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    • 专利摘要:
    Process for preparing a cellulose pulp suitable for dissolving cellulose and hemicellulose from a high viscosity metal ion-containing, non-dried paper cellulose pulp and a process for preparing a fiber spinning solution of cellulose and hemicellulose. According to the invention, the cellulose pulp is contacted with endoglucanase for modification of the cellulose and the pH value of the cellulose pulp thus obtained is adjusted to a value of about 2 to 3 to remove metal ions. The cellulose pulp is washed with water to raise the pH to above 4, and then the solids content of the washed cellulose pulp is raised to at least 30%. The aqueous modified cellulose pulp thus obtained can be dissolved in liquid phase by the use of a solvent, such as an ionic liquid, to form a spinning solution.
    公开号:FI20185448A1
    申请号:FI20185448
    申请日:2018-05-15
    公开日:2019-11-16
    发明作者:Anna Suurnäkki；Kari Kovasin
    申请人:Metsae Fibre Oy；
    IPC主号:
    专利说明:

    Method for pretreating paper pulp
    Field of the Invention
    The present invention relates to the use of paper pulp for the preparation of solutions containing cellulose. In particular, the invention relates to a process for pretreating paper pulp before leaching with ionic liquids or similar organic solvents and subsequent processing into cellulose-based structures such as fibers, filaments or film.
    Background
    Wood pulp (pulp) is suitable for direct leaching with ionic liquids, i.e. ionic solvents (IL), and for the production of staple fiber.
    Swatlowski et al. (US 6,824,599 (B2), EP 2,325,246 (B1) and EP 1,458,805 (B1)) were the first to describe a process in which pure, dry cellulose is dissolved in anhydrous ionic liquid and the resulting solution is regenerated by a syringe such as water. . The process described uses an ionic liquid having a nitrogen-containing base component of up to 5% by weight. The dissolution process can be enhanced by microwave heating. Swatlowaki et al. also states that cellulose used as a raw material may be wood pulp.
    The use of moist sulphate pulp (also referred to herein as "paper pulp") in solubilizing cellulose and hemicellulose in an ionic liquid is first described in TITK Patent Publication No. EP 1 763 596. Cellulose, or paper pulp, is fed into the leaching process pressed to about 50% subsequently soluble in ionic liquid. The patent also first describes the air gap spinning process of cellulose fibers from ionic solvents.
    The dissolution of paper pulp in an ionic solution is also described later (2007) in CA 2 627 879.
    20185448 prh 15 -05- 2018
    Undried paper is advantageous because its drying is an expensive operation and on the other hand drying causes the fibers to cornify. Horned fiber is less reactive for various chemical further treatments and cellulose leaching.
    However, paper pulp has some properties that it is difficult to use as such for direct IL leaching. Thus, the average degree of polymerization (DP) of cellulose fiber, or "viscosity" in the language of the pulp world, is too high. The viscosity of Havu paper pulp is in the order of 850-900 ml / g, while the viscosity required for IL10 leaching is typically 400-600 ml / g.
    Furthermore, the molecular weight distribution of paper pulp is not suitable, but must be modified so that the viscoelastic and other theological properties of the IL solution spinning solution and coagulating filament are suitable for the spinning process. In other words, paper pulp as such does not provide stable spinning.
    Paper pulp also typically contains excessively high (mainly divalent) metal ions (e.g., alkaline earth metals such as Ca and Mg and transition metals such as Fe, Mn, Co and Ni). The concentration of these metal ions must be reduced prior to IL-lysis.
    The regulation of the viscosity and metal content of paper pulp by acid treatment is known in the art and is disclosed in U.S. Application Publication No. 2002 / 0064654A1.
    The viscosity control of paper pulp by acid treatment is based on the ability of the strong acid to break the cellulose fibers hydrolytically at elevated temperature. At a sufficiently low pH, i.e., <3, the metal cations bound to the pulp are also released. The pH required to adjust the viscosity by acid treatment is typically pH 1-1.5 or even lower. This means that after treatment, the de-acidification by washing the cellulose suspension requires a very efficient washing process and plenty of water. Raising the pH can also be done with an alkaline chemical, e.g. However, this increases the Na content of the pulp and represents an additional cost. On the other hand, the acid treatment has a limited ability to adjust the molecular weight distribution as desired.
    20185448 prh 15 -05- 2018
    It is also known that cellulose hydrolyzing enzymes can be used to control the viscosity of both paper pulp and soluble pulp. Paper pulp viscosity has been found to decrease differently with different enzyme activities as endoglucanase treatments reduce viscosity significantly more than cellobiohydrolase treatments (Pere et al., 1995). The use of enzymes in both soluble and paper pulp bleaching sequences or as a final step in bleaching to control the viscosity prior to the NMMO-based Lyocell process is known (US 2009/0165969 AI). Thus, Weyerhaeuser in WO1999016960 A1 describes a method of treating chemical pulp first with an alkali swelling and thereafter with an enzyme preparation containing endoglucanase so that it becomes particularly suitable for the preparation of Lyocell fibers. Reference should also be made to WO 2009088635A3, of the same family as US 2009/0165969, in which Weyerhaeuser discloses a process for preparing a Lyocell process pulp by a bleaching process comprising a single enzyme treatment step. Lyocell pulp produced by the bleaching process is said to have acceptable, low DP and acceptable viscosity, although no numerical values are given.
    Paper pulp and soluble pulp may be pretreated by enzymatic, mechanical and combining treatments. The purpose of these treatments is to open the surface and wall of the fiber in a manner that facilitates the dissolution of the cellulose in either an alkaline aqueous solution or an NMMO solvent. Reference is made to EP-A-2 116 557 (A1); Grönqvist et al. 2015, and for the NMMO solvent, U.S. Patent Application Publication No. 2009/0165969 A1. It is also known (Michud et al. 2015) that in the dissolution of soluble cellulose, the molecular weight distribution of the pulp can be adjusted to theology advantageously by spinning the soluble cellulose of different molecular weight in a suitable ratio.
    Among other reasons, for the reasons stated above, pulp is not generally used as the main raw material for cellulose-based staple fibers. Paper pulp is significantly cheaper than soluble pulp, so replacing the soluble pulp with a cheaper raw material would be advantageous.
    20185448 prh 15 -05- 2018
    Summary of the Invention
    It is an object of the present invention to eliminate at least some of the problems associated with the prior art and to provide a novel solution for converting paper pulp to dissolve and process cellulose and possibly hemicellulose into cellulose and hemicellulose based structures such as fiber, filament and film.
    It has now surprisingly been found that by combining the paper pulp endoglucanase treatment with an acid scrubber, IL leaching produces, inter alia, a pulp soluble in ionic liquids 10 and further, a solution whose Theological properties are suitable for staple fiber spinning.
    The invention provides a process for producing a pulp suitable for dissolving cellulose from, inter alia, metal ion-containing chemical pulp suitable for papermaking.
    The invention also provides a process for preparing a spinning solution of fibers from cellulose and hemicellulose of cellulose pulp. According to the method, the chemical pulp is used as a raw material for papermaking, containing at least some metal ions from the pulp raw material, and the pulp is dissolved in a liquid in which the cellulose and hemicellulose are soluble and from which the cellulose and hemicellulose can be precipitated , such as fibers, fibers and film, and other cellulose-based particles.
    In the invention, the undried pulp is first contacted in an aqueous suspension with an enzyme preparation containing endoglucanase as its main activity to modify the pulp. The pH of the pulp thus obtained is slightly acidified to separate the metal ions from the pulp. Subsequently, the pH of the modified pulp is raised above 4, in particular above 5, and the consistency of the pulp is increased to a value suitable for leaching, typically at least 30% by weight or more, but most preferably less than 50% by weight.
    More particularly, the invention is characterized by what is set forth in the characterizing parts of the independent claims.
    The invention provides significant advantages. Treatment with endoglucanase at an elevated fiber consistency (typically greater than 15% by weight dry matter) is capable of controlling the viscosity of undried paper pulp in a controlled manner, while simultaneously producing an IL leaching and molecular weight pulp for staple fiber spinning. The removal of the harmful metal cations can then be carried out at the higher pH (typically 2.5-3) of the acid treatment described above, which is sufficient to remove the metal ions. Removing such acidity by washing from the treated fiber suspension is clearly easier compared to having a low pH (such as pH 1-1.5 or lower) required for viscosity control.
    According to the present solution, the metal content of the paper pulp can be lowered below 100 ppm, in particular below 50 ppm.
    The state-of-the-art process can be integrated into a paper pulp producing pulp process with advantageous process solutions. Also, the pretreatment does not turn into difficult-to-handle streams of filtrate or wastewater, since the dilute aqueous solutions that can be used can be used in the manufacture of paper pulp as process wash waters, e.g.
    The enzyme-acid washing treatment of the invention, followed by dewatering to a fiber consistency of 30-50%, provides a feed mass suitable for the IL leaching process.
    The stretch rheological properties of the fiber filament required by the air gap spinning process are generated by operating according to the present method, thereby providing a controlled adjustment of the molecular weight distribution of the cellulose.
    Surprisingly, it has been found that the solution disclosed can easily dissolve cellulose having a molecular weight distribution which is at the same level as, or possibly even higher than, soluble cellulose. It has also been found that the viscosity of the spun solution made from the pulp treated with the ionic solvent by the present solution is lower than that of
    20185448 prh 15 -05-2018 from a solution of an acid-treated pulp having the same viscosity as the present pulp. This allows the polymer content of the spinning solution to be increased, thus making the process more efficient.
    By the process of the invention, the cellulose it contains, the hemicellulose it contains, and even the lignin can be dissolved. Thus, the invention provides a process for producing cellulose and optionally hemicellulose from pulp containing nonionic, high viscosity metal pulp containing metal ions.
    The invention will now be further explored by way of detailed description with reference to the accompanying drawing.
    The figure shows a simplified process diagram of a pretreatment process according to one embodiment.
    applications
    In the present solution, the term "pulp" means a chemical pulp, i.e. a chemical cooking process such as sulphate, polysulphide or organosolvent pulp, a pulp made from a cellulosic raw material, typically an industrial pulp containing cellulose and at least some hemicellulose. In this context, the term "hemicellulose" is used interchangeably with all hemicellulose in the pulp. The amount of hemicellulose is generally less than 20% by weight, preferably less than about 7.5% by weight, for example up to 2% by weight on a dry weight basis.
    In addition to the above-mentioned components, the pulp may also contain lignin, typically trace amounts of lignin (less than 4%, particularly less than 2%, preferably less than 0.5% by dry weight of the pulp). An example of lignin-containing pulps is the so-called brown pulp. The pulp may be, for example, oxygen-delignified pulp.
    20185448 prh 15 -05- 2018
    Particularly preferably, the present solution employs bleached chemical pulp, in particular fully bleached chemical pulp.
    In the present context, the term "pulp" has the same meaning as "pulp", unless otherwise stated.
    In particular, woody plants, i.e. wood such as conifers or hardwoods or mixtures thereof, are used as the raw material. In the first embodiment, the wood raw material is softwood, such as pine or spruce or larch.
    In another embodiment, the wood raw material is hardwood, such as birch, aspen, poplar, alder, maple, eucalyptus or mixed Tropical Hardwood.
    One or more annual plants can also be used for pulp production.
    In the present solution, "undried pulp" means a pulp that has not been dried after more than 50% by weight of the dry matter in the dry state. The term 'non-dried pulp' corresponds to the English term 'never-dried pulp'.
    "Paper pulp" or "paper pulp" means pulp which is suitable and can be used, inter alia, to make paper on a paper machine.
    The pulp used in the present context has a viscosity (intrinsic viscosity, as measured, e.g., in accordance with T 230 om-08) of typically about 700 to 900 g / l.
    In the present context, the pulp is contacted with an enzyme preparation capable of reducing the viscosity of the pulp by at least 5%, in particular from 30 to 15%, preferably at least 30%. In particular, the viscosity of the pulp is reduced by up to 75% by enzyme treatment, preferably up to about 70%. Particularly preferably, the viscosity is reduced by 30-60%.
    20185448 prh 15 -05-2018 "Enzyme preparation" means a composition containing at least one enzyme. The enzyme preparation may be a culture solution or a cell extract containing one or more enzymes. It may also be an isolated enzyme and a mixture of two or more enzymes. In addition to enzyme activity, the enzyme preparation typically contains excipients. Such adjuvants include, for example, buffers and stabilizers.
    Particularly preferably, the enzyme preparation contains endoglucanase as the main activity.
    "Endoglucanase activity" refers mainly to the hydrolyzing enzyme activity of cellulose, which cleaves cellulose bonds in the middle of the cellulose chain.
    The treatment with the above enzyme preparation is also referred to herein as "enzyme treatment".
    "Tonic liquid" and "ionic solvent" and "ionic solvent" are used interchangeably with each other. These substances are typical salts and liquid below 100 ° C and most, but not all, are liquid at room temperature.
    As stated above, the present technology is suitable for treating paper pulp in a form suitable for pulping. Typically, paper pulp contains metal ions derived from cellulosic feedstock, as noted above. In addition, paper pulp is not particularly suitable for leaching in terms of viscosity or molecular weight distribution to provide spinning solutions for making fibers or films. In particular, the continuous drawing of fibers requires that the spinning solution be substantially free of metal ions and that the cellulose dissolved in the solution has an appropriate average degree of polymerization and molecular weight distribution.
    In one embodiment, the pulp is contacted with the enzyme preparation in an aqueous suspension to modify the pulp. In particular, the enzyme preparation preferably contains endoglucanase as the main activity. The pH of the modified pulp obtained by enzyme treatment is adjusted to a value of not more than 3, preferably less than 3, of the metal ions.
    20185448 prh 15 -05-2018, after which the pH of the pulp is raised above 4, in particular above 5, by washing with water. Finally, the consistency of the washed mass is increased to at least 30% by weight.
    In one embodiment, the pulp is contacted with the enzyme preparation at a consistency of at least 5 to 10%. It is preferable to operate at a consistency of 15-30% since sufficiently high solids content enhances enzyme treatment.
    In particular, the enzyme treatment is carried out at a pH higher than 5. The treatment duration is 0.1 to 10 h and the temperature is 10-75 ° C, especially about 20-50 ° C.
    The endoglucanase activity of the enzyme preparation may be based on a monocomponent enzyme.
    The dosage of the enzyme preparation is usually about 0.001 to 100 mg protein / g treated weight (dry weight). In particular, the enzyme preparation is administered by administering 0.01-10 mg protein / g of pulp (dry weight) of endoglucanase activity.
    By enzyme treatment, the average degree of polymerization of the pulp, DP, can be calculated. It can also be used to modify the molecular weight distribution of pulp so that it is more suitable for leaching.
    The consistency (i.e. the solids content of the mixture) of the modified pulp from the enzyme treatment is adjusted to 1-20% by weight, especially about 5-15% by weight.
    Most preferably, the pH of the modified pulp obtained from the enzymatic treatment is adjusted to 2-3, for example by adding an acid such as mineral acid to the pulp stock, particularly in the form of an aqueous solution. Sulfuric acid or its aqueous solution is particularly preferably used. Nitric acid may also be used. In principle, other mineral acids can also be used, as long as potential corrosion problems are taken into account in the process equipment. Other suitable acids include organic acids such as aliphatic or aromatic carboxylic acids such as formic acid.
    20185448 prh 15 -05- 2018
    In one embodiment, the metal content of the modified pulp from the enzyme treatment, in particular the alkaline earth metals and transition metals, is adjusted to less than 1% by weight, in particular less than 0.1% by weight, preferably less than 0.01% by weight, in particular less than 0.001%, typically less than 0.0001% by weight, e.g.
    less than 0.00005% by weight on a dry basis.
    In one embodiment, the viscosity of the pulp is reduced by about 30-60% by enzyme treatment, especially endoglucanase treatment. The acid treatment following the enzyme treatment can typically further reduce the viscosity by up to 10 percentage units.
    The pulp viscosity is typically 400-600 ml / g after the above treatment.
    After the acid treatment, the pulp is preferably washed with water or an aqueous solution. The washing may be carried out in a conventional process apparatus, such as a washing filter.
    During or after washing, the consistency of the pulp is increased to a level suitable for dissolution. According to one embodiment, the consistency of the pulp, i.e. the dry matter content, is increased to at least 30% by weight. Preferably, it is kept at 50% by weight, e.g., at 30-45% by weight.
    In the context of the invention, it has been found to be advantageous to maintain consistency at the above dry solids content to prevent corneal mass.
    In one embodiment, the consistency is increased to at least 35 wt%, preferably about 35 to 40 wt% water removal.
    The dewatering is implemented in one embodiment by mechanical dewatering.
    According to a particularly preferred embodiment, the pulp temperature is maintained below 50 ° C during desiccation, preferably from about 10 ° C to 45 ° C.
    20185448 prh 15 -05- 2018
    The resulting pulp is suitable for preparing a solution suitable for spinning fiber fibers. In the dissolution process, pulp can be dissolved directly in an anhydrous or aqueous organic solvent
    In a particularly preferred embodiment, the modified pulp is dissolved in an ionic liquid.
    Examples of ionic liquids used in this context include e.g. imidazole-based ionic liquids such as:
    1-ethyl-3-methylimidazolium chloride ([Emim] [Cl]),
    -ethyl 3-methylimidazolium acetate ([Emim] [Ac]),
    -ethyl 3-methylimidazolium dimethyl phosphate ([Emim] [Me2PO4]
    -ethyl 3-methylimidazolium diethyl phosphate, ([Emim] [DEtPCU]),
    -ethyl 3-methylimidazolium methyl phosphonate [Emim] [(MeO) (H) PC> 2],
    1-butyl-3-methylimidazolium chloride ([Bmim] [Cl]), 1-butyl 3-methylimidazolium acetate ([Bmim] [Ac]),
    butyl-3-methylimidazolium dicyanamide ([Bmim] [N / CN]],
    butyl-3-methylimidazolium bis [(trifluoromethyl) sulfonyl] imide ([Bmim] [TFSI]) and 1-allyl-3-methylimidazolium chloride ([Amim] [Cl]).
    Particularly preferred examples of ionic liquids are conjugated acids consisting of an organic base, especially a so-called super base such as 1,1,3,3-tetramethylguanidine (TMG), 1,1,2,3,3-pentamethylguanidine (PMG). , 2,3,4,6,7,8-hexahydro-1H-pyrimido [1,2-a] pyrimidine (TBD), 7-Methyl-1,5,7-triazabicyclo [4.4.0] dec-5-enium ( mTBD), 1,5-diazabicyclo [4.3.0] non-5-enium (DBN) or 1,8-diazabicyclo [5.4.0] undec7-ene (DBU) with inorganic or organic conjugated acids such as acetic acid (or other carboxylic acids), hydrochloric acid, methyl dihydrogen phosphonate, dimethyl hydrogen phosphate or phosphinic acid.
    Examples include:
    1,1,3,3-tetramethylguanidium acetate ([TMGH] [OAc]),
    20185448 prh 15 -05- 2018
    1.1.3.3-tetramethylguanidium propionate ([TMGH] [EtCO2]),
    1.1.2.3.3-Pentamethyl guanidine acetate ([PMG] [OAc]),
    1.1.2.3.3-Pentamethyl guanidine propionate ([PMG] [EtCO2), 1,5-diazabicyclo [4.3.0] non-5-enium acetate ([DBNH] [OAc]), 1,5-diazabicyclo [4.3.0] non-5-enium propionate ([DBNH] [EtCO2]),
    1.8-diazabicyclo [5.4.0] undec-7-ene acetate ([DBU] [OAc]),
    2.3.4.6.7.8-Hexahydro-1H-pyrimido [1,2-a] pyrimidine acetate ([TBDH] [OAc]), 7-Methyl-1,5,7-triazabicyclo [4.4.0] dec-5- enium acetate ([mTBD] [OAc])
    2.3.4.6.7.8-Hexahydro-1H-pyrimido [1,2-a] pyrimidine-propionate ([TBDH] [EtCO2] and trioctylmethylphosphonium acetate ([Ρχχκι] [OAc]) and mixtures thereof.
    It should be noted that the above lists are given by way of example only and are not exhaustive.
    However, the pulp provided by the present solution is also suitable for other organic cellulosic solvents, such as NMM0 and combinations of DMAc and / or LiCl.
    According to one embodiment, the present technology provides a process for preparing a fiber spinning solution from pulp using paper pulp as the raw material, which contains at least some metal ions derived from the pulp raw material.
    In the process, the pulp modified as above is dissolved in a liquid to which the pulp is at least partially soluble, preferably completely soluble. By the treatment described, 25 pulps are preferably modified so that at least 90% by weight, preferably at least 95% by weight, in particular at least 99.5% by weight of pulp is soluble in the solvent. Hereby, both the main pulp component, cellulose, and its hemicellulose, and possibly also lignin, are soluble in the liquid.
    In the present technology, the pulp is considered to be completely dissolved when the mother liquor containing at least 10% by weight of pulp in the solvent is clear by light microscopy. Possible insolubles, for example consisting of inorganic materials
    20185448 prh 15 -05-2018 impurities or non-cellulosic components of the raw material may be removed by mechanical means such as filtration, sieving or centrifugation.
    In one embodiment, the spinning solution is prepared by dissolving the modified cellulose directly in a solvent, typically an ionic liquid, to form a spinning solution.
    Dissolution can be accomplished, for example, by mixing the above-described water-cellulose composition with a pulp solvent to form a mixture and raising - preferably with continuous stirring to the temperature of the mixture to remove water and dissolve the pulp.
    Typically, the pulp is dissolved so that the polymer content in the solution (dry matter) becomes about 1-25% by weight, for example about 5-20% by weight.
    Cellulose and hemicellulose dissolved therein may be precipitated from the cell solution, for example by lowering the temperature or by using a precipitant or by a combination of these operations.
    As a precipitant for cellulose and hemicellulose, a polar liquid such as water or an aliphatic or aromatic alcohol can be used.
    Figure 1 shows an advantageous way of carrying out a pretreatment integrated with papermaking:
    The bleached, undried pulp is pumped from the bleached pulp storage tower 1 by a pulp pump 2 to an accompanying press device 3,
    Enzyme is added to the thickened paper pulp and the consistency is set at 10-30%. The pulp is then transferred to a delay tank 4 where it is held until a predetermined viscosity level and a molecular weight distribution of cellulose have been achieved.
    The pulp is then transferred to a lag tank 5 where the pulp is acid treated at pH 2.5-3 and. at a consistency of 1-20%.
    After acid treatment, the pulp is diluted with water and washed with scrubber 6 with water until the pH of the pulp suspension is> pH 4.
    20185448 prh 15 -05- 2018
    The pulp is then thickened to a dry solids content of 30-50% by means of press 7. The pulp thus obtained is ready to be introduced into the pulp leaching process.
    The following examples illustrate applications for the pretreatment of paper pulp prior to the leaching-spinning process with ionic solutions:
    Example 1
    The effect of prior art acid hydrolysis and combined enzyme treatment and acid metal removal on chemical pulp properties was compared. Non-dried, bleached softwood sulphate pulp was used as the pulp.
    The metal contents and molecular weight distributions of the pulps thus obtained were compared at the same viscosity level of 400 ml / g.
    The dry matter content of the pulp used as the raw material was 40% by weight.
    In Comparative Example, the pulp sample (45 g q.s.) was treated with 15 g / L sulfuric acid at 10% consistency at 90 ° C for 60 min. The acid-treated pulp was then washed with water.
    In the second experiment, a 45 g (k.a.) pulp sample was first treated with a dose of 0.7 mg protein / g endoglucanase at 20% consistency at pH 6 and 50 ° C. The mass was diluted with 5% hot water and boiled for 10 minutes, after which the mass was filtered and washed with water. The washed mass was maintained at a pH of 2.5-3 for 60 minutes, followed by a water wash until the pH reached 5-6. The masses were determined by their metal content, viscosity (ISO 5351: 2004) and molecular weight distribution by size exclusion chromatography (GC).
    The results are shown in Tables 1-2
    Table 1. Metal concentrations of pulps
    Mass Ca mg / kg Co mg / kg Cu mg / kg Fe mg / kg Mg mg / kg Mn mg / kg Si mg / kg The starting material 51.6 <0.5 0.17 19.3 173 0.7 156 Comparison 73.2 <0.5 <0.5 17.6 58.8 0.6 91.3 Acid and enzyme treated pulp 7.1 <0.5 <0.5 6.6 23.7 <0.3 98.2
    Table 2. Molecular mass distributions of pulps
    Mass Viscosity in ml / g Mn Daltons Mw Daltons Mz Daltons Polydispersity pV * sec The starting material 850 85,601 1081 340 4,005,609 12.6 Comparison 450 41,900 408,050 1,537,303 9.7 Acid and enzyme treated pulp 450 44,950 422,250 1,610,251 9.4
    Example 2
    The solubility and spinability of the treated pulps prepared in Example 1 were evaluated using 1-butyl-3-methylimidazolium acetate (BMIMAc) as a solvent. The pulp was dissolved to a 13% cellulose content and 1.7 dtex fibers were spun from the spinning solution.
    The results are shown in Table 3.
    20185448 prh 15 -05- 2018
    Table 3. Properties and Spinability of Spinning Solution
    Mass Solids content,% Zero Shear Viscosity, Pas (80 ° C) Soluble spinnability Comparison 13 7633 Yes unstable E-A pulp 13 4903 Yes stable
    As the results show, the combination of enzyme treatment with endoglucanase and treatment under mildly acidic conditions yields bleached sulphate pulp, such as sulphate pulp suitable for papermaking, which is suitable for the production of fiber spinning solution by an IL leaching process.
    Reference List of Publications
    patent Literature
    EP 2 116 557 AI.
    EP 2,452,015
    US 2009/0165969 AI
    Other publications
    Michud, A., Hummel, M., Sixta, H. 2015. Polymer (2015) 75: 1-9.
    Pere J, Siika-Aho M, Buchert J, Viikari L., Tappi J 1995; 78: 71-8.
    Grönqvist, S. et al., Cellulose 22 (6) 2015: 3981-3990.
    权利要求:
    Claims (14)
    [1]
    1. A process for producing cellulose, optionally hemicellulose leachable pulp, containing metal ions, undried and having a high viscosity
    5 pulp, known for its combination that
    - contacting the pulp in an aqueous suspension with an enzyme preparation to reduce the viscosity of the pulp,
    adjusting the pH of the pulp thus obtained to a value of about 2-3 to separate the metal ions from the pulp,
    10 - the pH of the pulp is raised above 4 by washing with water and
    - the consistency of the washed cellulosic pulp is increased to at least 30%.
    [2]
    Process according to claim 1, characterized in that the pulp is contacted with an enzyme preparation containing endoglucanase activity in the pulp.
    15 to reduce viscosity.
    [3]
    Process according to claim 1 or 2, characterized in that the pulp is contacted with an enzyme preparation containing endoglucanase activity at a pH higher than 4, in particular higher than 5.
    [4]
    Process according to one of Claims 1 to 3, characterized in that the pulp is contacted with an enzyme preparation containing endoglucanase activity for 0.1 to 10 h and at a temperature of 10 to 75 ° C, in particular 20 to 60 ° C.
    5. A method according to any one of the preceding claims, characterized in that the enzymatic treatment modifies the viscosity of the pulp as well as DP and possibly the molecular weight distribution.
    A method according to any one of the preceding claims, characterized in that
    The cellulose pulp is contacted with the enzyme preparation at a consistency of at least 10%, preferably 1530%.
    20185448 prh 15 -05- 2018
    Method according to one of the preceding claims, characterized in that the viscosity of the pulp is reduced by 5-75%, in particular by about 15-70%, preferably by about 3060%.
    [5]
    8. A process according to any one of the preceding claims, characterized in that the consistency of the modified pulp obtained from the enzyme treatment is adjusted to 1-20% by weight, in particular about 5-15% by weight.
    [6]
    Method according to one of the preceding claims, characterized in that
    [7]
    The pH of the modified pulp obtained from the enzymatic treatment is preferably adjusted to 2-3 by addition of an acid such as mineral acid to the pulp stock, especially in the form of an aqueous solution.
    Method according to one of the preceding claims, characterized in that
    The metal content of the modified pulp obtained from the enzymatic treatment, in particular of the alkaline earth metals and transition metals, is adjusted by acid treatment to a value less than 100 ppm, in particular less than 50 ppm, by weight of the substance.
    [8]
    A method according to any one of the preceding claims, characterized in that
    After removal of the metal ions, the pulp is washed mechanically with water or an aqueous solution, for example in a washing machine.
    [9]
    Process according to Claim 11, characterized in that the pulp from the washing is dewatered and then the pulp is thickened to a concentration of about 30-49% by weight, preferably about 35-45% by weight.
    [10]
    Process according to one of the preceding claims, characterized in that the resulting pulp is subjected to a process for dissolving cellulose and hemicellulose.
    30
    [11]
    A process according to claim 12, characterized in that the resulting pulp is subjected to a process for dissolving cellulose and hemicellulose, wherein the cellulose and hemicellulose are dissolved directly in a solvent using a solvent such as an ionic liquid.
    20185448 prh 15 -05- 2018
    [12]
    15. A process for preparing a fiber spinning solution from cellulose and hemicellulose comprising:
    - the raw materials used for cellulose and hemicellulose are, inter alia, paper
    5 a chemical pulp suitable for manufacturing, containing at least some metal ions derived from the raw material of the pulp; and
    - the cellulose and hemicellulose are dissolved in a liquid in which the cellulose and hemicellulose are soluble and from which the dissolved cellulose and hemicellulose can be precipitated during spinning to produce cellulosic structures,
    10 characterized in that
    - contacting the pulp in an aqueous suspension with an enzyme preparation, in particular an enzyme preparation containing endoglucanase as its main activity, to reduce the viscosity of the pulp,
    - adjusting the pH of the pulp to a value of 3 or less for metal ions
    15 after which
    - the pH of the pulp is increased to more than 4 by washing with water,
    - the consistency of the washed pulp is increased to at least 30%, after which
    the wet modified cellulose pulp is dissolved in the liquid phase using a solubilizing agent such as an ionic liquid to form a spinning solution.
    [13]
    Process according to Claim 15, characterized in that the molecular weight distribution of the pulp is modified by enzymatic treatment such that at least 90% by weight, preferably at least 95% by weight, in particular at least 99.5% by weight of the pulp is soluble in the solvent.
    [14]
    Process according to Claim 15 or 16, characterized in that the metal content of the pulp obtained from the enzymatic treatment is reduced to a value of less than 0.0001% by weight by adjusting the pH of the pulp to a value of 2-3.
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    同族专利:
    公开号 | 公开日
    FI129226B|2021-09-30|
    EP3794177A1|2021-03-24|
    WO2019220014A1|2019-11-21|
    EP3794177A4|2022-01-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA2777801C|2009-10-16|2017-05-02|Aracruz Celulose S.A.|Differentiated cellulosic fibres from an enzymatic treatment having an acid step|
    FI129086B|2012-09-14|2021-06-30|Teknologian Tutkimuskeskus Vtt Oy|Method of producing dissolving pulp|
    US20150184338A1|2013-12-31|2015-07-02|Weyerhaeuser Nr Company|Treated kraft pulp compositions and methods of making the same|
    法律状态:
    2019-03-21| PC| Transfer of assignment of patent|Owner name: METSA SPRING OY |
    2021-09-30| FG| Patent granted|Ref document number: 129226 Country of ref document: FI Kind code of ref document: B |
    优先权:
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    FI20185448A|FI129226B|2018-05-15|2018-05-15|Method for the pretreatment of paper pulp|FI20185448A| FI129226B|2018-05-15|2018-05-15|Method for the pretreatment of paper pulp|
    PCT/FI2019/050381| WO2019220014A1|2018-05-15|2019-05-15|A method for pre/treatment of paper pulp|
    EP19803486.0A| EP3794177A4|2018-05-15|2019-05-15|A method for pre/treatment of paper pulp|
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