EP3443159B1 - Processus continu destiné à la production de pâte de cellulose - Google Patents

Processus continu destiné à la production de pâte de cellulose Download PDF

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EP3443159B1
EP3443159B1 EP16722693.5A EP16722693A EP3443159B1 EP 3443159 B1 EP3443159 B1 EP 3443159B1 EP 16722693 A EP16722693 A EP 16722693A EP 3443159 B1 EP3443159 B1 EP 3443159B1
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linne
cellulose pulp
bleaching
cellulose
feedstock
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EP3443159A1 (fr
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Marinko Mikulic
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Priority to PL16722693T priority patent/PL3443159T3/pl
Priority to RS20200820A priority patent/RS60519B1/sr
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    • 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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • 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
    • D21C9/1063—Bleaching ; Apparatus therefor with compounds not otherwise provided for, e.g. activated gases
    • 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
    • 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

Definitions

  • the invention is related to an improved continuous process for production of cellulose pulp of very high whiteness, >90%, and lignin content ⁇ 5% w/w, from comminuted grass-like feedstock such as miscanthus (Miscanthus x giganteus, Andersson).
  • the main technical problem, solved by the present invention is formation of the novel process for production of cellulose pulp having high whiteness, from a grass-like feedstock in an effective way.
  • This effective way is achieved by using as little as possible of inexpensive environmentally-acceptable chemicals and under as mild as possible digestion and bleaching conditions. Also, such process should ensure maximal preservation of natural cellulose fibers from the starting feedstock.
  • the first technical problem solved with the disclosed invention is to use milder and optimized chemical reagents during digestion and bleaching steps and very high whiteness, higher than 90%, thus avoiding harsh and high energy-consuming manufacturing conditions, dangerous and sulphur-based chemicals, and environment pollution with waste waters containing residues of all these processing chemicals.
  • the technical problem solved with the disclosed invention is to find a solution within the frame of "green"-chemical technology, characterized by:
  • this is the first eco-friendly process for cellulose pulp manufacturing that operates at such mild digestion conditions, with very low water consumption, low energy consumption, which can produce cellulose of very high whiteness, higher than 90%, with ⁇ 5% w/w of lignin, which can yield top-quality paper of excellent mechanical properties.
  • the process according to this invention does operate well only when grass-like feedstock is employed.
  • miscanthus ( Miscanthus x giganteus, Andersson) is one of most suitable grass-like feedstock for such use; see references 1 and 2:
  • Such solution of digesting chemicals is also known as "white liquor", representing either fresh or regenerated solution of digestion chemicals.
  • the white liquor helps to remove non-cellulosic materials, which are thus dissolved in the solution, leaving relatively pure cellulose fibers suspended in this liquid phase.
  • Cooked feedstock with removed non-cellulosic materials i.e. a "pulp" is, at the end of digestion, suspended in used solution, which contains various chemical forms of non-cellulosic plant ingredients and remains of digestion chemicals.
  • This aqueous phase is called the "black liquor”.
  • the pulp after the digestion is a suspension of essentially pure cellulose fibers in the black liquor.
  • One of the most environmentally-friendly sulphur-free processes uses sodium hydroxide-based technology.
  • the use of sodium hydroxide (NaOH) as sole digesting chemical is known in the art and also specifically in the processed based on grass-like feedstock such as rice straw, esparto, reed, jute, and others.
  • One of the processes is performed with 5% aqueous solution of sodium hydroxide (NaOH) at 90 °C for several hours; see reference 3: 3) GB 770,687 ; Method of producing cellulose; applicant Aillesburger Zellstoffwerke (DE).
  • the digestion steps can be performed with microwave (MW) assisted heating.
  • MW microwave
  • Zhu and co-workers described the pretreatment process of miscanthus / Miscanthus x giganteus, Andersson/ with sodium hydroxide (NaOH) solution at very high temperatures (130-200 °C) at elevated pressures during 20 minutes under MW heating.
  • Such pretreated miscanthus further gave much better yield in sulphuric acid (H 2 SO 4 )-catalysed hydrolysis to glucose as a feedstock to fermentation into bioethanol; see reference 4: 4)
  • the bleaching is another important key step in manufacturing of cellulose of high whiteness is the bleaching step.
  • the most common systems for cellulose bleaching are those based on chlorine-containing systems, e.g. sodium hypochlorite (NaOCl), or hydrogen peroxide (H 2 O 2 )-based systems, the latter one being preferred.
  • the present invention is also based on hydrogen peroxide (H 2 O 2 )-bleaching, but the main, crucial, and advantageous difference is in the use of a combination of H 2 O 2 and sodium silicate solution (xNa 2 O•ySiO 2 ), essentially without the use of sodium hydroxide (NaOH) as a co-reagent which, in reaction with H 2 O 2 , generates equilibrium concentration of hydroperoxide anions (HOO - ) as actual oxidizing species.
  • H 2 O 2 hydrogen peroxide
  • xNa 2 O•ySiO 2 sodium silicate solution
  • NaOH sodium hydroxide
  • Law and co-workers described the method for cellulose pulp bleaching by the use of MW-heating and a combination of bleaching chemicals consisting of hydrogen peroxide (H 2 O 2 ) and sodium hydroxide (NaOH).
  • bleaching chemicals consisting of hydrogen peroxide (H 2 O 2 ) and sodium hydroxide (NaOH).
  • sodium silicate solution can also be optionally employed as the stabilizer for H 2 O 2 ; see reference 7: 7)
  • one feature of the process for manufacturing of cellulose pulp of very high whiteness is certainly whether the cooking chemicals from the digestion phase is removed from the pulp or they can be retained in the pulp before the bleaching step.
  • the older processes performed removal of the black liquor which contains digesting chemicals, lignin, and other non-cellulosic by-products.
  • Abu and co-workers disclosed a process for production of fibrous cellulose material which includes: (1) comminuting of plant material, (2) mixing it with 0.5-1% aqueous sodium hydroxide (NaOH) solution, (3) sieving, (4) passing thus obtained material from extruder wherein the material is mixed with hydrogen peroxide (H 2 O 2 ) at 120-150 °C at 20 bar, and (5) discharging out from the extruder and washing with water; see reference 8: 8) DE19603491A1 ; Production of fibrous cellulose material free from other plant components; applicants: S. I. Abu, D. Kistmacher, R. Berg (DE).
  • the present invention is also characterized by one of key details that it does not involve washing out of remaining cooking chemicals after digestion phase, but directly undergoes to disperging and bleaching steps.
  • Mikulic disclosed a continuous process for production of cellulose pulp from grass-like feedstock such as miscanthus ( Miscanthus x giganteus, Andersson), using a vertical digester with smooth internal walls without any screen or mixing element inside, by the use of very dilute cooking chemicals, sodium hydroxide (NaOH) and sodium chloride (NaCl) or sodium sulphite (Na 2 SO 3 ), with the following average composition of digesting suspension:
  • this process is also based on subsequent processing of cooked pulp within the screening and fractionation device which isolate a good cellulose pulp fraction and separate the improper one.
  • the later is further subjected to pulp milling in one or more suitable pulp mills yielding the proper cellulose pulp.
  • pulp milling in one or more suitable pulp mills yielding the proper cellulose pulp.
  • This can be further optionally bleached with conventional bleaching chemicals to yield high quality cellulose suitable for paper production.
  • the digestion (a) and bleaching (c) processes can be performed by microwave (MW)-assisted heating with comparable good results within significantly shorter period of time for each step.
  • steps (a)-(c) results in very high quality cellulose pulp of very high whiteness, >90%, with ⁇ 5% w/w of lignin, which cannot be produced by the process disclosed in the reference 9.
  • the process from this invention uses roughly similar electrolytic reactor for removal of lignin and other by-products and for parallel regeneration of cooking chemicals, NaOH + NaCl solution (white liquor), but the main and crucial difference is in the fact that the electrolytic process in this invention works with the black liquor solution comprising dilute sodium lignin and sodium chloride (NaCl).
  • the black liquor solution from this invention is of better conductance due to sodium chloride presence, whilst the process from reference 10 is based on processing sole sodium lignin from Organosolv technology for cellulose manufacturing.
  • the process from the present invention provides very high quality cellulose of very high whiteness, >90%, at high yield, at very low water and energy consumption.
  • the technology for production of cellulose pulp from grass-like feedstock according to this invention represents a novel and inventive technology, as is disclosed in the detailed description of the invention.
  • the present invention discloses a continuous process for production of cellulose pulp of very high whiteness from grass-like plant feedstock.
  • the process comprising the steps of:
  • the continuous process for production of cellulose pulp according to the present invention optionally further involves the following manufacturing steps:
  • the cooking chemicals for the digestion step (ii) are introduced as a mixture of concentrated aqueous solutions of 20-50% w/w NaOH and 10-30% w/w of NaCl.
  • the continuous digestion phase (ii) is preferably carried out at 90-100 °C.
  • the bleaching chemicals for the bleaching step (iii) are introduced to the continuous bleaching reactor (6) in the form of concentrated aqueous solutions of 30-45% w/w sodium silicate (xNa 2 O•ySiO 2 ); and 20-40% w/w of hydrogen peroxide (H 2 O 2 ).
  • the continuous bleaching process is preferably performed at 85-100 °C.
  • the continuous process for production of cellulose pulp according to the present invention can be alternatively carried out by the use of microwave (MW)-assisted heating.
  • the heating units in the continuous digester (1) and/or continuous bleaching reactor (6) are microwave (MW)-generating magnetrons.
  • the grass-like feedstock that can be processed by the process of this invention includes the stems of plant species selected from the group of: wheat ( Triticum vulgare, Linne); rice ( Oryza sativa, Linne); barley ( Horedum vulgare, Linne); oat ( Avena sativa, Linne); flax ( Linum usitatissimum, Linne); maize ( Zea mays, Linne); millets: proso millet ( Panicum miliaceum, Linne), pearl millet ( Pennisetum glaucum, Linne), browntop millet ( Panicum ramosum, Linne), and barnyard ( Echinochloa frumentaceae, Linne); triticale (x Triticosecale, Wittm.
  • Camus Camus
  • buckwheat Fagopyrum esculentum, Moench
  • miscanthus Miscanthus x giganteus, Andersson
  • switchgrass Panicum virgatum, Linne
  • sorghum Sorghum species, Linne
  • common reed Phragmites australis, Cav.
  • giant reed Arundo donax, Linne
  • burma reed Neyraudia reynaudiana, Kunth.
  • reed-mace Typha spp., Linne
  • paper reed Cyperus papyrus, Linne
  • bur-reed Sparganium spp., Linne
  • thatching reed Thamnochortus insignis, Linne
  • esparto grass Stipa tenacissima, Linne and Lygeum spartum, Linne
  • jute Corchorus olitorius, Linne
  • bamboo Bambusoidea
  • the grass-like feedstock is miscanthus (Miscanthus x giganteus, Andersson).
  • microwave (MW)-heating can be optionally employed; marked with intermittent line.
  • the invention is related to an improved continuous process for production of cellulose pulp of very high whiteness, higher than 90%, of 10% w/w dry matter, and lignin content ⁇ 5% w/w, from comminuted grass-like feedstock such as miscanthus ( Miscanthus x giganteus, Andersson).
  • Such grass-like feedstock usually contains roughly 30-45% w/w of cellulose with 15-32% w/w of lignin; see literature reference 11: 11) C. Ververis, K. Georghiou, N. Christodoulakis, P. Santas, R. Santas: Fiber dimensions, lignin and cellulose content of various plant materials and their suitability for paper production, Industrial Crops Prod. 19 (2004) 245-254 .
  • the process is performed in a continuous manner through several manufacturing phases, as shown in Figures 1 and 2 :
  • the feedstock is prepared by comminuting, to produce a material with longitudinal size distributed from 5-30 mm and diameter of 0.1-2 mm.
  • Comminution of the starting grass-like material is carried out by conventional devices for comminuting or supplied directly from the fields, if the crops were collected by suitable combine harvester equipped with adequate chopping device yielding the plant material of above-stated particles dimensions.
  • the comminution should be performed in a mild manner yielding fibrous material predominantly comminuted along the fibers, in order to preserve them.
  • the comminuted material is subjected to dedusting by removal of fine, dusty, non-fibrous plant material, which would otherwise reduce the quality of resulting cellulose pulp. This is done by suitable fan which produces a strong air circulation that enable blowing away of fine light particles.
  • collected fine non-fibrous dust can be used in the process as a fuel in energy production or as raw material in manufacturing of xylan.
  • Continuous digestion or cooking of a grass-like dust-free plant feedstock prepared in step (i) is performed in a continuous digester (1) formed as a longitudinal column, internally equipped with worm screw conveyor and a heating unit, where grass-like plant feedstock is continuously fed directly on the top of the said digester via conveyor (4).
  • the chemicals for digestion sodium hydroxide (NaOH) and sodium chloride (NaCl), and fresh water and/or regenerated white liquor, are introduced continuously on the top of said digester (1); maintaining the digestion temperature from 70-120 °C and average composition of thus formed suspension during said continuous digestion is keeping within the following ranges:
  • the continuous digestion process according to this invention is performed by introduction of cooking chemicals as concentrated aqueous solutions of 20-50% w/w sodium hydroxide (NaOH) and 10-30% w/w of sodium chloride (NaCl).
  • sodium hydroxide and sodium chloride solutions can be added as a previously prepared mixture.
  • the preferred range is 90-100 °C.
  • the cooked cellulose pulp is continuously, by equal rate as being feedstock fed into the digester (1), discharged from the said digester (1), via conveyor, directly into disperger (5) to perform disperging phase (iii), where the suspended cellulose pulp is subjected to main disperging, yielding finely disperged/separated cellulose fibers.
  • disperger (5) in this phase of the process is absolutely essential for high quality cellulose pulp.
  • the bleaching is carried out with a solution of bleaching chemicals that are:
  • bleaching chemicals are preferably introduced into the continuous bleaching reactor (6) separately in the form of the manner that is well known in the art.
  • Typical example of such optical brightener is Tinopal ABP-A liquid (from CIBA Specialty Chemicals Corporation), which contains 22-24% dry matter of fluorescent brightener from triazinyl stilbene-type.
  • Such products are typically added at 0.25-0.50% w/w dosage to the dry matter content of cellulose pulp.
  • This treatment can be performed in order to further increase whiteness of the final cellulose when the highest possible, top-quality products are manufactured.
  • the suspension of thus obtained bleached cellulose pulp, discharged from the bleaching step (iv), is optionally further subjected to additional disperging (phase v), through the disperger (8) .
  • the cellulose pulp is transferred into the dewaterer (9), where the bleached and eventually additionally disperged cellulose pulp is dewatered, separated from the black liquor yielding:
  • the black liquor from the dewatering step (vi) is transported via manifold (10) into the electrolytic reactor (19) for regeneration of cooking chemicals solution and isolation of lignin and other non-cellulosic by-products.
  • black liquor includes the process effluent from both digestion (ii) and bleaching (iv) phases; it contains residual sodium hydroxide (NaOH), sodium chloride (NaCl), solubilized lignin, other non-cellulosic by-products, and eventually traces of remaining hydrogen peroxide.
  • the black liquor can be partially concentrated in evaporator (16) to yield regenerated water which is transported back to the washing step (vii) and concentrated back liquor which goes to the electrolytic reactor (19) via manifold (18).
  • the bleached cellulose pulp is additionally washed (phase vii) in the washing vessel (12) with additional fresh water, which is introduced through the manifold (13), giving:
  • washing process water includes the process effluent from the continuous washing process (vii phase); it contains residuals of the black liquor that always remains adsorbed on cellulose fibers within the pulp that comes out from the dewatering phase (vi). Therefore, the washing process water is more likely as very diluted black liquor.
  • optimal degree of the black liquor concentration is preferably up to 0.9-1.05 w/w of sodium (as Na + ) in the concentrated black liquor that enters the electrolytic reactor (19).
  • evaporator involves not only classical evaporation devices which are based on either distillation or vacuum distillation, but also all other means of water removal from the aqueous solutions, e.g. by reverse osmosis, ion-exchange process, electrodeionization, etc.
  • either original (“as is”) combined black liquor (a) or concentrated black liquor (b) is subjected to electrolysis with direct electric current (DC) between two electrodes, at electric potential of 3-30 V, and electric current density of 1-10 A/dm 2 , at 10-95 °C, wherein the lignin and by-products are separated on the top of the electrolyte solution in the anode compartment, and continuously removed from the electrolytic reactor.
  • DC direct electric current
  • electrolytic lignin removal is performed in the electrolytic cell similar or identical to those disclosed in the literature reference 10, wherein cathode and anode compartments are separated by a suitable semi-permeable membrane or diaphragm.
  • Electrodes, cathode and anode are made from suitable electroconductive materials resistant to highly reactive chemicals formed in their compartments, e.g. to NaOH of high pH value.
  • suitable materials are: metals such as carbon steel or stainless steels, graphite, magnetite, etc.
  • cathode is made from a carbon steel, e.g. of type A36, or stainless steels, e.g. of types AISI 304, 316, 321, whilst anode is formed from graphite or magnetite.
  • Electrodes can be formed in various shapes, of which plates and wire mesh are preferred.
  • Diaphragm is made from materials selected from the group comprising: asbestos, rock wool (stone wool), Portland cement, aluminium oxide (Al 2 O 3 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), polyethylene (PE), polyetersulfone (PES), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE; Teflon R ), polyvinylidene fluoride (PVDF), sulfonated polytetrafluoroethylene (Nafion R ), clay and sodium silicate, from combinations of said materials, or from other suitable chemically resistant materials.
  • materials selected from the group comprising: asbestos, rock wool (stone wool), Portland cement, aluminium oxide (Al 2 O 3 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), polyethylene (PE), polyetersulfone (PES), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE; Teflon
  • the electrolytic lignin removal and white liquor regeneration is conducted at electric potential of 3-10 V and electric current density of 3-7 A/dm 2 .
  • the alkaline black liquor from the cellulose-manufacturing process is introduced into the anode compartment.
  • the lignin and other by-products are separated on the top of the electrolyte solution from the anode (+) compartment, and are removed out from the process by conventional mechanic means, via conveyor or so. Separation of lignin within the anode (+) compartment is facilitated by the evolution of gaseous oxygen (O 2 ) as a by-product of accompanied water electrolysis.
  • O 2 gaseous oxygen
  • the resulting electrolyte solution with regenerated sodium hydroxide (NaOH) and sodium chloride (NaCl) solution, representing the white liquor, is regenerated back to the digesting/cooking process, via manifold (21), to the continuous digester (1), closing the whole cellulose-manufacturing process.
  • the term "white liquor” includes the process effluent from the phase (viii) of the continuous electrolytic regeneration of cooking chemicals, NaOH and NaCl, solution. It contains mainly diluted sodium hydroxide and sodium chloride, with trace amounts of lignin and other non-cellulosics originating from the black liquor.
  • the lignin is separating at the top of the electrolyte solution in the cathode compartment and is continuously removing via conventional conveyor type transporter (20).
  • electrolytic reactor in the present invention includes single or a battery (series) of several or large number of combined electrolytic cells. This depends on the capacity or scale of cellulose pulp manufacturing by using the process according to this invention. For instance, larger manufacturing facility may comprise a series of 10-100 electrolytic cells. In the case of high tonnage manufacturing facility, such "electrolytic reactor” can comprise several hundreds of such electrolytic cells.
  • the process for production of cellulose pulp, of very high whiteness further comprises the manufacturing steps of screening, fractionation, and milling.
  • the diluted suspension from the step (viii) is further processed through a screening and fractionation device (22) equipped with 0.1-0.5 mm sieve, yielding two fractions;
  • a continuous process for production of cellulose pulp, of very high whiteness, according to the present invention can be performed by employing the microwave (MW) heating in the continuous digester (1) and/or continuous bleaching reactor (6) in the manner that is known in the art.
  • the heating units in the continuous digester (1) and/or continuous bleaching reactor (6) are microwave (MW)-generating magnetrons, or series of the magnetrons.
  • the grass-like feedstock that can be used as starting raw material for the process of the present invention includes stems of plant species selected from the group of: wheat ( Triticum vulgare, Linne); rice ( Oryza sativa, Linne); barley ( Horedum vulgare, Linne); oat ( Avena sativa, Linne); flax ( Linum usitatissimum, Linne); maize ( Zea mays, Linne); millets: proso millet ( Panicum miliaceum, Linne), pearl millet ( Pennisetum glaucum, Linne), browntop millet ( Panicum ramosum, Linne), and barnyard ( Echinochloa frumentaceae, Linne); triticale (x Triticosecale, Wittm.
  • Camus Camus
  • buckwheat Fagopyrum esculentum, Moench
  • miscanthus Miscanthus x giganteus, Andersson
  • switchgrass Panicum virgatum, Linne
  • sorghum Sorghum species, Linne
  • common reed Phragmites australis, Cav.
  • giant reed Arundo donax, Linne
  • burma reed Neyraudia reynaudiana, Kunth.
  • reed-mace Typha spp., Linne
  • paper reed Cyperus papyrus, Linne
  • bur-reed Sparganium spp., Linne
  • thatching reed Thamnochortus insignis, Linne
  • esparto grass Stipa tenacissima, Linne and Lygeum spartum, Linne
  • jute Corchorus olitorius, Linne
  • bamboo Bambusoide
  • Table 1 Comparison of paper properties prepared from cellulose obtained by the process from the present invention and from cellulose obtained by the process from the closest prior art, reference 9 (as the control). No . Parameter Method Unit Cellulose from prior art, ref.
  • Eventual changes of the process parameters can result in some further improvement of key quality parameters of resulting cellulose, but such changes are considered to be within the scope of this invention.
  • the present invention is obviously industrial applicable.

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Claims (10)

  1. Procédé en continu pour la production d'une pâte cellulosique d'une blancheur très élevée à partir d'une matière première végétale semblable à de l'herbe, où ledit procédé comprend les étapes :
    (i) de préparation de la matière première végétale semblable à de l'herbe par fragmentation pour produire une matière première ayant une taille longitudinale répartie entre 5 et 30 mm et un diamètre compris entre 0,1 et 2 mm et ayant de fines particules poussiéreuses éliminées par dépoussiérage de ladite matière première avec un ventilateur ;
    (ii) de digestion continue d'une matière première végétale exempte de poussière semblable à de l'herbe préparée à l'étape (i) dans un lessiveur en continu (1) formé sous la forme d'une colonne longitudinale munie en son sein d'un convoyeur à vis sans fin et d'une unité de chauffage ; où la matière première végétale semblable à de l'herbe est acheminée en continu directement sur la partie supérieure dudit lessiveur par le biais du convoyeur(4) ;
    caractérisé en ce que,
    en parallèle avec l'introduction de ladite matière première, les produits chimiques pour la digestion : le NaOH, le NaCl, et de l'eau douce et/ou une liqueur blanche régénérée ; sont introduits en continu sur la partie supérieure dudit lessiveur (1) ; le maintien de la température de digestion comprise entre 70 et 120 °C et une composition moyenne d'une suspension ainsi formée pendant ladite digestion continue est maintenue dans les plages suivantes :
    (a) entre 0,50 et 2,00 % p/p de NaOH ;
    (b) entre 0,50 et 1,50 % p/p de NaCl ;
    (c) entre 10 et 15 % p/p de matière première végétale semblable à de l'herbe ; et
    (d) de l'eau de fabrication ; jusqu'à 100 % p/p de la suspension ;
    dans lequel les pourcentages en poids des ingrédients sont calculés sur le poids de la suspension entière ; et
    où une dissolution de substances non cellulosiques se produit pendant le transfert de masse d'un côté à l'autre dudit lessiveur longitudinal qui dure entre 1,5 et 3 heures ;
    (iii) où la pulpe cuite est en continu, à une vitesse égale au fur et à mesure que la matière première est acheminée dans le lessiveur (1), déchargée dudit lessiveur (1), par le biais dudit convoyeur, directement dans un appareil de dispersion (5), où la pâte cellulosique suspendue est en outre soumise à une dispersion principale, produisant des fibres cellulosiques finement dispersées ;
    (iv) où une suspension fine de la pâte cellulosique dispersée de l'étape (iii) est en outre soumise à un blanchiment :
    (a) sans une quelconque élimination de produits chimiques de la phase de digestion (ii) ; et
    (b) sans l'utilisation de NaOH supplémentaire à des fins de blanchiment ;
    où la pâte cellulosique dispersée est acheminée en continu dans le réacteur de blanchiment en continu (6) qui est formé sous la forme d'une colonne longitudinale équipée d'un convoyeur à vis sans fin et d'une unité de chauffage ; et
    où les produits chimiques de blanchiment sont :
    (a) une solution aqueuse de peroxyde d'hydrogène (H2O2) ayant entre 20 et 40 % p/p de H2O2 ; et
    (b) une solution aqueuse de silicate de sodium (xNa2O•ySiO2) ayant entre 30 et 45 % de Na2O + SiO2 combiné, le rapport molaire Na2O:SiO2 = de 1:1 à 3,3:1 ;
    et où lesdits produits chimiques sont introduits au moyen d'un collecteur (7) dans le réacteur de blanchiment (6), maintenant la température de blanchiment comprise entre 70 et 100 °C, pendant 45 minutes à 1,5 h et une composition moyenne de la suspension ainsi formée pendant tout le processus de blanchiment est maintenu dans les plages suivantes :
    (a) entre 0,50 et 2,00 % p/p de ladite solution de H2O2 ;
    (b) entre 0,50 et 2,00 % p/p de ladite solution de xNa2O•ySiO2 ;
    (c) entre 10 et 15 % p/p de cellulose ; et
    (d) de l'eau de fabrication ; jusqu'à 100 % p/p de la suspension ;
    dans lequel les pourcentages en poids des ingrédients sont calculés sur le poids de la suspension entière ;
    (v) de la suspension de la pâte cellulosique blanchie ainsi obtenue, déchargée de l'étape de blanchiment (iv), est, facultativement, en outre traitée au moyen de l'appareil de dispersion (8) ; et ensuite transférée dans l'épaississeur (9) ;
    (vi) où la pâte cellulosique blanchie et éventuellement en plus dispersée provenant de l'étape (v) est épaissie, séparée de la liqueur noire, ce qui produit :
    (a) une pâte cellulosique blanchie composée de 10 à 15 % p/p de matière sèche ; et
    (b) la liqueur noire contenant de la lignine et d'autres sous-produits de cuisson et de blanchiment ; et
    (vii) la pâte cellulosique blanchie est de plus lavée dans la cuve de lavage (12) avec de l'eau douce supplémentaire, qui est introduite au moyen du collecteur (13), ce qui donne :
    (a) une pâte cellulosique finale blanchie et lavée d'une blancheur très élevée, supérieure à 90 %, composée de 10% p/p de matière sèche et d'une teneur en lignine inférieure à 5 % p/p, qui est transportée durant tout le procédé au moyen d'un collecteur (14) ; et
    (b) une quantité supplémentaire d'eau de traitement de lavage qui est transférée par le biais d'un collecteur (15), conjointement avec la liqueur noire provenant de l'étape d'épaississement (vi), qui est transportée par le biais d'un collecteur (10) dans le réacteur électrolytique (19) ;
    (viii) où la liqueur noire et l'eau de traitement de lavage sont en outre soumises à une électrolyse avec un courant électrique continu entre deux électrodes, à un potentiel électrique compris entre 3 et 30 V, et une densité de courant électrique comprise entre 1 et 10 A/dm2, à une température comprise entre 10 et 95 °C, dans lequel la lignine et les sous-produits sont séparés sur la partie supérieure de la solution électrolytique dans le compartiment anodique et éliminés de manière continue du réacteur électrolytique ; et
    dans lequel la solution électrolytique résultante avec une solution de NaOH et de NaCl régénérée, représentant la liqueur blanche, est régénérée passant du compartiment cathodique, après le processus de cuisson, par le biais d'un collecteur (21), au lessiveur en continu (1), ce qui permet de terminer tout le processus de fabrication de cellulose.
  2. Procédé en continu pour la production d'une pâte cellulosique selon la revendication 1, caractérisé en ce qu'il comprend en outre les étapes :
    (ix) de classage et de fractionnement, où la suspension diluée de l'étape (viii) dans la revendication 1, est traitée au moyen d'un dispositif de classage et de fractionnement (22) équipé d'un tamis de 0,1 à 0,5 mm, ce qui produit deux fractions ;
    (a) la première fraction qui ne passe pas à travers le tamis de 0,1 à 0,5 mm ; et
    (b) la seconde fraction qui passe à travers le tamis de 0,1 à 0,5 mm, qui est considérée être une bonne pâte cellulosique d'une blancheur très élevée, supérieure à 90 %, appropriée pour la fabrication d'un papier de qualité supérieure ou de feuilles de cellulose, qui est transportée durant tout le procédé au moyen d'un collecteur (23) ; et
    (x) où la fraction (a) de la pâte cellulosique de l'étape (ix) est soumise à un ou deux traitements ultérieurs au moyen des usines de pâte à papier (24, 25) produisant la pâte cellulosique, qui est transférée, par le biais d'un collecteur (26), à nouveau au dispositif de classage et de fractionnement (22).
  3. Procédé en continu pour la production d'une pâte cellulosique selon l'une quelconque des revendications précédentes, caractérisé en ce que les produits chimiques pour la digestion à l'étape (ii) dans la revendication 1 sont introduits sous la forme d'un mélange de solutions aqueuses concentrées de 20 à 50 % p/p de NaOH et de 10 à 30 % p/p de NaCl.
  4. Procédé en continu pour la production d'une pâte cellulosique selon l'une quelconque des revendications précédentes, caractérisé en ce que la température de digestion est maintenu dans la plage comprise entre 90 et 100 °C.
  5. Procédé en continu pour la production d'une pâte cellulosique selon l'une quelconque des revendications précédentes, caractérisé en ce que la température de blanchiment est maintenu dans la plage comprise entre 85 et 100 °C.
  6. Procédé en continu pour la production d'une pâte cellulosique selon l'une quelconque des revendications précédentes, caractérisé en ce que les unités de chauffage dans le lessiveur en continu (1) et le réacteur de blanchiment en continu (6) sont des magnétrons générant des micro-ondes (MW).
  7. Procédé en continu pour la production d'une pâte cellulosique selon l'une quelconque des revendications précédentes, caractérisé en ce que la liqueur noire et les eaux de traitement de lavage combinées qui émanent des étapes (vi) et (vii) dans la revendication 1 par le biais de collecteurs (10) et (15) sont facultativement concentrées jusqu'à la teneur de sodium total comprise entre 0,90 et 1,05 % p/p dans l'évaporateur (16) avant un traitement ultérieur dans un réacteur électrolytique (19).
  8. Procédé en continu pour la production d'une pâte cellulosique selon l'une quelconque des revendications précédentes, caractérisé en ce que l'élimination électrolytique de la lignine et la régénération de la liqueur blanche à l'étape (viii) de la revendication 1 dans le réacteur électrolytique (19) sont menées avec une anode en graphite et une cathode en acier au carbone ou en acier inoxydable, à un potentiel électrique compris entre 3 et 10 V, une densité de courant électrique comprise entre 3 et 7 A/dm2.
  9. Procédé en continu pour la production d'une pâte cellulosique selon l'une quelconque des revendications précédentes, caractérisé en ce que la matière première semblable à de l'herbe comprend des tiges d'espèces végétales sélectionnées dans le groupe constitué par : le blé (Triticum vulgare, Linne) ; le riz (Oryza sativa, Linne) ; l'orge (Horedum vulgare, Linne) ; l'avoine (Avena sativa, Linne) ; le lin (Linum usitatissimum, Linne) ; le maïs (Zea mays, Linne) ; les millets : le millet commun (Panicum miliaceum, Linne), le millet à chandelle (Pennisetum glaucum, Linne), le panic rameux (Panicum ramosum, Linne) et le pied-de-coq cultivé (Echinochloa frumentaceae, Linne) ; le triticale (x Triticosecale, Wittm. ex A. Camus) ; le sarrasin (Fagopyrum esculentum, Moench) ; le miscanthus (Miscanthus x giganteus, Andersson) ; le panic érigé (Panicum virgatum, Linne) ; le sorgho (Sorghum species, Linne) ; le roseau commun (Phragmites australis, Cav.), la canne de Provence (Arundo donax, Linne) ; le roseau de Birmanie (Neyraudia reynaudiana, Kunth.), la quenouille (Typha spp., Linne), le papyrus (Cyperus papyrus, Linne), le rubanier (Sparganium spp., Linne), le roseau de chaume (Thamnochortus insignis, Linne) ; le sparte (Stipa tenacissima, Linne et Lygeum spartum, Linne) ; le jute (Corchorus olitorius, Linne), le bambou (Bambusoideae spp., Linne), la bagasse ou des mélanges de ceux-ci.
  10. Procédé en continu pour la production d'une pâte cellulosique selon la revendication 8, caractérisé en ce que la matière première semblable à de l'herbe est le miscanthus (Miscanthus x giganteus, Andersson).
EP16722693.5A 2016-04-15 2016-04-15 Processus continu destiné à la production de pâte de cellulose Active EP3443159B1 (fr)

Priority Applications (3)

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HRP20200981TT HRP20200981T1 (hr) 2016-04-15 2016-04-15 Kontinuirani postupak za dobivanje celulozne pulpe
PL16722693T PL3443159T3 (pl) 2016-04-15 2016-04-15 Ciągły sposób wytwarzania masy celulozowej
RS20200820A RS60519B1 (sr) 2016-04-15 2016-04-15 Kontinuirani postupak za proizvodnju celulozne pulpe

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PCT/HR2016/000014 WO2017178849A1 (fr) 2016-04-15 2016-04-15 Processus continu destiné à la production de pâte de cellulose

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HRP20190259A2 (hr) * 2019-02-07 2020-08-21 Marinko Mikulić Kontinuirani postupak proizvodnje celulozne pulpe iz travnatih sirovina
EP4269687B1 (fr) * 2022-04-26 2026-04-08 Wepa Professional GmbH Procédé de production de cellulose et d'extraction de lignine à partir d'une lignocellulose à partir des matières premières végétales du genre miscanthus
CA3170366A1 (fr) * 2022-08-12 2024-02-12 Sixring Inc. Optimisation de la consommation de produits chimiques dans la delignification de biomasse
CN118756519B (zh) * 2024-08-09 2025-05-27 山东银鹰股份有限公司 一种高甲种纤维素含量的棉浆粕的制备方法

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US2692181A (en) 1950-03-08 1954-10-19 Buffalo Electro Chem Co Treatment of unbleached sulfite pulp
FR1112830A (fr) 1953-09-30 1956-03-19 Aschaffenburger Zellstoffwerke Procédé pour la fabrication de semi-cellulose à partir de bois feuillu
GB1217833A (en) * 1967-01-16 1970-12-31 Electric Reduction Co Improved cellulosic pulp process
SE400997B (sv) * 1972-12-15 1978-04-17 Erco Envirotech Ltd Sett for avlegsnande av natriumklorid ur regenererad vitlut
AU4404285A (en) * 1984-05-15 1985-12-13 Flinck Karl-Evert Method of bleaching fibre pulp for the production of paper and paperboard
US4584075A (en) 1984-11-26 1986-04-22 Ionics Incorporated Process and apparatus for electrically desorbing components selectively sorbed on an electrolytically conducting barrier
CA2038651C (fr) 1991-03-19 1995-12-12 Kwei-Nam Law Methode et appareil de blanchiment de la pate a papier
SE470538C (sv) * 1992-12-02 1996-02-26 Kvaerner Pulping Tech Sätt vid blekning av massa utan användning av klorhaltiga kemikalier
DE19603491C2 (de) 1996-01-31 1999-04-08 Abu Shaar Isam Verfahren zur Herstellung eines fasrigen Zellulosestoffes und dessen Verwendung
FI126563B (en) * 2012-03-12 2017-02-15 Upm Kymmene Corp A method and system for treating fluid flows at a pulp mill
CA2944123A1 (fr) 2014-03-31 2015-10-08 Marinko Mikulic Procede continu de production de pate de cellulose a partir de matieres premieres vegetales semblables a l'herbe

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* Cited by examiner, † Cited by third party
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DK3443159T3 (da) 2020-07-27
ES2806475T3 (es) 2021-02-17
RS60519B1 (sr) 2020-08-31
PL3443159T3 (pl) 2020-09-21
EP3443159A1 (fr) 2019-02-20
WO2017178849A1 (fr) 2017-10-19

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