JP2019534391A - Methods for denaturing pulp containing cellulase enzymes and their products - Google Patents

Abstract

A method is provided for producing enzyme-modified fiber pulp, wherein the modified pulp improves properties for the papermaking process. Modified pulp and methods of use thereof are also provided.

Description

This application claims the benefit of the filing date of US Provisional Application No. 62 / 395,698, filed September 16, 2016 (US Provisional Application No. 62 / 395,698).

Reference to Sequence Listings The present invention includes sequence listings electronically submitted in ASCII format, which is incorporated herein by reference in its entirety. The ASCII copy created on September 13, 2017 is 205666_5069_WO_566976_ST25.txt and the size is 48542 bytes.

The following background art description refers to specific structures and / or methods. However, the following references should not be construed as an admission that these structures and / or methods constitute prior art. Applicants explicitly retain the right to prove that such structures and / or methods are not eligible for prior art.

  Cellulose enzymes can be used in pulp and paper applications such as improving drainage, reducing refining energy, deinking, reactivating waste paper pulp furnish, and increasing tensile strength under certain circumstances What can be used in is well-established knowledge as well as commercial practice. For example, U.S. Pat. No. 4,923,565 (USP 4,923,565) (Fuentes et al.), EP 058310 (EP 058310) (Leclerc), and U.S. Pat. No. 5,169,497 (USP 5). 169, 497) (Sarkar et al.). The use of cellulase treatment in combination with various papermaking agents or polymers has also been reported. These uses have various names for the drugs or polymers used, such as dry strength agents, wet strength agents, retention agents, flocculants, fixatives, antifouling agents, and enzyme stabilizers. These agents include cationic polymers, anionic polymers, nonionic polymers, amphoteric polymers, and various anionic and nonionic surfactants. For example, US Pat. No. 5,169,497 (USP 5,169,497) (Sarkar et al.), US Pat. No. 5,423,946 (USP 5,423,946), US Pat. No. 507,914 (USP 5,507,914), U.S. Pat. No. 6,939,437 (USP 6,939,437) (Hill et al.), U.S. Pat. No. 2002-0084046 (US Publ. 2002-0084046) (Hsu et al.), US Pat. No. 6,066,233 (USP 6,066,233) (Olsen et al.), US Pat. No. 6,770,170 (USP 6,770,170) (Covarrubias), US Patent Application Publication No. 2011-0168344 (US Publn. No. 2011-0168). 44) (Klein et al.), U.S. Patent Application Publication No. 2014-0116635 (US Publn. No. 2014-0116635) (Porto et al.), And U.S. Patent No. 9,011,643 (USP 9,011,643). ) (Gu et al.).

  The cellulase enzyme is sometimes combined with the appropriate hemicellulase enzyme associated with the furnish to be treated to hydrolyze the hydrated fiber surface (“gel”) layer as produced by beating or mechanical action. It is generally understood by those skilled in the art that it works to improve drainage and drainage. It will also be understood by those skilled in the art that the endoglucanase action of cellulase acts on the amorphous region of the fiber for beating and softens the fiber. It is also generally recognized that cellulase enzymes, when properly formulated or administered, act on the fiber surface to cause fibrillation outside the fiber surface, thus improving the bond strength or tensile strength. Those skilled in the art recognize that cellulase treatment can cause damage inside the fiber, which can adversely affect the strength properties of the fiber and the reduction in fiber length. As a result, in the application of the cellulase enzyme to wood fibers for papermaking, care is taken not to cause internal damage to the fibers, thus preserving the strength and length of the fibers.

Mechanical pulping consumes enormous amounts of electrical energy for defiberization and pulp fiberization. Various strategies have been used or proposed to reduce electrical energy requirements. Conventional commercial practices include SO ₂ or bisulfite addition (eg, CTMP), alkaline peroxide addition (eg, APMP), high temperature and duration treatment (eg, thermo-pulp), steam explosion, and cold Includes soda pretreatment. In research research, various chemical pretreatments have been evaluated. For example, catalytic oxygenation can be achieved with a 50% energy reduction and, for example, based on vanadyl organic complexes or vanadyl sulfate in an impressifiner process or a coarse beating process involving secondary waste for mechanical pulping. Substantially improved fiber compliance has been reported. For example, see International Patent Publication No. 1998020199 (WO 199802019).

  There is an unmet need in the art for fiber pulps with improved properties for papermaking and other products. The present disclosure addresses this need.

SUMMARY OF THE INVENTION The following summary is not an extensive overview. It is not intended to identify the footsteps or key elements of the various embodiments or to delineate their scope.

  The present disclosure relates to a method for producing modified pulp. The method intentionally causes a controlled degree of fiber internal damage, as exemplified by a significant fiber length reduction at a given freeness. The resulting fibers are useful in a variety of applications for the production of paper, pulp or web. Specifically, a significant but controlled degree of fiber internal modification or “fiber internal damage” (in addition to fiber surface modification) is intentionally caused, as exemplified by a significant fiber length reduction. Thus, various papermaking advantages can be exploited in synergy with the selected papermaking chemicals.

  Contacting a pulp comprising papermaking fibers with (a) a cellulose hydrolyzable enzyme and (b) a fiber length reduction enhancement agent under conditions that cause damage within the fibers; (i) 5% to 96% reduction in papermaking fiber length after passing through or bypassing the refiner and (ii) pulp freeness level of about 200 Canadian Standard Freeness (CSF) to about 700 CSF. There is provided a method for modifying a papermaking pulp comprising producing a modified pulp having the same. The modified pulp may be a mechanically beaten pulp.

  Contact between the pulp and the fiber length reduction promoter preferably occurs after contacting the pulp with the enzyme. Instead, the contact between the pulp and the fiber length reduction promoter occurs before or simultaneously with the contact between the pulp and the enzyme.

  The method comprises a hydrolysis polymer or copolymer of vinylformamide having a degree of hydrolysis greater than 70%, a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride, a copolymer of acrylamide and diallyldimethylammonium chloride, free glyoxal, and their A fiber length reduction promoter selected from the group consisting of more than two arbitrary mixtures may be used.

  The method may use a cellulose hydrolyzing enzyme which is a cellulase enzyme or a cellulase functionalized hemicellulase enzyme. Cellulose hydrolyzing enzymes are derived from or derived from Chrysosporium lucknowense / Myceliophthora thermophilia, or a cellulase derived from them, Humicola insolens. It may be a cellulase selected from the group consisting of a cellulase, a cellulase obtained from or derived from Aspergillus, a cellulase obtained from or derived from Trichoderma, and combinations thereof.

  The pulp of the method may comprise papermaking fibers selected from the group consisting of softwood pulp, hardwood pulp, and mixtures thereof.

  The fiber length reduction accelerator of the method is selected from the group consisting of a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis of greater than 70%, and a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride. The reduction in papermaking fiber length is from about 5% to about 20%, and the pulp freeness of the modified pulp is from about 300 CSF to about 650 CSF.

  The papermaking fibers of the method may be wood fibers and the fiber length reduction promoter is a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis greater than 70%, and acrylamide and acryloxyethyltrimethylammonium chloride. And present in a dosage of 0.5 kilogram (0.5 kg / ton (pulp)) to about 29 kg / ton (pulp) per ton of pulp, wherein the pulp of the modified pulp The freeness is from about 350 CSF to about 650 CSF.

  The fiber length reduction promoter of the method is selected from the group consisting of a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis of greater than 70%, and a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride, and pulp 1 Present at a dosage of 0.5 kilogram per ton (0.5 kg / ton (pulp)) to about 29 kg / ton (pulp), the reduction in the length of the modified pulp papermaking fiber is from about 5% to about 20 The pulp freeness of the modified pulp is from about 300 CSF to about 650 CSF.

  Also provided are enzyme pulps modified with any of the methods described above or described herein.

  There is also provided a method for modifying pulp fibers comprising contacting a pulp comprising papermaking fibers with a thermostable or super thermostable cellulose hydrolyzing enzyme at a temperature of about 70 ° C to about 125 ° C. The cellulase enzyme is substantially inactive at a temperature of about 35 ° C to about 55 ° C. The beating energy of the pulp or fibrous material of the method may be reduced by at least 10%. The modified pulp of the above method contains a hemicellulose content that is reduced by at least 0.2% by weight compared to the hemicellose content of the pulp produced without contact with a thermostable or hyperthermostable cellulose hydrolyzing enzyme. Can have a quantity. The cellulose hydrolyzing enzyme of the method may be a cellulase, a cellulase functionalized hemicellulase enzyme, or a cellulase comprising an associated hemicellulase enzyme function, such as xylanase, mannanase, glucanase, and beta-glucanase. The cellulose hydrolyzing enzyme of the method may be a cellulase selected from the group consisting of a cellulase of SEQ ID NO: 6 and a cellulase of SEQ ID NO: 2. The contacting step of the method may further comprise a thermostable or hyperthermostable enzyme selected from the group consisting of hemicellulase, mannanase, xylanase, pectinase, laccase, lignin peroxidase, manganese peroxidase, and oxidoreductase. The pulp of the method comprises papermaking fibers selected from the group consisting of softwood pulp, hardwood pulp, and mixtures thereof. The enzyme contacting step of the method further comprises an intracrystalline selected from the group consisting of ionic liquids, N-alkylated ureas, N-alkylated lactams, N-alkylated amides, polyol ethers, polyols, and combinations thereof. An lignocellulosic agent may be included. The pulp of the method includes kraft pulp, sulfite pulp, mechanical pulp, semi-chemical pulp, semi-mechanical pulp, fluff pulp, dissolving pulp, waste paper pulp, biorefinery pulp, or deinked pulp. Also considered are fiber pulps modified with the enzyme produced by the method.

  (1) FQA length—pulp containing coniferous fibers having a fiber length of about 2.1 mm to about 2.8 mm as measured by weighted average fiber length, and a cellulose hydrolyzing enzyme, about 35 ° C. to about 125 (2) beating the modified pulp, (i) a fiber length of about 0.6 mm to about 1.7 mm, and (ii) about 400 Canadian Standard Freeness (CSF) to about 700 CSF. Also provided is a method for modifying a papermaking pulp comprising producing a modified pulp having pulp freeness. The contacting step of the method may be performed at a temperature of about 35 ° C. to about 125 ° C. for about 30 minutes to about 10 hours. Instead, the contacting step is performed at a temperature of about 35 ° C. to about 65 ° C. and at an enzyme dosage of about 0.2 kilograms per ton of pulp (about 0.2 kg / T) to about 20 kg / T. Good. Cellulose hydrolyzing enzyme of said method is obtained from or derived from Chrysosporium lucknowense / Myceliophthora thermophilia, Humicola insolens A cellulase selected from the group consisting of: a cellulase derived from, a cellulase obtained from or derived from Aspergillus, a cellulase obtained from or derived from Trichoderma, and combinations thereof Good. The contacting step of the method may be performed at a temperature of about 66 ° C. to about 125 ° C. and at an enzyme dosage of about 0.2 kilograms per ton of pulp (about 0.2 kg / T) to about 20 kg / T. . The cellulose hydrolyzing enzyme of the method may be a cellulase enzyme or a cellulase functionalized hemicellulase enzyme. The cellulose hydrolyzing enzyme of the method may be a cellulase of SEQ ID NO: 6 or SEQ ID NO: 2. The method may also include contacting the pulp with a fiber length reduction promoter. The method of bringing the pulp into contact with the fiber length reduction accelerator is preferably carried out after bringing the pulp into contact with the enzyme.

  An enzyme-modified softwood fiber pulp having (i) a fiber length of about 0.6 mm to about 1.7 mm, and (ii) a pulp freeness of about 400 Canadian Standard Freeness (CSF) to about 700 CSF Provided.

  Also described herein is a web or pulp product comprising a modified pulp produced by any of the methods of the present disclosure. Paper or pulp products are printed writing paper, wrapping paper, paperboard, personal care and hygiene products, tissue paper, paper towels, paper napkins, paper wipes, paper plates, paper cups, paper containers, deinked paper, recycled paper, fine paper It may be selected from the group consisting of crystalline cellulose, microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, dissolving pulp, and base paper for polymer impregnation or base paper for composites.

  It is understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further description of the disclosed compounds, compositions, and methods. I want.

  For the purpose of illustrating various products, compositions and methods, specific embodiments are depicted in the drawings. However, the products, compositions, methods for making them, and methods for using them are not limited to the exact arrangement and means of the embodiments depicted in the drawings.

FIG. 1 illustrates a graph plotting freeness (CSF, Canadian standard freeness) against PFI mill rotation for control pulp and pulp treated with two enzymes. FIG. 2 illustrates a graph plotting specific tensile strength (NM / g) against PFI mill rotation for control pulp and pulp treated with two enzymes. FIG. 3 shows Seafield smoothness versus PFI mill rotation for control pulp, pulp treated with two enzymes, and pulp treated with one enzyme and subsequently contacted with a fiber length reduction promoter prior to beating. A graph plotting (ml / min) is shown. FIG. 4 shows the sheet versus freeness (CSA) for control pulp, pulp treated with two enzymes, and pulp treated with one enzyme and subsequently contacted with a fiber length reduction promoter prior to beating. Figure 3 illustrates a graph plotting field smoothness (ml / min). FIG. 5 shows length-weight versus freeness for control pulp, pulp treated with two enzymes, and pulp treated with one enzyme and subsequently contacted with a fiber length reduction promoter prior to beating. Figure 3 illustrates a graph plotting average fiber length (LWAFL). FIG. 6 illustrates a graph plotting freeness (CSF, Canadian standard freeness) against Valley-beater refining time (minutes) for control pulp and pulp treated with one enzyme. To do. The freeness was measured on the pulp after blending with Xelorex ^™ . FIG. 7 plots paper bulk (cc / g) against volley beater beat time (minutes) for DSF (Dynamic Sheet Former) sheets from the control pulp and enzyme treated pulp of FIG. The graph is illustrated. The pulp was blended with Xelorex ^™ after volley beater beating and into a DSF sheet. FIG. 8 plots paper bulk (cc / g) against freeness (CSF) after beaten beater for a DSF (dynamic sheet former) sheet from the control pulp and enzyme treated pulp of FIG. The graph is illustrated. The pulp was blended with Xelorex ^™ after volley beater beating and into a DSF sheet. FIG. 9 shows the MD (longitudinal) tensile strength (Kgf) versus freeness (CSF) after beating the valley beater for DSF (dynamic sheet former) sheets from the control pulp and enzyme treated pulp of FIG. / Mm) is plotted. The pulp was blended with Xelorex ^™ after volley beater beating and into a DSF sheet. FIG. 10 shows the CD (horizontal) tear strength of the paper against the freeness (CSF) after beating the valley beater for DSF (dynamic sheet former) sheets from the control pulp and enzyme treated pulp of FIG. A graph plotting gf) is illustrated. The pulp was blended with Xelorex ^™ after volley beater beating and into a DSF sheet. FIG. 11 illustrates a graph plotting freeness (CSF) versus volley beater beats (minutes) for control pulp and pulp treated with cellulase B, a super thermostable cellulase. FIG. 12 shows volley beater beats (minutes) for control pulp (no enzyme), pulp treated with cellulase A at 3 different doses at 55 ° C., and pulp treated with cellulase B at 3 different doses at 70 ° C. ) Is a graph plotting freeness (CSF) against. X = Pulp not treated with enzyme. Black triangle = 10 kg / T, cellulase B at 70 ° C. Black square = 15 kg / T, Cellulase B at 70 ° C. Black circle = 20 kg / T, cellulase B at 70 ° C. The open symbols are data for cellulase A at 55 ° C .; the triangular dotted line is 0.2 kg / T data, the square dotted line is 0.4 kg / T data, and the round dotted line is 2 kg. / T data. FIG. 13 shows volley beater beating (minutes) for control pulp (no enzyme), pulp treated with cellulase A at 3 different doses at 55 ° C., and pulp treated with cellulase B at 2 different doses at 70 ° C. ) Is a graph plotting length-weighted average fiber length (LWAFL). FIG. 14 shows freeness (CSF) for control pulp (no enzyme), pulp treated with cellulase A at three different doses at 55 ° C., and pulp treated with cellulase B at two different doses at 70 ° C. ) Is a graph plotting length-weighted average fiber length (LWAFL). FIG. 15 shows a control pulp (no enzyme), a control pulp co-refined with Percol®, and treated with cellulase A at a dosage of 0.4 kg / T and either Percol® or FIG. 6 illustrates a graph plotting freeness (CSF) versus valley beater beats (minutes) for pulp co-beaten with Xelorex ^™ . FIG. 16 shows control pulp (no enzyme), control pulp co-beaten with Percol®, and treated with cellulase A at a dose of 0.4 kg / T and co-beaten with Percol® or Xelorex ^™. Figure 2 illustrates a graph plotting length-weighted average fiber length (LWAFL) against freeness (CSF) for the finished pulp. FIG. 17 shows control pulp (no enzyme), pulp treated with cellulase A at a dose of 0.4 kg / T or 2 kg / T, and treated with cellulase A at a dose of 0.4 kg / T, beaten, And illustrates a graph plotting length-weighted average fiber length (LWAFL) against freeness (CSF) for pulp combined with Percol® or Xelorex ^™ . FIG. 18 illustrates a graph plotting freeness (CSF) versus volley beater beats (minutes) for control pulp (no enzyme) and pulp treated with cellulase B at 85 ° C. FIG. 19 shows the freeness (specific edge load) (SEL; J / m) for the pulp treated with control pulp (no enzyme) and cellulase A (1 kg / T dose) at 50 ° C. Fig. 2 illustrates a graph plotting CSF). FIG. 20 shows the freeness (specific refining energy) (KW-h / ton) for pulp treated with control pulp (no enzyme) and cellulase A (1 kg / T dose) at 50 ° C. Fig. 2 illustrates a graph plotting CSF). FIG. 21 shows freeness for control pulp (no enzyme), pulp treated with cellulase A (1 kg / T dose) at 50 ° C. with or without Percol® after enzyme beating. Figure 2 illustrates a graph plotting length-weighted average fiber length (LWAFL) against (CSF). Figure 22 shows the length-weighted average fiber length (LWAFL) versus specific beating energy (KW-h / ton) for pulp treated with control pulp (no enzyme) and cellulase A (1 kg / T dose) at 50 ° C. ) Is plotted.

Description There is a need in the art for fiber pulp having improved properties for papermaking and other products. The present disclosure addresses this need by providing a method for producing modified fiber pulp. Accordingly, a method is provided for modifying papermaking fibers in the pulp to cause damage inside the fibers, where the modified pulp provides benefits in the papermaking process compared to unmodified pulp. Modified pulp provides at least one of the following benefits in relation to the corresponding unmodified pulp: (1) Papermaking properties that allow the use of more coniferous fibers instead of hardwood fibers, for example Improved formation; (2) improved paper bulk at a given freeness; (3) improved smoothness of paper; (4) reduced energy costs for beating; and (5) Reduction in hemicellulose content. Additional advantages will become apparent based on the above disclosure. Modified pulp and methods of use thereof are also provided.

Definitions As used herein, each of the following terms has the associated meaning in this paragraph. Additional definitions exist throughout this disclosure.

  The articles “a” and “an” are used herein to refer to one or more (ie, at least one) of the grammatical objects of the article. By way of example, “an element” means one element or more than one element.

  The term “about” will be understood by those of ordinary skill in the art and will vary to some extent on the context in which it is used. As used herein, the term “about” means that the number being described may deviate by plus or minus 5 percent of that number. For example, “about 250 g” means 237.5 to 262.5 g. Where the term “about” is used in a range, the lower limit may be on the order of minus 5% of the lower limit number, and the upper limit may be extended to plus 5% of the upper limit number. For example, a range of about 100 to about 200 g indicates a low range of 95 g to 210 g.

  Scope: Throughout this disclosure, various aspects of this disclosure can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, the description of ranges such as 1 to 6 includes partial ranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc. Are to be considered as specifically disclosing, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the width of the range.

  As contemplated in the present disclosure with respect to the disclosed compositions and methods, in one aspect, embodiments of the present disclosure include the disclosed components and / or steps. In other aspects, embodiments of the present disclosure consist essentially of the disclosed components and / or steps. In yet other aspects, embodiments of the present disclosure consist of the disclosed components and / or steps.

DETAILED DESCRIPTION Reduction of fiber length In conventional papermaking, cellulase enzyme treatment is performed to improve drainage or to improve beating strength. In such cellulase enzyme treatment, degradation of internal fibers is always avoided, as reflected by a reduction in fiber length. Contrary to this conventional view, Applicants have found that beneficial papermaking and paper product properties are intentionally altered in fiber morphology and fiber length by a combination of cellulase treatment and beating as disclosed herein. We have found that this can be achieved by causing a reduction. More specifically, Applicants have induced 5% to 96% after passing through or bypassing a refiner, inducing a degree of fiber internal damage controlled by the use of cellulose hydrolyzing enzymes. While having a reduced papermaking fiber length, while maintaining a pulp drainage level of 200 CSF to 700 CSF compared to unpulled pulp, paper, paper products, or other pulp products It has been found to produce pulp having improved properties when used to make.

  5% to 96% after contacting paper refiner, cellulose hydrolyzing enzyme, and fiber length reduction promoter under conditions that cause damage inside the fiber, after passing through the refiner or bypassing the refiner Provided herein is a method for modifying paper pulp by reducing the length of papermaking fibers and producing modified pulp having a pulp freeness level of from about 200 Canadian Standard Freeness (CSF) to about 700 CSF. Is done. The reduction in papermaking fiber length refers to the corresponding pulp that has not been treated with a cellulose hydrolyzable enzyme and a fiber length reduction promoter.

  Exemplary dosages for enzyme treatment are from 0.2 kilograms per ton of pulp (enzyme) to about 25 kg / tons, and about 0.2 kilograms per ton of pulp (about 0.0. 2 kg / ton) to about 20 kg / ton, about 2 kilograms per ton of pulp (about 2 kg / ton) to about 10 kg / ton, or about 0.2 kg / ton to about 2 kg / ton.

  Enzymatic treatment may be performed at a temperature in the range of about 40 ° C. to about 50 ° C., typical paper mill temperatures. Alternatively, the enzyme treatment may be performed at a temperature above about 55 ° C, such as from about 70 ° C to about 125 ° C. Exemplary cellulolytic enzymes for use in carrying out the method at any temperature range are discussed in detail below. Cellulose hydrolyzing enzymes such as cellulases are hemicellulase, mannanase, xylanase, pectinase, esterase, lipase, manganese peroxidase, lignin peroxidase, laccase, dioxygenase, monooxidase, chloroperoxidase, glyoxal oxidase, glucose oxidase, cellobiose dehydrogenase, and It may be used in combination with other enzymes commonly applied in the pulp and paper field, including cellobiose quinone oxidoreductase.

  The duration of the enzyme treatment should be sufficient to cause damage inside the fiber reflected by a reduction in fiber length. For example, the duration of the enzyme treatment may be 1 hour or more, or 1 to 10 hours.

  Enzymatic treatment can be performed anywhere from the pulp mill processing after cooking to the paper mill raw material preparation, providing sufficient enzyme reaction time or temperature. Exemplary locations for enzyme treatment include a beating process, a bleach plant process, a pulp high density (HD) tower, a tank, and a pulper / repulper. In one embodiment, the enzymatic treatment of pulp fibers is performed in a bleach plant process, such as a bleach HD tower.

  The enzyme contacting step may be performed before or after kraft pulping, before, during or after oxygen delignification, before or after any bleaching, before or after chemical or modified chemical pulping, before semichemical pulping or Can be done later.

  Fiber length reduction enhancer (also referred to herein as “length reduction enhancer”) is a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis greater than 70%, acrylamide and acryloxy Copolymers with ethyltrimethylammonium chloride, copolymers of acrylamide and diallyldimethylammonium chloride, free glyoxal, or mixtures thereof. The length reduction promoter is added before the enzyme treatment, during the enzyme treatment, or after the enzyme treatment.

  The pulp freeness of the modified pulp may be from about 200 CSF to about 700 CSF, from about 300 CSF to about 650 CSF, or from about 400 CSF to about 600 CSF.

  Modified pulp is a papermaking fiber furnish of 10% to 100% (blended with an untreated beaten pulp source or an untreated beaten pulp raw material) for the formation of papermaking or web base material May be used.

  Paper is usually formed from wood fibers, ie conifers and hardwoods. The main differences between coniferous and hardwood fibers are the length of individual cellulose fibers in the wood, the roughness of the fibers, and the stiffness or contractibility of the fibers. Both smoothness and formation are affected, inter alia, by fiber length, morphology and shrinkability. It is well known that softwood fibers provide stronger strength than hardwood fibers, but are substantially inferior to hardwood fibers in paper formation due to fiber length and printing smoothness due to fiber roughness. The smoothness of paper formation and printing is increasingly in demand for wrapping paper, such as paperboard and other high quality packaging and printing paper. This is an important strategic and economic issue. For example, in the southeastern United States where huge amounts of pulp and paper products are being produced, coniferous fibers are more available than hardwood fibers.

  Previous methods of modifying fiber morphology using conventional enzyme treatment (enzymatic beating) have been found to be inadequate and are not cost effective. See, for example, US Pat. No. 8,262,850 (US 8,262,850). Previous methods to address the disadvantages of enzymatic beating include peroxide based catalytic oxidation strategies and hypochlorite or hypochlorous acid strategies combined with beating. For example, US Patent No. 8,262,850 (US 8,262,850), US Patent No. 8,007,635 (US 8,007,635), US Patent No. 8,282,774 (US 8,282,774) and U.S. Patent No. 8,753,484 (US 8,753,484).

  One advantage of the modified pulp made by the disclosed method is the modification of the fiber form of the coniferous fibers so that the modified coniferous fibers can be used in place of the hardwood fibers. The present disclosure provides a strategy based on the contribution of a combination of enzyme beating and selective chemicals (fiber length reduction promoters) to provide a practical and cost-effective treated softwood fiber for papermaking To do.

  Accordingly, the method of the present disclosure can be practiced with pulp comprising or consisting of coniferous fibers. In practicing the method of the present disclosure, the length of the coniferous fiber is adjusted to a pulp freeness of about 200 CSF to about 700 CSF, about 350 CSF to about 650 CSF, about 350 CSF to about 650 CSF, or about 400 CSF to about 650 CSF after passing through a refiner. Can be reduced by 5% to 96%. The length of the coniferous fiber may be reduced by 10% -96%, 15% -96%, or 20% -96%. Exemplary dosages for enzyme treatment range from about 0.2 kilograms per ton pulp (about 0.2 kg / ton) to about 25 kg / tons, about 0.2 kilograms per ton pulp (about 0.2 kg). To about 20 kg / ton, about 2 kilograms per ton of pulp (about 2 kg / ton) to about 10 kg / ton, or about 0.2 kg / ton to about 2 kg / ton. Enzymatic treatment can be performed anywhere from pulp mill processing after cooking to paper mill raw material preparation, eg, bleach plant process or pulp high density (HD) tower, with sufficient enzyme Reaction time or temperature is provided. Exemplary dosages of fiber length reduction promoters are 0.5 kg / ton to 20 kg / ton, or 2 kg / ton to 10 kg / ton before, during, or after the beating step with the enzyme. It may be.

  Modified softwood fiber pulp is 10% to 100% (untreated beaten pulp source or untreated beaten for the formation of improved papermaking properties, such as paper or paper stock having a texture. May be used in papermaking fiber furnishes (blended with no pulp stock). The improved properties advantageously make it possible to replace more hardwood fibers with modified softwood fibers in the papermaking process.

  In one aspect, the length of the coniferous fiber is reduced by 10% to 96%, 15% to 96%, or 20% to 96% with an enzyme dosage of 0.2 kg / ton to 2 kg / ton, The length reduction accelerator is a hydrolyzed polymer or copolymer of vinyl formaldehyde having a degree of hydrolysis greater than 70%, or a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride (before applying the beating step by the enzyme treatment, the beating step) Applied at a dosage of 0.5 kg / ton to 20 kg / ton, or 2 kg / ton to 10 kg / ton) (in the middle or after the beating step), wherein the pulp freeness is 300 CSF to 650 CSF, or 400 CSF to 650 CSF It may be.

  In one aspect, the fiber length may be reduced by 5% to 20% by contacting the conifer or hardwood pulp with a length reduction promoter before, during or after the enzymatic beating treatment, Pulp freeness may be between 300 CSF and 650 CSF. The length reduction promoter is applied at a dosage of 0.5 kg / ton to 20 kg / ton, or 2 kg / ton to 10 kg / ton before, during or after the enzyme beating step, degree of hydrolysis 70% Highly hydrolyzed polymers or copolymers of vinylformamide with super, copolymers of acrylamide and acryloxyethyl-trimethylammonium chloride. It has been found that paper or paperboard products made using modified softwood pulp advantageously have improved papermaking bulk at a given freeness.

  In one aspect, the fiber length of the conifer may be reduced by 5% to 20% by contacting the conifer pulp with a length reduction promoter before, during or after the enzymatic beating treatment, and the pulp of the modified pulp The freeness may be from 300 CSF to 650 CSF. It has been found that paper or paperboard products made using modified softwood pulp advantageously have an improved papermaking bulk with a given tensile strength.

  In one embodiment, the elevation treatment may be carried out in the presence of a fiber length reduction promoter (co-beating), wherein the conifer or hardwood fiber length is reduced by 5-20% and the modified pulp Pulp freeness may be between 300 CSF and 650 CSF. It has been found that paper or paperboard products made using modified softwood pulp advantageously have improved smoothness. The modified softwood pulp may have reduced container flaking / fluffing.

  Enzymatic treatment of the method discussed above is well known to be used in conjunction with cellulase enzymatic hydrolysis and xylanase enzymatic bleaching, and anionic, nonionic, cationic and zwitterionic surfactants and It may be carried out using dispersants and any surfactants and / or dispersants including those surfactants and dispersants known to us in pulping, washing, and papermaking systems.

  The disclosed method modifies the morphology of hardwood fibers, increases fiber occupancy, and / or reduces hardwood fiber roughness, thereby improving hardwood fibers for tissue and personal care applications For this purpose, it may be carried out with pulp comprising hardwood fibers or consisting of hardwood fibers. For example, some hardwood fibers may have high roughness and long fiber lengths, including but not limited to, mixed hardwood pulps in the southern US, which may be modified to approach more desirable fiber fiber properties, such as Eucalyptus, poplar, or acacia. Further disclosure regarding fibers for performance of the disclosed method is found in “Wood and Non-Wood Pulp Fibers”.

  The disclosed method can be used to treat pulp fibers for use in dissolving pulp and fluff pulp modification.

High Temperature Enzymatic Treatment of Pulp Modern mechanical pulping, such as thermomechanical pulping (TMP, CTMP, APMP), is performed at very high temperatures of 70 ° C. to 120 ° C. at various pulping process locations. This high temperature is due to the reduction of beating energy, even though various enzyme approaches including cellulase, hemicellulase, pectinase, laccase, and various peroxidases have been historically studied in the research process to reduce energy. The use of cellulase enzymes has been hindered in the commercialization of Despite being claimed to be useful for removing pitch and extract and thus somewhat reducing the beating energy required for fiber development, lipase enzymes directly to beating energy to any significant level Does not affect.

  The most commercially available cellulases for papermaking applications are enzymes that can only work effectively up to 50 ° C or up to 55 ° C. Even though some cellulase enzymes have been expanded to work at higher temperatures, these enzymes work very well or more effectively at lower temperatures.

  Applicants have found that some cellulase enzymes that do not work at lower temperatures (ie, typical papermaking temperatures) work very effectively at temperatures substantially above the papermaking temperature.

  Accordingly, the present disclosure further provides a method for modifying pulp fibers comprising contacting the pulp and cellulose at a temperature from about 70 ° C to about 125 ° C, or from about 80 ° C to about 100 ° C. Preferably, the cellulose hydrolyzing enzyme is substantially inactive at a temperature of less than about 60 ° C, or less than about 55 ° C, such as from about 35 ° C to about 55 ° C.

  In one embodiment, the method advantageously results in a reduced energy consumption for beating, for example a saving of at least about 10% of beating electrical energy in paper beating or chip beating. The reduction in energy consumption is for pulp that is comparable to the same treatment (but no enzyme) at temperatures from about 70 ° C to about 125 ° C. Example 8 shows such energy savings obtained with enzymatic treatment at 85 ° C.

  In one embodiment, the method can provide a modified pulp having improved papermaking properties. In one aspect, the hemicellulose content of the treated pulp after pulping and / or bleaching is reduced by at least about 0.2% by weight or more in other cases compared to pulp produced without such enzymatic treatment. Is done.

  The high temperature range is higher than the operating temperature of the paper mill department (including raw material preparation department, refiner department, paper machine department, and paper machine white water recirculation). Cellulase enzymes that remain in the paper mill due to the treated paper fiber are preferably inert at typical paper mill temperatures and therefore do not affect other paper grades and do not affect white water system chemicals. Therefore, it enables long-term paper machine operation. Thus, modified pulp is advantageous for use in many paper products. The high temperature process overcomes a major hurdle that has so far limited the widespread use of cellulase enzymes in paper mills.

  For example, exemplary cellulosic hydrolysability for use in carrying out the method in a temperature range from about 70 ° C to about 125 ° C, from about 75 ° C to about 120 ° C, or from about 80 ° C to about 100 ° C. The enzyme is described in detail below. Cellulose hydrolyzing enzymes have enzymatic activity in these temperature ranges and are referred to herein as thermostable and hyperthermostable enzymes. Thermostable and super thermostable cellulosic hydrolyzing enzymes can provide additional advantageous factors that do not affect other process streams or products in the subsequent papermaking process, such as temperatures in subsequent processes, for example, less than 60 ° C. Or substantially inactive below 55 ° C.

  Exemplary dosages for high temperature enzyme treatment range from 0.2 kilograms per ton of pulp (enzyme) to about 25 kg / tons, about 0.2 kilograms per ton of pulp (about 0.2 kg / ton) to about 20 kg / ton, about 2 kilograms per ton of pulp (about 2 kg / ton) to about 10 kg / ton, or about 0.2 kg / ton to about 2 kg / ton.

  Cellulose hydrolyzing enzyme treatment can optionally be performed in conjunction with other super thermostable hemicellulases such as super thermostable mannanase or super thermostable xylanase. For example, several hyperthermostable xylanases between 70 ° C. and 90 ° C., and optionally up to 100 ° C., are described in International Patent Publication No. 2007095398 (WO 2007095398) (Weiner et al.), International Patent Publication No. 2009045627. (WO 2009045627) (Gray et al.), And International Patent Publication No. 20116073610 (WO2016073610) (Widner et al.).

  The fibers may be wood fibers or non-wood fibers or fibrous materials. The disclosed method modifies the morphology of hardwood fibers, increases fiber occupancy, and / or reduces hardwood fiber roughness, thereby improving hardwood fibers for tissue and personal care applications For this purpose, it may be carried out with pulp comprising hardwood fibers or consisting of hardwood fibers. Further disclosure regarding fibers for performance of the disclosed method is found in “Wood and Non-Wood Pulp Fibers”. Fibers are treated by mechanical fiber degradation, such as impression refiners, wood crushers, disc refiners, extruders, kneaders, homogenizers, shredders, before, during, or after the super heat-stable lurose hydrolyzing enzyme treatment step. You may receive.

  The duration of the enzyme treatment may be up to about 30 minutes to 10 hours.

  The high temperature enzyme treatment can be performed anywhere from the pulp mill processing stage after cooking to the paper mill raw material preparation, providing sufficient enzyme reaction time or temperature. Exemplary locations for enzyme treatment include a beating process, a bleach plant process, a pulp high density (HD) tower, a tank, and a pulper / repulper. The high-temperature enzyme treatment may be performed as a pretreatment, for example, by an impression refiner before beating, or may be performed on refiner waste before beating is eliminated.

  Optionally, any effective dispersant, penetrant, surfactant (anionic, nonionic, cationic, zwitterionic), and / or polymeric carrier may be used in conjunction with the enzyme treatment.

  As described above, in one embodiment of the high temperature enzyme treatment method, the hemicellulose content of the treated pulp is reduced. A method for denaturing paper pulp fibers comprises a paper pulp and a cellulose hydrolyzing enzyme such as a cellulase enzyme, a hemicellulase enzyme containing cellulase enzyme activity, or a mixture of a cellulase enzyme and a hemicellulase enzyme. Including contacting at a temperature of up to 125 ° C., or from about 80 ° C. to about 100 ° C., for a reaction time of from about 30 minutes to about 10 hours, wherein the pulped and / or bleached pulp is It has a hemicellulase content reduced by at least about 0.2% by weight or more when compared to pulp made without high temperature enzyme treatment. Preferably, the cellulosic enzyme is substantially inactive at a temperature of less than about 60 ° C, or less than about 55 ° C, such as from about 35 ° C to about 55 ° C.

  The super thermostable enzyme may be applied before pulping, in the middle of the pulping process, and after pulping. The pulping is mechanical pulping, optional chemical pulping, optional semichemical pulping, optional semimechanical pulping, optional chemical mechanical pulping, waste paper pulping, or deinking pulping. For example, pulping can be sulfite pulping, kraft pulping, prehydrolyzed kraft pulping, waste paper pulping, solvent pulping, steam / hot water pretreatment (with or without explosion) pulping, ammonia (with or without explosion) No explosion) pulping, sodium carbonate pulping, NSSC pulping, various TMP or RMP pulping, etc., as well as the modified pulping disclosed, for example, U.S. Pat. No. 8,328,983 (US 8328983), U.S. Pat. No. 8,182,650. No. (US 8182650), and US Pat. No. 7,520,958 (US Pat. No. 7,520,958). The hyperthermostable enzyme may be applied before, during or after the bleach plant operation. The enzyme treatment step may be performed before, during or after oxygen delignification.

  The resulting modified pulp can be used as an improved dissolving pulp with improved chemical reactivity due to chemical induction and reaction. The modified pulp advantageously has one or more of reduced fluff crushing energy, modified liquid absorption capacity, modified surface free energy / contact angle, and modified liquid acquisition time. Can be used as Such fluff pulp is useful in diapers or personal hygiene products. Modified pulp can be used as tissue pulp for tissue softness. The modified pulp may be a papermaking pulp having an elevated bulk. Under certain conditions with such super heat stable cellulase treatment, the modified pulp may be further processed into microcrystalline cellulose, microfibrillated cellulose, nanofibrillated cellulose, nanocellulose, and other specialty cellulose products. Instead of modified pulp, biorefinery use of removed hemicellulose sugars is also conceivable, for example steam / hot water pretreatment (explosion or no explosion) pulping, ammonia (explosion or no explosion) pulping, sodium carbonate pulp , NSSC pulping, various TMP or RMP pulping and the like.

  The high temperature treatment may be applied after kraft pulping, for example in the Braw HD tower (with or without oxygen delignification upstream). The treatment may be applied after sulfite pulping. The treatment may be applied before pulping. Said treatment may be applied in the middle of the bleaching step and / or after bleaching in the Bleached HD tower.

  In one aspect, the high temperature treatment is preferably performed after mechanical fiber degradation, for example by an impression refiner or other mechanical device, followed by mechanochemical (craft, sulfurous acid, or solvent) pulping or semi-chemical pulping. Used with wood chips or non-wood chips or fibrous materials together with thermostable cellulases and super thermostable hemicellulases (eg, xylanase, mannanase, and / or pectinase). These constitute a modified pulping method for paper, paperboard, fluff pulp, tissue fiber, biorefinery (with sugar), or dissolving pulp. In addition to the super thermostable cellulase enzyme described above, exemplary super thermostable xylanases are disclosed in the patents WO 2007/095398 (WO 2007/095398) (Weiner et al.), WO 2009/095. 045627 (WO 2009/045627) (Gray et al.) And those described in International Publication No. 2016/073610 (WO 2016/073610) (Widner et al.).

  The paper mill temperature is usually 40 ° C to 55 ° C. Accordingly, cellulase enzymes that are not active in these temperature ranges are preferred for carrying out the disclosed method for papermaking fibers. Preferably, the cellulase enzyme will only be active at temperatures above 55 ° C or above 60 ° C. In general, cellulase enzymes that are only active at about 60 ° C to 125 ° C, about 65 ° C to 125 ° C, or about 70 ° C to 125 ° C are used to deliver fiber processing and papermaking functions in the disclosed methods. It's okay. This is the temperature range of hyperthermophilic bacteria.

In one aspect, the high temperature enzyme treatment is performed at the end of the bleaching process of the bleach plant in a Bleached HD tower (or separation tank). Optionally, out-of-range heating, such as steam injection or hot water supply, may be performed. Reducing agents (eg, SO ₂ , sulfites, or thiosulfates) can optionally be added to remove residual oxidants (eg, ClO ₂ or peroxides), thus cellulose from these bleach plant residual chemicals. Minimize or prevent inactivation of hydrolyzable enzymes. For the Bleached HD column, the method is carried out with a cellulase enzyme that is only active above 60 ° C., eg 60 ° -75 ° C., or above 65 ° C., eg 65 ° -75 ° C.

  If the enzyme temperature and pH tolerance are appropriate, the high temperature enzyme treatment can be performed before or during the bleaching process, where after the enzyme treatment the bleaching process may help to inactivate the enzyme. Alternatively, the washer may help remove the enzyme from the treated fiber. For example, the cellulase enzyme treatment may be performed in a preliminary or excess bleach tower. Cellulose hydrolyzing enzymes that are thermostable above 65 ° C, or above 70 ° C, or above 75 ° C are compatible with the bleach plant stream process temperature.

  High temperature enzyme treatment for paper pulp fibers may be carried out in a paper mill after chemical pulping or oxygen delignification, for example in a Brown HD tank, where the temperature is usually between 65 ° C. and 90 ° C., Or 70 to 90 degreeC may be sufficient. In the case of mechanical pulping or chemical mechanical pulping, the temperature may be between 70 ° C. and 120 ° C. depending on the position in the paper mill process.

  Optionally, the enzyme treatment may be performed in combination with an intracrystalline lignocellulose agent. Exemplary intracrystalline lignocellulosic agents include ionic liquids, N-alkylated ureas, N-alkylated lactams, N-alkylated amides, polyol ethers, and polyols.

  All dispersants, penetrants, surfactants mentioned above or known for use in the pulp and paper industries may be included for use with the high temperature enzyme treatment or may be used as a separate treatment. .

Reduction of fiber length-conifers for replacement of hardwood fibers In this specification, (1) FQA length-conifer fibers having a fiber length of about 2.1 mm to about 2.8 mm as measured by weighted average fiber length. The pulp having a cellulose hydrolyzable enzyme is contacted at a temperature of about 35 ° C. to about 125 ° C., and (2) denature the modified pulp to denature the pulp conifer fiber for papermaking, thereby (i) about A method of producing a modified pulp having a fiber length of 0.6 mm to about 1.7 mm and (ii) a pulp freeness of about 400 Canadian Standard Freeness (CSF) to about 700 CSF is provided. The reduction in papermaking fiber length relates to the corresponding pulp that has not been treated with a cellulose hydrolyzing enzyme. Advantageously, the process allows a beating energy saving of at least 20% compared to controlled beating without enzyme treatment. Furthermore, the modified softwood fiber pulp can advantageously be replaced with hardwood fiber pulp in the manufacture of webs or pulp fibers.

  Enzymatic treatment can be performed anywhere from the pulp mill processing stage after cooking until the paper mill raw material preparation, providing sufficient enzyme reaction time or temperature. Exemplary locations for enzyme treatment include a beating process, a bleach plant process, a pulp high density (HD) tower, a tank, and a pulper / repulper. In one embodiment, the enzymatic treatment of pulp fibers is performed in a bleach plant stage, such as a bleach HD tower.

  The beating step is performed with sufficient refiner strength with either a disc refiner or a conical refiner.

  The contacting step of the method may be performed at a temperature of about 35 ° C. to about 125 ° C. for about 30 minutes to about 10 hours, or at a temperature of about 35 ° C. to about 125 ° C. for about 30 minutes to about 10 hours.

  Exemplary dosages for enzyme treatment range from 0.2 kilograms per ton pulp (0.2 kg / ton) to about 25 kg / tons, and about 0.2 kilograms per ton pulp (about 0.2 kg / tonnes). ) To about 20 kg / ton, about 2 kilograms per ton of pulp (about 2 kg / ton) to about 10 kg / ton, or about 0.2 kg / ton to about 2 kg / ton.

  Enzymatic treatment may be performed at a temperature in the range of about 35 ° C. to about 65 ° C., typical paper mill temperatures. Alternatively, the enzyme treatment may be performed at about 65 ° C to about 125 ° C. Exemplary cellulolytic enzymes for use in carrying out the method at any temperature range are discussed in detail below. Cellulose hydrolyzing enzymes such as cellulases are hemicellulase, mannanase, xylanase, pectinase, esterase, lipase, manganese peroxidase, lignin peroxidase, laccase, dioxygenase, monooxidase, chloroperoxidase, glyoxal oxidase, glucose oxidase, cellobiose dehydrogenase, and It may be used in combination with other enzymes commonly applied in the pulp and paper field, including cellobiose quinone oxidoreductase.

  Optionally, pulp having coniferous fibers is also contacted with a fiber length reduction promoter. The pulp can be contacted with a fiber length reduction promoter, the pulp can be contacted simultaneously with the enzyme, or the pulp can be contacted after the enzyme contacting and beating steps. Fiber length reduction accelerators include hydrolyzed polymers or copolymers of vinylformamide having a degree of hydrolysis greater than 70%, copolymers of acrylamide and acryloxyethyltrimethylammonium chloride, copolymers of acrylamide and diallyldimethylammonium chloride, free glyoxal, Glyoxalated polyacrylamide, or a mixture thereof.

Reuse and deinking with super thermostable cellulases Thermostable and super thermostable cellulases can be used for enzymatic paper recycling and at very high temperatures, eg, above 70 ° C, above 75 ° C, or above 80 ° C Allows deinking. The recycling and / or deinking process may be performed using a thermostable or super thermostable cellulase at about 80 ° C to about 125 ° C. Operation at very high temperatures allows for more efficient reuse in collapse or wet strength bonding, adhesive removal, polymer additives, latex softening and removal. The high temperature process advantageously also allows for softening and more efficient removal of ink toner, polymer, fat / fatty oil, and ink components.

  In addition to the super thermostable cellulase and xylanase, the recycling and / or deinking process may include a super thermostable alpha-amylase enzyme, as well as other enzymes such as lipases and esterases. Super thermostable alpha amylases include high temperature alpha-amylases such as those available from Novozymes and BASF Enzymes. Exemplary high temperature alpha-amylases are described in US Pat. No. 7,273,740 (US 7,273,740) (Callen et al.) At temperatures as high as 110 ° C., 120 ° C., and 125 ° C. May be used.

  Thermostable and hyperthermostable enzymes can be used in combination with a deinking accelerator. Exemplary deinking accelerators include ionic liquids, N-alkylated ureas, N-alkylated lactams, N-alkylated amides, alkyl ethoxylates, phenol ethoxylates, polyol ethers, and polyols. Exemplary deinking accelerators also include N-methyl pyrrolidone, N-ethyl pyrrolidone, cyclohexyl pyrrolidone, hexyl pyrrolidone, octyl pyrrolidone, cellosolve (2-ethoxyethanol), and butyl cellosolve (2-butoxyethanol). Exemplary ionic liquids include 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, or other anionic salts.

  The deinking process may further include a mineral aid. Exemplary mineral aids include diatomaceous earth, calcined clay, hydrous clay, heavy calcium carbonate, precipitated calcium carbonate, aluminum oxide, calcium silicate, chalk and talc.

Cellulose hydrolyzing enzymes Various cellulose hydrolyzing enzymes can be used in the methods of the present disclosure. Cellulose hydrolyzing enzymes suitable for use in the methods of the present disclosure may be active at temperatures in the range of about 40 ° C. to 55 ° C., or are thermally stable as further discussed elsewhere herein. Alternatively, it may be a super heat stable cellulose hydrolyzing enzyme.

  Cellulose hydrolyzing enzymes are mainly cellulase enzymes and / or cellulase functionalized hemicellulase enzymes. Cellulase enzymes include various types of endoglucanases, exoglucanases including various cellobiohydrase types, and other related enzymes such as glucosidases. Cellulose hydrolyzing enzyme complexes including pure endoglucanase, cellulase mixtures, and cellulosomes may be used in the methods of the present disclosure. Cellulases isolated from, derived from, or modified from bacterial, fungal, archaeal, animal, and plant sources can be used in the methods of the present disclosure. In addition, any isolated, synthetic or recombinant polypeptide having cellulolytic activity is included. In addition, cellulases containing associated hemicellulase enzyme functions, such as xylanases, mannanases, glucanases, and beta-glucanases can be used in the disclosed methods.

  The cellulase used in this disclosure is any glycoside hydrolase containing cellulose hydrolyzable function, including GH family 1, 3, 5-9, 12, 26, 44, 45, 48, 51, 61, and 74 The GH family (Henrissat, 1991, Biochem. J. 280: 309-316) may be included. The cellulase may be of any modular structure, such as a catalytic domain, carbohydrate binding domain, immunoglobulin domain, fibrinectin domain, or dockerin domain. Various complex truncated cellulases may also be used. Cellulases modified by any protein engineering tool may be further used, including various “directed evolution” strategies, and various rational designs.

  The cellulase enzyme used in the methods of the present disclosure can include various amounts of beta-glucanase activity. The cellulase enzyme may also include various types of hemicellulase enzyme activity. Also included are various hemicellulase enzymes or polypeptides that contain concomitant cellulase function or that exhibit cellulase function in specific environmental conditions such as pH, temperature, and ion / salt ranges. Cellulases that contain associated hemicellulase enzyme functions, such as xylanases, mannanases, glucanases, and beta-glucanases can be used in the disclosed methods.

An exemplary cellulose hydrolyzing enzyme useful in the methods of the present disclosure is a cellulase, Humicola insolens obtained from or derived from Chrysosporium lucknowense / Myceliophthora thermophilia. cellulases obtained from or derived from (or produced from Aspergillus) and cellulases obtained from or derived from Trichoderma, but are not limited thereto. Exemplary cellulolytic enzymes useful in the methods of the present disclosure are commercially available. Some exemplary commercial cellulases are listed, but not exhaustive. Exemplary enzymes from Novozymes (Denmark) include Novozym® 613, Novozym® 476, and Celluzyme®, Celluclast®, Carezyme® and FiberCare®. ) Includes products in the family. FibreZyme® G4 powder or liquid is an exemplary enzyme from Dyadic International (Jupiter, FL). Exemplary enzymes from Genencor (DuPont) include Multifect® A40 and cellulases from the Pergalase® or Optimase® family. ONOZUKA cellulase (Yakult Pharmaceutical Co., Ltd., Japan) is a further exemplary enzyme. Pyrolase (R) and Pyrolase (R) 200, Pyrolase (R) HT, Pyrolase (R) HT, super thermostable cellulase from BASF Enzymes LLC (San Diego, CA) Are further exemplary enzymes. Several industrial prepared for biomass / biorefinery hydrolyzable cellulase, e.g. Novozymes Co. Cellic (registered trademark) CTec, CTec2, and CTec3, DuPont Co. Accellerase ^TM 1000, Accellerase ^TM 1500, and Accellerase ^TM TRIO, as well as AlteraFuel CMAX from Dyadic, may also be used in the disclosed method. One particular cellulase enzyme product is Biocellulase W (manufactured by Kerry Food Ingredts Ltd.) manufactured from Tricoderma reesei.

  Cellulases can be produced from a vast microbial source. They can generally be produced from brown rot fungi, white rot fungi, soft rot fungi, bacteria, and actinomycetes. Some genera names include Aspergillus (eg, A. niger, A. oryzae, etc.), Melanocarpus (M. albomyces) ), Humicola (e.g., H. insolens and H. grisea), Tricoderma (e.g., T. reesei, T. biride ( T. viride), T. longibrachiatum), Fusarium (eg F. oxysporium), Myceliophthora, Penicillium ), Bacillus (e.g., B. subtilis and B. licheniformis), Pseudomonas (e.g., P. cellulosa). losa)), Rhodothermus, Phanerochaete, Trametes, Clostridium (for example, C. thermocellum), Cellulomonas (for example, C. fimi (C. fimi)), Streptomyces, and Thermonospora (eg, T. fusca). Some of the microorganisms that contain cellulase activity can be present in the rumen of cattle or other ruminants, but cellulase activity from symbiotic microorganisms can be found in arthropods, such as termites, and certain grasshoppers, or cockroach intestines. Can also be found.

  Several commercial cellulase production sources may be cited herein by way of example, but are not limited thereto. For example, Chrysosporium lucknowense / Myceliophthora thermophilia ("C1 technology") is used by DuPont (formerly Dyadic) for G4 cellulase enzyme production. All cellulase enzymes, including all diversity, modifications, and formulations, or synthetic or recombinant cellulase functional polypeptides isolated from DuPont C1 technology are for the methods of this disclosure. Suitable as an enzyme. Exemplary cellulases include US Pat. No. 7,892,812 (USP 7,892,812), US Pat. No. 7,883,872 (USP 7,883,872), US Pat. 673,618 (USP 8,673,618) and U.S. Pat. No. 8,916,363 (USP 8,916,363). As another example, Humicola insolens and related molecular biological modifications are used as a source by Novozymes for cellulase production. Melanocarpus albomyces is used as the AB enzyme cellulase. Tricoderma is also often used as a source of industrial cellulase enzymes. For example, Tricoderma reesei is known to produce exocellulase and endocellulase enzyme activity, generally along with significant beta-glucanase, xylanase, mannanase and hemicellulase. All of these enzymes and enzyme functions from the genus Tricoderma are included both by natural fermentation and by various genetic modifications including various enzyme modules, domains, and fusion proteins. Cellulase enzymes with enormous beta-glucanase and / or hemicellulase activity sometimes synergize lignocellulosic fibers including OCC pulp, kraft pulp, mechanical pulp, semi-chemical pulp, paper pulp, fluff pulp and dissolving pulp Yes. For fluff pulp, the enzyme modifies the surface fiber chemical and mycellulose distribution and the smoothness / surface morphology of the fiber, which is useful for transporting or sucking liquids with minimal fiber length reduction. Good. In order to dissolve the pulp, the cellulase will remove pulp viscosity (typically less than 10 cps, or less than 7 cps, as required by breaking pulp specifications, while further removing xylan, glucomannan, and other hemicellulose content. ). In one embodiment, the enzyme or polypeptide comprising both cellulase activity and hemicellulase activity is a fusion protein. It should be noted that despite the famous microbial source, the final industrial production of cellulase may be performed from different host organisms. Non-limiting examples of host microorganisms to produce include Aspergillus, Bacillus, E. coli, Pseudomonos, Saccharomyces, and Pichia pastoris )including. Various molecular biology and protein engineering tools can be applied before the enzyme is produced industrially. All these cellulase enzymes, polypeptides containing cellulase activity (including all their variants, modifications) are suitable for use in the methods of the present disclosure as long as appropriate enzyme activity is retained.

Thermostable and hyperthermostable enzymes Thermostable and hyperthermostable cellulase enzymes useful in the methods of the present disclosure are active at temperatures above 60 ° C, above 65 ° C, or above 70 ° C. These temperatures exceed the papermaking temperature range of 40 ° C to 55 ° C.

  Specific examples of thermostable and hyperthermostable cellulase enzymes include cellulase enzyme products from BASF Enzymes. As described herein, the treatment with the cellulase of SEQ ID NO: 6 on the fiber, even in the upper range of the papermaking (paper machine) temperature of 55 ° C., is the fiber length after post-beating of the disclosed method. Did not result in a reduction. However, this cellulase worked very effectively in reducing fiber length at 70 ° C or above 70 ° C. This inactivation and subsequent beating of the cellulase of SEQ ID NO: 6 at papermaking temperature is an unexpected finding. For this disclosure, a temperature range of 60 ° C. to 95 ° C., preferably 65 ° C. to 90 ° C., more preferably 70 ° C. to 85 ° C. is recommended for the cellulase of SEQ ID NO: 6. SEQ ID NOs: 5 and 7 are exemplary coding sequences for the cellulase of SEQ ID NO: 6. High temperatures are recommended for some other types of cellulases. As illustrated, for the cellulase of SEQ ID NO: 2, the recommended temperature range for enzyme treatment is 65 ° C to 120 ° C, preferably 70 ° C to 120 ° C, more preferably 80 ° C to 115 ° C. The pH range may vary from pH 4 to pH 12, pH 5 to pH 12, pH 6 to pH 12, pH 6 to pH 11, pH 6 to pH 10.5, pH 6 to pH 10, or pH 6 to pH 9.5. Exemplary coding sequences for the cellulase of SEQ ID NO: 2 include SEQ ID NOs: 1 and 3.

  In addition, cellulases, such as the exemplary cellulases of SEQ ID NOs: 2 and 6, may be engineered to further improve activity. For example, they may be concentrated (eg by membrane) to a higher enzyme concentration (and therefore activity) during manufacture. They may be dried, for example by freeze-drying or by spray-drying, together with inactivated and / or protective materials, into powders with a higher enzyme content (and therefore activity) during enzyme production. Inert materials include various types of clay, kaolin, bentonite, mineral particles, aluminum oxide, calcium silicate, calcium carbonate, talc, silica gel, silica oxide, sand, diatomaceous earth, zeolite, sorbitol, xylitol, mannitol, maltodextrin, It may be trehalose, resistant starch or the like. Protective materials, when used, are glycerol, low molecular weight PEG, medium high molecular weight PEG, Tween, polyethylene oxide, polyacrylamide, anionic polyacrylamide, glycerol ester (eg ethoxylate), PEG ester (eg ethoxylate), and Phenol ester (eg ethoxylate), albumin, protein, soy protein, milk protein, casein, sodium caseinate, whey protein, milk protein isolate, gelatin, low viscosity alginate, low viscosity CMC, low viscosity gellan gum, low viscosity polyvinyl Pyrrolidone (PVP) can be included.

  Cellulases can be further improved in terms of fermentation yield by both molecular biology and process improvement.

  In a broad sense, the hyperthermostable enzyme may be derived from a hyperthermophilic microorganism. They can also be further improved, modified, synthesized, or recombinant beyond any wild type source via any known molecular biology and protein engineering tools. Those tools include both random and site-specific mutations.

  Preferably, these enzymes are derived from hyperthermostable microorganisms. Examples of hyperthermophilic organisms are bacteria, such as Thermotoga (eg, various Thermotoga maritima strains, T. neapolitana, and T. thermarum), Includes Thermocrinis (T. ruber), and Aquifex (A. pyrophilus and A. aeolicus). Some thermophilic bacteria are associated with hyperthermophilic organisms such as Calderobacterium hydrogenophilum, Thermosipho africanus, and Fervidobacterium hydrogenophilum Yes. The cellulase enzyme from the bacterium, Rhodothermus marinus, has also been reported to function as a super thermostable cellulase that was stable at 90-100 ° C. (Hreggvidson et al. (1996) Appl. Env. Microbiology, 62 (8): 3047-3049). Examples of extreme thermostability also include enzymes isolated or genetically engineered from various strains of Dictyoglomus thermophilum.

  Examples of hyperthermophilic archaea and some related archaea are Sulfolobus (S. acidocaldarius, S. solfatarius), Metallosphaera. ) (M. sedula), Acidianus (A. infernus), Stygiolobus azoricus, Sulfurococcus mirabilis, Sulfrisfera・ Sulfurisphaera ohwakuensis, Thermoproteus tenax, Pyrobaculum (P. islandicum), P. aerophilum, Thermofilum (T. pendens, T. librum), Thermocladium (Thermocladium) (T. modestius), Caldivirga (C. maquilingensis), Desulfurcoccus (D. mucosus) D. fermentans), Staphylothermus (S. marinus), Sulfophobococcus (S. zilligii), Stetteria (S. hydrogenophila), Aeropyrum (A. pernix), Ignicoccus (I. islandicus), Thermos Thermosphaera (T. aggregans), Thermodiscus (T. maritimus), Pyrodictium (Pyrodictium) (P. P. occultum), Hyperthermus (H. butylicus), Pyrolobus (P. fumarii), Thermococcus (T) T. cele), Pyrococcus (P. furiosus), P. abyssi, P. horikoshii, P. woesii ), Archaeoglobus (A. fulgidus, A. veneficus, A. profundus), Ferroglobus (F. placidus) )), Methanothermus (M. fervidus, M. sociabilis), Methanococcus (M. janaschii), M. Igneu (M. igneus), M. thermolitho-trophicus), Methanopyrus (M. kandleri), and Thermoplasma (T. acid film (T. acidophilum), T. volcanium).

  All cellulases derived from said hyperthermophilic and hyperthermophilic archaea, and related bacteria and archaea may be used in the methods of the present disclosure. Furthermore, any cellulase and beta derived from said hyperthermophilic organism, isolated from said hyperthermophilic organism, encoded by a modified gene or synthesized, or comprising a segment of such gene Glucanases are included in the present disclosure provided they exhibit appropriate enzyme activity. Improved cellulases by directed evolution, by site-directed mutagenesis, or by other approaches such as enrichment of hyperthermophilic organisms growing on suitable cellulose substrates (Graham et al. (2011) Nature Communications ) May be used in the methods of the present disclosure.

  Thermotoga seed strain FjSS3-B. 1, Thermotoga maritima MSB8, and cellulase derived from Thermotoga neapolitana (Endoglucanase, Exoglucanase) (Sunna et al. (1997) “Glycosyl hydrolases frm 13”. Are specifically mentioned for use in the methods of the present disclosure. US Patent No. 5,925,749 (USP 5,925,749), US Patent No. 5,962,258 (USP 5,962,258), US Patent No. 6,008,032 (USP) All cellulases from Thermotoga maritima as described in US Pat. No. 6,245,547 and US Pat. No. 6,245,547 (USP 6,245,547) are disclosed herein. Suitable for use in the method. US Pat. No. 5,789,228 (USP 5,789,228), US Pat. No. 6,001,984 (USP 6,001,984), US Pat. No. 6,074,867 (USP) 6,074,867), US Pat. No. 6,329,187 (USP 6,329,187) and US Pat. No. 7,465,571 (USP 7,465,571). Also useful are glucanases, particularly endoglucanases from "AEPII la". All cellulases or glucanases, as well as US Pat. No. 7,9601,48 (USP 7,9601,48) (Steer et al., 2011), US Patent Application Publication No. 20140295523 (US Publication No. 20140295523) (Steer et al.) No. 7,422,876 (USP 7,422,876) (Short et al.) And US Pat. No. 8,426,184 (USP 8,426,184) (Blum et al.). Those polypeptide sequences and fragments as taught in are suitable for use in the methods of the present disclosure. U.S. Patent Application Publication No. 20150072397 (US Publication No. 1) containing various nucleotide sequence modifications and variants encoding cellulases or polypeptides in various combinations, for example, variants related to Thermotoga maritima cellulase. 20150072397) is suitable for use in the method of the present disclosure. The methods used for enzymatic modification are error prone PCR, shuffling, oligonucleotide-specific mutagenesis, assembly PCR, sexual PCR mutagenesis, in vivo mutagenesis, cassette mutagenesis, recursive ensemble mutagenesis. mutagenesis), exponential ensemble mutagenesis, site-directed mutagenesis, gene restructuring, gene site saturation mutagenesis (GSSM), synthetic ligation ligation SL ), Chromosomal Saturation Mutagen sis) (CSM), or combinations thereof. In other embodiments, the modification methods include recombination, recursive sequence recombination, phosphothiolate modified NDA mutagenesis, uracil-containing template mutagenesis, gap double stranded mutagenesis, point mismatch repair mutagenesis, repair deficient host strain mutation Induction-reduction host purification mutagenesis, chemical mutagenesis, radioactive mutagenesis, deletion mutagenesis, restriction-selection mutagenesis, restriction enzyme purification mutagenesis, gene synthesis Ensemble mutagenesis, creation of chimeric nucleic acid multimers and combinations thereof.

Some cellulases from hyperthermophilic bacteria and / or their non-naturally occurring variants are described in International Patent Publication No. 2009/020459 (PCT publication WO 2009/020458). In their entirety). Included in the entire specification of International Patent Publication No. 2009/0204059 (WO 2009/02059), which is incorporated herein by reference, is the DNA and amino acid SEQ ID NOs listed below. It is. They include the following:
International Patent Publication No. 2009/020449 SEQ ID NO: 1 and 2 (wild-type “parent” T. maritima cellulase), disclosed herein as SEQ ID NOs: 5 and 6, respectively;
International Patent Publication No. 2009/020449 SEQ ID NO: 3 (wild-type DNA, modified to eliminate alternating start), disclosed herein as SEQ ID NO: 7;
• International Patent Publication No. 2009/020458 SEQ ID NO: 6 and 7 (gene site saturation mutagenesis (“GSSM”) mutation in combination with “7X”), disclosed herein as SEQ ID NOs: 8 and 9, respectively. ;
International Patent Publication No. 2009/020459 SEQ ID NOs: 8 and 9 (GSSM mutations in combination with “12X-6”), disclosed herein as SEQ ID NOs: 3 and 2, respectively;
International Patent Publication No. 2009/020459 SEQ ID NOs: 10 and 11 (GSSM mutations in combination with “13X-1”), disclosed herein as SEQ ID NOs: 10 and 11, respectively;
International Patent Publication No. 2009/020459 SEQ ID NOs: 12 and 13 (GSSM mutations in combination with “12X-1”), disclosed herein as SEQ ID NOs: 12 and 13, respectively;
International Patent Publication No. 2009/020459 SEQ ID NOs: 16 and 17 (alternative cellulase breakers from Thermotoga species), disclosed herein as SEQ ID NOs: 14 and 15, respectively;
International Patent Publication No. 2009/020449 SEQ ID NOs: 18 and 19 ("7X" codon optimized version of T. maritima cellulase for maize expression), SEQ ID NOS: 16 and 17, respectively, herein And International Patent Publication No. 2009/020659 SEQ ID NOs: 20 and 21 ("12X-6" codon optimized version of T. maritima cellulase for maize expression), this Disclosed in the specification as SEQ ID NOS: 18 and 19, respectively.

  In addition to the nucleotide and amino acid sequences described above relating to wild-type and evolved variants of cellulase from Thermotoga maritima strain MSB8, Table 2 from International Patent Publication No. 2009/020458 and Example 5 Additional variants listed in are also cellulase enzymes useful in the practice of the disclosed methods. The cellulases encoded by SEQ ID NOs: 1, 4 and 20, and the cellulase of SEQ ID NO: 21 are other cellulases useful in the methods of the present disclosure.

  In addition to the super thermostable cellulase enzyme, an exemplary super thermostable xylanase is a patented international publication no. (WO 2009/045627) (Gray et al.) And those described in International Publication No. 2016/073610 (WO 2016/073610) (Widner et al.). SEQ ID NO: 22 is a sequence of a xylanase useful in the disclosed method. SEQ ID NO: 23 is an exemplary coding sequence for the xylanase of SEQ ID NO: 22.

Thermostable and hyperthermostable cellulase and hemicellulase sequences Embodiments disclosed herein are used for their use in the manufacture of pulp and paper, from 70 ° C to 125 ° C, optionally from 80 ° C to Superthermostable polypeptides having cellulase activity or in combination with hemicellulase activity may be used at a temperature of 100 ° C. In some embodiments, the hyperthermostable cellulase and / or hemicellulase is from bacteria, fungi, or archaea, or any combination (mixture) thereof. Further useful in the methods of the present disclosure are (i) at least about 50%, 51%, 52%, 53%, for any one of the exemplary polypeptides described herein, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70% 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87 %, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more, or 100% (complete) sequence An isolated, synthetic or recombinant polypeptide having cellulase activity, including amino acid sequences having identity It may be in, where, in one aspect (optionally), sequence identity is determined by or by visual inspection analysis by sequence comparison algorithm.

Table 1 shows exemplary thermostable and hyperthermostable cellulases and hemicellulases that may be used in the methods of the present disclosure.

Fiber Length Reduction Accelerator As shown herein, copolymers of acrylamide and acryloxyethyl-trimethylammonium chloride have been found to be very effective in operations to effect enzymatic fiber length reduction. Has been. These copolymers are commercially available from, for example, BASF polymers, such as Percol® (eg, Percol® 3232L, Percol® 3035, etc.), Organopol® (eg, Organopol®). Trademark) 5585, Organopol® 6465, Organopol® 6485, etc.), including Zetag polymer, less than about 10 kilograms (drug) per ton of pulp (less than about 10 kg / ton), less than about 5 kg / ton, Used at a dosage of about 0.2 kg / ton to about 5 kg / ton, or about 1 kg / ton to less than about 5 kg / ton. At doses higher than 10 kg / ton (pulp), these copolymers usually have an adverse effect on enzyme beating in the present disclosure. Copolymers of acrylamide and diallyldimethylammonium chloride may also be used at dosages of about 0.2 kg / ton to about 5 kg / ton.

Other agents useful as length reduction promoters are vinylamine (or vinylamine-containing) polymers or copolymers. These include, for example, commercially available polymers of BASF, such as Xelorex ^™ (eg, Xelorex ^™ RS1300, which is a highly hydrolyzed poly n-vinylformamide with more than 90% amine groups). As shown herein, these agents in combination with enzyme treatment have a surprisingly good effect on fine bulk at reduced fiber length, fine smoothness, or a given freeness. The required dose is usually higher than 5 kg / ton or 10 kg / ton to demonstrate the effect.

  Another drug useful as a length reduction promoter is free glyoxal. As shown herein, free glyoxal in combination with enzyme beating provides a surprisingly improved beneficial fiber length reduction. A suitable dose of free glyoxal is 0.2 kg / ton to 1 kg / ton, or 1 kg / ton to 5 kg / ton. Optionally, the free glyoxal may be mixed with the copolymer of acrylamide and acryloxyethyl-trimethylammonium chloride or the copolymer of acrylamide and diallyldimethylammonium chloride discussed above, or mixed with a polymer or copolymer containing vinylamine. Good. Optionally, free glyoxal may be added in combination with the glyoxal peroxidase enzyme.

  In general, a partially or fully hydrolyzed polymer n-vinylformamide, or a polymer n-vinylacetamide, polymer, preferably having a degree of hydrolysis greater than 75%, or a degree of hydrolysis greater than 85% An n-vinyl imide, such as a polymer n-vinyl succinimide, may be used in the disclosed method. Also included are copolymers of n-vinylformamide and vinylamine or its hydrochloride salt, preferably those having more than 75% vinylamine. Other copolymers include copolymers of n-vinylformamide and diallyldimethylammonium chloride, copolymers of n-vinylformamide and acrylamide, all having varying degrees of free amine groups. Various polyallylamides are also included. Polyvinylamines produced by any method included from polyacrylamide by the Hoffman degradation method are useful in the methods disclosed herein.

Any chemical agent Any chemical agent may be listed herein, some of which have some favorable effect on enzymatic fiber length reduction, but at lower dosages than the fiber length reduction promoters described above. Has an effect. They can in principle be used as well, but may also be used together as further additives for the present disclosure.

  Other exemplary chemical agents include g-Pam (glyoxalate polyacrylamide with low levels of free glyoxal), which may be used to increase tensile strength or wet strength, but enzymatic fiber Has little effect on length reduction. Also included is polyDADMAC, which is a cation-retaining polymer with very limited effectiveness. Polyethyleneimine is also included, but has some favorable effects, but the dosage is less effective and has the side effect of yellowing.

  Other applicable paper additives are other copolymers of diallyldimethylammonium chloride (DADMAC), copolymers of vinylpyrrolidone (VP) and quaternized diethylaminoethyl methacrylate (DEAMEMA), cationic polyurethane latex, cationic polyvinyl Alcohols, polyalkylamines, dicyandiamide copolymers, amine glycidyl addition polymers, poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene] dichloride, poly (hexamethylenebiguanide hydrochloride) (ie PHMB), cationic metal ions such as Water-soluble aluminum, calcium, and zirconium salts (these bound ions serve as active complex sites for sizing and other paper chemicals Rukoto can), and cationic dendrimers include, for example, PAMAM having an amino surface groups (polyamidoamine) dendrimers, and polypropylene imine dendrimer having an amino surface groups. They are used during papermaking or fiber networking to form crosslinkers such as cationic starch, dialdehyde starch, dialdehyde maltodextrin, multifunctional carboxylic acids such as l, 2,3,4-butanetetracarboxylic acid (BTCA). , Poly (maleic acid), (PMA), poly (itaconic acid), citric acid (preferably with catalyst), and water-dispersible or water-soluble bifunctional, multifunctional carbodiimides and / or polycarbodiimides, such as 1 1,6-hexamethylenebis (ethylcarbodiimide); 1,8-octamethylenebis (ethylcarbodiimide); 1,10-decamethylenebis (ethylcarbodiimide); 1,12 dodecamethylenebis (ethylcarbodiimide); PEG-bis ( Propyl (ethylcarbodiimide)); 2,2′-dithioethylbis ( Chill carbodiimide); 1,1'-dithio -p- phenylene bis (ethylcarbodiimide); and 1,1'-dithio -m- phenylene bis (ethylcarbodiimide) including.

  Further processing of the modified pulp fiber of the disclosed method may be an internal sizing agent for the fiber, such as an AKD sizing agent or an ASA sizing agent. Further processing is, for example, with starch surface sizing, as well as non-reactive sizing agents such as, but not limited to, non-reactive polymer surface size emulsions BASOPLAST® 335D, Air Products and Chemicals (Allentown, manufactured by BASF) PA) emulsion of vinyl acetate and butyl acrylate copolymer FLEXBOND® 325, and Solenis (formerly Ashland Water Technologies, Wilmington, DE) non-reactive sizing agent PENTAPRINT® It may be a surface treatment for the formed web.

Wood and Non-Wood Pulp Fiber As used herein, “pulp fiber” refers to both wood pulp and non-wood pulp. Wood pulp fibers are those derived from hardwoods, conifers, or a combination of hardwoods and conifers prepared for use in papermaking furnishes by any known appropriate digestion / pulping, beating, or bleaching operation included. For example, the pulp can be of any type, such as but not limited to mechanical pulp, thermomechanical pulp, CTMP, RMP, APMP, groundwood pulp, soda pulp, soda AQ pulp, steam explosion or aqueous water extraction pulp, green liquor pulp , Sodium carbonate pulp, ammonia pulping, various variations of kraft pulp, prehydrolyzed kraft pulp, various sulfites pulp, acidic sulfite pulp, neutral sulfite pulp, NSSC pulp, polysulfide pulp, various solvent pulped pulp, alcohol pulp, alcohol -SO ₂ pulp may be pulp from ASAM pulps, and any other known pulping methods or fiber decomposition.

  As used herein, the term “broadwood pulp” refers to fibrous pulp derived from deciduous tree (angiosperm) woody material, while “conifer pulp” is derived from woody material of coniferous tree (gymnosperm). Refers to the fibrous pulp to be used.

  Useful pulp fibers include, but are not limited to, kenaf, hemp, jute, flax, sisal hemp, abaca, wheat straw, rice straw, bagasse, bamboo, corn strain, corn cobwebs, corn It may be derived from kernel fiber, peanut shell, ramie, seaweed, seaweed, sugar beet, orange peel, orange (fruit) fiber, lemon peel, switchgrass, and cotton linter. Any bleached pulp, partially bleached or semi-bleached pulp, unbleached pulp, high copper pulp, dissolving pulp, fluff pulp, sawdust pulp are included. Bleached or unbleached waste paper pulp and deinked pulp may also be utilized in the disclosed process. The pulp may have undergone any processing history that is usual in pulping and bleaching, or for example water / steam processing, ammonia pulping (with or without explosion), or caustic soda extraction of chips prior to pulping It may be intentionally modified by acid hydrolysis of chips or pulp, enzyme (cellulase or hemicellulase) hydrolysis of pulp or chips, oxygen delignification, and “cold soda” treatment of chips or pulp. Any bleaching chemicals as known in the pulp and paper industry or academia are included.

Intracrystalline Swelling Agent for Cellulase The present disclosure can also be used in combination with any intracrystalline swelling agent that can effectively swell cellulose fibers. This is particularly useful when used in combination with super thermostable cellulases, hemicellulases, and laccases. The two main types of intracrystalline cellulose swelling agents are ionic liquids and selective organic solvents. Some intracrystalline cellulose swelling agents can act as dissolution solvents for cellulose under certain conditions. Accordingly, such intracrystalline swelling agents are used only at dosages (in the aqueous phase) or reaction conditions that are sufficient to cause intracrystalline swelling of the cellulose fibers but not sufficient to dissolve the cellulose.

  Examples of such intracrystalline swelling agents include ionic liquids (IL). Ionic liquids consist of large amounts of organic cationic and anionic moieties. The cation of IL may typically be based on ions of imidazolium, pyridinium, pyrazolium, pyrrolidinium, triazolium, thiazolium, phosphonium, ammonium, guanidinium, and corinium. In the present disclosure, ILs based on imidazolium, ammonium, guanidinium, and pyridinium cations are all included together with applicable anions. Examples of specific ILs included in this disclosure include, but are not limited to, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride 1-N-butyl-2,3-dimethylimidazolium chloride, 1-N-2,3-dimethylimidazolium bromide, 1-butyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium Mate, N-ethyl-N-methylimidazolium methylphosphonate, 3-methyl-N-butylpyridinium chloride, benzyldimethyl (tetradecyl) ammonium chloride, and 1,1,3,3-tetramethylguanidinium acetate. One preferred IL is 1-ethyl-3-methylimidazolium acetate. In addition, 1-butyl-3-methylimidazolium acetate is preferable. Other intracrystalline swelling agents, N-methylmorpholine-N-oxide (NMMO) are also mentioned here. The amount of IL used is based on conditions that cause intracrystalline swelling, but is still not sufficient to dissolve the cellulose. For example, in one option, 0.2% to 50% IL can be applied. The treatment temperature depends on the thermostable enzyme and is usually between 70 ° C and 120 ° C, between 75 ° C and 120 ° C, or between 80 ° C and 105 ° C.

  Examples of such intracrystalline cellulose swellable organic solvents (in the aqueous phase) include, but are not limited to, formamide, DMSO, N-alkylated lactams, N-alkylated ureas, N-alkylated amides, and especially tetramethylurea Tetraethylurea, dimethylpropyleneurea, dimethylethyleneurea, N-cyclohexylpyrrolidinone, N-methylpyrrolidinone, N-ethylpyrrolidone, N-octylpyrrolidone, dimethylacetamide and hexamethylphosphoric acid amide. They include various polyols or glycol ethers such as cellosolve (2-ethoxyethanol), butylcellosolve (ethylene glycol monobutyl ether), butyl carbitol (diethylene glycol monobutyl ether), ethyl carbitol, propylene glycol monomethyl ether, dipropylene glycol Also includes monomethyl ether.

Paper, Pulp and Products The disclosed method provides modified pulps useful for making any paper and paper stock material. Accordingly, the present disclosure includes products containing modified pulp. Paper and web products containing the modified pulp of the present disclosure may be of various paper grades, uncoated or coated, unbleached, semi-bleached or fully bleached paper grades, all types of printing and writing paper , Uncoated free sheet, surface sized paper, high yield paper (including mechanical or chemical mechanical pulp), newspaper web, LWC, film coated machine grade, surface treatment machine grade, all types of paperboard, uncoated paperboard, coated paperboard , White paperboard, brown paperboard, SUS, SBS, multilayer paperboard, FBB, folding carton, liner board, craft paper, sack paper, wrapping paper, release paper, silicone paper, recycled brown paper, recycled white paper, deinked paper, paper filter , Mercer paper, polymer impregnating base paper, composite base paper, APPI paper plate, paper cup, impregnating paper such as Formica, sulfite paper, Interleaving paper and cardboard, tissue, towels, napkins, wipes, non-woven fabrics, personal care pads, cigarette paper, fluff pulp rolls, dissolving pulp rolls and sheets, any cellulose-containing web used as printing or digital printing media Including.

  The method of the present disclosure comprises a lignin-free or lignin-containing (wood or non-wood) pulp processed according to the method of the present invention from special materials such as cellulose foam, cellulose film, microcrystalline cellulose, microfibrillated cellulose, nanocellulose. Alternatively, it can be used to produce nanofibrillated cellulose materials. Accordingly, the present disclosure is a product containing a modified pulp, cellulose foam, cellulose film, microcrystalline cellulose, micronized from lignin-free or lignin-containing (wood or non-wood) pulp processed by the method of the present disclosure. Includes products comprising fibrillated cellulose, nanocellulose or nanofibrillated cellulose material.

Examples Products, compositions, methods of manufacture and methods of use are described in more detail by reference to the following experimental examples. These examples are provided for purposes of illustration only and are not intended to be limiting unless otherwise specified. Accordingly, the products, compositions and methods of the present disclosure should in no way be construed as limited to the following examples, but rather include all the variations that will become apparent as a result of the teaching provided herein. That should be interpreted.

  The following materials were used in the examples.

  Cellulase A is a commercially available powdered enzyme product obtained from Chrysosporium lucknowense / Myceliophthora thermophilia and has mainly endoglucanase activity.

  Cellulase B is a super thermostable cellulase having the amino acid sequence shown in SEQ ID NO: 6. Usually, it is marketed as a diluted enzyme solution having endoglucanase activity at 80 ° C. Considering the diluted concentration of the enzyme solution, it was used at a high dose in the examples.

Xelorex ^™ RS1300 (BASF Corporation, Florham Park, NJ) is a highly hydrolyzed polyvinylformamide with over 90% amine groups.

  Percol® 3232L (BASF Corporation, Florham Park, NJ) is a copolymer of acrylamide and acryloxyethyl-trimethylammonium chloride.

  The following experimental methods were used in the examples.

  PFI refining or beating is a standard laboratory scale pulp refiner used in the pulp and paper industry, as described in TAPPI standard T248.

  TAPPI Handsheets (TAPPI handsheets) were performed according to TAPPI standards T205 and T220.

  TAPPI Freeness was tested according to TAPPI standard T227.

  TAPPI Tensile Strength and index (TAPPI tensile strength and index) were tested according to TAPPI standard T494.

  TAPPI Shelffield Smoothness (TAPPI Sheffield smoothness) was tested according to TAPPI standard T538.

  TAPPI Tear Strength (TAPPI Tear Strength) was tested according to TAPPI T414. In this study, T414 was also used for DSF (Dynamic Sheet Former) sheet CD tensile test (“CD” = “lateral eye”).

  TAPPI Bursting Strength was tested according to TAPPI T403 om-10.

  Volley beater beating was performed under the total load of a 12 kg weighing plate and for each beating experiment, a total of 400 o. d. Gram pulp was beaten at 2% concentration with different beat times (od = furnace drying).

Dynamic sheet forming machine (DSF) sheet production is carried out with hand-sheet 70 g / m ² , and 2% concentrated paper stock is diluted with tap water to 0.5% concentrated stock stock. did. The DSF settings were: drum speed = 1200 m / min, pump speed = 500 rds / min, spray nozzle: 2515. The formed DSF handsheet was pressed at 60 psi and dried at 240 ° F. for 5 minutes on a drum dryer. The dried sheet was then subjected to standard laboratory conditions: 72 ° F. ± 5 ° F., 50% ± 5% R.D. H. Adjusted overnight. The adjusted handsheet was then tested.

  Fiber Length Distributions (fiber length distribution) were tested at the FQA Fiber Length Analyzer by OpTest, Model LDA02.

  Paper bulk was measured according to TAPPI standard T411.

Example 1 PFI enzyme beating Bleached US Southern Pine Craft Pulp with Cellulase A at a dosage of 0.2 kg (enzyme) / ton (pulp) (kg / T) and a dosage of 2.0 kg / T , 55 ° C papermaking temperature, 4% pulp concentration and pH 6 for 1 hour. The enzyme treated pulp was then subjected to standard TAPPI PFI beating (gap 0.2 mm), from which a TAPPI standard 1.2 gram handsheet was produced and tested. The results are shown in Table 2. Freeness and tensile index data as a function of energy (PFI rpm) are plotted in FIGS. 1 and 2, respectively. In Table 2, “NA” means “not tested”.

  FIG. 1 shows that enzymatic treatment of Southern pine pulp can reduce beating energy. FIG. 2 shows that enzyme treatment can enhance the development of paper strength for the case of unbeaten pulp or for low levels of beating. However, at higher beating levels (or lower freeness levels), the inherent strength is not improved over the control conifer.

  In practice, these results can be used to reduce the beating energy, de-bottle-neck refiner capability and / or improve the strength of the paper of a certain freeness target. . Note that for recycled furnishes or once dried pulp, the beneficial effect is typically more pronounced due to the action of the enzyme on removing the “keratinization” caused by drying, finishing and utilization. Pulp species and various refiner types / strengths will also have dramatic effects.

Example 2 Enzyme treatment by co-beating with Xelorex ^{™ In} this example, Southern pine kraft pulp was treated with 2 kg / T cellulase A under the same conditions as in Example 1. After enzyme treatment, Xelorex ^™ RS1300 was added to the pulp at a dose of 10 kg / T and the pulp was beaten together. Sheffield smoothness and fiber length distribution (tested with FQA fiber length analyzer) were tested. PFI beating and test results are also listed in Table 2. Smoothness is plotted in FIGS. 3 and 4 as a function of energy (PFI revolution) and freeness (CSF), respectively. The fiber length distribution is plotted in FIG. 5 as a function of freeness.

FIG. 3 and FIG. 4 show that the cellulase enzyme treatment and subsequent co-beating with Xelorex ^™ unexpectedly improved smoothness (decreased Sheffield value) after co-beating. This substantially better smoothness after co-beating was also clearly shown for a given freeness versus control beating. In comparison, treatment with cellulase enzyme alone (no Xelorex ^™ ) at any dose tested showed no improvement in smoothness when compared at similar freeness (FIG. 4). However, the smoothness improvement for cellulase enzyme treatment and subsequent co-beating with Xelorex ^™ could be accelerated or accelerated by cellulase enzyme beating.

The data in FIGS. 3 and 4 suggests that controlled internal fiber modification (“damage”), exemplified by enzymatic fiber length reduction, has demonstrated a synergistic effect with Xelorex ^™ co-beating. The synergistic effect is also evident in the fiber length reduction data shown in FIG. 5, which corresponds to the apparent synergy.

  This beating synergy in smoothness is expected to be used to improve the paper surface and printing properties of rough fibers such as Southern pine fibers, Southern hardwood fibers, or other rough fibers such as Douglas fir and hemlock. The It can also be used to alleviate fuzz on the paper surface and the paper peeling problem of hardwood containers.

Example 3 Bulk Improvement by Energy Saving against Beating Enzyme treatment was performed at 48 ° C., 4% concentration, pH 6.6, 2 kg / T cellulase A enzyme dosage for commercial resurrected bleached southern pine kraft pulp For 1 hour. After the enzyme treatment, the pulp was diluted to 2% concentration and beaten to various freeness levels with a beater at various beat times (minutes). The enzyme beaten pulp is then blended with 10 kg / T Xelorex ^™ RS1300 and made into a target DSF (dynamic sheet former) sheet of 70 g / m ² , dried, adapted and tested for paper properties did. The control pulp was not enzyme treated and not blended with Xelorex ^™ prior to DSF sheeting. The results normalized at 70 g / m ² are listed in Table 3.

FIGS. 6, 7 and 8 show that beating energy savings were achieved with the enzyme, but the paper bulk increased significantly after beating as well. Surprisingly, an increase in paper bulk was also shown when compared to a given beaten freeness. However, it should be noted that the paper bulk before beating did not show increased paper bulk. It is believed that the synergistic action of the enzyme beating process and Xelorex ^™ resulted in bulk evolution.

  Contrary to prior art claims that cellulase enzyme in combination with polyvinylamine substantially improves paper strength, FIG. 9 is identical in the general papermaking freeness range of 400-600 csf, except for unbeaten pulp. It shows that there is almost no change in tensile strength by beating freeness. Unbeaten pulp refers to pulp that has not been beaten, that is, pulp at 0 minutes. This was also indicated by tear strength (see Figure 10) and burst strength (see Table 3), which actually decreased after beating (except for unbeaten pulp). These findings are consistent with intentional and controlled damage inside the fiber, as exemplified by the reduction in fiber length during enzyme beating.

Example 4 Super thermostable cellulase enzyme-does not affect beating energy at papermaking temperature (comparison)
A commercially available diluted enzyme preparation containing a super thermostable cellulase, cellulase B, was used in this example. Enzymatic treatment was performed on fresh bleached southern pine pulp under the same conditions as in Example 1 for 1 hour at a typical paper (paper machine) temperature of 55 ° C., pH 6 and a concentration of 4%. The treated pulp was beaten at a 2% concentration with a valley beater. Beating / beater data is shown in Table 4 and plotted in FIG. Unlike the results using cellulase A, the thermostable cellulase B enzyme at this temperature (55 ° C.) was beaten despite the use of a very high enzyme dose (20 kg / ton) of cellulase B. It showed no effect on energy.

Example 5 Possibility of use of super thermostable cellulase enzyme in papermaking As shown in Example 4, the super thermostable enzyme cellulase B did not function effectively at typical papermaking temperatures. Therefore, the function of cellulase B was tested at a higher temperature in this example as well as in Example 8. In this experiment, the enzyme treatment was performed for 4 hours at 70 ° C. and pH 6 against another source of Southern pine pulp. Conditions comparable to these experimental conditions are actually obtained / achieved upstream, for example, in an industrial paper mill pulp mill process, bleach plant process, brown HD tower, or bleach HD tower. Control pulp (no enzyme treatment) and various enzyme treated pulps were beaten with a valley beater as before. The freeness and fiber length distribution (FQA fiber average length) were evaluated. The data is shown in Table 5 and graphed in FIGS. The resulting beating / beater curve is written alongside cellulase A (55 ° C., 4 hours), indicating that cellulase B actually works very well under these conditions (70 ° C., pH 6). FIG. 12 demonstrates that super thermostable cellulase B may be effective for beating. FIG. 13 shows the effectiveness of super thermostable cellulase B in reducing fiber length.

Table 5 summarizes the volley beater beat data of these experiments, including the effects of previously demonstrated fiber length reduction promoters such as Percol® 3232L and Xelorex ^™ RS1300.

  One of the unique advantages of using a thermostable enzyme that operates at a pulp mill or bleach plant temperature that has a higher temperature than the paper / paper mill is that the enzyme-treated pulp (with or without washing) is used in the papermaking process. When transferred to (stock preparation or paper machine), it has little or no enzyme activity function at the temperature of the paper machine white water system and therefore has no long-term side effects on the paper making system. Unlike in the case of normal (mesophilic) cellulases (eg cellulase A), the remaining superheat-stable enzyme is inhibited during the papermaking temperature, if still present in the pulp, and is inactive by the drying process. Will be modified / denatured. Another option is to perform cellulase enzyme treatment (both normal cellulase and thermostable cellulase embodiments) in the bleach HD tower (end of bleach plant operation), which is optionally extended. Retention (and reaction) time is also provided, thus allowing a reduction in enzyme dosage.

Example 6 Transformation of Southern Pine Fiber Morphology by Cellulase Enzyme (Valley Beater Experiment)
This example provides a low-strength laboratory beating device such as Southern Pine by a Valley Beater while maintaining pulp freeness in the range of 400 CSF to 650 CSF (preferred papermaking region) and preferably in the range of 500 CSF to 650 CSF for paperboard. The reduction of the fiber length (length weighted average length) from 2.3 mm to 2.5 mm to 0.6 mm to 1.8 mm is shown.
Note that these trends are relative comparisons since the trends are expected to be similar, but the disc refiners have different values (disc refiners or methods using the Conflo refiners are discussed in Example 9). .

  The fiber length numbers obtained in this example are summarized in Table 5 along with the enzyme and beating data. Fiber length data is plotted in FIG. These data show that, relative to speaking, it is possible to reach the target area by enzyme beating alone, but require a higher dose of enzyme. Large enzyme dosages are not preferred because they can not only be economical, but also affect excessive degradation of paper strength characteristics at such large enzyme dosages.

Example 7 Transformation of Southern Pine Fiber Form at Optimal Enzyme Dose in Synergy with Fiber Length Reduction Promoter This example is combined with a fiber length reducer (Xelorex ^™ or Percol®) ( Demonstrate the use of optimal (economic) doses of enzyme with energy savings, fiber length reduction to the target freeness range. Furthermore, this example demonstrates the use of an enzyme in combination with a fiber length reducing agent (Xelorex ^™ or Percol®) added after beating.

  Data are shown in Table 6. Again, these data are relative comparisons using a Valley Beater as a refiner. Trends are expected to be similar, but values based on disc refiners will be different.

15 and 16 show that the co-beating control with Percol 3232 (no enzyme treatment) slightly increased the beating energy consumption over the control single beating, but had no effect on the relationship between fiber length and freeness. Indicates that there was no. Surprisingly, however, the fibers treated with the 0.4 kg / ton cellulase A dose were still co-beaten with 2 kg / ton Percol® 3232 or 10 kg / ton Xeleorex ^™ RS1300. It showed a synergistic effect on fiber length reduction while maintaining beating energy savings. Thus, enzyme / chemical co-beating makes it possible economically to allow small doses of enzyme treatment to reach the target fiber reduction zone, while also having target freeness.

FIG. 17 shows fiber length reduction while beating after 0.4 kg / T cellulase A enzyme treatment followed by addition of 2 kg / ton Percol® 3232 achieves the energy savings provided by cellulase A. Shows that it was possible to reach the target freeness range (FIG. 15). At this 0.4 kg / T enzyme dose, Xelerox ^™ added later also improved the fiber length difference and drainage relationship when compared to 0.4 kg / ton single enzyme beating Was not sufficient to reach the preferred target freeness region. Larger doses of enzyme treatment are expected to allow reaching the preferred target freeness region. In contrast, single 0.4 kg / T cellulase A beating failed to achieve fiber length reduction in the target freeness region. A higher dose (2 kg / ton) of cellulase A treatment could reach part of the target fiber length-freeness range, but with 2 kg / ton of Percol® 3232 added later. Even lower freeness levels compared to the combined 0.4 kg / ton cellulase A treatment.

Example 8 Superthermostable Cellulase B Enzyme Treatment at 85 ° C. to Save Beating Energy In this example, a commercial Southern Pine market kraft pulp is reslurried and dosed 20 kg (enzyme) / ton (pulp) And treated with super thermostable cellulase B at 85 ° C., pH 6.6, 4% concentration for 4 hours. As a control, Southern pine slurry was also treated for 4 hours at 85 ° C., pH 6.6, 4% concentration without enzyme. Both the treated pulp and the control pulp were beaten with a valley beater at a time interval of 5 minutes. The results are summarized in Table 7 and plotted in FIG. 18 below.

  These data clearly demonstrate that the super thermostable cellulase treatment at 85 ° C. resulted in substantial energy savings in the mechanical beating of the pulp. For example, it took 15 to about 30 minutes of valley beater time to reach a freeness of 600 to 400 CSF for the control. In sharp contrast, only about 7 to about 14 minutes was required to reach a similar range of freeness for pulp treated with the hyperthermostable enzyme.

Example 9 Cellulase Enzyme Beating Strategy for Converting Coniferous Fibers to Hardwood Fiber Lengths Within the Papermaking Freeness Range In this example, while maintaining pulp freeness in the papermaking freeness range, coniferous fibers A strategy of cellulase enzyme purification for converting to hardwood fiber length was presented. Northern bleached softwood kraft pulp was reslurried in tap water and treated with cellulase A at a dose of 1 kg (enzyme) / ton (pulp) at about 50 ° C. for 1.5 hours. The enzyme and pulp system was inactivated with 0.05% sodium hypochlorite (20 ppm sodium hypochlorite with respect to the total water slurry) for 15 minutes based on the weight of the pulp. The treated softwood pulp was beaten on a pilot scale Suns Deflator Conflo JC-00 Conical Refiner (Varaoke International, Finland). The beating operation was performed by increasing the beating strength, eg, specific end load (SEL), while maintaining the mass flow rate, rpm, and CEL (beating plate parameters) substantially the same. The net load of increasing energy was achieved by changing the plate gap size. The results are summarized in Table 8 below.

  The freeness versus specific end load data for the control and enzyme treated pulps is plotted in FIG. FIG. 19 shows that the beating drainage of the enzyme-treated softwood was substantially affected by SEL, while the control (no enzyme) pulp was hardly affected.

  The freeness versus beating energy data for the control and enzyme treated pulps is plotted in FIG. FIG. 20 shows that the electrical energy consumption of the enzyme treated pulp was substantially reduced compared to the electrical energy consumption of the control pulp beating.

  FIG. 21 is a plot of data on average length (length-weighted) of softwood fibers versus beating freeness. FIG. 21 shows that the length of the softwood fiber treated with the enzyme (starting in the range of ˜2.1 mm to 2.3 mm) and the hardwood fiber length (usually 0.8 mm to 1.2 mm) while maintaining the freeness above 400 CSF. It shows that it was successfully reduced by beating to (range). In contrast, the fiber length of the control (no enzyme) beating conifer pulp was not significantly affected. In fact, when it is necessary to achieve a significant fiber length reduction, the control softwood beating unduly reduces the freeness to be useful (or practically feasible) in papermaking. FIG. 21 also plots data showing the synergistic effect of Percol® 3232 added after beating and enzyme beating.

  FIG. 22 is a plot of fiber average length (length-weighted) versus beating energy. Furthermore, it is explained that controlled beating requires too much electrical energy to significantly reduce fiber length. In contrast, the length of coniferous fibers treated with enzymes can be converted to the length range of hardwood fibers with very little electrical energy consumption.

Example 10 Enzymatic Removal of Hemicellulose at 75 ° C. for Modified Pulp In this example, the effect of a thermostable hemicellulase enzyme, such as the xylanase of SEQ ID NO: 22, in removing hemicellulose content to produce a modified pulp. Has been described. In general, the removal of hemicellulose-containing material by the xylanase of SEQ ID NO: 22 is more pronounced when treated with normal pulp, for example, paper grade kraft pulp having a high hemicellulose content. In this example, hemicellulose was measured by the Pentosan test (TAPPI method T223 CM-01). Using the xylanase of SEQ ID NO: 22, hemicellulose removal higher than 0.5% by weight can be achieved with normal kraft pulp. The data show that pretreatment with mechanical beating followed by xylanase treatment with the xylanase of SEQ ID NO: 22 can further increase this effect, for example, by removing more than 1% by weight of hemicellulose over normal kraft pulp. Is shown. Dissolving pulp has a very low hemicellulose content and the remaining hemicellulose in the dissolving pulp is also more resistant to enzymatic removal processes and is dissolved due to the fact that it has historically been done with strong alkaline extraction Removal of hemicellulose from pulp is very difficult.

  In this example, the data show that a thermostable xylanase treatment (eg, with a xylanase of SEQ ID NO: 22) on a dissolving pulp results in a cellulase enzyme (eg, hyperthermostable cellulase B, preferably or optionally in crystalline cellulose swelling It is further increased in combination with an agent such as an ionic liquid. Dissolving pulp treatment with hemicellulase enzymes or with a combination of hemicellulase enzymes and cellulase enzymes can be further augmented with pretreatment by mechanical beating as well.

  Table 9 shows the experimental results for the use of a super thermostable enzyme to remove hemicellulose (or Pentosan content) on dissolving pulp. All enzyme treatments (0.6 kg / ton dose of xylanase of SEQ ID NO: 22 or 20 kg / ton dose of cellulase B) were carried out at 75 ° C. for 4 hours. The ionic liquid used is 1-ethyl-3-methylimidazolium acetate at a dose of 10 kg / ton.

  The modified pulp herein has any improved source and / or reactivity, including any source (eg paper pulp, dissolving pulp, fluff pulp, personal care pulp, industrial pulp, polymer impregnated pulp, etc.). Can be used as an enhanced pulp.

  The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference in their entirety for all purposes.

  While products, compositions, methods of making them, and methods of using them are disclosed with reference to particular embodiments, other embodiments and variations are the true essence of the described products and methods. It will be apparent that those skilled in the art can invent the present invention without departing from its spirit and scope. The appended claims are intended to be construed to include all such embodiments and equivalent variations.

Claims (33)

A method for modifying a papermaking pulp, comprising pulp containing papermaking fibers;
(A) contacting a cellulose hydrolyzable enzyme and (b) a fiber length reduction promoter under conditions that cause damage inside the fiber;
(I) 5% to 96% reduction in papermaking fiber length after passing through or bypassing the refiner and (ii) pulp freeness from about 200 Canadian Standard Freeness (CSF) to about 700 CSF A method for modifying a papermaking pulp, comprising producing a modified pulp having a level.   The method according to claim 1, wherein the modified pulp is a beaten pulp.   The process according to claim 1, wherein the contact between the pulp and the fiber length reduction promoter occurs preferably after contacting the pulp and the enzyme.   Fiber length reduction accelerator is a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis greater than 70%, a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride, a copolymer of acrylamide and diallyldimethylammonium chloride, free glyoxal, And a method according to any one of claims 1 to 3, selected from the group consisting of any mixture thereof and more than two thereof.   The method according to any one of claims 1 to 4, wherein the cellulose hydrolyzing enzyme is a cellulase enzyme or a cellulase-functionalized hemicellulase enzyme.   Cellulose hydrolysable enzymes are obtained from or derived from Chrysosporium lucknowense / Myceliophthora thermophilia or cellulases derived from them, Humicola insolens. Cellulase derived from, derived from or derived from Aspergillus, cellulase derived from or derived from Trichoderma, cellulase, and combinations thereof The method according to any one of claims 1 to 5.   The method of any one of claims 1 to 6, wherein the pulp comprises papermaking fibers selected from the group consisting of softwood pulp, hardwood pulp, and mixtures thereof.   The fiber length reduction accelerator is selected from the group consisting of a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis of greater than 70%, and a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride, and a modified pulp papermaking fiber The method of any one of claims 1 to 7, wherein the length reduction is from about 5% to about 20% and the pulp freeness level of the modified pulp is from about 300 CSF to about 650 CSF. .   The papermaking fibers are wood fibers and the fiber length reduction accelerator consists of a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis greater than 70% and a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride. A dosage of 0.5 kilogram (0.5 kg / ton (pulp)) to about 29 kg / ton (pulp) per ton of pulp, wherein the pulp freeness level of the modified pulp is about 8. The method of any one of claims 1 to 7, wherein the method is from 350 CSF to about 650 CSF.   The fiber length reduction promoter is selected from the group consisting of a hydrolyzed polymer or copolymer of vinylformamide having a degree of hydrolysis of greater than 70%, and a copolymer of acrylamide and acryloxyethyltrimethylammonium chloride, and the agent per tonne of pulp A dosage of 0.5 kilograms (0.5 kg / ton (pulp)) to about 29 kg / ton (pulp), and a reduction in the length of the modified pulp papermaking fiber is about 5% to about 20% The method of any one of claims 1 to 7, wherein the pulp freeness level of the modified pulp is from about 300 CSF to about 650 CSF.   A fiber pulp modified with the enzyme according to any one of claims 1 to 10.   A method for denaturing a pulp fiber, comprising contacting a pulp containing a papermaking fiber with a thermostable or superheat-stable cellulose hydrolyzing enzyme at a temperature of about 70 ° C to about 125 ° C, comprising: A process for modifying pulp fibers, wherein the process is substantially inert at a temperature of from about 35C to about 55C.   13. A method according to claim 12, wherein the beating energy of the pulp or fibrous material is reduced by at least 10%.   The modified pulp has a hemicellulose content that is reduced by at least 0.2% by weight compared to the hemicellose content of the pulp produced without contact with the thermostable or super-stable cellulose hydrolyzable, 14. A method according to claim 12 or 13.   The cellulase hydrolyzing enzyme is a cellulase, a cellulase functionalized hemicellulase enzyme, or a cellulase comprising an associated hemicellulase enzyme function, such as xylanase, mannanase, glucanase, and beta-glucanase. 2. The method according to item 1.   The method according to any one of claims 12 to 15, wherein the cellulose hydrolyzing enzyme is a cellulase selected from the group consisting of SEQ ID NO: 2 and SEQ ID NO: 6.   17. The contact step further comprises a thermostable or hyperthermostable enzyme selected from the group consisting of hemicellulase, mannanase, xylanase, pectinase, laccase, lignin peroxidase, manganese peroxidase, and oxidoreductase. The method according to any one of the above.   18. A method according to any one of claims 12 to 17, wherein the pulp comprises papermaking fibers selected from the group consisting of softwood pulp, hardwood pulp, and mixtures thereof.   Intracrystalline lignocellulosic agent wherein the enzyme contacting step is further selected from the group consisting of ionic liquids, N-alkylated ureas, N-alkylated lactams, N-alkylated amides, polyol ethers, polyols, and combinations thereof. 19. A method according to any one of claims 12 to 18 comprising:   The pulp comprises kraft pulp, sulfite pulp, mechanical pulp, semi-chemical pulp, semi-mechanical pulp, chemical mechanical pulp, fluff pulp, tissue pulp, dissolving pulp, waste paper pulp, biorefinery pulp, or deinked pulp. 20. The method according to any one of items 19 to 19.   A fiber pulp modified with the enzyme according to any one of claims 12 to 20. A method for modifying paper pulp,
(1) FQA length—pulp containing coniferous fibers having a fiber length of about 2.1 mm to about 2.8 mm as measured by weighted average fiber length, and a cellulose hydrolyzing enzyme, about 35 ° C. to about 125 Contact at a temperature of ℃
(2) Beating the modified pulp,
Papermaking comprising producing a modified pulp having a fiber length of about 0.6 mm to about 1.7 mm and (ii) a pulp freeness level of about 400 Canadian Standard Freeness (CSF) to about 700 CSF For pulp modification.   23. The method of claim 22, wherein the contacting step is performed at a temperature of about 35 [deg.] C to about 125 [deg.] C for about 30 minutes to about 10 hours.   23. The contacting step is performed at a temperature of about 35 ° C. to about 65 ° C. and an enzyme dosage of about 0.2 kilograms of enzyme per ton of pulp (about 0.2 kg / T) to about 20 kg / T. Or the method according to 23.   Cellulose hydrolysable enzymes are obtained from or derived from Chrysosporium lucknowense / Myceliophthora thermophilia or cellulases derived from them, Humicola insolens. Cellulase derived from, derived from or derived from Aspergillus, cellulase derived from or derived from Trichoderma, cellulase, and combinations thereof 25. The method of claim 24.   23. The contacting step is performed at a temperature of about 66 ° C. to about 125 ° C. and an enzyme dosage of about 0.2 kilograms of enzyme (about 0.2 kg / T) to about 20 kg / T per ton of pulp. 25. The method according to any one of items 1 to 24.   27. The method according to any one of claims 22 to 26, wherein the cellulose hydrolyzing enzyme is a cellulase enzyme or a cellulase functionalized hemicellulase enzyme.   28. The method according to claim 26 or 27, wherein the cellulose hydrolyzing enzyme is a cellulase selected from the group consisting of SEQ ID NO: 2 and SEQ ID NO: 6.   29. A method according to any one of claims 22 to 28, further comprising contacting the pulp with a fiber length reduction promoter.   30. The method of claim 29, wherein the contact between the pulp and the fiber length reduction promoter preferably occurs after contacting the pulp and the enzyme. Enzyme-modified softwood fiber pulp having (i) a fiber length of about 0.6 mm to about 1.7 mm, and (ii) a pulp freeness level of about 400 Canadian Standard Freeness (CSF) to about 700 CSF .   A web or a pulp product comprising the modified pulp according to any one of claims 1 to 31.   33. A web or pulp product according to claim 32, which is printed writing paper, wrapping paper, paperboard, personal care and hygiene products, paper tissue, paper towels, paper napkins, paper wipes, paper plates, paper cups, paper containers, Selected from the group consisting of deinked paper, recycled paper, microcrystalline cellulose, microfibrillated cellulose, nanofibrillated cellulose, nanocrystalline cellulose, dissolving pulp, and base paper for polymer impregnation or base paper for composites, Paper web or pulp product.

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