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.

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

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• 2010
  • 2010-07-19 EP EP10737503.2A patent/EP2596166A1/de not_active Withdrawn
  • 2010-07-19 WO PCT/EP2010/004390 patent/WO2012010181A1/en active Application Filing

Non-Patent Citations (1)

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