WO2022027080A1 - Procédé de fabrication de produits d'emballage à base de fibres cellulosiques et produit d'emballage à base de fibres cellulosiques - Google Patents

Procédé de fabrication de produits d'emballage à base de fibres cellulosiques et produit d'emballage à base de fibres cellulosiques Download PDF

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Publication number
WO2022027080A1
WO2022027080A1 PCT/AT2021/060272 AT2021060272W WO2022027080A1 WO 2022027080 A1 WO2022027080 A1 WO 2022027080A1 AT 2021060272 W AT2021060272 W AT 2021060272W WO 2022027080 A1 WO2022027080 A1 WO 2022027080A1
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Prior art keywords
pulp
weight
chemical
semi
cellulose
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PCT/AT2021/060272
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German (de)
English (en)
Inventor
Elisabeth SCHWAIGER
Harald Meysel
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Mondi Ag
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Publication of WO2022027080A1 publication Critical patent/WO2022027080A1/fr

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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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/10—Mixtures of chemical and mechanical pulp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/08—Corrugated paper or cardboard
    • 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
    • D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply

Definitions

  • the invention relates to a method for producing cellulose fiber-based packaging products and a cellulose fiber-based packaging product.
  • waste paper for the production of paper packaging solutions has become established in recent years and decades wherever possible and sensible. Although this is fundamentally desirable from an ecological point of view, the increasing demand for paper packaging already brings with it problems insofar as at least in some cases there is not enough waste paper available as a raw material for paper packaging solutions. This is also because waste paper cannot be cyclically reprocessed indefinitely due to the degradation during recycling, in particular due to the reduction in the length of the cellulose fibers in each recycling process.
  • the object of the present invention was to provide a method that is as efficient as possible from a technical, economic and ecological point of view, by means of which cellulose-based packaging products can be produced with little effort, but which packaging products still meet the requirements for packaging materials in the best possible way.
  • the process is used to manufacture cellulose fiber-based packaging products and includes the steps:
  • the first material used is a chemical half-pulp containing cellulose fibers with a length-weighted average fiber length according to ISO 16065-2:2014 of 0.6 mm to 1.2 mm and hemicelluloses and, based on 100% by weight of dry matter of the chemical half-pulp, having a lignin -Content according to JAYME/KNOLLE/RAPP from 8% to 18% by weight and an extract content according to ISO 14453:2014 from 0.2% to 1.5% by weight.
  • the first material can also be referred to as the first starting material.
  • 100% by weight of dry matter or the term “dry matter” of the chemical half-pulp is here and below to be understood as the absolutely dry chemical half-pulp under the term “atro”, i.e. its atro-mass.
  • the term “bone dry weight” is often used as a synonym for an absolute dry mass. The term “dry mass” is therefore to be understood as meaning material without any water content.
  • the procedure for the gravimetric determination of the lignin content according to JAYME/KNOLLE/RAPP can JAYME G complicat KNOLLE H. & G. RAPP, "Development and final version of the lignin determination method according to JAYME-KNOLLE", Das Textil 12, 464 - 467 (1958), No. 17/18.
  • the procedure described herein comprises an extraction using an extraction mixture of methanol and benzene, it being possible to use dichloromethane as the extraction agent instead, as is known per se today and is customary.
  • the chemical semi-pulp can preferably have a lignin content according to JAYME/KNOLLE/RAPP of 9 to 17% by weight, based on 100% by weight dry matter of the chemical semi-pulp.
  • the chemical semi-pulp can contain at least 50 wt. %, preferably at least 70 wt. % dry matter of the chemical semi-pulp about 15 to 30% by weight, preferably 20 to 25% by weight, hemicelluloses.
  • the chemical half-pulp can have 51 to 75% by weight, in particular 58 to 70% by weight, cellulose fibers with the specified length-weighted, mean fiber-length range according to ISO 16065-2:2014.
  • the chemical semi-pulp may comprise cellulosic fibers having a length-weighted mean fiber length according to ISO 16065-2:2014 of 0.8 mm to 1.1 mm.
  • packaging products produced in this way meet the requirements of the packaging industry surprisingly well, as will be explained in more detail below using examples.
  • packaging products manufactured according to the specified method have surprisingly good mechanical robustness, so that the packaging products are well suited for many packages. This is evident above all from the production and processing of the at least one first nonwoven web comprising the chemical semi-cellulose with the specified properties or substances and substance parameters.
  • the chemical semi-pulp can be made from crushed hardwood.
  • the specified method is efficient from a technical, economic and ecological point of view.
  • the production of the packaging product can be carried out in large quantities by means of a few process steps which are customary per se in the paper industry or by means of systems and machines which are customary in the paper industry.
  • Elaborate processing steps for example of heavily contaminated recycling material, or complex digestion or extraction steps for the production of cellulose can essentially be dispensed with.
  • the packaging products produced by means of the process have the properties that are required or desired overall in the packaging industry, despite the efficient process control with standard process steps without great effort.
  • the specified measures can be used to produce the semi-pulp with a particularly good wood yield.
  • the specified contents or content ranges of lignin and extract can be used to give the packaging product, for example, the slightly brown color desired in the packaging industry.
  • a process step for decolorizing or coloring, which is required for example when recycling waste paper, can be omitted since the packaging product can be given a desired coloration practically without having to take any further measures due to the specified parameters of the chemical semi-pulp.
  • mean fiber length ranges surprisingly good mechanical properties, such as good crush resistance, which is particularly important in the packaging industry, can also be imparted to the packaging products produced.
  • the packaging products can be provided or produced, for example, in the form of paper, cardboard or cardboard.
  • the first material or the chemical semi-cellulose with the indicated Parameters also further nonwoven webs are processed together with the at least one first nonwoven web to form a packaging product.
  • Such other fleece webs can also include the chemical semi-chemical pulp.
  • non-woven webs comprising other cellulose-based pulps or wood pulp or other non-woven, woven or web materials made of plastics, for example, can be processed with the at least one first non-woven web to form a packaging product, the chemical semi-cellulose produced with the specified parameters favorable properties can also be found in such combined packaging products.
  • a packaging product can be manufactured as a cardboard box with a corrugated middle layer and two smooth outer layers, as is customary per se.
  • the chemical semi-cellulose is used as the sole cellulose fiber source for the production of the packaging product, or that only the at least one first fleece web is processed into the packaging product.
  • the at least one, first aqueous suspension and/or the at least one, first nonwoven web can of course also be added to the chemical semi-pulp and other additives that are customary in the paper industry, such as fillers, starch, etc., with such additives preferably only being added in small amounts are used.
  • nonwoven webs are processed to form a packaging product, the same can in principle be processed or connected to one another using methods known per se in papermaking. For example, joining the fleece webs together in an already pre-dried state using a binding agent is conceivable. Alternatively, if necessary, several fleece webs can also be wet-pressed together before a drying step, which is often also referred to as couching in technical jargon. Before the fleece webs are joined or connected, they can also be individually preformed, for example corrugated or smoothed as required. As is known per se, the fleece web(s) can be dried in stages, as is customary in paper machines. In general, paper finishing steps that are customary in practice can also be used for individual fleece webs.
  • the cellulose fiber-based packaging product obtained can of course also be made up according to the requirements, with usually a conversion into rolls or endless packaging products takes place, which can then be further divided up for use and formed into packaging.
  • a chemical semi-pulp based on 100% by weight dry matter of the semi-pulp, having an extract content according to ISO 14453:2014 of 0.3% by weight 1.0% by weight is produced as the first material.
  • This measure has a particularly advantageous effect on the process management itself, in particular the successive drying of the at least one, first fleece web.
  • the chemical semi-pulp can be produced by a process comprising chemically treating crushed hardwood in a pulping solution containing 9 g/L to 50 g/L of active alkali expressed as NaOH.
  • a temperature of the digestion solution during the chemical treatment may be 150°C to 180°C, and a duration of the chemical treatment may be 25 minutes to 45 minutes.
  • the chemical semi-pulp may be produced by a process comprising chemically treating crushed hardwood in a pulping solution having 15 g/L to 34 g/L active alkali expressed as NaOH.
  • the term active alkali primarily includes the sum of the hydroxyl and hydrosulfite species of the digestion solution, as described, for example, in SCAN-N 2:88, 1988, and can be determined, for example, according to the titration procedure described in SCAN-N 30 will.
  • the concentration is given by converting the values obtained using the molecular weight of NaOH ( ⁇ 40 g/mol).
  • a pulping solution/wood ratio usually also referred to as the hydromodulus, can be, for example, 3 to 8 m 3 /bdt wood, preferably about 4.5 to 7 m 3 /bdt wood, in the chemical treatment of the hardwood.
  • bdt refers to the term "bone dry ton” commonly used in paper technology and thus refers to one ton of absolutely dry wood in terms of the atro weight.
  • the term or the unit "bon dry metric ton”, abbreviated bdmt, is also common and to be understood synonymously.
  • the comminuted hardwood may be chemically treated in a pulping solution comprising an amount of active alkali of about 7.5% to 15%, preferably 10% to 15%, based on the total weight of dry wood.
  • a sulfidity of the digestion solution can be, for example, 60 to 65% based on active alkali.
  • the chemical semi-pulp is produced by a process comprising chemical treatment of comminuted hardwood in a pulping solution containing from 3 g/L to 21 g/L NaOH, preferably 6 g/L up to 14 g/L NaOH.
  • the chemical semi-pulp can be produced by a process comprising chemically treating crushed hardwood in a pulping solution comprising from 6 g/L to 29 g/L Na2S, preferably from 9 g/L to 20 g/L Na2S expressed as NaOH.
  • the chemical semi-pulp is produced by a process comprising chemical treatment of comminuted hardwood in a pulping solution containing from 10 g/L to 50 g/L Na2CO3, preferably from 17 g/L to 34 g/L Na2CO3 , expressed as NaOH.
  • the digestion solution can, of course, have the above-mentioned components together, ie NaOH, Na2S and Na2CO3, the active alkali being formed primarily by NaOH and Na2S. It has also proven particularly advantageous if a mixture of 60% by weight to 90% by weight comminuted beech wood and 10% by weight to 40% by weight comminuted oak wood is used as comminuted hardwood to produce the chemical semi-pulp.
  • Such high-consistency defibration can specifically reduce the shives content in the chemical semi-pulp. This in turn can have a positive effect both on the product properties and on the process itself, for example on the drying behavior of the chemical semi-pulp, as will be demonstrated below using examples.
  • the solid suspension is defibrated to a splinter content of less than 15% according to T 275 sp-02:2007 with a Schopper-Riegler value according to ISO 5267-1:1999 of more than 28°SR.
  • the splinter content according to T 275 sp-02:2007 can be determined in particular with a Somerville apparatus with a slit width of 0.15 mm. Additionally or independently of this, however, it can also be useful to carry out mechanical processing and grinding of an aqueous solid suspension of the chemical semi-pulp in a low-consistency refiner after the mechanical processing and defibration in the high-consistency defibrator or after the chemical treatment.
  • Such a low-consistency grinding of the chemical half-pulp can positively influence in particular the mechanical properties of the packaging products subsequently produced from the chemical half-pulp, in particular the mechanical properties of the packaging products can be further improved, as is also described in more detail below with reference to examples.
  • the chemical semi-cellulose is produced with a water retention value according to ISO 23714:2014 of 130% to 195%.
  • This method measure is particularly advantageous with regard to the dewatering or drying steps carried out in the method, since the aqueous nonwoven web guided in the method can be dewatered better or with less effort and also more energetically, including the chemical semi-cellulose.
  • the at least one, first fleece web based on 100% by weight of dry matter of the fleece web, is produced with a content of at least 50% by weight of the chemical semi-cellulose.
  • the at least one, first nonwoven web can be produced with a content of at least 80% by weight of the chemical semi-cellulose, based on 100% by weight of dry matter of the nonwoven web.
  • the at least one, first aqueous suspension and/or the at least one, first nonwoven web can in principle also be admixed with other additives or additives customary in the paper industry, such as fillers, starch, etc., with such additives preferably only being used in small amounts .
  • a consistency of the at least one, first aqueous suspension before equalization and pre-drying to form the at least one, first nonwoven web can be adjusted to a value of 0.5% to 1.8%.
  • a chemical semi-pulp with an ash residue according to ISO 1762:2015 of less than 2% by weight can be produced as the first material.
  • Packaging products made from such a chemical semi-pulp primarily have good aging resistance. Furthermore, in particular the mechanical strength of the packaging products can be further improved in this way.
  • a material with no detectable content of diisopropylnaphthalenes is produced as the first material.
  • a range of uses for the packaging products produced can be expanded as a result of this measure. For example, this also at least enables use as a food packaging product or for packaging food.
  • diisopropylnaphthalenes can be detected by extraction with dichloromethane or acetone, for example with the aid of an ultrasonic bath, and subsequent gas chromatography-mass spectrometer (GC-MS) analysis according to DIN EN 14719:2005.
  • GC-MS gas chromatography-mass spectrometer
  • At least 30% by weight of the first material or the chemical semi-pulp can be used to produce a cellulose fiber-based packaging product, based on 100% by weight of the total dry mass of materials or starting materials used.
  • the cellulose-based packaging products can also be given the advantageous properties provided by the chemical semi-pulp with the specified parameters.
  • at least 60% by weight of the first material is used to produce a cellulose fiber-based packaging product, based on 100% by weight of the total dry mass of materials used.
  • water-containing nonwoven webs are connected to produce a cellulose fiber-based packaging product, with the at least one first, water-containing nonwoven web comprising the chemical semi-cellulose being arranged as the outer nonwoven web.
  • a packaging product can be delimited at least on one side by a layer comprising the chemical semi-cellulose.
  • a second or further water-containing nonwoven web comprising the chemical semi-cellulose can also be arranged on the outside opposite the at least one, first nonwoven web in the process, and a packaging product can thus be provided which is delimited by two layers comprising the chemical semi-cellulose.
  • a cellulose fiber-based packaging product for the production of a cellulose fiber-based packaging product, only a plurality of water-containing, first fleece webs comprising the chemical semi-cellulose are connected to one another.
  • a cellulose fiber-based packaging product it is also possible for the production of a cellulose fiber-based packaging product to only process, in particular dry, the at least one water-containing, first nonwoven web comprising the chemical semi-cellulose.
  • the object of the invention is also achieved by a cellulose fiber-based packaging product, which packaging product can be produced by the method described above or by means of the method measures specified above.
  • the cellulose fiber-based packaging product consists of at least 30% by weight of a chemical semi-pulp containing cellulose fibers with a longitudinal weighted average fiber length according to ISO 16065-2:2014 from 0.6 mm to 1.2 mm as well as hemicelluloses and, based on 100% by weight dry matter of the semi-pulp, having a lignin content according to JAYME/KNOLLE/RAPP of 8 weight % to 18% by weight and an extract content according to ISO 14453:2014 of 0.2% by weight to 1.5% by weight.
  • Such a cellulose fiber-based packaging product meets the requirements of the packaging industry surprisingly well, as will be explained in more detail below using examples.
  • packaging products have surprisingly good mechanical robustness, so that the packaging products are well suited for many types of packaging.
  • the packaging product comprising the chemical semi-pulp with the specified contents or content ranges of lignin and extract can also be given the slightly brownish color desired in the packaging industry, for example.
  • a packaging product also has surprisingly good mechanical properties, such as good crush resistance, which is particularly important in the packaging industry.
  • a packaging product can be formed, for example, by paper, cardboard or paperboard, and can accordingly consist of one ply or several connected plies or paper plies containing cellulose fibers.
  • Individual layers can be shaped as is usual in the paper industry or packaging industry, for example designed as smooth layers, or have a corrugated design, as is often used in the case of cardboard.
  • Individual layers or even the entire packaging product can have additives or additives that are customary in the paper industry, such as fillers or starch, with such additives preferably being present only in small amounts.
  • the chemical semi-pulp can preferably have a lignin content according to JAYME/KNOLLE/RAPP of 9-17% by weight, based on 100% by weight dry matter of the chemical semi-pulp.
  • the chemical semi-pulp can contain at least 50 wt. %, preferably at least 70 wt Weight % dry matter of chemical semi-pulp about 15 to 30 wt.%, Preferably 20 to 25 wt.% Have hemicelluloses.
  • the chemical half-pulp can have 51-75% by weight, in particular 58-70% by weight, cellulose fibers with the specified length-weighted, average fiber-length range according to ISO 16065-2:2014.
  • the chemical semi-pulp may comprise cellulosic fibers having a length-weighted mean fiber length according to ISO 16065-2:2014 of 0.8 mm to 1.1 mm.
  • the packaging product consists of at least 60% by weight of the chemical semi-cellulose with the specified properties.
  • it can preferably be provided that it consists of several connected paper layers, with at least one paper layer of the packaging product comprising the chemical semi-pulp.
  • At least one outer paper ply of the packaging product may comprise the chemical semi-pulp.
  • a packaging product can be delimited by a paper layer comprising the chemical half-cellulose, as a result of which the advantageous properties of the chemical half-cellulose come into their own.
  • the at least one paper layer comprising the chemical semi-chemical pulp can preferably consist of at least 60% by weight of the chemical semi-chemical pulp.
  • At least 80% of its outer surface can be characterized in the L*a*b* color space according to ISO 5631-2:2015 by an L* value of 47 to 54, an a* value of 6 .2 to 7.5 and a b* value of 14.0 to 18.5.
  • Such coloring essentially corresponds to the packaging standards that are customary in the packaging industry, such as in the case of a package, and a packaging product with a high level of acceptance among retailers and consumers can be provided as a result.
  • 100% of the outer surface of the packaging product can also be characterized by the specified color values in the L*a*b* color space according to ISO 5631-2:2015, whereby in practice labels that can be printed on the outer surface of a packaging product, pre-printed labels, Packaging etc. can be applied.
  • a packaging product in which the chemical semi-cellulose has an ash residue of less than 2% by weight according to ISO 1762:2015 is also of particular advantage.
  • the chemical semi-cellulose has no detectable content of diisopropylnaphthalenes.
  • diisopropylnaphthalenes can be detected according to DIN EN 14719:2005 by extraction with acetone or dichloromethane, for example with the aid of an ultrasonic bath, and subsequent gas chromatography-mass spectrometer (GC-MS) analysis.
  • GC-MS gas chromatography-mass spectrometer
  • a corresponding cellulose fiber-based packaging product is also suitable for packaging food, for example.
  • FIG. 1 shows an exemplary embodiment of a process scheme for producing the first material comprising at least one cellulose fibers or the chemical semi-pulp;
  • FIG. 2 shows an exemplary embodiment of a process scheme for the mechanical processing of an aqueous solid suspension of the chemical semi-chemical pulp
  • 3 shows an exemplary embodiment of a process diagram of a headbox and a wire section
  • FIG. 5 shows an exemplary embodiment of a process scheme for producing a composite nonwoven web
  • FIG. 6 shows an exemplary embodiment of a process diagram of a drying section
  • FIG. 7 shows a detail of an exemplary embodiment of a cellulose fiber-based packaging product in longitudinal section
  • FIG. 8 shows a detail of a further exemplary embodiment of a cellulose fiber-based packaging product in longitudinal section
  • FIG. 9 shows a detail of a further exemplary embodiment of a cellulose fiber-based packaging product in longitudinal section.
  • the method for producing cellulose fiber-based packaging products begins, as shown roughly schematically in Fig.l, with the production of at least one first material 1 comprising cellulose fibers.
  • comminuted hardwood 2 or a mixture of different, comminuted hardwoods 2 can be used as a starting material for producing the at least one first material 1 comprising cellulose fibers. It can preferably be provided that for the production of the at least one cellulose fiber comprising first material 1 as comminuted hardwood 2, a mixture of 60% by weight to 90% by weight chopped beech wood and 10% by weight to 40% by weight chopped oak wood. In particular, a mixture of 70% by weight to 85% by weight comminuted beech wood and 15% by weight to 30% by weight comminuted oak wood can be used. Mixtures of these comminuted hardwoods 2 in the stated weight percent ranges have proven to be particularly well suited for producing the at least one, first material 1 with the desired parameters or properties, as will be described below.
  • the comminuted hardwood 2 is then produced by a process comprising chemical treatment of the comminuted hardwood 2 in a digester 3 or pulp digester 3 .
  • the first material comprising at least one cellulose fiber
  • 100% by weight dry matter of the chemical semi-pulp 6 means the absolutely dry chemical semi-pulp 6 under the term “atro”, ie its atro mass.
  • the chemical semi-pulp 6 can preferably be produced with a lignin content according to JAYME/KNOLLE/RAPP of 9 to 17% by weight, based on 100% by weight dry matter of the chemical semi-pulp 6 .
  • the chemical semi-pulp 6 can contain at least 50 wt. %, preferably at least 70 wt about 15 to 30% by weight, preferably 20 to 25% by weight, of hemicelluloses based on 100% by weight of dry matter of the chemical semi-pulp.
  • the chemical half-pulp 6 can have 51 to 75% by weight, in particular 58 to 70% by weight, cellulose fibers with the specified length-weighted, average fiber-length range according to ISO 16065-2:2014.
  • the chemical semi-pulp 6 may have cellulosic fibers with a length-weighted average fiber length according to ISO 16065-2:2014 of 0.8 mm to 1.1 mm.
  • a chemical semi-pulp 6 can be produced as the first material, based on 100% by weight dry matter of the semi-pulp 6 having an extract content according to ISO 14453:2014 of 0.3% by weight 1.0% by weight.
  • the first material 1 is a chemical semi-pulp 6 with an ash residue according to ISO 1762:2015 of less than 2% by weight.
  • a chemical half-pulp 6 with no detectable content of diisopropylnaphthalenes is produced as the first material 1 .
  • these measures can improve the aging resistance of the manufactured packaging product, but above all, a possible scope of use of the packaging products can also be expanded, for example into the food packaging sector.
  • diisopropylnaphthalenes can be detected according to DIN EN 14719:2005 by extraction with acetone or dichloromethane, for example with the aid of an ultrasonic bath, and subsequent gas chromatography-mass spectrometer (GC-MS) analysis.
  • GC-MS gas chromatography-mass spectrometer
  • the crushed hardwood 2 or the mixture of hardwoods 2 can be chemically treated using or in a pulping solution containing 9 g/L to 50 g/L of active alkali, expressed as NaOH.
  • active alkali primarily includes the sum of the hydroxyl and hydrosulfite species of the digestion solution, as described, for example, in SCAN-N 2:88, 1988, and can be determined, for example, according to the titration procedure described in SCAN-N 30 will.
  • the concentration is given by converting the values obtained using the molecular weight of NaOH ( ⁇ 40 g/mol).
  • the crushed hardwood 2 or the mixture of hardwoods 2 can be chemically treated by means of or in a pulping solution containing 15 g/L to 34 g/L of active alkali, expressed as NaOH.
  • a temperature of the digestion solution during the chemical treatment can be 150° C. to 180° C., preferably 160° C. to 175° C., and a duration of the chemical treatment can be 25 minutes to 45 minutes, preferably 30 minutes to 40 minutes.
  • a weight ratio of pulping solution/hardwood can be, for example, 3 to 8 m 3 /bdt wood, preferably about 4.5 to 7 m 3 /bdt wood, in the chemical treatment of the hardwood 2 .
  • the abbreviation or unit bdt refers to the term "bone dry ton" commonly used in paper technology and refers to thus one tonne of absolutely dry wood in terms of the Atro weight.
  • the comminuted hardwood may be chemically treated in a pulping solution comprising an amount of active alkali of about 7.5% to 15%, preferably 10% to 15%, based on the total weight of dry wood.
  • a sulfidity of the digestion solution can be, for example, 60 to 65% based on active alkali.
  • the first material 1 comprising at least one cellulose fiber can be prepared by a process comprising chemical treatment of comminuted hardwood 2 in a pulping solution having from 3 g/L to 21 g/L NaOH, preferably having from 6 g/L to 14 g/L NaOH are produced. Furthermore, it can be provided that the first material 1 comprising at least one cellulose fiber is treated chemically by a process comprising chemical treatment of comminuted hardwood 2 in a pulping solution containing from 6 g/L to 29 g/L Na2S, preferably from 9 g/L to 20 g/L Na2S expressed as NaOH is produced.
  • the first material 1 comprising at least one cellulose fiber can also be produced by a process comprising chemical treatment of comminuted hardwood 2 in a pulping solution containing from 10 g/L to 50 g/L Na2COs, preferably from 17 g/L to 34 g/L Na2COs, expressed as NaOH. This has particularly advantageous effects on the production process itself, since the digestion solution can be recovered in a simplified manner, as described below.
  • the digestion solution can, of course, have the above-mentioned components together, ie NaOH, Na2S and Na2COs, with the active alkali being formed primarily by NaOH and Na2S.
  • the digestion solution from the digester 3 can optionally be further treated in a blow tank 4 after the chemical treatment.
  • the first material 1 comprising cellulose fibers can then be separated from the digestion solution obtained after the chemical treatment, also referred to as black liquor, for example by means of washing presses 5. After the black liquor has been separated, the chemical semi-pulp 6 obtained can still be processed in a process shown in Fig. 1 process step not shown in detail and then further processed.
  • the black liquor obtained by boiling in the digester 3 can, as roughly illustrated in FIG. 1, be processed via a recovery section 7 and used again as a digestion solution be returned to the digester 3.
  • a treatment line 7 can include a concentration or evaporation of the black liquor and then incineration of the evaporated black liquor.
  • a reusable pulping solution can then be produced from the resulting inorganic melt, as is customary in the paper industry, by diluting it with water and/or fresh thin white liquor and fed back to the boiler 3 .
  • white liquor it has been shown here that no comprehensive or complete processing of the black liquor into a so-called white liquor is necessary for the production of the chemical semi-pulp 6 or the first material 1 comprising cellulose fibers.
  • the pulping solution used in the digester 3 to produce the chemical semi-pulp 6 can expediently contain Na2COs in the concentration range already specified above, which means that complete causticization in the processing of the black liquor can be dispensed with.
  • a digestion solution containing Na2COs can also be referred to as green liquor in technical jargon.
  • the first material 1 comprising at least one cellulose fiber or the chemical semi-cellulose 6 can then be further processed.
  • mechanical processing and defibration of an aqueous solid suspension of the chemical semi-chemical pulp 6 is carried out in a high-consistency defibrator 8 or high-consistency refiner 8 .
  • the chemical semi-pulp 6 can first be diluted in a tank 9 with an optional circulating device to form an aqueous suspension of solids.
  • a consistency of the solids suspension before mechanical processing and defibration in the high-consistency defibrator 8 can be set to 30% to 40%, for example.
  • Such defibration in a high-consistency defibrator 8 serves, among other things, to reduce the so-called splinter content of the chemical half-pulp 6, ie the dissolution of pulp agglomerates that are still wood-like. It has proven advantageous if the solid suspension of the chemical semi-pulp 6 defibrates to a shive content of less than 15% according to T 275 sp-02:2007 with a Schopper-Riegler value according to ISO 5267-1:1999 of more than 28°SR will.
  • the splinter content according to T 275 sp-02:2007 can be determined in particular with a Somerville apparatus with a slit width of 0.15 mm. As is also shown in Fig.
  • mechanical processing of the chemical semi-cellulose 6 can also be entirely unnecessary.
  • Mechanical processing or defibration of the chemical semi-pulp 6 primarily has a positive effect on drying behavior in the course of further processing of the chemical semi-pulp 6 and on the air permeability or porosity and, for example, the mechanical properties of the packaging products produced.
  • a chemical composition of the at least one, first aqueous suspension can also be set or adjusted before further processing, as is known per se in paper or pulp technology.
  • the at least one first aqueous suspension can be admixed with additives or aggregates and auxiliaries that are customary in paper technology, such as fillers, starch, etc.
  • additives or aggregates and auxiliaries that are customary in paper technology, such as fillers, starch, etc.
  • auxiliaries that are customary in paper technology, such as fillers, starch, etc.
  • a constant part of conventional design can be provided, which was represented only schematically by tank 12 in FIG. 3 . In reality, such a constant part can of course also include other common components.
  • a consistency of the at least one, first aqueous suspension can be adjusted to a value of 0.5% to 1.8%, preferably 0.8% to 1.5%, before further processing. This can be done, for example, by feeding water into the tank 12. The further processing of this at least one first suspension can then take place in a known manner using a paper machine, as is described roughly schematically below with reference to FIGS.
  • the at least one, first aqueous suspension comprising the chemical semi-chemical pulp 6 can be applied to a circulating endless wire 13 of a wire section 14, as is known per se.
  • the at least one, first aqueous suspension is equalized and pre-dried to form at least one water-containing, first nonwoven web 15 , as is illustrated schematically in FIG. 3 .
  • the wire 13 can here be guided over dewatering means 16 of the wire section 14, which dewatering means 16 can be formed, for example, by suction strips. In principle, dewatering in a wire section 14 can only be effected by gravity.
  • the dewatering or pre-drying of the at least one, first nonwoven web 15 can be supported by generating a vacuum using a vacuum device 17.
  • the at least one first fleece web 15 comprising the chemical semi-chemical pulp 6 can be pre-dried by means of the wire section 14 to a water content of 70% by weight to 85% by weight, for example.
  • the at least one, first aqueous suspension or the at least one, first nonwoven web 15 can, in principle, also be admixed with other additives or additives customary in the paper industry, such as fillers, starch, etc., with such additives preferably only being used in small amounts will. It can preferably be provided that the at least one, first fleece web 15, based on 100 wt.
  • the at least one, first fleece web 15 can then be dried further by means of a press section 18 as shown in FIG. 4 .
  • the at least one, first fleece web 15 can, as shown, be guided between rollers 19 of the press section 18 and thereby be further dewatered under high pressure.
  • further drying can be additionally supported by means of absorbent support material, as is known per se, for example by the felt mats 20 shown in Fig. 4.
  • a water content of the at least one, first nonwoven web 15 after it has been passed through a press section 18 can, for example, be approx % by weight to 65% by weight, based on the total mass of the fleece web 15 .
  • a press section 18 is shown only in part for the purpose of better clarity, as can also be seen from the tear lines.
  • a press section 18, as is known per se, can comprise more than just two rolls 19; in particular, several pairs of rolls formed by rolls 19 can be arranged one after the other, with individual pairs of rolls being able to be designed quite differently.
  • a so-called shoe press and a so-called nip press should be mentioned at this point as examples of possible designs of press sections.
  • the at least one, first nonwoven web 15 comprising the cellulose fibers
  • FIG. 5 Such an example for the production of a cellulose fiber-based packaging product, made from several nonwoven webs, will now be explained in more detail with reference to FIG The method shown schematically in FIG. 5 is selected purely as an example. Of course, other embodiments of the method than that shown in FIG. 5 are also possible.
  • one or more further water-containing fleece web(s) 21, 22 can optionally be made from one or more material(s) comprising cellulose fibers via the production of one or more further aqueous suspensions) and their Pre-drying ready or made.
  • Such further fleece webs 21, 22 can basically be produced analogously or in a similar way to that described above with reference to FIGS. 1 to 4. However, it is of course also possible for further fleece webs 21, 22 to be produced in a different manner using other methods known per se in the paper industry. In principle, such further fleece webs can also comprise the first material 1 comprising cellulose fibers or the chemical semi-cellulose 6 or consist largely of it. However, it is of course also possible for further fleece webs 21, 22 to be produced from other materials comprising cellulose fibers, for example by recycling methods from waste paper or from hardwood or softwood or other plants containing cellulose by mechanical, thermomechanical and/or chemical processing methods, subsequent equalization and drying to nonwoven webs. For example, such further nonwoven webs 21, 22 may comprise mechanical pulp or chemically processed pulp. Such further fleece webs 21, 22, like the at least one, first fleece web 15, can optionally be admixed with additives customary in the paper industry.
  • one of the other fleece webs 21 can be produced in this fleece web 21 by corrugating rollers 23, which can optionally be heated, to produce a packaging box. Subsequently, such a corrugated fleece web 21 can be connected to the at least one, first fleece web 15 and optionally to one or more further fleece web(s) 22 .
  • a connection of the non-woven webs 15, 21, 22 can, for example, in principle take place before further drying by wet pressing, but can also take place, for example, by gluing or gluing. In this respect it is possible that a Nonwoven webs 15, 21, 22 are produced and dried in different systems or paper machines, with the nonwoven webs 15, 21, 22 then being connected afterwards by gluing or gluing.
  • optional, further fleece webs 21, 22 may also include the chemical semi-cellulose 6.
  • more or fewer nonwoven webs 21, 22 than shown in the exemplary embodiment according to FIG. 5 are combined to produce the packaging product.
  • only the at least one, first water-containing fleece web 15 is processed into a packaging product.
  • the water-containing first fleece web 15 and optionally further, water-containing fleece webs 21, 22 are finally processed further to form the cellulose-fiber-based packaging product with further drying of the fleece web(s) 15, 21, 22.
  • the fleece web(s) 15, 21, 22 are finally dried by means of a drying section 24 to a desired water content.
  • a drying section 24 For better clarity, only the at least one, first fleece web 15 is shown in FIG.
  • a drying section 24 can comprise numerous rotating drying cylinders 26 over which the at least one, first nonwoven web 15 or optionally the nonwoven web composite 25 can be guided.
  • the drying cylinders can be heated directly.
  • heating ducts not shown in detail in FIG.
  • a temperature of the drying cylinders 26 of a drying section 24 can, for example, increase successively in the direction in which the at least one nonwoven web 15 or optionally a nonwoven web composite 25 is fed through.
  • a drying section 24 can additionally comprise further dewatering aids, such as the wire webs 27 shown in FIG.
  • Such screen webs 27 can, for example, prevent the at least one, first fleece web 15 or the fleece web composite 25 from running off the hot drying cylinders 26 .
  • a first nonwoven web 15 or optionally the nonwoven web composite 25 can be dried by means of the drying section 24, for example to a water content of 1% by weight to 10% by weight.
  • the cellulose fiber-based packaging product obtained can, of course, also be made up according to the requirements, which is usually made up into roll or endless packaging products.
  • first nonwoven web 15 comprising the chemical semi-chemical pulp 6
  • cellulose fiber-based packaging products 29 are shown in longitudinal section in sections, these three exemplary embodiments being purely exemplary and, of course, further embodiment variants being possible, as has already been explained above with reference to the description of the method.
  • a cellulose fiber-based packaging product can be produced in particular according to the method steps or measures described above.
  • a cellulose fiber-based packaging product 29 consists of at least 30% by weight of a chemical semi-pulp 6, comprising cellulose fibers with a length-weighted, mean fiber length according to ISO 16065-2:2014 from 0.6 mm to 1.2 mm and hemicelluloses and, based on 100% by weight of dry matter of the semi-pulp, having a lignin content JAYME/TUBE/RAPP from 8% to 18% by weight and an extract content according to ISO 14453:2014 from 0.2% to 1.5% by weight.
  • a chemical semi-pulp 6 comprising cellulose fibers with a length-weighted, mean fiber length according to ISO 16065-2:2014 from 0.6 mm to 1.2 mm and hemicelluloses and, based on 100% by weight of dry matter of the semi-pulp, having a lignin content JAYME/TUBE/RAPP from 8% to 18% by weight and an extract content according to ISO 14453:2014 from 0.2% to 1.5% by weight.
  • the chemical semi-pulp 6 can preferably have a lignin content according to JAYME/KNOLLE/RAPP of 9 to 17% by weight, based on 100% by weight dry matter of the chemical semi-pulp 6 .
  • the chemical semi-pulp 6 may contain at least 50 wt. %, preferably at least 70 wt. %, cellulose fibers having the specified length-weighted average fiber length range, based on 100 wt about 15 to 30% by weight, preferably 20 to 25% by weight, of hemicelluloses.
  • the chemical half-pulp 6 can have 51 to 75% by weight, in particular 58 to 70% by weight, cellulose fibers with the specified length-weighted, mean fiber-length range according to ISO 16065-2:2014.
  • the chemical semi-pulp 6 may have cellulosic fibers with a length-weighted average fiber length according to ISO 16065-2:2014 of 0.8 mm to 1.1 mm.
  • the chemical half-pulp 6 can particularly preferably have an extract content according to ISO 14453:2014 of 0.3% by weight 1.0% by weight, based on 100% by weight of dry matter of the half-pulp 6 .
  • a cellulose fiber-based packaging product 29 consists of at least 60% by weight of the chemical half-cellulose 6 .
  • the cellulose fiber-based packaging product 29 consists of two paper layers 30, 31 connected to one another, with at least one paper layer 30 comprising the chemical half-cellulose 6 or at least predominantly consisting of the chemical half-cellulose 6.
  • the other paper layer 31 can comprise another material having cellulose fibers, for example wood pulp, cellulose or recycling material or processed waste paper.
  • the layer 31 can also comprise other non-fiber-based materials such as plastics, metals or other materials or mixtures of materials.
  • the packaging product 29 in the form of a box consists of a total of three paper layers 30, 31, 32 connected to one another, with a corrugated paper layer 32 being surrounded by two uncorrugated paper webs or layers 30, 31 in this embodiment .
  • at least one paper ply 30 can comprise the chemical semi-chemical pulp 6 or consist at least predominantly of the chemical semi-chemical pulp 6 .
  • the corrugated paper layer 32 can, for example, comprise recycled waste paper or cellulose fibers obtained from waste paper, while the second uncorrugated paper layer 31 can comprise, for example, another cellulose, such as kraft pulp.
  • the two outer, uncorrugated paper layers 30 , 31 may comprise the chemical half-cellulose 6 or to consist at least predominantly of the chemical half-cellulose 6 .
  • the two outer, uncorrugated paper layers 30 , 31 may comprise the chemical half-cellulose 6 or to consist at least predominantly of the chemical half-cellulose 6 .
  • At least one outer paper layer 30 of the packaging product 29 comprises the chemical semi-chemical pulp 6 or consists at least predominantly of the chemical semi-chemical pulp 6 .
  • this at least one paper ply 30 consists of at least 60% by weight of the chemical half-pulp 6 .
  • a cellulose fiber-based packaging product can preferably be characterized in that at least 80% of its outer surface is characterized by an L* value of 47 to 54 in the L*a*b* color space according to ISO 5631-2:2015, an a* value of 6.2 to 7.5 and a b* value of 14.0 to 18.5.
  • L* value 47 to 54 in the L*a*b* color space according to ISO 5631-2:2015
  • a* value of 6.2 to 7.5 and a b* value of 14.0 to 18.5.
  • Such a color quite closely conforms to packaging standards common in the packaging industry, such as a package, and can thereby provide a packaging product with high merchant and consumer acceptance.
  • the chemical semi-chemical pulp of the packaging product 29 has an ash residue according to ISO 1762:2015 of less than 2% by weight.
  • the chemical half-cellulose of the packaging product 29 has no detectable content of diisopropylnaphthalenes according to DIN EN 14719:2005.
  • these features can above all expand a possible scope of use of the packaging product produced, for example into the food packaging sector. Diisopropylnaphthalenes can be detected, for example, by means of GC-MS analysis.
  • the chemical semi-pulp was produced by chemically treating or boiling a mixture of comminuted hardwoods consisting of 80% by weight comminuted beech wood and 20% by weight comminuted oak wood, based on the total mass of comminuted hardwood.
  • This comminuted hardwood mixture was chemically treated at 168° C. for 35 minutes in a pulping solution with a weight ratio of pulping solution/hardwood or hydromodulus of 7m 3 /bdt (bone dry ton) hardwood.
  • the active alkali content of the digestion solution was varied as follows:
  • Semi-pulp sample A approx. 10% active alkali based on total dry mass
  • Semi-pulp sample B about 7.5% active alkali based on the total mass of dry hardwood; Sulfidity 62 to 63% based on active alkali.
  • Semi-pulp sample C about 15% active alkali based on the total mass of dry hardwood; Sulfidity 62 to 63% based on active alkali.
  • a length-weighted average fiber length of the cellulose fibers of 0.75 to 1.09 mm according to ISO 16065-2:2014 was determined for all chemical semi-pulps used to produce paper samples A to C.
  • Extract content 0.9% by weight to 1.0% by weight
  • Semi-pulp sample B lignin content: 14 wt% to 16 wt%
  • Extract content 1.1% by weight to 1.3% by weight
  • Semi-pulp sample C Lignin content: 9 wt% to 11 wt% Extract content: 0.6 wt% to 0.7 wt%
  • Semi-pulp samples A, B, C were further processed by mechanical processing or grinding in a low-consistency refiner, Double Disc LC Refiner (TwinFlow IIIB), with 250 to 450kWh/adt in two or one stage at a consistency of 4%, and were derived from these semi-pulp samples then paper samples A, B and C were produced according to ISO 5269-2:2004 and examined with regard to mechanical properties.
  • SCT index was determined according to ISO 9895:2008, which characterizes the compression resistance or compression strength, which is important in the packaging industry.
  • Paper samples A SCT index 27.1 to 29.2 Nm/g Paper samples B: SCT index 21.6 to 28.9 Nm/g Paper samples C: SCT index 29.0 to 30.9 Nm/g
  • Lignin and extract contents in excess of this as in the case of the semi-pulp or paper samples B, which can be obtained by reducing the concentration of active alkali during the chemical treatment, result in a deterioration in the mechanical properties of the products made from them.
  • a further reduction in the lignin and extract contents compared to the half-pulp and paper samples A as in the case of the half-pulp and paper samples C are significantly more inefficient and also more expensive from a procedural point of view, and do not lead to a significant extent to a further improvement of the mechanical Properties.
  • the values determined for the SCT index for the paper samples A are at least in the vicinity of the range which can be determined for comparative paper samples made from almost completely delignified pulp.
  • Such chemical pulps can be produced, for example, by the so-called Kraft pulping or the known sulphate process, and comparative paper samples produced therefrom in accordance with ISO 5269-2:2004 have SCT indices of 30.0 Nm/g to 32.0 Nm/g .
  • typical paper samples made from pulp obtained using waste paper recycling methods have SCT indices of 18.0 Nm/g to 20.0 Nm/g.
  • semi-pulp samples A were processed in different ways using a high-consistency pulper, 36 inch double disc HC refiner with a gap width of 6 to 10 mm and in the second stage with 60 - 120 kWh/adt at a consistency of over 30%, shredded. This was followed by mechanical processing using a low-consistency refiner, Double Disc LC Refiner (Twin-Flow IIIB), with 250 to 450 kWh/adt in two or one stage at a consistency of 4%.
  • the semi-pulp samples mechanically treated in this way were examined according to ISO 5267-1:1999 with regard to drainage behavior.
  • paper samples were again produced from the variably treated semi-pulp samples A in accordance with ISO 5269-2:2004.
  • paper samples according to ISO 5269-2:2004 were also prepared from untreated semi-pulp samples A.
  • Half-pulp sample Al prepared from untreated half-pulp samples A.
  • Half-pulp sample A2 prepared from half-pulp samples A treated with a high-consistency pulper
  • Semi-pulp sample A3 prepared from low-consistency refining semi-pulp samples A
  • Semi-pulp sample A4 prepared from semi-pulp samples A treated with a high-consistency defibrator and then with a low-consistency refiner
  • Paper samples A1 to A4 were in turn produced from these semi-pulp samples A1 to A4 in accordance with ISO 5269-2:2004, and their mechanical properties were examined.
  • All examined paper samples A made from semi-pulp samples A, have a surface which is characterized in the L*a*b* color space according to ISO 5631-2:2015 by an L* value of 47 to 52, an a* value of 6.2 to 7.0 and a b* value of 14.0 to 16.5.

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Abstract

L'invention concerne un procédé de fabrication de produits d'emballage à base de fibres cellulosiques ainsi qu'un produit d'emballage à base de fibres cellulosiques. Le procédé comprend la fabrication au moins d'une première matière comprenant des fibres cellulosiques, au moins d'une première suspension contenant cette première matière, puis son traitement et son séchage pour obtenir une première bande nappée. En temps que première matière, est fabriquée une pâte mi-chimique, présentant des fibres cellulosiques d'une longueur moyenne des fibres pondérée en longueur selon ISO 16065-2:2014 de 0,6 mm à 1,2 mm ainsi que des hémicelluloses, et présentant par rapport à 100 % en poids de masse sèche de la pâte mi-chimique une teneur en lignine selon J A YME/KN OLLE/RAPP comprise entre 8 % en poids et 18 % en poids ainsi qu'une teneur en extrait selon ISO 14453:2014 comprise entre 0,2 % en poids et 1,5 % en poids.
PCT/AT2021/060272 2020-08-06 2021-08-05 Procédé de fabrication de produits d'emballage à base de fibres cellulosiques et produit d'emballage à base de fibres cellulosiques WO2022027080A1 (fr)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
EP1375734A1 (fr) * 2002-06-17 2004-01-02 SCA Hygiene Products GmbH Pâte chimique au sulfite blanchie et résistante, procédé de production et produits obtenus
WO2012115526A1 (fr) * 2011-02-24 2012-08-30 Wpi International Ltd Procédé amélioré de production de pâte à partir de pinus radiata
WO2015200772A2 (fr) * 2014-06-26 2015-12-30 Api Intellectual Property Holdings, Llc Fibres de cellulose renforcées par de la nanocellulose
WO2018049522A1 (fr) * 2016-09-14 2018-03-22 Fpinnovations Procédé de transformation de fibres de pâte à haute consistance en matériaux fibreux semi-secs et secs pré-dispersés
US20180127919A1 (en) * 2016-11-01 2018-05-10 International Paper Company Process for producing increased bulk pulp fibers, pulp fibers obtained, and products incorporating same
WO2018086672A1 (fr) * 2016-11-11 2018-05-17 Teknologisk Institut Procédé de préparation d'une fraction de fibre riche en cellulose et sous-produits de valeur
WO2020152178A1 (fr) * 2019-01-22 2020-07-30 Jena Trading Aps Préparation de fibres de cellulose

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1375734A1 (fr) * 2002-06-17 2004-01-02 SCA Hygiene Products GmbH Pâte chimique au sulfite blanchie et résistante, procédé de production et produits obtenus
WO2012115526A1 (fr) * 2011-02-24 2012-08-30 Wpi International Ltd Procédé amélioré de production de pâte à partir de pinus radiata
WO2015200772A2 (fr) * 2014-06-26 2015-12-30 Api Intellectual Property Holdings, Llc Fibres de cellulose renforcées par de la nanocellulose
WO2018049522A1 (fr) * 2016-09-14 2018-03-22 Fpinnovations Procédé de transformation de fibres de pâte à haute consistance en matériaux fibreux semi-secs et secs pré-dispersés
US20180127919A1 (en) * 2016-11-01 2018-05-10 International Paper Company Process for producing increased bulk pulp fibers, pulp fibers obtained, and products incorporating same
WO2018086672A1 (fr) * 2016-11-11 2018-05-17 Teknologisk Institut Procédé de préparation d'une fraction de fibre riche en cellulose et sous-produits de valeur
WO2020152178A1 (fr) * 2019-01-22 2020-07-30 Jena Trading Aps Préparation de fibres de cellulose

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Title
JAYME G.KNOLLE H. U. G. RAPP: "Entwicklung und endgültige Fassung der Lignin-Bestimmungsmethode nach JAYME-KNOLLE", DAS PAPIER, vol. 12, no. 17/18, 1958, pages 464 - 467

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