WO2012010181A1 - Marine plants processing method for the production of pulp for the production of paper - Google Patents

Marine plants processing method for the production of pulp for the production of paper Download PDF

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Publication number
WO2012010181A1
WO2012010181A1 PCT/EP2010/004390 EP2010004390W WO2012010181A1 WO 2012010181 A1 WO2012010181 A1 WO 2012010181A1 EP 2010004390 W EP2010004390 W EP 2010004390W WO 2012010181 A1 WO2012010181 A1 WO 2012010181A1
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WO
WIPO (PCT)
Prior art keywords
cellulose
phase
paper
high content
product
Prior art date
Application number
PCT/EP2010/004390
Other languages
French (fr)
Inventor
Francesco Benvegnu'
Marco Pez
Original Assignee
Benvegnu Francesco
Marco Pez
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Benvegnu Francesco, Marco Pez filed Critical Benvegnu Francesco
Priority to PCT/EP2010/004390 priority Critical patent/WO2012010181A1/en
Priority to EP10737503.2A priority patent/EP2596166A1/en
Publication of WO2012010181A1 publication Critical patent/WO2012010181A1/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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/14—Disintegrating in mills
    • D21B1/16—Disintegrating in mills in the presence of chemical agents
    • 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
    • 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
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
    • 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
    • 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
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • the present invention relates to a marine plants processing method for the production of pulp for the production of paper according to the characteristics of the pre-characterizing part of claim 1 .
  • the present invention also relates to the paper obtained by the pulp obtained by means of the described method.
  • paper generically indicates all of the types of paper with basic weighs up to 140 g/m 2 , as well as paperboard with basic weighs between 140 g/m 2 and 400 g/m 2 cardboard with basic weighs higher than 400 g/m 2 , and the corrugated board.
  • it is intended as a material essentially consisting of vegetal fibers, joined together by feltration, that is by means of firm reciprocal connection of the fibers starting from a suspension to be dried, with possible addition of bonding agents, minerals, dyes and additives or superficial films.
  • selection product one intends the just collected product, as well as already in a partial maceration phase product, and the previously dried product which is successively re-humidified, possibly with addition of anti fermentation agents.
  • a quantity of water so as to obtain the superficial covering of the matter to be treated it is intended that the matter is placed in a container having dimensions corresponding to the volume of the matter and water is added until the matter is superficially covered.
  • a quantity of about 10-20 liters is needed depending on the shape of the container and on the consistence of the matter.
  • the normally used manufacturing process provides, starting from the wood, a preparation phase of the fibers by means of pulping obtaining a mixture of fibers in a liquid suspension, a bleaching phase, a forming phase of the sheet and a relative pressing, possible phases of surface treating and a drying phase.
  • the process occurs directly using a cellulose pulp obtained elsewhere or deriving from the recycling of other paper.
  • other types of fibres can also be used, e.g. cotton, linen and hemp.
  • GB508671 discloses a processing method of algae marine to obtain a pulp to be used in the production process of the paper based on a digestion process of the algae in an acid aqueous solution.
  • GB363353 discloses a processing method of algae marine for the extraction of salts, alginic acids and cellulose that provides the use of solutions based on Calcium Chloride.
  • EP0488486 describes a processing method to obtain a pulp applied to particular types of algae which essentially are unicellular algae belonging to the genus of closterium and pleutotaenuim containing cellulose and having a relation between length of the body and width of the body between 10 and 200.
  • EP0565920 describes a treatment process of algae marine in which the algae marine are submitted to a washing phase which is followed by an anti-fermenting treatment and to a grinding phase until sizes lower than 500 micron are obtained for a successive blending with cellulose fibers which are usually used in the production of paper.
  • the process to obtain paper starting from the wood presents many drawbacks, above all from the environmental point of view, both due to the need to cut trees, and due to the need to use chemical compounds for the defibration of the lignin, e.g. caustic soda and sodium sulfide, besides chemical compounds for the bleaching, e.g. chlorine or chlorine dioxide.
  • the process has environmental disadvantages (sulphur generates smell of bad eggs, and many aqueous waste products are present) and yield disadvantages (only 50% of the wood is transformed in paper pulp, even if many waste products are burnt obtaining energy).
  • a defibration phase of the lignin has to be provided, though therein the lignin content is lower.
  • the process disclosed in GB508671 has the disadvantage to need the use of a digestion process using strong acids, with resulting problems relative to precautions to be adopted during the process to avoid the exposure to such acids, in addition to the treatment and disposal problems of the processing residues and to the need of alkaline treatments of the obtained pulp to neutralize the acids themselves.
  • the process described for the production of paper or cardboard anyway requires the addition of the pulp obtained by the algae to a traditional pulp, limiting the benefits coming from the use of the algae and anyway involving the problems previously described relatively to the obtainment of the pulp which is traditionally used in the production of paper.
  • the process disclosed in GB363353 presents the disadvantage of the use of chemical compounds which require a lot of care during their handling and use, and in particular it makes use of Calcium Chloride, in addition to the treatment and disposal problems of the processing residues.
  • the described process does not describes how the following paper production occurs, but it is limited to the description of the extraction of the cellulose from the algae without specifying how it will be used, supposedly by means of addiction of the pulp obtained by the algae to a traditional pulp, limiting the benefits deriving from the use of the algae and anyway involving the problems previously described relatively to the obtainment of the pulp which is traditionally used in the production of paper.
  • EP0488486 describes a method which is applicable only to microalgae which live in fresh water which are very different from macroalgae marine and marine plants.
  • EP0565920 anyway requires the addition of the pulp obtained from the algae to a traditional pulp, limiting the benefits deriving from the use of the algae and anyway involving the problems previously described relatively to the obtainment of the pulp which is traditionally used in the production of paper.
  • the aim of the present invention is to supply a marine plants processing method for the production of paper which allows to obtain paper without the use of pulp derived from trees.
  • the method according to the present invention does not need of the use of reactors containing chlorine or its derivates for the bleaching process! This is a considerable advantage from the environmental point of view with respect to the normal paper production processes starting from the wood or in the recycling processes of the paper itself. Moreover, advantageously the use of marine plants allows to obtain also the disposal of the marine plants or parts of the marine plants which deposit on the the littoral zones and which are normally sent to garbage dump.
  • Fig. 1 represents a flow diagram showing the production method of paper from marine plants according to the present invention.
  • the processing method of marine plants for the production of paper according to the present invention preferably but not limitatively occurs by means of the use of marine plants known as fanerogame marine, which are higher plants which are very different from algae, because they are provided with roots, leaves and true flowers.
  • Fanerogame marine live in the waters of the littoral zones and cover the sea bed forming prairies.
  • fanerogame marine useful in the use for the present invention the following ones are present: Zostera, Posidonia, Cymodocea, Syringonium, Thalassia, Halophila, Thalassodendron.
  • Cymodocea also Cymodocea nodosa, Cymodocea rotundata, Cymodocea serrulata, etc. are intended to be included.
  • Syringonium also Syringonium filiforme, Syringonium isoetifolium, etc. are intended to be included.
  • Halophila also Halophila beccarii, Halophila decipiens, Halophila minor, Halophila ovalis, etc. are intended to be included.
  • Zostera also Zostera marina, Zostera noltii, etc. are intended to be included.
  • Posidonia also Posidonia oceanica, Posidonia australis, Posidonia sinuosa, etc. are intended to be included.
  • Thalassia also Thalassia hemprichii, Thalassia testudinum, etc. are intended to be included.
  • the method according to the present invention does not need of the use of reactors containing chlorine or its derivates for the bleaching process. This is a considerable advantage from the environmental point of view with respect to the normal paper production processes starting from the wood or in the recycling processes of the paper itself.
  • marine plants allows to obtain also the disposal of the marine plants or parts of the marine plants which deposit on the the littoral zones and which are normally sent to garbage dump.
  • the inventors found that the thus obtained sheet presents a good absorbent power of the ink also without the need to use further treatments and additives, with further benefits from the environmental point of view.
  • the inventors believe that the surprising obtained results are due to the high content of cellulose of the used marine plants, in particular the fanerogame marine and, more in detail the listed fanerogame marine and the poseidonia oceanica.
  • additives can be added to obtain the desired properties, e.g. starch, polymeric glossing agents e.g. vinyl polyacetate (PVA).
  • PVA vinyl polyacetate
  • a glossing phase can also improve the surface smoothing it.
  • kaolin can be provided in a smoothing phase of the paper or the use of a transparent layer, for example consisting of enamel, to give the paper a polished aspect.
  • the solution containing cellulose obtained according to the described method is drained by a flow case with a drain of about 3% of cellulose as a dry residue.
  • the drain occurs through a fissure onto a canvas sliding in a continuous way: the fibers concentrates and are compacted forming the initial sheet with a content of about 80% of water.
  • a pressing phase follows which is performed in a continuous way in a dry-end with rollers which are provided with felts: the fibers are compacted to a higher extent and the sheet undergoes a rolling still losing water and reaching a concentration of about 3-4%.
  • the production method of paper, paperboard, cardboard, substitutes and derivatives according to the present invention provides the use of the pulp having a high content of cellulose which is obtained as previously described following the phases which are performed successively to the phases relative to the method to obtain the pulp having a high content of cellulose obtained from marine plants:
  • the described production process of pulp does not involve the use of chlorine or derivates for the bleaching operation, obtaining satisfactory results with important advantages from the environmental point of view and from the disposal costs of the working residues.
  • the collection product can be a just collected product (green), as well as an already partially macerating product, as well as a product which was previoulsy dryed and successively re-humidified, possibly with addition of anti fermenting agents.
  • the collection phase it will be apparent that, depending on how the collection itself occurs, in the collection product also elements other than marine plants and/or algae marine can be present, e.g. sand, other vegetals, etc.
  • elements other than marine plants and/or algae marine can be present, e.g. sand, other vegetals, etc.
  • sieving phase is done, for example by means of vibrating screens or sieves, both in a humid condition and in a dry condition.
  • the possibly present sand instead, will be eliminated by means of washing the collection product itself, preferably after the sieving phase, but it will be apparent that the two phases also could be inverted.
  • this phase is equivalent to a preliminary cooking of the product, but the inventors, during the tests which were carried out have found that this phase can also be omitted if the collection product is already partially macerated before the collection or before its use.
  • the treatment can occur in a range of temperatures between 80°C and 250° and for a time between 10 and 60 minutes, preferably for a time between 15 and 30 minutes.
  • the treatment temperature as well as the treatment time can change depending on to the maceration degree of the product subjected to the treatment as well as on the quantity of the product subjected to the treatment and on the arrangement of the product in the cooking chamber.
  • the treatment can occur at a temperature of 180° - 220° for times on the order of 15-30 minutes, with most short times being preferred in the case in which the product to be treated is spread enough inside the treatment chamber, while most long times will be preferred in the case in which the product to be treated is amassed and concentrate. In a similar way most long times will be necessary for higher quantities of product to be treated. If the product is already partially macerated, then lower treatment times will be sufficient and if the product is at a greater maceration state the treatment can also be omitted.
  • the scraping phase is needed to increase the etcheable surface of the reactive which is used in the following phases.
  • this operation has been made manually but it can be made automatic, for example by means of a passage in a mill or in cylinders; the increasing of the chemically etcheable surface of the product is obtained by means of the scraping of the product, with a partial defibration/breakage of the fibers.
  • the disgregation phase of the fibers by means of boiling in a solution of sodium hydroxide, it will continue until the desired maceration degree- is reached.
  • the quantities of sodium hydroxide to be used, as well as the time of the treatment can change depending on the collection product quality.
  • the desired maceration degree can be defined by the end average dimension of the obtained disgregated fibers.
  • other disgregating agents can be used provided that they have the characteristic not to excessively disgregate the cellulose fibers.
  • the chemical disgregation can also be coupled to a mechanical disgregation, even if it can be omitted depending on the maturation degree of the collection product and/or on the maceration degree.
  • the quantity of sodium hydroxide for example using 99% sodium hydroxide in a solid form, the use is provided of 100-200g of sodium hydroxide for every 4 kg of product to be submitted to disgregation in a quantity of water so as to obtain the superficial covering of the matter to be treated, about 10-20 liters.
  • the solution of sodium hydroxide can also be prepared starting by sodium hydroxide in solution, obtaining concentrations corresponding the indicated ones.
  • the successive separation phase of the fibers can occur for example by means of filtering.
  • the bleaching phase of the fibers it occurs by means of a treatment with a chemical bleaching agent, preferably by means of a heat treatment, preferably with hydrogen peroxide in an aqueous solution.
  • concentrations of chemical bleaching agent can change depending on the properties of the bleaching agent itself, as well as depending on the desired bleaching degree.
  • hydrogen peroxide starting from 40 volume hydrogen peroxide, the use is provided of 150-300 ml of 40 volume hydrogen peroxide for every 4 kg of product to be submitted to bleaching in a quantity of water so as to obtain the superficial covering of the matter to be treated, about 10-20 liters.
  • the hydrogen peroxide can also be supplied starting from starting solutions with different concentrations, e.g.
  • hydrogen peroxide diluted 1/4 In general, therefore, for every 4 kg of product to be submitted to bleaching one can use hydrogen peroxide in a quantity such as to supply concentrations corresponding to the ones which are obtained adding in water 40 volume hydrogen peroxide for every 4 kg of product to be submitted to bleaching in quantities between 150 and 300 ml of 40 volume hydrogen peroxide, in a quantity of water so as to obtain the superficial covering of the matter to be treated, which for 4 kg of product is equal to about 10-20 liters.
  • the hydrogen peroxide will be gradually added in successive times, modulating its quantity depending on the bleaching state and on the desired end quality.
  • the treatment preferably occurs in hot conditions at a temperature between 60°C and the boiling-point. The treatment continues for a time between 15-60 minutes depending on the desired quality of the finished product, namely of the color, most long treatment time corresponding to a greater bleaching.
  • the successive suspension phase in water of the product obtained after the filtering and washing phase of the bleached fibers will preferably occur in a container in which the product which was obtained in the previous phases is placed adding water so as to obtain the superficial covering of the product itself.
  • the process according to the present invention can comprise a phase of addition of a bonding agent or glue which can occur in a phase (x) successively to the phase (ix) and previously to the phase (xi) and/or simultaneously to phase (xi) and/or in a phase (xii) following the phase (xi).
  • this addition occurs before the triturating phase to obtain a better amalgamation of the components.
  • the addiction of the bonding agent can occur successively in the case in which the preparation phase of the pulp is separated by the phase of its effective use for the production of the paper.
  • the present invention also allows to stop the process after the triturating phase and before the addition of the bonding agent or anyway in other intermediate stages, for example also to allow the delivery or the preservation of the product, which can possibly be filtered and/or addittivated with possible anti - fermenting agents and/or partially dried for its successive use.
  • a mixing phase to amalgamate the components will be needed.
  • the bonding agent addition will occur in quantities in the range between 10 and 90 ml for every 4 kg of the product, even more preferably in quantities between 25 and 50 ml for every 4 kg of the product, even more preferably 35 ml for every 4 kg of the product, the bonding agent being preferably vinyl glue.
  • the preferred quantities could undergo changing depending on the properties of the bonding agent itself.
  • Posidonia oceanica marine plants have been collected which have been preliminarily cleaned-up from fibres and undesired materials by means of sieving, e.g. foreign bodies which was possibly present.
  • the sieved Posidonia oceanica marine plants have been washed in water and have been left in a suspension condition for 15 minutes in water in order to let the sand decant.
  • the Posidonia oceanica marine plants have been heated by means of passage in a stove for 15 - 20 minutes in order to improve their workability.
  • The' thus obtained product has been boiled with 150g of 99% sodium hydroxide in solid form to in a quantity of water so as to obtain the superficial covering of the product to be treated, about 20-25 litres.
  • the treatment has been continued until a desired disgregation degree was reached, obtaining the disgregation of the fibres. In certain tests a mechanical agitation action has been used obtaining better results and/or shorter times.
  • the disgregated fibers have been separated by means of filtering with a recovery of the corresponding liquid phase; the corresponding recovered liquid phase can be reutiiized for successive treatments by reintegration of sodium hydroxide or it can be disposed after neutralizing the same.
  • a bleaching operation has been performed by means of heat treatment with 225 ml of 40 volume hydrogen peroxide in a quantity of water so as to obtain the superficial covering of the matter to be treated, about 20-25 litres.
  • the treatment temperature was 80°C.
  • a suspension in water of the obtained product has been prepared and one proceeded with a trituration of the fibres in the suspension.
  • Example III Another test was carried out following exactly the same steps of the example I or in an equivalent way of the example II, in the same quantities.
  • the sheets after the drying phase showed pleating, one proceeded with a re-humidification of the sheet itself with an additional successive passage in the press.
  • the additional humidification of the sheet occurred by means of a sponge. After the extraction of the sheet from the press one observed that an effective elimination of the previously present pleating was obtained.

Abstract

Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives, comprising the steps of: (i). Sieving the collection product eliminating possible foreign bodies which are present in the collection product; (ii). Washing the sieved product by means of water removing possible sand which can be present; (v). Obtaining disgregated fibers by means of disgregation of the fibers by means of a treatment with a chemical disgregating agent which does not etches the cellulose fibers, possibly combined with a mechanical disgregation treatment; (vi). Separation of the fibers from the liquid phase by means of filtration recovering the corresponding liquid phase; (vii). Bleaching the fibers obtained from the previous phase by means of a treatment with a chemical bleaching agent; (viii). Filtering, w.ashing by means of water and/or pH balancing treatment.of the bleached fibers and obtainment of an essentially neutral pH; (ix). Suspension of the product obtained from the previous phase in water in a container; (xi). Triturating the suspension obtained from the previous phase obtaining a pulp with a high content of cellulose; said method being further characterised in that said collection product is a marine plants collection product.

Description

DESCRIPTION
MARINE PLANTS PROCESSING METHOD FOR THE PRODUCTION OF PULP FOR THE
PRODUCTION OF PAPER
Technical field
The present invention relates to a marine plants processing method for the production of pulp for the production of paper according to the characteristics of the pre-characterizing part of claim 1 . The present invention also relates to the paper obtained by the pulp obtained by means of the described method.
Definitions
In the present description and in the appended claims the following terms must be intended according to the following definitions. The term "paper" generically indicates all of the types of paper with basic weighs up to 140 g/m2, as well as paperboard with basic weighs between 140 g/m2 and 400 g/m2 cardboard with basic weighs higher than 400 g/m2, and the corrugated board. In general it is intended as a material essentially consisting of vegetal fibers, joined together by feltration, that is by means of firm reciprocal connection of the fibers starting from a suspension to be dried, with possible addition of bonding agents, minerals, dyes and additives or superficial films. With the term "collection product" one intends the just collected product, as well as already in a partial maceration phase product, and the previously dried product which is successively re-humidified, possibly with addition of anti fermentation agents. When one indicates "a quantity of water so as to obtain the superficial covering of the matter to be treated" it is intended that the matter is placed in a container having dimensions corresponding to the volume of the matter and water is added until the matter is superficially covered. Indicatively for 4kg of matter, a quantity of about 10-20 liters is needed depending on the shape of the container and on the consistence of the matter.
Prior art
In the field of the production of the paper the normally used manufacturing process provides, starting from the wood, a preparation phase of the fibers by means of pulping obtaining a mixture of fibers in a liquid suspension, a bleaching phase, a forming phase of the sheet and a relative pressing, possible phases of surface treating and a drying phase. Alternatively the process occurs directly using a cellulose pulp obtained elsewhere or deriving from the recycling of other paper. Depending on the destination of use of the paper other types of fibres can also be used, e.g. cotton, linen and hemp.
GB508671 discloses a processing method of algae marine to obtain a pulp to be used in the production process of the paper based on a digestion process of the algae in an acid aqueous solution.
GB363353 discloses a processing method of algae marine for the extraction of salts, alginic acids and cellulose that provides the use of solutions based on Calcium Chloride.
EP0488486 describes a processing method to obtain a pulp applied to particular types of algae which essentially are unicellular algae belonging to the genus of closterium and pleutotaenuim containing cellulose and having a relation between length of the body and width of the body between 10 and 200.
EP0565920 describes a treatment process of algae marine in which the algae marine are submitted to a washing phase which is followed by an anti-fermenting treatment and to a grinding phase until sizes lower than 500 micron are obtained for a successive blending with cellulose fibers which are usually used in the production of paper.
Problems of the prior art
The process to obtain paper starting from the wood presents many drawbacks, above all from the environmental point of view, both due to the need to cut trees, and due to the need to use chemical compounds for the defibration of the lignin, e.g. caustic soda and sodium sulfide, besides chemical compounds for the bleaching, e.g. chlorine or chlorine dioxide. The process has environmental disadvantages (sulphur generates smell of bad eggs, and many aqueous waste products are present) and yield disadvantages (only 50% of the wood is transformed in paper pulp, even if many waste products are burnt obtaining energy). Also in the case of the use of different fibers, e.g. cotton, linen and hemp, a defibration phase of the lignin has to be provided, though therein the lignin content is lower.
The process disclosed in GB508671 has the disadvantage to need the use of a digestion process using strong acids, with resulting problems relative to precautions to be adopted during the process to avoid the exposure to such acids, in addition to the treatment and disposal problems of the processing residues and to the need of alkaline treatments of the obtained pulp to neutralize the acids themselves. Moreover the process described for the production of paper or cardboard anyway requires the addition of the pulp obtained by the algae to a traditional pulp, limiting the benefits coming from the use of the algae and anyway involving the problems previously described relatively to the obtainment of the pulp which is traditionally used in the production of paper.
Also the process disclosed in GB363353 presents the disadvantage of the use of chemical compounds which require a lot of care during their handling and use, and in particular it makes use of Calcium Chloride, in addition to the treatment and disposal problems of the processing residues. Moreover the described process does not describes how the following paper production occurs, but it is limited to the description of the extraction of the cellulose from the algae without specifying how it will be used, supposedly by means of addiction of the pulp obtained by the algae to a traditional pulp, limiting the benefits deriving from the use of the algae and anyway involving the problems previously described relatively to the obtainment of the pulp which is traditionally used in the production of paper.
EP0488486 describes a method which is applicable only to microalgae which live in fresh water which are very different from macroalgae marine and marine plants.
The process disclosed in EP0565920 anyway requires the addition of the pulp obtained from the algae to a traditional pulp, limiting the benefits deriving from the use of the algae and anyway involving the problems previously described relatively to the obtainment of the pulp which is traditionally used in the production of paper.
Aim of the invention
The aim of the present invention is to supply a marine plants processing method for the production of paper which allows to obtain paper without the use of pulp derived from trees.
Concept of the invention
The aim is reached with the characteristics of the main claim. The dependent claims represent advantageous solutions.
Advantageous effects of the invention
The solution according to the present invention, by the considerable creative contribution whose effect represents an immediate and significant technical improvement, has many advantages. With the described processing method and using the indicated marine plants, paper can be obtained which is 100% obtained from the marine plants themselves, without making use of pulp coming from trees.
Advantageously the method according to the present invention does not need of the use of reactors containing chlorine or its derivates for the bleaching process! This is a considerable advantage from the environmental point of view with respect to the normal paper production processes starting from the wood or in the recycling processes of the paper itself. Moreover, advantageously the use of marine plants allows to obtain also the disposal of the marine plants or parts of the marine plants which deposit on the the littoral zones and which are normally sent to garbage dump.
Description of the drawings
A practical embodiment is described hereafter with reference to the included drawings to be considered as a non-limitative example of the present invention in which
Fig. 1 represents a flow diagram showing the production method of paper from marine plants according to the present invention.
Description of the invention The processing method of marine plants for the production of paper according to the present invention preferably but not limitatively occurs by means of the use of marine plants known as fanerogame marine, which are higher plants which are very different from algae, because they are provided with roots, leaves and true flowers. Fanerogame marine live in the waters of the littoral zones and cover the sea bed forming prairies.
Among the fanerogame marine useful in the use for the present invention the following ones are present: Zostera, Posidonia, Cymodocea, Syringonium, Thalassia, Halophila, Thalassodendron.
The corresponding different species are meant to be included too. For example with reference to Cymodocea, also Cymodocea nodosa, Cymodocea rotundata, Cymodocea serrulata, etc. are intended to be included. For example with reference to Syringonium, also Syringonium filiforme, Syringonium isoetifolium, etc. are intended to be included. For example with reference to Halophila, also Halophila beccarii, Halophila decipiens, Halophila minor, Halophila ovalis, etc. are intended to be included. For example with reference to Zostera, also Zostera marina, Zostera noltii, etc. are intended to be included. For example with reference to Posidonia, also Posidonia oceanica, Posidonia australis, Posidonia sinuosa, etc. are intended to be included. For example with reference to Thalassia, also Thalassia hemprichii, Thalassia testudinum, etc. are intended to be included.
These marine plants are different from algae due to the presence of a structure comprising of roots, fust, and leaves. The leaves come off and can arrive to littoral zones constituting a source of various problems for example due to their putrefaction. With the described processing method and using the indicated marine plants, paper can be obtained which is 100% obtained from the marine plants themselves, without making use of pulp coming from trees.
The present description will make reference to the method applied to case of marine plants which are known with the name of Posidonia oceanica because they are more easily available on the littoral zones, but the same process can be used, in general, for all of the fanerogame marine as for tests made by the inventors.
However it is possible to to use all of the types of algae or marine plants having a high content of cellulose. As a matter of fact, a characteristic which is common to the indicated marine plants is the high content of cellulose, above all in the relative leaves, with a corresponding absence or scarceness of lignin.
Advantageously the method according to the present invention does not need of the use of reactors containing chlorine or its derivates for the bleaching process. This is a considerable advantage from the environmental point of view with respect to the normal paper production processes starting from the wood or in the recycling processes of the paper itself.
Moreover, advantageously the use of marine plants allows to obtain also the disposal of the marine plants or parts of the marine plants which deposit on the the littoral zones and which are normally sent to garbage dump.
The process according to the present invention (Fig. 1) for the production of pulp having a high cellulose content for the production of paper provides the following steps:
(0) . Collection of the marine plants or algae marine, preferably fanerogame marine, even more preferably fanerogame marine selected from the group consisting of Zostera, Posidonia, Cymodocea, Syringonium, Thalassia, Halophila, Thalassodendron;
(1) . Sieving the collection product eliminating possible foreign bodies which are present in the collection product itself obtaining a sieved product, preferably obtaining a sieved product with a marine plants content equal or higher to 75 % in weight of the dry total collection product after sieving, even more preferably with a marine plants content equal or higher to 95 % in weight of the dry total collection product after sieving;
(ii). Washing the sieved product by means of water removing possible sand which can be present; (iii) . Possible treatment of the humid washed product by means of a treatment in a oven at a temperature between 80 and 250 °C, for a time between 10 and 60 minutes, preferably for a time between 15 and 30 minutes, the time and the temperature being selected depending on the maceration degree of the collection product;
(iv) . Possible scraping treatment of the obtained product, the scraping causing a partial grinding/breaking of the fibers and causing an increasing of the chemically etcheable surface, the scraping treatment preferably occurring by means of a passage in a mill or in cylinders;
(v). Obtaining disgregated fibers by means of disgregation of the fibers by means of a treatment with a chemical disgregating agent which does not etches the cellulose fibers, possibly combined with a mechanical disgregation treatment, the chemical disgregation preferably occurring by means of boiling the product in an aqueous solution of sodium hydroxide, obtaining disgregated fibers;
(vi). Separation of the fibers from the liquid phase by means of filtration recovering the corresponding liquid phase;
(vii). Bleaching the fibers obtained from the previous phase by means of a treatment with a chemical bleaching agent, preferably by means of a heat treatment, preferably with hydrogen peroxide in an aqueous solution;
(viii). Filtering, washing by means of water and/or pH balancing treatment of the bleached fibers and obtainment of an essentially neutral pH; preferably the pH balancing treatment being a washing by means of water of the bleached fibers until obtaining an essentially neutral pH between pH 6 and pH 8 recovering the corresponding liquid phase;
(ix). Suspension of the product obtained by the previous phase in water in a container;
(x). Possible addition of a bonding agent; (xi) . Triturating the suspension obtained from the previous phase with possible addition of a bonding agent during the triturating phase itself, obtaining a pulp with a high content of cellulose;
(xii) . Possible addition of a bonding agent;
(xiii). Introducing the pulp with a high content of cellulose in a withdrawal basin;
(xiv). Withdrawing the pulp with a high content of cellulose from the withdrawal basin;
(xxiii) . Pressing and drying the pulp with a high content of cellulose preferably for 6 - 8 hours obtaining a sheet of paper;
(xxiv) . Verification of the paper sheet and possible re-humidification with a following further pressing and drying operation;
(xxv) . Removing and withdrawing the finished paper sheet.
Surprisingly and unexpectedly the inventors found that the thus obtained sheet presents a good absorbent power of the ink also without the need to use further treatments and additives, with further benefits from the environmental point of view.
Advantageously, therefore, it is possible to obtain paper, paperboard, cardboard, substitutes and derivatives obtained by pulp having a high content of cellulose produced by means of the method according to the present invention in which 100% of the pulp is obtained from marine plants, contrarily to the teachings of the prior art which anyway provide a significant contribution of pulp obtained by the wood.
It will be however apparent that, according to the desired end quality of the paper one can anyway use the pulp obtained by marine plants with pulp obtained by wood or substitutes, obtaining paper, paperboard, cardboard, substitutes and derivatives obtained by pulp having a high content of cellulose produced by means of the method according to the present invention in which at least 50% of the pulp is obtained by marine plants.
Without entering the merits, the inventors believe that the surprising obtained results are due to the high content of cellulose of the used marine plants, in particular the fanerogame marine and, more in detail the listed fanerogame marine and the poseidonia oceanica.
However it will be apparent that, according to the desired end quality degree, additives can be added to obtain the desired properties, e.g. starch, polymeric glossing agents e.g. vinyl polyacetate (PVA). A glossing phase can also improve the surface smoothing it.
Moreover the further use of kaolin can be provided in a smoothing phase of the paper or the use of a transparent layer, for example consisting of enamel, to give the paper a polished aspect.
While, for simplicity, the described process makes reference to a handicraft process for the production of paper in sheets, the process can be easily adapted for the industrial production of paper coils and sheets.
In this case one will adopt a continuous production process in which the solution containing cellulose obtained according to the described method is drained by a flow case with a drain of about 3% of cellulose as a dry residue. The drain occurs through a fissure onto a canvas sliding in a continuous way: the fibers concentrates and are compacted forming the initial sheet with a content of about 80% of water. A pressing phase follows which is performed in a continuous way in a dry-end with rollers which are provided with felts: the fibers are compacted to a higher extent and the sheet undergoes a rolling still losing water and reaching a concentration of about 3-4%. In conclusion the production method of paper, paperboard, cardboard, substitutes and derivatives according to the present invention provides the use of the pulp having a high content of cellulose which is obtained as previously described following the phases which are performed successively to the phases relative to the method to obtain the pulp having a high content of cellulose obtained from marine plants:
(xiii). Introduction of the pulp having a high content of cellulose in a flow-box having a draining between 2 and 5 % of cellulose as dry residue; (xiv) . Draining the pulp having a high content of cellulose on a continuously sliding conveyor for the production of paper coils;
(xv) . Continuous pressing with rollers.
Advantageously the described production process of pulp does not involve the use of chlorine or derivates for the bleaching operation, obtaining satisfactory results with important advantages from the environmental point of view and from the disposal costs of the working residues.
The collection product can be a just collected product (green), as well as an already partially macerating product, as well as a product which was previoulsy dryed and successively re-humidified, possibly with addition of anti fermenting agents.
With reference to the collection phase it will be apparent that, depending on how the collection itself occurs, in the collection product also elements other than marine plants and/or algae marine can be present, e.g. sand, other vegetals, etc. To eliminate possibile foreign bodies having larger dimensions is made the following sieving phase is done, for example by means of vibrating screens or sieves, both in a humid condition and in a dry condition. The possibly present sand, instead, will be eliminated by means of washing the collection product itself, preferably after the sieving phase, but it will be apparent that the two phases also could be inverted.
Relatively to the treatment phase of the humid washing product by means of a treatment in an oven this phase is equivalent to a preliminary cooking of the product, but the inventors, during the tests which were carried out have found that this phase can also be omitted if the collection product is already partially macerated before the collection or before its use. The treatment can occur in a range of temperatures between 80°C and 250° and for a time between 10 and 60 minutes, preferably for a time between 15 and 30 minutes. The treatment temperature as well as the treatment time can change depending on to the maceration degree of the product subjected to the treatment as well as on the quantity of the product subjected to the treatment and on the arrangement of the product in the cooking chamber. For example for a product quantity equal to 3-6 kg of collection product that substantially has not undergone a maceration the treatment can occur at a temperature of 180° - 220° for times on the order of 15-30 minutes, with most short times being preferred in the case in which the product to be treated is spread enough inside the treatment chamber, while most long times will be preferred in the case in which the product to be treated is amassed and concentrate. In a similar way most long times will be necessary for higher quantities of product to be treated. If the product is already partially macerated, then lower treatment times will be sufficient and if the product is at a greater maceration state the treatment can also be omitted.
The scraping phase is needed to increase the etcheable surface of the reactive which is used in the following phases. In the performed tests this operation has been made manually but it can be made automatic, for example by means of a passage in a mill or in cylinders; the increasing of the chemically etcheable surface of the product is obtained by means of the scraping of the product, with a partial defibration/breakage of the fibers.
Referring to the disgregation phase of the fibers by means of boiling in a solution of sodium hydroxide, it will continue until the desired maceration degree- is reached. The quantities of sodium hydroxide to be used, as well as the time of the treatment can change depending on the collection product quality. Indicatively, anyway the desired maceration degree can be defined by the end average dimension of the obtained disgregated fibers. Also other disgregating agents can be used provided that they have the characteristic not to excessively disgregate the cellulose fibers. The chemical disgregation can also be coupled to a mechanical disgregation, even if it can be omitted depending on the maturation degree of the collection product and/or on the maceration degree. Referring to the quantity of sodium hydroxide, for example using 99% sodium hydroxide in a solid form, the use is provided of 100-200g of sodium hydroxide for every 4 kg of product to be submitted to disgregation in a quantity of water so as to obtain the superficial covering of the matter to be treated, about 10-20 liters. However it will be obvious that the solution of sodium hydroxide can also be prepared starting by sodium hydroxide in solution, obtaining concentrations corresponding the indicated ones.
The successive separation phase of the fibers can occur for example by means of filtering.
By means of washing with water, as previously explained, one can act on the pH until the disappearing of the basic pH in favour of a neutral pH with a recovery of the corresponding basic liquid phase which can successively be utilized again in the process.
Referring to the bleaching phase of the fibers it occurs by means of a treatment with a chemical bleaching agent, preferably by means of a heat treatment, preferably with hydrogen peroxide in an aqueous solution. The concentrations of chemical bleaching agent can change depending on the properties of the bleaching agent itself, as well as depending on the desired bleaching degree. For example with regard to hydrogen peroxide, starting from 40 volume hydrogen peroxide, the use is provided of 150-300 ml of 40 volume hydrogen peroxide for every 4 kg of product to be submitted to bleaching in a quantity of water so as to obtain the superficial covering of the matter to be treated, about 10-20 liters. Obviously the hydrogen peroxide can also be supplied starting from starting solutions with different concentrations, e.g. 130 hydrogen peroxide diluted 1/4. In general, therefore, for every 4 kg of product to be submitted to bleaching one can use hydrogen peroxide in a quantity such as to supply concentrations corresponding to the ones which are obtained adding in water 40 volume hydrogen peroxide for every 4 kg of product to be submitted to bleaching in quantities between 150 and 300 ml of 40 volume hydrogen peroxide, in a quantity of water so as to obtain the superficial covering of the matter to be treated, which for 4 kg of product is equal to about 10-20 liters. Preferably the hydrogen peroxide will be gradually added in successive times, modulating its quantity depending on the bleaching state and on the desired end quality. The treatment preferably occurs in hot conditions at a temperature between 60°C and the boiling-point. The treatment continues for a time between 15-60 minutes depending on the desired quality of the finished product, namely of the color, most long treatment time corresponding to a greater bleaching.
The successive suspension phase in water of the product obtained after the filtering and washing phase of the bleached fibers will preferably occur in a container in which the product which was obtained in the previous phases is placed adding water so as to obtain the superficial covering of the product itself.
The inventors found that the bonding agent addition can occur with good results first or after or during the triturating phase or also both before, after and during the triturating phase. Therefore, in general, the process according to the present invention can comprise a phase of addition of a bonding agent or glue which can occur in a phase (x) successively to the phase (ix) and previously to the phase (xi) and/or simultaneously to phase (xi) and/or in a phase (xii) following the phase (xi). Preferably this addition occurs before the triturating phase to obtain a better amalgamation of the components. Possibly the addiction of the bonding agent can occur successively in the case in which the preparation phase of the pulp is separated by the phase of its effective use for the production of the paper. As matter of fact the present invention also allows to stop the process after the triturating phase and before the addition of the bonding agent or anyway in other intermediate stages, for example also to allow the delivery or the preservation of the product, which can possibly be filtered and/or addittivated with possible anti - fermenting agents and/or partially dried for its successive use. If the addition of the bonding agent occurs after the triturating phase, also a mixing phase to amalgamate the components will be needed. The bonding agent addition will occur in quantities in the range between 10 and 90 ml for every 4 kg of the product, even more preferably in quantities between 25 and 50 ml for every 4 kg of the product, even more preferably 35 ml for every 4 kg of the product, the bonding agent being preferably vinyl glue. For bonding agents of a different type with respect to the vinyl glue, the preferred quantities could undergo changing depending on the properties of the bonding agent itself.
Examples will follow showing the process in a greater detail.
Example I
Following the described process Posidonia oceanica marine plants have been collected which have been preliminarily cleaned-up from fibres and undesired materials by means of sieving, e.g. foreign bodies which was possibly present.
Quantities of 4 - 4,5 Kg of sieved Posidonia oceanica marine plants have been taken.
The sieved Posidonia oceanica marine plants have been washed in water and have been left in a suspension condition for 15 minutes in water in order to let the sand decant.
The Posidonia oceanica marine plants have been heated by means of passage in a stove for 15 - 20 minutes in order to improve their workability.
The thus obtained product has been submitted to a scraping treatment in order to increase the etcheable surface of the reactive which is used in the following phases.
The' thus obtained product has been boiled with 150g of 99% sodium hydroxide in solid form to in a quantity of water so as to obtain the superficial covering of the product to be treated, about 20-25 litres. The treatment has been continued until a desired disgregation degree was reached, obtaining the disgregation of the fibres. In certain tests a mechanical agitation action has been used obtaining better results and/or shorter times.
The disgregated fibers have been separated by means of filtering with a recovery of the corresponding liquid phase; the corresponding recovered liquid phase can be reutiiized for successive treatments by reintegration of sodium hydroxide or it can be disposed after neutralizing the same.
A bleaching operation has been performed by means of heat treatment with 225 ml of 40 volume hydrogen peroxide in a quantity of water so as to obtain the superficial covering of the matter to be treated, about 20-25 litres. The treatment temperature was 80°C.
Successively one have proceeded with a washing phase of the the mass of bleached fibres with a consequent pH measurement and the washing procedure has been continued until the disappearing of the basic pH in favour of a neutral pH.
A suspension in water of the obtained product has been prepared and one proceeded with a trituration of the fibres in the suspension.
Successively 30-35 ml of a bonding agent have been added, which in the disclosed example was vinylic glue and one proceeded with the mixing of the thus obtained mixture until the same was homogenized.
In this experimental phase the drawing of the obtained pulp having a high content of cellulose occurred following the following steps:
(xiv). Drawing the pulp having a high content of cellulose from the withdrawal basin by means of a screen;
(xv). Applying a rug on the screen;
(xvi). Positioning a first felt on the rug on the opposed side with respect to the side with the pulp having a high content of cellulose;
(xvii). Applying a first rigid support on the first felt, the rigid support having sizes corresponding to the sizes of the screen;
(xviii). 180 degrees overturning of the assembly consisting of first rigid support, first felt, rug, pulp having a high content of cellulose and screen;
(xix). Removing the screen;
(xx). Positioning a second felt on the pulp having a high content of cellulose in correspondence of the opposite side with respect to the side on which the rug was placed;
(xxi). Applying a second rigid support on the second felt, the rigid support having sizes corresponding to the sizes of the screen, forming a sandwich construction; (xxii) . Pressing and exsiccation of the sandwich construction obtained at the previous phase for 6 - 8 hours obtaining a sheet of paper;
(xxiii) . Verification of the paper sheet and possible re-humidification with reintroduction in the press and exsiccation;
(xxiv). Removing and drawing the paper sheet.
In particular a certain quantity of fibers and bonding agent solution has been separated by a screen having A4 sheet sizes. On the screen a clean and undamaged rug has been applied in correspodence of the future paper sheet and the rug has been padded in order to let the fibers adhere to the same. A felt was then placed on the rug on the opposed side with respect to the side with the fibres and a plywood rectangle has been applied above the felt. The assembly was then overturned and the rug with the sheet was detached from the net of the screen. Another and another felt rug were then applied on the surface covered by the fibers, encompassing everything with an additional plywood rectangle, therefore obtaining a sandwich construction consisting of: plywood, felt, rug, fibers, rug, felt, plywood. The thus obtained sandwich construction has been placed in a press for 6 - 8 hours. Successively the drying of the sheets has been completed, maintaining the rug in a tensioned condition.' Once the drying was completed the sheets have been detached.
With the indicated quantities a hand-crafted sheet of paper was obtained having a weight of about 6 gr., corresponding to a basic weigh of 50g/m2 having a A4 size with Havana yellow coloring.
-Example II
Another test was carried out following exactly the same steps of the example I, in the same quantities, but with the addition of the bonding agent before the triturating phase. It has been observed that with this process a better amalgamation of the bonding agent with the triturated fibers is obtained, obtaining a qualitatively better end product.
.Example III Another test was carried out following exactly the same steps of the example I or in an equivalent way of the example II, in the same quantities. In the case in which the sheets, after the drying phase showed pleating, one proceeded with a re-humidification of the sheet itself with an additional successive passage in the press. In the example the additional humidification of the sheet occurred by means of a sponge. After the extraction of the sheet from the press one observed that an effective elimination of the previously present pleating was obtained.
Example IV
Proceeding as in the example I, in the disgregation phase different quantities have been tested of sodium hydroxide obtaining satisfactory results in a range between 100 and 200 gr. for every 4 kg of product, with the best results obtained for values of about 120 gr. of 99% sodium hydroxide in solid form in a water quantity so as to obtain the superficial covering of the matter to be treated, about 10-20 liters.
Example V
Proceeding as in the example I, in the bleaching phase different quantities of 40 volume hydrogen peroxide have been tested obtaining satisfactory results in a range between 150 and" 300 gr'.' for' every 4 kg of product, with the best results obtained* for values of about 180 gr. of peroxide gr. of 40 volume hydrogen peroxide.
Example VI
Proceeding as in the example I, different quantities of bonding agent have been tested, in particular vinyl glue, obtaining satisfactory results in a range between 10 and 90 ml each 4 kg of triturated product, preferably in quantity included between 25 and 50 ml for every 4 kg of triturated product, with the best results obtained for values of about 35 ml for every 4 kg of triturated product.
Example VII
Proceeding as in the example I, the real content of fanerogame marine has been analyzed in relation with the available collection product, finding that the described method finds an advantageous application in the case in which the collection product has a fanerogame marine content equal or higher than 75%, the remaining 25 % possibly consisitng of other types of algae or marine plants. Good results were obtained even with a fanerogame marine content equal or higher than 95% in weight of the dry total collection product after sieving.
Example VIII
Proceeding as in the example I, different trituration degrees of the fibers have been tested, observing that the trituration phase must not be excessively prolonged to avoid to have too much small fibers. In general good results have been found with sizes of the fibers corresponding to those obtained in the production process of the paper starting from recycled paper. It will be apparent that depending on the used trituration device and on the introduced quantities the trituration times can be different.
The description of this invention has been made with reference to the enclosed figures showing a preferred embodiment of the invention itself, but it is evident that many possible alterations, modifications and variations will be immediately apparent to those skilled in the art in light of the foregoing description. Thus, it should be understood that the invention is not limited by the foregoing description, but embraces all such alterations, modifications and variations in accordance with the spirit' and scope of the appended claims.

Claims

Claims
1. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives, comprising the steps of:
(i) . Sieving the collection product eliminating possible foreign bodies which are present in the collection product;
(ii) . Washing the sieved product by means of water removing possible sand which can be present;
(v) . Obtaining disgregated fibers by means of disgregation of the fibers by means of a treatment with a chemical disgregating agent which does not etches the cellulose fibers, possibly combined with a mechanical disgregation treatment;
(vi) . Separation of the fibers from the liquid phase by means of filtration recovering the corresponding liquid phase;
(vii) . Bleaching the fibers obtained from the previous phase by means of a treatment with a chemical bleaching agent;
(viii) . Filtering/ washing by means of water and/or pH balancing treatment of the bleached fibers and obtainment of an essentially neutral pH;
(ix) . Suspension of the product obtained from the previous phase in water in a container;
(xi). Triturating the suspension obtained from the previous phase obtaining a pulp with a high content of cellulose;
said method being further characterised in that said collection product is a marine plants collection product.
2. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to the previous claim characterised in that said collection product is a collection product of marine plants preferably with a marine plants content equal or higher to 75 % in weight of the dry total collection product after sieving, even more preferably with a marine plants content equal or higher to 95 % in weight of the dry total collection product after sieving.
3. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 2 characterised in that said marine plants are fanerogame marine.
4. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 2 characterised in that said marine plants are selected from the group consisting of Zostera, Posidonia, Cymodocea, Syringonium, Thalassia, Halophila, Thalassodendron.
5. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 2 characterised in that said marine plants are selected from the group consisting of Cymodocea nodosa, Cymodocea rotundata, Cymodocea serrulata, Syringonium- filiforme, Syringonium isoetifolium, Halophila beccarii, Halophila decipiens, Halophila minor, Halophila ovalis, Zostera marina, Zostera noltii, Posidonia oceanica, Posidonia australis, Posidonia sinuosa, Thalassia hemprichii, Thalassia testudinum.
6. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 5 characterised in that it includes a further phase (iii) following to the phase (ii), said phase (iii) providing a treatment of the washed product at a temperature between 80°C and 250° and for a time between 10 and 60 minutes, preferably for a time between 15 and 30 minutes, even more preferably at a temperature between 180° - 220° for a time between 15 and 30 minutes, the time and the temperature being selected depending on the maceration degree of the collection product.
7. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 6 characterised in that it includes a further phase (iv) prior to the phase (v), said phase (iv) being a scraping phase providing a scraping treatment of the product..
8. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to the previous claim characterised in that said scraping phase occurs by means of a passage of the product in a mill or in cylinders.
9. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 8 characterised in that said disgregation phase (v) of the fibres by means of said treatment with said disgregating chemical agent occurs by means of a boiling treatment in aqueous solution of sodium hydroxide.
10. Method to obtain pulp having a high content of cellulose for the use in a process of production* of -paper; -paperboard, cardboard; -substitutes and derivatives* according to the previous claim characterised in that said disgregation phase (v) of the fibers by means of said treatment with said disgregating chemical agent occurs by means of a boiling treatment in aqueous solution of sodium hydroxide in concentrations corresponding to those obtained dissolving 99% sodium hydroxide in solid form in quantities between 100g and 200g of sodium hydroxide for every 4 kg of product to be submitted to disgregation in a water quantity so as to obtain the superficial covering of the matter to be treated.
11. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 10 characterised in that said phase (vii) relative to the bleaching of the fibers occurs by means of treatment with hydrogen peroxide in an aqueous solution preferably in hot conditions at a temperature between 60°C and the boiling-point.
12. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to the previous claim characterised in that said treatment with hydrogen peroxide in an aqueous solution occurs with hydrogen peroxide in an aqueous solution in concentrations corresponding to those obtained adding in water 40 volume hydrogen peroxide for every 4 kg of product to be submitted to bleaching in quantities between 150 and 300 ml of 40 volume hydrogen peroxide, in a water quantity so as to obtain the superficial covering of the matter to be treated.
13. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to the previous claim characterised in that said treatment with hydrogen peroxide is continued for a time between 15 and 60 minutes depending on the end bleaching degree.
14. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 1 to 13 characterised in that it includes a further phase of bonding agent addition, said bonding agent addition phase being able to occur in a further phase (x) after the phase (ix) and before the phase (xi) and/or simultaneously with respect to the phase (xi) and/or in a further phase (xii) after the phase (xi).
15. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to the previous claim characterised in that said bonding agent is added in quantities between 10 and 90 ml for every 4 kg of product, preferably in quantities between 25 and 50 ml for every 4 kg of product, even more preferably 35 ml for every 4 kg of product.
16. Method to obtain pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives according to any of the previous claims 14 to 15 characterised in that said bonding agent is vinyl glue.
17. Pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives characterised in that said pulp having a high content of cellulose is obtained by means of a method to obtain pulp having a high content of cellulose according to any of the previous claims 1 to 16.
18. Paper, paperboard, cardboard, substitutes and derivatives obtained by pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives characterized in that at least 50 % of said pulp having a high content of cellulose is obtained by means of a method to obtain pulp having a high content of cellulose according to any of the previous claims from 1 to 16.
19. Paper, paperboard, cardboard, substitutes and derivatives obtained by pulp having a high content of cellulose for the use in a process of production of paper, paperboard, cardboard, substitutes and derivatives characterized in that 100 % of said pulp having a high content of cellulose is obtained by means of a method to obtain pulp having a high content of cellulose according to any of the previous claims from 1 to 16.
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US20150068693A1 (en) * 2012-03-13 2015-03-12 D'AGNONE Uwe Composition of Fibrous Material
US9074324B2 (en) 2013-06-10 2015-07-07 Kimberly-Clark Worldwide, Inc. Layered tissue structures comprising macroalgae
KR20160063348A (en) * 2013-09-27 2016-06-03 킴벌리-클라크 월드와이드, 인크. Tree-free fiber compositions and uses in containerboard packaging
GR1009204B (en) * 2016-08-09 2018-01-23 Ιωαννης Λαζαρου Παυλακης Environmentally-friendly panel made of dry seaweed leaves of the posidonia oceanica family
US9908680B2 (en) 2012-09-28 2018-03-06 Kimberly-Clark Worldwide, Inc. Tree-free fiber compositions and uses in containerboard packaging
US11053643B2 (en) 2017-02-22 2021-07-06 Kimberly-Clark Worldwide, Inc. Layered tissue comprising non-wood fibers

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150068693A1 (en) * 2012-03-13 2015-03-12 D'AGNONE Uwe Composition of Fibrous Material
KR101840514B1 (en) 2012-03-13 2018-03-20 우베 디＇아그논 Fibrous material composition
US9976255B2 (en) * 2012-03-13 2018-05-22 Uwe D'Agnone Composition of fibrous material
WO2014049476A1 (en) * 2012-09-28 2014-04-03 Kimberly-Clark Worldwide, Inc. Hybrid fiber compositions and uses in containerboard packaging
US9816233B2 (en) 2012-09-28 2017-11-14 Kimberly-Clark Worldwide, Inc. Hybrid fiber compositions and uses in containerboard packaging
US9908680B2 (en) 2012-09-28 2018-03-06 Kimberly-Clark Worldwide, Inc. Tree-free fiber compositions and uses in containerboard packaging
US9074324B2 (en) 2013-06-10 2015-07-07 Kimberly-Clark Worldwide, Inc. Layered tissue structures comprising macroalgae
KR20160063348A (en) * 2013-09-27 2016-06-03 킴벌리-클라크 월드와이드, 인크. Tree-free fiber compositions and uses in containerboard packaging
KR102369548B1 (en) * 2013-09-27 2022-03-03 킴벌리-클라크 월드와이드, 인크. Tree-free fiber compositions and uses in containerboard packaging
GR1009204B (en) * 2016-08-09 2018-01-23 Ιωαννης Λαζαρου Παυλακης Environmentally-friendly panel made of dry seaweed leaves of the posidonia oceanica family
US11053643B2 (en) 2017-02-22 2021-07-06 Kimberly-Clark Worldwide, Inc. Layered tissue comprising non-wood fibers
US11634870B2 (en) 2017-02-22 2023-04-25 Kimberly-Clark Worldwide, Inc. Layered tissue comprising non-wood fibers

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