EP1080270B1 - Ein verfahren zur herstellung von papier - Google Patents

Ein verfahren zur herstellung von papier Download PDF

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Publication number
EP1080270B1
EP1080270B1 EP99945723A EP99945723A EP1080270B1 EP 1080270 B1 EP1080270 B1 EP 1080270B1 EP 99945723 A EP99945723 A EP 99945723A EP 99945723 A EP99945723 A EP 99945723A EP 1080270 B1 EP1080270 B1 EP 1080270B1
Authority
EP
European Patent Office
Prior art keywords
process according
carbon allotrope
shell
particles
microparticles
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.)
Expired - Lifetime
Application number
EP99945723A
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English (en)
French (fr)
Other versions
EP1080270A1 (de
Inventor
Rein Sikkar
Michael Persson
Maria Norell
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.)
Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Akzo Nobel NV
Eka Chemicals AB
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Publication date
Application filed by Akzo Nobel NV, Eka Chemicals AB filed Critical Akzo Nobel NV
Priority to EP99945723A priority Critical patent/EP1080270B1/de
Publication of EP1080270A1 publication Critical patent/EP1080270A1/de
Application granted granted Critical
Publication of EP1080270B1 publication Critical patent/EP1080270B1/de
Anticipated expiration legal-status Critical
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads

Definitions

  • the present invention relates to a paper production process.
  • paper production process is intended to encompass the entire paper production process, i.e. from the defibration of the wood until the paper product is ready to be supplied to the market.
  • the present invention also relates to paper obtainable by said process, whereby "paper” is to be understood to include also board, paperboard, fibreboard, and cardboard, as well as any other similar cellulosic fibre containing product.
  • the invention relates to paper making additives such as drainage and retention agents that may be used in such a process.
  • the paper making process usually involves the use of various additives in order to control the paper production process as such and/or the properties of the produced paper. Drainage and retention agents are among the most common paper making additives.
  • a wide variety of drainage and retention agents are known in the art. These additives are included in the papermaking stock in order to facilitate drainage and/or to increase adsorption of fine particles and additives onto the cellulose fibres so that they are retained with the fibres.
  • the drainage and retention agents employed include natural and synthetic organic polymers, particles of inorganic materials and many combinations thereof. Usually, oppositely charged materials are used. Certain microsize particles, namely colloidal silica particles, in combination with cationic starch, such as for example disclosed in EP-B-41,056 is an example of a commonly used drainage and retention agent. The particles act as flocculants, binding the polymer molecules to larger aggregates.
  • EP-A-534,656 discloses a papermaking process involving addition of a mineral filler, a cationic charge-biasing species, an anionic flocculant, and microparticles being of inorganic cationic source of aluminium.
  • Shell-formed carbon allotrope particles are, however, not described therein.
  • WO 97/30220 discloses a process for making filled paper comprising adding an anionic micro particulate material to the cellulosic suspension.
  • the anionic particulate material can be e.g. swelling clays, zeolites and synthetic particulate silica compounds.
  • WO 97/30220 does not relate to shell-formed carbon allotrope particles.
  • microparticles A common feature of the drainage and retention agents referred to above is their contents of certain microsize particles, below referred to as microparticles. It would be desirable to be able to provide a paper production process in which other microparticles than those presently known in the art are used as that would provide, at least ceteris panbus, for a bigger supply of microparticles. In a drainage/retention agent it would be desirable to use micropartides that could provide, at least potentially, for better flocculation. Microparticles that could provide for all of this would of course be especially desirable.
  • the problem. to be solved by the present invention is to provide a paper production process in which such microparticles are used.
  • the present invention relates to a process for the production of paper comprising cellulosic fibres, in which at least some of the fibres are treated at some part of the process with microparticles comprising shell-formed carbon allotrope particles.
  • microparticles having a high particle charge density provide for a potentially better flocculation in a drainage/retention operation. The reason for this is as follows:
  • a cationic polymer and anionic microparticles form complex agglomerates in the stock, which agglomerates are bound together by the anionic microparticles, and the cationic polymer becomes associated with filler material having a more or less anionic surface.
  • the cationic polymer also becomes associated with the cellulosic fibres and fines, both of which are anionic.
  • the association between the agglomerates and the cellulosic fibres provides flocculation. It would seem that a higher particle charge density of the anionic microparticles would provide for more anionic groups on the particle surface, in turn providing more bond sites and, as a consequence, potentially bigger agglomerate.
  • microparticle indicates a particle having a particle size of up to about 10 ⁇ m, preferably up to about 100 nm, and most preferably up to about 20 nm.
  • microparticles used in the present invention comprise shell-formed carbon allotrope particles, which may mean that each microparticle consists of one or more shell-formed carbon allotrope particles, but may just as well mean that the microparticles are only partly made up of shell-formed carbon allotrope particles whereas the other part is made up of some other substance.
  • shell-formed carbon allotrope any carbon allotrope in which the atoms are arranged so as to form a shell, preferably a closed shell having an essentially spherical form.
  • An open shell form such as for instance the form of a tube with one or more openings, is however not excluded.
  • the shell form is defined by the atomic lattice, i.e. each unit of this lattice constitutes an individual shell.
  • An illustrative and preferred example of this embodiment is of course the fullerene allotrope, e.g. a [60]fullerene or a [70]fullerene.
  • the shell-formed particles may be a so-called "hollow carbon microbeads" as disclosed by K. Esumi et al in Colloids and Surfaces, A: Physicochem. Eng. Aspects 108 (1996) 113-116, in which the shell form is defined by a plurality of atomic lattice units.
  • the shell-formed carbon allotrope comprises one or more heteroatom, such as for instance a Si, B, N, S, or P atom.
  • the carbon allotrope is a heterofullerene such as described in "The Chemistry of the Fullerenes" by A. Hirsch, (Georg Thime Verlag, Stuttgart, New York 1994, chapter 9.4.2, page 196).
  • the carbon allotrope particles may be furnished with addends and/or substituents; the particles may for instance be hydroxylated, sulphonated, or carboxylated.
  • carbon allotrope particles may be polyhydroxylated fullerene derivatives, so-called fullerols, e.g. prepared according to the methods described by Jing Li et al in J. Chem. Soc., Chem. Commun., 1993, pp 1784-5 ("C 60 Fullerol Formation catalysed by Quartary Ammonium Hydroxides”), or EP 540 311.
  • the invention can be used in a variety of flocculation operations, including for instance sludge dewatering, waste water treatment, wine clarification; this listing of flocculation operations is of course not exhaustive.
  • the particles are used for the purpose of improving the dewatering/retention performance of a paper making process, whereby the microparticles are preferably combined with a polymer.
  • the particles and the polymer are added, either mixed or separated from each other, either simultaneously or consecutively, to the papermaking stock, whereby the shell-formed carbon allotrope particles are at least partially hydrophilic, and preferably soluble in aqueous solutions.
  • the carbon allotrope is preferably an anionic fullerene derivative, e.g. a hydroxylated, sulphonated, or carboxylated fullerene derivative.
  • the carbon allotrope particles are preferably associated with each other, e.g.
  • bonds may for instance be constituted by means of one and more hydrocarbyl groups and/or one or more atoms chosen among N, O, P, S, B, and Si.
  • Said atoms may farm an integrated part of the particles or be comprised in an addend or substituent to the particles, but may also form a bridge between addends or substituents of two or more allotrope particles.
  • the hydrocarbyl group may be an addend or substituent common to two or more allotrope particles, but may also form a bridge between addends or substituents of two or more allotrope particles, for instance between atoms chosen among N, O, P, S, B, and Si.
  • the allotrope microparticles may for instance be combined with a polymer having a branched or unbranched hydrocarbon chain, with or without substituents; it may for instance be chosen among starches, chitosans, seed gums such as guar gums, acrylamide-based polymers, poly(diallyldimethyl ammonium chloride), polyethylene imines. polyamines, polyamidoamines, melamine-formaldehyde resins, urea-formaldehyde resins, N-vinylamide-based polymers, or a combination thereof. In one preferred embodiment the polymer has a branched hydrocarbon chain.
  • the allotrope microparticles are present in the papermaking stock in an amount of at least 0,005 kg/tonne of pulp, particularly preferred in an amount from about 0,03 to 5 kg/ton of pulp.
  • the unit kg/ton is calculated as dry on dry fibres and optional fillers, and by a "ton" is meant a metric ton.
  • the present invention also relates to paper obtainable from this dewatering/retention performance improved paper making process.
  • the present invention relates to a drainage or retention agent comprising at least partially hydrophilic, anionic microparticles comprising shell-formed carbon allotrope particles, which is adapted to be used in said dewatering/retention performance improved paper making process.
  • the partially hydrophilic, anionic microparticles are at least partially made up of carbon allotrope particles that are associated with each other, e.g. by means of covalent bonds, electrostatic bonds, ionic bonds, or any similar kind of bonds.
  • the bonds may for instance be constituted by means of one and more hydrocarbyl groups and/or one or more atoms chosen among N, O, P, S, B, and Si.
  • Said atoms may form an integrated part of the particles or be comprised in an addend or substituent to the particles, but may also form a bridge between addends or substituents of two or more allotrope particles.
  • the hydrocarbyl group may be an addend or substituent common to two or more allotrope particles, but may also form a bridge between addends or substituents of two or more allotrope particles, for instance between atoms chosen among N, O, P, S, B, and Si.
  • Example 1 Polyhydroxylated fullerene derivatives, so-called fulferols, were prepared essentially according to the method described by Jing Li et al in J. Chem. Soc., Chem. Commun., 1993, pp 1784-5 ("C 60 Fullerol Formation catalysed by Quartary Ammonium Hydroxides"). More particularly, two kinds of fullerols, fullerol A and fullerol B, were produced:
  • Fullerol A and B were produced according to the following procedure: C-60 Fullerene was mixed with 1,7-diaminoheptane ( molar ratio of 2:1) in benzene. The reagents were stirred at ambient temperature for 48 hours after which the reaction mixture, consisting of coupled aminofullerenes, was subjected to hydroxylation according to the method described by Jing-Li et al in J. Chem. Soc., Chem. Commun., 1993, pp 1784-5 ("C60 Fullerol Formation catalysed by Quartary Ammonium Hydroxides"). The watersoluble reaction mixture was precipitated by addition of methanol which yielded Fullerol A as a brownish solid. The mother liquor was evaporated to dryness and the residue again dissolved in water and precipitated by methanol yielding Fullerol B as an almost black solid. The mass yields of Fullerol A and B were about equal. The two fractions were used in the following examples.
  • Example 2 In the following tests, drainage performance was evaluated by means of a Dynamic Drainage Analyser (DDA), available from Akribi AB, Sundsvall, Sweden, which measures the time required to drain a set volume of stock through a wire when removing a plug and applying a vacuum to the side of the wire opposite the stock.
  • DDA Dynamic Drainage Analyser
  • the drainage tests were made using a stock having a pH of 8,5 and a consistency of 0,3 %, which contained 70 % cellulosic fibres, 60 % bleached hardwood Kraft and 40 % bleached softwood Kraft and 30 % Hydrocarb 60.
  • the stock further contained 0,3 g/l Na 2 SO 4 *10 H 2 O
  • microparticles according to the present invention were tested in conjunction with a cationic polymer, Raisamyl 142, which is a conventional medium-high cationised starch having a degree of substitution of 0.042, which was added to the stock in an amount of 12 kg/ton.
  • test 2B microparticles according to the present invention were tested in conjunction with a cationic polyacrylamide of 10 mole-% cationic charge and a molecular weight of about 6 million Da, which was added to the stock in an amount of 1 kg/ton.
  • the stock was stirred in a baffled jar at a speed of 1500 rpm throughout the test and chemical additions to the stock were conducted as follows:
  • Table I shows the drainage results, in seconds, obtained in test 2A when using varying dosages of fullerols A and B; shorter drainage times means better drainage performance of the fullerols.
  • the stock had a drainage time of 18 seconds.
  • Microparticles 0.25 kg/ton 0.5 kg/ton 0.75 kg/ton 1.0 kg/ton 1.5 kg/ton 2.0 kg/ton 2.5 kg/ton Fullerol A 15.9 12.8 11.5 9.78 8.57 6.79 6.7 Fullerol B 16.2 14.6 13.5 12.2 9.41 8.87 10.5
  • Table II shows the drainage results, in seconds, obtained in test 2B when using varying dosages of fullerols A and B. Without addition of microparticles, the stock had a drainage time of 16.9 seconds. Microparticles 0.1 kg/ton 0.25 kg/ton 0.5 kg/ton 0.75 kg/ton 1.0 kg/ton 2.0 kg/ton Fullerol A 15.6 14.3 13.1 12.8 13.6 - Fullerol B 16.2 15.4 15.2 15.3 15.1 15.7
  • the microparticles according to the invention had a clear effect on the drainage performance.
  • Example 3 In these test series, retention was evaluated by means of the DDA used in Example 2 in combination with a nephelometer. First pass retention was evaluated by measuring the turbidity of the filtrate, the white water, obtained by draining the stock. Additives and addition order in test 3A were the same as in test 2A, and the conditions prevailing in test 3B were also applied in test 2B.
  • Table III shows the retention effect measured in test 3A as turbidity of white water obtained by dosing varying amounts of fullerols A and B, where dosages are in kg/ton. Without addition of microparticles, the stock had a turbidity of 119 NTU. Microparticles 0.5 kg/ton 0.75 kg/ton 1.0 kg/ton 1.5 kg/ton 2.0 kg/ton 2.0 kg/ton Fullerol A 97 89 83 72 75 66 Fullerol B 106 102 97 73 76 86
  • Table IV shows the retention effect measured in test 3B as turbidity of white water obtained by dosing varying amounts of fullerols A and B, where dosages are in kg/ton. Without addition of microparticles, the stock had a turbidity of 96 NTU. Microparticles 0.1 kg/ton 0.5 kg/ton 0.75 kg/ton 1.0 kg/ton 2.0 kg/ton Fullerol A 94 73 71 78 - Fullerol B 92 83 85 88 91
  • microparticles according to the invention had a clear impact on the retention effect.

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  • Paper (AREA)

Claims (13)

  1. Verfahren zur Herstellung von Papier, das Cellulosefasern umfasst, wobei mindestens ein Teil der Fasern in einem Abschnitt des Verfahrens mit Mikroteilchen behandelt wird, dadurch gekennzeichnet, dass die Mikroteilchen schalenförmige allotrope Kohlenstoffteilchen umfassen.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass der allotrope Kohlenstoff ein Fulleren und/oder ein Fullerenderivat ist.
  3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, dass das Fulleren ein [60]Fulleren oder ein [70]Fulleren ist.
  4. Verfahren gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der schalenförmige allotrope Kohlenstoff mindestens ein Heteroatom umfasst.
  5. Verfahren gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die allotropen Kohlenstoffteilchen mit Zusätzen und/oder Substituenten versehen sind.
  6. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Mikroteilchen und ein Polymer einer Stoffmasse zur Papierherstellung zugegeben werden und die schalenförmigen allotropen Kohlenstoffteilchen mindestens teilweise hydrophil sind.
  7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, dass die schalenförmigen allotropen Kohlenstoffteilchen in wässrigen Lösungen löslich sind.
  8. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, dass der allotrope Kohlenstoff ein anionisches Fullerenderivat ist.
  9. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, dass der allotrope Kohlenstoff ein hydroxyliertes, sulfoniertes oder carboxyliertes Fullerenderivat ist.
  10. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, dass zwei oder mehrere der schalenförmigen allotropen Kohlenstoffteilchen miteinander assoziiert sind.
  11. Verfahren gemäß Anspruch 10, dadurch gekennzeichnet, dass zwei oder mehrere der schalenförmigen allotropen Kohlenstoffteilchen miteinander durch mindestens einen Kohlenwasserstoffrest und/oder mindestens ein aus N, O, P, S, B und Si ausgewähltes Atom assoziiert sind.
  12. Verfahren gemäß Anspruch 10, dadurch gekennzeichnet, dass das Polymer aus Stärken, Chitosanen, Guargummis, Polymeren auf Acrylamidbasis, Poly(diallyldimethylammoniumchlorid), Polyethyleniminen, Polyaminen, Polyamidoaminen, Melaminformaldehydharzen, Harnstoffformaldehydharzen, Polymeren auf N-Vinylamidbasis oder einer Kombination davon ausgewählt ist.
  13. Papier, erhältlich durch das Verfahren nach einem der Ansprüche 6 bis 12.
EP99945723A 1998-04-23 1999-04-08 Ein verfahren zur herstellung von papier Expired - Lifetime EP1080270B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99945723A EP1080270B1 (de) 1998-04-23 1999-04-08 Ein verfahren zur herstellung von papier

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US8278498P 1998-04-23 1998-04-23
EP98850061 1998-04-23
EP98850061 1998-04-23
US82784P 1998-04-23
PCT/SE1999/000574 WO1999054551A1 (en) 1998-04-23 1999-04-08 A process for the production of paper
EP99945723A EP1080270B1 (de) 1998-04-23 1999-04-08 Ein verfahren zur herstellung von papier

Publications (2)

Publication Number Publication Date
EP1080270A1 EP1080270A1 (de) 2001-03-07
EP1080270B1 true EP1080270B1 (de) 2004-11-17

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EP99945723A Expired - Lifetime EP1080270B1 (de) 1998-04-23 1999-04-08 Ein verfahren zur herstellung von papier

Country Status (5)

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EP (1) EP1080270B1 (de)
AU (1) AU4297699A (de)
DE (1) DE69921989T2 (de)
ES (1) ES2229765T3 (de)
WO (1) WO1999054551A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6942142B2 (ja) * 2015-12-14 2021-09-29 エコラブ ユーエスエイ インク 製紙プロセスのためのボロン酸含有ポリマー

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5221435A (en) * 1991-09-27 1993-06-22 Nalco Chemical Company Papermaking process
US5827398A (en) * 1996-02-13 1998-10-27 Allied Colloids Limited Production of filled paper

Also Published As

Publication number Publication date
EP1080270A1 (de) 2001-03-07
DE69921989T2 (de) 2005-11-24
WO1999054551A1 (en) 1999-10-28
ES2229765T3 (es) 2005-04-16
DE69921989D1 (de) 2004-12-23
AU4297699A (en) 1999-11-08

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