巴西专利BR112012026155B1 METHOD FOR MAKING PAPER OR CARDBOARD

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专利摘要:
A method of making paper or paperboard A method of making paper or paperboard comprising applying an enzyme-containing composition and cationic coagulant to the papermaking pulp prior to forming the paper to preferably improve drainage, retention or both. the pulp sheets from which the paper or cardboard products are manufactured according to the method may exhibit excellent drainage, excellent retention of pulp fines, or both. the method can also be applied to other pulp treatments, such as wastewater treatments. a system is also provided for performing such pulp mass compounding treatments.
公开号:BR112012026155B1
申请号:R112012026155-0
申请日:2011-04-14
公开日:2021-07-27
发明作者:Weiping Ban；Gary Headrick；Rosa M. Covarrubias
申请人:Buckman Laboratories International, Inc；
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专利说明:

Background of the invention
[001] The present invention relates to papermaking processes and the system for the processes. More specifically, the present invention relates to a papermaking process and system utilizing a combination of enzyme and cationic coagulant to improve drainage and/or retention of cellulosic pulp.
[002] Conventional papermaking processes generally include the following steps: (1) forming an aqueous suspension of cellulosic fibers, commonly referred to as pulp; (2) add various paper processing and enhancing materials, such as reinforcement, retention, drainage and/or sizing aids, or other functional additives; (3) cutting and drying the fibers to form a desired cellulosic mat; and (4) post-treating the mat to provide various desired characteristics to the resulting paper, such as applying surface sizing materials and the like. Some cellulase enzymes can be used to treat cellulosic fiber and to improve the drainage of the fiber suspension slurry. However, the use of enzyme requires an additional pre-treatment process of heating the cellulosic pulp, such as pre-heating the pulp to approximately 50°C for about 30-120 minutes before adding the enzyme. These pre-heating operations for enzyme utilization require additional energy consumption and installation of equipment. Furthermore, enzymes can be expensive and their application in papermaking could result in significant increases in production cost.
[003] The investigators of the present invention have found the need for additives useful in the papermaking process to produce paper with improved drainage and cellulosic pulp retention at reduced costs. Invention Summary
[004] A feature of the present invention is to provide a method for making paper with improved drainage and/or retention of cellulosic pulp.
[005] Another feature of the present invention is to provide a papermaking method that uses enzymes without requiring preheat treatments of the pulp to obtain improved drainage and retention of cellulosic pulp.
[006] A further feature of the present invention is to provide a papermaking system, operable to use enzymes without requiring pulp preheating equipment, to obtain improved cellulosic pulp drainage and/or retention.
[007] Additional features and advantages of the present invention will be set forth in part in the description below and in part will be apparent from the report, or may be learned by practicing the present invention. The objectives and other advantages of the present invention will be understood and obtained through the elements and combinations particularly pointed out in the written report and in the appended claims.
[008] To obtain these and other advantages and in accordance with the object of the present invention, as embodied and broadly described herein, the present invention relates to a method for manufacturing paper or cardboard. The method includes applying a composition containing at least one enzyme and at least one cationic coagulant to a papermaking pulp to form a treated pulp. The enzyme and cationic coagulant can be applied to a papermaking pulp at the same time as a premix, or as separately added components. The enzyme and cationic coagulant, as another option, can be added sequentially in a period of time short enough to allow the components to interact in combination with the pulp. The treated pulp can also be treated with at least one flocculant. The resulting treated pulp is then formed into a pulp sheet, which may have improved drainage and/or retention properties compared to conventional treatments that do not utilize a combination enzyme and cationic coagulant composition.
[009] The present invention also relates to a papermaking system for performing the methods as described above. The system may include a supply of pulp for paper production, a processing unit for forming the pulp into a paper or cardboard, equipped with at least one filter for collecting pulp, and a processing unit for forming a paper sheet for receiving pulp. of the filter, a supply of composition containing at least one aqueous dispersion of at least one enzyme and at least one cationic coagulant, and a feed device for feeding the composition to pulp for application thereto prior to paper formation, and a supply of at least one flocculant and a feed device for feeding the flocculant to the treated pulp downstream from where the enzyme and cationic coagulant composition is applied to the pulp and a white water silo for white water recirculation.
[0010] Although illustrated for papermaking processing, the use of the enzyme and cationic coagulant combination may also relate to its application to another material containing cellulosic fiber to improve dewatering in various other industries, such as wastewater treatment . The present invention also relates, for example, to a method of treating cellulosic pulp comprising applying a composition containing enzyme and cationic coagulant to a cellulosic pulp dispersed or otherwise contained in a liquid medium to form a treated pulp, and optionally, dehydrating the treated pulp.
[0011] It is to be understood that both the above general description and the detailed description below are for the sole purpose of exemplifying and explaining the invention, merely intending to provide a further explanation of the present invention, according to the claims.
[0012] As used herein, the term "coagulant" refers to a material that can create larger particles by neutralizing electrical charges surrounding small particles in solution, for example, neutralizing repulsive electrical charges (e.g., negative charges) surrounding the particles, allowing them to "clump together" creating clumps or flakes.
[0013] "Flocculant" refers to a material that can facilitate the agglomeration or aggregation of coagulated particles to form larger floccules.
[0014] "Enzyme" refers to a material comprising a protein or conjugated protein that can function as a biochemical catalyst.
[0015] The accompanying drawings, which are hereby incorporated and which form part of the present application, illustrate various aspects of the present invention and together with the description, serve to explain the principles of the present invention. Brief description of the drawings
[0016] Figure 1 is a flowchart showing a papermaking method according to the present invention;
[0017] Figure 2 is a flowchart showing a papermaking method in accordance with the present invention;
[0018] Figure 3 shows the effects of enzyme combined with cationic coagulant on the drainage (g/50 sec) and turbidity (NTU) of the OCC paper stock composition ("furnish") at an enzyme addition level of 5% as shown in Example 1;
[0019] Figure 4 shows the effects of enzyme combined with cationic coagulant on drainage (g/30 sec) and turbidity (NTU) of the OCC paper stock composition at an enzyme addition level of 1% as shown in the Example 1;
[0020] Figure 5 shows the effects of enzyme combined with cationic coagulant on drainage (g/30 sec) and turbidity (NTU) of the OCC paper stock composition at an enzyme addition level of 0.2% as stated from Example 1;
[0021] Figure 6 shows the effects of enzyme combined with cationic coagulant on drainage (g/30 sec) and turbidity (NTU) of newsprint stock composition at an enzyme addition level of 1% as shown in the Example 1;
[0022] Figure 7 shows the effects of enzyme combined with cationic coagulant on drainage (g/30 sec) and turbidity (NTU) of the OCC paper stock composition at a cost equal to regular coagulant without enzyme addition, as stated from Example 1;
[0023] Figure 8 compares the drainage (g/30 sec) of cationic coagulant from the paper stock composition in recirculating white water with a combination of enzyme and cationic coagulant and without the combination, as shown in Example 1;
[0024] Figure 9 compares the turbidity (NTU) of cationic coagulant of the paper stock composition in recirculating white water with a combination of enzyme and cationic coagulant and without the enzyme combination as shown in Example 1;
[0025] Figure 10 compares the drainage (g/30 sec) of cationic coagulant from the paper stock composition in recirculating white water with a combination of enzyme and cationic coagulant, of cationic coagulant without enzyme combination, and of enzyme without combination of cationic coagulant and without the enzyme combination as shown in Example 2;
[0026] Figure 11 compares the turbidity (NTU) of cationic coagulant of the paper stock composition in recirculating white water with a combination of enzyme and cationic coagulant, cationic coagulant without enzyme combination, and enzyme without cationic coagulant combination , as shown in Example 2;
[0027] Figure 12 shows the effects of enzyme combined with cationic coagulant on the drainage (g/50 sec) of OCC paper stock composition at enzyme addition levels of 5%, 10% and 15%, as shown in Example 3;
[0028] Figure 13 shows the effects of enzyme combined with cationic coagulant on the drainage (g/50 sec) of OCC paper stock composition at contact times of 0 minutes, 20 minutes and 40 minutes, as shown in Example 3 ;
[0029] Figure 14 shows the effects of enzyme combined with cationic coagulant on the drainage (g/50 sec) of OCC paper stock composition at temperatures of 20°C, 40°C, and 60°C as shown in the Example 3;
[0030] Figure 15 shows the effects of enzyme combined with cationic coagulant on the drainage (g/50 sec) of OCC paper stock composition for coagulants other than BUFLOC®5031 and BUFLOC®597, and flocculant of BUFLOC®5511, as shown in Example 3;
[0031] Figure 16 shows the effects of enzyme combined with cationic coagulant, coagulant individually, and flocculant individually, on the drainage (g/50 sec) of OCC paper stock composition, as shown in Example 3;
[0032] Figure 17 shows the effects of enzyme combined with cationic coagulant on turbidity (NTU) of OCC paper stock composition at enzyme addition levels of 5%, 10% and 15% as shown in Example 3;
[0033] Figure 18 shows the effects of enzyme combined with cationic coagulant on turbidity (NTU) of OCC paper stock composition at contact times of 0 minutes, 20 minutes and 40 minutes, as shown in Example 3;
[0034] Figure 19 shows the effects of enzyme combined with cationic coagulant on turbidity (NTU) of OCC paper stock composition, at temperatures of 20°C, 40°C and 60°C, as shown in Example 3;
[0035] Figure 20 shows the effects of enzyme combined with cationic coagulant on the turbidity (NTU) of OCC paper stock composition for different BUFLOC®5031 and BUFLOC®597 coagulants and BUFLOC®5511 flocculant, as shown in the Example 3; and
[0036] Figure 21 shows the results of a white water recirculation simulation showing enzyme effects on time-related drainage (g) as shown in Example 3. Detailed description of the present invention
[0037] The present invention provides methods for manufacturing paper or cardboard. The enzyme(s) and cationic coagulant(s) can be applied to a papermaking pulp, either simultaneously or sequentially in a sufficiently short period of time to allow the components to interact in combination with the pulp. The enzyme(s) and cationic coagulant(s) can be pre-combined in premix form, and then added together in a composition common to the pulp. In another option, the enzyme(s) and cationic coagulant(s) can be mixed in the addition piping or other feed line that feeds the resulting mix to a port(s) of introduction, such as a door in a pulp processing unit. In yet another option, the enzyme composition(s) and cationic coagulant(s) can be added individually or simultaneously to the pulp from different introduction ports in the same processing unit. As another option, the enzyme and cationic coagulant composition can be introduced sequentially, that is, separately at separate times, from the same or different ports or locations of introduction into the papermaking system in a short period of time. In sequential addition, the enzyme and cationic coagulant components can be added separately at the appropriate time with the two components brought into contact with the pulp within a short period of time, for example in approximately 5 minutes between each other, or in approximately 4 minutes each other or within approximately 2 minutes of each other or within approximately 1 minute of each other, or within approximately 30 seconds of each other, or in shorter periods of time. After contacting the pulp with the enzyme(s) and cationic coagulant(s), the resulting pulp can also be processed and formed into paper or cardboard. The pulp sheets from which paper or cardboard products are made can exhibit excellent drainage and/or excellent retention of pulp fines, exceeding any expectations that may hold about the individual effects of the enzyme and cationic coagulant components. Improvements can be synergistic. Likewise, these improvements in drainage and retention performance can be obtained without the need to heat the pulp to temperatures of approximately 40°C or more before applying the enzyme to the pulp. Flocculant(s) may be added to the pulp or pulp stream after addition of enzyme and cationic polymer composition and prior to paper formation. For purposes of this application, the terms "raw material" and "papermaking raw material" are used interchangeably. Likewise, when terms such as enzyme or coagulant are used in the singular, it is understood that more than one type may be used (eg one or more enzymes, one or more coagulants, etc.).
[0038] The method of the present invention can be practiced in conventional papermaking machines, with modifications that can be easily implemented in view of the present invention. The method of the present invention can be practiced, for example, in the wet section assembly of a conventional papermaking machine with modifications that can be easily implemented in view of the present invention. The method can employ many different types of papermaking pulp or combinations thereof. Pulps treated on papermaking machines with the cationic enzyme and coagulant composition exhibit improved drainage performance, retention performance, or both. For example, the drainage (mass/time, eg g/30 sec) of pulp treated with the enzyme and cationic coagulant, may be, for example, at least approximately 5% greater, or at least approximately 10% greater, or at least approximately 25% greater than treatment with either the enzyme or the cationic coagulant alone (ie without the enzyme or without the cationic coagulant). For example, a 100g/30 second drainage obtained by treating a pulp mass with a composition containing cationic coagulant or enzyme, but not both, can be increased by treatment with a combination of the two components (eg, in the form of pre -mix), for example, in at least about 105g/30 seconds or in at least about 110g/30 seconds or more, or in at least about 125g/30 seconds or more, respectively. The turbidity (NTU) of pulp, as measured from both first retention and colloidal retention, treated with the enzyme and cationic coagulant may be, for example, approximately at least 5% lower, or approximately at least 10% lower, or approximately at least 25% less than treatment with just one enzyme or cationic coagulant (ie without enzyme or without cationic coagulant). In one option, the above-mentioned percentage changes in drainage, turbidity, or both can be determined in relation to an observed value when only the cationic coagulant is used (ie, without the enzyme). In another option, the above-cited percentage changes can be determined relative to a value observed when only the enzyme is used (ie without the cationic coagulant. It has also been found that the combined use of enzyme with cationic coagulant allows for enzyme accumulation in white water recirculation or other closure recirculation in papermaking methods to reduce the overall requirements for addition of enzyme, which still remains at sufficient levels to carry out desired enzymatic reactions with the fiber in the papermaking method. methods of the present invention make it feasible to eliminate pre-treatments of cellulose pulp prior to enzyme application. No processing with heat treatment and associated heating equipment for pulp prior to enzyme application is required in the methods of the present invention to obtain pulp with low body consistency, which can translate into significant energy and equipment savings. ments. For example, the pulp does not need to be heated to a temperature of approximately 40°C or more, or 45°C or more, or 50°C or more, before applying the enzyme and cationic coagulant composition to the pulp, to that the enzyme exerts the desired activity in relation to the fiber. To put it another way, pulp can be kept at or stored at a temperature of less than about 40°C, or less than about 35°C or less than about 33°C (eg, 10°C to 39°C), for the entire period prior to application of the enzyme and cationic coagulant composition to the pulp in the methods of the present invention, without compromising the ability of the enzyme to exert the desired activity in relation to the pulp fiber. In addition, the combination of enzyme and cationic coagulant can be applied as a treatment to papermaking pulp at any convenient addition point or points in the papermaking system prior to formation of the same, without requiring any further modification of a program in the existing wet section. Likewise, by combining enzyme and cationic coagulant, coagulant dosage can be significantly reduced and still allow for significant improvements in pulp drainage and turbidity without increasing the cost of chemical additives. In addition, and as an alternative to the above uses and benefits, the enzyme and cationic coagulant composition can be applied as a coagulant source for any program that requires coagulant in a papermaking process. In another option, the enzyme and cationic coagulant composition can be applied as an enzyme source for any program that requires an enzyme treatment process for various pulps.
[0039] The enzymatic component of the enzyme used with a cationic coagulant to treat pulp, according to the present invention, may include, for example, an enzyme with cellulytic activity. For example, the enzyme may have an activity that affects fiber hydrolysis. The enzyme can be, for example, cellulase, hemicellulase, pectinase, β-glucanase, CMcase, amylase, glucosidase, galactosidase, lipase, protease, laccase and any combination thereof. The cellulase enzyme can be, for example, a cellulase, such as an endocellulase, exocellulase, cellobiase, oxidative cellulase, cellulose phosphorylases, or any combination thereof. Endocellulases that can be used, for example, are endoglucanase with binding domain (NOVOZYM®476, Novozymes), endoglucanase enriched with high cellulase units (NOVOZYM®51081, Novozymes) or combinations thereof, or other known or useful endocellulases. A single type of enzyme or a combination of two or more different types of enzymes can be used together with the cationic coagulant.
[0040] Cellulases are usually enzymes that degrade cellulose, a linear glucose polymer that occurs in plant cell walls. Hemicellulases (eg, xylanase, arabinase, mannose) are often involved in the hydrolysis of hemicellulose, which, like cellulose, is a polysaccharide found in plants. Pectinases are usually enzymes involved in the degradation of pectin, a carbohydrate whose main component is a sugar acid. β-glucanases are enzymes involved in the hydrolysis of β-glucans that are also similar to cellulose as they are linear glucose polymers. Liquid enzymatic compositions containing cellulases are also available under the names Celluclast® and Novozym® 188, both supplied by Novo Nordisk.
[0041] The following paragraphs present examples of enzymes that can be used alone or in combination in the present invention. Novo Nordisk's PULPZYM® product and Alko Biotechnology's ECOPULP® product are two examples of liquid enzymatic compositions available on the market, containing xylanase-based bleaching enzymes.
In their class, hemicellulases may include a mixture of hemicellulase and galactomannanase. Commercial liquid enzymatic compositions containing hemicellulases are available as PULPZYM® from Novo, ECOPULP® from Alko Biotechnology and Novozym® 280 and GamanaseTM, which are products of Novo Nordisk.
The pectinases consist of endopolygalacturonase, exopolygalacturonase, endopectate lyase (transeliminase), exopectate lyase (transeliminase), and endopectin lyase (transeliminase). Commercial liquid enzymatic compositions containing pectinases are available under the names PctinexTMUltra SP and PectinexTM*, both from Novo Nordisk.
[0044] The β-glucanases comprise lichenase, laminarinase, and exoglucanase. Commercial liquid enzymatic compositions containing β-glucanases are available under the names Novozym®234, Cereflo®, BAN, Finizym® and Ceremix®, all supplied by Novo Nordisk.
Two additional classes of industrially and commercially useful enzymes are lipases and phospholipases. Lipases and phospholipases are esterase enzymes.
Novo Nordisk markets two liquid enzymatic preparations under the names ResinaseTMA and ResinaseTMA 2X.
[0047] Alkaline lipases can be used. Commercial liquid enzymatic compositions containing lipases are available under the names Lipolase 100, Greasex 50L, PalataseTM, PalataseTMM and nipozymeTM, all supplied by Novo Nordisk.
With respect to commercially useful phospholipases, pancreatic phospholipase A2 can be used. It is also possible to use isomerases.
[0049] Redoz enzymes can also be used. Redox enzymes can include peroxidase, superoxide dismutase, alcohol oxidase, polyphenol oxidase, xanthine oxidase, sulfhydryl oxidase, hydroxylases, cholesterol oxidase, laccase, alcohol dehydrogenase, or steroid dehydrogenases.
[0050] As indicated, in one option, the enzyme and cationic coagulant components can be pre-mixed into a common composition used to treat pulp. An enzyme pre-formulated in a liquid composition can be used as a source of the enzyme combined with the cationic coagulant component. A cellulytic enzyme composition can contain, for example, from about 5% by weight to about 20% by weight of enzyme. Such enzyme compositions may further contain, for example, polyethylene glycol, hexylene glycol, polyvinylpyrrolidone, tetrahydrofuryl alcohol, glycerin, water, and other conventional enzyme composition additives, for example, as described in U.S. Patent No. 5,356,800, the disclosure of which is herein. incorporated by reference in its entirety.
[0051] Other suitable enzymes and compositions containing enzyme include those described in U.S. Patent Nos. 5,356,800 and 4,923,565 and in International US Patent Application Publication No. WO 99/43780, all incorporated herein by reference in their entirety. Other representative enzymes for papermaking and pulp treatment are BUZYME®2523 and BUZYME®2524, both from Buckman Laboratories International, Inc., Memphis, Tenn.
[0052] The enzyme can be added to the pulp in an amount, for example, from about 0.01% by weight to about 10% by weight of enzyme based on the dry weight of the pulp, or from about 0.05 % by weight to about 5% by weight, or from about 0.1 by weight to about 2.5% by weight or from about 0.2% by weight to about 1.5% by weight of enzyme , based on the dry weight of the pulp, although other amounts may be employed. These enzyme addition amounts relative to pulp may apply to the use of enzyme premixes and cationic coagulant in a common composition, as well as the other addition options listed here to introduce the enzyme and cationic coagulant separately to the pulp ( simultaneously or sequentially). Any amount, percentage or proportion of enzyme described herein can be on an active enzyme basis. For example, an amount of enzyme designated as 1% by weight of enzyme may refer to 1% by weight of active enzyme.
[0053] The cationic coagulant component can be or include a cationic organic polymer coagulant, an inorganic cationic coagulant, or combinations thereof. In addition to the synergistic effects with the enzyme, the cationic coagulant can reduce the negative surface charges present on particles in the papermaking raw material, particularly the surface charges of cellulosic fines and mineral charges, and may thus generate some degree of agglomeration of such particles .
[0054] Cationic organic polymer coagulants can be, for example, cationic starch(s), polyamine, polyamidoaminoglycol, polyvinylamine (PVAm), polyethyleneimine, polydiallyldimethylammonium chloride (Poly-DADMAC), glyoxalated cationic polyacrylamide, copolymer of vinylamine and acrylamide, and any combinations thereof. The cationic coagulant can be or include polyacrylamide(s). The cationic coagulant can be considered, for the purposes of the present invention, a coagulant and/or act as a flocculant. Cationic coagulant can be synthetic, natural, or a combination thereof.
[0055] The cationic organic polymer coagulant can be a cationic polymer of high charge and low molecular weight. The molecular weight (number average Mw) of the cationic organic polymer coagulant can be, for example, from about 1,000 to about 25,000,000, or from about 2,000 to about 1,000,000, or from about 5,000 to about 750,000 or from about 10,000 to 500,000, or from about 2,000,000 to 20,000,000, or from about 5,000 to 15,000,000 or from about 10,000,000 to 20,000,000. Cationic polyvinylamines may include those described in U.S. Patent No. 4,421,602 and U.S. Patent Application Publication No. 2009/0314446 A1, both of which are incorporated herein by reference in their entirety. Cationic organic polymers can be or include, for example, the following commercially available polymers: BUFLOC®5031, a low molecular weight cationic polyamine with a charge density of 100% and a molecular weight in the range of about 100,000 to about 300,000; BUFLOC®5551, a cationic polyvinylamine with a charge density of 100% and a molecular weight in the range of about 2000 to about 4000; and BUFLOC®597, a cationic modified polyethyleneimine with a charge density of 100% and a molecular weight in the range of about 2,000,000 to about 3,000,000, all supplied by Buckman Laboratoris International, Inc. (Memphis TN). For purposes of the present invention, molecular weights are determined based on intrinsic viscosity as an analytical technique.
[0056] The amount of cationic organic polymer used as the cationic coagulant may vary depending on the specific chemical used, and it can generally be added to the pulp in an amount, for example, of about 0.23 kg (0.5 pounds) of cationic organic polymer per ton of papermaking raw material, based on the dry solids of the pulp, or in an amount of from about 0.5 lb to about 3.63 kg/ton (8 pounds per ton) of raw material for papermaking, or from about 0.45 kg (1 pound) to about 2.72 kg/ton (6 pounds per ton) of raw material, or from about 0.68 kg (1.5 lb) to about 1.81 kg/ton (4 pounds per ton) of feedstock, or from about 0.91 kg (2 pounds) to about 1.36 kg (3 pounds) of cationic organic polymer per ton of feedstock , based on dry pulp solids, although other amounts may be used. These addition amounts of cationic organic coagulant to pulp may apply to the use of premixes of the enzyme and cationic organic coagulant in a common composition, as well as the other addition options listed here for introducing the enzyme and cationic coagulant separately to the pulp.
[0057] Cationic coagulants can be or include inorganic cationic chemicals (e.g., aluminum sulfate (alum), aluminum chloride, ferric chloride, ferric sulfate), cationic inorganic polymers (e.g., polyaluminum chloride (PAC), polyaluminum sulfate (PAS), polyaluminum silicate sulfate (PASS)), water-dispersible cationic mineral particles (eg, cationic alumina mineral particles, a cationic colloidal silica sol), aluminum hydrochloride (ACH), or any combinations thereof.
[0058] PAC can be used in the form of a very low molecular weight charged cationic dipolymer, such as those supplied by Buckman Laboratories International, Inc., as BUFLOC®5041 or BUFLOC®569. The cationic microparticle can be a natural or synthetic cationic hectorite, bentonite, zeolite, alumina sol, or any combination thereof. Representative cationic mineral particles for use in the enzyme and coagulant compositions of the present invention may include fibrous cationic colloidal alumina microparticles as described in U.S. Patent No. 6,770,170 B2, the fibrous alumina products obtainable by the processes described in U.S. Patent No. 2,915,475 to Bugosh and those described in WO 97/41063, all incorporated herein by reference in their entirety.
[0059] The amount of inorganic cationic coagulant may vary depending on the specific chemical or mineral used and can generally be added to the pulp in an amount, for example, of at least about 0.045 kg/ton (0.1 pound per ton) of papermaking raw material, based on dry pulp solids, or from about 0.2 lb per ton of raw material to about 2.27 kg/ton (5.0 pounds per ton) of raw material, or from about 0.14 kg/ton (0.3 lb per ton) of raw material to about 1.81 kg/ton (4.0 pounds per ton) of raw material, or from about 0 .23 kg/ton (0.5 lb) to about 1.36 kg/ton (3.0 pounds per ton) of raw material, or from about 0.45 kg (1.0 lb) to about 0 .91 kg/ton (2.0 pounds per ton) of raw material, based on dry pulp solids, although other amounts may be used. These addition amounts of the cationic inorganic coagulant relative to pulp may apply to the use of premixes of the cationic inorganic coagulant and an enzyme in a common composition, as well as the other addition options listed here to introduce the enzyme and the cationic coagulant separately to the pulp.
[0060] As several illustrations, the cationic coagulant used in combination with the enzyme can include at least one or any combination of: 1). A simple type of cationic organic polymer (eg, polyamine); 2) blends or blends of different cationic organic polymers in combination (eg a combination of polyamine and poly-DADMAC); 3) a cationic organic polymer and cationic inorganic chemical coagulant blend (eg a combination of polyamine and PAC); 4) a cationic inorganic polymer or cationic inorganic chemical particles or cationic mineral particles, or any combination thereof. Optionally, the coagulant(s) used in the coagulant and enzyme composition is an organic polymer that has cationic charge functionalities representing, for example, at least 1%, at least 10%, at least 25%, at least 50%, at least 75%, at least 90%, or at least 95%, or at least 99%, or up to 100% of the functionalities containing the polymer's total ionic charge. In another option, the coagulant can be a multifunctional organic polymer having both cationic and anionic charge functionalities. In one option, the coagulant can be an organic polymer that has a net cationic charge, if multifunctional. In another option, the enzyme and cationic coagulant composition may further include at least one anionic coagulant compound (such as an anionic organic polymer, an anionic inorganic compound, or both) as a separately introduced component of the cationic coagulant compound or compounds in the composition. Anionic components can cause deposits (eg gels) in pulp or white water. Any amount of anionic components, anionic functionalities in components, or both, present in the coagulant and enzyme composition, can be controlled, for example, to reduce or prevent the formation of such deposits and be limited to amounts that do not compromise the performance of the composition of cationic coagulant and enzyme in pulp drainage and retention. Optionally, a premix or blend of the coagulant and enzyme composition can be used free or substantially free of any anionic components that cause gel deposits, compromise the composition's performance in pulp drainage/retention, or both.
[0061] As indicated, in one option, the enzyme and cationic coagulant composition and its components can be introduced into the papermaking process at the same time to form a pretreated pulp. As also indicated, the enzyme and cationic coagulant can be introduced to a pulp or pulp stream in the papermaking system at the same time or as a premixed composition. As options, the enzyme and cationic coagulant can be introduced as separate additions that combine during or after addition to the pulp. As an indicated option, for example, enzyme and cationic coagulant can be added separately or simultaneously to the pulp from different introduction ports in the same processing unit in the papermaking system. As another option, the enzyme composition and cationic coagulant can be introduced sequentially (eg at separate, non-overlapping times of addition) from the same or different ports or locations of introduction into the papermaking system or processing unit(s) of the same, where the enzyme and the cationic coagulant can contact the pulp fiber to be treated in a short period of time, for example, in about 5 minutes between each other, or in about 4 minutes between each other, or in about 2 minutes between each other, or in about 1 minute between each other, or in about 30 seconds between each other, or in about 10 seconds between each other or in about 5 seconds between each other, or in about 3 seconds between each other, or in about 2 seconds apart or about 1 second apart, or about 0.5 second apart or about 0.25 second apart, or about 0.25 second to about 5 minutes apart. each other, or in about 1 minute to about 5 minutes between each other, or in about 2 to about 5 minutes between each other or in about 2 minutes to about 4 minutes between each other.
Cationic enzyme and coagulant compositions based on premixes of these components may have, for example, from about 1% by weight to about 99% by weight of enzyme and from about 99% by weight to about 1% by weight cationic coagulant, or from about 1% by weight to about 25% by weight enzyme and from about 99% by weight to about 75% cationic coagulant, or about 2, 5% by weight to about 20% by weight enzyme and from about 97.5% to about 80% by weight cationic coagulant, or from about 5% to about 15% by weight enzyme and about from 95% to about 85% by weight of cationic coagulant, on a dry solids basis. When prepared as a premix, the composition based on the enzyme and cationic coagulant components can be formulated sequentially or simultaneously by combining the components in a fluid medium such as water. The order of addition of components is not limited. The various ingredients that make up the enzyme and coagulant compositions of the present invention can be mixed together using conventional mixing techniques, such as a blender, mixer, shaker and/or an open container. Before and/or after aqueous dispersion of the enzyme and cationic coagulant, the pH of the resulting combination can generally be controlled, for example, at a defined pH level of about 3 to about 10, or a pH of about 4 at about 10, or a pH of from about 7.0 to about 10.0, and more suitably from about 8.0 to about 9.0. These pH ranges can be applied to the composition and/or the composition in an aqueous solution. Adjusting the pH of the composition can be carried out, for example, by adding sodium hydroxide or ammonium hydroxide (aqueous ammonia). The enzyme and cationic coagulant composition can include one or more additives, such as dyes, pigments, defoamers, biocides, pH adjusting agents, and/or cationic starch, and/or other conventional paper making or processing additives. Optional additives, if used, should not compromise the unique combined effects of enzyme and cationic coagulant, such as with respect to improvements in drainage and/or retention. As indicated, anionic components, for example, can cause deposits (gels) in pulp or white water. The enzyme and cationic coagulant composition may contain, for example, less than about 3% or less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, of anionic components which they cause deposits or gels. The enzyme and cationic coagulant composition, as a premix, can be prepared as a physically stable aqueous dispersion, which can be more stable, for example, in a range of about 10% by weight to about 60% by weight of total solids, or from about 25% to about 50% by weight of total solids, or from about 35% by weight of total solids. At about 45% by weight of total solids, viscosity tends to fall within a flowable range. Higher levels of solids tend to gradually thicken during any storage before use.
[0063] The enzyme and cationic coagulant compositions, when prepared as premixes of these components, can be prepared as master batches for dilution at a later date, or the desirable concentration can be performed during preparation of the composition. The enzyme and cationic coagulant composition can be prepared on-site or off-site, or parts or components of the composition can be prepared or premixed off-site prior to final formation of the composition. Compositions comprising the enzyme premixes and cationic coagulant can be formed immediately before their introduction into the papermaking process or sheet making process, or the compositions can be prepared in advance, such as before use, minutes before use. use, hours before use, or days or weeks before use, and preferably within approximately 2-3 weeks of use. For example, when the compositions are introduced as enzyme premix and cationic coagulant, the premix can be prepared in about 1 hour to about 50 seconds before its introduction into the papermaking process, or about 1 hour to about 5 hours, or about 1 hour to about 10 hours, or about 1 hour to about 24 hours before use, or about 1 day to about 7 days, or about from 1 day to about 30 days, or from about 1 day to about 60 days, or from about 1 day to about 180 days, before use.
[0064] As indicated, the pulp or raw material can be treated with the composition, including both the enzyme and the cationic coagulant as a premix at any location in the papermaking system prior to forming continuous sheet paper on the filter, for example, a plus point before the inbox in the system. Separate additions of these components to the pulp in accordance with other indicated options can also be made at any of these locations in the papermaking system.
[0065] The enzyme and cationic coagulant composition comprising a premix of these components can be added to the papermaking raw material, for example, in an amount of at least about 0.23 kg/ton (0.5 pound per ton) of raw material, based on dry pulp solids, or at least about 0.45 kg/ton (1 lb per ton) of raw material, or about 0.23 kg (0.5) to about 4.54 kg/ton (10 pounds per ton) of raw material, or from about 0.34 kg (0.75) to about 3.40 kg/ton (7.5 pounds per ton) of raw material, or from about 0.45 kg (1) to about 1.81 kg/ton (5 pounds per ton) of raw material, or from about 0.57 kg (1.25) to about 1 .81 kg/ton (4 pounds per ton) of raw material, or from about 0.68 kg (1.5) to about 1.36 kg/ton (3 pounds per ton) of raw material, or about from 0.23 kg (0.5) to about 0.68 kg/ton (1.5 pounds per ton) of raw material, based on dry solids of the pulp in the material raw for papermaking, although other quantities may be used. When separate additions of enzyme and cationic coagulant to pulp are used in accordance with other options given herein, the combined amounts of these components relative to pulp may also fall in one or more of the above ranges.
[0066] A flocculant can be added before or after the addition of the enzyme and cationic coagulants to the papermaking raw material, typically being added after the addition. The flocculant can be added, for example, after addition of the composition and/or various shear steps of any refining process applied to the treated pulp. The flocculant can be, for example, a cationic, anionic, non-ionic, zwitterionic or amphoteric polymeric flocculant, which can also increase retention and/or drainage in a papermaking stock composition, in relation to the performance improvements provided by the composition of enzyme and cationic coagulant.
Suitable flocculants generally can have molecular weights (average MW), for example, greater than about 1,000,000 or greater than about 5,000,000, or greater than about 20,000,000, or greater than about 1,000. 000 to about 25,000,000. A polymeric flocculant can be prepared through vinyl-addition polymerization of one or more cationic, anionic, or nonionic monomers; by copolymerizing one or more cationic monomers with one or more nonionic monomers; by copolymerizing one or more anionic monomers with one or more nonionic monomers; by copolymerizing one or more cationic monomers with one or more anionic monomers and optionally one or more nonionic monomers to produce an amphoteric polymer; or by polymerizing one or more zwitterionic monomers and optionally one or more nonionic monomers to form a zwitterionic polymer. One or more zwitterionic monomers, and optionally one or more nonionic monomers, can also be copolymerized with one or more anionic or cationic monomers to impart cationic or anionic charge to the zwitterionic polymer.
[0068] The flocculant can be used in solid form, as an aqueous solution, in the form of a water-in-oil emulsion, or as a dispersion in water. Representative cationic polymers include, for example, copolymers and terpolymers of (meth)acrylamide with dimethylaminoethyl methacrylate (DMAEM); dimethylaminoethyl acrylate (DMAEA); diethylaminoethyl acrylate (DEAEA); diethylaminoethyl methacrylate (DEAEM); or its quaternary ammonium forms prepared with dimethyl sulfate, methyl chloride, or benzyl chloride. The flocculant can include, for example, copolymers of acrylamide and methyl chloride quaternary salt of dimethylaminoethylacrylate and acrylamide-sodium acrylate copolymers, and hydrolyzed polyacrylamide polymers. The flocculant can be a polyacrylamide(s).
[0069] The flocculant can be added, for example, in an amount of at least about 0.0005 kg (0.001 lb) of flocculant per ton of papermaking raw material, based on dry solids of the pulp or about from 0.005 (0.01) to about 4.5 kg/ton (10 pounds per ton) of raw material, or from about 0.045 kg (0.1) to about 2.72 kg/ton (6 pounds per ton) ton) of raw material, or from about 0.23 kg (0.5) to about 1.81 kg (4 pounds) of flocculant per ton of raw material, or from about 0.45 kg (1) to about 1.36 kg (3 pounds) of flocculant per ton of raw material, based on the dry solids of the pulp in the paper stock composition, although other amounts may be used.
[0070] The enzyme and cationic coagulant, as part of a simple premixed composition or as separate components, can be added to many different types of pulp, raw material or combinations of pulps or raw materials for papermaking. For example, the pulp may comprise virgin pulp and/or recycled pulp, such as virgin sulfite pulp, pulp chips, kraft pulp, thermomechanical pulp (TMP), alkaline peroxide mechanical pulp (APMP), chemothermomechanical pulp (CTMP), chemomechanical pulp (CMP), defibered wood pulp (GP), mixtures of such pulps and the like. The kraft pulp can be, for example, a hardwood (short fiber) kraft pulp, a softwood (long fiber) kraft pulp, or combinations thereof. Recycled pulp can be or include waste paper, OCC and other paper products and materials used. For example, there are a variety of mechanical pulping methods to which the present invention can be applied. For example, thermomechanical pulp (TMP) uses a combination of heated wood chips and mechanical processes. The Shredders Mechanical Pulp (SGW) process defibers and macerates the wood chips. Chemothermomechanical pulp (CTMP) uses a variety of chemicals, heat and defibering techniques to produce pulp. Different types of pulp require different types of paper, although many papers can use a combination or "blend" of several different types of pulp and recycled/reclaimed paper. The pulp or papermaking raw material may contain cellulosic fibers in an aqueous medium at a concentration, for example, of at least about 50% by weight of the total dry solids content in the pulp or raw material, although other concentrations may be used. Such pulp formulations may be referred to as fiber stock compositions.
[0071] The pulps or raw materials of the present invention can be treated with one or more optional additives in the papermaking system. Such optional additives can include, for example, polymers such as cationic, anionic and/or non-ionic polymers, clays, other fillers, dyes, pigments, defoamers, pH adjusting agents such as alum, sodium aluminate, and/ or inorganic acids, such as sulfuric acid, microbiocides, complementary water retention aids, such as cationic colloidal alumina microparticles, complementary coagulants, complementary flocculants, leveling agents, lubricants, defoamers, wetting agents, optical brighteners, pigment dispersing agents , crosslinkers, viscosity modifiers or thickeners, or any combination thereof, and/or other unconventional papermaking or processing additives. For example, the pH of (treated) pulp can generally, but not exclusively, be controlled to a defined level of from about 4.0 to about 8.5, and more suitably from about 4.5 to about 8. 0.
[0072] The pulps or raw materials of the present invention can be further treated with one or more other components, including polymers such as anionic and non-ionic polymers, clays, other fillers, dyes, pigments, defoamers, pH adjusting agents , such as alum, microbiocides, microparticles (eg ACH) and other additives for conventional paper making or processing. These additives can be added before, during or after introduction of the enzyme composition and cationic coagulant.
[0073] The methods of the present invention can be practiced in any pulp-related applications, including, for example, when pulps are treated and dehydrated. The methods can be practiced, for example, on conventional papermaking machines (such as the Fourdrinier type machine), for example, on wet section sets of papermaking machines, with modifications that can be carried out in view of the present invention. A papermaking system flowchart for carrying out one of the methods of the present invention is shown in Figure 1. Figure 2 also shows optional addition points for flocculant. It is understood that the system shown is an example of the present invention, and that it is not intended to restrict its scope in any way. In the system of Figure 1, an enzyme and cationic coagulant composition at a desired concentration is combined with a papermaking pulp flow stream to form a treated pulp at one or more of Options 1-6 addition points, shown in Fig. 1. To simplify the illustration (and the illustration in Fig. 2), a composition of enzyme and cationic coagulant is shown added to the system as a premix of enzyme and cationic coagulant. These and/or other addition points for the enzyme and cationic coagulant composition can be used as long as the composition is introduced prior to paper formation in the headbox. The system may include a metering device for providing an adequate amount of enzyme composition and cationic coagulant to the pulp stream. Other measuring or dosing devices can also be provided for the other additives and ingredients that may be used during the method.
[0074] A flocculant may be added before or after introducing the enzyme and coagulant composition, such as in one or more of Additive Introduction Options 2A-6A, as shown in Fig. 2, and before the headbox. For example, when the enzyme and cationic coagulant composition is added in Option 1, flocculant can be added at any of the addition points, shown as Options 2A-6A in Fig. 2. When the cationic enzyme and coagulant composition is added in Option 2, flocculant can be added in any of Options 3A-6A and so on. The supply of the cationic enzyme and coagulant composition can be, for example, a storage tank with an outlet communicating with the inlet of a tank or line in the system. The flocculant supply can be, for example, a storage tank with an outlet communicating with a tank or line in the system. Other optional additives may be added at other points along the pulp or system-treated pulp stream as shown in Figure 1, such as at one or more of the addition location Options 1-6. Conventional valve and pump systems used for introducing the compositions and additives can be used.
[0075] In Figure 1, the pulp supply shown represents a pulp stream, for example, supplied by a storage tank or pulp silo. The pulp supply shown in Figure 1 may be a conduit, storage tank or mixing tank, or other container, passage or mixing zone for the pulp flow. The pulp is passed from the pulp tank through a refiner and then through a mixing tank, where the compositions and/or optional additives from the process can be combined with the pulp. The refiner has an inlet that communicates with an outlet of the treated pulp tank, and an outlet that communicates with an inlet of the mix tank. According to the embodiment of Fig. 1, the pulp in the mixing tank is passed from a mixing tank outlet through a communication with an inlet of a machine tank, where optional additives can also be combined with the treated pulp. The mixing tank and the machine tank can be of any conventional type known in the state of the art. The machine's tank ensures balance, that is, a constant pressure on the treated pulp or raw material throughout the downstream portion of the system, particularly in the headbox. From the machine tank, the slurry is passed to a white water silo and then to a fan pump, and then passed through a filter. The filter can be sized, for example, to allow water containing undesirable or unusable components of white water (eg fines) to pass through the filter, while at the same time retaining useful fibers that can be incorporated into the fibrous material supplied for the inbox. The filtered pulp passes to an inlet where a damp sheet of paper is formed on a screen and drained. The screen section can include equipment, for example, that is conventionally used and that can be easily adapted for use in methods of the present invention. The pulp collected as a wet mat on the forming fabric may also be processed, for example, such as in one or more drainage, pressing, drying, calendering, or other processes, as typically employed in a papermaking machine. , before it can be transported to a winder, and can be transported to a paper cutting station or coating and converting stations (not shown). In the system of Fig. 1, the drained pulp resulting from papermaking in the headbox is recirculated to the white water silo. Pulps or raw materials can also be treated with one or more other optional additives introduced at addition points 1-6, or other locations in the system.
[0076] As shown in Figure 1, for pulp treatment, the enzyme and cationic coagulant composition can be added before the headbox after the filter, or added before the filter, or added before the fan pump, or added before the white water silo, or before the machine tank, or before the mix tank, or before the first refiner in a papermaking process, or any combination of these addition sites. It may be useful to add the enzyme and cationic coagulant, at least in part, at a sufficient distance and upstream from the headbox to allow the enzyme and cationic coagulant components sufficient time and opportunity to interact with the pulp without the need for any pre- heating the pulp (eg, warm temperatures of about 40°C or more) prior to treatment with the composition. Process temperatures in the papermaking system are not limited, and can be, for example, from about 15°C to about 70°C or from about 30°C to about 60°C or about 15°C to about 35°C or from about 20°C to about 34°C, or from about 25°C to 33°C or about 32°C, although other temperatures may be used. Optionally, treated pulp temperatures for at least substantially (eg, at least about 90% to 100%) of the full contact period of the enzyme and cationic coagulant composition with the pulp in the papermaking system can be maintained from about 30°C to about 60°C and the contact period can be from about 1 minute to about 150 minutes or other periods. Other temperatures and treatment periods related to pulp treated with the enzyme composition and cationic coagulant can be, for example, from about 30°C to about 50°C and the contact time can be from about 2 minutes to about 100 minutes, or from about 32°C to about 40°C and the contact time can be from about 5 minutes to about 60 minutes, or other combinations of temperature and time.
[0077] A pulp or raw material treated with the composition that includes enzyme and cationic coagulant can exhibit good dehydration during the formation of the paper web on the web. The pulp or raw material may also exhibit a desirable high retention of fiber fines and fillers in the paper web products. The addition of flocculant or microparticles or both to the treated pulp can provide further improvements and improvements, such as, for example, in relation to dewatering and retention performance. Although illustrated for papermaking processing, the use of the enzyme and cationic coagulant combination may also refer to their application in other material containing cellulosic fiber to improve dewatering in wastewater treatments and other industries.
[0078] The present invention includes the following aspects/embodiments/features in any order and/or combination: 1. The present invention relates to a method for manufacturing paper or cardboard comprising: a) applying a composition comprising enzyme and coagulant cationic to a papermaking pulp to form a treated pulp; and b) forming the treated pulp into paper or cardboard. 2. A method according to any embodiment/feature/aspect above or recited below, wherein the pulp is maintained at a temperature or temperatures below about 40°C prior to applying the composition to the pulp. 3. A method according to any embodiment/feature/aspect above or recited below, wherein the composition comprises from about 1% by weight to about 99% by weight of enzyme and from about 99% by weight to about 1% by weight cationic coagulant, based on dry solids weight. 4. Method according to any embodiment/feature/aspect above or recited below, wherein the enzyme is a cellulosic enzyme. 5. Method according to any embodiment/feature/aspect above or cited below, wherein the enzyme is cellulase, hemicellulase, pectinase, β-glucanase, CMcase, amylase, glucosidase, galactosidase, lipase, protease, laccase and any combination of same. 6. Method according to any embodiment/feature/aspect above or recited below, wherein the enzyme is endoglucanase. 7. Method according to any embodiment/feature/aspect above or cited below, wherein the cationic coagulant is a cationic organic polymer coagulant. 8. Method according to any embodiment/characteristic/aspect above or cited below, wherein the cationic coagulant is a polyamine, polyacrylamide, polyamidoaminoglycol, polyvinylamine, polyethyleneimine, polydiallyldimethylammonium chloride, glyoxed cationic polyacrylamide, cationic starch, or any combinations of the same. 9. Method according to any embodiment/feature/aspect above or recited below, wherein the cationic coagulant is a polyamine, polyamidoaminoglycol, polyvinylamine, polyethyleneimine, or any combinations thereof. 10. Method according to any embodiment/feature/aspect above or cited below, wherein the cationic coagulant is an inorganic cationic coagulant. 11. Method according to any embodiment/characteristic/aspect above or cited below, wherein the cationic coagulant is polyaluminum chloride, aluminum sulfate, water-dispersible alumina mineral particles, aluminum sulfate, aluminum chloride, ferric chloride , ferric sulfate, polyaluminum sulfate, polyaluminum silicate sulfate, cationic alumina mineral particles, a cationic colloidal silica sol, aluminum hydrochloride or any combination thereof. 12. A method according to any embodiment/feature/aspect above or recited below, wherein the composition is added to the pulp in an amount of at least about 0.5 pounds per ton based on dry solids weight of the pulp. 13. Method according to any embodiment/feature/aspect above or recited below, further comprising applying a flocculant to the pulp after application of the composition to the pulp and prior to paper formation. 14. A method according to any embodiment/feature/aspect above or recited below, wherein the temperature of the treated pulp for at least substantially the entire period of contact of the composition with the pulp is maintained at about 30°C to about 60°C and the contact time is from about 1 minute to about 150 minutes. 15. A method according to any embodiment/feature/aspect above or recited below, wherein the flocculant is added to the pulp in an amount of at least about 0.01 pound per ton based on dry solids weight of the pulp. 16. A method according to any embodiment/feature/aspect above or recited below, wherein the drainage (g/50 sec) is at least about 5% greater than the pulp treatment without the enzyme. 17. A method according to any embodiment/feature/aspect above or recited below, wherein the turbidity (NTU) is at least about 5% less than the pulp treatment without the enzyme. 18. A papermaking system comprising a supply of pulp for papermaking, a processing unit for forming the pulp into paper or cardboard, comprising a filter for collecting pulp, and a processing unit for forming a paper sheet that receives pulp. of the filter, a composition supply comprising an aqueous dispersion of enzyme and cationic coagulant, and a composition feeding device for feeding the composition to the pulp and for applying the same before paper formation and a flocculant supply and a feeding device of flocculant to feed the flocculant to the treated pulp downstream from where the enzyme and cationic coagulant composition is applied to the pulp, and a white water silo for white water recirculation. 19. System according to any embodiment/feature/aspect above or cited below, said processing unit for forming pulp comprising a mixing tank in communication with said supply of pulp, a fan pump in communication with the tank of mixing, the filter in communication with said fan pump, and an inlet as processing unit for forming paper in communication with said filter. 20. System according to any embodiment/feature/aspect above or cited below, wherein said white water silo has a first input in communication with said machine tank, a second input in communication with said inlet box, and a output in communication with said fan pump.
[0079] The present invention may include any combination of these features or embodiments above and/or hereinafter cited in sentences and/or paragraphs. Any combination of features described herein is considered to be part of the present invention, without restriction as to combinable features.
[0080] The present invention will also be elucidated by the following examples, which are intended simply to exemplify the present invention and in which parts and percentages are proportions by weight, unless otherwise specified. EXAMPLES Example 1
[0081] The drainage and retention properties of the compositions exemplifying the present invention were examined. Experimental
[0082] The materials and protocols described below were used in the experiments. pulp mass composition
[0083] Refined OCC pulps and white water were obtained from corrugated cardboard manufacturers such as Sonoco, Richmond, VA and International Paper, Valliant OK, under the names of CSF 220, CSF 410, and CSF 330. The composition of newsprint putty and white water were obtained from a newsprint manufacturer, such as Catalyst, Snowflake, AZ, under the name CSF 50. Chemical Substances and Dosages
[0084] The cationic coagulant used in the experiments was a low molecular weight cationic polyamine (BUFLOC®5031, Buckman Laboratories International, Inc.), and a typical dosage of 1.5 lb/ton (on dry solids basis) for composition of OCC mass and 4.0 lb/ton (on a dry solids basis) for newsprint. The flocculant was a polyacrylamide (BUFLOC® 5511, Buckman Laboratories International, Inc.) being used at a typical dosage of 0.2 lb/ton (dry solids basis) for testing. The selected enzyme was NOVOZYM®51081 from Novozymes. The enzyme was pre-mixed with the cationic coagulant before being applied to the pulp at planned addition levels. Different dosages or other additives in the tests are indicated, where applicable. Test Procedure
[0085] A MütekTM tester was applied in all drainage tests to measure drainage and turbidity. The consistency of the test dough composition was 1.0%. The chemical addition program consisted of first adding the coagulant and then the flocculant. To simulate white water circulation, the filtrate was collected after testing and reused in the next test sample. The sample temperature for all tests was controlled at 32°C. Results
[0086] Tables 1-3 show the results of the effects of enzyme combined with cationic coagulant on drainage and turbidity of OCC mass composition at different levels of enzyme addition, 5%, 1% and 0.2% by weight, respectively. For these experiments, the OCC mass composition (CSF 220) was treated with enzyme (NOVOZYM® 51081), 1.5 lb/ton of coagulant (BUFLOC® 5031) and 0.2 lb/ton (on a dry solids basis ) of flocculant (BUFLOC® 5511) except 0.2% enzyme operation, and also 1.0 lb/ton (on dry solids basis) of microparticle (BUFLOC®5461) (anionic colloidal silica) was included. The results are shown graphically in Figures 3-5, respectively. Table 1
Table 2
Table 3

[0087] Table 4 shows the results of the effects of enzyme combined with cationic coagulant on the drainage and turbidity of newsprint composition at 1% by weight enzyme addition level. For this experiment, newsprint (CSF 50) was treated with 1% by weight enzyme (NOVOZYM® 51081), 4.0 lb/ton (on dry solids basis) coagulant (BUFLOC® 5031) and 0.2 lb /ton (on dry solids basis) of flocculant (BUFLOC® 5511). The results are graphically shown in Figure 6. Table 4

[0088] Table 5 shows results of the effects of enzyme combined with cationic coagulant on the drainage and turbidity of OCC mass composition at 1% by weight of enzyme addition level for a cost similar to regular coagulant without added enzyme. For this experiment, the OCC mass composition (CSF 410) was treated with 1% by weight of enzyme (NOVOZYM® 51081), 2.0 lb/ton (on dry basis) of coagulant (BUFLOC® 5031) and 0.2 lb/ton dry solids) of flocculant (BUFLOC® 5511). The are graphically shown in Figure 7. Table 5

[0089] Table 6 shows the results of the effects of enzyme combined with cationic coagulant, and cationic coagulant without enzyme, on drainage and turbidity of OCC mass composition in white water recirculation. For this experiment, the OCC mass composition (CSF 410) was treated with 1% by weight enzyme (NOVOZYM® 51081) or without enzyme, 1.5 lb/ton (on dry solids basis) of coagulant (BUFLOC® 5031 ) and 0.2 lb/ton (on a dry solids basis) of flocculant (BUFLOC® 5511). The results are shown graphically in Figures 8 and 9. Table 6
Example 2
[0090] The drainage and retention properties of additional compositions exemplifying the present invention were examined. Experimental
[0091] The materials and protocols described below were used in the experiments. pulp mass composition
[0092] Refined OCC pulp was obtained from a corrugated cardboard manufacturer, such as Sonoco, Richmond, VA, under the name CSF 220. Chemical Substances and Dosages
[0093] The cationic coagulant used in the experiments was BUFLOC®5031 (Buckman Laboratories International, Inc.), and the dosage of 1.5 lb/ton (on dry solids basis) for OCC mass composition. The flocculant was BUFLOC® 5511 (Buckman Laboratories International, Inc.) used at a dosage of 0.2 lb/ton (on a dry solids basis) for testing. The enzyme selected was NOVOZYM®51081 from Novozymes at a dosage of about 1% by weight. The enzyme was pre-mixed with cationic coagulant before being applied to the pulp at planned addition levels. Test Procedure
[0094] The test procedure used was similar to that of Example 1. Results
[0095] Table 7 shows the results of the effects of enzyme combined with cationic coagulant and cationic coagulant without enzyme combination, and enzyme without cationic coagulant combination on drainage and turbidity of OCC mass composition. The results are graphically shown in Figures 10 and 11, respectively. The results show that drainage was higher and turbidity lower for OCC mass composition treated with enzyme combined with cationic coagulant in all circulation periods, compared to mass composition treated with cationic coagulant without enzyme combination and with cationic coagulant composition. enzyme-treated mass without combination of cationic coagulant. Table 7
Example 3
[0096] The drainage and retention properties of additional compositions exemplifying the present invention were examined. Experimental
[0097] The following materials and protocols were used in the experiments. pulp mass composition
[0098] Refined OCC pulp was obtained from a corrugated cardboard manufacturer, such as Sonoco, Richmond, VA, under the name CSF 220. Chemical Substances and Dosages
[0099] The cationic coagulants used in the experiments were low molecular weight cationic polyamine (BUFLOC® 5031, Buckman Laboratories International, Inc.), polyamidoaminoglycol (BUFLOC® 597, Buckman Laboratories International) and low molecular weight cationic polyamine (BUFLOC® 5551 , Buckman Laboratories International, Inc.). The coagulant dosage was 1.5 lb/ton (on a dry solids basis). The flocculant was a polyacrylamide (BUFLOC® 5511, Buckman Laboratories International, Inc.) used at a dosage of 0.2 lb/ton (dry solids basis) for all tests. The selected enzyme was NOVOZYM®51081 from Novozymes. The enzyme was pre-mixed with coagulants before being applied to the pulp at planned addition levels. The microparticle used was BUFLOC® 5461, Buckman Laboratories International Inc., at a dosage of 1.0 lb/ton (on a dry solids basis). Test Procedure
[00100] An Experimental Orthogonal Lq(34) Design was applied in this experiment. The experimental design strategy is shown, for example, in Hinkelmann, K. et al., (2008), Design and Analysis of Experiments. I and II (second edition), ISBN 978-0-470-38551-7, and Ghosh, S. et al., (1996), Design and Analysis of Experiments. Handbook of Statistics, 13, North-Holland, ISBN 0-444-82061-2. The selected variables and ranges are shown in Table 8. The results and experimental analyzes for both drainage and turbidity are summarized in Table 9-10.
[00101] A MüTekTM tester has been applied in all drainage tests to measure drainage and turbidity. The consistency of the test dough composition was 1.0%. The chemical addition program consisted of first adding coagulant then flocculant. To simulate white water circulation, the filtrate was collected after testing and reused in the next test sample. The temperature of the test sample was controlled as indicated. Table 8 - Variables and Level
Table 9 - Experimental Design and Drainage Analysis

[00102] The statistical analysis of the orthogonal experimental design was approached to clarify the significant levels of influence of all process factors on the drainage performance. Ki was the sum of drainage at level (i). The ki value for each level of a parameter was the average of four values shown in Table 9, and the range (R) value for each factor was the difference between the maximum and minimum value of the three levels. Based on the band analysis results, the importance of the contributions of the studied factors to drainage is therefore ranked as follows: Temperature > Time > Coagulant type > Enzyme dosage
[00103] Similar turbidity analysis is shown in Table 10. Time and Temperature demonstrated similar impact on turbidity and are the most significant factors for turbidity. The type and dosage of the enzyme showed less impact. Table 10 - Experimental Design and Turbidity Analysis

[00104] Regarding the effect on drainage, based on the range analysis, the significance of all selected variables can be ordered according to importance, that is, from the most important to the least important, as follows: a) temperature; b) contact time and type of coagulant; c) level of enzyme content in the coagulant. In the experimental range used, the increase in enzyme content from 5% to 10% by weight and up to 15% by weight, combined with the cationic coagulant did not show significant effects on drainage obtained at a lower level of enzyme, as shown in Figure 12. A longer contact time usually improves drainage, as shown in Figure 13. Temperature leads to the drainage of the dough composition, as shown in Figure 14. However, it should be understood that the contribution of temperature to drainage is not totally attributed to the activated enzyme, as it is believed that the higher temperature exerts an effect on the fluidity of the pulp and the water to accelerate the drainage, as shown in Figure 16, in this case without the addition of enzyme. The enzyme content in the coagulant/enzyme combination is based on total coagulant and enzyme solids, which means that the increase in enzyme content results in a reduction in the coagulant content. Whereas the enzyme addition in this experiment ranged from 5-15% of total solids in the coagulant/enzyme combination, the percentage of coagulant in the combination ranged from 95-85%. The result revealed that the enzyme acted to improve drainage only when a sufficient amount of coagulant could be used. At certain coagulant dosages, a higher ratio of enzyme in combination led to a smaller amount of coagulant addition in the pulp mass composition, and resulted in slower drainage. For the experiments shown in Figure 16, some pulps were only tested with one or the other cationic coagulant indicated (ie BUFLOC® 5031 or BUFLOC® 5551) but not enzyme, and other pulps were treated with a combination of enzyme and cationic coagulant (BUFLOC® 5031). Likewise, the choice of cationic coagulant for combination with the enzyme showed some effect on the drainage results, as shown in Figure 15. Among the coagulants tested, BUFLOC®5031 demonstrated the best efficacy with the enzyme on drainage, and the effects on drainage observed with pulps treated with BUFLOC®5551 and BUFLOC®597 were also considered beneficial.
[00105] With respect to effects on turbidity, turbidity can be used to achieve retention performance. The results are shown in Table 10 and are plotted in Figs. 17-20. Both time and temperature showed significant effects on turbidity, but very different from the effect on drainage. Prolonging the contact time of the enzyme with cellulosic fibers increases drainage, but also increases turbidity, as shown in Fig. 18. Generally, the higher temperature reduces turbidity, which improves retention, as shown in Figure 19. The choice of cationic coagulant has also shown effects on turbidity results. Pulps treated with BUFLOC®5551 exhibited the lowest turbidity when combined with enzyme, and the effects on turbidity observed with pulps treated with BUFLOC®5031 and BUFLOC®597 were also found to be beneficial. The enzyme content seems to be a less significant factor compared to others mentioned about turbidity, as shown in Fig. 17.
[00106] With respect to the white water recirculation simulation and the impact on the enzyme effect, a preliminary white water circulation simulation was carried out to investigate the enzyme effect on the white water circulation. The results are shown in Fig. 21. An apparent increase in drainage was observed when performing a series of tests using circulated water. These results indicate that it is an efficient and viable solution to increase the contact time of the enzyme with fibers, leading to the overcoming of an obstacle related to the application of the enzyme as a regular coagulant. Without wishing to be bound by any theory, it is believed that white water recirculation can allow additional time to achieve performance improvements provided by the use of the enzyme and cationic coagulant composition and can demonstrate the benefit of adding the composition later in the process.
[00107] Depositors specifically incorporate the contents of all references cited in this report. Furthermore, when an amount, concentration, or other value or parameter is cited as a range, preferred range, or a list of preferred minimum and maximum values, they should be considered as a specific description of all the ranges formed of any pair of maximum range limit or preferred value, and any minimum range limit or preferred value, regardless of whether those ranges are separately described. When a range of numerical values is referenced herein, unless otherwise noted, the range is intended to include the extreme points of the range, and all whole numbers and fractions within that range. The scope of the invention is not intended to limit the specific values cited when defining a range.
[00108] It is evident to those skilled in the art that various modifications and variations may be made in the embodiments of the present invention without departing from the scope and spirit of the invention. Thus, it is intended that the present invention cover other modifications and variations of the present invention, provided they fall within the scope of the appended claims and their equivalents.

权利要求:
Claims (15)
[0001]
1. A method for making paper or cardboard, characterized in that it comprises: a) applying a composition comprising enzyme and cationic coagulant to a papermaking pulp to form a treated pulp, said composition being added in a manufacturing process. paper to a pulp for papermaking after a white water silo and before at least one of a fan pump, a screen, and an inlet box from which the filtrate drained from the pulp is recirculated to said silo of white water, the composition comprising from 1% by weight to 99% by weight of enzyme and from 99% by weight to 1% by weight of cationic coagulant, based on dry solids weight, and the composition is added to the pulp in an amount of 0.23 kg/ton (0.5 lb per ton) to 4.55 kg/ton (10 lb per ton) based on pulp dry solids weight; and b) forming the treated pulp into paper or cardboard, whereby the temperatures of the treated pulp for at least substantially a complete period of contact of the composition with the pulp are maintained at 30°C to 60°C and the contact time is 1 minute to 150 minutes.
[0002]
2. Method according to claim 1, characterized in that the pulp is maintained at a temperature or temperatures below 40°C before applying the composition to the pulp.
[0003]
3. Method according to claim 1, characterized in that the enzyme is a cellulosic enzyme.
[0004]
4. Method according to claim 1, characterized in that the enzyme is cellulase, hemicellulase, pectinase, β-glucanase, CMcase, amylase, glucosidase, galactosidase, lipase, protease, laccase and any combination thereof.
[0005]
5. Method according to claim 1, characterized in that the enzyme is endoglucanase.
[0006]
6. Method according to claim 1, characterized in that the cationic coagulant is a cationic organic polymer coagulant.
[0007]
7. Method according to claim 1, characterized in that the cationic coagulant is a polyamine, polyacrylamide, polyamidoaminoglycol, polyvinylamine, polyethyleneimine, polydiallyldimethylammonium chloride, cationic starch, or any combinations thereof.
[0008]
8. Method according to claim 1, characterized in that the cationic coagulant is a polyamine, polyamidoaminoglycol, polyvinylamine, polyethyleneimine, or any combinations thereof.
[0009]
9. Method according to claim 1, characterized in that the cationic coagulant is an inorganic cationic coagulant.
[0010]
10. Method according to claim 1, characterized in that the cationic coagulant is polyaluminum chloride, aluminum sulfate, water-dispersible alumina mineral particles, aluminum sulfate, aluminum chloride, ferric chloride, ferric sulfate, sulfate of polyaluminum, polyaluminum silicate sulfate, cationic alumina mineral particles, a cationic colloidal silica sol, aluminum hydrochloride or any combination thereof.
[0011]
11. Method according to claim 1, characterized in that it further comprises the application of a flocculant to the pulp after applying the composition to the pulp and before the formation of the paper.
[0012]
12. Method according to claim 11, characterized in that the flocculant is added to the pulp in an amount of at least 0.005 kg/ton (0.01 lb per ton) based on the dry solids weights of the pulp.
[0013]
13. Method according to claim 1, characterized in that the drainage (g/50 sec) is at least about 5% greater than in the pulp treatment without the enzyme.
[0014]
14. Method according to claim 1, characterized in that the turbidity (NTU) is at least about 5% lower than in the pulp treatment without the enzyme.
[0015]
15. The method of claim 1 wherein said composition is added in a papermaking process to a papermaking pulp after a white water silo and before a fan pump.

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同族专利:

公开号 | 公开日

CA2796258A1|2011-10-20|

BR112012026155A2|2021-03-23|

JP5831994B2|2015-12-16|

US20110253333A1|2011-10-20|

CN102985613A|2013-03-20|

EP2558640B1|2016-10-19|

EP2558640A4|2014-10-01|

WO2011130503A2|2011-10-20|

WO2011130503A4|2012-06-21|

AU2011239595A1|2012-11-08|

US8454798B2|2013-06-04|

EP2558640A2|2013-02-20|

WO2011130503A3|2012-04-05|

PT2558640T|2016-11-30|

MX2012011703A|2012-11-06|

JP2013527885A|2013-07-04|

CA2796258C|2018-06-12|

ES2603398T3|2017-02-27|

AU2011239595B2|2013-11-14|

CN102985613B|2015-11-25|

NZ602637A|2014-10-31|

ZA201207192B|2014-02-26|

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法律状态:
2021-04-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2021-04-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-07-27| 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 14/04/2011, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |

优先权:

申请号 | 申请日 | 专利标题

US32449910P| true| 2010-04-15|2010-04-15|

US61/324,499|2010-04-15|

PCT/US2011/032475|WO2011130503A2|2010-04-15|2011-04-14|Paper making processes and system using enzyme and cationic coagulant combination|

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