WO2019116245A1 - Procédé d'oxydation de cellulose - Google Patents

Procédé d'oxydation de cellulose Download PDF

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Publication number
WO2019116245A1
WO2019116245A1 PCT/IB2018/059917 IB2018059917W WO2019116245A1 WO 2019116245 A1 WO2019116245 A1 WO 2019116245A1 IB 2018059917 W IB2018059917 W IB 2018059917W WO 2019116245 A1 WO2019116245 A1 WO 2019116245A1
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cellulose
periodate solution
dac
range
aqueous
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PCT/IB2018/059917
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English (en)
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Adrianna SVENSSON
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Stora Enso Oyj
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Priority to JP2020532590A priority Critical patent/JP2021507016A/ja
Priority to EP18847219.5A priority patent/EP3724233A1/fr
Publication of WO2019116245A1 publication Critical patent/WO2019116245A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/22—Oxygen compounds of iodine
    • 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

Definitions

  • the present disclosure relates to methods for oxidation of cellulose to dialdehyde cellulose (DAC) for use in the formation of DAC films, and particularly to
  • MFC films comprising microfibrillated cellulose (MFC), have proven to give excellent barrier properties. Flowever, the gas barrier properties are very dependent on the moisture and the relative humidity in the surrounding environment. Therefore, it is common that MFC films must for example be coated with a polymer film to prevent moisture or water vapor to swell and disrupt the MFC film.
  • MFC films must for example be coated with a polymer film to prevent moisture or water vapor to swell and disrupt the MFC film.
  • Another way to decrease the moisture sensitivity of cellulose is to chemically modify the cellulose with sodium periodate to obtain dialdehyde cellulose (DAC).
  • DAC dialdehyde cellulose
  • dialdehyde fibers By mechanically processing the dialdehyde fibers, it is possible to disintegrate them into fibrils. Periodate oxidation can be seen as the pretreatment to liberate microfibrils. Using fibrillated dialdehyde cellulose, barrier films with improved moisture resistance can be produced.
  • periodate oxidants are environmentally harmful and also expensive. In order to achieve a realistic industrial production, an efficient regeneration and recycling of periodate is essential. Flowever, oxidation of polysaccharides in general, and cellulose in particular, using periodate oxidants are complex processes, involving many different reactions and possible byproducts.
  • Periodate/iodate solutions obtained during the cellulose oxidation also typically include a complex mixture of species that affect the regeneration processes.
  • Other objects may be to obtain environmental, health and/or economical benefits of reduced emission of chemicals used in a method for oxidation of cellulose to dialdehyde cellulose.
  • a method for oxidation of cellulose to dialdehyde cellulose comprising: a) oxidizing cellulose with an aqueous periodate solution having a pH in the range of 3 to 5 to form oxidized cellulose comprising DAC; b) separating the aqueous periodate solution from the oxidized cellulose; c) regenerating the separated aqueous periodate solution by electrolytic oxidation; d) adjusting of the pH of the regenerated aqueous periodate solution to a value in the range of 3 to 5; e) reusing the pH adjusted regenerated aqueous periodate solution, optionally combined with a make-up amount of fresh aqueous periodate solution, as the aqueous periodate solution in step a).
  • the aqueous periodate solution separated in step b) will also comprise iodate.
  • the formed iodate must again be converted to periodate.
  • the method of the present disclosure allows for multiple cycles of regeneration and reuse of the same aqueous periodate solution without the addition of chemical oxidants in the regeneration step and without the need for time consuming and costly purification steps.
  • Electrolytic oxidation has previously been used for regeneration of periodate solutions used in the oxidation of starch.
  • oxidation of starch produces less byproducts than oxidation of cellulose.
  • Oxidation byproducts can react further with periodate in the solution leading to a decrease in periodate available for the main oxidation reaction and thereby inferior DAC products.
  • Oxidation byproducts in the used periodate solution may also interfere with the electrolytic oxidation process, leading to higher currents or reaction time required to reach a desired degree of regeneration.
  • the inventor has found that by adjusting the pH of the regenerated periodate solution to the range of 3-5 following the electrolytic oxidation, formation of byproducts during the main oxidation reaction can be reduced. This, in turn, has been found to allow for reusing the periodate solution in multiple cycles without the need for time consuming and costly purification steps between each use.
  • the method according the present disclosure has been shown to successfully allow for 6 oxidation and regeneration cycles, and it is envisaged that it would be possible to increase the number of cycles even further, e.g. to 10 or more, without significant deterioration of the process or the obtained material. It appears that if the pH of the filtrate is not adjusted after the electrolytic oxidation, iodine is formed due to unwanted periodate reduction.
  • the aqueous periodate solution in step a) has a pH in the range 3.5 to 4.5, preferably a pH of about 4.
  • the periodate solution preferably comprises an aqueous solution of sodium periodate.
  • Sodium periodate is the inorganic salt of periodic acid. It is composed of sodium, iodine and oxygen. Periodate can exists either as IO4 or IOQ 5 . When DAC is being produced, it is the metaperiodate form, IO4 that reacts with cellulose according to:
  • the cellulose in step a) is in the form of pulp having a cellulose concentration in the range of 1 -10 wt%, preferably in the range of 1 -5 wt%, more preferably in the range of 1 -3 wt%.
  • the aqueous periodate solution in step a) comprises periodate ions at a starting concentration in the range of 100-230 mM, preferably in the range of 120-160 mM, more preferably of about 140 mM.
  • the aqueous periodate solution in step a) has a molar ratio of periodate ion to cellulose from 0.30 - 1 .14. Fine tuning of pH and of the molar ratio of periodate to cellulose ensures a balance between optimized yield and minimized overoxidation.
  • the reaction temperature of the cellulose oxidation is preferably selected so as to obtain a high reaction rate while not causing an unacceptable degree of
  • the cellulose in step a) is contacted with the aqueous periodate solution at a temperature in the range of 30-70 °C, preferably in the range of 30-60 °C, more preferably of about 50 °C.
  • reaction time required for the cellulose oxidation will of course vary depending on the reaction conditions.
  • the cellulose in step a) is contacted with the aqueous periodate solution for a period in the range of 0.5-5 hours, preferably in the range of 1 -4 hours, more preferably in the range of 2-3 hours.
  • longer or shorter reaction time may be required depending, e.g., on the pH, periodate concentration, temperature and desired oxidation degree.
  • the oxidized cellulose obtained should preferably have an oxidation degree of at least 20 %, preferably at least 30 %. Accordingly, in some embodiments at least 20 %, preferably at least 30 %, of the cellulose in step a) is oxidized to DAC.
  • the method of the present disclosure is further advantageous since it allows for the repeated regeneration and recycling of periodate solutions without the use of added chemical oxidants.
  • the aqueous periodate solution is regenerated by electrolytic oxidation without addition of chemical oxidants. Less added chemicals results in less required work-up and purification of the periodate solution, less waste and better process economy.
  • the electrolytic oxidation is performed in an electrolytic cell comprising a cathode chamber and an anode chamber separated by a cation exchange membrane, and wherein the cathode chamber comprises a cathode, preferably made of stainless steel, and the anode chamber comprises an anode, preferably made of Pb02 on a Ti substrate.
  • the reaction rate of the regeneration step depends on a number of parameters, including the type, configuration and size of the electrolytic cell, the current density and the temperature. The skilled person understands that different combinations of parameters can be used to achieve substantially the same result. According to some exemplary embodiments, the electrolytic oxidation is performed at a current density in the range of 100-2000 mA per dm 2 , such as in the range of 300 to 650 mA per dm 2 .
  • the electrolytic oxidation is performed at a temperature in the range of 10-30 °C, preferably in the range of 20-30 °C. According to some exemplary embodiments, the electrolytic oxidation is performed for a period in the range of 5-30 hours.
  • the aqueous periodate solution to be used in step a) should preferably comprise periodate ions at a starting concentration in the range of 100-230 mM, preferably in the range of 120-160 mM, more preferably of about 140 mM. Accordingly, in to some embodiments the regenerated aqueous periodate solution comprises periodate ions at a concentration of at least 100 mM, preferably at least 120 mM, and more preferably at least 140 mM.
  • the pH of the aqueous periodate solution after the electrolytic oxidation is typically below 2, such as below 1.5.
  • the pH value is then adjusted to a value in the range of 3 to 5.
  • the pH of the regenerated aqueous periodate solution in step d) is adjusted to a value in the range of 3.5 to 4.5, preferably to a pH of about 4.0.
  • the inventors have found that a pH value of about 4 gives the least formation of byproducts and the best conditions for repeated recycling of the periodate solution.
  • the pH is adjusted by addition of NaOH.
  • the base such as NaOH
  • the base such as NaOH
  • the pH is adjusted by addition of solid NaOH or aqueous NaOH having a concentration of at least 0.1 M.
  • the regenerated aqueous periodate solution is reused directly after regeneration and adjustment of the pH, without further purification.
  • each oxidation and regeneration cycle will involve a certain loss of periodate solution.
  • the solution can be supplemented with a make-up amount of fresh aqueous periodate solution.
  • the fresh aqueous periodate solution may preferably have a
  • the make-up amount of fresh aqueous periodate solution constitutes 1 -30 %, preferably 1 -20 %, more preferably 1 -10 %, of the total volume of the aqueous periodate solution used in step a).
  • the volume and concentration of the aqueous periodate solution may also be adjusted by addition of water.
  • the same aqueous periodate solution can be effectively regenerated and reused at least five times without additional work-up and purification steps.
  • the same aqueous periodate solution is regenerated and reused at least three times, preferably at least four times, more preferably at least five times.
  • the inventor has further shown that the DAC films formed from DAC prepared using periodate solution regenerated according to the inventive method up to at least five times retained their barrier properties as compared to DAC films formed from DAC prepared using fresh (i.e. not previously used and regenerated) periodate solution.
  • the oxidized cellulose comprising DAC must first be fibrillated.
  • the method further comprises the step e) subjecting the separated oxidized cellulose comprising DAC, optionally together with microfibrillated cellulose (MFC), to fibrillation to obtain microfibrillated DAC or a microfibrillated mixture of DAC and MFC.
  • MFC microfibrillated cellulose
  • DAC dialdehyde cellulose
  • MFC microfibrillated cellulose
  • the suspension comprises between 20-95 wt% of microfibrillated DAC based on the total fiber weight of the mixture.
  • the amount of microfibrillated DAC may vary.
  • the suspension comprises between 5-80 % of MFC based on the total fiber weight of the mixture.
  • the dry content of the mixture applied to the substrate is between 1 -10 wt%. Depending on the substrate onto which the mixture is applied the dry content of the mixture may vary.
  • the at least one layer of the film is produced by applying said mixture to a substrate to form a fibrous web and drying said web to form at least one layer of said film.
  • the drying of said web may be done in any conventional way.
  • the dry content of the at least one layer of the film after drying is preferably above 95 wt%.
  • the substrate for the film formation is preferably a polymer or metal substrate. It is preferred that the mixture is cast coated onto said substrate.
  • the cast coated fibrous web can be dried in any conventional manner and thereafter optionally peeled off from the substrate. It may be possible to cast or coat more than one layer onto the substrate forming a multilayer film. It is possible to produce a film comprising more than one layer wherein at least one of the layers comprises the mixture according to the invention. It may also be possible that more than one layer of the film comprises the mixture according to the invention. It may also be possible that one or more layers of the film only comprises microfibrillated cellulose, i.e. it does not comprise microfibrillated dialdehyde cellulose.
  • the film may comprise two, three, four, five, six, seven, eight, nine, ten or more layers.
  • the substrate may also be a porous wire of a paper making machine, i.e. any kind of paper making machine known to a person skilled in the art used for making paper, paperboard, tissue or any similar products.
  • a paper making machine i.e. any kind of paper making machine known to a person skilled in the art used for making paper, paperboard, tissue or any similar products.
  • the method may further comprise the step of pressing the film after drying. It has been shown that the barrier properties of the film is increased if the film is subjected to increased pressure after drying.
  • the pressure applied in the pressing is preferably above 40kN/m 2 (over pressure), more preferably between 100-900 kN/m 2 .
  • the pressing may last for a period of less than 10 minutes, preferably between 1 second to 10 minutes. It is preferred that the pressing is done at elevated temperatures.
  • the temperature is preferably increased to between 50- 200°C, preferably between 100-150°C during pressing of the film.
  • the pressing may be done in any conventional equipment such as presses or calenders. By combining the use of pressing, preferably hot pressing of the formed film the barrier of the film is strongly increased.
  • the mixture may further comprise additives, preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof. Additive may be added to the first suspension, the second suspension and/or to the mixture.
  • the microfibrillated DAC has an oxidation degree of at least 20 %. In some embodiments, the microfibrillated DAC has an oxidation degree of between 25-75 %.
  • the mixture further comprises any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof.
  • microfibrillated cellulose is microfibrillated cellulose produced from
  • the microfibrillated cellulose is preferably produced from kraft pulp.
  • the microfibrillated cellulose preferably has a Schopper Riegler value (SR°) of more than 90.
  • the MFC may have a Schopper Riegler value (SR°) of more than 93.
  • the MFC may have a Schopper Riegler value (SR°) of more than 95.
  • the Schopper-Riegler value can be obtained through the standard method defined in EN ISO 5267-1. This high SR value is determined for a pulp, with or without additional chemicals, thus the fibers have not consolidated into a film or started e.g. hornification.
  • the dry solid content of this kind of web, before disintegrated and measuring SR is less than 50 % (w/w).
  • the Schopper Riegler value it is preferable to take a sample just after the wire section where the wet web consistency is relatively low.
  • paper making chemicals such as retention agents or dewatering agents, have an impact on the SR value.
  • the SR value specified herein is to be understood as an indication but not a limitation, to reflect the characteristics of the MFC material itself.
  • the microfibrillated dialdehyde cellulose should in this context mean a dialdehyde cellulose treated in such way that it is microfibrillated.
  • the production of the microfibrillated dialdehyde cellulose is done by treating dialdehyde cellulose for example by a homogenizer or in any other way such that fibrillation occurs to produce microfibrillated dialdehyde cellulose.
  • the microfibrillated dialdehyde cellulose preferably has an oxidation degree between 25-75 %, preferably between 30-65 %, even more preferably between 30-50 % or most preferred between 35-45 %.
  • the degree of oxidation was determined according to the following description: after the dialdehyde cellulose reaction, the amount of C2-C3 bonds in the cellulose that are converted to dialdehydes are measured. The degree of oxidation is the amount of C2-C3 bonds that are converted compared to all C2-C3 bonds. This is measured with a method by H. Zhao and N.D. Heindel, “Determination of Degree of Substitution of Formyl Groups in Polyaldehyde Dexran by the Hydroxylamine Hydrochloride Method”, Pharmaceutical Research, vol. 8, pp. 400-402, 1991 , where the available aldehyde groups reacts with hydroxylamine hydrochloride. This forms oxime groups and releases hydrochloric acid.
  • the hydrochloric acid is titrated with sodium hydroxide until pH 4 is reached, and the degree of oxidation is thereafter calculated from according to the formula below.
  • the received aldehyde content is divided by two to get the value of the degree of oxidation, since an oxidized anhydroglucose unit has two aldehyde groups.
  • VNaOH the amount of sodium hydroxide needed to reach pH 4 (I)
  • ITIsample dry weight of the analysed DAC sample (g)
  • Mw 160 g/mol, which is the molecular weight of the dialdehyde cellulose unit
  • the mixture may further comprise additives, preferably any one of a starch, carboxymethyl cellulose, a filler, retention chemicals, flocculation additives, deflocculating additives, dry strength additives, softeners, or mixtures thereof. It may be possible to add additives that will improve different properties of the mixture and/or the produced film. It may be possible to add the additive to the first suspension, the second suspension and/or to the mixture. It has been shown that the use of a softener, such as sorbitol, glycerol, polyethylene glycol, sorbic acid, propylene glycol, erythritol, maltitol or polyethylene oxides, will modify and improve some of the mechanical properties of the film, especially the stretch at break properties.
  • the amount of sorbitol used is preferably between 1 -20 % by dry weight of the film.
  • the film comprising microfibrillated cellulose and microfibrillated dialdehyde cellulose, has an oxygen transmission rate in the range of from 0.1 to 300 cc/m 2 /24h measured according to the standard ASTM D-3985, at a relative humidity of 50 % at 23 ° C and/or at a relative humidity of 90 % at 38 ° C.
  • the amount of microfibrillated cellulose in the produced film is preferably between 5-80 wt% by total dry weight of the film, preferably between 10-60 wt% by total dry weight of the film and even more preferred between 10-40 wt% by total dry weight of the film.
  • the amount of microfibrillated dialdehyde cellulose in the produced film is preferably between 20-95 wt% by total dry weight of the film, preferably between 40-90 wt% by total dry weight of the film and even more preferred between 60-90 wt% by total dry weight of the film.
  • the film may have a basis weight of less than 50 g/m 2 , or less than 35 g/m 2 , or less than 25 g/m 2 .
  • the basis weight is preferably at least 10 g/m 2 , preferably between 10-50 g/m 2 , even more preferred between 10-35 g/m 2 and most preferred between 10-25 g/m 2 .
  • Microfibrillated cellulose shall in the context of the patent application mean a nano scale cellulose fiber or fibril with at least one dimension less than 100 nm.
  • MFC comprises partly or totally fibrillated cellulose or lignocellulose fibers.
  • the liberated fibrils have a diameter less than 100 nm, whereas the actual fibril diameter or particle size distribution and/or aspect ratio (length/width) depends on the source and the manufacturing methods.
  • the smallest fibril is called elementary fibril and has a diameter of approximately 2-4 nm (see e.g.
  • Chinga-Carrasco G., Cellulose fibres, nanofibrils and microfibrils, : The morphological sequence of MFC components from a plant physiology and fibre technology point of view, Nanoscale research letters 201 1, 6:417), while it is common that the aggregated form of the elementary fibrils, also defined as microfibril ( Fengel , D., Ultrastructural behavior of cell wall polysaccharides, Tappi J., March 1970, Vol 53, No. 3.), is the main product that is obtained when making MFC e.g. by using an extended refining process or pressure-drop disintegration process. Depending on the source and the manufacturing process, the length of the fibrils can vary from around 1 to more than 10 micrometers.
  • a coarse MFC grade might contain a substantial fraction of fibrillated fibers, i.e. protruding fibrils from the tracheid (cellulose fiber), and with a certain amount of fibrils liberated from the tracheid (cellulose fiber).
  • MFC cellulose microfibrils, fibrillated cellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers, cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulose microfibril aggregates.
  • MFC can also be characterized by various physical or physical-chemical properties such as large surface area or its ability to form a gel-like material at low solids (1 -5 wt%) when dispersed in water.
  • the cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 200 m2/g, or more preferably 50-200 m2/g when determined for a freeze-dried material with the BET method.
  • MFC multi-pass refining
  • pre hydrolysis followed by refining or high shear disintegration or liberation of fibrils.
  • One or several pre-treatment step is usually required in order to make MFC manufacturing both energy efficient and sustainable.
  • the cellulose fibers of the pulp to be supplied may thus be pre-treated enzymatically or chemically, for example to hydrolyse or swell fiber or reduce the quantity of hemicellulose or lignin.
  • the cellulose fibers may be chemically modified before fibrillation, wherein the cellulose molecules contain functional groups other (or more) than found in the original cellulose.
  • Such groups include, among others, carboxymethyl (CMC), aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxydation, for example "TEMPO”), or quaternary ammonium (cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC or nanofibrillar size or NFC.
  • CMC carboxymethyl
  • aldehyde aldehyde and/or carboxyl groups
  • cellulose obtained by N-oxyl mediated oxydation for example "TEMPO”
  • quaternary ammonium cationic cellulose
  • the nanofibrillar cellulose may contain some hemicelluloses; the amount is dependent on the plant source.
  • Mechanical disintegration of the pre-treated fibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer.
  • the product might also contain fines, or nanocrystalline cellulose or e.g. other chemicals present in wood fibers or in papermaking process.
  • the product might also contain various amounts of micron size fiber particles that have not been efficiently fibrillated.
  • MFC is produced from wood cellulose fibers, both from hardwood or softwood fibers. It can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. It is preferably made from pulp including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. It can also be made from broke or recycled paper.
  • MFC includes, but is not limited to, the new proposed TAPPI standard W13021 on cellulose nanofibril (CNF) defining a cellulose nanofiber material containing multiple elementary fibrils with both crystalline and amorphous regions, having a high aspect ratio with width of 5- 30nm and aspect ratio usually greater than 50.
  • CNF cellulose nanofibril
  • Figure 1 is a photograph of sample bottles containing periodate solution filtrates obtained in Example 2, where pH was not adjusted after the regeneration. The samples were collected after one oxidation and one regeneration (left), and three oxidations and two regenerations (middle and right). Examples
  • Example 1 Cellulose oxidation and periodate regeneration with pH adjustment
  • the pulp was oxidized using sodium periodate in aqueous solution.
  • the pulp concentration, in tap water, was 2 % and the pH value was adjusted to pH 4.0 with 0.5 M H2SO4 at the beginning.
  • a pulp concentration of 2% corresponds to 123 mM
  • Periodate concentration is 140 mM which in its turn corresponds to a molar ratio of periodate ion to cellulose of 1 .14.
  • Periodate concentration was monitored using a UV-Vis spectrophotometer - to follow the regeneration steps.
  • UV-Vis spectrophotometer (Evolution 201 , UV-visible, Thermo Scientific, US) and a quartz cuvette were used for the periodate analysis.
  • the sample was diluted 2500x in deionized water, in two steps and the absorbance was measured in the range between 400 and 200 nm. The measurement was repeated 2 times and the obtained absorbances for the peaks at ca 219 nm (ABS.1 and Abs.2) were used for calculating the periodate concentration:
  • the calibration curve was made for the solutions containing periodate and iodate in different rations, but the sum of their concentrations was always 140 mM. Solutions containing from 70 mM to 140 mM periodate were used.
  • Example 2 Cellulose oxidation and periodate
  • Example 1 was repeated as set out in Table 2, except no pH adjustment of the regenerated filtrate was performed. Table 2. Selected parameters of the
  • DAC films were made from each of the DAC products of Example 1. The following method was used 6 times, for each DAC product. 3 % DAC was mixed with 3 % MFC in the ratio 3:2. The obtained suspension was fluidized 3 times and vacuum- filtrated to get the round films at a grammage of about 40 gsm. The films were hot pressed at 100 °C for 10 seconds under a pressure of 10 kPa. The OTR value for films comprising mixtures of MFC and DA-MFC were first measured at a humidity of 50 % at 23 °C (23/50) and then at a humidity of 90 % at 38 °C (38/90) at two different cycles.
  • the OTR values were measured according to standard ASTM D-3985, except the fact that not all values have reached the steady state.
  • the films were stored at room temperature (humidity of 50 % at 23 °C) for 24 hours between two measurements in (38/90) and the OTR value was once again measured at a high humidity of 90 % at 38 °C. As shown in Table 3, the films obtained after each oxidation retained their barrier properties.

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Abstract

L'invention concerne un procédé d'oxydation de cellulose en cellulose dialdéhyde (DAC), ledit procédé comprenant : a) l'oxydation de cellulose avec une solution aqueuse de periodate ayant un pH dans la plage de 3 à 5 pour former de la cellulose oxydée comprenant de la DAC ; b) la séparation de la solution aqueuse de periodate à partir de la cellulose oxydée ; c) la régénération de la solution aqueuse de periodate séparée par oxydation électrolytique ; d) l'ajustement du pH de la solution aqueuse de periodate régénérée à une valeur dans la plage de 3 à 5 ; et e) la réutilisation de la solution aqueuse de periodate régénérée à pH ajusté, éventuellement combinée à une quantité d'appoint de solution aqueuse de periodate fraîche, en tant que solution aqueuse de periodate à l'étape a).
PCT/IB2018/059917 2017-12-13 2018-12-12 Procédé d'oxydation de cellulose WO2019116245A1 (fr)

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