METHOD FOR CONTROLLING ORGANIC CONTAMINANTS AND COMPOSITION

专利摘要:
method to control organic contaminants, composition and paper product. a method is provided to control organic contaminants, such as xylans, pitch, or both, that interfere with fiber bleaching and / or cause other interference in papermaking systems. the method includes contacting fibers prior to bleaching them with a composition containing a hemicellulase and an organic contaminant removal aid to release organic contaminants from the fibers. the treated fibers can then be bleached and still used, for example, in papermaking. the present invention also relates to treatment compositions and paper products made from fiber materials treated with these compositions. a method is also provided to improve enzymatic degradation of a substrate as well as formulations and systems to achieve it. various substrates can be degraded or processed differently, including biomass, paper mill sludge, and animal hides. enzymatic degradation can be improved by including one or more polymeric surfactants. 1/1
公开号:BR112014009918B1
申请号:R112014009918-9
申请日:2012-10-26
公开日:2021-03-30
发明作者:Daniel E. Glover；Stephen D. Bryant；Kevin J. Macdonald；Bernard Janse；Xiangdong Zhou；Philip Hoekstra
申请人:Buckman Laboratories International, Inc；
IPC主号:

专利说明:

Field of invention
[0001] The present invention relates to a method and composition for controlling organic contaminants that interfere with bleaching fibers in papermaking systems. More particularly, the present invention relates to a method and composition useful for controlling such organic contaminants comprising contacting fibers prior to any bleaching of them with a composition including at least one hemicellulase (enzyme) and at least one removal agent. organic contaminant to release interfering organic contaminants from fiber bleaching. The present invention also relates to paper products with fiber materials treated with these compositions. The present invention also relates to methods for improving the enzymatic activity of enzymes in various contexts. History of the invention
[0002] Lignocellulosic material in the form of fibers is used on a large commercial scale as a raw material for the manufacture of paper and other paper products. Usually, in the manufacture of paper, the wood fibers are treated by combining them with other additives, and the fibers are then processed in a network of wood fibers, which can constitute a paper or other thin sheet of fibrous material. A variety of paper and paper products are discolored, that is, whitened or bleached, before they are commercialized. The manufacture of discolored paper products usually includes stages of pulping, bleaching, and papermaking. In order to produce paper-making fibers that are strong and capable of being bleached, wood or pulp fibers are usually treated to remove lignin, and commonly, the initial part of this treatment takes place in a digester in the presence of chemicals such as sodium hydroxide and sodium sulfide (to produce a kraft pulp (paste)) or sulfites, usually sodium or magnesium (to produce a sulfite pulp (paste)), thus producing chemical pulps (pastes). Lignin removal is referred to as delignification. Usually, the lignin content of wood pulps can be measured by an oxidation test with permanganate according to the standard method of the “Technical Association of the Pulp and Paper Industry” (TAPPI), and can be reported as an index Kappa. At this stage, the chemical pulp from the digester still contains an appreciable amount of lignin, and in some cases is suitable for making packaging or assembly paper without further purification. For most applications, such as the manufacture of printing, writing and hygienic papers, for example, the pulp (paste) is usually very dark in color and must be bleached by bleaching it before making the paper. The whiteness of the paper product is dictated mainly by the whiteness of the pulp provided prior to the manufacture of paper. There are some modifications in stock preparation that can change the whiteness of paper to some extent, such as filler, size, bleaching agent, etc. However, pulp whiteness (pulp) is a basic or limiting factor over paper whiteness that can ultimately be obtained in pulp-derived paper products.
[0003] Unbleached pulps can exhibit a wide range of whiteness values. In general, it is understood that groups of chromophores in lignin are mainly responsible for the color of the pulp. See, for example, G.A. Smook, “Handbook for Pulp and Paper Technologists”, Chapter 11: “Bleaching”, 163-164, TAPPI Pr. (1992), which is incorporated here entirely by reference. Heavy metal ions (eg, iron, copper) are also known to form colored complexes with phenolic groups of lignin. Extraction materials can also contribute to the color of mechanical pulps from resinous woods. To produce stable, high-quality paper pulps having a more permanent whitening effect, methods that discolour the pulp have been used. However, it is often undesirable to use large quantities of bleaching agents to obtain a specific level of discoloration.
[0004] Conventional methods for bleaching pulp have used a variety of multi-stage bleaching sequences, including multiple stages or stages, with or without washing between stages. Bleaching sequences have traditionally been based on the use of chlorine and chlorine-containing compounds, in one form or another. Some of the chlorine-containing compounds that have been used are chlorine, indicated by "C" as a simplified designation used in the industry, chlorine dioxide, indicated by "D", and hypochlorites, indicated by "H", usually sodium hypochlorite. Chlorine, with or without mixing with chlorine dioxide, has been commonly used for the decolorization of chemical pulp, followed by alkaline (caustic) extraction, indicated by “E”, from the pulp treated with chlorine in an aqueous alkaline medium, which together are indicated “CE”. Oxygen, hypochlorite, or oxygen generators such as peroxides, have also been used as a bleaching agent in the bleaching stage, in combination with the alkaline extraction stage, or both. Washing units have been used after bleaching (bleaching) stages and between oxidation and extraction stages. Additional information on conventional bleaching systems and their process designs is shown, for example, in the aforementioned section of the “Handbook for Pulp and Paper Technologists”.
[0005] Enzymes have also been studied for their use in the treatment of wood fibers to degrade lignocellulosic material. The wood fibers used to make paper products usually include cellulose, hemicellulose, and lignin. The amounts of these three constituents present in the wood fiber may depend on the fiber source and their amounts in paper products made from the fiber may depend on the manufacturing process used. The cohesion of the plant cell wall is mainly due to the presence of its main components: the crystalline polymer, cellulose, the three-dimensional macromolecule, lignin, comprising a lignocellulosic material. These components are fixed in a matrix of pectic and hemicellulosic polysaccharides of various natures. In general, it is accepted that the relationships between these different polymers are established through bonds of different chemical natures. For example, lignin blocks are associated through hemicellulose chains. Hemicellulose, another major component of lignocellulosic material, consists largely of 4-O-methyl-glucoronoxylane, which includes the β-1,4- binding polymer of D-xylose, and here referred to as “xylan”. Generally hardwood pulps contain higher amounts of xylan than white wood pulps. Such xylan can be hydrolyzed enzymatically producing xylose by an endoxylanase, β-1,4-D-xylan xylan hydrolase, indicated as EC 3.2.1.8, and a xylosidase, β-1,4-D-xyl hydrolase. Xylanases per se have been mentioned for degradation of xylan in the pulp and paper industry in the pretreatment of pulps before chemical bleaching. See, for example, F.I.J. Pastor et al., “Xylanases: Molecular Properties and Applications”, Industrial Enzymes, 65-67, 74-79, 2007. In addition, untreated wood also generally contains some amount of pitch, which is typically located in parenchyma cells and on the fiber surfaces. Based on the solubility in ethyl ether values, the pitch can comprise, for example, from about 0.7 to about 2.4 weight percent of hardwoods, such as beech and birch, and from about 0 , 7 to about 4.3 percent by weight of white woods such as Canadian pine and “Pinus banksiana”, based on the total weight of wood not extracted (kiln dried). It was mentioned the addition of lipase and cationic polymer in a cellulosic slurry to control pitch deposit. See, for example, U.S. Patent No. 5,256,252, which is incorporated herein entirely by reference.
[0006] The present invention recognizes the need to control constituents that interfere in the bleaching of wood fiber by treating the fibers before bleaching with a combination of agents that can increase pulp luster obtained from bleaching in a way not predicted by the effects of the individual components of the pretreatment composition.
[0007] Enzymes are significant elements of many industrial processes such as paper production, leather preparation, waste treatment, and processing of biomass into fuel. Although enzymes can appreciably increase the rate of chemical reactions, it is difficult to find the right conditions to carry out enzyme optimization. As a consequence, when enzymes are used, they are employed in a way that produces under-optimized enzyme activity. That inefficiency causes the need to use additional, often expensive, enzymes, as well as longer production times and additional energy consumption. Consequently, there is a need to improve enzyme activity to provide more efficient and cost-effective processes. Summary of the present invention
[0008] A feature of the present invention is to provide a method for controlling organic contaminants that comprise xylans, pitch, and / or other fiber components that can interfere with the discoloration of the fibers and / or cause other interference in papermaking systems.
[0009] A feature of the present invention is to provide a method for controlling organic contaminants that interfere with bleaching which comprises contacting fibers before any bleaching of them with a composition comprising a hemicellulase and an organic contaminant removal aid to release organic contaminants of the fibers.
[0010] Another feature of the present invention is to provide a composition comprising a hemicellulase and an organic contaminant removal adjuvant to pre-treat the fibers prior to bleaching the fibers in papermaking systems.
[0011] An additional feature of the present invention is to provide paper products that are produced using the compositions indicated in the indicated methods.
[0012] Another feature of the present invention is to provide a method to improve the enzymatic activity of one or more enzymes using a polymeric surfactant that increases the enzymatic activity and allows cost reduction using less enzyme.
[0013] A feature of the present invention is also to provide a formulation containing an enzyme and a polymeric surfactant, for example, which together can be applied to a substrate composition for degradation thereof, with the polymeric surfactant significantly increasing the activity of the enzyme.
[0014] An additional feature of the present invention is to provide better systems for degrading substrate compositions in the presence of an enzyme and a polymeric surfactant, the system allowing the enzyme to better penetrate the substrates.
[0015] Additional features and advantages will be shown in part in the description that follows, and in part will become obvious from the description, or can be learned by practicing the present invention. The objectives and other advantages of the present invention will be understood and achieved by means of the elements and combinations indicated particularly in the description and the appended claims.
[0016] To achieve these and other advantages, and in accordance with the purposes of the present invention, when incorporated and widely described herein, the present invention relates, in part, to a method for controlling organic contaminants comprising xylans, rosin, and / or other fiber components that can interfere with the discoloration of the fibers and / or cause other interference in papermaking systems. The method includes contacting, prior to any bleaching step (bleaching), fibers with a composition comprising at least one hemicellulase and at least one organic contaminant removal adjuvant to provide treated fibers that release contaminants from the fibers in an amount greater than they are. would release if they were contacted with the composition without the organic contaminant removal aid, and then discolor the treated fibers. The interfering organic contaminants that are released by treating the fibers with the composition can comprise one or more xylans, one or more component compounds, or both. As an option, the contact step of the method removes at least 50% by weight of the total xylans and breus components present in the fibers prior to contact. As an option, the organic contaminant removal aid can be a non-ionic surfactant. As another option, the nonionic surfactant can be a poloxamer, such as, for example, a poloxamer having an HLB index greater than or equal to 16. The hemicellulase can be xylanase, mannanase, or both. The composition may further comprise a lipolytic enzyme. The composition can be introduced in an amount providing about 100 to about 1,000 grams of said hemicellulase per ton of fibers on a dry fiber basis, and from about 2 to about 100 grams of said organic contaminant removal aid per ton of the fibers on a dry fiber basis. For the purposes of the entire present invention, unless otherwise stated, references to “ton” are references to “metric ton” (1000 kg, currently indicated as mega-gram (Mg)). As an option, the bleached fibers can be molded into a paper product, and the paper product can have an ISO gloss that is about 0.5 to about 1.0 units higher than that of a paper product produced with the same method without the organic contaminant removal aid included in the pretreatment composition.
[0017] The present invention also relates to a composition comprising at least one hemicellulase and at least one organic contaminant removal adjuvant capable of removing organic contaminants comprising one or more xylans, one or more component compounds, or both, of fibers in an amount greater than that of fibers that are contacted with the same composition without the organic contaminant removal aid included in the composition. The organic contaminant removal aid may comprise the materials indicated. The compositions can comprise from about 10% to about 90% by weight of the hemicellulase, and from about 1% to about 10% by weight of the organic contaminant removal aid, based on the total solids weight of the composition.
[0018] The present invention also relates to a product formed by the paper-forming method of the present invention.
[0019] The present invention also relates to a method for improving the enzymatic degradation of a substrate. The method may include adding at least one polymeric surfactant and at least one enzyme to a composition for degrading a substrate. For example, the composition may contain paper pulp, paper mill sludge, animal leather, other materials, and the like. For example, a nonionic polymeric surfactant can be used. The polymeric surfactant can include at least one non-ionic block copolymer of the PEO-PPO-PEO type that ends in primary hydroxyl groups. The nonionic polymeric surfactant can have a hydrophilic-lipophilic balance (HLB) of at least 17. The nonionic polymeric surfactant can include a propoxylated block copolymer having an HLB value of at least 20. For example, the enzyme can include a cellulase , a xylanase, a laccase, an amylase, a lipase, a protease, a peroxidase, or any combination thereof. The substrate composition can be degraded in the presence of the polymeric surfactant and the enzyme to form a degradation product and the degradation product can be optionally dehydrated.
[0020] The present invention also relates to systems for carrying out the described methods and formulations containing an enzyme and a polymeric surfactant for use in the methods. The present invention can be practiced according to or using components, compositions, methods, steps, and / or systems described, for example in U.S. Patent Application Publication No. 2011/0300587, which is incorporated herein entirely by reference.
[0021] When used here, a "contaminant" refers to a component with the fiber and / or the fiber, and / or the fiber that may cause interference, in a negative or harmful way, in the processing and / or result in a system papermaking.
[0022] When used here, a "hemicellulase" refers to an enzyme that causes the hydrolysis of hemicellulose.
[0023] When used herein, “rosin” refers to a variety of naturally occurring hydrophobic organic resins of low and medium molecular weight in wood fiber that includes glycerol fatty acid esters (such as triglycerides), as well as other fats, fatty acids, sterols, and waxes.
[0024] When used here, a “non-ionic surfactant” is an organic compound that is amphiphilic and has no charged group in any terminal end group, the organic compound being able to decrease the surface tension of a liquid to interfacial tension between two liquids, or between a liquid and a solid.
[0025] When used herein, a "poloxamer" refers to a non-ionic triblock copolymer comprising a center block of a hydrophobic poly (alkylene oxide) block, which is between side blocks of poly (alkylene oxide) hydrophilic.
[0026] When used here, “bleaching” refers to the removal of pulp color.
[0027] When used here, "brightness" is a measure of how much light is reflected by paper under specified conditions and is usually reported as a percentage of how much light is reflected. Thus, a higher gloss index generally represents a brighter or whiter paper, and conversely, a paper with a lower gloss index represents a less glossy or less white paper. ISO standards, or TAPPI T 452 or T 525 standards, can be used as measures of brightness. The pulps can be manually molded into sheets to determine their gloss according to accepted practices in the paper industry.
[0028] When used here, the "whiteness" of pulp or paper refers to the extent to which the paper reflects by diffusing light of all wavelengths across the entire spectrum of visible light, that is, the magnitude and uniformity of spectral reflectance measured as the percentage of light reflectance for the entire wavelength range. Procedural standards for the measurement of whiteness are explained in ISO 11475. The L * (luminance) value of C * L * a * b * colorimetric scale values can also be used here to indicate the relative whiteness of a pulp or paper. Black has L * equal to zero, and higher L * values indicate greater whiteness. The value a * refers to the color red to the color green, and the value b * refers to the color yellow to the color blue. The pulps can also be molded manually into sheets to determine their whiteness.
[0029] When used herein, "release" refers to an activity of a composition in contact with the fiber to cause the release of the specified contaminant or contaminants from the fiber, such as in the forms of degraded hydrolysis products, intact molecular residues, or as other forms released, the content of the contaminant or contaminants in the fiber being reduced by treatment.
[0030] When used here, "Kappa number" or "Kappa index" is a measure of the residual lignin content remaining in the cellulosic fiber. The Kappa index for pulps can be determined by ISO 302. The presence of lignin requires that a greater amount of an oxidizer (environmental and cost problems) be incurred in order to whiten the fiber to a desired point.
[0031] It is understood that both the previous general description and the detailed description below are only exemplary and explanatory and are intended to provide a further explanation of the present invention, as claimed.
[0032] The accompanying drawings here are incorporated and constitute a part of this patent application, illustrate some of the embodiments of the present invention and together with the description, serve to explain the principles of the present invention. Brief description of the drawings
[0033] Figure 1 is a process flow chart showing a method according to an example of the present patent application.
[0034] Figure 2 is a structure of a poloxamer that can be used in a composition according to an example of the present patent application.
[0035] Figure 3 is a data table showing different compositions containing different additives or none (control) used to pre-treat wood fiber pulps before a bleaching process, and gloss (% ISO), gloss increase , and L * a * b * CIE scale values determined for the pulps after a chlorine bleaching stage D and Ep extraction stage, and the pulps were treated with a composition containing xylanase and non-ionic surfactant according to the examples of this patent application (“XylA + Surf”, “XylB + Surf”) and other comparison pulps have been pre-treated with either xylanase (“XylA”, “XylB”), or a commercial enzyme complex (“LBL CONC ”), Or any enzyme or surfactant additives (control).
[0036] Figure 4 is a bar graph showing the brightness (% ISO) after a bleaching stage (Do) and an alkaline extraction stage (Ep) of a pulp fiber processing of pulp fiber samples shown in Figure 3.
[0037] Figure 5 is a bar graph showing the Ep gloss increase for the pulp fiber samples treated by the different compositions shown in Figures 3-4 with the gloss increase values determined by comparison with the gloss value of the Control sample that has not been treated with xylanase or surfactant.
[0038] Figure 6 is a bar graph showing the Kappa index (K) of a pulp fiber after enzyme and surfactant treatment before the bleaching and alkaline extraction stages performed on the pulp fiber samples according to an example of present patent application or without pre-treatment (Control).
[0039] Figure 7 is a bar graph showing the brightness (% ISO) on the yarn and felt side of the pulp fiber samples of the example shown in Figure 6 after pretreatment and bleaching and alkaline extraction stages according to with an example of the present patent application or without any pretreatment (Control). Detailed description of the present invention
[0040] The present invention provides enzymatic treatments and compositions for them that can improve the pulp quality by removing unwanted materials, and these enzymatic activities improve unexpectedly through the use of non-ionic surfactants described here. The effects of the compositions of the present invention may comprise, for example, (I) removal of xylans / hemicellulose that retain colored bodies using hemicellulases, (II) removal of pitch that causes dirt spots and causes deposits using lipases or esterases, and / or (III) improving the activity and efficacy of many other enzymes, and / or other effects of the compositions of the present invention.
[0041] The present invention provides compositions useful for pretreatments in the fiber prior to bleaching, which improves the release and removal of substances that interfere with shoring and / or other interfering substances, such as xylans and component components, from the fiber prior to bleaching. bleaching. For example, xylans can interfere with bleaching and / or cause other interference in papermaking systems. Pitch, for example, can compromise the pulp quality or interfere with production efficiency and / or cause other interferences in papermaking systems. The compositions may contain hemicellulase and organic contaminant removal adjuvant, which, combined, exert greater capacities for removing interfering contaminant in fiber bleaching than those predicted or expected from the individual effects of the components. In addition, the pretreatment of wood fiber before bleaching with the indicated compositions of the present invention can increase brightness, whiteness, or both of paper and pulp, obtained from bleaching, in magnitudes not predicted by the effects of the individual ingredients. In addition, the pretreatment of the wood fiber with the indicated compositions of the present invention can reduce the Kappa index of the treated pulp before bleaching when compared to untreated pulps with the compositions. The present inventors have recognized and resolved the need for a pre-treatment of wood fiber prior to bleaching which can increase bleaching for a given amount of bleaching agent used, or alternatively allow a similar level of bleaching to be provided using reduced amounts of bleaching. bleaching agent and associated costs. The combination of the organic contaminant removal adjuvant with the hemicellulase in the composition used to pre-treat the wood fiber before bleaching can increase the release (separation) and removal of xylans and / or pitch and the like from the wood fiber when comparing with quantity released by pretreatment with a composition containing only the enzyme, at least about 5% by weight, or at least about 10% by weight, or at least about 20% by weight, or at least about 30% by weight, or at least about 40% by weight, or at least about 50% by weight, or greater amounts, or from about 5% to about 90% by weight, or about from 10% to about 85% by weight, or from about 20% to about 80% by weight, or from about 30% to about 70% by weight, or other amounts. As an option, the present invention can therefore provide a bleaching composition that can save on the oxidizing agent charge (eg chlorine charge) needed to obtain a specific pulp shine, which can reduce the amount and cost of fiber bleaching agents that are needed and used.
[0042] According to the present invention, a method is provided to improve the enzymatic degradation of a substrate. The method may include adding a polymeric surfactant to an enzyme composition to thereby increase the effectiveness of the enzyme in degrading the substrate. Any desired substrate or substrate composition can be treated, for example, paper pulp, paper mill sludge, animal leather, or the like. Any suitable polymeric surfactant can be used, for example, a nonionic polymeric surfactant. The polymeric surfactant may include a non-ionic block copolymer of the PEO-PPO-PEO type, for example, which terminates in primary hydroxyl groups. The nonionic polymeric surfactant can have a hydrophilic-lipophilic balance (HLB) value of at least 17. The nonionic polymeric surfactant can include a propoxylated block copolymer having an HLB value of at least 20.
[0043] Any desired enzyme can be used in the compositions of the present invention. For example, the enzyme can include a cellulase, xylanase, laccase, amylase, lipase, protease, peroxidase, or a combination thereof. The substrate composition can be degraded in the presence of the polymeric surfactant and the enzyme to form a degradation product which, optionally, can be dehydrated. The present invention also provides systems for carrying out the described methods and formulations containing an enzyme and a polymeric surfactant for use in the methods.
[0044] The methods, formulations, and systems of the present invention have a large number of different uses; follow examples of such utilities. Fiber modification can be performed to reduce refining energy and / or to increase paper strength. Sticky substances and pitch can be reduced or eliminated from papermaking processes, resulting in better quality paper and reducing downtime. Sludge from the paper mill can be degraded, thereby reducing transportation and waste disposal costs (landfill). Pre-bleaching of paper mill pulp can be performed to improve bleaching efficiency. Sludge from the paper mill can be dehydrated more effectively. Hair removal and degreasing processes for leather making can be improved. You can clean the paper machine more efficiently. Washing and conditioning of paper machine felt can be improved. Enzymatic cleaning of the heat exchanger can be improved.
[0045] Any suitable substrate composition can be treated according to the invention. For example, the substrate composition may contain pulp and / or papermaking sludge and / or other sources. The substrate composition can comprise biomass. The term “biomass” includes any non-fossilized material, that is, renewable organic matter. The various types of biomass include plant biomass, microbial biomass, animal biomass (any animal by-product, animal waste, or the like) and urban waste biomass (light commercial and residential waste with recyclables, such as metal and glass, removed). The term biomass also includes virgin or post-consumer cellulosic materials, such as pieces of cloth and towels made from cotton or a cotton blend. The substrate composition may include, but is not limited to, compositions containing one or more types of fibers from one or more types of wood. The substrate composition may contain fibers of one or more lengths, including fines. The substrate composition may include other items, for example, ASA sizing materials or other sizing materials, hydrolyzed sizing materials, polymers, sticky materials, glues, printing inks, fillers, other impurities, such as recycled paper, defoamers, and the like. The substrate composition can be pre-processed before enzymatic degradation and can be further processed after enzymatic degradation.
[0046] The methods of the present invention can be used to convert various species of biomass into fuel, food, and other products. The terms "plant biomass" and "lignocellulosic biomass" can include any organic matter derived from the plant (woody or non-woody). Plant biomass can include, for example, agricultural or food crops (for example, sugar cane, beet sugar or edible part of corn) or extract thereof (for example, cane sugar, and corn maize starch), agricultural crops and agricultural crop waste and residues such as corn stalks and leaves, wheat straw, rice straw, sugarcane bagasse, cotton, and the like. Plant biomass can include, for example, trees, woody plants to produce energy, waste and wood waste such as thinning of white wood forest, cork waste, sawdust, pulp and paper industry effluent streams, wood fiber , and the like. Plant biomass includes grassland, for example, fast-growing grass. Plant biomass can include park waste (for example, leaves) and vegetable processing waste.
[0047] The enzyme and polymeric surfactant for use in the methods of the present invention can be provided separately or together as an enzyme formulation. For example, the enzyme formulation may contain the enzyme, polymeric surfactant, water, and optional ingredients for stabilizing the formulation. Stabilizing agents that can be used can include, for example, a polyamide oligomer. The formulations can be incorporated into various products, for example, fiber modifying enzyme products, enzyme products to control pitch and sticky substances, enzymatic products for treating paper mill sludge, enzymatic products for water treatment, enzymatic products for depilation in leather manufacture, enzymatic degreasing products, pulp pre-bleaching products, and enzymatic water treatment products for use in swimming pools, cooling towers, and other contexts.
[0048] According to the present invention, the enzyme activity of the enzyme can be greatly increased by the presence of the polymeric surfactant. For example, the enzyme activity of the enzyme can be increased by at least 10% when compared to that of using the enzyme alone without any polymeric surfactant present. This increased activity can be at least 10% greater, at least 20% greater, at least 25% greater, at least 40% greater, at least greater than or equal to 35%, or from about 10% to about 50% greater , in enzymatic activity than in the absence of polymeric surfactant. These increases can be synergistic between enzymes and surfactants, and can perform significantly better than products without the enzyme / surfactant combination.
[0049] The fiber material that is pre-treated with the compositions of the present invention before bleaching can be referred to as "pulp" or "fiber pulp". The fiber or pulp that can be pretreated with the compositions of the present invention can be virgin wood fiber, recycled paper (e.g., paper, cardboard, cardboard), or any combination thereof.
[0050] As an option, bleached fibers that have been pre-treated with a composition of the present invention can be molded into a paper product that has an ISO gloss (% ISO) that is about 0.5 to about 5.0 greater, or from 0.5 to about 1.0 units larger, or from 0.6 to about 1.0 units larger, or from 0.7 to about 1.0 units larger, than the of a product produced with the same method without the organic contaminant removal adjuvant included in the composition used to pre-treat the wood fiber before bleaching (that is, if the pre-treatment composition contains the hemicellulase, but not the adjuvant removal of organic contaminants). These increases in gloss values can be applied to hand sheets prepared from the bleached pulp or dry paper prepared with the bleached pulp. The effect of the non-ionic surfactant, if used alone in the pre-treatment composition, on the ISO brightness values obtained in the fiber by bleaching is usually none, a reduction or unpredictable. However, in combination with hemicellulase, the brightness increases significantly compared to what can be achieved by using the enzyme alone. There are also provided paper products produced with the pre-treated and bleached fiber according to the methods of the present invention. Bleached paper products can be provided with improved paper whiteness and brightness, or both, with reduced need for bleaching chemicals, with reduced addition of bleaching and brightening additives to the paper stock, or both benefits. As an option, fibers treated with the composition of the present invention can have a Kappa index that is about 0.2 to about 3.0 units less, or about 0.2 to about 1.0 unit less, or from about 0.25 to about 0.95 unit smaller, or from about 0.3 to about 0.9 unit smaller, or from about 0.35 to about 0.85 unit smaller, or about 0.4 to about 0.8 unit less, or other values less than that of fibers not treated with the composition.
[0051] The hemicellulase and organic contaminant removal adjuvant components of the composition of the present invention can be added together or separately to the pulp being treated in a papermaking system, as long as they are both added before any discoloration of the wood fiber and in such a way as to allow both components to be distributed substantially uniformly throughout the pulp before pulping begins to decolorize. In general, "before bleaching" can mean that the composition of the present invention is added from five seconds to thirty minutes to an hour or more before bleaching. For example, the bleaching step can be immediately the next step in the papermaking process after treating the pulp fibers with the composition of the present invention. As an option, the hemicellulase and organic contaminant removal adjuvant components can be combined into a single composition before use or can be added separately at the same time or almost the same time (from 1 second to 1 hour from each other) and / or can be added sequentially or in any order. As an option, the composition can contain both components indicated in water dispersible forms, for example, as an aqueous premix containing both components. The composition can be added to the pulp with sufficient agitation of the aqueous medium containing the pulp to substantially uniformly disperse the components introduced throughout the pulp.
[0052] The composition can comprise from about 10% to about 90% by weight of the hemicellulase, and from about 1.0% to about 10% by weight of the organic contaminant removal adjuvant, based on the total weight composition solids. The composition can comprise from about 20% to about 80% by weight of the hemicellulase, and from about 2.0% to about 8.0% by weight of the organic contaminant removal aid, based on the total weight of composition solids. The composition can comprise from about 30% to about 70% by weight of the hemicellulase, and from about 3.0% to about 6.0% by weight of the organic contaminant removal aid, on a dry weight basis based on in the total weight of dry composition solids. The composition can be introduced in an amount from about 100 to about 1,000 g of hemicellulase per ton of fibers on a dry fiber basis, and from about 2.0 to about 20 g of organic contaminant removal aid per ton of fibers in a dry fiber base. The composition can be introduced in an amount providing about 200 to about 800 g of the hemicellulase per ton of the fibers on a dry fiber basis, and from about 4.0 to about 18 g of the organic contaminant removal aid per ton of the fibers on a dry fiber basis. The composition can be introduced in an amount providing about 400 to about 600 g of the hemicellulase per ton of the fibers on a dry fiber basis, and from about 5.0 to about 15 g of the organic contaminant removal aid per ton of the fibers on a dry fiber basis.
[0053] Referring to the process shown in Figure 1, the composition containing the hemicellulase and organic contaminant removal aid of the present invention can contact fibers to release xylan, pitch, or both from the fibers (step 101). The treated fibers can then be bleached (step 102). Bleached fibers can be extracted with an alkaline material, such as by dissolving reaction products (step 103). After extraction, the bleached fibers can be evaluated for gloss, such as measuring the gloss of leaves prepared manually with the bleached and extracted fibers (step 104). Measuring the gloss of manually prepared sheets is an accepted procedure in the paper industry to assess pulp gloss. If the fiber brightness determined is sufficiently high to satisfy any applicable specification (step 105), the bleached fibers can proceed to use in papermaking (processing stage 106). If not, the fibers can be recirculated to the bleaching stage shown (or alternatively to a previous pulping stage, not shown).
[0054] The composition comprising hemicellulase and the organic contaminant removal adjuvant can be added to the fibers at any available addition site prior to bleaching. As an option, the composition can be added to the raw paste. The washed raw pulp can be stored in a high density storage tower before being pumped in the first bleaching stage. The composition can be added to the pulp when the pulp is pumped into the high density storage tower, and acts on the pulp when it is flowing through this tower. Typically, it can take 20 minutes to three hours before the pulp leaves the storage tower. After leaving the storage towers, the pulp may be ready to be bleached. Pretreatment with the composition containing both the enzyme and the organic contaminant removal adjuvant makes the pulp more prone to bleaching than if treated by the enzyme alone. The pH of an aqueous medium containing the fibers to be pretreated by the present method can be neutral or alkaline, such as from about 7.0 to about 11.0, or from about 7.0 to about 8, 0, or from about 7.0 to about 7.7, or from about 7.1 to about 7.5, or other pH values. In this regard, conventional pH modifiers can be used to preset the pH of the fiber slurry or other aqueous dispersed form of the fibers prior to treatment with the present composition. As an option, conventional stirrers can be used to stir the aqueous fibrous material and add composition if kept temporarily in tanks or towers during pretreatment. You can perform the pretreatment for a period of time of at least about 20 minutes, or at least about 30 minutes, or from about 20 minutes to about 180 minutes, or about 30 minutes at about 120 minutes, or about 45 minutes to about 90 minutes, or other time periods. As an option, pretreatment can be carried out at a temperature below any enzyme deactivation temperature, such as from about 25 ° C to about 90 ° C, or from about 30 ° C to about 80 ° C , or from about 35 ° C to about 70 ° C, or from about 40 ° C to about 60 ° C, or other temperatures. As an option, pretreatment can be carried out at a temperature below the boiling point of the aqueous medium in which the fibers form the slurry or are distributed differently, and some enzymes can also operate above the boiling point of the aqueous medium. As an option, increasingly higher pretreatment temperatures can cause faster or more extensive effects to release xylan, pitch, or both, or other contaminants interfering with bleaching or other contaminants of different interference, from the fibers. After pre-treatment with the present compositions, the pre-treated pulp or fiber can be introduced directly into a bleaching system. Alternatively, as an option, the pre-treated pulp or fiber can be dehydrated (for example, sieved, filtered), optionally washed, and transformed back into a semi-fluid paste before bleaching.
[0055] As an option, the contact step of the present method, for example, step 101 illustrated in Figure 1, removes at least 50% by weight, or at least about 60% by weight, or at least about 70% by weight, or at least about 80% by weight, or at least about 90% by weight, or at least about 95% by weight, or from about 50% to about 99% by weight, or about from 60% to about 95% by weight, or from about 70% to about 90% by weight of the total components xylans and breus present in the fibers before being contacted by the composition.
[0056] The bleaching process can use arrangements that include at least one bleaching stage and at least one extraction stage. Bleaching sequences can be based on the use of chlorine or chlorine-containing compounds (for example, chlorine dioxide, hypochlorites), in one form or another of chlorine dioxide (indicated by “D”) or chlorine (indicated by “C ”) Or ozone (indicated by“ Z ”) or any combination thereof, such as chlorine dioxide and chlorine, can be used to bleach the pulp, followed by alkaline (caustic) extraction of the bleached pulp in an aqueous alkaline medium. The bleaching agents used in the pretreated pulp can break down lignin into smaller oxygen-containing molecules and these broken products are generally water-soluble, specifically if the pH is greater than 7. Many of the reaction products can be carboxylic acids. These materials can be removed between bleaching stages. In this regard, extraction stages can be used in which the bleached pulp is treated with an alkaline solution (eg NaOH solution), and then optionally washed before an additional bleaching stage. The extraction stage or stages can solubilize and remove a major portion of the oxidized and chlorinated residual lignin, and can also remove some hemicellulose. Optionally, washing units can be used between the oxidation and extraction stages, or after the final bleaching stage has ended and before the bleached pulp is advanced into a papermaking and processing system. The charge of chlorine dioxide (or chlorine, or chlorine plus chlorine dioxide) in the bleaching stage can be proportional to the lignin content of the pulp being treated. Oxygen (indicated by “O”), oxygen generators such as peroxide (indicated by “P”), or combinations of them, can be used in combination with the bleaching agent in the bleaching stage or stages. Oxygen, oxygen generators such as a peroxide, or hypochlorite (indicated by "H"), or combinations of them, may be used in combination with the alkaline extraction material in the extraction stage or stages. For the extraction stage or stages, the alkaline extraction material can be used in combination with hydrogen peroxide (indicated by “Ep”). The alkaline extraction stage following the bleaching stage may contain other oxidizing agents or combinations of oxidizing agents, such as oxidizing extraction stages indicated as Eo (oxygen), Epo (peroxide and oxygen), or Eho (hypochlorite and oxygen). The bleaching process can comprise any of the following sequences: Do-Ep; or Do-Lavador-Ep; or of; or D-Washer-E; or Do-Washer-Ep- Washer-Do-washer; or Do-Washer-Ep-Washer-Do-Washer-Ep-Do-Washer; C-E; Zip code; or other strings.
[0057] Hemicellulases that have shown advantages in pretreating wood fiber in combination with an organic contaminant removal aid before bleaching include, for example, xylanases and / or mannanases. Hemicellulases can act on the hemicellulose portion of the pulp. Hemicellulose in the pulp can have two types of structures with main polysaccharide chains, which are arabinoxylan and glycomanane. Xylanase can be, for example, 1,4-beta-D-xylan-xylohydrolase (E.C. 3.2.1.8) which catalyzes the endo-hydrolysis of beta-D-xylidic bonds in xylans. Xylanase may have xylan degradation activity, pitch release activity, or both, in the co-presence of the organic contaminant removal adjuvant. When used herein, the term "xylan degradation activity" can be, for example, a biological activity that hydrolyzes material containing xylan. The mannanases can be, for example, endo-mannanases, such as endo-β-mannanase. Mannanase can have activity contributing to xylan release activity, pitch release activity, or both, in the co-presence of the organic contaminant removal adjuvant.
[0058] Hemicellulases can be used individually or in combinations with each other or with different types of enzymes. Other enzymes optionally used include those having lipolytic activity, such as lipase, esterase, cutinase, individually or in any combination thereof. The effect of including lipase or another lipolytic enzyme in the compositions of the present invention may, for example, be to increase hydrolysis of triglycerides associated with the components thereof. If included, lipase or another lipolytic enzyme can be used in an amount sufficient for this purpose as in similar concentrations indicated herein for hemicellulases.
[0059] Hemicellulases can be extracted, for example, from various fungi, and from other plant tissues, and can be produced by fermentation of selected microorganisms. For example, xylanases can be obtained by fermentation of a fungus strain of the species Aspergillis awamori or by fermentation of bacterial strains of Streptomyces olivochromogenes or Bacillus subtilis, or other fermentation processes. Mannanase preparations, for example, are commercially obtainable, including types that can be manufactured with the aid of genetically modified microorganisms (for example, Bacillus and Trichoderma types). Hemicellulases can be obtained commercially in ready-to-use preparations, from suppliers such as Novozymes A / S (Bagsvaerd, Denmark), or Dyadic International (Jupiter, FL) or Iogen Corporation (Ottawa, Ontario, Canada). The enzymes can be a dry or granulated powder, a non-powdered granulate, a liquid, a stabilized liquid, or a stabilized protected enzyme, or other forms suitable for addition to the fiber slurry or similar fiber-containing material. Liquid enzyme preparations can, for example, be stabilized by adding stabilizers such as a sugar, sugar alcohol or other polyol, and / or lactic acid or other organic acid according to established procedures. Dry powder forms can be lyophilized and include substrates. If enzyme substrates are present with dry powder forms of the enzymes, the substrates should not adversely interact with or interfere with fiber processing stages, such as bleaching, extraction, or papermaking processes. If used, lipolytic enzymes can be obtained and used similarly.
[0060] The methods, formulations, and systems of the present invention can use any appropriate enzyme or combination of two or more enzymes. One or more enzymes classified by The International Union of Biochemistry and Molecular Biology can be used, including oxidoreductases (EC1) to catalyze oxidation / reduction reactions, transferases (EC2) to catalyze transfer of a functional group, hydrolases (EC3) to catalyze the hydrolysis of several bonds, lyases (EC4) to catalyze the cleavage of several bonds by means other than hydrolysis and oxidation, isomerases (EC5) to catalyze isomerization changes within a single molecule, and ligases (EC6) to catalyze the union of two molecules with covalent bonds.
[0061] Many other enzymes can be used in the present invention. Enzymes can be used to produce bulk products, such as glucose and fructose, for food processing, for detergents, and for the textile, pulp and paper, and animal feed industries. Food production enzymes can be used. Fungal and plant amylases can be used in the production of starch sugars, for example, in the manufacture of high fructose corn syrup, and in baking. Proteases can be used to decrease the protein content of flour to make various baked goods. Trypsin can be used to pre-digest baby foods. Brewery and fermentation enzymes can be used, for example, Barley enzymes, amylase, glycanase, protease, betaglycanase, arabinoxylanase, amyloglycosidases, pululanases, cysteine endopeptidases, glycoamylases, and aceto-lactate-carboxylase. Cellulases and pectinases can be used to clarify fruit juices. Dairy enzymes can be used, for example, renin enzymes and coagulants for making cheese, lipases for curing cheese, lactase for breaking down lactose in dairy compositions, hydrolysates, transglutaminases, and beta-galactosidases. Papain can be used to tenderize meat. Enzymes can be used to convert starch into sugars and sweeteners, for example, amylase, amyloglycosidase, glycoamylase, and glucose isomerase. Paper industry enzymes can be used, for example, amylases, xylanases, cellulases, hemicellulases, laccases, and ligninases. Examples of enzymes include lipase to control sticky substances, xylanase for pre-bleaching, and cellulase for fiber modification. Biofuel enzymes can be used, for example, cellulases to break down cellulose for fermentation, and lignases. Proteases can be used to clean contact lenses and recycle films. Catalase can be used to convert latex to foam rubber. Proteases can be used to remove hair and lipases to remove fat from animal leathers in the leather industry. Detergent enzymes, for example, proteases, amylases, lipases, cellulases and mannanases, can be used. Textile enzymes can be used for fiber peeling, silk degumming, fiber bleaching, and denim aging (denim twill). Enzymes for oil fields, wastewater, and polymerization applications can also be used.
[0062] The enzyme or formulation containing the enzyme (for example, a preformed formulation containing the enzyme and polymeric surfactant of the present invention) can have an enzymatic activity of at least 10 units / g. For example, the enzyme or formulation containing the enzyme may have an enzyme activity of at least 15 units / g, at least 20 units / g, at least 25 units / g, at least 100 units / g, or at least 500 units / g, for example, from 15 units / g to 1,500 units / g.
[0063] The enzyme can be present in any appropriate amount or concentration based on the target substrate or composition-substrate. For example, the enzyme can be present in a concentration of about 0.5% by weight to about 5% by weight, based on the total weight of an enzyme formulation containing at least the enzyme and the polymeric surfactant. For example, the concentration of the enzyme can be from 0.1% by weight to 35% by weight, from 0.5% by weight to 35% by weight, from 1.0% by weight to 35% by weight, from 2 % by weight to 35% by weight, from 5% by weight to 35% by weight, from 10% by weight to 35% by weight, from 15% by weight to 35% by weight, from 20% by weight to 35% in weight, or more, based on the total weight of the enzyme formulation. When a given amount of water is present in the enzyme formulation, these percentages will be reduced proportionately by a dilution factor. Once the enzyme formulation is added to the substrate composition, the percentages will again be reduced by a dilution factor.
[0064] As indicated, measurement of brightness and whiteness values of fibers treated with compositions of the present invention can be used to evaluate the pretreatment effects of the compositions containing the enzyme and organic contaminant removal adjuvant of the present invention on the bleaching of fibers. Methods for assessing xylan degradation activity by compositions of the present invention on fiber prior to bleaching can also be measured, for example, by determining the reducing sugars formed from the various types of xylan, or by colorimetric determination of carbohydrates, as shown, for example , in US Patent Application Publication No. 2011/0078830 A1, which is incorporated here entirely by reference, or by adapting other conventional methods that are used to assess xylanolitic activity.
[0065] The polymeric surfactant can be at least one poloxamer. The polymeric surfactant can be a block copolymer of the PEO-PPO-PEO type. For the avoidance of doubt, the descriptions (and examples provided here) with respect to surfactant and organic contaminant removal adjuvant apply equally to both and are interchangeable.
[0066] The organic contaminant removal adjuvant can be at least a non-ionic surfactant. The nonionic surfactant can be at least one poloxamer. Poloxamers can be copolymers in non-ionic triblocks that comprise a central block of a hydrophobic poly (alkylene oxide) block, which is in the middle of two hydrophilic poly (alkylene oxide) blocks. The poly (alkylene oxide) blocks of the poloxamers can independently comprise lower alkylene oxide chains, such as C2, C3, or C4 alkylene oxide chains. As an option, the poloxamer can comprise a central block of poly (propylene oxide) (PPO) or poly (butylene oxide) (PBO), sandwiched between two blocks of poly (ethylene oxide) (PEO). Poloxamers can be copolymers of PEO-PPO-PEO which can have the general formula I: HO (C2H4O) a (C3H6O) b (C2H4O) aH, where a and b are the respective average numbers of monomeric units of EO and PO in the blocks. Applicable PEO and PPO. The PEO-PPO-PEO structure can be a bifunctional block copolymer surfactant that ends in primary hydroxyl groups. Figure 2 shows the structure of a poloxamer that can be used. Because of their amphiphilic structure, poloxamers can have non-ionic (that is, no-charge) surfactant properties.
[0067] Poloxamers can be synthesized sequentially. For example, a central block can be first polymerized from PO to form PPO, then external blocks of PEO can be added at the ends of the central PPO block in a second polymerization step using EO. Commercial sources of poloxamers are, for example, PLURONIC® copolymers from BASF Corporation (Florham Park, New Jersey, USA). These compounds are commonly named with the word Poloxamer followed by a number to indicate the specific copolymer, for example, Poloxamer 407 having two PEG blocks of about 101 units (each y1 and y3 equal to 101) and a polypropylene block of about of 56 units. This polymer is obtainable from BASF under the trade name LUTROL ™ F-17. In BASF's PLURONIC® code, the alphabetical designation can be derived from the physical form of the product at room temperature: L for liquids, P for pastes, and F (solid) flake forms. In the numerical designation, the last digit multiplied by 10 can indicate the approximate percentage (weight / weight) of the hydrophilic portions in the PLURONIC® copolymer. Trade names of the poloxamer that can be used in the present methods and compositions may include, for example, PLURONIC® F38, PLURONIC® F68, PLURONIC® F88, PLURONIC® F98, PLURONIC® F108, PLURONIC® F87, PLURONIC® P105, and PLURONIC® F127. For example, PLURONIC® F108 can comprise about 80% PEO (total): about 20% PPO on a weight: weight (w / w) basis, and an average molecular weight of about 14,600 g / mol. Liquid copolymer formulations in ethylene oxide, propylene oxide, for example, PLURAFLO® L 1060 and PLURAFLO® L 1220, obtainable from BASF, can be used. The physical properties of poloxamers can range from low-viscosity liquids to pastes to solids, depending on the precise combination of molecular weight and PEO: PPO ratio. The weight ratio of total PEO to PPO can be from about 1: 9 to about 9: 1, or from about 1: 9 to about 8: 2, or from about 2: 8 to about 8: 2, or from about 2.5: 7.5 to about 7.5: 2.5, or from about 4: 6 to about 6: 4, or other values. The proportion of PEO can comprise at least a predominant amount (i.e.,> 50%) of the total PEO content of the poloxamer PPO on a weight basis. A poloxamer that can be used can comprise a PEO: PPO ratio, on a weight: weight (w / w) basis, from about 50:50 to about 95: 5, or from about 60:40 to about 90 : 10, or about 75:25 to about 85:15, or about 78:22 to about 82:18, or about 80:20, or other values. In general, poloxamers can have molecular weights, for example, from about 1,000 g / mol to about 25,000 g / mol, or from about 2,500 to about 22,500 g / mol, or from about 5,000 g / mol to about 20,000 g / mol, or about 7,500 g / mol to about 18,000 g / mol, or about 10,000 g / mol to about 16,000 g / mol, or about 12,000 g / mol to about 15,000 g / mol, from about 12,000 g / mol to about 17,000 g / mol, from about 13,500 g / mol to about 16,000 g / mol, or about 15,000 g / mol, or other values.
[0068] The solubility in water of non-ionic surfactants such as poloxamers can be related to their value or number of hydrophilic-lipophilic balance (HLB). HLB values can be calculated by means known in the art, for example, see “The HLB System”, ICI Americas, Inc., 1980. HLB values can be calculated for molecules, for example, of surfactants or emulsifiers that have hydrophilic characteristics and / or lipophilic. HLB values can be determined theoretically, experimentally and / or estimated differently. The HLB value can correspond to the weight percentage of the hydrophilic portion of the molecule divided by a factor for 100% hydrophilic molecule would have an HLB value of 20. For example, a poloxamer containing 80 mol% of PEO (total) would have a value of HLB calculated to be 16 (that is, 80/5 = 16). HLB values that exceed 20 are relative or comparative values. The percentage of the molecule that is hydrophilic can be determined theoretically by dividing the molecular weight of the hydrophilic portion of the molecule by the total molecular weight of the molecule. HLB values of the polymeric surfactants used in the present invention can be at least about 15, at least about 16, at least about 17, at least about 19, at least about 20, at least about 22, at least about 24, at least about 25, at least about 26, at least about 28, at least about 30, at least about 35, at least about 40, or at least about 50. Other polymeric surfactants that can be used may have HLB values less than about 15. Nonionic surfactants, cationic surfactants, anionic surfactants, zuiterionic surfactants, amphiphilic surfactants, or combinations of the same. In addition to the polymeric surfactant, non-polymeric surfactants can also be used.
[0069] The presence of the hydrophilic PEO end portions in the poloxamers means that the surfactant molecules normally have an HLB value that is greater than zero, that is, they have some hydrophilic character. PPO can have an HLB value close to zero, for example, less than 0.5. Where the PEO content of the poloxamers comprises a predominant amount of the copolymer, the hydrophilic character of the copolymer can be expected to be more than the lipophilic character of the molecule. The HLB values of poloxamers that contain a predominant amount of PEO can be, for example, at least about 10, or at least about 11, or at least about 12, or at least about 13, or at least about 14, or at least about 15, or at least about 16, or at least about 17, or at least about 18, or at least about 19, or about 10 to about 19.9, or about 11 to about 19, or about 12 to about 18, or about 13 to about 17.5, or about 14 to about 17, or other values. HLB values can be estimated by experimental methods, so that HLB values are aligned or normalized with one or more molecules having a known HLB value. An experimental method of determining HLB may involve mixing the unknown molecule in varying ratios with a known HLB molecule, and using the mixture to emulsify an oil having a known required HLB. The best performing mixture can be considered to have an HLB value approximately equal to the required HLB of the oil. You can then calculate the HBL value of the unknown. You can repeat the experimental procedure and consider the average. HLB values can also be estimated from the dispersibility or water solubility of a molecule.
[0070] The amount of polymeric surfactant used can be, for example, an amount of about 0.5% by weight to about 30% by weight, from about 0.5% by weight to about 15% by weight , from about 1.0% by weight to about 25% by weight, from about 1.0% by weight to about 10% by weight, from about 2.5% by weight to about 20% by weight weight, from about 5.0% by weight to about 15% by weight, from about 7.5% by weight to about 17.5% by weight, or from about 10% by weight to about 15 % by weight, based on the total weight of an enzyme formulation. The polymeric surfactant can be present in an amount of at least 0.1% by weight, at least 0.5% by weight, at least 1.0% by weight, at least 5.0% by weight, or at least 10% by weight, based on the total weight of the substrate or the substrate composition. The enzyme and polymeric surfactant can be present in a weight ratio of enzyme to nonionic polymeric surfactant from about 0.01: 10 to about 10: 0.01, or from about 0.1: 10 to about 10: 0.1, or from about 0.5: 5.0 to about 5.0: 0.5, or from about 1.0: 2.0 to about 2.0: 1.0.
[0071] When formulated in an enzyme formulation that can be used to treat a substrate, the enzyme formulation can include the enzyme, polymeric surfactant, water, and other ingredients for formula stabilization. Dosages of the enzyme formulation that can be used can be, for example, from about 0.01 to about 10.0 pounds / tonne of dry substrate, from about 0.1 to about 5.0 pounds / tonne of dry substrate, from about 0.25 to about 2.5 pound / tonne of dry substrate, or from 0.5 to about 2.0 pound / tonne of dry substrate. The same dosage amounts can be used if the enzyme is added alone, without the surfactant. If the enzyme and surfactant are added separately, the amount of surfactant dosage can be, for example, from about 0.001 to about 5.0 pound / tonne of dry substrate, from about 0.0015 to about 3.0 pound / tonne of dry substrate, from about 0.01 to about 1.0 pound / tonne of dry substrate, or from 0.025 to about 0.75 pound / tonne of dry substrate.
[0072] Any suitable non-ionic or different polymeric surfactant can be used. For example, poly (ethylene glycol), including esters derived therefrom, such as its methyl ester or fatty acid esters (for example, PEG palmitate). PEO-PPO-PEO block polymers and random PEO-PPO polymers can be used. TRITON-X-100 (poly (ethylene glycol) p- (1,1,3,3-tetramethyl butyl) -phenyl ether) can be used, which is a non-ionic surfactant that contains a portion of poly (ethylene glycol) . Examples of some polymeric surfactants that can be used include the following: polyoxyethylene sorbitan monopalmitate (TWEEN 40), poly (ethylene glycol) sorbitan monolaurate, polyoxyethylene sorbitan monolaurate (TWEEN 20), TERGITOL 15-S-20, TERGITOL 15- S-30, TERGITOL 15-S-40, poly (ethylene glycol-block-poly (propylene glycol) -block-poly (ethylene glycol) (PEG-PPG-PEG, PLURONIC® F-68), poly (ethylene glycol- block-poly (propylene glycol) -block-poly (ethylene glycol) (PEG-PPG-PEG, PLURONIC® F-108), polyoxyethylene (150) dinonyl phenyl ether, polyoxyethylene, dinonyl phenyl and nonyl phenyl ethers, branched (IGEPAL® DM-970), polyoxyethylene (100) stearyl ether (BRIJ® S 100), poly (ethylene glycol-block-poly (propylene glycol) -block-poly (ethylene glycol) (PEG-PPG-PEG, PLURONIC® L-35 ), polyoxyethylene (40) nonyl phenyl ether, branched (IGEPAL® CO-890), and poly (ethylene glycol) hexadecyl ether, polyoxyethylene (20) cetyl ether (BRIJ® 58). Sigma-Aldrich (St. Louis, Missouri), except TERGITOL surfactants, which are obtainable from Dow Chemical (Midland, Michigan). The polymeric surfactant can have an average molecular weight (in Dalton) of 1,000 to about 20,000, for example, from about 2,000 to about 15,000, from about 3,000 to about 12,000, from about 5,000 to about 20,000, from about 10,000 to about 20,000, from about 12,000 to about 17,000, from about 13,500 to about 16,000, at least about 20,000, at least about 50,000, at least about 100,000, or at least 500,000. The fiber that can be treated by compositions of the present invention before bleaching is not necessarily limited. As indicated, the fiber may be in the form of pulp, although it is not limited to this. The wood fiber can be a particulate form of a wood fiber source that is made into a slurry, dispersed, or suspended in an aqueous medium. As indicated, the pulp can be virgin wood fiber pulp, recycled fiber pulp, or any combination thereof. The wood fiber can be hardwood, white wood, or any combination thereof. The pulp to be treated can be, for example, kraft pulp, sulfite pulp, sulfate pulp, soda pulp, mechanical pulp, thermomechanical pulp, chemo-thermomechanical pulp, recycled paper pulp, or any combination thereof. Typical pulp slurries in paper applications may contain, for example, from about 0.2 to about 18% by weight of organic matter, based on the total weight of 100% slurry. Organic matter is typically made up of wood fiber (or pulp) and any derivatives. Generally, organic matter comprises from about 90% to about 99% by weight of wood fiber (or pulp), based on the total weight of 100% organic matter. The fiber may derive at least partially from recycled paper, for example, at least 5%, or at least 10%, or at least 25%, or at least 50%, or at least 75% by weight of recycled paper, based on in the total fiber used on a dry weight basis. The pulp slurry may also contain additives known in the art. Examples of such additives include, but are not limited to, algaecides, sodium hydroxide (or other base), peroxide stabilizers, such as sodium silicate, magnesium sulfate, and polyphosphates, chelating agents, such as EDTA, fatty acids, and any combinations thereof. Optional additives, if used, must not interfere with the indicated action of the pretreatment compositions of the present invention, or with the bleaching process or with other downstream processes.
[0073] Paper products are also provided with pre-treated and bleached fiber according to the methods of the present invention. Discolored paper products can be, for example, sheets of paper capable of printing or painting, sheets for construction of cardboard, tissue paper, coating or sheet materials for personal care and hygiene, and other paper-based products. Paper products made by the methods of the present invention can achieve the same% ISO gloss when compared to paper products made with (a) more extensive bleaching, and therefore more expensive bleaching, or (b) when modified during papermaking for contain larger amounts of brightening or bleach additives added irrelevantly, and therefore needs more expensive additives. Brightening additives or brighteners that have been used in papermaking include, for example, mineral bleaches (for example, titanium dioxide, barium sulfate), and organic brighteners (for example, fluorescent bleaches / brighteners). A reduction in the quantities of use of these additives can reduce costs. As an option, paper products made by methods using compositions of the present invention in fiber pretreatments before bleaching can achieve the same% ISO gloss with total reduction of brightening and whitening additives during papermaking as made paper products without pretreatment with the present compositions. As an option, paper products made by methods using compositions of the present invention in fiber pretreatments prior to bleaching can reduce the total amount of brightening additives or bleaches needed to obtain a specific gloss of at least about 5% by weight , or at least about 10% by weight, or at least 15% by weight, or at least 20% by weight, or other amounts. For example, if titanium dioxide was added to the paper during papermaking to provide 78% ISO gloss, the addition of the pretreatment of the present invention can reduce the titanium dioxide requirements to obtain that same gloss for at least 5% by weight or more.
[0074] In addition to the enzyme and the polymeric surfactant, other components can be used in addition, such as preservatives, stabilizers, deodorants, fillers, diluents, and the like. For example, at least one stabilizer, such as PVP, can be used, with or without glycerol. In addition, one or more salts, such as calcium chloride or other salts, may be present. The enzyme and polymeric surfactant can be diluted or prepared in water or other aqueous solutions. For example, the glycerol or similar component can be present in an amount of 5.0% by weight to about 30% by weight, based on the total weight of an enzyme formulation (without dilution with water). PVP, such as PVP K90 or similar component, can be present in an amount of about 1.0% by weight to about 10% by weight based on the total weight of the enzyme formulation (without dilution with water). CaCl2 or similar component can be present in an amount of about 0.1% by weight to about 2.0% by weight based on the total weight of the enzyme formulation (without dilution with water). A preservative (preservative), such as BUSAN® 1078, can be present in an amount of 0.05% by weight to about 0.2% by weight based on the total weight of the enzyme formulation (without dilution with water).
[0075] Biocides can be used to preserve the formulations of the present invention for storage purposes. Biocides that can be used include, for example, biocides from Buckman Laboratories International, such as BUSAN® 1078. If biocides are present, the amounts may be below 1.0% by weight, less than 0.5% by weight, less than 0.1% by weight, or from about 0.001% by weight to about 0.01% by weight based on the total weight of the components that form the enzyme formulation (without dilution with water), or based on weight of dry substrate.
[0076] In the present invention, the enzyme, polymeric surfactant, and any optional components can be added together as a preformed enzyme formulation or each individual component or any combination of components can be added separately, such as sequentially, in batch, or at the same time through different injection entry points. The enzyme formulation or components thereof can be introduced in any time, for example, from about 10 seconds to about 150 hours or more, can be introduced periodically, or can be introduced all at once. The addition of the polymeric surfactant and the enzyme can be simultaneous, sequential, or alternating. For example, the addition of the enzyme and polymeric surfactant can occur within 10 seconds of each other, within 1 minute of each other, within 10 minutes of each other, within 30 minutes of each other, within an interval 1 hour apart from each other, within 6 hours of each other, within 12 hours of each other, in any order. An enzyme formulation can be prepared by mixing the components in any order. Water or an aqueous solution or component can be used to form the enzyme formulation. Water or an aqueous solution or component can be present in an amount of about 10% by weight to about 90% by weight based on the total weight of the enzyme formulation diluted with water.
[0077] The enzyme formulation of the present invention or the components forming the enzyme formulation of the present invention can be applied or introduced in any way to the substrate or substrate composition, such as by spraying, draining, injection, mixing, and the like. Any contact technique can be used to bring the components of the enzyme formulation of the present invention into contact with the substrate or substrate composition. The enzyme formulation or the components that make up the enzyme formulation can be subsequently mixed with the substrate composition or differently dispersed in the substrate composition in order to improve the rate of degradation. The enzyme formulation can be in liquid form, in solid form, in dry form, in tablet form, or semi-solid form. The enzyme formulation can be incorporated or present in a cartridge, or it can be present in a membrane or filter or on any surface that contacts the composition-substrate.
[0078] The enzyme formulation of the present invention or components that make up the enzyme formulation can be introduced into the substrate composition in a tank, in a settling tank, and / or in another retention location. The water content of the substrate composition being treated can be any water content, such as from about 1.0% by weight to about 99% by weight based on the total (wet) weight of the substrate composition.
[0079] According to the present invention, after the enzyme and polymeric surfactant contact the composition-substrate, the treatment can last for any appropriate contact time. For example, the contact time can be about 30 minutes to about 48 hours or more, or about 1.0 hour to about 150 hours or more. In other examples, the contact time can be from 5.0 hours to 100 hours, from about 10 hours to about 75 hours, from about 24 hours to about 72 hours, or at least about 48 hours or more. Contact time can be based on the particular process used at the location of the substrate composition. Reaction conditions for degradation can be variable or constant with respect to pH, temperature, or any other relevant parameter. Degradation can be carried out at a temperature of about 5 ° C to about 95 ° C, about 15 ° C to about 80 ° C, about 25 ° C to about 60 ° C, or about from 35 ° C to about 50 ° C. The pH of the substrate composition, including added enzyme and polymeric surfactant, can be about 2.0 to about 12, about 4.0 to about 10, or about 6.0 to about 8, 0. After the contact time, dehydration of the degradation product may occur. Any method known in the art can be used to dehydrate the degradation product. For example, dehydration can be achieved using a settling tank or tank and then, pressing, extruding, filtering, centrifuging, and the like.
[0080] The present invention includes the following aspects / incorporations / characteristics in any order and / or in any incorporation: 1. Method for controlling organic contaminants that interfere with fiber bleaching in a papermaking system, characterized by the fact that it comprises: (a) before any bleaching step, contact the fibers with a composition comprising at least one hemicellulase and at least one adjuvant of organic contaminant removal to provide treated fibers in which organic contaminants release the fibers in greater quantity than where the fibers are contacted with the composition without said organic contaminant removal adjuvant, with organic contaminants comprising one or more xylans, a or more pitch components, or both; and (b) bleaching treated fibers to form bleached fibers.2. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that it also comprises: (c) converting the bleached fibers into a paper product.3. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the paper product has an ISO gloss that is about 0.5 units to about 5.0 units higher than that of a paper product. paper produced with the method without said organic contaminant removal adjuvant included in the composition.4. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that said contact removes at least 50% by weight of xylans and pitch total components present in the fibers before said contact.5. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that said bleaching comprises contacting the fibers treated with a bleaching agent which is chlorine dioxide, hydrogen peroxide, oxygen, elemental chlorine, hypochlorite, ozone , or any combinations thereof.6. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that said organic contaminant removal adjuvant is at least a non-ionic surfactant.7. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that said organic contaminant removal adjuvant is a poloxamer.8. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the organic contaminant removal adjuvant is a poloxamer having an HLB index greater than or equal to 16.9. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the hemicellulase is xylanase, mannanase, or both.10. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the composition also comprises a lipolytic enzyme.11. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the composition also comprises a lipolytic enzyme which is lipase, esterase, cutinase, or any combinations thereof.12. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that said composition is introduced in an amount providing from about 100 to about 1,000 grams of said hemicellulase per ton of said fibers on a dry fiber basis, and from about 1.0 to about 100 grams of said organic contaminant removal aid per ton of said fibers on a dry fiber basis.13. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that said fibers treated with said composition have a Kappa index that is about 0.2 to about 3.0 units lower than non-fibers treated with said composition. 14. Composition, characterized by the fact that it comprises a hemicellulase and an organic contaminant removal adjuvant capable of removing organic contaminants comprising one or more xylans, one or more pitch components, or both, of fibers in an amount greater than where the fibers are contacted with the composition without said organic contaminant removal adjuvant.15. Composition, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the organic contaminant removal adjuvant is a non-ionic surfactant.16. Composition, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the organic contaminant removal adjuvant is a poloxamer.17. Composition, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the organic contaminant removal adjuvant is a poloxamer having an HLB index greater than or equal to 16.18. Composition, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the hemicellulase is xylanase, or mannanase, or any combination thereof.19. Composition, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that it also comprises a lipolytic enzyme.20. Composition, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that it comprises from about 10% to about 90% by weight of said hemicellulase, and from about 1.0% to about 10% in weight of said organic contaminant removal adjuvant, based on the weight of total solids of said composition.21. Paper product, characterized by the fact that it is obtained by the method as defined by any previous or next incorporation, characteristic / aspect.22. Paper product, characterized by the fact that it contains the composition as defined by any incorporation, previous or next feature / aspect.23. Method for improving enzymatic degradation of a substrate, characterized by the fact that it comprises: adding at least one non-ionic polymeric surfactant in a substrate composition, the surfactant having a hydrophilic-lipophilic balance (HLB) of at least 17; adding at least one enzyme to the substrate composition, the enzyme comprising a cellulase, a xylanase, a laccase, an amylase, a protease, a peroxidase, or any combination thereof; and degrade the substrate composition in the presence of the nonionic polymeric surfactant and the enzyme to form a degradation product.24. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the nonionic polymeric surfactant is present in an amount of at least 0.1% by weight, based on the total weight of the substrate composition.25. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the enzyme and the nonionic polymeric surfactant are present in a weight ratio of enzyme to nonionic polymeric surfactant from 0.01: 10 to 10: 0, 01. 26. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that an enzyme activity of the enzyme in the presence of the nonionic polymeric surfactant is at least 10% greater than the enzyme activity of the enzyme alone.27. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the degradation is carried out at a temperature of about 5 ° C to about 80 ° C.28. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the nonionic polymeric surfactant is a block copolymer of the type PEO-PPO-PEO.29. Method, according to any incorporation, previous or next feature / aspect, characterized by the fact that the HLB is from about 22 to about 30.30. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the nonionic polymeric surfactant and the enzyme are added sequentially with a difference of 30 minutes from each other in any order.31. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the nonionic polymeric surfactant has an average molecular weight of about 12,000 Dalton to about 17,000 Dalton.32. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the substrate composition comprises paper pulp, paper mill sludge, or animal leather. 33. Method for improving enzymatic degradation of a substrate, characterized by the fact that it comprises: adding at least one polymeric surfactant in a substrate composition, the polymeric surfactant comprising at least one non-ionic block copolymer of the type PEO-PPO-PEO ending in groups primary hydroxyl; adding at least one enzyme to the substrate composition, the enzyme comprising a cellulase, a xylanase, a laccase, an amylase, a protease, a peroxidase, or any combination thereof; and degrade the substrate composition in the presence of the polymeric surfactant and the enzyme to form a degradation product.34. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the polymeric surfactant is present in an amount of at least 0.1% by weight, based on the total weight of the substrate composition.35. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the enzyme and the polymeric surfactant are present in a weight ratio of enzyme to polymeric surfactant from 0.1: 10 to 10: 0.1.36. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that an enzyme activity of the enzyme in the presence of the polymeric surfactant is at least 10% greater than the enzyme activity of the enzyme alone.37. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the degradation is carried out at a temperature of about 5 ° C to about 80 ° C.38. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the polymeric surfactant exhibits an HLB of at least 20.39. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the HLB is from about 22 to about 30.40. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the polymeric surfactant and the enzyme are added sequentially with a difference of 30 minutes from each other in any order.41. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the nonionic polymeric surfactant has an average molecular weight of about 12,000 Dalton to about 17,000 Dalton.42. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the substrate composition comprises fibers, paper pulp, paper mill sludge, or animal leather.43. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that it also comprises dehydrating the degradation product.44. Method for improving enzymatic degradation of a substrate, characterized by the fact that it comprises: adding at least one nonionic polymeric surfactant in a substrate composition, the nonionic polymeric surfactant comprising a propoxylated block copolymer having a hydrophilic-lipophilic balance (HLB) of hair minus 20; adding at least one enzyme to the substrate composition; and degrade the substrate composition in the presence of the nonionic polymeric surfactant and the enzyme to form a degradation product.45. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the nonionic polymeric surfactant is present in an amount of at least 0.1% by weight, based on the total weight of the substrate composition.46. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the enzyme and the nonionic polymeric surfactant are present in a weight ratio of enzyme to polymeric surfactant from 0.1: 10 to 10: 0.1.47. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that an enzyme activity of the enzyme in the presence of the polymeric surfactant is at least 10% greater than the enzyme activity of the enzyme alone.48. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the HLB is from about 22 to about 30.49. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the nonionic polymeric surfactant has an average molecular weight of about 13,500 to about 16,000.50. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that the substrate composition comprises paper pulp, paper mill sludge, or animal leather.51. Method, according to any incorporation, previous or next characteristic / aspect, characterized by the fact that it also comprises dehydrating the degradation product.
[0081] The present invention can include any combination of these various features or embodiments above and / or below shown in the sentences and / or paragraphs. Any combination of features disclosed herein is considered to be part of the present invention and there is no intention of limitation with respect to combinable features.
[0082] The present invention will be further clarified by the following examples, which are intended to be exemplary of the present invention only. Unless otherwise indicated, all quantities, percentages, ratios and the like used here are by weight.
[0083] The following Examples provide results for gloss (% ISO), gloss increases, and L * a * b * CIE scale, and / or Kappa index values for bleached pulps that are pretreated before bleaching with different compositions containing different additives. The “Control” was not pre-treated. Example 1:
[0084] AlPac pulp (Alberta, Canada) was obtained. The type of fiber was kraft wood bleached from the north. The treatment process applied to the pulp included three stages, including a pretreatment stage (X) in which the pulp was treated with a composition containing xylanase and a poloxamer, a chlorine dioxide bleaching stage including oxygen (Do), and an alkaline extraction stage including hydrogen peroxide (Ep). Xylanase ("XylA") was obtained commercially as an aqueous suspension (approximately 5% by weight of active enzyme solids) from Iogen Corporation. Xylanase (“XylB”) was obtained commercially as an aqueous suspension (approximately 5% by weight of active enzyme solids) from Novozymes. The activity of xylanase (“XylB”) attested by the supplier was 1,000 AXU / g or 1,000 AXU / mL. The poloxamer was the surfactant (“Surf”) of block copolymer PLURONIC® F108, obtained from BASF Corporation. The xylanase and poloxamer were dispersed in an aqueous medium in concentrations shown in the table in Figure 3 in units of “g / ton” or “gram / metric ton” (“Table I”). One metric ton is equal to 1,000 kg. A comparison composition (“CONC LBL”) used was a cellulase and hemicellulase complex, obtained as FIBREZYME® LBL, from Dyadic International Inc., Jupiter, FL, USA The conditions for the stages of the bleaching process are as follows: Stage X - 60 minutes, 50 ° C, pH 7.3-7.4, concentration of 10% by weight of xylanase + poloxamer composition; Do Stage - 45 minutes, pH 2.0-2.1, 8% concentration, ClO2 in 10 kg / metric ton of fiber; Ep stage - 60 minutes, 65 ° C, pH 11.7-11.8, 10% concentration, H2O2 in 6 kg / metric ton of fiber and 1.2% NaOH by weight.
[0085] It was included as a Control, a pulp that was not pre-treated (that is, no stage X before the stages Do and Ep). The brightness (ISO) of the pulps was determined after the extraction stage in leaves prepared manually from the pulps. The sheets were prepared according to TAPPI T 218 (“Forming Handsheets for Reflectance Tests of Pulp”) or a substantially equivalent method. The whiteness and color of the pulps were evaluated by measuring L * a * b * CIE scale values for the leaves prepared manually using a colorimeter.
[0086] The table in Figure 3 shows the brightness (% ISO), brightness increase, and L * a * b * CIE scale values for those after the Do bleaching stage with sulfur dioxide and the alkaline extraction stage Ep . The data in the table in Figure 3 and the bar graphs in Figure 4 show that the gloss (% ISO) after the pretreatment stage (if used), the bleaching stage, and the alkaline extraction stage of fiber processing of pulp was maximum for the pulps pretreated with a composition comprising xylanase and poloxamer according to the present invention when compared to the Control (without X stage), or pulps treated only with the enzyme (xylanase) before the bleaching stages and extraction, or comparison composition (CONC LBL). The data in the table in Figure 3 and the bar graph in Figure 5 show that the brightness increase after the pretreatment stage (if used), the bleaching stage, and the alkaline extraction stage of pulp fiber processing was maximal for the pulps pretreated with a composition comprising xylanase and poloxamer according to the present invention when compared to the Control (without X stage), or pulps treated only with the enzyme (xylanase) before the bleaching and extraction stages, or the comparison composition (CONC LBL). The brightness increase values in the table in Figure 3 are normalized in relation to the value of the Control sample.
[0087] With respect to the L * a * b * scale values shown in the table in Figure 3, the L * values were maximum for the pulps pretreated with a composition comprising xylanase and poloxamer according to the present invention when compared to o Control (without stage X), or pulps treated only with the enzyme (xylanase) before the bleaching and extraction stages, or the comparison composition (CONC LBL).
[0088] The three coordinates of CIELAB represent the color illumination (L * = 0 produces black and L * = 100 indicates diffuse white; specular white can be greater), its position between red / magenta and green (a *, negative values indicate green while positive values indicate magenta) and its position between yellow and blue (b *, negative values indicate blue while positive values indicate yellow). With respect to the data in the table shown in Figure 3, higher L * values observed for pulps pretreated with a composition comprising xylanase and poloxamer according to the present invention means that those pulps were whiter than the Control pulp and that the pulps treated only with the enzyme (xylanase) before the bleaching and extraction stages, or the comparison composition (CONC LBL). Example 2:
[0089] A range of experimental formulations containing the same organic contaminant removal adjuvant as Example 1 was prepared based on different dosages of raw material xylanase (PULPZYME® HC, from Novozymes A / S, Denmark) for pulp treatment . The experiments were used to compare the potential effectiveness of xylanase in reducing the Kappa index and subsequently improving the brightness.
[0090] The composition of the experimental formulation used for these experiments is shown in Table 1 below:

[0091] The "Stabilizer" in Formulation 1 in Table 1 is an aqueous solution containing propylene glycol and polyvinylpyrrolidone.
[0092] A pulp that has not been pre-treated is included as a Control (that is, no X stage before the Do and Ep stages). In the test, the Kappa index (amount of xylans adhering to the cellulosic fibers) was determined in the pulp fiber samples after treatment with the Formulation 1 enzyme composition and for the Control composition. The pulp used in these experiments was similar to that used in Example 1. The conditions at all stages of the process were as follows:
[0093] Stage X: Known weights of fiber samples were treated with known concentrations of enzyme samples with the composition of Formulation 1 for a predetermined time and temperature, similar to those used in Example 1. Depending on the properties of xylanase, the pH is typically slightly alkaline (pH = 8).
[0094] Stage Do: Then, the acidity of the treatments was reduced to pH = 2, and a known amount of an oxidant solution (typically ClO2) was added, similar to the conditions used in Example 1.
[0095] Ep stage: The acid and enzyme in each sample were neutralized with base and peroxide, and the fiber is rinsed, similar to the conditions used in Example 1.
[0096] After determining Kappa indices after enzyme treatment (post-X stage) with Formulation 1, and after the Do and Ep stages, samples of treated and bleached fibers were used to prepare paper samples (“hand sheets”) for brightness measurements. Brightness was determined for both the wire side and the felt side of the hand sheets. During the papermaking process, the side of the paper that does not touch the yarn in the paper machine is the felt side, which is opposite the yarn side. For the Control, the fiber that was not treated with Formulation 1 was bleached and used to prepare paper samples (“hand sheets”) for brightness measurements. L * a * b * data was also measured for manual sheets. Table 2 shows the results.

[0097] The data in Table 2 demonstrate that there is a progressive reduction in the Kappa index of the fiber with increased dosage (g / ton) of xylanase with PLURONIC® F108 in the formulation used in the experiment. These results are shown in the bar graphs in Figure 6, which show the highest Kappa index for the untreated control fiber (Control) when compared to the treated fiber samples. As an additional observed result of the enzymatic reduction of the Kappa index in the pulp fiber is the simultaneous improvement in the fiber luster in the manual leaf products prepared with the treated fiber, measured by a laboratory instrument. This is shown in Figure 7. An unexpectedly improved enzymatic tool (xylanase + PLURONIC® F108) to assist removal of xylans is shown by the measured reduction in Kappa index and improvement in brightness (% ISO) in a given set of conditions under which the Formulation 1. The maximum effective dosage of formulation for increasing gloss for these experiments was identified as 500 g / ton. Examples 3:
[0098] A lipase was tested for its enzymatic activity in a laboratory setup in the presence of several different surfactants. Lipase was added first in the test system. Then, a surfactant was added to the system, which included a substrate composition containing lipids. The enzyme activity of the enzyme was compared in the presence of a surfactant with the activity of the same enzyme but not in the presence of the surfactant. Table 3 shows the results. PLURONIC® F108, a nonionic polymeric surfactant, was able to improve lipase activity by 54.4%. Two cationic surfactants, BFL-5031 and BFL-5376, were used instead of PLURONIC® F108 and actually inhibited lipase activity by 45.9% and 57.7%, respectively. Another non-ionic surfactant, TOMADOL 1-7, improved lipase activity by 13.9%. PLURONIC® F108 was much better than TOMADOL 1-7 for improving lipase activity. U, anionic surfactant, BSP-275, showed a negative effect reduced lipase activity by 12.8%.

[0099] Applicants specifically incorporate the entire contents of all references cited in this disclosure. In addition, when an amount, concentration, or other value or parameter is given as a range, preferred range, or a list of preferable upper values and preferable lower values, it is to be understood as specifically disclosing all ranges formed by any pair of any upper limit of range or preferred value and any lower limit of range or preferred value, regardless of whether the ranges are disclosed separately. Where a range of numerical values is mentioned here, unless otherwise stated, the range is intended to include the extreme points of the range, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values mentioned when defining the range.
[0100] Other embodiments of the present invention will become obvious to those skilled in the art from consideration of the present report and practice of the present invention disclosed herein. It is intended that the present specification and examples are considered only as examples with the true scope and spirit of the invention being indicated by the following and equivalent claims of the same.

权利要求:
Claims (29)
[0001]
1. Method for controlling organic contaminants, which interfere with bleaching fibers in papermaking systems, characterized by the fact that it comprises: (a) contacting, before any bleaching step, fibers with a composition comprising at least one hemicellulolytic enzyme and at least one organic contaminant removal adjuvant to provide treated fibers in which organic contaminants release the fibers in greater quantity than where the fibers are contacted with the composition without said organic contaminant removal adjuvant, the organic contaminants comprising a or more xylans, one or more pitch components, or both; and (b) bleaching the treated fibers to form bleached fibers.
[0002]
2. Method according to claim 1, characterized by the fact that it further comprises: (c) converting the bleached fibers into a paper product.
[0003]
3. Method, according to claim 2, characterized by the fact that the paper product has an ISO gloss that is 0.5 units to 5.0 units higher than that of a paper product produced with the method without said organic contaminant removal aid included in the composition.
[0004]
4. Method according to claim 1, characterized in that said contact removes at least 50% by weight of xylans and total pitch components present in the fibers before said contact.
[0005]
5. Method according to claim 1, characterized in that said bleaching comprises contacting the fibers treated with a bleaching agent which is chlorine dioxide, hydrogen peroxide, oxygen, elemental chlorine, hypochlorite, ozone, or any combinations of the same.
[0006]
6. Method according to claim 1, characterized in that said organic contaminant removal adjuvant is at least a non-ionic surfactant.
[0007]
Method according to claim 1, characterized in that said organic contaminant removal adjuvant is a poloxamer.
[0008]
8. Method according to claim 1, characterized in that the organic contaminant removal adjuvant is a poloxamer having an HLB index greater than or equal to 16.
[0009]
9. Method according to claim 1, characterized in that the hemicellulase is xylanase, mannanase, or both.
[0010]
10. Method according to claim 1, characterized in that the composition further comprises a lipolytic enzyme.
[0011]
11. Method according to claim 1, characterized in that the composition further comprises a lipolytic enzyme which is lipase, esterase, cutinase, or any combination thereof.
[0012]
12. Method according to claim 1, characterized in that said composition is introduced in an amount providing from 100 to 1,000 grams of said hemicellulase per ton of said fibers on a dry fiber basis, and from 1.0 to 100 grams of said organic contaminant removal aid per ton of said fibers on a dry fiber basis.
[0013]
13. Method according to claim 1, characterized in that said fibers treated with said composition have a Kappa index that is 0.2 to 3.0 units lower than fibers not treated with said composition.
[0014]
14. Composition, characterized by the fact that it comprises a hemicellulolytic enzyme and an organic contaminant removal adjuvant capable of removing organic contaminants comprising one or more xylans, one or more pitch components, or both, of fibers in a greater amount than when the fibers are contacted with the composition without said organic contaminant removal adjuvant and said organic contaminant removal adjuvant being a block copolymer of polyalkylene oxide.
[0015]
15. Composition according to claim 14, characterized in that the organic contaminant removal aid is a non-ionic surfactant.
[0016]
16. Composition according to claim 14, characterized in that the organic contaminant removal aid is a poloxamer.
[0017]
17. Composition according to claim 16, characterized in that the poloxamer comprises PLURONIC® F38, PLURONIC® F68, PLURONIC® F88, PLURONIC® F98, PLURONIC® F108, PLURONIC® F87, PLURONIC® P105, and PLURONIC® F127 , or any combination thereof.
[0018]
18. Composition according to claim 14, characterized in that the organic contaminant removal aid is a poloxamer having an HLB index greater than or equal to 16.
[0019]
19. Composition according to claim 14, characterized in that the hemicellulolytic enzyme is xylanase, or mannanase, or any combination thereof.
[0020]
20. Composition according to claim 14, characterized by the fact that it also comprises a lipolytic enzyme.
[0021]
21. Composition according to claim 14, characterized by the fact that it also comprises from 10% to 90% by weight of said hemicellulolytic enzyme, and from 1.0% to 10% by weight of said organic contaminant removal adjuvant, based on the total solids weight of said composition.
[0022]
22. Composition according to claim 14, characterized in that the polyalkylene oxide block copolymer comprises a first block of a first lower alkylene oxide monomer.
[0023]
23. Composition according to claim 22, characterized in that the first lower alkylene oxide monomer comprises a C2 to C3, or C4, alkylene oxide chain.
[0024]
24. Composition according to claim 22, characterized in that the polyalkylene oxide block copolymer comprises a second block of a second lower alkylene oxide monomer, the second lower alkylene oxide monomer being different from first lower alkylene oxide monomer.
[0025]
25. Composition according to claim 24, characterized in that the first and second block monomers comprise a polyethylene oxide (PEO) block monomer and a polypropylene oxide (PPO) monomer block, respectively, or a polypropylene oxide (PPO) monomer block and a polyethylene oxide (PEO) monomer block, respectively.
[0026]
26. Composition according to claim 14, characterized in that the polyalkylene oxide block copolymer is amphiphilic.
[0027]
27. Composition according to claim 14, characterized in that the polyalkylene oxide block copolymer comprises a hydrophilic polyalkylene block and a hydrophobic polyalkylene block.
[0028]
28. Composition according to claim 14, characterized in that the polyalkylene oxide block copolymer is a surfactant of the difunctional block copolymer.
[0029]
29. Composition according to claim 14, characterized in that the polyalkylene oxide block copolymer ends in primary hydroxyl groups.

类似技术:

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公开号 | 公开日 | 专利标题

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BR112014009918B1|2021-03-30|METHOD FOR CONTROLLING ORGANIC CONTAMINANTS AND COMPOSITION

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Mussatto et al.2008|Hydrogen peroxide bleaching of cellulose pulps obtained from brewer’s spent grain

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Suurnäkki et al.1997|Hemicellulases in the bleaching of chemical pulps

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Valls et al.2010|New xylanases to obtain modified eucalypt fibres with high-cellulose content

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Cadena et al.2011|On hexenuronic acid | removal and mediator coupling to pulp fiber in the laccase/mediator treatment

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Valls et al.2010|Obtaining low-HexA-content cellulose from eucalypt fibres: Which glycosil hydrolase family is more efficient?

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Nguyen et al.2008|Bleaching of kraft pulp by a commercial lipase: Accessory enzymes degrade hexenuronic acids

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Martín-Sampedro et al.2012|Effect of steam explosion and enzymatic pre-treatments on pulping and bleaching of Hesperaloe funifera

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同族专利:

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公开号 | 公开日

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US20140069599A1|2014-03-13|

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CA2853478A1|2013-05-02|

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WO2013063356A3|2013-08-15|

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US20130105100A1|2013-05-02|

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US8652301B2|2014-02-18|

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JP6508816B2|2019-05-08|

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EP2771508A2|2014-09-03|

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AU2012328637A1|2014-05-15|

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CA2853478C|2017-01-31|

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EP2771508B1|2022-02-16|

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AU2012328637B2|2016-06-02|

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JP6556790B2|2019-08-07|

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CN103998680A|2014-08-20|

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MX2014004984A|2014-05-22|

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JP2014532819A|2014-12-08|

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ZA201405478B|2016-06-29|

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JP2018009279A|2018-01-18|

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CA2932194C|2019-07-23|

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NZ624070A|2016-06-24|

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CN103998680B|2017-04-26|

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WO2013063356A2|2013-05-02|

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BR112014009918A2|2017-04-25|

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MX351672B|2017-10-24|

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CA2932194A1|2013-05-02|

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US8784613B2|2014-07-22|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161552007P| true| 2011-10-27|2011-10-27|

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US61/552,007|2011-10-27|

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PCT/US2012/062058|WO2013063356A2|2011-10-27|2012-10-26|Method and composition for enzymatic treatment of fiber for papermaking, and paper products made therewith|

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