WO2003021033A1 - Enzymatic treatment of pulp to increase strength - Google Patents
Enzymatic treatment of pulp to increase strength Download PDFInfo
- Publication number
- WO2003021033A1 WO2003021033A1 PCT/US2002/013532 US0213532W WO03021033A1 WO 2003021033 A1 WO2003021033 A1 WO 2003021033A1 US 0213532 W US0213532 W US 0213532W WO 03021033 A1 WO03021033 A1 WO 03021033A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aqueous suspension
- fibers
- hydrolytic enzyme
- truncated
- percent
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
Definitions
- the invention resides in a method for treating papermaking fibers comprising mixing an aqueous suspension of papermaking fibers and one or more hydrolytic enzymes, optionally in the presence of surfactants.optionally in the presence of other non-cellulolytic enzymes or non-hydrolytic chemical reagents, wherein aldehyde groups are formed predominantly at or near the surface of the fibers.
- the invention resides in a method for handling the aqueous suspension of aldehyde-rich, enzyme-treated fibers comprising mechanical beating or kneading if desired, and/or mixing with supplemental chemical additives as needed.
- the invention resides in a method for making a paper sheet comprising: (a) forming an aqueous suspension of papermaking fibers treated with one or more hydrolytic enzymes capable of randomly hydrolyzing cellulose or hemicellulose to create aldehyde groups; (b) feeding the aqueous suspension into a papermaking headbox; (c) depositing the aqueous suspension onto a forming fabric, whereby the fibers are retained on the surface of the forming fabric in the form of a web while water containing the hydrolytic enzyme(s) passes through the fabric; (d) collecting and recycling the water to recombine the hydrolytic enzyme(s) with additional papermaking fibers to form an aqueous suspension; and (e) drying the web to form a paper sheet.
- hydrolytic enzymes useful for purposes of this invention are those enzymes which randomly hydrolyze cellulose and/or hemicellulose to create aldehyde groups.
- Such enzymes include, without limitation, cellulases, hemicellulases, endo- cellulases, en /o-hemicellulases, carboxymethylcellulases (“CMCases”) and endo- glucanases. It is known that these enzymes, in particular the cellulases, will degrade the fibrous cell wall, eventually improving pliability, flexibility or softness in coarser webs, but certainly impairing tensile properties at the same time.
- enzymes are not freed of their cellulose binding domain (a step called truncation), they require the presence of a surfactant to moderate the reaction and attain the desired hydrolysis under more controlled conditions.
- Particularly suitable enzymes for this purpose are truncated endo- glucanases and carboxymethylcellulases, which do not require the presence of a surfactant.
- truncated monocomponent en /o-glucanases or truncated carboxymethylcellulases can be advantageous relative to multi-component cellulases because of their purity (in particular, low or no exocellulase activity) and hence greater treatment control resulting in minimal cell wall damage.
- truncated multicomponent cellulases can also work well, since the reactivity of the exo-glucanase portion is severely restricted by chance.
- a suitable commercially available truncated encto-glucanase is sold by Novozymes North America, Inc. (Franklinton, North Carolina), under the name Novozyme® 613, SP 988 or Novozyme® 51016.
- CBD-free CMCase is the commercial preparation EG-40N offered by Clariant Corporation (Charlotte, North Carolina). Still, any other hydrolytic enzymes (natural, modified or even an artificial array of peptides) which possess encfo-glucanase or carboxymethylcellulase activity can essentially produce similar results.
- Suitable papermaking fibers include any virgin or recycled papermaking fibers known in the art, particularly including softwood fibers, such as northern softwood kraft fibers, and hardwood fibers, such as eucalyptus fibers.
- a surfactant is a nonionic surfactant, commercially available Tween® 80 (ICI Specialties) or any of the other Tween® 60 series products which are POE sorbitan derivatives.
- suitable nonionoic surfactants include DI600® from High Point Chemical Corp.; DI600® is an alkoxylated fatty acid.
- aryl alkyl polyetheralcohol e.g.
- Union Carbide's Triton® X-100 series of surfactants alkyl phenyl ether of polyethylene glycol, e.g Union Carbide's Tergitol® series of surfactants; alkylphenolethylene oxide condensation products, e.g. Rhone Poulenc, Incorporated's Igepal® series of surfactants.
- an anionic surfactant may be used depending on the type of pulp used.
- Suitable anionic surfactants are: ammonium or sodium salts of a sulfated ethoxylate derived from a 12 to 14 carbon linear primary alcohol; such as Vista's Alfonic® 1412A or 1412S; and sulfonated naphthalene formaldehyde condensates, e.g. Rohm and Haas's Tamol® SN.
- a cationic surfactant can be used, especially when debonding is also desired.
- Suitable cationic surfactants include imidazole compounds, e.g. Ciba- Geigy's Amasoft® 16-7 and Sapamine® P quaternary ammonium compounds; Quaker Chemicals' Quaker® 2001 ; and American Cyanamid's Cyanatex®.
- the amount of surfactant can be from about 0.5 to about 6 pounds per metric ton of pulp, more specifically from about 1 to about 5 pounds per metric ton of pulp, more specifically from about 2 to about 4 pounds per metric ton of pulp, and still more specifically from about 2 to about 3 pounds per metric ton of pulp.
- the specific amount will vary depending upon the particular enzyme being used and the enzyme dosage. The extent of the hydrolytic modification will depend on the dosage of enzyme applied.
- the amount of enzyme administered can be denoted in terms of its activity (in enzymatic units) per mass of dry pulp.
- CMCase activity in cellulases can be assayed by viscosimetry using carboxymethylcellulose (CMC) as a substrate.
- CMC carboxymethylcellulose
- Novo Nordisk Analytical Method 302.1/1-GB, available on request, can be used to assay endoglucanase activity. It calls for the determination of the viscosity loss of a particular solution of CMC (such as Aqualon 7LFD, initial concentration 34gpL) after 30 minutes of incubation with a given enzyme preparation at pH 7.5 (phosphate buffer) at 40°C.
- CMC carboxymethylcellulose
- the method relies on the construction of a calibration curve using a standard enzyme of known carboxymethylcellulase activity such as /S, Bagsvaerd Carezyme (batch 17-1196, nominal activity 4931 ECU/g), provided by Novozymes A, Denmark.
- ECU stands for endocellulase units. Determinations of unknown activities are done relative to the standard(s) by interpolation in the calibration curve, with all preparations reacting under the same conditions.
- the instrument used to measure viscosity reduction is a vibrating rod viscometer, such as the MIVI 6001 unit, manufactured by Sofraser S.A., Villemandeur, France. Still, any other type of viscometer could be used, provided that the same CMC grade is used, a known CMCase standard is employed and the same incubation conditions are followed.
- enzyme dosages can vary depending on the desired extent of the treatment and can be from about 5000 to about 200,000
- ECU/kilogram of oven dry fibers more specifically from about 10,000 to about 100,000 ECU/kg, more specifically from about 10,000/kg to about 75,000 ECU/kg, and still more specifically from about 12,000 to about 60,000 ECU/kg. Mixing is desirable to achieve initial homogeneous dispersion and continuous contact between the enzyme and the substrate.
- the consistency of the aqueous fiber suspension (weight percent fiber in the total pulp slurry) can be accommodated to meet usual paper mill practices. Low consistencies of about 1% or lower are workable; and consistencies as high as 16% still show sufficient enzyme activity in a pulper. For economical reasons, a consistency in the range of about 8 to about 10% is advantageous.
- the reaction conditions for these enzymes can be chosen to provide a pH of about 4 to about 9, more specifically from about 6 to about 8. Temperatures can range from about 0°C (above freezing) to about 70°C. However, it can be envisioned that in the future thermostabilized endo-glucanases could react more effectively at extreme temperatures (such as at the boiling point of water), or that alkali-stabilized endo- glucanases could react efficiently at high pH ranges (for instance at pH above 11).
- reaction times are also very flexible and depend on the application of enzyme and on the desired extent of the modification. But if kept short, fiber cell wall damage is avoided even with regular cellulases especially in the presence of surfactants. In general, suitable reaction times can be from about 10 to about 180 minutes, more specifically from about 15 to about 60 minutes.
- a measure of the effectiveness of the enzyme treatment is the increase in the "copper number" of cellulose.
- the copper number is defined as the number of grams of copper resulting from the reduction of cupric sulfate by 100 grams of pulp. The procedure for determining the copper number is described in TAPPI Standard T 430 om-94 "Copper Number of Pulp". Historically, copper number determinations have been used to detect damage to cellulose after hydrolytic or specific oxidative treatments. An increase in reducing groups can indicate deterioration that will have a detrimental impact on mechanical strengths, since the evolution of aldehyde groups has been normally proportional to the random split of the cellulose chain and the decrease of its degree of polymerization throughout the fiber.
- the copper number measures the improvement in the cross-linking ability of the fibers since the chemical modification is substantially restricted to the surface or the surface-near region of the fibers so as to maintain the integrity of the fiber cell walls.
- the fibers treated in accordance with this invention have a copper number of about 0.10 or more grams of copper per 100 grams of oven-dried pulp, more specifically from about 0.10 to about 1.0 gram of copper per 100 grams of oven-dried pulp, and still more specifically from about 0.15 to about 0.70 gram of copper per 100 grams of oven-dried pulp.
- the strength increases associated with the treated fibers of this invention is about 40 percent or greater, more specifically about 50 percent or greater, more specifically about 60 percent or greater, more specifically about 70 percent or greater, more specifically from about 40 to about 150 percent, more specifically from about 50 to about 140 percent, still more specifically from about 60 to about 140 percent, and still more specifically from about 80 to about 140 percent.
- These strength increases are attributable solely to the enzymatic treatment of the fibers and is without the assistance or contribution of any other supplemental additive(s) or mechanical action that alters the fiber structure, such as refining.
- Dried paper made from the treated fibers of this invention can be repulped, a new handsheet formed and dried without significant loss of the dry tensile strength. Examples Example 1.
- Table 1 shows the increase of the copper numbers for the two fully bleached kraft pulps before and after treatment of the fibers with Novozyme 613®.
- the data listed in Table 1 under Reaction Time 0 is an indication for the number of aldehyde groups originally present throughout the fibers and not only for those placed on the fiber surfaces. To avoid the loss in mechanical strength through hydrolysis, it is essential to restrict the extent of chemical modification to the surface of the fibers, so as to maintain the integrity of the cell wall.
- handsheets were made from northern softwood bleached kraft pulp and eucalyptus bleached kraft pulp fibers treated with the enzyme as described above (dosage 83,000 ECU/kg of oven-dried fibers). More specifically, handsheets having a basis weight of 60 grams per square meter were prepared by diluting a fiber sample in water to a consistency of 1.2 weight percent in a British Pulp Disintegrator and allowing the dispersed sample to soak for 5 minutes.
- the sample was then pulped for 5 minutes at ambient temperature, diluted to 0.3 percent consistency and formed into a handsheet on a square (9x9 inches) Valley Handsheet Mold (Voith Inc., Appleton, WI).
- the handsheet is couched off the mold by hand using a blotter and pressed wire-side up at 100 pounds per square inch for 1 minute.
- the handsheet was dried wire-side up for 2 minutes to absolute dryness using a Valley Steam Hotplate (Voith Inc., Appleton, WI) and a standard weighted canvas cover having a lead-filled (4.75 pounds) brass tube at one end to maintain uniform tension.
- the resulting handsheet was then conditioned in a humidity-controlled room (23°C, 50% relative humidity) prior to testing.
- Dry tensile strength is the peak load measured at the point of failure of a handsheet strip 1 inch wide and 5 inches long in an Instron Testing Machine Mini 55, running at a loading rate of 0.5 inch per minute.
- Wet tensile strength is the peak load measured at the point of failure of a handsheet strip 1 inch wide and 5 inches long in an Instron Testing Machine Mini 55, running at a loading rate of 0.5 inch per minute, where the handsheet strip is wetted thoroughly as described in Tappi Standard T456 om-87.
- Table 4 summarizes the results of treatment of northern softwood Kraft fibers with Novozyme® 476. In this case, tear strength drops dramatically, showing that the intrinsic strength of the fibers has been debilitated.
- handsheets were made from northern softwood bleached kraft pulp treated with CBD-free endoglucanase Novozyme 988® under experimental conditions as described above (dosage 14,000 ECU/kg of oven-dried fibers). Table 5 below summarizes the results.
- enzymatic activity can be slowed down by removal of excess liquor (thickening and dilution) which contains the enzyme.
- Table 6 shows the activity of an original solution and that of a recovered filtrate and a washing liquor.
- a northern softwood kraft pulp sample (30 g.o.d.) was treated at 5% consistency with a dose of Novozyme® 613 equivalent to 83,000 ECU/kg. After one hour of gentle mixing at 45°C at pH 7, the pulp slurry was filtered under vacuum to form a fiber mat of approx. 15% consistency.
- the corresponding filtrate of 400mL had an enzyme activity of 2.42_ECU/mL (1). This represents a total activity of 968 ECU or 39% recovery of the initial enzyme activity.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2457785A CA2457785C (en) | 2001-08-29 | 2002-04-30 | Enzymatic treatment of pulp to increase strength using truncated hydrolytic enzymes |
AU2002259075A AU2002259075B2 (en) | 2001-08-29 | 2002-04-30 | Enzymatic treatment of pulp to increase strength |
MXPA04001389A MXPA04001389A (en) | 2001-08-29 | 2002-04-30 | Enzymatic treatment of pulp to increase strength. |
BRPI0211930-7B1A BR0211930B1 (en) | 2001-08-29 | 2002-04-30 | process for treating papermaking fibers. |
SE0400280A SE528610C2 (en) | 2001-08-29 | 2004-02-11 | Enzymatic pulp treatment to increase strength |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/942,468 US6635146B2 (en) | 1998-07-08 | 2001-08-29 | Enzymatic treatment of pulp to increase strength using truncated hydrolytic enzymes |
US09/942,468 | 2001-08-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003021033A1 true WO2003021033A1 (en) | 2003-03-13 |
Family
ID=25478108
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/013532 WO2003021033A1 (en) | 2001-08-29 | 2002-04-30 | Enzymatic treatment of pulp to increase strength |
Country Status (7)
Country | Link |
---|---|
US (1) | US6635146B2 (en) |
AU (1) | AU2002259075B2 (en) |
BR (1) | BR0211930B1 (en) |
CA (1) | CA2457785C (en) |
MX (1) | MXPA04001389A (en) |
SE (1) | SE528610C2 (en) |
WO (1) | WO2003021033A1 (en) |
Cited By (6)
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---|---|---|---|---|
US6808595B1 (en) | 2000-10-10 | 2004-10-26 | Kimberly-Clark Worldwide, Inc. | Soft paper products with low lint and slough |
WO2006071598A1 (en) * | 2004-12-23 | 2006-07-06 | Genencor International, Inc. | Neutral cellulase catalytic core and method of producing same |
WO2007039867A1 (en) * | 2005-10-03 | 2007-04-12 | The Procter & Gamble Company | Densified fibrous structures and methods for making same |
WO2013090272A1 (en) | 2011-12-12 | 2013-06-20 | Enzymatic Deinking Technologies, L.L.C. | Enzymatic pre-treatment of market pulp to improve fiber drainage and physical properties |
US10519597B2 (en) | 2009-10-16 | 2019-12-31 | Suzano S.A. | Process for producing differentiated cellulose fibers comprising an enzymatic treatment in association with an acid step |
US11248344B2 (en) | 2015-12-29 | 2022-02-15 | Suzano S.A. | Method for producing cellulose pulp, cellulose pulp and use thereof, paper |
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SE526681C2 (en) * | 2002-12-18 | 2005-10-25 | Korsnaes Ab Publ | Fiber suspension of enzyme treated sulphate pulp as raw material for packaging |
WO2004101889A2 (en) * | 2003-05-06 | 2004-11-25 | Novozymes North America, Inc. | Use of hemicellulase composition in mechanical pulp production |
GB0425102D0 (en) * | 2004-11-15 | 2004-12-15 | Ciba Spec Chem Water Treat Ltd | Polymeric compositions and methods of employing them in papermaking processes |
US7922705B2 (en) * | 2005-10-03 | 2011-04-12 | The Procter & Gamble Company | Densified fibrous structures and methods for making same |
US8187421B2 (en) * | 2006-03-21 | 2012-05-29 | Georgia-Pacific Consumer Products Lp | Absorbent sheet incorporating regenerated cellulose microfiber |
US8187422B2 (en) | 2006-03-21 | 2012-05-29 | Georgia-Pacific Consumer Products Lp | Disposable cellulosic wiper |
US7718036B2 (en) | 2006-03-21 | 2010-05-18 | Georgia Pacific Consumer Products Lp | Absorbent sheet having regenerated cellulose microfiber network |
US7951264B2 (en) * | 2007-01-19 | 2011-05-31 | Georgia-Pacific Consumer Products Lp | Absorbent cellulosic products with regenerated cellulose formed in-situ |
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CN102535215A (en) * | 2011-11-14 | 2012-07-04 | 东莞市绿微康生物科技有限公司 | Papermaking plant fiber pretreatment method |
WO2014058846A1 (en) | 2012-10-09 | 2014-04-17 | Hercules Incorporated | Cellulase composition containing cellulase and papermaking polymers for paper dry strength application |
CN104452397B (en) * | 2014-11-21 | 2017-01-25 | 福建农林大学 | Method for improving reactive performance of prehydrolysis sulfate dissolving pulp |
CA3102221A1 (en) * | 2018-07-10 | 2020-01-16 | Novozymes A/S | Method of making paper or board |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6808595B1 (en) | 2000-10-10 | 2004-10-26 | Kimberly-Clark Worldwide, Inc. | Soft paper products with low lint and slough |
WO2006071598A1 (en) * | 2004-12-23 | 2006-07-06 | Genencor International, Inc. | Neutral cellulase catalytic core and method of producing same |
WO2007039867A1 (en) * | 2005-10-03 | 2007-04-12 | The Procter & Gamble Company | Densified fibrous structures and methods for making same |
US10519597B2 (en) | 2009-10-16 | 2019-12-31 | Suzano S.A. | Process for producing differentiated cellulose fibers comprising an enzymatic treatment in association with an acid step |
WO2013090272A1 (en) | 2011-12-12 | 2013-06-20 | Enzymatic Deinking Technologies, L.L.C. | Enzymatic pre-treatment of market pulp to improve fiber drainage and physical properties |
EP2791412A1 (en) * | 2011-12-12 | 2014-10-22 | Enzymatic Deinking Technologies, LLC | Enzymatic pre-treatment of market pulp to improve fiber drainage and physical properties |
US10718088B2 (en) | 2011-12-12 | 2020-07-21 | Enzymatic Deinking Technologies, L.L.C. | Enzymatic pre-treatment of market pulp to improve fiber drainage and physical properties |
EP2791412B1 (en) * | 2011-12-12 | 2023-01-18 | Enzymatic Deinking Technologies, LLC | Enzymatic pre-treatment of market pulp to improve fiber drainage and physical properties |
US11248344B2 (en) | 2015-12-29 | 2022-02-15 | Suzano S.A. | Method for producing cellulose pulp, cellulose pulp and use thereof, paper |
Also Published As
Publication number | Publication date |
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SE0400280L (en) | 2004-04-29 |
BR0211930A (en) | 2004-10-26 |
US20020088575A1 (en) | 2002-07-11 |
MXPA04001389A (en) | 2004-05-27 |
SE528610C2 (en) | 2006-12-27 |
AU2002259075B2 (en) | 2007-02-15 |
BR0211930B1 (en) | 2013-06-11 |
CA2457785C (en) | 2010-02-23 |
CA2457785A1 (en) | 2003-03-13 |
US6635146B2 (en) | 2003-10-21 |
SE0400280D0 (en) | 2004-02-11 |
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