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WO1998004775A1 - Use of complexing agents for cellulose and wood bleaching, paper production and used paper deinking - Google Patents

Use of complexing agents for cellulose and wood bleaching, paper production and used paper deinking Download PDF

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Publication number
WO1998004775A1
WO1998004775A1 PCT/EP1997/003741 EP9703741W WO9804775A1 WO 1998004775 A1 WO1998004775 A1 WO 1998004775A1 EP 9703741 W EP9703741 W EP 9703741W WO 9804775 A1 WO9804775 A1 WO 9804775A1
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WO
WIPO (PCT)
Prior art keywords
paper
complexing agents
acid
bleaching
deinking
Prior art date
Application number
PCT/EP1997/003741
Other languages
German (de)
French (fr)
Inventor
Birgit Potthoff-Karl
Primoz Lorencak
Original Assignee
Basf Aktiengesellschaft
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Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU36234/97A priority Critical patent/AU3623497A/en
Publication of WO1998004775A1 publication Critical patent/WO1998004775A1/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
    • D21C3/22—Other features of pulping processes
    • 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
    • D21C5/025—De-inking
    • D21C5/027—Chemicals therefor
    • 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
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents
    • 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

Definitions

  • the invention relates to the use of ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, hydroxypropylenediaminodisuccinic acid, its alkali metal or ammonium salts and mixtures of the compounds mentioned as complexing agents for alkaline earth metal and heavy metal ions in pulp and pulp bleaching, waste paper production and deinking.
  • Ethylene diamine disuccinic acid, 2-hydroxypropylene diaindisuccinic acid and ethylene diamine di glutaric acid and their alkali metal, alkaline earth metal and ammonium salts are known. They are used, for example, as complexing agents in detergents or in textile washing to reduce corrosion on washing machines, cf. WO-A-94/20599, WO-A-95/29220, WO-A-94/11099 and WO-A-94/03572.
  • WO-A-95/25159 discloses the use of manganese salts of ethylenediaminedisuccinic acid as a bleaching catalyst in detergents which contain conventional surfactants, perborate or percarbonate and a bleach activator.
  • the invention has for its object to provide new complexing agents for the paper industry, the pulp industry and deinking of printed waste paper.
  • the object is achieved with the use of ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, hydroxypropylenediaminedisuccinic acid, their alkali metal or ammonium salts and mixtures of the compounds mentioned as complexing agents for alkaline earth metal and heavy metal ions in the Pulp and wood pulp bleaching, paper production and deinking of waste paper.
  • the biodegradable S, S enantiomer of ethylenediaminedisuccinic acid is obtained by reacting 2 mol sodium acetate with
  • 1,2-dibromoethane 1 mol of 1,2-dibromoethane can be prepared.
  • the racemate of ethylenediamine disuccinic acid arises, for example, from the reaction of
  • Ethylene diaminediglutaric acid can be obtained, for example, by reacting 1,2-dibromoethane with sodium glutamate in a molar ratio of 1: 2.
  • 2-Hydroxypropylenediamine disuccinic acid can be obtained by reacting 2-hydroxy-1,3-dibro propane with sodium aspartate in a molar ratio of 1: 2.
  • a detailed description of the production of ethylenediamine disuccinic acid is given, for example, in US-A-3 158 635. At least 50% of the compounds described above are biodegradable.
  • the complexing agents described above are used in pulp bleaching, pulp production, pulp bleaching and deinking of printed waste paper.
  • the technical raw materials and auxiliary materials used in paper production mostly contain traces of heavy metals, especially iron and manganese ions.
  • the complexing agents to be used according to the invention can, for example, already be used in the mechanical pulping of wood in the so-called integrated paper factories in which fibrous material obtained from wood is processed into paper and paper products.
  • Known methods for mechanical wood pulping include conventional stone grinding GMP (Groundwood Mechanical-Pulp), refiner wood pulp RMP (Refiner-Mechanical-Pulp), thermomechanical wood pulp TMP (Thermo-Mechanical Pulp) and pressure grinding PGW (Pressure Groundwood).
  • Refiner wood pulp and thermomechanical wood pulp can optionally be subjected to a chemical pretreatment. They are then called CRMP or CTMP. You also know the so-called brown cut.
  • the above-mentioned types of wood pulp contain different splinter contents, long fiber, short fiber and fine material.
  • TMP and CTMP materials contain hardly any splinters and can be processed into papers with significantly better strengths than the other wood materials. You can bleach both fine sanding, normal sanding and coarse sanding.
  • iron III ions react with constituents of the wood to form dark-colored compounds.
  • complexing agents In the manufacture of the paper raw materials, in particular in the pulp bleaching process, the paper raw material can already be brightened, so that after the bleaching is finished, the whiteness is about 2-3 points higher than without the use of complexing agents.
  • an increase in whiteness is achieved in oxidative, reductive or combined bleaching compared to substances which do not contain any complexing agents.
  • Processes for reductive pulp bleaching with dithionite and for oxidative bleaching with hydrogen peroxide are known, cf. H. Schroter, Die Holzschliffbleiche, Günther-Staib-Verlag, Biberach an der Riß, 1976.
  • the compounds to be used according to the invention are also used as de-complexing agents in deinking of printed waste paper.
  • the printed waste paper is opened and treated with a combination of peroxide, sodium hydroxide, water glass, dispersant and collector.
  • peroxide sodium hydroxide
  • water glass water glass
  • dispersant and collector a combination of peroxide, sodium hydroxide, water glass, dispersant and collector.
  • the use of the compounds to be used according to the invention in papermaking prevents or reduces the negative influence of water hardness in papermaking. Due to the ever increasing closure of the water cycle in paper machines, there is a constant accumulation of hardness builders. This can lead to a precipitation of carbonates and silicates, which can directly impair the paper properties, such as strength, absorbency, dyeability and the dust behavior of the paper. The hardening agents can also adversely affect the effectiveness of auxiliaries and the properties of dyes.
  • the use of the complexing agents to be used according to the invention in papermaking also has the advantage that precipitations of hardness agents with resin glue or cellulose resin and precipitation products of aluminum sulfate are suppressed or dissolved, so that laying of the wet felts of the paper machines can be largely prevented. This keeps the felts drained for a longer period of time.
  • ethylenediaminedisuccinic acid or the mono-, di-, tri- or tetrasodium salts of ethylenediaminedisuccinic acid.
  • Based on dry fiber material for example 0.02 to 0.5, preferably 0.1 to 0.3% by weight of a complexing agent is used.
  • 100 g of a wood pulp suspension with a consistency of 4% are filled into a polyethylene bag and mixed with 1% sodium dithionite and 0.06% ethylene-N, N'-diaminedisuccinic acid in the form of the tetrasodium salt, based on dry wood pulp.
  • the pH of the groundwood slurry is 6.
  • the bag is then closed and the contents are homogenized by intensive kneading. After mixing the contents, the bag is placed in a water bath at a temperature of 60 ° C for 1 hour.
  • Example 1 was repeated with the only exception that the bleaching was carried out in the absence of a complexing agent.
  • the whiteness of sheets of paper made from the bleached wood pulp slurry was 69.8%.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Abstract

Ethylene diamine disuccinic acid, ethylene diamine diglutaric acid, hydroxypropylene diamine disuccinic acid, their alkaline metal salts or ammonium salts and mixtures of said compounds are used as complexing agents for alkaline earth metal ions and heavy metal ions during cellulose and wood bleaching, paper production and used paper deinking.

Description

VERWENDUNG VON KOMPLEXBILDNER FÜR DIE ZELLSTOFF- UND HOLZSTOFFBLEICHE, DIE PAPIERHERSTELLUNG SOWIE DAS DEINKING VON ALTPAPIERUSE OF COMPLEX IMAGERS FOR THE FABRIC AND WOOD FABRICS, PAPER PRODUCTION AND THE DEINKING OF WASTE PAPER
Beschreibungdescription
Die Erfindung betrifft die Verwendung von Ethylendiamindibern- steinsäure, Ethylendiamindiglutarsäure, Hydroxypropylendiamin- dibernsteinsaure, deren Alkalimetall- oder Ammoniumsalzen und Mischungen der genannten Verbindungen als Komplexbildner für Erdalkalimetall- und Schwermetallionen bei der Zellstoff- und Holz- stoffbleiche, der Papierherstellung und dem Deinking von Altpapier.The invention relates to the use of ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, hydroxypropylenediaminodisuccinic acid, its alkali metal or ammonium salts and mixtures of the compounds mentioned as complexing agents for alkaline earth metal and heavy metal ions in pulp and pulp bleaching, waste paper production and deinking.
Sowohl bei der oxidativen als auch bei der reduktiven Bleiche von Faserstoffen, die für die Herstellung von Papier eingesetzt werden, insbesondere von Holzschliff, ist es üblich, Komplexbildner zu verwenden. Ihre wesentliche Aufgabe besteht darin, störende Metallionen zu komplexieren. Komplexbildner, die u.a. auch in der Papierindustrie angewendet werden, sind beispielsweise Nitrilo- triessigsäure, Ethylendiamintetraessigsäure und Ethylendiamin- tetramethylenphosphonsäure, vgl. Technische Information Papierherstellung "Die Trilon® Marken der BASF für die Papierindustrie", Ausgabe April 1996.Both in the oxidative and in the reductive bleaching of fibrous materials which are used for the production of paper, in particular wood pulp, it is common to use complexing agents. Their main task is to complex interfering metal ions. Complexing agents which are also used in the paper industry, for example, are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediaminetetramethylenephosphonic acid, cf. Technical information paper production "The Trilon ® brands of BASF for the paper industry", edition April 1996.
Ethylendiamindibernsteinsäure, 2 -Hydroxypropylendia indibern- steinsäure und Ethylendiamindiglutarsäure sowie deren Alkalimetall-, Erdalkalimetall- und Ammoniumsalze sind bekannt. Sie werden beispielsweise als Komplexbildner in Waschmitteln oder bei der Textilwäsche zur Verringerung der Korrosion an Waschmaschinen verwendet, vgl. WO-A-94/20599 , WO-A-95/29220, WO-A-94/11099 und WO-A-94/03572. Aus der WO-A-95/25159 ist die Verwendung von Mangansalzen von Ethylendiamindibernsteinsäure als Bleich- katalysator in Waschmitteln bekannt, die übliche Tenside, Perbo- rat oder Percarbonat und einen Bleichaktivator enthalten.Ethylene diamine disuccinic acid, 2-hydroxypropylene diaindisuccinic acid and ethylene diamine di glutaric acid and their alkali metal, alkaline earth metal and ammonium salts are known. They are used, for example, as complexing agents in detergents or in textile washing to reduce corrosion on washing machines, cf. WO-A-94/20599, WO-A-95/29220, WO-A-94/11099 and WO-A-94/03572. WO-A-95/25159 discloses the use of manganese salts of ethylenediaminedisuccinic acid as a bleaching catalyst in detergents which contain conventional surfactants, perborate or percarbonate and a bleach activator.
Der Erfindung liegt die Aufgabe zugrunde, neue Komplexbildner für die Papierindustrie, die Zellstoffindustrie und das Deinking von bedrucktem Altpapier zur Verfügung zu stellen.The invention has for its object to provide new complexing agents for the paper industry, the pulp industry and deinking of printed waste paper.
Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von Ethylendiamindibernsteinsäure, Ethylendiamindiglutarsäure, Hydro- xypropylendiamindibernsteinsäure, deren Alkalimetall- oder Ammoniumsalzen und Mischungen der genannten Verbindungen als Ko - plexbildner für Erdalkalimetall- und Schwermetallionen bei der Zellstoff- und Holzstoffbleiche, der Papierherstellung und dem Deinking von Altpapier.The object is achieved with the use of ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, hydroxypropylenediaminedisuccinic acid, their alkali metal or ammonium salts and mixtures of the compounds mentioned as complexing agents for alkaline earth metal and heavy metal ions in the Pulp and wood pulp bleaching, paper production and deinking of waste paper.
Das biologisch abbaubare S, S-Enantiomer von Ethylendiamindi - bernsteinsäure ist durch Umsetzung von 2 mol Natriumacetat mitThe biodegradable S, S enantiomer of ethylenediaminedisuccinic acid is obtained by reacting 2 mol sodium acetate with
1 mol 1, 2 -Dibromethan herstellbar. Das Racemat von Ethylendiamindibernsteinsäure entsteht beispielsweise bei der Umsetzung von1 mol of 1,2-dibromoethane can be prepared. The racemate of ethylenediamine disuccinic acid arises, for example, from the reaction of
2 mol Maleinsäureanhydrid mit 1 mol Ethylendiamin. Die Herstellung dieser Verbindungen ist beispielsweise in der WO-A-95/29220 beschrieben. Ethylendiamindiglutarsäure ist beispielsweise durch Umsetzung von 1, 2 -Dibromethan mit Natriumglutamat im Mol- verhältnis 1:2 erhältlich. 2 -Hydroxypropylendiamindibernstein- säure ist durch Umsetzung von 2 -Hydroxy-1, 3 -dibro propan mit Na- triumaspartat im Molverhältnis 1:2 erhältlich. Eine detaillierte Beschreibung zur Herstellung von Ethylendiamindibernsteinsäure wird beispielsweise in US-A-3 158 635 gegeben. Die oben beschriebenen Verbindungen sind etwa zu mindestens 50 % biologisch abbau- bar .2 mol maleic anhydride with 1 mol ethylenediamine. The preparation of these compounds is described, for example, in WO-A-95/29220. Ethylene diaminediglutaric acid can be obtained, for example, by reacting 1,2-dibromoethane with sodium glutamate in a molar ratio of 1: 2. 2-Hydroxypropylenediamine disuccinic acid can be obtained by reacting 2-hydroxy-1,3-dibro propane with sodium aspartate in a molar ratio of 1: 2. A detailed description of the production of ethylenediamine disuccinic acid is given, for example, in US-A-3 158 635. At least 50% of the compounds described above are biodegradable.
Die oben beschriebenen Komplexbildner werden bei der Zellstoff - bleiche, der Zellstoffherstellung, der Holzstoffbleiche und dem Deinking von bedrucktem Altpapier verwendet. Die bei der Papier - herstellung eingesetzten technischen Rohstoffe und Hilfsstoffe enthalten meistens Spuren von Schwermetallen, vor allem Eisen- und Manganionen. Die erfindungsgemäß zu verwendenden Komplexbildner können beispielsweise bereits beim mechanischen Aufschluß von Holz in den sogenannten integrierten Papierfabriken, in denen aus Holz gewonnener Faserstoff zu Papier und Papierprodukten verarbeitet wird, eingesetzt werden. Bekannte Verfahren für den mecha- nischen Holzaufschluß sind beispielsweise konventioneller Steinschliff GMP (Groundwood Mechanical -Pulp) , Refiner Holzstoff RMP (Refiner-Mechanical-Pulp) , thermomechanischer Holzstoff TMP (Thermo-Mechanical Pulp) und Druckschliff PGW {Pressure Groundwood) . Refiner Holzstoff und thermomechanischer Holzstoff können gegebenenfalls einer chemischen Vorbehandlung unterworfen werden. Sie werden dann als CRMP bzw. CTMP bezeichnet. Außerdem kennt man den sogenannten Braunschliff. Die oben angegebenen HolzstoffSorten enthalten unterschiedliche Splittergehalte, Langfaser-, Kurz - faser- und Feinstoffanteile . TMP- und CTMP- Stoffe enthalten kaum Splitter und können im Vergleich zu den anderen Holzstoffen zu Papieren mit bedeutend besseren Festigkeiten verarbeitet werden. Man kann sowohl Feinschliff, Normalschli f und Grobschliff bleichen.The complexing agents described above are used in pulp bleaching, pulp production, pulp bleaching and deinking of printed waste paper. The technical raw materials and auxiliary materials used in paper production mostly contain traces of heavy metals, especially iron and manganese ions. The complexing agents to be used according to the invention can, for example, already be used in the mechanical pulping of wood in the so-called integrated paper factories in which fibrous material obtained from wood is processed into paper and paper products. Known methods for mechanical wood pulping include conventional stone grinding GMP (Groundwood Mechanical-Pulp), refiner wood pulp RMP (Refiner-Mechanical-Pulp), thermomechanical wood pulp TMP (Thermo-Mechanical Pulp) and pressure grinding PGW (Pressure Groundwood). Refiner wood pulp and thermomechanical wood pulp can optionally be subjected to a chemical pretreatment. They are then called CRMP or CTMP. You also know the so-called brown cut. The above-mentioned types of wood pulp contain different splinter contents, long fiber, short fiber and fine material. TMP and CTMP materials contain hardly any splinters and can be processed into papers with significantly better strengths than the other wood materials. You can bleach both fine sanding, normal sanding and coarse sanding.
Im Gegensatz zu Eisen- II - ionen reagieren Eisen- III- ionen mit Bestandteilen des Holzes unter Bildung dunkel gefärbter Verbindungen. Durch den unmi telbaren Einsatz von Komplexbildnern bei der Herstellung der Papierrohstoffe, insbesondere bei der Holzschliffbleiche, kann bereits eine Aufhellung des Papierrohstoffs erzielt werden, so daß nach beendeter Bleiche der Weißgrad um etwa 2-3 Punkte hoher liegt als ohne Verwendung von Komplex- bildnern. Durch den Zusatz der erfindungsgemäß einzusetzenden Komplexbildner erzielt man bei der oxidativen, der reduktiven oder der kombinierten Bleiche eine Weißgradsteigerung gegenüber solchen Stoffen, die keine Komplexbildner enthalten. Verfahren zur reduktiven Holzschliffbleiche mit Dithionit und zur oxidativen Bleiche mit Wasserstoffperoxid sind bekannt, vgl. H. Schroter, Die Holzschliffbleiche, Günther-Staib-Verlag, Biberach an der Riß, 1976.In contrast to iron II ions, iron III ions react with constituents of the wood to form dark-colored compounds. Through the direct use of complexing agents In the manufacture of the paper raw materials, in particular in the pulp bleaching process, the paper raw material can already be brightened, so that after the bleaching is finished, the whiteness is about 2-3 points higher than without the use of complexing agents. By adding the complexing agents to be used according to the invention, an increase in whiteness is achieved in oxidative, reductive or combined bleaching compared to substances which do not contain any complexing agents. Processes for reductive pulp bleaching with dithionite and for oxidative bleaching with hydrogen peroxide are known, cf. H. Schroter, Die Holzschliffbleiche, Günther-Staib-Verlag, Biberach an der Riß, 1976.
Auch bei der oxidativen Bleiche mit wäßrigen Peroxidlosungen wir- ken bereits Spuren von Schwermetallionen störend, weil sie die wäßrigen Peroxidlόsungen zersetzen. Zur Stabilisierung der Peroxidlosungen verwendet man deshalb üblicherweise beim Ansetzen der Bleichlόsungen größere Mengen an Wasserglas als Stabilisator. Der Einsatz von Wasserglas führt jedoch zu einer Verschlechterung der Entwässerung des gebleichten Papierstoffs und kann darüber hinaus Ablagerungen auf dem Papier und den Filzen an den Papiermaschinen verursachen. Das in den Bleichlosungen vorhandene Wasserglas kann durch die erfindungsgemäß zu verwendenden Verbindungen ersetzt werden, so daß man ein Bleichergebnis er- zielt, das dem Bleichergebnis entspricht, das mit üblichen Mengen an Wasserglas in der Bleichlösung erhalten wird. Die Verwendung der erfindungsgemäß einzusetzenden Verbindungen in Bleichlosungen fuhrt außerdem zu einer Einsparung an Wasserstoffperoxid bei der oxidativen Bleiche.Even with oxidative bleaching with aqueous peroxide solutions, traces of heavy metal ions are already disruptive because they decompose the aqueous peroxide solutions. To stabilize the peroxide solutions, larger amounts of water glass are therefore usually used as a stabilizer when preparing the bleaching solutions. However, the use of water glass leads to a deterioration in the dewatering of the bleached paper stock and can also cause deposits on the paper and the felts on the paper machines. The water glass present in the bleaching solutions can be replaced by the compounds to be used according to the invention, so that a bleaching result is obtained which corresponds to the bleaching result obtained with conventional amounts of water glass in the bleaching solution. The use of the compounds to be used according to the invention in bleaching solutions also leads to a saving in hydrogen peroxide in oxidative bleaching.
Die erfindungsgemäß zu verwendenden Verbindungen werden außerdem bei Deinken von bedrucktem Altpapier als Komplexbildner eingesetzt. Beim Deinking wird das bedruckte Altpapier aufgeschlagen und mit einer Kombination aus Peroxid, Natriumhydroxid, Wasser- glas, Dispergiermittel und Sammler behandelt. Je nach Rohstoff - gualität kann man bis zu 100 Gew. -% der sonst üblichen Wasserglasmenge einsparen, wenn man die erfindungsgemäß zu verwendenden Komplexbildner einsetzt. Außerdem kann man einen signifikanten Anteil an Wasserstoffperoxid einsparen, ohne eine Einbuße an Weißgrad beim deinkten Altpapier hinnehmen zu müssen.The compounds to be used according to the invention are also used as de-complexing agents in deinking of printed waste paper. During deinking, the printed waste paper is opened and treated with a combination of peroxide, sodium hydroxide, water glass, dispersant and collector. Depending on the quality of the raw material, it is possible to save up to 100% by weight of the otherwise customary amount of water glass if the complexing agents to be used according to the invention are used. You can also save a significant amount of hydrogen peroxide without sacrificing whiteness in deinked waste paper.
Der Einsatz der erfindungsgemäß zu verwendenden Verbindungen bei der Papierherstellung verhindert bzw. vermindert den negativen Einfluß von Härtebildnern des Wassers bei der Papierherstellung. Aufgrund der immer stärkeren Schließung der Wasserkreislaufe in Papiermaschinen findet darin eine stetige Anreicherung von Härte - bildnern statt. Dies kann u.a. zu einer Ausfällung von Carbonaten und Silikaten führen, wodurch die Papiereigenschaften unmittelbar beeinträchtigt werden können, z.B. Festigkeit, Saugfähigkeit, Anfärbbarkeit und das Staubverhalten des Papiers. Die Härte - bildner können außerdem die Wirksamkeit von Hilfsmitteln und die Eigenschaften von Farbstoffen nachteilig beeinflussen. Der Einsatz der erfindungsgemäß zu verwendenden Komplexbildner bei der Papierherstellung hat außerdem den Vorteil, daß Ausfällungen von Härtebildnern mit Harzleim bzw. Zellstoffharz und Fällungsprodukten des Aluminiumsulfats zurückgedrängt bzw. aufgelöst werden, so daß ein Verlegen der Naßfilze der Papiermaschinen weitgehend verhindert werden kann. Die Entwässerungsfähigkeit der Filze bleibt dadurch über einen längeren Zeitraum erhalten.The use of the compounds to be used according to the invention in papermaking prevents or reduces the negative influence of water hardness in papermaking. Due to the ever increasing closure of the water cycle in paper machines, there is a constant accumulation of hardness builders. This can lead to a precipitation of carbonates and silicates, which can directly impair the paper properties, such as strength, absorbency, dyeability and the dust behavior of the paper. The hardening agents can also adversely affect the effectiveness of auxiliaries and the properties of dyes. The use of the complexing agents to be used according to the invention in papermaking also has the advantage that precipitations of hardness agents with resin glue or cellulose resin and precipitation products of aluminum sulfate are suppressed or dissolved, so that laying of the wet felts of the paper machines can be largely prevented. This keeps the felts drained for a longer period of time.
Von den oben angegebenen Komplexbildnern setzt man vorzugsweise Ethylendiamindibernsteinsäure oder die Mono-, Di-, Tri- oder Tetranatriumsalze von Ethylendiamindibernsteinsäure ein. Bezogen auf trockenen Faserstoff verwendet man beispielsweise 0,02 bis 0,5, vorzugsweise 0,1 bis 0,3 Gew. -% eines Komplexbildners.Of the complexing agents specified above, preference is given to using ethylenediaminedisuccinic acid or the mono-, di-, tri- or tetrasodium salts of ethylenediaminedisuccinic acid. Based on dry fiber material, for example 0.02 to 0.5, preferably 0.1 to 0.3% by weight of a complexing agent is used.
Die Prozentangaben in den Beispielen sind Gew. -%, sofern aus dem Zusammenhang nichts anderes hervorgeht.The percentages in the examples are% by weight, unless the context indicates otherwise.
Beispiel 1example 1
100 g einer HolzschliffSuspension mit einer Stoffdichte von 4 % werden in einen Beutel aus Polyethylen gefüllt und mit, jeweils bezogen auf trockenen Holzschliff, 1 % Natriumdithionit und 0,06 % Ethylen-N,N' -diamindibernsteinsäure in Form des Tetranatriumsalzes versetzt. Der pH-Wert der Holzschliffaufschlämmung beträgt 6. Der Beutel wird dann verschlossen und der Inhalt durch intensives Kneten homogenisiert. Der Beutel wird nach dem Durchmischen des Inhalts für 1 Stunde in ein Wasserbad eingebracht, das eine Temperatur von 60°C hat. Zur Bestimmung des Bleichergebnisses bildet man aus dem gebleichten Papierstoff auf einem Ra- pid-Köthen-Blattbildner jeweils 2 Blätter mit einem Flächengewicht von 400 g/m2, trocknet die Blätter und bestimmt die Weiße der Papierblätter mit einem Elrepho-Photometer bei einer Wellenlänge von 457 nm als Prozent Remissionsgrad. Die Weiße der Papierblätter betrug 71,0 %. Aus dem ungebleichten Papierstoff wurden ebenfalls Blätter hergestellt, die eine Weiße von 61,7 % hatten. Vergleichsbeispiel100 g of a wood pulp suspension with a consistency of 4% are filled into a polyethylene bag and mixed with 1% sodium dithionite and 0.06% ethylene-N, N'-diaminedisuccinic acid in the form of the tetrasodium salt, based on dry wood pulp. The pH of the groundwood slurry is 6. The bag is then closed and the contents are homogenized by intensive kneading. After mixing the contents, the bag is placed in a water bath at a temperature of 60 ° C for 1 hour. To determine the bleaching result, 2 sheets each with a basis weight of 400 g / m 2 are formed from the bleached paper stock on a Rapid-Köthen sheet former, the sheets are dried and the whiteness of the paper sheets is determined using an Elrepho photometer at a wavelength of 457 nm as percent reflectance. The whiteness of the paper sheets was 71.0%. Sheets were also made from the unbleached paper stock, which had a whiteness of 61.7%. Comparative example
Beispiel 1 wurde mit der einzigen Ausnahme wiederholt, daß man die Bleiche in Abwesenheit eines Komplexbildners durchführte. Die Weiße von Papierblättern, die aus der gebleichten Holzschliffauf - schlämmung hergestellt wurden, betrug 69,8 %. Example 1 was repeated with the only exception that the bleaching was carried out in the absence of a complexing agent. The whiteness of sheets of paper made from the bleached wood pulp slurry was 69.8%.

Claims

Patentansprüche claims
1. Verwendung von Ethylendiamindibernsteinsäure, Ethylendiamindiglutarsäure, Hydroxypropylendia indibernsteinsäure, deren Alkalimetall- oder Ammoniumsalzen und Mischungen der genannten Verbindungen als Komplexbildner für Erdalkalimetall- und Schwermetallionen bei der Zellstoff- und Holzstoffbleiche, der Papierherstellung und dem Deinking von Altpapier.1. Use of ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, hydroxypropylenediaindisuccinic acid, its alkali metal or ammonium salts and mixtures of the compounds mentioned as complexing agents for alkaline earth metal and heavy metal ions in pulp and wood pulp bleaching, paper manufacture and deinking of waste paper.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man Ethylendiamindibernsteinsäure oder deren Alkalimetall- oder Ammoniumsalze als Komplexbildner bei der Zellstoff- oder Holzstoffbleiche einsetzt.2. Use according to claim 1, characterized in that ethylenediaminedisuccinic acid or its alkali metal or ammonium salts are used as complexing agents in the pulp or pulp bleaching.
3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man Ethylendiamindibernsteinsäure oder deren Alkalimetall- oder Ammoniumsalze als Komplexbildner beim Deinking von Altpapier einsetzt. 3. Use according to claim 1, characterized in that ethylenediaminedisuccinic acid or its alkali metal or ammonium salts are used as complexing agents in the deinking of waste paper.
PCT/EP1997/003741 1996-07-26 1997-07-14 Use of complexing agents for cellulose and wood bleaching, paper production and used paper deinking WO1998004775A1 (en)

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DE1996130278 DE19630278A1 (en) 1996-07-26 1996-07-26 Complexing agent for pulp and pulp bleaching, paper production and deinking of waste paper

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Publication number Priority date Publication date Assignee Title
GB2333772A (en) * 1998-01-31 1999-08-04 Procter & Gamble Complexing agents (eg ethylenediamine disuccinic acid) for use in selectively complexing copper, iron, zinc, nickel and cobalt in the presence of calcium
BE1011784A3 (en) * 1998-03-10 2000-01-11 Solvay Bleaching pulp process.

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128084A1 (en) * 1991-08-24 1993-02-25 Basf Ag Beta-alanine-N,N-di:acetic acid, alkali or ammonium salt complex former in paper mfr. - useful for biodegradable alkaline earth and heavy metal ion complexant in bleaching mechanical wood pulp and printed waste paper de inking
WO1994003553A1 (en) * 1992-08-01 1994-02-17 The Procter & Gamble Company Peroxy bleaching composition stabilized with ethylenediamine-n,n'-disuccinic acid
WO1994020599A1 (en) * 1993-03-05 1994-09-15 The Procter & Gamble Company Detergent compositions containing ethylenediamine-n,n'-diglutaric acid or 2-hydroxypropylenediamine-n,n'-disuccinic acid
WO1994028464A1 (en) * 1993-05-20 1994-12-08 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
WO1997030208A1 (en) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Process for the treatment of chemical pulp
WO1997030209A1 (en) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Process for bleaching of a high yield pulp

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128084A1 (en) * 1991-08-24 1993-02-25 Basf Ag Beta-alanine-N,N-di:acetic acid, alkali or ammonium salt complex former in paper mfr. - useful for biodegradable alkaline earth and heavy metal ion complexant in bleaching mechanical wood pulp and printed waste paper de inking
WO1994003553A1 (en) * 1992-08-01 1994-02-17 The Procter & Gamble Company Peroxy bleaching composition stabilized with ethylenediamine-n,n'-disuccinic acid
WO1994020599A1 (en) * 1993-03-05 1994-09-15 The Procter & Gamble Company Detergent compositions containing ethylenediamine-n,n'-diglutaric acid or 2-hydroxypropylenediamine-n,n'-disuccinic acid
WO1994028464A1 (en) * 1993-05-20 1994-12-08 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
WO1997030208A1 (en) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Process for the treatment of chemical pulp
WO1997030209A1 (en) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Process for bleaching of a high yield pulp

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