de compositions de fibre cellulosique. Le procédé concerne en outre des compositions de fibre cellulosique, telles que du papier ou du carton, qui incorporent l'amidon modifié avec des silicates de métaux.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6258608P | 2008-01-28 | 2008-01-28 | |
PCT/US2009/000538 WO2009097111A1 (fr) | 2008-01-28 | 2009-01-27 | Procédé de modification d'amidon pour des performances accrues de rétention de et d'égouttage de machine à papier |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2238294A1 true EP2238294A1 (fr) | 2010-10-13 |
Family
ID=40627680
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09705709A Withdrawn EP2238294A1 (fr) | 2008-01-28 | 2009-01-27 | Procédé de modification d'amidon pour des performances accrues de rétention de et d'égouttage de machine à papier |
Country Status (12)
Country | Link |
---|---|
US (1) | US20090188640A1 (fr) |
EP (1) | EP2238294A1 (fr) |
JP (1) | JP2011511178A (fr) |
KR (1) | KR20100105897A (fr) |
CN (1) | CN101981253A (fr) |
AU (1) | AU2009209479A1 (fr) |
BR (1) | BRPI0906623A2 (fr) |
CA (1) | CA2713429A1 (fr) |
MX (1) | MX2010008223A (fr) |
TW (1) | TW201002908A (fr) |
WO (1) | WO2009097111A1 (fr) |
ZA (1) | ZA201006156B (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7981250B2 (en) * | 2006-09-14 | 2011-07-19 | Kemira Oyj | Method for paper processing |
CN103741543B (zh) * | 2012-09-20 | 2016-06-08 | 金东纸业(江苏)股份有限公司 | 淀粉组合物及其制备方法,应用该淀粉组合物的浆料 |
CN107254804B (zh) * | 2017-06-07 | 2019-08-30 | 天门顺康纸业有限公司 | 一种复合造纸用固着剂的制备方法 |
FI20185272A1 (en) * | 2018-03-22 | 2019-09-23 | Kemira Oyj | The dry strength composition, its use, and the method of making paper, board or the like |
BR112021014630A2 (pt) * | 2019-02-08 | 2021-09-21 | Kemira Oyj | Composição de amido |
CN114318937A (zh) * | 2020-09-27 | 2022-04-12 | 牡丹江市海洋新材料科技有限责任公司 | 可溶性硅酸盐、聚合氯化铝、絮凝剂在多领域组合使用的新方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2614945A (en) * | 1949-09-14 | 1952-10-21 | George A Krisan | Method of making mobile starch powders |
US2573677A (en) * | 1949-12-10 | 1951-11-06 | Vanderbilt Co R T | Process for the production of apigment complex, including a reacted starch |
DE1667443C2 (de) * | 1966-06-18 | 1982-10-21 | Degussa Ag, 6000 Frankfurt | Verfahren zur Herstellung feinteiliger Papierfüllstoffe auf Basis von organisch modifizierten Silikaten |
US3946061A (en) * | 1969-01-27 | 1976-03-23 | Buckman Laboratories, Inc. | Organo-silica polymers |
US5071512A (en) * | 1988-06-24 | 1991-12-10 | Delta Chemicals, Inc. | Paper making using hectorite and cationic starch |
US5185206A (en) * | 1988-09-16 | 1993-02-09 | E. I. Du Pont De Nemours And Company | Polysilicate microgels as retention/drainage aids in papermaking |
US5670021A (en) * | 1992-01-29 | 1997-09-23 | Kemira Kemi Aktiebolag | Process for production of paper |
CA2393797C (fr) * | 1999-12-20 | 2007-04-24 | Akzo Nobel N.V. | Sols a base de silice |
FI120318B (fi) * | 2004-06-23 | 2009-09-15 | M Real Oyj | Tärkkelyksen piitä sisältävät komposiitit, menetelmä niiden valmistamiseksi ja käyttö paperin ja kartongin valmistuksessa |
-
2009
- 2009-01-27 KR KR1020107019064A patent/KR20100105897A/ko not_active Application Discontinuation
- 2009-01-27 MX MX2010008223A patent/MX2010008223A/es unknown
- 2009-01-27 AU AU2009209479A patent/AU2009209479A1/en not_active Abandoned
- 2009-01-27 BR BRPI0906623-3A patent/BRPI0906623A2/pt not_active IP Right Cessation
- 2009-01-27 US US12/321,991 patent/US20090188640A1/en not_active Abandoned
- 2009-01-27 CA CA2713429A patent/CA2713429A1/fr not_active Abandoned
- 2009-01-27 JP JP2010545012A patent/JP2011511178A/ja active Pending
- 2009-01-27 EP EP09705709A patent/EP2238294A1/fr not_active Withdrawn
- 2009-01-27 CN CN2009801114401A patent/CN101981253A/zh active Pending
- 2009-01-27 WO PCT/US2009/000538 patent/WO2009097111A1/fr active Application Filing
- 2009-02-02 TW TW098103272A patent/TW201002908A/zh unknown
-
2010
- 2010-08-27 ZA ZA2010/06156A patent/ZA201006156B/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2009097111A1 * |
Also Published As
Publication number | Publication date |
---|---|
ZA201006156B (en) | 2012-02-29 |
CA2713429A1 (fr) | 2009-08-06 |
AU2009209479A1 (en) | 2009-08-06 |
WO2009097111A1 (fr) | 2009-08-06 |
MX2010008223A (es) | 2010-09-07 |
BRPI0906623A2 (pt) | 2015-07-14 |
JP2011511178A (ja) | 2011-04-07 |
US20090188640A1 (en) | 2009-07-30 |
CN101981253A (zh) | 2011-02-23 |
KR20100105897A (ko) | 2010-09-30 |
TW201002908A (en) | 2010-01-16 |
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