WO2002099183A1 - Eucalyptus biomechanical pulping process - Google Patents
Eucalyptus biomechanical pulping process Download PDFInfo
- Publication number
- WO2002099183A1 WO2002099183A1 PCT/US2002/016889 US0216889W WO02099183A1 WO 2002099183 A1 WO2002099183 A1 WO 2002099183A1 US 0216889 W US0216889 W US 0216889W WO 02099183 A1 WO02099183 A1 WO 02099183A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wood chips
- wood
- fungus
- pulp
- paper
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/14—Disintegrating in mills
- D21B1/16—Disintegrating in mills in the presence of chemical agents
-
- 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
- D21C1/00—Pretreatment of the finely-divided materials before digesting
- D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
-
- 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
-
- 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
- D21H11/10—Mixtures of chemical and mechanical pulp
Definitions
- the wood In the manufacture of paper from wood, the wood is first reduced to an intermediate stage in which the wood fibers are separated from their natural environment and transformed into a viscous liquid suspension known as a pulp.
- a pulp There are several classes of techniques which are known, and in general commercial use, for the production of pulp from various types of wood. The simplest in concept of these techniques is the so-called refiner mechanical pulping (RMP) method, in which the input wood is simply ground or abraded in water through a mechanical milling operation until the fibers are of a defined desired state of freeness from each other.
- RMP refiner mechanical pulping
- Other pulping methodologies include thermo-mechanical pulping (TMP), chemical treatment with thermo-mechanical pulping (CTMP), chemi-mechanical pulping (CMP) and the so-called kraft or sulfate process for pulping wood.
- the concept is to separate the wood fibers to a desired level of freeness from the complex matrix in which they are embedded in the native wood.
- the cellulose polymers are the predominate molecule which is desired for retention in the pulp for paper production.
- lignin physically protects the cellulose polysaccharides in complexes known as lignocellulosics, and those lignocellulosics must be disrupted for there to be marked enzyme accessibility to the polysaccharides, or to separate lignin from the matrix of the wood fibers.
- a desirable biological system would be one which is intended to liberate cellulose fibers from the lignin matrix by taking advantage of the natural abilities of a biological organism.
- Research in this area has focused on a type of fungi referred to as white-rot wood decay fungi. These fungi are referred to as white-rot, since the characteristic appearance of wood infected by these fungi is a pale color, which color is the result of the depletion of lignin in the wood, the lignin having been degraded or modified by the fungi. Since the fungi appear to preferentially degrade or modify lignin, they make a logical choice for fungi to be utilized in biological treatments to pulp wood, referred to as biopulping.
- eucalyptus wood is partially degraded with a culture of the fungus Ceriporiopsis subvermispora, followed by mechanical pulping of the treated wood.
- the present invention is directed toward the biological pretreatment of wood chips for pulp making for paper manufacture. It has been particularly found here that through the use of a particular species of fungus, and the maintenance of relatively forgiving conditions during the treatment of wood chips by said fungus, it is possible to utilize a biological treatment or pretreatment as a part of a process of pulping eucalyptus wood, a wood resource of high commercial importance in many parts of the World. It has further been found that the pulping process results in a paper which has a strength which is increased over paper made from eucalyptus wood by purely mechanical pulping and over paper made from other species of wood by biomechanical pulping.
- the eucalyptus biomechanical pulping method of the present invention results in a dramatic savings in the energy expended during the mechanical pulping process.
- the process of biomechanical pulping of eucalyptus wood of the present invention not only results in energy savings; it also results in a stronger product.
- This process of the present invention makes use of white rot fungi, preferably, a culture of C. subvermispora, more preferably a culture of C. subvermispora L- 14807-SS-3.
- white rot fungi preferably, a culture of C. subvermispora, more preferably a culture of C. subvermispora L- 14807-SS-3.
- PDA potato-dextrose-agar
- Stock slants may routinely be prepared from an original culture for routine use and may be refrigerated until used.
- the particular strain of C. subvermispora utilized in the examples below, L-14807-SS-3 was obtained from the Center for Mycology Research, Forest Products Laboratory, Madison, Wisconsin.
- strain of fungus was particularly well-suited for biomechanical pulping of eucalyptus wood, according to the process of the present invention.
- other strains of C. Subvermispora such as - CZ-3, L-9186-SP, FP-105732, and FP-105752- SS5
- other white rot fungi such as Hyphodontia setulosa, Phlebia subserialis, Phlebia brevispora, Phlebia tremellosa, Phanerochaete chrysosporium would be suitable for use in the methods of the present invention.
- the process of the present invention is intended for and particularly adapted for the biopulping of eucalyptus.
- the wood is converted to chips through a conventional technology. Wood chips are heat treated, preferably with steam, to disable but not necessarily sterilize the chips prior to inoculation with the fungus.
- the moisture content in the chips is kept at fiber saturation point or greater. A preferred moisture content would be approximately 50-55% of the total wood based on wet weight basis of the chips.
- Fungi are preferably applied to the wood as follows.
- a starter inoculum may be prepared.
- PDA plates are inoculated from PDA slants and incubated at 27 ⁇ 1°C and 70-90% relative humidity. These plates are used to inoculate 1 liter Erlenmeyer flasks containing potato dextrose broth and yeast extract. The inoculated flasks are incubated without agitation in an incubator at 27 ⁇ 1°C and 70-90% relative humidity for 7-10 days.
- the surface of the medium is covered with the fungus in the form of mat.
- the fungal mat is removed from the medium, washed with sterilized water on sterilized buchner funnel to remove all the medium.
- the fungal mat is transferred into a sterile waring blender with sterile forceps and blended with sterile water. This suspension is used to inoculate wood chips.
- Scaling up the foregoing culture steps for preparing the fungal inoculation involves preparation of media in commercial scale vats, and growth of fungi in commercial scale fermenters. Using industrial scale equipment, fungal cultures in 500-1500 gallon batches are readily obtainable.
- Fungal treatment of wood chips is carried in bioreactor which may be any of a number of styles capable of handling solid media fermentation culture. It is merely required that the stationary or solid phase reactor have sufficient aeration so as to ensure adequate O 2 flow to the fungus and significant removal of CO therefrom.
- the process it is an advantage of the process that it can be conducted in static fermentation procedure without the need for an exotic or moving fermenting chamber thereby allowing the process to be used more practically on a large scale.
- Aeration, humidity and temperature are all preferably controlled, to at least some extent.
- the inoculated chip mass may be incubated in cylindrical silos or in open chip piles of 20-200 tons, under nonstick conditions, provided proper ventilation is maintained, as discussed more fully hereafter.
- wood chips are put in the bioreactor, autoclaved and cooled to room temperature, or exposed to steam to disable native microorganism populations without absolute sterilization.
- the wood chips to be treated are inoculated with starter culture.
- the amount of inoculum added to the chips can vary. It should be sufficient to ensure growth and spread to all chips in the bioreactor. Inoculum level of 1 to 5 gm per ton of wood chips was found to be sufficient.
- the chips so inoculated will then be incubated during a time period in which the fungal mycelia will penetrate throughout the wood chips. It has been found that nutrients are not required during fungal treatment of eucalyptus wood chips. Addition of nutrients does not give additional biopulping benefits but result in more loss in the weight of wood chips and unbleached pulp yield. The most desired temperature range depends on the fungal strains.
- Eucalyptus pulp made according to the biomechanical pulping procedure of the present method can then be bleached in a multistage bleaching process and made into paper using standard paper-making techniques. Paper made from eucalyptus biomechanical pulp is better in quality, strength and texture to that created from eucalyputs through a simple mechanical pulping process and to that created from other woods through either simple mechanical or biomechanical pulping processes.
- Effective biopulping can be carried out under nonsterile conditions in which naturally occurring flora are present and viable. However, better results are obtained with steamed or autoclaved wood chips.* Eucalyptus wood chips are exposed to live steam resulting in elevating their surface temperature to about 90° to 100°C, as measured immediately after steam treatment. The exposure time is a function of the temperature of the superheated vapor and also the inlet pressure. While 101° to 108°C influent steam at 15 to 75 in line psi for exposure times of 3 to 50 seconds is adequate, the optimum values are best determined in a few empirical process runs for the particular type and configuration of equipment, as hereinafter described in more detail.
- the chamber in which steam treatment takes place should not be too tightly packed. Open space of about under 10% to over 65% of the volume capacity is sufficient to allow penetration of steam to all chip surfaces provided that the chips can be mechanically turned or agitated to prevent impeded exposure to steam at touching surfaces.
- the open space above the chips in the conveyor was found to be approximately 57% to 69%.
- the void space between the chips in the preferred embodiment amounted to approximately 61%. Therefore, the total void space in the conveyor amounted to approximately 83% (large chips) to 88% (small chips). Uniformity of steam treatment is very important, as the naturally occurring flora must be uniformly disabled or biosuppressed physiologically to avoid spots of overgrowth by contaminants during the subsequent incubation step.
- a particularly efficient method of steam treatment is by injecting steam into a continuous flow screw or auger bearing the chips at about 30% to 45% spacial density as discussed above. It was found that exposure time of chips adequate for the present process could be only 40 seconds compared to 5-10 minutes in a quiescent batch mode. Steam was released at moderate pressure and applied ambiently without pressurizing the vessel.
- a number of species of contaminating organisms can readily be isolated from moistened wood chips including Aspergillis spp., Colletotrichum spp., Trichoderma spp., Gliocladium spp., Ophiostoma spp., Penicillium spp., Ceratocystis spp. , Nectria spp., Cytospora spp., and Alternaria spp. Many of these are more physiologically robust and faster growing than the inoculating lignin-degrading or modifying fungi of choice. Growth of these organisms is also enhanced in many instances by the nutrient adjuvants contained in the fungal inoculum. Therefore, addition of such nutrients is avoided.
- the chips are preferably cooled prior to inoculation of the biopulping fungi to minimize the possiblity of killing or disabling the organisms in the inoculum.
- Chips steam treated on a continuously moving path are passed through heat transfer means which cool the chips to an appropriate temperature for inoculation. Applicants have found that the most cost effective and simplest method is to place an in-line air blower manifold directly in the conveyance path, and adjust the air flow to a rate that will cool the passing chips adequately.
- Chips to be inoculated with Ceriporiopsis subvermispora L-14807 SS-3 are preferably cooled to no more than about 50°C, more preferably to a temperature between about 40°C and about 45 °C.
- the highest temperature tolerated by biopulping organisms will vary from species to species or even from strain to strain of the same species, so that empirical tests may be necessary to determine a physiologically suitable temperature for inoculation of wood chips with any given type of culture. Cooling only to the highest physiologically suitable temperature minimizes the cooling time and speeds the process, and reduces the energy consumed. Inoculation of the biopulping fungi is preferably carried out in-line, and applied as a liquid spray to the passing wood chips.
- the working action of agitated conveyor or auger allows inoculum to be uniformly adsorbed onto the chip surfaces by tumbling and churning during rotary or other agitated conveyance. It is important that the inoculum be applied substantially thoroughly and uniformly to the chip surfaces. If the biopulping fungi are to maintain dominance over other flora, the contaminating flora should not be given a sufficient opportunity to reestablish themselves in local areas of the chip surfaces where coverage of inoculum is uneven.
- the temperature of chip piles can be adequately controlled and maintained at levels biocompatible with the continued propagation and dominance of the fungus by loading the chips onto an air pervious frame defining a plurality of ducts through which forced air is passed. It has been empirically determined that the humidity of the air should be in a range from at least 30% up to over 95% relative humidity, preferably about 85%, and the flow rate should be adjusted seasonally to maintain the temperature in the core of the pile within the active growth range of the fungus, which must be determined for each species. In the case of C. subvermispora, the range is approximately 27° to 32°C.
- the chips may be conveniently collected in large piles. Temperature and humidity control are important for optimal fungal propagation and lignin degradation or modification. It has been determined that practical control can be maintained for piles loaded onto the bottom frame referred to above having dimensions about 40-55 feet high, 100 feet wide and any length. Two 400 foot long piles can accommodate a pulp plant utilizing 600 tons of chips daily. To obtain proper humidity, wet bulb/dry bulb tests can be performed on the influent air. Relative humidity should preferably be maintained at about 70%-90%. Humidification of air by conventional means such as fogging prior to pumping or fanning into the frame ducts is generally necessary.
- the amount of heat generated in the pile generally requires continuous dissipation by forced air flow even during the winter months in the northern climes. Incubation times are related to the degree of lignin digestion or modification desired, the type of wood chips being handled, and the particular fungus or combination of fungi being utilized in the process. Useful periods of incubation range from a few days to four weeks. On the other hand, prolonged incubation results in larger standing inventories of chips and larger on site storage capacity.
- Tubular reactors can also be used for biopulping. This silo reactor has a large-scale (multiton) capacity. A perforated plate at the bottom of the reactor supports the chips approximately 5 cm above the bottom of the reactor. Air is supplied to this void space at the bottom center of the reactor. A baffle plate immediately above the air inlet distributes the air more evenly across the bottom of the reactor.
- the wood chips are then preferably subjected to a conventional mechanical refining process to make wood pulp of the desired level of freeness.
- Dilution water is added to the chips and the chips are run through a mechanical refiner through a number of passes.
- the number of passes of the chips/pulp mixture will depend upon the freeness desired for the particular paper application to be made.
- the chip/pulp mixture is fed through the refiner until the desired level of freeness is achieved. Thus freeness may be periodically monitored to determine the progress of the pulps toward the freeness level which is desired for the paper. Between passes the wood pulp may be dewatered as necessary.
- the biomechanical pulps made through this procedure may then be made into paper using standard paper making techniques. It has been found that the standard techniques as described by the Technical Association of the Paper and Pulp Industry (TAPPI) which are known to work with mechanically refined pulps work equally well with the biomechanically refined pulps of the type created by the process described herein. Accordingly, the paper may be made in conventional methodologies.
- the paper from the biomechanically created pulp can be compared in quality, strength and texture to that created through simple mechanical pulping and it will be found that the biomechanically created pulp has significantly increased strength properties.
- the process of the present invention does not sacrifice the quality or strength of the paper in order to achieve the highly desirable energy savings, but in fact results in a unique combination of both significant reduction in energy utilization in the process, and an increase in the strength properties of the resulting paper.
- Biomechanical pulping of eucalyptus wood according to the process of the present invention produces paper of surprisingly high quality compared to previous studies with other woods. In previous studies, we have seen some improvements in paper strength properties during biomechanical pulping of both hardwood and softwood species with several white-rot fungi (U.S. patent 5,750,005 "Method of Enhancing Biopulping Efficacy," Akhtar (1998)).
- Phlebia subserialis RLG 6074-sp 0 0 Hyphodontia setulosa FP 106976 0 0 Phlebia brevispora HHB 7099 0 19 Phlebia tremelosa FP 102557-sp 0 24
- Biomechanical eucalyptus pulp behave more like a softwood mechanical pulp, with the strength characteristics of such a pulp, than it behaves like a traditional hardwood pulp.
- Eucalyptus wood chips were supplied by a mechanical pulp mill in Brazil. Chips were placed in plastic bags and frozen to prevent the growth of contaminating microorganisms.
- Bioreactors containing 1.5 kg of chips (dry weight basis) were steam sterilized for 10 min. prior to inoculation. After cooling at room temperature, these chips were inoculated with a suspension containing, water, unsterilized corn steep liquor and fungus. The inoculated bioreactors were incubated for 2 weeks at 27 °C and 65% relative humidity. The control and fungus-treated wood chips were refined to a pulp and then used to produce paper. The chips were heat treated with steam pressurized to 15 p.s.i.g. for 1 minute and 15 seconds.
- the chips were sent through a thermo-mechanical refiner (Sprout-Bauer, model # 1210P, having a plate pattern D2B505, and 300-mm diameter) for fiberization.
- the pulp produced was subsequently fiberized in a Sprout-Waldron Model D2202 single rotating 300 mm diameter disk atmospheric refiner. Pulp was collected at each pass as hot water slurry. Between the passes the pulp slurry was dewatered to approximately 25% solids in a porous bag by vacuum. Dilution water at 85°C was then added each time as the pulp was fed into the refiner. Samples of the pulp were taken and tested for the Canadian Standard Freeness (CSF) and the process continued until the samples were refined to 300-500 CSF. Hand sheets were also prepared and tested using TAPPI standard testing methods.
- CSF Canadian Standard Freeness
- Fungal pretreatment of eucalyptus wood chips was found to enhance paper strength properties substantially compared to the untreated control (see Table 4, below).
- the fungal pretreatment increased burst index by 70%, tear index by 184%, tensile strength by 120% and breaking length by 120% compared to the control.
- Kraft pulp fibers are generally included in most papers because of their high strength and low lignin content.
- kraft pulp fibers are expensive to produce. Kraft pulp is mixed with mechanical pulp to cut down on costs of production. However, there is generally a limit to what proportion of a pulp can comprise mechanical pulp fibers, without compromising the quality of the paper produced therefrom.
- Eucalyptus wood was pulped in separate portions as described in Examples 1- 2, using mechanical or biomechanical pulping techniques. Paper was produced from a furnish of an untreated pulp of 50% mechanical pulp, 40% hardwood bleached kraft pulp, and 10% softwood kraft pulp was prepared as a control, above. Paper was also produced from a furnish of treated pulp of 90% biomechanical ecucalyptus fibers and 10% softwood fungus-treated kraft pulp, and compared to paper produced from the control pulp. The results of this study are presented in Table 6, below.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0210119-0A BR0210119A (en) | 2001-06-01 | 2002-05-30 | Eucalyptus biomechanical pulping process |
NZ530337A NZ530337A (en) | 2001-06-01 | 2002-05-30 | Process fro making wood pulp from eucalyptus using the white rot fungus Ceriporiopsis subvermispora followed by mechanical pulping |
US10/478,941 US7008505B2 (en) | 2001-06-01 | 2002-05-30 | Eucalyptus biomechanical pulping process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US29545401P | 2001-06-01 | 2001-06-01 | |
US60/295,454 | 2001-06-01 |
Publications (1)
Publication Number | Publication Date |
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WO2002099183A1 true WO2002099183A1 (en) | 2002-12-12 |
Family
ID=23137800
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/016889 WO2002099183A1 (en) | 2001-06-01 | 2002-05-30 | Eucalyptus biomechanical pulping process |
Country Status (4)
Country | Link |
---|---|
US (1) | US7008505B2 (en) |
BR (1) | BR0210119A (en) |
NZ (1) | NZ530337A (en) |
WO (1) | WO2002099183A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1809630B (en) * | 2003-04-24 | 2013-08-28 | 怀卡托大学 | Isolation and use of decay fungi |
WO2016003727A1 (en) * | 2014-06-30 | 2016-01-07 | Weyerhaeuser Nr Company | Modified fiber, methods, and systems |
CN108049229A (en) * | 2017-12-08 | 2018-05-18 | 齐鲁工业大学 | A kind of environment-protecting clean pulping process |
CN111364271A (en) * | 2020-04-02 | 2020-07-03 | 长沙瑞福尼新材料科技有限公司 | Method for preparing bio-mechanical pulp by utilizing whole straw of corn straw |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040104003A1 (en) * | 2000-11-28 | 2004-06-03 | Biopulping International, Inc. | Eucalyptus biokraft pulping process |
WO2003040462A1 (en) * | 2001-11-09 | 2003-05-15 | Biopulping International, Inc. | Microwave pre-treatment of logs for use in making paper and other wood products |
TW592629B (en) * | 2003-02-26 | 2004-06-21 | Yuen Foong Yu Paper Mfg Co Ltd | The manufacturing method for a plant fiber mulching mat |
US8317975B2 (en) | 2004-04-20 | 2012-11-27 | The Research Foundation Of The State University Of New York | Product and processes from an integrated forest biorefinery |
US20080264588A1 (en) * | 2006-09-01 | 2008-10-30 | Masood Akhtar | Method of Making Medium Density Fiberboard |
US8114659B2 (en) | 2008-01-14 | 2012-02-14 | Robert William Rawson | Apparatus and method for catalytic treatment of a media |
US9145640B2 (en) | 2013-01-31 | 2015-09-29 | University Of New Brunswick | Enzymatic treatment of wood chips |
US9127401B2 (en) | 2013-01-31 | 2015-09-08 | University Of New Brunswick | Wood pulp treatment |
WO2023157007A1 (en) * | 2022-02-17 | 2023-08-24 | Futuragene Israel Ltd. | Kits and methods for selecting eucalyptus genotypes resistant to physiological disturbance |
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- 2002-05-30 NZ NZ530337A patent/NZ530337A/en unknown
- 2002-05-30 US US10/478,941 patent/US7008505B2/en not_active Expired - Fee Related
- 2002-05-30 WO PCT/US2002/016889 patent/WO2002099183A1/en not_active Application Discontinuation
- 2002-05-30 BR BR0210119-0A patent/BR0210119A/en not_active IP Right Cessation
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CN1809630B (en) * | 2003-04-24 | 2013-08-28 | 怀卡托大学 | Isolation and use of decay fungi |
WO2016003727A1 (en) * | 2014-06-30 | 2016-01-07 | Weyerhaeuser Nr Company | Modified fiber, methods, and systems |
US9995000B2 (en) | 2014-06-30 | 2018-06-12 | International Paper Company | Modified fiber, methods, and systems |
US10900174B2 (en) | 2014-06-30 | 2021-01-26 | International PaperCompany | Modified fiber, methods, and systems |
CN108049229A (en) * | 2017-12-08 | 2018-05-18 | 齐鲁工业大学 | A kind of environment-protecting clean pulping process |
CN111364271A (en) * | 2020-04-02 | 2020-07-03 | 长沙瑞福尼新材料科技有限公司 | Method for preparing bio-mechanical pulp by utilizing whole straw of corn straw |
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US7008505B2 (en) | 2006-03-07 |
BR0210119A (en) | 2004-06-08 |
US20040154762A1 (en) | 2004-08-12 |
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