EP0961851A1 - Process for producing fibrous materials with improved properties - Google Patents

Process for producing fibrous materials with improved properties

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Publication number
EP0961851A1
EP0961851A1 EP98904108A EP98904108A EP0961851A1 EP 0961851 A1 EP0961851 A1 EP 0961851A1 EP 98904108 A EP98904108 A EP 98904108A EP 98904108 A EP98904108 A EP 98904108A EP 0961851 A1 EP0961851 A1 EP 0961851A1
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EP
European Patent Office
Prior art keywords
polyester
wood
tri
dicarboxylic acid
weight
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.)
Granted
Application number
EP98904108A
Other languages
German (de)
French (fr)
Other versions
EP0961851B1 (en
Inventor
Ingo Von Medvey
Thomas Rajcsanyi
Peter HÄNSSLE
Joachim Werres
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stockhausen GmbH and Co KG
Original Assignee
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
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Publication of EP0961851A1 publication Critical patent/EP0961851A1/en
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Publication of EP0961851B1 publication Critical patent/EP0961851B1/en
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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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/003—Pulping cellulose-containing materials with organic compounds
    • 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
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres

Definitions

  • the invention relates to a process for the production of fibrous materials for the production of pulp, paper or wood-based panels using at least one dicarboxylic acid dialkyl ester and / or a fatty acid polyol mono, di, tri and / or higher polyester and / or polyester-polyether copolymers as well as the products made from these fibrous materials such as cellulose, paper and wood-based panels.
  • Fibers or fiber raw materials such as mechanical pulps and long fiber raw materials and in particular thermo-mechanical pulp (TMP) or chemi-thermo-mechanical pulp (CTMP) are used in mechanical wood pulping by chamfering shredded wood materials with separation and fibrillation of the individual fibers after a thermal or chemical-thermal pretreatment (see Römpp chemistry lexicon, 9th edition 1991, pages 3208 and 4345).
  • TMP is better suited as wood pulp to replace cellulose and is therefore also used in the production of bulk printing paper such as rotary printing paper, thin printing paper and cardboard for cost reasons.
  • efforts are made to reduce the substance content of lignin and hemicellulose by delignification and / or oxidative or reductive bleaching processes in order to reduce the yellowing of the products produced with these substances.
  • HU-Süss and W.Eul report extensively on the efforts to bleach wood pulp in the weekly paper for paper manufacture 9 (1986) pp. 320-325.
  • the pulp pulp is delignified with a mixture of monopersulfuric acid and sulfuric acid with subsequent neutralization.
  • portions of degradation products of native strength of the wood pulp suspensions are still added to fix resins, but these are easily subject to microbiological degradation in the material circulation, unless countermeasures are taken.
  • WO 94/29510 and WO96 / 18770 for the treatment of lignin-containing materials, multi-component systems consisting of oxidizing agents and catalysts as well as mediators from the group of hydroxylamines, hydroxamic acids, aliphatic, cycloaliphatic, heterocyclic or aromatic compounds with N-hydroxy, oxime, N-oxi or N, N-dioxi functions and comediators, which contain aromatic alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins, are described.
  • This object is achieved according to the invention by using one or more dicarboxylic acid dialkyl esters and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyester-polyether copolymers in the impregnating pretreatment of the comminuted wood raw materials.
  • the invention accordingly relates to a process for the production of fibrous materials, preferably mechanical pulps, such as Thermo-Mechanical Pulp (TMP) or Chemi-Thermo-Mechanical Pulp (CTMP) and wood pulp, characterized in that during the production process, in particular in the Pretreatment for impregnating the comminuted wood raw materials or in the comminution of the wood raw materials, at least one dialkyl dicarboxylic acid and / or one or more fatty acid polyol mono, di, tri and / or higher polyester and / or polyester-polyether copolymers are added.
  • TMP Thermo-Mechanical Pulp
  • CTMP Chemi-Thermo-Mechanical Pulp
  • the invention relates to an agent for the production of fibrous materials, preferably TMP, CTMP and wood pulp, characterized in that the agent has one or more dialkyl dicarboxylic acids and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or contains polyester-polyether copolymers.
  • dicarboxylic acid dialkyl esters and / or fatty acid polyol mono, di, tri and / or higher polyesters and / or polyester-polyether copolymers are surprisingly effective in the pretreatment of shredded wood and / or plant materials and that they are so Primary fibers produced are cleaned to a greater extent of the adhering lignin, resin components and other wood constituents, so that substances with improved optical properties are obtained in the highest yield.
  • the brightness, whiteness, the color tint and the color saturation of the mechanical wood materials are improved without the other properties, in particular the strength properties of the fiber materials, being impaired.
  • the dicarboxylic acid dialkyl esters are the dicarboxylic acid dialkyl and / or diisoalkyl esters of C2 - C12 dicarboxylic acids with Cl - C13 n- and / or iso-alkanols, such as di-n-butyl oxalate, di-n-butylmalonate and di-n-butyl succinate , Di-n-butyl glutarate, di-n-butyl adipate, di-n-butyl suberate, di-n-butyl sebacate, dimethyl adipate, diethyl adipate, di-n-propyl adipate, diisopropyl adipate, diisobutyl adipate, di-tert-butyl adipate, di-isoamate -n-hexyl adipate, di- (2-ethylbutyl) adipate
  • esters of saturated and / or unsaturated C8 to Cl8 fatty acids with polyhydric alkanols having 2 to 6 carbon atoms such as glycol, trimethylolpropane, glycerol, sorbitol and sorbitan esters of the fatty acids mentioned, for.
  • polyhydric alkanols having 2 to 6 carbon atoms such as glycol, trimethylolpropane, glycerol, sorbitol and sorbitan esters of the fatty acids mentioned, for.
  • the esters of adipic acid or esters of sorbitan are preferably used, and particularly preferably the adipic acid esters of Cl to C6 n- and / or iso- Alkanols, such as dimethyl adipate, diethyl adipate, di-n-isopropyl adipate and diisopropyl adipate, di-n-butyl adipate and / or diisobutyl adipate, as well as the mixed esters of the dicarboxylic acids and alkanols mentioned, glycerol trioleate and sorbitan monooleate.
  • the adipic acid esters of Cl to C6 n- and / or iso- Alkanols such as dimethyl adipate, diethyl adipate, di-n-isopropyl adipate and diisopropyl adipate, di-n-butyl adipate and / or di
  • esters mentioned are used alone or as a mixture in an amount of 0.001 to 5.00% by weight, preferably 0.01 to 2.0% by weight and particularly preferably 0.01 to 1.0% by weight, based on the amounts of wood and / or the amount of plants used directly as a substance or in dissolved or dispersed liquid form.
  • the esters are used directly or as a dilute or concentrated water-containing or water-free solution or 1 in the form of water-containing dispersions.
  • Suitable solvents are n- and iso-alkanols, liquid hydrocarbons and acetone.
  • esters can be used alone or in combination with such water-soluble or water-insoluble solvents to give dispersed emulsions, nonionic, ionic and amphoteric, in particular nonionic and anionic, surfactants being used as emulsifiers.
  • Suitable nonionic emulsifiers are, for example, oxalkyl ethers, preferably oxethylates and / or terminally blocked oxethylates of fatty alcohols and fatty acids or oils.
  • Anionic emulsifiers are alkyl and / or aryl sulfonates, ⁇ -olefin sulfonates, ⁇ -sulfofatty acid esters, sulfosuccinic acid esters as well as alkyl sulfates and ether sulfates as well as carboxymethylated oxethylates and soaps.
  • the preparation of the preferably stable emulsions to be used according to the invention is known.
  • the hydrophobic phase which contains the ester component, is introduced into the aqueous emulsifier-containing phase and dispersed with stirring or pumping.
  • dicarboxylic acid dialkyl esters and / or fatty acid polyol mono- and / or - polyester and / or polyester-polyether copolymers according to the invention listed above can be used together with other components, namely liquid derivatives of vegetable or animal oils or fats, such as rapeseed oil methyl ester, rapeseed oil methyl ester, palm oil methyl ester, Soybean oil methyl ester and tallow fat methyl ester and synthetic ester oils are used.
  • esters mentioned are preferably added in the form of an aqueous, concentrated or dilute dispersion which, if appropriate, is prepared in a known manner with the addition of nonionic, anionic or cationic surfactants, alone or in combination with water-soluble or water-insoluble solvents.
  • the agents to be used according to the invention can also be used for the digestion of raw materials based on other suitable plant materials, e.g. B. of cereal straw or in the digestion of long fiber raw materials from reeds, reeds, parts of oil palms and / or other C4 plants, in particular for defibration in the refiner or in the cooker, from which, for example, wood-based fiberboard is produced.
  • the process according to the invention is suitable for the production of fibrous materials, in particular for the production of TMP, CTMP and wood pulp and also for the production of refiner wood pulp (refiner mechanical pulp) and also refiner wood material (chemical refiner mechanical pulp) produced by chemical pretreatment.
  • refiner wood pulp reffiner mechanical pulp
  • refiner wood material chemical refiner mechanical pulp
  • shredded woods in particular wood chips from softwood or hardwood, are used as starting materials in fresh or stored condition. Wood chips from sawmill waste or other wood waste or from broken wood are also suitable.
  • the raw materials mentioned can also be used together with other fibrous materials, eg. B. waste paper materials are processed.
  • the mechanical wood pulps are produced with a high yield under known process conditions, the wood chips being fed to the impregnator after pre-steaming and uniform wetting.
  • the addition of at least one dicarboxylic acid dialkyl ester and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyethylene terephthalate and / or polyoxyethylene terephthalate copolymers takes place separately or together with water and optionally one further impregnation liquid.
  • the wood chips are impregnated evenly and after 1 - 60 min, preferably 15 - 30 min or brief, 1 - 10 min, preferably 1 - 5 min, preheating to 110 - 180 ° C, preferably 140 - 170 ° C of the first Refiner stage fed, in which the separation into individual fibers and defibrillation / fibrillation takes place again under pressure between the grinding disks under predetermined load-bearing conditions.
  • the refiner material is then optionally fed to a refiner post-grinding in a second refiner stage.
  • a refiner post-grinding in a second refiner stage.
  • a steam-heated pulper can usually additionally treatment with chemicals, for. B.
  • a latency elimination and the bleaching of the wood pulp can be made.
  • the agents to be used according to the invention can be added at any point before the actual mechanical pulping of the wood pulp or plant materials, for example in the manufacture of wood pulp separately or together with the water introduced into the grinding zone.
  • the mechanical wood pulp can also be subjected to bleaching, whereby the increase in brightness and whiteness with the same opacity as well as the strength of the fibers, in particular the values of the tearing length, the tearing work and breaking load, are wholly or approximately retained.
  • the lignin content of the substance is reduced by approximately 1% by weight when the esters mentioned are used according to the invention.
  • the process according to the invention can also be carried out in such a way that the additional bleaching is dispensed with while maintaining the previously attainable brightness values and degrees of whiteness, or in such a way that the bleaching is carried out with a significant saving in the amount of chemicals. In this way, subsequent yellowing of the fiber materials by adding alkalis can be avoided.
  • the dicarboxylic acid dialkyl esters to be used according to the invention and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyethylene phthalate and / or polyoxyethylene terephthalate copolymers can be used as agents for the chemical treatment of wood chips which are produced by the known methods pulp or wood-based panels or their preliminary products.
  • TMP was produced in a plant for the production of high-yield fiber materials with the following characteristics: Throughputs 40 - 65 kg otro / h
  • Di-n-butyl adipate, glycerol trioleate and glycerol trioleate in combination with rapeseed oil methyl ester in a ratio of 1: 1 were used as impregnating agents, which in the state of an aqueous emulsion consisted of 14% by weight of the agent and 8% by weight of a nonionic emulsifier based on ethoxylated fatty alcohol or a highly ethoxyethylated vegetable oil. The amount used was 2.8 g / kg wood chips each.
  • the preheater they were briefly subjected to further treatment at temperatures between 110 and 160 ° C for about 20 minutes and then fed to the first refiner stage of the CD 300 type via 2 screw conveyors.
  • refiner fabric After leaving the grinding zone, refiner fabric was blown into a cyclone, where the steam and fiber material were separated.
  • a partial amount of the TMP produced was at a consistency of 10% by weight, a bleach (bag bleach) using 1.8% water glass, 0.5% complexing agent, 1.8% NaOH and 3.8% H 2 O 2 (the percentages by weight relate in each case to the amount of wood pulp used).
  • the bleached fabric was washed and acidified to pH 8.0-8.5 with SO.
  • optical properties were assessed by Rapid-Koethen's sheet formation.
  • 500 g of TMP (approx. 20% by weight of dry substance) were whipped in 10 1 of tap water in the pulper.
  • the amount of fabric weighed 375 g per sheet.
  • Table 1 contains the manufacturing data and the data of the TMP generated, the abbreviations meaning:
  • Table 2 contains the optical property data of the unbleached and bleached TMP.
  • the data of the examples show that when the agents according to the invention are used, the brightness and whiteness increase by 3-4 points.
  • the increase over the comparison sample, as well as the opacity, is retained if bleaching of the TMP is also carried out.
  • di-n-butyl adipate amount 5.6 kg / t 5 di-n-butyl adipate and rapeseed oil methyl ester (1: 1) 5.6 kg / t 6 glycerol trioleate 5.6 kg / t 7 sorbitan monooleate 5.6 kg / t 8 polyester / polyether copolymer 5.6 kg / t (Soil dissolver-PES-ET 1/30 Hüls AG) 9 glycerol trioleate 2.8 kg / t
  • Tables 3 and 4 show that a marked improvement in the degree of whiteness, brightness, hue and saturation is achieved.

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  • Paper (AREA)
  • Inorganic Fibers (AREA)
  • Multicomponent Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

A process for producing fibrous materials for the manufacture of cellulose, paper or wood materials by using at least one dicarboxylic acid dialkyl ester and/or a copolymer of polyester-polyether and/or fatty acid polyol monopolyester, dipolyester, tripolyester and or higher polyester. Fibrous materials with an improved quality and higher yield are thus produced.

Description

Verfahren zur Herstellung von Faserstoffen mit verbesserten Eigenschaften Process for the production of fibrous materials with improved properties
Die Erfindung betrifft ein Verfahren zur Herstellung von Faserstoffen für die Erzeugung von Zellstoff, Papier oder Holzwerkstoffplatten unter Verwendung mindestens eines Dicarbonsäuredialkylesters und/oder eines Fettsäurepolyol- mono, -di, -tri- und/oder höhere Polyester und/oder Polyester- Polyether-Copolymeren sowie die aus diesen Faserstoffen hergestellten Erzeugnisse wie Zellstoff, Papier und Holzwerkstoffplatten.The invention relates to a process for the production of fibrous materials for the production of pulp, paper or wood-based panels using at least one dicarboxylic acid dialkyl ester and / or a fatty acid polyol mono, di, tri and / or higher polyester and / or polyester-polyether copolymers as well as the products made from these fibrous materials such as cellulose, paper and wood-based panels.
Faserstoffe bzw. Faserrohstoffe, wie mechanische Holzstoffe und Langfaser-Rohstoffe und insbesondere Thermo-Mechanical Pulp (TMP) bzw. Chemi-Thermo-Mechanical Pulp (CTMP) werden beim mechanischen Holzaufschluß durch Zerfasung von zerkleinerten Holzmaterialien unter Separierung und Fibrillierung der Einzelfasern nach einer thermischen bzw. chemisch-thermischen Vorbehandlung gewonnen (s. hierzu Römpp-Chemielexikon, 9. Auflage 1991, Seiten 3208 und 4345).Fibers or fiber raw materials, such as mechanical pulps and long fiber raw materials and in particular thermo-mechanical pulp (TMP) or chemi-thermo-mechanical pulp (CTMP) are used in mechanical wood pulping by chamfering shredded wood materials with separation and fibrillation of the individual fibers after a thermal or chemical-thermal pretreatment (see Römpp chemistry lexicon, 9th edition 1991, pages 3208 and 4345).
Aufgrund der größeren Faserlängen und Helligkeit ist TMP besser als Holzschliff zum Ersatz von Zellstoff geeignet und wird deshalb auch aus Kostengründen bei der Herstellung von Massendruckpapieren, wie Rotationsdruckpapier, Dünndruckpapier und Kartonagen verwendet. Bei der Erzeugung der Halbzellstoffe ist man, wie bei der Zellstoffgewinnung, bestrebt, den Stoffgehalt an Lignin und Hemicellulose durch Delignifizierung und/oder oxidative bzw. reduktive Bleichverfahren zu senken, um die Vergilbung der mit diesen Stoffen hergestellten Erzeugnisse herabzusetzen. Über die Bemühungen bei der Bleiche von Holzstoffen wird von H.U-Süss und W.Eul im Wochenblatt für die Papierfabrikation 9 (1986) S. 320 - 325 ausführlich berichtet. Dabei wird festgestellt, daß eine von der Dosierung der Bleichchemikalien abhängige Vergilbung der Stoffe eintreten kann, welche die Weißgradstabilisierung der Erzeugnisse beeinträchtigt. In DE 41 03 572 C2 wird als Variante der bekannten Alcell- bzw. Organocell-Verfahren die Delignifizierung von Pflanzenfasermaterialien, insbesondere von Holzhackschnitzeln in der Weise durchgeführt, daß die Hackschnitzel zuerst durchgehend mit Alkohol imprägniert werden, um eine faserschädigende Wirkung des nachfolgenden Alkalizusatzes zu vermeiden. In WO 94/12721 und WO 94/12722 werden Delignifizierungsprozesse unter Verwendung von Peressigsäure und Komplexverbindungen mit anschließender Bleiche mittels Ozon oder Natriumdithionit beschrieben, während nach DE 195 09 401 AI mit Holzstoffen und Sekundärfaserhalbstoffen eine mehrstufige Peroxidbleiche unter Druck durchgeführt wird, wobei die verwendeten Komplexbildner die Wirkung des Perhydroxylanions gegenüber im Faserinneren befindlichen Ligninchromophoren verbessern sollen.Due to the larger fiber lengths and brightness, TMP is better suited as wood pulp to replace cellulose and is therefore also used in the production of bulk printing paper such as rotary printing paper, thin printing paper and cardboard for cost reasons. In the production of the semi-pulp, as in the production of pulp, efforts are made to reduce the substance content of lignin and hemicellulose by delignification and / or oxidative or reductive bleaching processes in order to reduce the yellowing of the products produced with these substances. HU-Süss and W.Eul report extensively on the efforts to bleach wood pulp in the weekly paper for paper manufacture 9 (1986) pp. 320-325. It is found that a yellowing of the substances depending on the dosage of the bleaching chemicals can occur, which affects the whiteness stabilization of the products. In DE 41 03 572 C2, as a variant of the known Alcell or Organocell process, the delignification of plant fiber materials, in particular wood chips, is carried out in such a way that the chips are first continuously impregnated with alcohol in order to avoid a fiber-damaging effect of the subsequent addition of alkali . In WO 94/12721 and WO 94/12722 delignification processes using peracetic acid and complex compounds with subsequent bleaching using ozone or sodium dithionite are described, while according to DE 195 09 401 AI a multistage peroxide bleaching is carried out under pressure with wood pulps and secondary fiber pulps, the complexing agents used to improve the effect of the perhydroxyl anion against lignin chromophores located in the interior of the fiber.
Nach EP 553 649 Bl wird die Delignifizierung von Zellstoffpulp mit einem Gemisch von Monoperschwefelsäure und Schwefelsäure unter anschließender Neutralisation durchgeführt.According to EP 553 649 B1, the pulp pulp is delignified with a mixture of monopersulfuric acid and sulfuric acid with subsequent neutralization.
Da die Verwendung von Chemikalien bei der Herstellung von CTMP zu Abwasserproblemen führt, wird nach dem Verfahren zur Herstellung von Holzfaserplatten nach EP 639 434 Bl darauf verzichtet, die Chemikalien nach dem Aufschluß zu entfernen.Since the use of chemicals in the production of CTMP leads to wastewater problems, the process for the production of wood fiber boards according to EP 639 434 B1 means that the chemicals are not removed after the digestion.
Die Bleiche von ligninhaltigen Materialien mit Oxidationsmitteln unter Verwendung von Hydroxylamin- und Hydroxamsäureverbindungen bzw. einer großen Zahl von Verbindungen mit einer N-hydroxy-, Oxi-, N-Oxi- oder N, N'- Dioxi-Funktion werden in EP 717 143 AI beschrieben, wobei Ester des 1-Hydroxybenztriazols, der Zimtsäure sowie der 4-tert. Butylbenzoesäure als Verfahrenskomponenten benannt werden.The bleaching of lignin-containing materials with oxidizing agents using hydroxylamine and hydroxamic acid compounds or a large number of compounds with an N-hydroxy, oxi, N-oxi or N, N'-dioxi function are described in EP 717 143 AI described, wherein esters of 1-hydroxybenzotriazole, cinnamic acid and 4-tert. Butylbenzoic acid can be named as process components.
Zur Fixierung von Harzen werden nach WO 95/00704 weiterhin Anteile von Abbauprodukten von nativer Stärke der Holzstoffsuspensionen zugesetzt, die jedoch im Stoffumlauf leicht einem mikrobiologischen Abbau unterliegen, sofern nicht Gegenmaßnahmen getroffen werden.According to WO 95/00704, portions of degradation products of native strength of the wood pulp suspensions are still added to fix resins, but these are easily subject to microbiological degradation in the material circulation, unless countermeasures are taken.
In ähnlicher Weise sollen nach DE 195 15 272 AI durch Alkoxylierung von C10 - C22 - Carbonsäurederivaten und/oder C10 - C22-Carbonsäuren mit OH-Gruppen, z. B. aus Sojaoder Leinöl hergestellte Produkte, zur Kontrolle des Absetzens von Harzen zugesetzt werden, wobei die Harze nach diesem Verfahren in Zellstoff- und/oder Holzstoff- Suspensionen bzw. Primärfaser-Suspensionen zur Vermeidung von Störungen im Prozessablauf der Primärfasern wahrscheinlich in verbessertem Maße dispergiert werden sollen. Angaben zur Wirksamkeit dieser Verbindungen werden nicht gemacht.Similarly, according to DE 195 15 272 AI by alkoxylation of C10 - C22 - carboxylic acid derivatives and / or C10 - C22 carboxylic acids with OH groups, eg. B. products made from soybean or linseed oil are added to control the settling of resins, the resins being dispersed in this process in pulp and / or wood pulp suspensions or primary fiber suspensions to avoid disturbances in the process flow of the primary fibers probably to an improved extent should be. No information is given on the effectiveness of these compounds.
In der WO 94/29510 und der WO96/18770 werden zur Behandlung ligninhaltiger Materialien Mehrfachkomponentensysteme aus Oxydationsmitteln und -katalysatoren sowie Mediatoren aus der Gruppe der Hydroxylamine, Hydroxamsäuren, der aliphatischen, cycloaliphatischen, heterocyclischen oder aromatischen Verbindungen mit N-Hydroxy-, Oxim-, N-Oxi- oder N,N- Dioxi-Funktionen und Comediatoren, die aromatische Alkohole, Carbonylverbindungen, aliphatische Ether, Phenolether und/oder Olefine sind, enthalten, beschrieben.In WO 94/29510 and WO96 / 18770 for the treatment of lignin-containing materials, multi-component systems consisting of oxidizing agents and catalysts as well as mediators from the group of hydroxylamines, hydroxamic acids, aliphatic, cycloaliphatic, heterocyclic or aromatic compounds with N-hydroxy, oxime, N-oxi or N, N-dioxi functions and comediators, which contain aromatic alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins, are described.
Die bekannten Verfahren zur Herstellung von Holzstoffen sind demnach durch die Verwendung einer Vielzahl von komplex wirkenden, verschiedenartigen Hilfsmitteln gekennzeichnet, deren Anwendung abhängig von den eingesetzten Rohstoffen und Herstellungsbedingungen umfangreich zu kontrollieren ist und deren Wirksamkeit begrenzt ist. Es bestand daher die Aufgabe, ein Verfahren zur Herstellung von Faserstoffen zu finden, das ohne die genannten Nachteile durchgeführt werden kann und bei dem Faserstoffe mit gleichwertigen oder verbesserten Eigenschaften erhalten werden können.The known processes for the production of wood materials are therefore characterized by the use of a large number of complex-acting, different auxiliaries, the use of which, depending on the raw materials and production conditions used, can be controlled extensively and the effectiveness of which is limited. The object was therefore to find a process for the production of fibrous materials which can be carried out without the disadvantages mentioned and in which fibrous materials with equivalent or improved properties can be obtained.
Weiterhin bestand die Aufgabe, Mittel zur Verwendung bei der Herstellung Faserstoffen zu finden, welche die Herstellung verbesserter Faserstoffe, insbesondere von TMP und CTMP, sowie die Herstellung verbesserter oder preiswerterer Erzeugnisse auf der Basis dieser Rohstoffe insbesondere auch unter Berücksichtigung ökologischer Aspekte, wie die Einschränkung der Verwendung von umweltbelastenden Chemikalien oder die Verwertung von Rohstoffen minderer Qualität oder von Abfallrohstoffen ermöglichen.Furthermore, there was the task of finding agents for use in the production of fiber materials, which the production of improved fiber materials, in particular TMP and CTMP, as well as the production of improved or cheaper products based on these raw materials, in particular also taking into account ecological aspects, such as the limitation of Enable the use of environmentally harmful chemicals or the recycling of raw materials of inferior quality or waste raw materials.
Diese Aufgabe wird erfindungsgemäß durch die Verwendung eines oder mehrerer Dicarbonsäuredialkylester und/oder eines oder mehrerer Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyester- Polyether-Copolymeren bei der imprägnierenden Vorbehandlung der zerkleinerten Holzrohstoffe gelöst.This object is achieved according to the invention by using one or more dicarboxylic acid dialkyl esters and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyester-polyether copolymers in the impregnating pretreatment of the comminuted wood raw materials.
Gegenstand der Erfindung ist demnach ein Verfahren zur Herstellung von Faserstoffen, vorzugsweise von mechanischen Holzstoffen, wie Thermo-Mechanical Pulp (TMP) bzw. Chemi-Thermo-Mechanical Pulp (CTMP) und Holzschliff, dadurch gekennzeichnet, daß während des Herstellungsprozesses, insbesondere bei der Vorbehandlung zum Imprägnieren der zerkleinerten Holzrohstoffe oder bei der Zerkleinerung der Holzrohstoffe mindestens ein Dicarbonsäuredialkylester und/oder ein oder mehrere Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyester- Polyether- Copolymere zugesetzt werden.The invention accordingly relates to a process for the production of fibrous materials, preferably mechanical pulps, such as Thermo-Mechanical Pulp (TMP) or Chemi-Thermo-Mechanical Pulp (CTMP) and wood pulp, characterized in that during the production process, in particular in the Pretreatment for impregnating the comminuted wood raw materials or in the comminution of the wood raw materials, at least one dialkyl dicarboxylic acid and / or one or more fatty acid polyol mono, di, tri and / or higher polyester and / or polyester-polyether copolymers are added.
Gegenstand der Erfindung ist ein Mittel zur Herstellung von Faserstoffen, vorzugsweise TMP, CTMP und Holzschliff, dadurch gekennzeichnet, daß das Mittel einen oder mehrere Dicarbonsäuredialkylester und/oder einen oder mehrere Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyester- Polyether- Copolymere enthält. Es wurde festgestellt, daß Dicarbonsäuredialkylester und/oder Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyester- Polyether- Copolymere überraschenderweise bei der Vorbehandlung von zerkleinerten Holz- und/oder Pflanzenmaterialien wirksam sind und daß die damit erzeugten Primärfasern in stärkerem Maße vom anhaftenden Lignin, von Harzanteilen und anderen Holzinhaltsstoffen gereinigt werden, so daß in höchster Ausbeute Stoffe mit verbesserten optischen Eigenschaften erhalten werden. Erfindungsgemäß werden insbesondere die Helligkeit, Weiße, die Farbtönung und die Farbsättigung der mechanischen Holzstoffe verbessert, ohne daß die übrigen Eigenschaften insbesondere die Festigkeitseigenschaften der Faserstoffe beeinträchtigt werden.The invention relates to an agent for the production of fibrous materials, preferably TMP, CTMP and wood pulp, characterized in that the agent has one or more dialkyl dicarboxylic acids and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or contains polyester-polyether copolymers. It has been found that dicarboxylic acid dialkyl esters and / or fatty acid polyol mono, di, tri and / or higher polyesters and / or polyester-polyether copolymers are surprisingly effective in the pretreatment of shredded wood and / or plant materials and that they are so Primary fibers produced are cleaned to a greater extent of the adhering lignin, resin components and other wood constituents, so that substances with improved optical properties are obtained in the highest yield. According to the invention, in particular the brightness, whiteness, the color tint and the color saturation of the mechanical wood materials are improved without the other properties, in particular the strength properties of the fiber materials, being impaired.
Erfindungsgemäß werden als Dicarbonsäuredialkylester die Dicarbonsäure-dialkyl- und/oder - diisoalkylester von C2 - C12 Dicarbonsäuren mit Cl - C13 n- und /oder iso-alkanolen, wie Di-n-butyloxalat, Di-n-butylmalonat, Di-n-butylsuccinat, Di-n-butylglutarat, Di-n-butyladipat, Di-n-butylsuberat, Di-n-butylsebacat, Dimethyladipat, Diethyladipat, Di-n-propyladipat, Diisopropyladipat, Diisobutyladipat, Di-tert-butyladipat, Di-isoamyladipat, Di-n-hexyladipat, Di-(2-ethylbutyl)adipat, Di-(2-ethylhexyl)adipat, Diisodecyladipat, Dimethylphthalat, Diethylphthalat, Di-n-butylphthalat, Diisobutylphthalat, Di-(2-ethylhexyl)phthalat und Diisodecylphthalat sowie die Diester der C9 -Dicarbonsäure (Trimethyladipinsäure) und der Dodecandicarbonsäure verwendet.According to the invention, the dicarboxylic acid dialkyl esters are the dicarboxylic acid dialkyl and / or diisoalkyl esters of C2 - C12 dicarboxylic acids with Cl - C13 n- and / or iso-alkanols, such as di-n-butyl oxalate, di-n-butylmalonate and di-n-butyl succinate , Di-n-butyl glutarate, di-n-butyl adipate, di-n-butyl suberate, di-n-butyl sebacate, dimethyl adipate, diethyl adipate, di-n-propyl adipate, diisopropyl adipate, diisobutyl adipate, di-tert-butyl adipate, di-isoamate -n-hexyl adipate, di- (2-ethylbutyl) adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di- (2-ethylhexyl) phthalate and diisodecyl phthalate and the diesters the C9 dicarboxylic acid (trimethyladipic acid) and the dodecanedicarboxylic acid used.
Ebenso werden erfindungsgemäß die Ester von gesättigten und/oder ungesättigten C8 bis Cl 8-Fettsäuren mit mehrwertigen Alkanolen mit 2 bis 6 Kohlenstoffatomen, wie Glykol-, Trimethylolpropan-, Glycerin-, Sorbitol- und Sorbitanester der genannten Fettsäuren, z. B. Glycerinmono- und/oder Glycerindi- und/oder Glycerintrifettsäureester, Sorbitolmono- und - difettsäureester und Sorbitanmono- und/oder Sorbitandifettsäureester und/oder Sorbitantrifettsäureester verwendet.Likewise, the esters of saturated and / or unsaturated C8 to Cl8 fatty acids with polyhydric alkanols having 2 to 6 carbon atoms, such as glycol, trimethylolpropane, glycerol, sorbitol and sorbitan esters of the fatty acids mentioned, for. B. glycerol mono- and / or glycerol di- and / or glycerol trifatty acid esters, sorbitol mono- and - difatty acid esters and sorbitan mono- and / or sorbitan difatty acid esters and / or sorbitan trifatty acid esters.
Weiterhin haben sich überraschenderweise sogenannte Schmutzlöseagentien, die bisher zur Reinigung oder Soil-Releaseagentien-Ausrüstung von Synthesefasern verwendet wurden, insbesondere Polyester-Polyether-Copolymere, wie beispielsweise Polyethylenterephthalat und/oder Polyoxyethylenterephthalat-Copolymere als erfindungsgemäß zu verwendende Mittel erwiesen.Surprisingly, so-called dirt-dissolving agents which have hitherto been used for cleaning or soil-release agent finishing of synthetic fibers, in particular polyester-polyether copolymers, such as, for example, polyethylene terephthalate and / or polyoxyethylene terephthalate copolymers, have also surprisingly been found to be agents to be used according to the invention.
Vorzugsweise werden erfindungsgemäß die Ester der Adipinsäure bzw. Ester des Sorbitans verwendet und besonders bevorzugt die Adipinsäureester von Cl bis C6 n- und/oder iso- Alkanolen, wie Dimethyladipat, Diethyladipat, Di-n-isopropyladipat und Diisopropyladipat, Di-n-butyladipat und/oder Diisobutyladipat, sowie die gemischten Ester der genannten Dicarbonsäuren und Alkanole, Glycerintrioleat und Sorbitanmonooleat.According to the invention, the esters of adipic acid or esters of sorbitan are preferably used, and particularly preferably the adipic acid esters of Cl to C6 n- and / or iso- Alkanols, such as dimethyl adipate, diethyl adipate, di-n-isopropyl adipate and diisopropyl adipate, di-n-butyl adipate and / or diisobutyl adipate, as well as the mixed esters of the dicarboxylic acids and alkanols mentioned, glycerol trioleate and sorbitan monooleate.
Die genannten Ester werden allein oder als Mischung in einer Menge von 0,001 - 5,00 Gew.%, vorzugsweise 0,01 - 2,0 Gew.% und besonders bevorzugt 0,01 - 1,0 Gew.%, bezogen auf die Holzmengen und/oder Pflanzenmenge direkt als Substanz oder in gelöster oder in dispergierter flüssiger Form eingesetzt. Die Ester werden direkt oder als verdünnte oder konzentrierte wasserhaltige oder wasserfreie Lösung oder1 in Form von wasserhaltigen Dispersionen verwendet. Geeignete Lösungsmittel sind n- und iso-Alkanole, flüssige Kohlenwasserstoffe und Aceton. Die Ester können allein oder in Kombination mit solchen wasserlöslichen oder wasserunlöslichen Lösungsmitteln zu Emulsionen dispergiert zum Einsatz gelangen, wobei nicht-ionogene, ionische und amphotere, insbesondere nichtionische und anionische Tenside als Emulgatoren verwendet werden.The esters mentioned are used alone or as a mixture in an amount of 0.001 to 5.00% by weight, preferably 0.01 to 2.0% by weight and particularly preferably 0.01 to 1.0% by weight, based on the amounts of wood and / or the amount of plants used directly as a substance or in dissolved or dispersed liquid form. The esters are used directly or as a dilute or concentrated water-containing or water-free solution or 1 in the form of water-containing dispersions. Suitable solvents are n- and iso-alkanols, liquid hydrocarbons and acetone. The esters can be used alone or in combination with such water-soluble or water-insoluble solvents to give dispersed emulsions, nonionic, ionic and amphoteric, in particular nonionic and anionic, surfactants being used as emulsifiers.
Geeignete nichtionische Emulgatoren sind beispielsweise Oxalkylether, vorzugsweise Oxethylate und/oder endständig blockierte Oxethylate von Fettalkoholen und Fettsäuren bzw. Ölen. Als anionische Emulgatoren sind Alkyl- und/oder Arylsulfonate, α-Olefinsulfonate, α- Sulfofettsäureester, Sulfobernsteinsäureeester sowie Alkylsulfate und Ethersulfate sowie carboxymethylierte Oxethylate und Seifen. Die Herstellung der erfindungsgemäß zu verwendenden, vorzugsweise stabilen Emulsionen ist bekannt. Beispielsweise wird die hydrophobe Phase, welche die Esterkomponente enthält, in die wässrige emulgatorhaltige Phase eingetragen und unter Rühren oder Umpumpen dispergiert.Suitable nonionic emulsifiers are, for example, oxalkyl ethers, preferably oxethylates and / or terminally blocked oxethylates of fatty alcohols and fatty acids or oils. Anionic emulsifiers are alkyl and / or aryl sulfonates, α-olefin sulfonates, α-sulfofatty acid esters, sulfosuccinic acid esters as well as alkyl sulfates and ether sulfates as well as carboxymethylated oxethylates and soaps. The preparation of the preferably stable emulsions to be used according to the invention is known. For example, the hydrophobic phase, which contains the ester component, is introduced into the aqueous emulsifier-containing phase and dispersed with stirring or pumping.
Die vorstehend aufgeführten erfindungsgemäßen Dicarbonsäuredialkylester und/oder Fettsäurepolyol- mono- und/oder - polyester und/oder Polyester- Polyether- Copolymere können zusammen mit weiteren Komponenten, und zwar flüssigen Derivaten von pflanzlichen oder tierischen Ölen oder Fetten, wie Rapsölmethylester, Rübölmethylester, Palmölmethylester, Sojaölmethylester und Talgfettmethylester und synhetischen Esterölen eingesetzt werden. Vorzugsweise erfolgt die Zugabe der genannten Ester in Form einer wässrigen, konzentrierten oder verdünnten Dispersion, die ggf. unter Zusatz von nichtionogenen, anionischen oder kationischen Tensiden, allein oder in Kombination mit wasserlöslichen oder wasserunlöslichen Lösungsmitteln, in bekannter Weise hergestellt werden. Die erfindungsgemäß zu verwendenden Mittel können auch beim Aufschluß von Rohstoffen auf der Basis anderer geeigneter Pflanzenmaterialien, z. B. von Getreide-Stroh oder beim Aufschluß von Langfaser-Rohstoffen aus Schilf, Rohr, Teilen von Ölpalmen und/oder anderen C4-Pflanzen, insbesondere bei der Zerfaserung im Refiner oder im Kocher verwendet werden, aus denen beispielsweise Holzwerkstoff-Faserplatten erzeugt werden.The dicarboxylic acid dialkyl esters and / or fatty acid polyol mono- and / or - polyester and / or polyester-polyether copolymers according to the invention listed above can be used together with other components, namely liquid derivatives of vegetable or animal oils or fats, such as rapeseed oil methyl ester, rapeseed oil methyl ester, palm oil methyl ester, Soybean oil methyl ester and tallow fat methyl ester and synthetic ester oils are used. The esters mentioned are preferably added in the form of an aqueous, concentrated or dilute dispersion which, if appropriate, is prepared in a known manner with the addition of nonionic, anionic or cationic surfactants, alone or in combination with water-soluble or water-insoluble solvents. The agents to be used according to the invention can also be used for the digestion of raw materials based on other suitable plant materials, e.g. B. of cereal straw or in the digestion of long fiber raw materials from reeds, reeds, parts of oil palms and / or other C4 plants, in particular for defibration in the refiner or in the cooker, from which, for example, wood-based fiberboard is produced.
Das erfindungsgemäße Verfahren ist zur Herstellung von Faserstoffen, insbesondere zur Herstellung von TMP, CTMP und Holzschliff und daneben zur Herstellung von Refinerholzstoff (Refiner-Mechanical Pulp) sowie durch chemische Vorbehandlung hergestellten Refinerholzstoff (Chemical-Refiner-Mechanical Pulp) geeignet.The process according to the invention is suitable for the production of fibrous materials, in particular for the production of TMP, CTMP and wood pulp and also for the production of refiner wood pulp (refiner mechanical pulp) and also refiner wood material (chemical refiner mechanical pulp) produced by chemical pretreatment.
Beim erfindungsgemäßen Verfahren werden als Ausgangsmaterialien vorzugsweise zerkleinerte Hölzer, insbesondere Holzhackschnitzel von Nadel- oder Laubhölzern in frischem oder gelagertem Zustand verwendet. Ebenso sind Hackschnitzel von Sägewerksabfällen oder anderen Holzabfällen oder von Bruchhölzern geeignet. Die genannten Rohstoffe können nach dem erfindungsgemäßen Verfahren auch zusammen mit anderen Faserstoffen, z. B. Altpapierstoffen verarbeitet werden.In the process according to the invention, preferably shredded woods, in particular wood chips from softwood or hardwood, are used as starting materials in fresh or stored condition. Wood chips from sawmill waste or other wood waste or from broken wood are also suitable. The raw materials mentioned can also be used together with other fibrous materials, eg. B. waste paper materials are processed.
Die Herstellung der mechanischen Holzstoffe mit hoher Ausbeute erfolgt unter bekannten Verfahrensbedingungen, wobei die Hackschnitzel nach Vordämpfung und gleichmäßiger Durchfeuchtung dem Imprägnator zugeführt werden. Dort erfolgt beispielsweise erfindungsgemäß die Zugabe mindestens eines Dicarbonsäuredialkylesters und/oder eines oder mehrerer Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyethylenterephthalat- und/oder Polyoxyethylenterephthalat-Copolymerer separat oder zusammen mit Wasser und ggf. einer weiteren Imprägnierflüssigkeit. Unter Kompression werden die Hackschnitzel gleichmäßig imprägniert und nach 1 - 60 min, vorzugsweise 15 - 30 min dauernder oder kurzzeitiger, 1 - 10 min, vorzugsweise 1 - 5 min andauernder Vorwärmung auf 110 - 180 °C, vorzugsweise 140 - 170 °C der ersten Refinerstufe zugeführt, in der wiederum unter Druck zwischen den Mahlscheiben unter vorgegebenen Lastaufnahmebedingungen die Seperierung zu Einzelfasern und Defibrierung/Fibrilierung erfolgt. Der Refinerstoff wird dann nach Passieren der Mahlzone und Dampfabtrennung ggf. einer Refinernachmahlung in einer 2. Refinerstufe zugeführt. In dieser Stufe oder separat, z. B. in einem dampfbeheizten Stofflöser kann üblicherweise zusätzlich eine Behandlung mit Chemikalien, z. B. eine Latenzbeseitigung sowie die Bleiche des Holzstoffes vorgenommen werden. Die Zugabe der erfindungsgemäß zu verwendenden Mittel kann an beliebiger Stelle vor der eigentlichen mechanischen, unter Zerfaserung erfolgenden Erschließung des Holzstoffs bzw. der Pflanzenmaterialien erfolgen, beispielsweise bei der Holzschliffherstellung separat oder zusammen mit dem in die Schleifzone eingebrachten Wasser.The mechanical wood pulps are produced with a high yield under known process conditions, the wood chips being fed to the impregnator after pre-steaming and uniform wetting. There, for example, according to the invention, the addition of at least one dicarboxylic acid dialkyl ester and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyethylene terephthalate and / or polyoxyethylene terephthalate copolymers takes place separately or together with water and optionally one further impregnation liquid. With compression, the wood chips are impregnated evenly and after 1 - 60 min, preferably 15 - 30 min or brief, 1 - 10 min, preferably 1 - 5 min, preheating to 110 - 180 ° C, preferably 140 - 170 ° C of the first Refiner stage fed, in which the separation into individual fibers and defibrillation / fibrillation takes place again under pressure between the grinding disks under predetermined load-bearing conditions. After passing through the grinding zone and steam separation, the refiner material is then optionally fed to a refiner post-grinding in a second refiner stage. At this stage or separately, e.g. B. in a steam-heated pulper can usually additionally treatment with chemicals, for. B. a latency elimination and the bleaching of the wood pulp can be made. The agents to be used according to the invention can be added at any point before the actual mechanical pulping of the wood pulp or plant materials, for example in the manufacture of wood pulp separately or together with the water introduced into the grinding zone.
Durch den erfindungsgemäßen Zusatz der Dicarbonsäuredialkylester und/oder eines oder mehrerer Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyester- Polyether-, bevorzugt Polyethylenterephthalat- und/oder Polyoxyethylenterephthalat- Copolymerer wird nach der 1. Refinerstufe ein Holzstoff tnit erhöhter Helligkeit und Weiße erhalten. Der mechanische Holzstoff kann zusätzlich einer Bleiche unterworfen werden, wobei die Steigerung der Helligkeit und Weiße bei gleichbleibender Opazität ebenso wie die Festigkeiten der Fasern, insbesondere die Werte der Reißlänge, der Reißarbeit und Bruchlast ganz oder annähernd erhalten bleiben. Der Ligningehalt des Stoffes wird bei erfindungsgemäßer Verwendung der genannten Ester um ca. 1 Gew.% gesenkt. Bei der erfindungsgemäßen Verwendung der Mittel zusammen mit Pflanzenölderivaten, wie beispielsweise Rapsölmethylester, wird ein erhöhter Wert des Holzextraktes festgestellt.By adding dicarboxylic acid dialkyl esters and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyester-polyether, preferably polyethylene terephthalate and / or polyoxyethylene terephthalate copolymers according to the invention after the 1st refiner stage a wood pulp with increased brightness and whiteness. The mechanical wood pulp can also be subjected to bleaching, whereby the increase in brightness and whiteness with the same opacity as well as the strength of the fibers, in particular the values of the tearing length, the tearing work and breaking load, are wholly or approximately retained. The lignin content of the substance is reduced by approximately 1% by weight when the esters mentioned are used according to the invention. When the agents according to the invention are used together with vegetable oil derivatives, such as rapeseed oil methyl ester, an increased value of the wood extract is found.
Das erfindungsgemäße Verfahren kann auch in der Weise durchgeführt werden, daß unter Beibehaltung der bisher erreichbaren Helligkeitswerte und Weißgrade auf die zusätzliche Bleichung verzichtet wird oder in der Weise, daß die Bleiche unter deutlicher Einsparung der Chemikalienmenge vorgenommen wird. Auf diese Weise kann insbesondere eine nachträgliche Vergilbung der Faserstoffe durch den Zusatz von Alkalien vermieden werden. Weiterhin können die erfindungsgemäß zu verwendenden Dicarbonsäuredialkylester und/oder ein oder mehrere Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyethylenphthalat- und/oder Polyoxyethylenterephthalat-Copolymere als Mittel zur chemischen Behandlung von Holzhackschnitzel verwendet werden, aus denen nach den bekannten Verfahren Zellstoffe oder Holzwerkstoffplatten oder deren Vorprodukte hergestellt werden.The process according to the invention can also be carried out in such a way that the additional bleaching is dispensed with while maintaining the previously attainable brightness values and degrees of whiteness, or in such a way that the bleaching is carried out with a significant saving in the amount of chemicals. In this way, subsequent yellowing of the fiber materials by adding alkalis can be avoided. Furthermore, the dicarboxylic acid dialkyl esters to be used according to the invention and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyethylene phthalate and / or polyoxyethylene terephthalate copolymers can be used as agents for the chemical treatment of wood chips which are produced by the known methods pulp or wood-based panels or their preliminary products.
Die folgenden Beispiele belegen in ergänzender Weise die Erfindung:The following examples additionally demonstrate the invention:
Beispiel 1 - 3Example 1-3
Die Herstellung von TMP erfolgte in einer Anlage zur Erzeugung von Hochausbeutefaserstoffen mit folgenden Kenndaten: Durchsatzmengen 40 - 65 kg otro/hTMP was produced in a plant for the production of high-yield fiber materials with the following characteristics: Throughputs 40 - 65 kg otro / h
Volumen des Vorwärmers 110 dm3 (l i m3)Volume of the preheater 110 dm 3 (lim 3 )
Imprägnatorvolumen 15 dm3 (1,5 m3)Impregnator volume 15 dm 3 (1.5 m 3 )
1. Refinerstufe:1st refiner level:
- Antriebsleistung 160 kw- Drive power 160 kw
- Drehzahl 1800 - 3600 U min" - speed 1800 - 3600 rpm "
Mahlgarnitur-Durchmesser 300 mmGrinding set diameter 300 mm
2. Refinerstufe:2nd refiner level:
- Antriebsleistung 160 kw- Drive power 160 kw
- Drehzahl 1485 U min" - speed 1485 rpm "
Die Versuche wurden bei einer Refinerdrehzahl von 3000 U min' bei 143 °C und einem Druck von 0,35 bar durchgeführt, wobei der spezifische Energieeintrag zur Vergleichbarkeit der Stoffeigenschaften bei Zugabe der Mittel durch Veränderung des Mahlspaltes an den Nullpunkt angeglichen wurde, während die Leistung, die Drehzahl sowie die Temperatur- und Druckwerte und der Durchsatz konstant blieben.The experiments were conducted at a Refinerdrehzahl of 3000 U 'at 143 ° C and a pressure of 0.35 performed bar min was the specific energy input for comparison of material properties with addition of the means by changing the grinding gap aligned with the zero point, while the power , the speed as well as the temperature and pressure values and the throughput remained constant.
40 kg vorsortierte Hackschnitzel mit einem Feuchteanteil von mindestens 30 Gew.%, bezogen auf otro Holzsubstanz, wurden jeweils im Hackschnitzeltrichter durch Vordämpfen entlüftet, gleichmäßig durchgefeuchtet und nach einer Verweilzeit von ca. 15 min über Förderschnecken zum Imprägnator gebracht, wobei die Hackschnitzel unter Kompression ausgepresst und unter kontinuierlicher Zudosierung der Imprägnierflüssigkeit aus einem Vorlagebehälter auf eine gleichmäßige Imprägnierung eingestellt. Als Imprägniermittel wurden Di-n-butyladipat, Glycerintrioleat sowie Glycerintrioleat in Kombination mit Rapsölmethylester im Mengenverhältnis 1 : 1, verwendet, die im Zustand einer wässrigen Emulsion bestehend aus 14 Gew.% des Mittels und 8 Gew.% eines nichtionogenen Emulgiermittels auf der Basis eines ethoxylierten Fettalkohols bzw. eines hochethoxyethylierten Pflanzenöls eingesetzt. Die verwendete Menge betrug jeweils 2,8 g/kg Hackschnitzel. Im Vorwärmer wurden sie kurzfristig während ca. 20 min einer Weiterbehandlung bei Temperaturen zwischen 110 und 160 °C ausgesetzt und danach über 2 Förderschnecken der 1. Refinerstufe vom Typ CD 300 zugeführt. Der entstandene Refinersto ff wurde nach Verlassen der Mahlzone zu einem Zyklon geblasen, wo die Trennung von Dampfund Faserstoff erfolgte. Eine Teilmenge des erzeugten TMP wurde bei einer Stoffdichte von 10 Gew.%, einer Bleiche (Beutelbleiche) unter Verwendung von 1 ,8 % Wasserglas, 0,5 % Komplexbildner, 1,8 % NaOH und 3,8 % H2O2 (die Gewichtsprozentangaben beziehen sich jeweils auf die eingesetzte Holzstoffmenge) unterworfen. Der gebleichte Stoff wurde gewaschen und mit SO auf einen pH-Wert im Bereich von 8,0 - 8,5 abgesäuert.40 kg of pre-sorted wood chips with a moisture content of at least 30% by weight, based on otro wood substance, were deaerated in the wood chip funnel by pre-steaming, moistened evenly and brought to the impregnator by conveyor screws after a dwell time of approx. 15 min, the wood chips being pressed out under compression and adjusted to a uniform impregnation with continuous addition of the impregnation liquid from a storage container. Di-n-butyl adipate, glycerol trioleate and glycerol trioleate in combination with rapeseed oil methyl ester in a ratio of 1: 1 were used as impregnating agents, which in the state of an aqueous emulsion consisted of 14% by weight of the agent and 8% by weight of a nonionic emulsifier based on ethoxylated fatty alcohol or a highly ethoxyethylated vegetable oil. The amount used was 2.8 g / kg wood chips each. In the preheater, they were briefly subjected to further treatment at temperatures between 110 and 160 ° C for about 20 minutes and then fed to the first refiner stage of the CD 300 type via 2 screw conveyors. The resulting one After leaving the grinding zone, refiner fabric was blown into a cyclone, where the steam and fiber material were separated. A partial amount of the TMP produced was at a consistency of 10% by weight, a bleach (bag bleach) using 1.8% water glass, 0.5% complexing agent, 1.8% NaOH and 3.8% H 2 O 2 ( the percentages by weight relate in each case to the amount of wood pulp used). The bleached fabric was washed and acidified to pH 8.0-8.5 with SO.
Die Beurteilung der optischen Eigenschaften erfolgte durch Blattbildung nach Rapid-Köthen. Hierzu wurden beispielsweise 500 g TMP (ca. 20 Gew.% Trockensubstanz) in 10 1 Leitungswasser im Pulper aufgeschlagen. Pro Blatt betrug die Stoffeinwaage 375 g.The optical properties were assessed by Rapid-Koethen's sheet formation. For this purpose, for example, 500 g of TMP (approx. 20% by weight of dry substance) were whipped in 10 1 of tap water in the pulper. The amount of fabric weighed 375 g per sheet.
Tabelle 1 enthält die Herstellungsdaten und die Daten des erzeugten TMP wobei die Abkürzungen bedeuten:Table 1 contains the manufacturing data and the data of the TMP generated, the abbreviations meaning:
Wspez: spez. EnergieentragWspec: spec. Energy
Mahl: MahlgradMeal: degree of grinding
EWZ: EntwässerungszeitEWZ: drainage time
TP2: die Angabe der mittleren FaserlaugeTP2: the indication of the medium fiber liquor
(ausgehend von 3 mm entsprechend 100 %) R: Splittergehalt(starting from 3 mm corresponding to 100%) R: splinter content
Tabelle 1Table 1
Tabelle 2 enthält die Daten der optischen Eigenschaften des ungebleichten und gebleichten TMP.Table 2 contains the optical property data of the unbleached and bleached TMP.
Tabelle 2Table 2
Die Daten der Beispiele zeigen, daß bei Verwendung der erfindungsgemäßen Mittel die Helligkeit und die Weiße um 3 - 4 Punkte ansteigen. Die Steigerung gegenüber dem Vergleichsmuster bleibt, ebenso wie die Opazität, erhalten, wenn zusätzlich eine Bleiche des TMP durchgeführt wird.The data of the examples show that when the agents according to the invention are used, the brightness and whiteness increase by 3-4 points. The increase over the comparison sample, as well as the opacity, is retained if bleaching of the TMP is also carried out.
Nach der vorgeschriebenen Verfahrensweise wurden weitere Proben von TMP hergestellt. Hierbei wurden verwendet:Further samples of TMP were produced according to the prescribed procedure. Here were used:
in Beispiel 4 Di-n-butyladipat Menge 5,6 kg/t 5 Di-n-butyladipat und Rapsölmethylester (1 : 1) 5,6 kg/t 6 Glycerintrioleat 5,6 kg/t 7 Sorbitanmonooleat 5,6 kg/t 8 Polyester/Polyether-Copolymer 5,6 kg/t (Schmutzlöse-PES-ET 1/30 Hüls AG) 9 Glycerintrioleat 2,8 kg/tin Example 4, di-n-butyl adipate amount 5.6 kg / t 5 di-n-butyl adipate and rapeseed oil methyl ester (1: 1) 5.6 kg / t 6 glycerol trioleate 5.6 kg / t 7 sorbitan monooleate 5.6 kg / t 8 polyester / polyether copolymer 5.6 kg / t (Soil dissolver-PES-ET 1/30 Hüls AG) 9 glycerol trioleate 2.8 kg / t
10 Glycerintrioleat 1,4 kg/t10 glycerol trioleate 1.4 kg / t
Die Beurteilung der TMP-Werte erfolgte widerum nach Blattbildung in der angegebenen Weise. Die Daten sind in der Tabelle 3 zusammengefaßt.The TMP values were again assessed after leaf formation in the manner indicated. The data are summarized in Table 3.
Tabelle 3Table 3
Weiterhin wurde jeweils eine Testmenge des nach den Beispielen 4 - 10 erhaltenen TMP, wie oben angegeben, einer Bleiche unterworfen. Danach wurden 300 g des Stoffs von ca. 20 % TS mit Leitungswasser auf 10 % TS (Trockensubstanz) verdünnt und zur Blattbildung 30 s mit einem Mixstab gerührt. Die Daten sind in Tabelle 4 zusammengefaßt. In addition, a test amount of the TMP obtained according to Examples 4-10, as stated above, was subjected to bleaching. Then 300 g of the substance were diluted from approx. 20% TS with tap water to 10% TS (dry substance) and stirred for 30 s with a mixing stick to form the leaf. The data are summarized in Table 4.
Tabelle 4Table 4
Die Werte der Tabellen 3 und 4 weisen aus, daß eine deutliche Verbesserung des Weißgrades, der Helligkeit, des Farbtons und der Sättigung erreicht werden. The values in Tables 3 and 4 show that a marked improvement in the degree of whiteness, brightness, hue and saturation is achieved.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Faserstoffen, dadurch gekennzeichnet, daß bei der Vorbehandlung zum Imprägnieren der zerkleinerten Holzrohstoffe und/oder Pflanzenmaterialien mindestens ein Dicarbonsäuredialkylester und/oder ein oder mehrere Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyester- Polyether- Copolymere, bevorzugt ein Polyethylenterephthalat- und/oder Polyoxyethylenterephthalat-Copolymeres, zugesetzt Werden.1. A process for the production of fibrous materials, characterized in that in the pretreatment for impregnating the comminuted wood raw materials and / or plant materials at least one dialkyl dicarboxylic acid and / or one or more fatty acid polyol mono, di, tri and / or higher polyesters and / or polyester-polyether copolymers, preferably a polyethylene terephthalate and / or polyoxyethylene terephthalate copolymer, can be added.
2. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß mindestens ein Dicarbonsäuredialkylester und/oder ein oder mehrere Fettsäurepolyol-mono, -di, -tri- und/oder höhere Polyester und/oder Polyester-Polyether-Copolymere, bevorzugt Polyethylenterephthalat- und/oder Polyoxyethylenterephthalat-Copolymere in einer Menge von 0,005 - 5,0 Gew.% vorzugsweise 0,01 - 2,0 Gew.% und besonders bevorzugt 0,01 - 1,0 Gew.% bezogen auf die eingesetzte Holz- oder Pflanzenmenge zugesetzt werden.2. The method according to claim 1, characterized in that at least one dicarboxylic acid dialkyl ester and / or one or more fatty acid polyol mono, -di, -tri- and / or higher polyester and / or polyester-polyether copolymers, preferably polyethylene terephthalate and / or polyoxyethylene terephthalate Copolymers in an amount of 0.005-5.0% by weight, preferably 0.01-2.0% by weight and particularly preferably 0.01-1.0% by weight, based on the amount of wood or plants used.
3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß der Faserstoff ein mechanischer Holzstoff, vorzugsweise Thermo-Mechanical Pulp, Chemi-Thermo- Mechanical Pulp oder Holzschliff ist.3. Process according to claims 1 and 2, characterized in that the fibrous material is a mechanical pulp, preferably thermo-mechanical pulp, chemi-thermo-mechanical pulp or wood pulp.
4. Verfahren nach den Ansprüchen 1 - 2 dadurch gekennzeichnet, daß der Faserstoff ein Langfaserrohstoff aus Schilf, Rohr, Teilen von Ölpalmen und anderen C4-Pflanzen ist.4. The method according to claims 1-2, characterized in that the fibrous material is a long fiber raw material from reeds, reed, parts of oil palms and other C4 plants.
5. Verfahren nach den Ansprüchen 1 bis 4 dadurch gekennzeichnet, daß als Dicarbonsäuredialkylester die Adipinsäureester von Cl - C6 n- und/oder iso-Alkanolen zugesetzt werden.5. Process according to claims 1 to 4, characterized in that the adipic acid esters of Cl - C6 n- and / or iso-alkanols are added as dicarboxylic acid dialkyl esters.
6. Verfahren nach den Ansprüchen 1 - 4 dadurch gekennzeichnet, daß als Fettsäurepolyol- mono, -di, -tri- und/oder höhere Polyester die Ester von gesättigten und/oder ungesättigten C8 - 18 Fettsäuren mit mehrwertigen Alkanolen, bevorzugt Glykol, Trimethylolpropan, Glycerin, Sorbitan und Sorbitol, insbesondere Sorbitanmonostearat und/oder Glycerintrioleat, zugesetzt werden. 6. Process according to claims 1-4, characterized in that the fatty acid polyol mono, di, tri and / or higher polyesters are the esters of saturated and / or unsaturated C8-18 fatty acids with polyhydric alkanols, preferably glycol, trimethylolpropane, Glycerin, sorbitan and sorbitol, in particular sorbitan monostearate and / or glycerol trioleate, can be added.
7. Verfahren nach den Ansprüchen 1 - 7 dadurch gekennzeichnet, daß die verwendeten Dicarbonsäure, Dialkylester und oder Fettsäurepolyol- mono,- di,- tri- und/oder höhere Polyester und/oder Polyester- Polyether-Copolymere, bevorzugt Polyethylenterephtalat - und/oder Polyoxiethylenterephtalat-Copolymere in Form einer wässrigen Emulsion zugesetzt werden.7. The method according to claims 1-7, characterized in that the dicarboxylic acid, dialkyl ester and or fatty acid polyol mono, - di, - tri- and / or higher polyester and / or polyester-polyether copolymers, preferably polyethylene terephthalate - and / or Polyoxyethylene terephthalate copolymers can be added in the form of an aqueous emulsion.
8. Verfahren nach den Ansprüchen 1 - 7 dadurch gekennzeichnet, daß die Dicarbonsäuredialkylester und/oder Fettsäurepolyol- mono-, di-, tri,- und/oder höhere Polyester und/oder Polyester- Polyether-Copolymere, bevorzugt Polyethylenterephtalat und/oder Polyoxyethylenterephtalat- Copolymere zusammen mit einem oder mehreren Derivaten pflanzlicher oder tierischer Öle in einer Menge von 0,001 bis 5,000 Gew.%, vorzugsweise 0,01 - 2,00 Gew.%, besonders bevorzugt 0,01 - 1,00 Gew.%» bezogen auf die eingesetzte Holz- bzw. Pflanzenmenge verwendet werden.8. The method according to claims 1-7, characterized in that the dicarboxylic acid dialkyl ester and / or fatty acid polyol mono-, di-, tri, - and / or higher polyester and / or polyester-polyether copolymers, preferably polyethylene terephthalate and / or polyoxyethylene terephthalate- Copolymers together with one or more derivatives of vegetable or animal oils in an amount of 0.001 to 5.000% by weight, preferably 0.01 to 2.00% by weight, particularly preferably 0.01 to 1.00% by weight, based on the the amount of wood or plants used.
9. Verfahren nach Anspruch 8 dadurch gekennzeichnet, daß als Derivate von pflanzlichen oder tierischen Ölen Rapsölmethylester, Palmölmethylester, Sojaölmethylester, Rübölmethylester und/oder Talgfettmethylester und/oder synthetische Esteröle zugesetzt werden.9. The method according to claim 8, characterized in that rapeseed oil methyl ester, palm oil methyl ester, soybean oil methyl ester, rape oil methyl ester and / or tallow fat methyl ester and / or synthetic ester oils are added as derivatives of vegetable or animal oils.
10. Verfahren nach den Ansprüchen 1 - 9 dadurch gekennzeichnet, daß die ggf. nachfolgende Bleiche unter Verwendung reduzierter Chemikalienmengen durchgeführt wird.10. The method according to claims 1-9, characterized in that the subsequent bleaching is carried out using reduced amounts of chemicals.
11. Verfahren nach den Ansprüchen 1 - 9 dadurch gekennzeichnet, daß auf eine zusätzliche Bleiche verzichtet wird.11. The method according to claims 1-9, characterized in that an additional bleaching is dispensed with.
12. Verwendung mindestens eines Dicarbonsäuredialkylesters und/oder eines oder mehrerer Fettsäurepolyol-mono, -di, -tri- und/oder höherer Polyester und/oder eines oder mehrerer Polyester- Polyether-Copolymere, bevorzugt eines Polyethylenterephthalat- und/oder Polyoxyethylenterephthalat-Copolymeren, bei der Herstellung von Zellstoff, Papier oder Holzwerkstoffplatten. 12. Use of at least one dicarboxylic acid dialkyl ester and / or one or more fatty acid polyol mono, di, tri and / or higher polyester and / or one or more polyester-polyether copolymers, preferably a polyethylene terephthalate and / or polyoxyethylene terephthalate copolymer, in the manufacture of cellulose, paper or wood-based panels.
EP98904108A 1997-02-04 1998-01-21 Process for producing fibrous materials with improved properties Expired - Lifetime EP0961851B1 (en)

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PCT/EP1998/000304 WO1998033970A1 (en) 1997-02-04 1998-01-21 Process for producing fibrous materials with improved properties

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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7809642B1 (en) 1998-06-22 2010-10-05 Jpmorgan Chase Bank, N.A. Debit purchasing of stored value card for use by and/or delivery to others
US6615189B1 (en) 1998-06-22 2003-09-02 Bank One, Delaware, National Association Debit purchasing of stored value card for use by and/or delivery to others
US7660763B1 (en) 1998-11-17 2010-02-09 Jpmorgan Chase Bank, N.A. Customer activated multi-value (CAM) card
JP2003524220A (en) 1998-12-23 2003-08-12 ジェイピーモルガン・チェース・バンク System and method for integrating trading activities including creation, processing and tracking of trading documents
US8793160B2 (en) 1999-12-07 2014-07-29 Steve Sorem System and method for processing transactions
DE19959826A1 (en) * 1999-12-10 2001-06-28 Stockhausen Chem Fab Gmbh Process for reducing and / or avoiding deposits of wood constituents
US7831467B1 (en) * 2000-10-17 2010-11-09 Jpmorgan Chase Bank, N.A. Method and system for retaining customer loyalty
AU2002224482A1 (en) 2000-11-06 2002-05-15 First Usa Bank, N.A. System and method for selectable funding of electronic transactions
US20040143553A1 (en) * 2000-12-01 2004-07-22 Torget John W. System and method for remotely generating instruments
US8805739B2 (en) * 2001-01-30 2014-08-12 Jpmorgan Chase Bank, National Association System and method for electronic bill pay and presentment
WO2003010701A1 (en) 2001-07-24 2003-02-06 First Usa Bank, N.A. Multiple account card and transaction routing
US8020754B2 (en) 2001-08-13 2011-09-20 Jpmorgan Chase Bank, N.A. System and method for funding a collective account by use of an electronic tag
US20040210498A1 (en) 2002-03-29 2004-10-21 Bank One, National Association Method and system for performing purchase and other transactions using tokens with multiple chips
AU2003230751A1 (en) 2002-03-29 2003-10-13 Bank One, Delaware, N.A. System and process for performing purchase transaction using tokens
US7809595B2 (en) 2002-09-17 2010-10-05 Jpmorgan Chase Bank, Na System and method for managing risks associated with outside service providers
US20040122736A1 (en) 2002-10-11 2004-06-24 Bank One, Delaware, N.A. System and method for granting promotional rewards to credit account holders
US7015274B2 (en) * 2003-05-02 2006-03-21 E. I. Du Pont De Nemours And Company Polymer precursor dispersion containing a micropulp and method of making the dispersion
US8306907B2 (en) 2003-05-30 2012-11-06 Jpmorgan Chase Bank N.A. System and method for offering risk-based interest rates in a credit instrument
US8175908B1 (en) 2003-09-04 2012-05-08 Jpmorgan Chase Bank, N.A. Systems and methods for constructing and utilizing a merchant database derived from customer purchase transactions data
US7401731B1 (en) 2005-05-27 2008-07-22 Jpmorgan Chase Bank, Na Method and system for implementing a card product with multiple customized relationships
US7822682B2 (en) 2005-06-08 2010-10-26 Jpmorgan Chase Bank, N.A. System and method for enhancing supply chain transactions
US8622308B1 (en) 2007-12-31 2014-01-07 Jpmorgan Chase Bank, N.A. System and method for processing transactions using a multi-account transactions device
US8595065B2 (en) * 2008-10-24 2013-11-26 Cardlytics, Inc. Offer placement system and methods for targeted marketing offer delivery system
EP2193899B1 (en) * 2008-12-05 2017-10-11 SWISS KRONO Tec AG Method for manufacturing wooden materials made of hackled products containing lignocellulose and such wooden materials
WO2013177487A2 (en) * 2012-05-25 2013-11-28 Biopulping International, Inc. Method of producing pulp using oxalic acid
WO2015036655A1 (en) * 2013-09-12 2015-03-19 Kemira Oyj Impregnation system and its use
US9058626B1 (en) 2013-11-13 2015-06-16 Jpmorgan Chase Bank, N.A. System and method for financial services device usage
EP3059056A1 (en) * 2015-02-23 2016-08-24 Basf Se Method for producing wood fibres and wood fibre boards

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE252322C (en) *
FR454137A (en) * 1913-02-10 1913-06-26 Burdett Loomis Method and apparatus for treating wood and fibrous materials in general
FR867537A (en) * 1940-02-13 1941-11-10 Improvements to a process for treating cellulosic fibers for papermaking; treated cellulosic fibers and paper made from said fibers
GB1069434A (en) * 1963-03-06 1967-05-17 Ici Ltd Non-woven bonded fibrous fabrics
US4013505A (en) * 1972-03-09 1977-03-22 Vyzkumny Ustav Papieru A Celulosy Method of deinking printed wastepapers
US4343858A (en) * 1981-04-17 1982-08-10 Champion International Corporation Pigmented coated paperboard
US5127993A (en) * 1990-01-10 1992-07-07 Betz Paperchem, Inc. Method of enhancing green liquor semi-chemical pulp production
DE4103572C2 (en) * 1991-02-06 1995-11-23 Organocell Ges Fuer Zellstoff Process for delignifying plant fiber material
JPH0672382B2 (en) * 1991-03-04 1994-09-14 株式会社日新化学研究所 Deinking agent for recycled waste paper
DE4127719A1 (en) * 1991-08-22 1993-02-25 Basf Ag A DECISIVE FOR THE PAPER INDUSTRY BASED ON OIL-IN-WATER EMULSIONS
US5316623A (en) * 1991-12-09 1994-05-31 Hercules Incorporated Absorbance and permanent wet-strength in tissue and toweling paper
IT1258844B (en) * 1992-01-31 1996-02-29 Ausimont Spa PROCEDURE FOR THE DELIGNIFICATION OF ROUGH CELLULOSE
US5609722A (en) * 1992-04-23 1997-03-11 Henkel Corporation Deinking wastepaper using reaction products of epoxidized C10 -C22
US5501769A (en) * 1992-06-09 1996-03-26 Chemstone, Inc. Pulping wood using fatty acid esters of polyoxyalkalene glycols to enhance pulping uniformity and pulp yield
US5298120A (en) * 1992-06-09 1994-03-29 Michael Blackstone Composition for enhancing the pulping of wood chips
PL309191A1 (en) * 1992-11-27 1995-09-18 Eka Nobel Ab Method delignifying a lignocellulose containing pulp
MX9307413A (en) * 1992-11-27 1994-07-29 Eka Nobel Ab PROCESS FOR WHITENING PULP CONTAINING LIGNOCELLULOSE.
US5705383A (en) * 1993-03-19 1998-01-06 Clariant Finance (Bvi) Limited Pitch and lignin degradation with white rot fungi
DE59409297D1 (en) * 1993-06-16 2000-05-25 Call Hans Peter MULTI-COMPONENT BLEACHING SYSTEM
DE4320453A1 (en) * 1993-06-21 1994-12-22 Henkel Kgaa Process for controlling the settling of resins from pulp and / or pulp suspensions
DE4327774A1 (en) * 1993-08-18 1995-02-23 Fraunhofer Ges Forschung Process for the production of medium density fibreboard (MDF)
FI942341A (en) * 1994-05-20 1995-11-21 Ahlstroem Oy Process for bleaching mechanical, chemical mechanical and / or recycled pulp with peroxide
EP0717143A1 (en) * 1994-12-16 1996-06-19 Lignozym GmbH Multicomponents system for modifying decomposing or bleaching of lignin or materials containing it or similar components and the way to use it
DE19515272A1 (en) * 1995-04-26 1996-10-31 Henkel Kgaa Controlling pptn. of resins from prim. cellulose fibre suspensions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9833970A1 *

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NO993554L (en) 1999-07-20
DE19704054C2 (en) 2000-08-10
ATE230814T1 (en) 2003-01-15
US6344108B1 (en) 2002-02-05
EP0961851B1 (en) 2003-01-08
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