Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
  • D21C9/086—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching with organic compounds or compositions comprising organic compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
  • D21C5/02—Working-up waste paper
  • D21C5/022—Chemicals therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/64—Paper recycling
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S162/00—Paper making and fiber liberation
  • Y10S162/04—Pitch control

Definitions

• the invention relates to a method for controlling the settling of adhesive contaminants from paper pulp suspensions in papermaking.
• stickies are in compact form, they can be removed relatively easily by mechanical means from sorting machines. As a rule, the stickies are not only available in a compact form, they are also contained in dispersed form in the pulp and are very difficult to remove in this form. In recent times, therefore, the increasing use of waste paper in paper production and the narrowing of the water cycles have increasingly led to the proportion of stickies in the circulating water increasing.
• Stickies not only cause a number of problems or faults in paper production, but also in paper processing. Because of their stickiness, deposits form on machine parts, tube walls, screens, wet felts, dry felts, drying cylinders, smoothing rolls, calender rolls and, moreover, also in the finished paper, which leads to web breaks in the paper machine and to a deterioration in the paper quality Holes, stains, markings come (see HL Baumgarten, Das Textil, 1984, 38, Issue 10A, pp. V121 - V125). HLBaumgar ⁇ ten notes that sticky soiling in industrial and institute publications has been called the biggest problem of waste paper recycling for years. Even minimal amounts of glue can still tear on paper and printing machines, so that cleaning and stands are required. Baumgarten explains: "If 2 g of adhesive is applied to a well-chosen point in the paper machine, several 100 kg of paper can be rejected" (loc. Cit., Page V122, right column).
• stickies come from the resin of wood, aids in paper production, binders for coating paper and cardboard, adhesives for paper processing, printing ink binders and materials for paper processing. Of particular importance in the context of the task of the present invention are those adhesive contaminations which come from the resin of the wood and the adhesives used in paper processing.
• the resins present in the pulp and wood pulp contain a proportion of about 1-5% by weight of so-called harmful resins. These can be in a colloidal unbound form or adhere to the paper fibers.
• harmful resins can be in a colloidal unbound form or adhere to the paper fibers.
• the adhesives used in paper processing can be divided into three groups: the pressure sensitive adhesives, the dispersion adhesives and the hot melt adhesives.
• the pressure sensitive adhesives are permanently adhesive and permanently adhesive products. Liability is achieved by pressing the surfaces of the parts to be bonded together.
• Typical base polymers include natural rubber, butyl rubber, styrene-butadiene copolymers (SBR rubber), acrylonitrile copolymers, polychloroprene, polyisobutylene, polyvinyl ether, acrylates, polyesters, polyurethanes, silicones.
• the polymers which are suitable for forming the adhesive layer are present as solid particles in an aqueous dispersant.
• the base monomers are first emulsified in an aqueous phase and then polymerized therein, a technique known as emulsion polymerization.
• the polymer is then in the form of small particles with different particle sizes, which can vary in the range from molecularly disperse to coarsely disperse.
• an aggregation and an associated sedimentation of the polymer particles are counteracted by adding protective colloids or emulsifiers to the system.
• hot melt adhesives also called “hot melts”
• thermoplastics These substances have the property of softening when heated, which makes them flowable. When they cool down, they solidify again.
• polymers which are used as hot-melt adhesives include polyamides, copolyamides, polyaminoamines, saturated polyesters and ethylene-vinyl acetate copolymers.
• Primary stickies are understood to mean those sticky contaminants which, due to their high resistance, are not dispersed during wet grinding. They are therefore in a compact form and are easy to excrete.
• the existence of the secondary stickies stems from the fact that the adhesive impurities change their properties in the course of the waste paper processing Subject to particle size caused by thermal, chemical and mechanical influences. This means that even impurities which are still in a rather coarse form at the beginning of the reprocessing can be more or less reduced in size when the waste paper is reprocessed.
• the processes in the hot shredder of waste paper processing result in dispersion of sticky contaminants.
• stickies with a low melting point are liquefied and then finely dispersed. Even crumbly or brittle stickies disintegrate into very small particles.
• the particle size of the dispersed stickies then ranges from coarse to colloidal to molecular.
• auxiliary agents are therefore often used, which are referred to as drainage or retention aids.
• retention agents as substances that bind fine fibers and fillers to the long paper fibers (long fibers). This binding of the short fibers and the fillers to the long fibers prevents a kind of fleece formation of the fine materials, which makes dewatering of the paper pulp suspension difficult. In this way, retention agents improve the drainability by binding the fine substances to the long fibers.
• the retention aids can be divided into three groups. A distinction is made between inorganic products such as aluminum sulfate or sodium aluminate, synthetic products such as polyethyleneines, polyamines or polyacrylamides and modified natural products such as cationic starch.
• the mode of action of the retention agents is based on the addition of fine substances and fillers to the paper fibers.
• cationic polyelectrolytes for example cationic starch, are suitable as scavengers for anionic contaminants (Wochenblatt für Textilfabrikation 1993, pages 163-170).
• the American patent application US Pat. No. 4,744,865 describes an SDC process in which the coagulation of adhesive contaminants by polymers containing methoxy groups is to be reduced.
• the subject of the American patent application US 4,871,424 is an SDC method using a polymer. which contain hydroxyl groups.
• cellulose derivatives such as hydroxypropylmethylcellulose and polyvinyl alcohol are explicitly disclosed as polymers. which is accessible by hydrolysis or partial hydrolysis from polyvinyl acetate.
• WO 91/01405 describes a process for the treatment of waste paper, in which alkoxylation products of OH-group-containing C ⁇ o-22 " 1 - arDonklarec * er ' ''” and / or OH-group-containing C ⁇ o-22-carboxylic acids are used.
• WO 91/01405 discloses that the substances mentioned are suitable for deinking, ie the removal of printing inks from waste paper. However, the suitability of the substances for controlling the settling of stickies from paper suspensions in papermaking has not been disclosed or suggested.
• the stated object was achieved according to the invention by a method for controlling the settling of sticky contaminants (stickies) from paper n pulp suspensions in papermaking, where the pulp suspensions 0.01 - 5.0% by weight - based on the fiber - of alkoxylation products, obtainable by reacting alkylene oxides with ClO ⁇ -C-carboxylic acid derivatives and / or C-22 ⁇ C ar bonic acids that contain carboxylic acid residues with at least one OH group in the 9, 10, 13 and / or 14 position.
• the present invention therefore relates to a process for controlling the settling of sticky impurities (stickies) from paper pulp suspensions in paper manufacture, which is characterized in that the paper pulp suspensions are 0.01-5.0% by weight. % - based on the fiber - of alkoxylation products, obtainable by reaction of alkylene oxides with C ⁇ o-22 _ C ar bonic acid derivatives and / or C ⁇ o-22-C ar bon acids, the carboxylic acid residues with at least one OH group in position 9, 10, 13 and / or 14 included.
• the method according to the invention is generally applicable to a wide variety of types of adhesive contaminants. However, it is particularly suitable for solving the problems caused by pressure-sensitive adhesives, dispersion adhesives and hotmelt adhesives.
• the method according to the invention relates to those pulp suspensions which have been produced from waste paper or from paper products which contain waste paper components.
• Another object of the invention is the use of alkoxylation products which can be obtained by reacting alkylene oxides with C ⁇ o-22 "carboxylic acid derivatives and / or C ⁇ o-22"' ar bonic acids, the carboxylic acid residues with at least one OH group in 9, 10, 13 and / or 14 included Control of the settling of sticky impurities (stickies) from paper pulp suspensions during paper manufacture.
• the alkoxylation products to be used according to the invention can in principle be metered in at any point in the entire process of paper production. They are either metered in in liquid form or in the form of an aqueous solution.
• the effective amount of alkoxylation products required depends on the extent to which the raw materials to be processed, e.g. B. waste paper or paper types that contain waste paper components contain adhesive contaminants.
• the alkoxylation products according to the invention are used in an amount in the range from 0.01 to 5.0% by weight, preferably 0.1 to 1.0% by weight, based on the fiber material.
• those alkoxylation products are used in the production of which ethylene oxide, propylene oxide and / or butylene oxide were used as alkylene oxides.
• the alkoxylation products to be used according to the invention can be prepared by conventional organic synthesis methods.
• C ar b ° nsauren are all OH-free unsaturated C ⁇ o-22 C ⁇ ar b onsauren natural and / or synthetic origin containing at least one or two compounds in Doppelbin ⁇ 9- and / or 13-position, for example 9c-dodecenoic acid, 9c-tetra-decenoic acid, 9c-hexadecenoic acid, 9c-0ctadecenoic acid, 9c, 12c-0ctadecadienoic acid, 9t-0ctadecenoic acid, 9c, 12c, 15c-0ctadecatrienoic acid, 9c-eicosenoic acid 13c-octadecenoic acid and / or mixtures with at least a high content of such unsaturated carboxylic acids, preferably Cis
• Ci6_22 carboxylic acids containing at least one or two double bonds in the 9- and / or 13-position.
• alkoxylated OH-containing C ⁇ o-22 -Car acid derivatives are any OH-group-free unsaturated, naturally occurring and / or synthetically hergeste11baren C ⁇ o-22 Carbonkladreder ⁇ vate ', the Car “bonchurereste with at least one or two double bonds in the 9 and / or Examples of unsaturated carboxylic acid residues with 10 to 22 carbon atoms are the carboxylic acids already mentioned above Unsaturated carboxylic acid derivatives which contain Ci6-22 ⁇ C arD or acid residues with at least one or two double bonds in the 9- and / or 13-position Are preferred as unsaturated C22 -22 carboxylic acid derivatives are, for example, -C22 "C arD on acid esters, amides, mono- and / or di-C 1-4 alkylamides and / or mono- and / or -di -Ci.4alkanolamides.
• Cl0-22-C a rbonklarealkylester having 1 to 18 carbon atoms are in the monovalent holrest Alko ⁇ and / or mono-, di- and / or triglycerides, the C ⁇ o-22 "C a i" bonklare- radicals having at least one or contain two double bonds in the 9- and / or 13-position.
• Examples of unsaturated C ⁇ o-22 "C 'bonic acid-C ⁇ _.i8-alkyl esters which are known per se by esterification of the corresponding unsaturated carboxylic acids or by transesterification of the corresponding mono-, di- and / or triglycerides with C ⁇ _i8-alkyl alcohols, for example methanol, ethanol, propanal, butanol, isobutanol, 2-ethylhexanol, decanol, and / or stearyl alcohol, are accessible, are Palmitoleinmethylester, methyl oleate, ethyl oleate, ölklareisobutylester, oleic acid-2-ethylhexyl ester and / or oleate, and / or C ⁇ o-22-C ar b ° acid -C ⁇ _i8-alkyl ester mixtures with at least a high content of such OH-group-free unsaturated
• Tallow fat ethyl ester Fats and / or oils of natural origin are particularly suitable as mono-, di- and / or triglycerides of OH-group-free unsaturated C ⁇ o-22 "Ca ' r bonic acids with at least one or two double bonds in the 9- and / or 13-position , the carboxylic acid content is überwie ⁇ neighborhood of unsaturated C ⁇ o-22 ⁇ C ar b ° nklaren with at least one or two double bonds in the 9 and / or 13-position, preferably predominantly unsaturated Ci5_22-carboxylic acids with at least one or two double bonds in 9- and / or 13-position, such as olive oil, linseed oil, sunflower oil, safflower oil, soybean oil, peanut oil, cotton wool seed oil, erucic acid-rich and / or erucic acid-poor rape oil, palm oil, lard and / or tallow.
• the unsaturated C22-22 carboxylic acid derivatives and / or unsaturated c 10-22 "carboxylic acids are formed, for example, by the process described in DE-PS 857 364 by reaction with peracetic acid in the presence of acidic catalysts or with in situ formic acid and hydrogen peroxide
• the iodine numbers of the epoxidation products obtained are less than 20, in particular less than 15.
• the choice of the method for determining the iodine number is of minor importance per se, but within the meaning of the present invention, the methods according to Hanus or Wijs are expressly referred to which have long been part of the CV department of the "DGF standard methods", as well as the equivalent newer method according to Fiebig (cf. Fat Sei. Technol. 1991, No. 1, pp. 13-19).
• the oxirane rings of the epoxidized carboxylic acid derivatives and / or carboxylic acids are then reacted with hydrogen or protic compounds, such as water, Ci-i ⁇ - alkyl- and / or C ⁇ _i8-alkenyl alcohols or saturated and / or unsaturated C ⁇ _22 "carboxylic acids, with the formation of The conditions of the splitting are chosen such that the acid derivative and acid groups present remain intact.
• the hydrogenation of epoxidized carboxylic acid derivatives and / or epoxidized carboxylic acids can, for example, analogously to the process described in DE-OS 2021 530 in the presence of catalysts based on heavy metals of group VIII of the periodic table at temperatures between 100 and 250 ° C. under hydrogen pressures be carried out between 10-5 and 5 • 10 ⁇ Pa.
• the reactions of epoxidized carboxylic acid derivatives and / or epoxidized carboxylic acids with protic compounds can be carried out according to the processes described in MS Malinovskii "Epoxides and their Derivatives", Sivon Press 1965, at temperatures between 50 and 200 ° C. and pressures between 10 ⁇ and 10- 5 Pa can be carried out.
• YAlkoholen the splitting of the oxirane rings with straight and branched chain or C ⁇ _i8-alkyl and / or C2-18 -A lk s, preferably with straight or branched chain and C ⁇ _ alkyl alcohols is preferably carried out in the presence of acidic catalysts such as sulfuric acid or p- Toluenesulfonic acid,
• the carboxylic acid derivatives and carboxylic acids obtainable by splitting the oxirane rings and containing carboxylic acid residues with at least one OH group in the 9-, 10-, 13- and / or 14-position are then, according to known industrial processes, with one or more alkylene oxides, preferably with Ethylene oxide, propylene oxide and / or butylene oxide at temperatures between 110 and 200 ° C, preferably between 140 and 180 ° C and at pressures between 10 ⁇ and 2. 10 ⁇ Pa, preferably between 3. 10 ⁇ and 5. l ⁇ 5 Pa alkoxylated (compare for example: "Chemical technology", volume 7, pages 131 to 132, Carl Hanser Verlag, Kunststoff / Vienna (1986)).
• the alkylene oxide content of the alkoxylated OH group-containing carboxylic acid derivatives and / or carboxylic acids is between 2 and 400% by weight, preferably between 40 and 70% by weight, in each case based on the non-alkoxylated compounds.
• the following examples serve to illustrate the invention and are not to be understood as restrictive.
• Example 1.1 Hydrogenated soybean oil epoxide was admixed with 6.2 g of a 30% strength by weight solution of potassium hydroxide in methanol, and among those in Example 1.1. specified conditions first with 440 g of ethylene oxide and then reacted in the same reactor with 232 g of propylene oxide. After removal of the traces of propylene oxide in vacuo and neutralization of the catalyst with 3.3 g of lactic acid, a golden yellow liquid with an OHN of 72.1 was obtained.
• Example 1.1 510 g of the ring-opening product of soybean oil epoxide with methanol were mixed with 7.5 g of a 30% strength by weight methanolic sodium methylate solution and added to those in Example 1.1. specified conditions at 175 ° C with 551 g of ethylene oxide. After removing the traces of ethylene oxide in vacuo, a red-brown liquid with an OHN of 110.6 was obtained.
• the consistency of the sample to be examined is determined using a Nutsche leaf.
• the following sample weight for the adhesive surface examination refers to 2 g otro fabric.
• the fabric sample is then diluted with tap water to a fabric density of 1% and sorted on the Haindl fractionator with a slot width of 0.15 mm.
• a wash water quantity of 10 l / min is set at a wash water pressure of 1.7-2.0 bar.
• the filters with the adhesive residue are distributed on a cover sheet for Rapid-Köthen sheets (adhesive surface facing upwards) and covered with black photo cardboard. After predrying in the sheet former (10 min at 95 ° C.), the covered filters between two steel plates are heated in a drying cabinet at 133 ° C. for 2 min at a specific surface load given by tightening screw clamps. Finally, the adhesive surface on the photo cardboard is evaluated with a DOT counter, version: 2.0. The adhesive surface is determined by particles> 0.05 mm in m ⁇ .2 / kg otro material.
• the alkoxylation product according to Example 6 according to the invention was metered into the process in various concentrations continuously before the disperser.
• Tested substance Product from example 1.6.

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• 1995
  • 1995-04-26 DE DE1995115273 patent/DE19515273A1/de not_active Withdrawn
• 1996
  • 1996-04-18 CA CA 2219139 patent/CA2219139A1/en not_active Abandoned
  • 1996-04-18 JP JP53214596A patent/JPH11504083A/ja active Pending
  • 1996-04-18 WO PCT/EP1996/001619 patent/WO1996034147A1/de not_active Application Discontinuation
  • 1996-04-18 EP EP96914941A patent/EP0823005A1/de not_active Withdrawn
  • 1996-04-18 US US08/945,494 patent/US5914006A/en not_active Expired - Fee Related
  • 1996-04-18 KR KR1019970707580A patent/KR19990008056A/ko not_active Application Discontinuation

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