EP4497869A1 - Procédé de production de cellulose microfibrillée à partir de pâte kraft à haut rendement, cellulose microfibrillée obtenue à partir de ce procédé et pâte kraft et produits papetiers comprenant ladite cellulose microfibrillée - Google Patents
Procédé de production de cellulose microfibrillée à partir de pâte kraft à haut rendement, cellulose microfibrillée obtenue à partir de ce procédé et pâte kraft et produits papetiers comprenant ladite cellulose microfibrillée Download PDFInfo
- Publication number
- EP4497869A1 EP4497869A1 EP23723251.7A EP23723251A EP4497869A1 EP 4497869 A1 EP4497869 A1 EP 4497869A1 EP 23723251 A EP23723251 A EP 23723251A EP 4497869 A1 EP4497869 A1 EP 4497869A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pulp
- microfibrillated cellulose
- hykep
- mfc
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 103
- 239000001913 cellulose Substances 0.000 title claims abstract description 91
- 239000002655 kraft paper Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 63
- 230000008569 process Effects 0.000 title claims abstract description 53
- 239000000123 paper Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 229920005610 lignin Polymers 0.000 claims abstract description 42
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 230000014759 maintenance of location Effects 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 244000166124 Eucalyptus globulus Species 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 12
- 230000002255 enzymatic effect Effects 0.000 claims description 7
- 239000011121 hardwood Substances 0.000 claims description 4
- 239000011122 softwood Substances 0.000 claims description 4
- 239000011111 cardboard Substances 0.000 claims description 2
- 238000009459 flexible packaging Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 235000010980 cellulose Nutrition 0.000 description 87
- 238000010411 cooking Methods 0.000 description 26
- 239000000835 fiber Substances 0.000 description 26
- 238000007670 refining Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 229920002472 Starch Polymers 0.000 description 12
- 239000008107 starch Substances 0.000 description 12
- 235000019698 starch Nutrition 0.000 description 12
- 238000011282 treatment Methods 0.000 description 12
- 238000010348 incorporation Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000004061 bleaching Methods 0.000 description 8
- 239000002023 wood Substances 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 6
- 238000001311 chemical methods and process Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 206010061592 cardiac fibrillation Diseases 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002600 fibrillogenic effect Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000004692 Eucalyptus globulus Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- ATSGLBOJGVTHHC-UHFFFAOYSA-N bis(ethane-1,2-diamine)copper(2+) Chemical compound [Cu+2].NCCN.NCCN ATSGLBOJGVTHHC-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 235000020044 madeira Nutrition 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
- D21H11/04—Kraft or sulfate pulp
-
- 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
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- 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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/005—Mechanical treatment
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/40—Multi-ply at least one of the sheets being non-planar, e.g. crêped
Definitions
- the present invention relates to a process for the production of microfibrillated cellulose from high-yield Kraft pulp. Furthermore, the invention concerns the microfibrillated cellulose obtainable by the process, and the Kraft pulp and paper products comprising the obtained microfibrillated cellulose. The invention has application in the field of the paper industry.
- Microfibrillated celluloses have been the target of increasing interest for different applications, namely in the area of pulp and paper production. They can be produced from different raw materials such as, for example, cellulosic fibers from, wood, lignocellulosic plants, herbs and tubers, among others, and through processes that may involve enzymatic, chemical and mechanical operations, individually or in several stages ( Klem et al, Nanocelluloses: A New Family of Nature-Based Materials, Angew. Chem., Int. Ed., 2011, 50, 5438 - 5466 ).
- microfibrillated celluloses are produced from pulp that has been delignified and preferably bleached ( Osong et al., Processing of wood-based microfibrillated cellulose and nanofibrillated cellulose, and applications relating to papermaking: A review, 2016, 23, 93-123 ; Klemm et al., Nanocellulose as a natural source for technological applications in materials science: Today's state, Materials Today, 2018, 7, 720-748 ).
- microfibrillated cellulose production processes are carried out from conventional cellulosic raw materials, that is, cellulosic pulps delignified by typical chemical cooking processes, such as Kraft or sulfite, and/or bleached, thus typically having total lignin contents inferior to 5% by weight.
- typical chemical cooking processes such as Kraft or sulfite, and/or bleached
- total lignin contents inferior to 5% by weight.
- Patent EP3341523B1 discloses a method of producing microfibrillated cellulose that requires fewer passes through refiners and, consequently, lower energy consumption, which involves refining, with blades of certain dimensions, of a chemical pulp of cellulosic fibers.
- Patent EP2494107B1 concerns a process for producing microfibrillated cellulose with the aid of an extruder, in which at least one chemical product (among carboxymethylcellulose, methylcellulose, polyvinyl alcohol, calcium stearate, alcohols, surfactants and tensioactives or other hydrophobic chemical products) is added to the extruder during processing of a mixture of fibers, preferably cellulosic but cotton fibers and fibers from agricultural products such as potatoes and cereals can also be included.
- at least one chemical product among carboxymethylcellulose, methylcellulose, polyvinyl alcohol, calcium stearate, alcohols, surfactants and tensioactives or other hydrophobic chemical products
- Patent application EP2196579A1 describes a method of producing microfibrillated cellulose, with a lower associated energy consumption, which involves passing a suspension of a cellulose pulp in a solvent (such as water, alcohols, dimethylsulfoxide, glycerol and mixtures thereof) through a hole of a homogenizer so that said suspension is subjected to a pressure drop. Said diameter of said hole is from 100 to 700 ⁇ m and said pressure drop has a maximum value of 100 MPa.
- a solvent such as water, alcohols, dimethylsulfoxide, glycerol and mixtures thereof
- Said diameter of said hole is from 100 to 700 ⁇ m and said pressure drop has a maximum value of 100 MPa.
- the cellulose pulps described in the patent application refer to conventional pulps and those obtained by typical production processes, such as bleached, semi-bleached and unbleached pulps, by sulfite and sulfate chemical processes.
- the patent application WO2014147293A1 discloses a microfibrillated cellulose production process which incorporates, in the chemical cooking, a physical/mechanical treatment, such as pressing and shearing, of an impregnated cellulosic fiber source, a treatment that is applied during or after the impregnation of the fiber or during or after fiber cooking, in which a change in the cellular structure of the fiber wall is observed, thus decreasing the energy consumption involved in the production of the microfibrillated pulp.
- the process then continues with the typical cooking steps, for example by Kraft cooking, washing and bleaching, and further refining with enzymes or solvent and, finally, the milling of the obtained fibril.
- the invention describes the use of fibers from herbaceous and non-herbaceous and combinations thereof.
- the patent EP2576629B1 describes a method of producing microfibrillated cellulose, said to be more efficient and cost-effective compared to the prior art, which involves acid hydrolysis at elevated temperature or acidification followed by washing and hydrolysis at elevated temperature of a cellulosic material.
- the lignin content of the cellulosic starting material is inferior to 5% by weight.
- As a cellulosic material it is considered chemical pulp of hardwoods or softwoods, bleached or unbleached, such as Kraft, sulfite and soda pulp.
- Patent EP2452014B1 describes a microfibrillated cellulose production process, more efficient compared to the prior art, which consists of processing a pulp of cellulosic fibers with an enzyme and a mechanical treatment, in which both are carried out simultaneously in a single step.
- Bleached fibers are used, for example softwood and hardwood fibers, since, as described in the aforementioned patent, the presence of lignin in unbleached pulps leads to greater energy consumption in the production of microfibrillated cellulose.
- Patent application US20160273165A1 discloses a method for producing a paper product with improved strength and filler and fine retention, which involves adding an anionically modified microfibrillated cellulose to a fiber suspension in an amount of 0,1 to 10% by weight.
- Patent application EP3433428A4 describes a paperboard with improved compression strength involving the use of a cellulose pulp with drainability values between 15 and 28 (in Schopper-Riegler values) to which it is added between 1 and 5% by weight of microfibrillated cellulose and a hydrophobic additive such as an alkylketene dimer, succinic anhydrides, rosins and a styrene maleic anhydride, or emulsions, modifications and mixtures thereof.
- a hydrophobic additive such as an alkylketene dimer, succinic anhydrides, rosins and a styrene maleic anhydride, or emulsions, modifications and mixtures thereof.
- EP2978894B1 describes a process for producing paper and paperboard with strength properties through a mixture of fibers which involves the addition, in a specific sequence, of microfibrillated cellulose, strength additives and microparticles such as silica and bentonite, to this mixture of fibers.
- Kraft cooking or sulfate cooking.
- This chemical process consists of cooking the wood in a cooking liquor usually consisting of sodium hydroxide and sodium sulfide, at temperatures of around 140 to 180 °C, in pressurized reactors ( Ek, Monica; Gellerstedt, Göran; Henriksson, Gunnar; Pulp and Paper Chemistry and Technology Volume 2, Pulping Chemistry and Technology, 2009, De Gruyter, Berlim ).
- This chemical cooking process typically ends with a total lignin content inferior to 5% by weight. It is necessary to extend the Kraft cooking process to lignin contents inferior to 5°, in order to be able to process the pulp, either for direct paper production or for subsequent bleaching.
- the Kraft cooking process is one of the processes typically used to produce the raw material used in state of the art microfibrillated cellulose production processes.
- the state of the art shows that the methods to produce microfibrillated cellulose, from the cellulosic materials conventionally used for microfibrillated cellulose production, understood as cellulosic pulps delignified by the typical chemical cooking processes, as Kraft or sulfite, and/or additionally bleached, include modifications, for increased efficiency and lower associated costs, involving the use of, for example, organic solvents, chemical treatments, such as hydrolysis, and fibrillation equipment developed for this purpose, in several stages or in combination. Cellulose pulps with a lignin content substantially inferior to 5% are also used as raw material, applying, for that, for example, bleaching treatments to the original cellulose pulps.
- microfibrillated cellulose production process which exempts the raw material from the application of complex chemical and/or mechanical treatments aiming at reducing the lignin content of the referred raw material to values inferior to 5% in weight and which also dismiss such treatments during its conversion into microfibrillated cellulose.
- a microfibrillated pulp production process that provides lower energy consumption, thus lower associated costs, and results in the production of a microfibrillated pulp that can be applied in the production of paper materials with increased strength properties, compared to microfibrillated celluloses produced by state of the art production processes using conventional cellulosic raw materials, i.e. with lignin contents inferior to 5%.
- a process for the production of microfillated cellulose wherein the process comprises the steps of:
- a second aspect of the present invention relates to a microfibrillated cellulose obtainable by the process according to the first aspect of the invention.
- a third aspect of the present invention relates to a Kraft pulp comprising the microfibrillated cellulose according to the second aspect.
- a fourth aspect of the present invention relates to a paper product comprising the microfibrillated cellulose according to the second aspect.
- microfibrillated cellulose also referred to in this description as MFC, for purposes of simplification
- a high-yield Kraft pulp i.e., in the context of the present invention, a Kraft pulp with a total lignin content of 5% to 30% by weight
- a conventional Kraft pulp to which is associated, a low lignin content, i.e., in the context of the present invention, a total lignin content inferior to 5% by weight
- the microfibrillated cellulose obtained presents a papermaking ability that provides increased mechanical strength properties to the paper products incorporating it, in comparison with conventional solutions of the use of microfibrillated celluloses produced through conventional cellulose pulps, i.e., delignified by the typical chemical cooking processes, such as Kraft or sulfite, and/
- Kraft cooking process refers to Kraft cooking or sulfate cooking. It is a chemical process well known in the art which consists in cooking the wood in a cooking liquor usually consisting of sodium hydroxide and sodium sulfide, at temperatures of the order of 140 to 180 °C, in pressurized reactors.
- a conventional Kraft process is here understood as a typical chemical cooking process that yields a pulp production yield of about 45-55%.
- Kraft pulp refers to a pulp obtained by Kraft cooking.
- unbleached Kraft pulp refers to a pulp produced by the conventional Kraft process, typically with a total lignin content inferior to 5% by weight.
- bleached Kraft pulp refers to a pulp produced by the conventional Kraft process, and which is further subjected to a bleaching step, with a total lignin content typically inferior to 1 % by weight.
- the purpose of the bleaching step is to continue the delignification by the action of oxidizing agents, such as oxygen, chlorine dioxide and hydrogen peroxide.
- high-yield Kraft pulp refers to a Kraft pulp produced by a chemical Kraft cooking process with a yield of more than 60%, the pulp thus produced having a total lignin content of between 5% and 30% by weight. Therefore, when reference is made in this description to "high-yield Kraft pulp” it is meant as a simplified reference to a Kraft pulp with a total lignin content of 5 % to 30 % by weight.
- the cooking yield is calculated by the following formula: pulp weight / wood weight ⁇ 100 Weights on an absolute dry basis
- the total lignin content by weight is the sum of the contents of insoluble lignin (determined in accordance with the standard Tappi 222 om-02) and soluble lignin (determined in accordance with the standard Tappi UM 250 modified with the addition of borohydride for spectrophotometric measurement - Pinto P., Influência da estrutura qu ⁇ mica dos componentes da madeira no seu desempenho nos processes de produç ⁇ o de pastas cellularósicas. Estudo comparative entre Eucalyptus globulus e outras folhosas, PhD Thesis, Universidade de Aveiro, 2005 ).
- microfibrillated cellulose refers to cellulose fibres composed of, at least, one elementary fibre containing crystalline, paracrystalline and amorphous regions, with aspect ratio (length/diameter) superior to 10, and may contain longitudinal fibrils, crosslinking between particles or net-like structures, being produced by mechanical and/or chemical treatments of wood, such as enzymatic treatments, for example.
- microfibrillated celluloses produced exclusively by mechanical treatments as “mechanical microfibrillated celluloses” and when produced through a combination of these with enzymatic treatments as "enzymatic microfibrillated celluloses", since, being chemically composed by the same elements as the raw material pulp, the intrinsic characteristics of the produced microfibrillated celluloses directly depend on the process used for their production, making it impossible to characterize them through their constituents due to their heterogeneous nature. This is also expected with other production methods and depending on the raw materials involved.
- percentage of fines refers to the percentage of fibrils with a length inferior or equal to 0.2 mm, measured on a L&W Fiber Tester 901 equipment, relative to the average length of the whole sample.
- mechanical defibration technology it is possible to achieve 100% of fines, combining modern machinery and adequate energy and time consumption.
- the content of fines to be achieved may be higher or lower.
- microfibrillated cellulose from high-yield Kraft pulp refers to microfibrillated cellulose produced from a high-yield Kraft pulp.
- microfibrillated cellulose from unbleached Kraft pulp refers to microfibrillated cellulose produced from an unbleached Kraft pulp.
- microfibrillated cellulose from bleached Kraft pulp refers to a microfibrillated cellulose produced from a bleached Kraft pulp.
- containerboard refers to the paper commonly used to make corrugated boards.
- the top and bottom layer of a corrugated board is called linerboard. It is usually a two-layer product, a top layer and a base layer.
- Virgin and recycled fibre are used in the production of this type of paper.
- the product is called kraftliner.
- the product is referred to as a testliner.
- the fluting between two liners is called fluting or corrugated medium.
- tissue paper refers to a paper used for hygienic and sanitary purposes, either at home or at public places.
- a process for producing microfibrillated cellulose from a high-yield Kraft pulp is described herein, the latter comprising, by definition, a high lignin content, that is, in the context of the present invention, a total lignin content of 5 % to 30 % by weight.
- the process of the invention simultaneously allows the production of microfibrillated cellulose with a lower energy consumption in comparison with the processes of the prior art using conventional Kraft pulps (with a total lignin content inferior to 5% by weight) and where the microfibrillated cellulose obtained has a papermaking ability that provides increased mechanical strength properties to the paper products incorporating it, in comparison with conventional solutions using microfibrillated celluloses produced through conventional cellulose pulps (i.e., delignified by typical chemical cooking processes, such as Kraft or sulfite, and/or bleached).
- the process of the present invention makes it possible to produce microfibrillated cellulose, with the above-mentioned advantages, from Kraft pulps with a high total lignin content (from 5% to 30% by weight), contrary to the established practice in the prior art which discourages the use of such high total lignin content pulps, also commonly referred to as high-yield Kraft pulps.
- the process further comprises, between the steps a) of selecting and b) of defibrating, a step of enzymatic hydrolyzing the pulp selected in step a).
- the pulp is selected from the group consisting of hardwood pulp, softwood pulp and mixtures thereof.
- the microfibrillated cellulose comprises a minimum content of fines of 15% by weight.
- the paper product is selected from the group consisting of kraftliner paper, testliner paper, corrugated cardboard, paper for bags, paper for shopping bags, flexible packaging paper, tissue paper and printing and writing paper.
- CMF HYKEP Process for the production of microfibrillated cellulose from high-yield eucalyptus Kraft pulp
- the second phase was carried out with the refining parameters: rotation speed 700 rpm, edge length 39,48 km/s, power 5,922 kW, SEL 0,10 Wm/s and specific energy 250 kWh/ton. Refining was conducted until a minimum fines content of 15 % by weight (length weighted average, based on the total sample and determined on a L&W Fiber Tester 912 equipment) was reached.
- Figure 1 depicts the microscopic analysis of the obtained microfibrillated cellulose suspensions. It was possible to verify the fibrillation obtained after mechanical treatment and the heterogeneity of sizes within the same sample.
- the samples were analyzed in a L&W Fiber Tester 912 equipment for particle size determination.
- Table 1 presents the length-weighted average of fibre lengths and diameters, as well as the degree of polymerization, calculated using the Mark Houwink equation (parameters and equation defined in Henrikson et al., Cellulose Nanopaper Structures of High Toughness, Biomacromolecules 2008, 9, 1579-1585 ) with the intrinsic viscosity values determined on the samples dissolved in cupriethylenediamine solutions, according to ISO 5351:2010. Table 1.
- Figure 2 depicts the percentage of fines (based on the total sample, weighted in length, measured on a L&W Fiber Tester 912 instrument) of microfibrillated cellulose produced with different refining energies.
- High-yield eucalyptus Kraft pulp with a total lignin content of 5% by weight, was subjected to disintegration and refining as described in Example 1. The results obtained also showed that a higher percentage of fines, using the same refining energy, was obtained with this high-yield Kraft pulp than with a bleached Kraft pulp obtained by the conventional Kraft process.
- High-yield eucalyptus Kraft pulp with a total lignin content of 10% by weight, was disintegrated and refined in a similar way as described in Example 1. A higher percentage of fines, for the same refining energy, was obtained with this high-yield Kraft pulp compared to a bleached Kraft pulp obtained by the conventional Kraft process.
- High-yield pine Kraft pulp with a total lignin content of 30% by weight, was subjected to disintegration and refining as described in Example 1. A higher percentage of fines was also obtained with this high-yield Kraft pulp than with a bleached Kraft pulp obtained by the conventional Kraft process, in agreement with the previous examples.
- MFC HYKEP After the production of MFC HYKEP, its papermaking ability was assessed, according to the following examples.
- the MFC HYKEP produced was added to a high-yield Kraft pulp (HYKEP) with a total lignin content of 7% by weight.
- HYKEP high-yield Kraft pulp
- this lignin content of the high-yield Kraft pulp to which MFC HYKEP is added is not linked to the corresponding content of the HYKEP pulp used for the production of MFC HYKEP.
- Any HYKEP pulp with a total lignin content of 5% to 30% by weight can be used.
- Example 6 Comparison of the papermaking ability of microfibrillated cellulose obtained from high-yield eucalyptus Kraft pulp (MFC HYKEP) incorporated into high-yield eucalyptus Kraft pulp (HYKEP) in relation to the papermaking ability of microfibrillated cellulose obtained from bleached eucalyptus Kraft pulp (MFC BEKP) incorporated into bleached eucalyptus Kraft pulp (BEKP)
- High-yield eucalyptus Kraft pulp at a consistency of 0.64% (volume/weight), was mixed with MFC HYKEP with a consistency of 0.5% (weight/weight) and 35% of fines, in proportions of 5 and 10% by weight.
- BEKP Bleached eucalyptus Kraft pulp
- Isotropic laboratory sheets were prepared on a bench sheet former. For this, the pulps were previously refined. The MFC suspension was added to the refined pulp suspension, in a beaker, and subjected to magnetic stirring for 120 s, time after which the mixture was poured into the sheet former, following the ISO 5269-1 standard for sheet formation.
- Tables 2 and 3 show the comparative results of the relative increases in the mechanical strength properties compared to the references of sheets produced from BEKP pulp without MFC BEKP and sheets produced from HYKEP pulp without the addition of CMF HYKEP.
- the mechanical properties were measured according to the corresponding standards: burst index (ISO 2758:2015), tear index (ISO 1974:2012, tensile index (ISO 1924-2:2008), Scott-Bond (TAPPI 403).
- Table 2. Increases in strength properties (%) obtained in sheets with 5% MFC incorporation, relative to the references (without MFC) .
- Example 7 Comparison of the papermaking ability of microfibrillated cellulose obtained from high-yield eucalyptus Kraft pulp (MFC HYKEP) or from commercial microfibrillated cellulose (MFC commercial) (white) incorporated into high-yield eucalyptus Kraft pulp (HYKEP)
- 135 g/m 2 (OD) sheets were prepared from high-yield eucalyptus Kraft pulp at a consistency of 0.64% (volume/weight) mixed with MFC HYKEP at a consistency of 0.5% (weight/weight).
- the procedure for forming the sheets was the same as in the previous example.
- Example 8 Comparison of the papermaking ability of microfibrillated cellulose obtained from high-yield eucalyptus Kraft pulp (MFC HYKEP) incorporated to high-yield eucalyptus Kraft pulp (HYKEP) with and without retention agent
- Sheets of 135 g/m 2 (OD) were prepared from HYKEP pulp and at a consistency of 0.64% (volume/weight) mixed with MFC HYKEP with a consistency of 0,5 % (weight/ weight).
- An additional series was produced with the addition of a retention agent according to the compositions shown in Table 5.
- Table 6 shows the comparative results for the mechanical strength properties of 150 g/m 2 sheets from pulps containing HYKEP pulp with different proportions of MFC HYKEP and of 150 g/m 2 sheets from HYKEP pulp without MFC HYKEP addition. Two series are presented, namely in the absence and presence of a retention agent (linear cationic polyacrylamide). Table 6. Increases in strength properties (%) relative to the reference (HYKEP without MFC HYKEP) in the presence and absence of a retention agent.
- MFC HYKEP 35% fine originated an increase in the mechanical strength properties in relation to the reference, both in the presence and in the absence of a retention agent (always positive results in table 4). Additionally, it was observed that in the presence of the retention agent the papermaking ability of MFC HYKEP is enhanced (increase relative to the reference without MFC higher than the one observed without retention agent).
- Example 9 Comparison of the papermaking ability of microfibrillated cellulose obtained from high-yield eucalyptus Kraft pulp (MFC HYKEP) incorporated to high-yield eucalyptus Kraft pulp (HYKEP) with and without cationic starch.
- MFC HYKEP high-yield eucalyptus Kraft pulp
- HYKEP high-yield eucalyptus Kraft pulp
- 135 g/m 2 (OD) sheets were prepared from HYKEP pulp, with cationic starch incorporated and at a consistency of 0.64 % (volume/weight) mixed with MFC HYKEP with a consistency of 0.5 % (weight/weight) and with a retention agent according to the compositions shown in Table 6.
- Table 8 shows the comparative results for the mechanical strength properties of 150 g/m 2 sheets from HYKEP pulps with different proportions of MFC HYKEP and 150 g/m 2 sheets from HYKEP pulp without addition of MFC HYKEP, with and without starch and with and without a retention agent. Table 8. Increases in strength properties (%) relative to the reference (HYKEP without MFC), in the presence and absence of bulk starch (added to the pulp suspension) and also in the presence of the retention agent.
- Example 10 Comparison of the papermaking ability of microfibrillated cellulose obtained from high-yield eucalyptus Kraft pulp (MFC HYKEP), with 35 or 41% fines, added to high-yield eucalyptus Kraft pulp (HYKEP)
- Sheets 135 g/m 2 (OD) were prepared from HYKEP pulp, with incorporated cationic starch and at a consistency of 0,64 % (volume/weight) mixed with MFC HYKEP produced with a fines content of 35 or 41 %, with a consistency of 0,5 % (weight/weight) in the presence and absence of a retention agent.
- the MFC HYKEP with higher fines content had a more pronounced effect on the strength properties, for example with a 50 % increase in the burst index when compared to the reference without MFC HYKEP.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PT117870A PT117870B (pt) | 2022-03-23 | 2022-03-23 | Processo de produção de celulose microfibrilada a partir de pasta kraft de alto rendimento, celulose microfibrilada obtida a partir do processo e pasta kraft e produtos papeleiros que compreendem a referida celulose microfibrilada |
| PCT/IB2023/052806 WO2023180947A1 (fr) | 2022-03-23 | 2023-03-22 | Procédé de production de cellulose microfibrillée à partir de pâte kraft à haut rendement, cellulose microfibrillée obtenue à partir de ce procédé et pâte kraft et produits papetiers comprenant ladite cellulose microfibrillée |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4497869A1 true EP4497869A1 (fr) | 2025-01-29 |
Family
ID=86331693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23723251.7A Pending EP4497869A1 (fr) | 2022-03-23 | 2023-03-22 | Procédé de production de cellulose microfibrillée à partir de pâte kraft à haut rendement, cellulose microfibrillée obtenue à partir de ce procédé et pâte kraft et produits papetiers comprenant ladite cellulose microfibrillée |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP4497869A1 (fr) |
| CN (1) | CN118661001A (fr) |
| CL (1) | CL2024002439A1 (fr) |
| PT (1) | PT117870B (fr) |
| WO (1) | WO2023180947A1 (fr) |
-
2022
- 2022-03-23 PT PT117870A patent/PT117870B/pt active IP Right Grant
-
2023
- 2023-03-22 EP EP23723251.7A patent/EP4497869A1/fr active Pending
- 2023-03-22 WO PCT/IB2023/052806 patent/WO2023180947A1/fr not_active Ceased
- 2023-03-22 CN CN202380020990.2A patent/CN118661001A/zh active Pending
-
2024
- 2024-08-14 CL CL2024002439A patent/CL2024002439A1/es unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PT117870B (pt) | 2025-01-24 |
| PT117870A (pt) | 2023-09-25 |
| CL2024002439A1 (es) | 2024-11-22 |
| WO2023180947A1 (fr) | 2023-09-28 |
| CN118661001A (zh) | 2024-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Albornoz-Palma et al. | Effect of lignin and hemicellulose on the properties of lignocellulose nanofibril suspensions | |
| JP6622219B2 (ja) | ナノフィブリル化セルロースの高効率な製造 | |
| EP2885458B1 (fr) | Procédé et intermédiaire pour la production de cellulose hautement raffinée ou microfibrillée | |
| Tarrés et al. | Evaluation of the fibrillation method on lignocellulosic nanofibers production from eucalyptus sawdust: A comparative study between high-pressure homogenization and grinding | |
| US20160024713A1 (en) | Chemical activation and refining of southern pine kraft fibers | |
| JP2015521694A (ja) | ナノセルロース繊維を製造するためのエネルギー効率に優れた方法 | |
| JP2019504215A (ja) | 紙、板紙等の製造方法 | |
| Gonzalez et al. | Suitability of Rapeseed Chemithermomechanical Pulp as Raw Material in Papermaking. | |
| Tarrés et al. | Lignocellulosic micro/nanofibers from wood sawdust applied to recycled fibers for the production of paper bags | |
| Najahi et al. | High-lignin-containing cellulose nanofibrils from date palm waste produced by hydrothermal treatment in the presence of maleic acid | |
| US11313082B2 (en) | Sheet material comprising fiber and nano-microscale organic fibrillated filler and method of producing said sheet material | |
| Paszner et al. | Beating behaviour and sheet strength development of coniferous organosolv fibers | |
| Liu et al. | Cellulose nanofiber extraction from unbleached kraft pulp for paper strengthening | |
| Guo et al. | PULP AND FIBER CHARACTERIZATION OF WHEAT STRAW AND EUCALUPTUS PULPS-A. | |
| Latifah et al. | Extraction of nanofibrillated cellulose from Kelempayan (Neolamarckia cadamba) and its use as strength additive in papermaking | |
| CN1089387C (zh) | 含有预热法木片化学磨木浆的柔软松厚吸湿纸 | |
| Moradbak et al. | Effects of Alkaline Sulfite Anthraquinone and Methanol Pulping Conditions on the Mechanical and Optical Paper Properties of Bamboo (Gigantochloa scortechinii). | |
| US20120018110A1 (en) | Fiber additive made from non-woody material and method of production and use | |
| Ismaeilimoghadam et al. | Investigating the effect of bleaching (HEQPH) intensity on cellulose content, crystallinity, degree of polymerization, and physico-mechanical properties of bleached wheat straw and cotton linter fluff pulps | |
| EP4497869A1 (fr) | Procédé de production de cellulose microfibrillée à partir de pâte kraft à haut rendement, cellulose microfibrillée obtenue à partir de ce procédé et pâte kraft et produits papetiers comprenant ladite cellulose microfibrillée | |
| Demunera et al. | Production and Characterization of CNF and LCNF, and Manufacture of LCNF-nanostructured Packaging Papers | |
| Tozluoglu et al. | Effects of cellulose micro/nanofibers as paper additives in kraft and kraft-NaBH4pulps | |
| US3445329A (en) | Storage of high consistency refined pulp | |
| EP2239370B1 (fr) | Amélioration de la résistance à la sécheresse et à l'humidité de produits à base de papier avec des tanins cationiques | |
| CN117403475A (zh) | 一种制备食品包装原纸的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20241011 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR |