EP3172378A1 - Method of preparing cellulose nano-fibres from stalks of annual plants - Google Patents

Method of preparing cellulose nano-fibres from stalks of annual plants

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Publication number
EP3172378A1
EP3172378A1 EP15730546.7A EP15730546A EP3172378A1 EP 3172378 A1 EP3172378 A1 EP 3172378A1 EP 15730546 A EP15730546 A EP 15730546A EP 3172378 A1 EP3172378 A1 EP 3172378A1
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EP
European Patent Office
Prior art keywords
minutes
cellulose
concentration
stalks
temperature
Prior art date
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Granted
Application number
EP15730546.7A
Other languages
German (de)
French (fr)
Other versions
EP3172378B1 (en
Inventor
Janusz KAZIMIERCZAK
Ewa KOPANIA
Arkadiusz BLODA
Grazyna KRZYZANOWSKA
Anna KLUSKA
Justyna WIETECHA
Danuta Ciechanska
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Instytut Biopolimerow I Wlokien Chemicznych
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Instytut Biopolimerow I Wlokien Chemicznych
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Priority to PL15730546T priority Critical patent/PL3172378T3/en
Publication of EP3172378A1 publication Critical patent/EP3172378A1/en
Application granted granted Critical
Publication of EP3172378B1 publication Critical patent/EP3172378B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—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
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
    • 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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • 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
    • D21C9/001—Modification of pulp properties
    • D21C9/007—Modification of pulp properties by mechanical or physical means
    • 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
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/123—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with Cl2O
    • 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

  • This invention relates to the preparation of cellulose nano-fibres from stalks of annual crops.
  • a method is known of preparing cellulose nano-fibers from a fibrous pulp derived from natural fibers, root crops, fibre crops which contain hemicellulose, lignin, pectin and mineral substance.
  • the method comprises several consecutive steps of preparing the nano-fibres: hydrolysis of the fibrous pulp by means of a diluted acid at temperature of 70 - 90°C, extraction in alkaline medium, cryogenic disintegration, and defibrillation in a homogenizer at high pressure.
  • the obtained nano- fibers may be used as reinforcement in resin composites prepared by film casting, forming or extrusion for application in medical devices and packaging.
  • EP 2 415 821 known is a method of preparing a cellulose gel.
  • the method consists in that the cellulose material is first treated with an oxidizing agent generating carboxylic groups on the cellulose surface.
  • the suspension of the cellulose material is then homogenized and the obtained suspension of nano-fibers is treated with an organic-or inorganic acid to cause the cellulose nano-fibers aggregate into a gel.
  • the liquid gel is again mechanically processed.
  • the outcome is a gel which contains cellulose nano-fibres holding free carboxylic groups on its surface.
  • the prepared cellulose gel reveals low water absorption and swelling due to that the unreacted carboxylic groups are not as prone to dissociation as those reacted to salts.
  • Patent US 8546558 describes a method of preparing micro-fibril cellulose from a hemicellulose-containing sulfite pulp derived preferably from coniferous wood. The method involves mechanical grinding, action of hemicellulase or cellulase or mixture of the two and a further mechanical homogenization. Prospective uses of the micro- fibril cellulose are in food, cosmetics, pharmacy, paper, composites, coatings and thickeners.
  • a method to make cellulose nano-fibrils is described in the international patent application WO 2010092239.
  • the method provides preparation of a suspension of cellulose fibers upon which adsorbed is a cellulose derivative (e.g. carboxymethylcellulose) or a polysaccharide or its derivative.
  • the fibers are then disintegrated to nano-fibrils.
  • Chemical-, mechanical-, thermo-mechanical or chemical- thermo-mechanical cellulose pulp was used as starting material. It was derived from wood, non-woody materials or recycled cellulose fibers.
  • the nano-fibrils sized below 1 micrometer find their uses in food, concrete, drilling fluids, coatings, cosmetics, drugs and paper.
  • WO 2013188657 is a method for the manufacture of nano-fibres from a cellulosic material by processing of an aqueous suspension with a cellulose depolymerizing agent such as ozone, cellulase or a combination of the two, and a parallel or subsequent mechanical disintegration which delivers nano-fibers from the cellulosic material.
  • a cellulose depolymerizing agent such as ozone, cellulase or a combination of the two
  • a parallel or subsequent mechanical disintegration which delivers nano-fibers from the cellulosic material.
  • Low energy consumption is an asset of the method in comparison to processes employing only mechanical disintegration.
  • Nano fibers from the method find their use in paper making.
  • the method of preparing cellulose nano-fibers from stalks of annual plants according to the invention consist in that the stalks cut into pieces 10-70 mm long are processed in following steps:
  • the digesting in step c) can, according to the invention, be run in a liquor with a content on dry mass of 5 - 15 wt.% of NaOH and 0,1 - 0,5 wt.% of anthraquinone or a liquor with 5 - 15 wt% of NaOH, 3 - 6 wt% of H 2 0 2 , 0.1 - 0,3 wt% of ethylenediaminetetraacetic acid (EDTA), 0,2 - 0,5 wt% of MgS0 4 and 2 - 5 wt% of water glass.
  • EDTA ethylenediaminetetraacetic acid
  • the cellulose pulp is, according to the invention, in addition to the bleaching in step e) preferably put to de-lignification by the action of 1 - 2 wt% of peracetic acid and 0,2 - 0,5 wt% of MgS0 4> calculated on dry mass.
  • the cellulose pulp holding about 50 - 70 wt% of water is, after the bleaching in step e) and prior to the enzymatic treatment in step f), preferably put for 20 - 90 minutes to mechanical defibrillation followed by homogenizing in water suspension.
  • the sediment formed after homogenization and centrifugation in step g) can be recirculated to step f) and put to repeated enzymatic treatment with a solution of cellulase.
  • the multi-stage de-lignification combined with bleaching of the lingo-cellulose raw material, according to the invention offers the chance of removing the non-cellulosic substance without a far-going degradation of cellulose thus providing a high output of cellulose pulp with excellent purity.
  • the multi-stage mechanical treatment of the pulp combined with enzymatic hydrolysis of cellulose makes it possible to prepare cellulose nano-fibres having a high proportion of length to thickness.
  • the method according to the invention enables the utilization of agriculture residues such as linen and hemp waste straw remaining after the separation of seeds for oil expression.
  • nano-fibres made according to the invention can be used as reinforcement in the production of composite materials, as thickener or constituent of a variety of coatings
  • Hemp stalks cut to pieces 40 - 60 long were loaded into a 15 dm swing digester and put for 10 minutes to the action of 2 bar steam and then three times defibrillated in the disk mill of Sprout- Waldron type with a consecutive decrease of the distance between the defibrillating elements (0,5, 0,2 and 0,1 mm).
  • the slackened plant raw material was for 60 minutes digested at 110°C in a liquor containing: 5 wt.% of NaOH, 5,5 wt.% of H 2 0 2 , 0,3 wt. of EDTA, 0,5 wt.% of MgS0 4 and 5% water glass calculated on dry mass at fluid module of 4: 1.
  • the fibrous pulp was subjected to delignification with oxygen in a medium containing 2,5 wt% of NaOH and 0,5 wt% of MgS0 4 on dry mass with oxygen pressure at start of 0,2 MPa, pulp concentration 8wt%, for 60 minutes, at 120°C.
  • the cellulose pulp was bleached twice with sodium chlorite at NaC10 2 concentration of l,4wt% and H 2 S0 4 concentration of 0,1 wt% at 70°C, for 120 minutes. After every chemical treatment, the cellulose pulp was washed with demi water and centrifuged.
  • the prepared cellulose pulp was characterized by lignin content of 0,45% and alfa-cellulose content of 85,5 wt%, and average polymerization degree of 1266. Total output of the process was 65,9%.
  • An aqueous 2,5 wt% suspension of the cellulose in a conical flask was placed on the platform of incubator with a rotation shaker Labfors (Infers) and put to enzymatic treatment with cellulase (Ecostone L900, AB Enzymes) having endo-l,4-beta-glucanase activity of 500 J/g at pH of 4.8 at 50°C, for 180 minutes at agitation rate of 150 rpm.
  • the 1.5wt% aqueous suspension was for 10 minutes homogenized in the homogenizer Ultra Turrax T50 (IKA) at 10000 rpm.
  • IKA homogenizer Ultra Turrax T50
  • the suspension was quenched with refrigerating brine at -15°C.
  • the prepared fibers were characterized by thickness in the range of 30 to 120 nm and average molecular degree of 130.
  • the prepared cellulose pulp was characterized by lignin content of 9 wt% and alfa-cellulose content of 80,3 wt%, and average polymerization degree of 1306. Total output of the process was 69,5%.
  • the cellulose pulp was put to mechanical treatment for 60 minutes at 40 rpm in a laboratory shredder.
  • the l,5wt% aqueous suspension of cellulose was put to enzymatic treatment like in Example 1 save amount of enzyme which was 300 J/g.
  • the residual enzyme in the cellulose pulp was deactivated like in Example 1.
  • the l,5wt.% aqueous suspension of cellulose was homogenized by means of the homogenizer Ultra Turrax T50 in 3 cycles with the G45F tool and 3 cycles with W65SK tool at 10 000 rpm for 3 minutes in each of the cycles. During the homogenization, the suspension was quenched with refrigerating brine at about -15°C. The cellulose suspension was centrifuged as in Example 1 and the cellulose- -nano-fibers- containing supernatant was separated. The prepared fibers were characterized by thickness in the range of 40 to 160 nm and average molecular degree of 155.
  • Stalks of oil flax cut to 30 - 60 mm pieces were steam-treated, defibrillated, digested, put to delignification in oxygen medium, bleached with sodium chlorite and alkaline- extracted like in Example 1.
  • the prepared cellulose pulp was characterized by lignin content of 14 wt% and alfa-cellulose content of 72,4 wt%, and average polymerization degree of 1151. Total output of the process was 92,3%.
  • the cellulose pulp was enzyme-treated like in Example 1.
  • a 2,5 wt% suspension of the cellulose in water was next prepared and put to homogenization in the homogenizer Ultra Turrax T50 at 10 000 rpm for 3 minutes in each of the 5 homogenization cycles.
  • the suspension was quenched with refrigerating brine at about -15°C.
  • the cellulose suspension was thereafter for 20 minutes centrifuged at 4 500 rpm.
  • the deposit was again put to enzyme treatment like in Example 1, employing cellulase with endo-l,4-beta-glucanase activity of 200 J/g.
  • From the remaining sediment prepared was a 1,5 wt% cellulose suspension in demi water which was for 3 minutes mechanically processed in each of the 3 cycles by means of the homogenizer Ultra Turrax T50 at 10 OOOrpm.
  • the suspension was in the consecutive step for 20 minutes centrifuged at 4 500 rpm. Supernatants from both steps of the processing were combined thus improving the output of the process.
  • the prepared fibers were characterized by thickness in the range of 45 to 200 nm and average molecular degree of 190.

Abstract

The method of manufacturing cellulose nano-fibres from stalks of annual crops consist in that pieces of the stalks of annual plants are in sequence subjected to the action of steam, mechanical defibrillation, digestion in a digesting liquor, oxygen delignification in aqueous medium containing NaOH and MgSO4, bleaching with sodium chlorite done at least twice, alkaline extraction in an NaOH solution, enzymatic treatment of the prepared cellulose pulp by cellulase with 10-1000 J/g activity of endo-l,4-beta- glucanase 10-1000 J/g. After washing and enzyme deactivation, the aqueous suspension of the cellulose is put to homogenization and centrifugation to obtain a supernatant which contains cellulose nano-fibers.

Description

Method of preparing cellulose nano-fibres from stalks of annual plants
This invention relates to the preparation of cellulose nano-fibres from stalks of annual crops.
From the patent application US 20080146701 a method is known of preparing cellulose nano-fibers from a fibrous pulp derived from natural fibers, root crops, fibre crops which contain hemicellulose, lignin, pectin and mineral substance. The method comprises several consecutive steps of preparing the nano-fibres: hydrolysis of the fibrous pulp by means of a diluted acid at temperature of 70 - 90°C, extraction in alkaline medium, cryogenic disintegration, and defibrillation in a homogenizer at high pressure. The obtained nano- fibers may be used as reinforcement in resin composites prepared by film casting, forming or extrusion for application in medical devices and packaging.
From the patent description EP 2 415 821 known is a method of preparing a cellulose gel. The method consists in that the cellulose material is first treated with an oxidizing agent generating carboxylic groups on the cellulose surface. The suspension of the cellulose material is then homogenized and the obtained suspension of nano-fibers is treated with an organic-or inorganic acid to cause the cellulose nano-fibers aggregate into a gel. In order to solidify the gel, it is subjected to UV irradiation or to the action of a cellulase preparation or ozone and peroxides. The liquid gel is again mechanically processed. The outcome is a gel which contains cellulose nano-fibres holding free carboxylic groups on its surface. The prepared cellulose gel reveals low water absorption and swelling due to that the unreacted carboxylic groups are not as prone to dissociation as those reacted to salts.
Patent US 8546558 describes a method of preparing micro-fibril cellulose from a hemicellulose-containing sulfite pulp derived preferably from coniferous wood. The method involves mechanical grinding, action of hemicellulase or cellulase or mixture of the two and a further mechanical homogenization. Prospective uses of the micro- fibril cellulose are in food, cosmetics, pharmacy, paper, composites, coatings and thickeners.
A method to make cellulose nano-fibrils is described in the international patent application WO 2010092239. The method provides preparation of a suspension of cellulose fibers upon which adsorbed is a cellulose derivative (e.g. carboxymethylcellulose) or a polysaccharide or its derivative. The fibers are then disintegrated to nano-fibrils. Chemical-, mechanical-, thermo-mechanical or chemical- thermo-mechanical cellulose pulp was used as starting material. It was derived from wood, non-woody materials or recycled cellulose fibers. The nano-fibrils sized below 1 micrometer find their uses in food, concrete, drilling fluids, coatings, cosmetics, drugs and paper.
Known from the international patent application WO 2013188657 is a method for the manufacture of nano-fibres from a cellulosic material by processing of an aqueous suspension with a cellulose depolymerizing agent such as ozone, cellulase or a combination of the two, and a parallel or subsequent mechanical disintegration which delivers nano-fibers from the cellulosic material. Low energy consumption is an asset of the method in comparison to processes employing only mechanical disintegration. Nano fibers from the method find their use in paper making.
The method of preparing cellulose nano-fibers from stalks of annual plants according to the invention consist in that the stalks cut into pieces 10-70 mm long are processed in following steps:
a) action of water vapor at 1 ,5-3 bar for 5-60 minutes
b) mechanical defibrillation in a disk mill for 3 - 10 minutes
c) digestion in a digesting liquor containing 5-15wt% of NaOH on dry mass of the stalks; liquor module from 3:1 to 8:1, time 60 to 120 minutes, temperature 110- 160°C
d) delignification with oxygen in a medium containing 2-4 wt% of NaOH and 0,2-0,5wt% of MgS04 on dry mass of the stalks. Conditions: oxygen pressure at start-0,2 - 0,5 MPa, pulp concentration 8-15wt.%, time 60 - 120 minutes, temperature 110 - 120°C e) bleaching at least twice with NaC102 at concentration of 1 - l,5wt.% and H2S04 concentration of 0,05 - 0,lwt.% at 60 - 70°C for 60-120 minutes, followed by alkaline extraction in aqueous NaOH with concentration of 0,5 - 1 wt% at 70 - 80°C, for 60- 120 minutes
f) enzymatic treatment of the prepared cellulose pulp by cellulase at activity of endo-l,4-beta-glucanase of 10-1000 J/g on dry mass ; pH of 4-7, temperature 40 - 60°C, time 30-480 minutes, agitation-50 - 500 followed by washing of the cellulose pulp with demi water, and vacuum filtration, and deactivation of the residual enzyme in the pulp at 90 - 125°C, for 10 - 30minutes
g) homogenizing of the aqueous cellulose suspension with concentration of 0,5 - 3 wt%, at 5000 - 20000 rpm for 1 - 10 minutes. During the agitation, the suspension is quenched with refrigeration brine at about -15°C. Next, the suspension is centrifuged at 4000 - 15000 rpm for 5-30 minutes to obtain a supernatant containing cellulose nano-fibres.
The digesting in step c) can, according to the invention, be run in a liquor with a content on dry mass of 5 - 15 wt.% of NaOH and 0,1 - 0,5 wt.% of anthraquinone or a liquor with 5 - 15 wt% of NaOH, 3 - 6 wt% of H202, 0.1 - 0,3 wt% of ethylenediaminetetraacetic acid (EDTA), 0,2 - 0,5 wt% of MgS04 and 2 - 5 wt% of water glass.
The cellulose pulp is, according to the invention, in addition to the bleaching in step e) preferably put to de-lignification by the action of 1 - 2 wt% of peracetic acid and 0,2 - 0,5 wt% of MgS04> calculated on dry mass. Conditions: temperature of 80 - 90°C for 60-120 minutes.
The cellulose pulp holding about 50 - 70 wt% of water is, after the bleaching in step e) and prior to the enzymatic treatment in step f), preferably put for 20 - 90 minutes to mechanical defibrillation followed by homogenizing in water suspension.
According to the invention, the sediment formed after homogenization and centrifugation in step g) can be recirculated to step f) and put to repeated enzymatic treatment with a solution of cellulase. The multi-stage de-lignification combined with bleaching of the lingo-cellulose raw material, according to the invention, offers the chance of removing the non-cellulosic substance without a far-going degradation of cellulose thus providing a high output of cellulose pulp with excellent purity. Moreover, the multi-stage mechanical treatment of the pulp combined with enzymatic hydrolysis of cellulose makes it possible to prepare cellulose nano-fibres having a high proportion of length to thickness. The method according to the invention enables the utilization of agriculture residues such as linen and hemp waste straw remaining after the separation of seeds for oil expression.
The nano-fibres made according to the invention can be used as reinforcement in the production of composite materials, as thickener or constituent of a variety of coatings
The invention is illustrated with following embodiments which should not be construed as limiting the invention in any manner.
Example 1
Hemp stalks cut to pieces 40 - 60 long were loaded into a 15 dm swing digester and put for 10 minutes to the action of 2 bar steam and then three times defibrillated in the disk mill of Sprout- Waldron type with a consecutive decrease of the distance between the defibrillating elements (0,5, 0,2 and 0,1 mm). The slackened plant raw material was for 60 minutes digested at 110°C in a liquor containing: 5 wt.% of NaOH, 5,5 wt.% of H202, 0,3 wt. of EDTA, 0,5 wt.% of MgS04 and 5% water glass calculated on dry mass at fluid module of 4: 1.
The fibrous pulp was subjected to delignification with oxygen in a medium containing 2,5 wt% of NaOH and 0,5 wt% of MgS04 on dry mass with oxygen pressure at start of 0,2 MPa, pulp concentration 8wt%, for 60 minutes, at 120°C. After the delignification, the cellulose pulp was bleached twice with sodium chlorite at NaC102 concentration of l,4wt% and H2S04 concentration of 0,1 wt% at 70°C, for 120 minutes. After every chemical treatment, the cellulose pulp was washed with demi water and centrifuged. The prepared cellulose pulp was characterized by lignin content of 0,45% and alfa-cellulose content of 85,5 wt%, and average polymerization degree of 1266. Total output of the process was 65,9%. An aqueous 2,5 wt% suspension of the cellulose in a conical flask was placed on the platform of incubator with a rotation shaker Labfors (Infers) and put to enzymatic treatment with cellulase (Ecostone L900, AB Enzymes) having endo-l,4-beta-glucanase activity of 500 J/g at pH of 4.8 at 50°C, for 180 minutes at agitation rate of 150 rpm. The processing finished and cellulose filtered on a Biichner funnel with filtration paper, the residual enzyme in the cellulose pulp was deactivated in an autoclave at 121 °C, for 20 minutes. The 1.5wt% aqueous suspension was for 10 minutes homogenized in the homogenizer Ultra Turrax T50 (IKA) at 10000 rpm. During the homogenization, the suspension was quenched with refrigerating brine at -15°C. Homogenization finished, the suspension was for 20 minutes centrifuged on centrifuge otina 420 at 4500 rpm to separate the cellulose- - nano-fibers- containing supernatant.
The prepared fibers were characterized by thickness in the range of 30 to 120 nm and average molecular degree of 130.
Example 2
Stalks of fire type flax cut to pieces 30 - 50 mm long were steam-processed and defibrillated as in Example 1 and, then, for 60 minutes at 160°C digested in a liquor containing 15wt.% of NaOH and 0,1 wt% of anthraquinone at fluid module of 7:1. Delignification, bleaching with sodium chlorite and alkaline extraction were carried out like in Example 1. The cellulose pulp was again put for 120 minutes at 80°C to delignification in a solution containing peracetic acid at concentration of 2 wt% and MgS04 at concentration of 0,5wt%. The obtained material was washed with demi water and centrifuged. The prepared cellulose pulp was characterized by lignin content of 9 wt% and alfa-cellulose content of 80,3 wt%, and average polymerization degree of 1306. Total output of the process was 69,5%. The cellulose pulp was put to mechanical treatment for 60 minutes at 40 rpm in a laboratory shredder. The l,5wt% aqueous suspension of cellulose was put to enzymatic treatment like in Example 1 save amount of enzyme which was 300 J/g. The residual enzyme in the cellulose pulp was deactivated like in Example 1. The l,5wt.% aqueous suspension of cellulose was homogenized by means of the homogenizer Ultra Turrax T50 in 3 cycles with the G45F tool and 3 cycles with W65SK tool at 10 000 rpm for 3 minutes in each of the cycles. During the homogenization, the suspension was quenched with refrigerating brine at about -15°C. The cellulose suspension was centrifuged as in Example 1 and the cellulose- -nano-fibers- containing supernatant was separated. The prepared fibers were characterized by thickness in the range of 40 to 160 nm and average molecular degree of 155.
Example 3
Stalks of oil flax cut to 30 - 60 mm pieces were steam-treated, defibrillated, digested, put to delignification in oxygen medium, bleached with sodium chlorite and alkaline- extracted like in Example 1. The prepared cellulose pulp was characterized by lignin content of 14 wt% and alfa-cellulose content of 72,4 wt%, and average polymerization degree of 1151. Total output of the process was 92,3%. The cellulose pulp was enzyme-treated like in Example 1. A 2,5 wt% suspension of the cellulose in water was next prepared and put to homogenization in the homogenizer Ultra Turrax T50 at 10 000 rpm for 3 minutes in each of the 5 homogenization cycles. During the homogenization, the suspension was quenched with refrigerating brine at about -15°C. The cellulose suspension was thereafter for 20 minutes centrifuged at 4 500 rpm. After the separation of the supernatant, the deposit was again put to enzyme treatment like in Example 1, employing cellulase with endo-l,4-beta-glucanase activity of 200 J/g. From the remaining sediment prepared was a 1,5 wt% cellulose suspension in demi water which was for 3 minutes mechanically processed in each of the 3 cycles by means of the homogenizer Ultra Turrax T50 at 10 OOOrpm. The suspension was in the consecutive step for 20 minutes centrifuged at 4 500 rpm. Supernatants from both steps of the processing were combined thus improving the output of the process. The prepared fibers were characterized by thickness in the range of 45 to 200 nm and average molecular degree of 190.

Claims

Claims
1. Method of manufacturing cellulose nano-fibres from stalks of annual plants characterized by that pieces of annual plants stalks 10-70 mm long are subjected to processing in following steps:
a) action of water steam at pressure of 1 ,5 - 3 bar during 5-60 minutes b) mechanical defibrillation for 3 to 10 minutes in a disk mill
c) digestion for 60 to 120 minutes at temperature of from 110 to 160°C in a pulping liquor with 5 -15 wt% content of NaOH calculated on dry mass of the stalks, at liquid module of from 3:1 to 8:1
d) oxygen delignification in aqueous medium containing 2 - 4 wt% of NaOH and 0,2 - 0,5 wt% of MgS04, on dry mass; process conditions: oxygen pressure at start 0,2 - 0,5 MPa, concentration of mass 8 -15wt% wag., time 60 - 120 minutes, temperature 110 - 120°C
e) bleaching, at least twice, with sodium chlorite at NaC102 concentration of 1 - l,5wt% and H2S04 concentration of 0,05 - 0,1 wt% at temperature of 60 - 70°C for 60-120 minutes, followed by alkaline extraction in aqueous NaOH with concentration of 0,5 - lwt% at temperature of 70 - 80°C for 60- 120 minutes
f) enzymatic treatment of the prepared cellulose pulp with cellulase at activity of endo-l,4-beta-glucanase of 10-1000 J/g on dry mass, at pH of 4 - 7, at temperature of 40 - 60°C, for 30-480 minutes, with agitation of 50 - 500 rpm followed by washing of the cellulose pulp with demi water, and vacuum filtration, and deactivation of the enzyme residual in the pulp at temperature of 90 - 125°C for 10 - 30minutes
g) homogenizing of the aqueous cellulose suspension with concentration of 0.5-3wt%, at agitation speed of 5000 - 20000 rpm for 1 - 10 minutes. During the agitation, the suspension is quenched with refrigeration brine at about -15°C. Next, the suspension is centrifuged at 4000 - 15000 rpm for 5 - 30 minutes to obtain a supernatant containing cellulose nano- fibres.
2. Method according to Claim 1 characterized in that the digesting liquor contains 0,1 wt% of anthraquinone.
3. Method according to Claim 1 characterized in that the digesting liquor contains 3 - 6 wt% of H202, 0,1 - 0,3 wt% of ethylenediaminetetraacetic acid (EDTA), 0,2 - 0,5 wt% of MgS04 and 2 - 5 wt% of water glass.
4. Method according to Claim 1 characterized in that the cellulose pulp after step e) is put to one more delignification with peracetic acid at concentration of 1 - 2 wt% and a 0,2 - 0,5 wt% concentration of MgS04, in proportion to dry mass, at temperature of 80 - 90°C, for 60- 120 minutes.
5. Method according to Claim 1 characterized in that that the cellulose pulp with moisture content of 50 - 70% after the bleaching in step e), is prior to the enzymatic treatment in step f) put to mechanical defibrillation for 20 - 90 minutes followed by homogenizing in aqueous suspension.
6. Method according to Claim 1 or 2 or 3 characterized in that that the sediment remaining after homogenization and centrifugation in step g) is recirculated to step e).
EP15730546.7A 2014-07-23 2015-05-05 Method of preparing cellulose nano-fibres from stalks of annual plants Active EP3172378B1 (en)

Priority Applications (1)

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PL408962A PL230426B1 (en) 2014-07-23 2014-07-23 Method for producing nanofibres from the stems of annual plants
PCT/PL2015/000075 WO2016013946A1 (en) 2014-07-23 2015-05-05 Method of preparing cellulose nano-fibres from stalks of annual plants

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US10287366B2 (en) 2017-02-15 2019-05-14 Cp Kelco Aps Methods of producing activated pectin-containing biomass compositions
US10196778B2 (en) 2017-03-20 2019-02-05 R.J. Reynolds Tobacco Company Tobacco-derived nanocellulose material
CN108193539A (en) * 2017-12-28 2018-06-22 云南云景林纸股份有限公司 A kind of preparation method for obtaining uniformly separation eucalyptus pulp fibers
CN108589365B (en) * 2018-05-22 2019-10-11 南京林业大学 The method that polishing prepares II crystal type nano fiber of lignocellulosic
CN113950550B (en) * 2019-01-22 2023-06-09 耶拿贸易有限公司 Preparation of cellulose fibers
CN110273312A (en) * 2019-07-23 2019-09-24 呼伦贝尔学院 A kind of extraction and preparation method of native grass based nano-fiber element
CN110744668B (en) * 2019-10-30 2021-09-28 凉山德农生物能源股份有限公司 Preparation method of jatropha curcas base nano paper pulp
CN111763992B (en) * 2020-06-23 2021-12-21 徐州璞素室内装饰材料有限公司 Ramie raw material kneading device for linen production for painting and calligraphy
CN112878085A (en) * 2021-02-09 2021-06-01 齐齐哈尔大学 Method for preparing nano cellulose by using hemp skin
CN113718541B (en) * 2021-07-13 2022-10-21 大连工业大学 Preparation method of intrinsic hydrophobic oleophylic nanocellulose

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US20080146701A1 (en) 2003-10-22 2008-06-19 Sain Mohini M Manufacturing process of cellulose nanofibers from renewable feed stocks
US8546558B2 (en) 2006-02-08 2013-10-01 Stfi-Packforsk Ab Method for the manufacture of microfibrillated cellulose
FI124724B (en) 2009-02-13 2014-12-31 Upm Kymmene Oyj A process for preparing modified cellulose
EP3617400B1 (en) * 2009-03-30 2022-09-21 FiberLean Technologies Limited Use of nanofibrillar cellulose suspensions
JP5330882B2 (en) 2009-03-30 2013-10-30 日本製紙株式会社 Method for producing cellulose gel dispersion
EP2861799B1 (en) 2012-06-13 2019-06-05 University of Maine System Board of Trustees Energy efficient process for preparing nanocellulose fibers

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EP3172378B1 (en) 2018-04-25
PL3172378T3 (en) 2018-08-31
WO2016013946A1 (en) 2016-01-28
PL408962A1 (en) 2016-02-01
PL230426B1 (en) 2018-10-31

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