Classifications

• • 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
  • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
• • 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
  • D21C3/00—Pulping cellulose-containing materials
  • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
• • 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
  • D21C3/00—Pulping cellulose-containing materials
  • D21C3/22—Other features of pulping processes
  • D21C3/222—Use of compounds accelerating the pulping processes
• • 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
• • 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
  • D21C9/10—Bleaching ; Apparatus therefor
• • 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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
  • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
• • 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
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/32—Bleaching agents
• • 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
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
  • D21H27/10—Packing paper
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1303—Paper containing [e.g., paperboard, cardboard, fiberboard, etc.]

Definitions

• the disclosure relates to articles of manufacture made from pulp compositions.
• Pulp is a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, or non- wood fiber sources.
• Pulping generally refers to the reduction of a bulk fiber source material into its component fibers.
• Wood and other plant materials used to make pulp generally contain three main components (apart from water): cellulose fibers (desired for papermaking), lignin (a three-dimensional polymer that binds the cellulose fibers together) and hemicelluloses (shorter branched carbohydrate polymers).
• the aim of pulping is to break down the bulk structure of the fiber source, be it chips, stems or other plant parts, into the constituent fibers.
• Chemical pulping achieves this by degrading the lignin into small, water-soluble molecules which can be washed away from the cellulose and hemicellulose fibers without depolymerizing them.
• Depolymerizing the cellulose weakens the fibers and lowers the strength of the pulp obtained. Although lignin in pulp may enhance strength, a pulp having a high degree of delignification may ease the bleaching process.
• agricultural renewable fiber is an organic compound
• ARF represents an economically-promising source of nonwood fibers. But, given the fragile nature of agricultural residues, ARF pulps currently available on the market do not have sufficient strength for many industrial uses, e.g., making printing and writing grade paper. Thus, there is a need for high quality, consistent ARF pulps that can substitute the pulps made from wood fibers for production of articles of manufacture.
• One aspect of the disclosure relates to an article of
• manufacture made from a pulp composition comprising an ARF pulp.
• the ARF pulp has an unbleached Kappa number of about 15 or less, and strength parameters sufficient for papermaking.
• the ARF pulp made from a pulping method comprising cooking a first mixture comprising fibers, water, an alkali, and a delignification selectivity enhancing chemical for a cooking time and at a cooking condition sufficient to form a first pulp having a desired Kappa number of about 15 or less and strength parameters sufficient for papermaking.
• Figure 2 Flowchart of a pulping process according to an embodiment of the present disclosure.
• One aspect of the disclosure relates to articles of manufacture made from a pulp composition comprising an ARF pulp.
• Examples of articles of manufacture produced from a pulp composition comprising an ARF pulp include, without limitation, tissue, printing and writing papers, communication papers, bleached board, food contact packaging papers such as OGR, bleached packaging grades, liquid packaging, the more exotic papers such as wet strength papers and release liner, recycled linerboard and molded packaging products.
• the ARF pulp may be a bleached or an unbleached pulp.
• Examples of articles of manufacture produced from a pulp composition comprising a bleached ARF pulp include, without limitation, tissue, printing and writing papers, communication papers, bleached board, food contact packaging papers such as oil and grease resistant (“OGR"), bleached packaging grades, liquid packaging and the more exotic papers such as wet strength papers and release liner.
• unbleached ARF pulp include, without limitation, recycled linerboard and molded packaging products.
• the use of the bleached or unbleached ARF pulp may improve the performance of the article of manufacture.
• ARF includes fibers obtained from agricultural productions.
• ARF include, without limitation, bagasse, wheat straw, rice straw, corn stover (stalks, leaves and husks), soy residuals, coconut tissues, cotton stalks, palm baskets, kenaf, industrial hemp, seed flax straw, textile flax straw, sisal, hesperaloe, rye grass, and mixtures thereof.
• the ARFs are bagasse or corn stover.
• the ARF pulp as disclosed herein exhibits exceptional bonding characteristics. Although the fibers in ARF pulp are generally short fibers, due to the superior bonding characteristics, the fibers unexpectedly perform more like long fibers, show physical dimensions similar to a hardwood fiber, and have a strength that allows them to substitute in portion, if not entirely, for Northern bleached softwood kraft (NBSK) or similar. These bonding characteristics result in outstanding final paper sheet strength to meet today's demanding customer specifications. This sheet strength is achieved with a fraction of the usual refining energy required by wood fibers, a significant cost savings to tissue applications and others requiring refining wood pulps to develop strength. In certain embodiments, the fiber count per milligram is 19,000.
• the ARF pulp has an unbleached Kappa number of about 15 or less, and strength parameters sufficient for papermaking.
• Kappa number reflects the hardness, bleachability, or degree of delignification of pulp.
• a pulp having a Kappa number of about 5 or lower can be bleached by chlorine dioxide (elemental chlorine free (ECF) techniques) or without chlorine compounds (totally chlorine free (TCF) techniques) to provide a bleached pulp having a desired brightness (e.g., ISO brightness of less than 50%, ISO brightness of about 60% or higher, about 70% or higher, about 80% or higher, about 84% or higher, about 88% or higher, about 80 to about 90%, or about 90% or higher).
• ECF mental chlorine free
• TCF total chlorine free
• a pulp having a higher Kappa number will make ECF or TCF bleaching difficult, requiring oxygen delignification and/or ozone, and/or far more peroxide.
• a pulp having a higher Kappa number can be bleached by chlorine. Therefore, an ARF pulp having a sufficiently low Kappa number and sufficiently high strength parameters will be appreciated in the art.
• the normal permanganate test provides a permanganate or "Kappa number," which is the number of cubic centimeters of tenth normal (0.1 N) potassium permanganate solution consumed by one gram of oven dried pulp under specified conditions. For example, it may be determined by TAPPI Standard Test T-236.
• the acceptable Kappa number range will vary depending upon the intended use of the pulp (e.g., the Kappa number requirements for brown paperboard may vary from about 50 to about 90, while the requirements for white paper stock may be less than 5) ⁇
• Tensile, tear index, and burst index are examples of strength parameters of a pulp to be used to make articles, e.g., paper or paper products. Generally higher strength parameters of a pulp are desired to provide higher strength for the articles made therefrom. A pulp obtained from wood fibers usually shows better strength parameters compared to a pulp obtained from non-wood fibers (e.g., ARFs such as bagasse). However, some of the strength parameters (e.g., tensile) of the pulp compositions disclosed herein are unexpectedly similar to or better than those of the pulp made from wood (see, e.g., Example 9, Table 2).
• Examples of the strength parameters of a pulp that are sufficient for papermaking include, without limitation, a tensile of at least about 5.50 km, a tear index of at least about 6.00 mN.m 2 /g, a burst index of at least about 3.00 kPa.m 2 /g, and combinations thereof.
• the pulp compositions have a Kappa number of about 15 or less, about 10 or less, or about 5 or less.
• the pulp compositions also have a high freeness.
• freeness refers to "pulp freeness,” refers to the drainage rate of pulp, or how “freely” the pulp will give up its water. Freeness is important in papermaking in that, if the freeness is too low, it is not possible to remove enough water on the paper machine to achieve good sheet structure and strength. Often, mechanical pulps have low freeness due to harsh action imparted to the raw material, which produces fines and particles which plug up the draining paper mat. Many chemical pulping processes using whole-stalk (both bast and core) nonwood fiber source materials have problems with poor freeness, due to characteristics of the core fraction. [0026] Some embodiments do not suffer from the freeness problems of prior art processes.
• ARF pulps disclosed herein have high freeness.
• the freeness is much higher than traditional nonwood pulps eliminating the concern about table capacity on the paper machine when substituting for wood based pulps.
• the term "high freeness” is meant to refer to freeness of at least about 400 mL CSF and above.
• the ARF pulp disclosed herein has freeness of at least about 400, 425, 450, 475, 500, 525, or 550 mL CSF.
• the ARF pulp has an ISO brightness of about 60% or higher, and strength parameters sufficient for
• the ARF pulp of the disclosure has an ISO brightness of less than 50%. In certain embodiments, the ARF pulp of the disclosure should have an ISO brightness of about 60% or higher (suitable for use in the manufacture of printing and writing grade paper).
• the ARF pulp has an ISO brightness of about 60% or higher, about 70% or higher, about 80% or higher, about 84% or higher, about 88% or higher, about 80 to about 90%, or about 90% or higher.
• the ARF pulp is made from a pulping method comprising cooking a first mixture comprising ARF fibers, water, an alkali, and a delignification selectivity enhancing chemical for a cooking time and at a cooking condition sufficient to form a first pulp having a desired Kappa number of about 15 or less, and strength parameters sufficient for papermaking.
• the cooking step can comprise a single cooking step to achieve the desired pulp.
• the fibers used in the pulping method are ARFs.
• the ARFs are bagasse or corn stover.
• the fibers used in the pulping method are wood fibers, e.g., hard or soft wood fibers.
• papermaking include, without limitation, a tensile of at least about 5.50 km, a tear index of at least about 6.00 mN.m 2 /g, a burst index of at least about 3.00 kPa.m z /g, where the starting material prior to cooking has a Kappa number of about 60 or greater, and combination thereof.
• the concentration of the alkali in the first mixture may be from about 10% to 30% by weight, about 15% by weight to about 25% by weight, about 20% by weight to about 22% by weight, about 20% by weight to about 22.5% by weight, about 20% by weight, about 21 % by weight, about 22% by weight, about 22.5% by weight, about 24%, or about 27% by weight of the fiber feed (oven dried).
• An example of the alkali is, without limitation, sodium or potassium hydroxide, which may also contain sulfur chemistries. As used herein, "OD,” and "O.D.” are oven-dried.
• suitable alkali additive include ammonia and ethanolamine or derivatives thereof.
• Examples of a delignification selectivity enhancing chemical include, without limitation, anthraquinone (AQ) or derivatives thereof.
• concentration of AQ or a derivative thereof in the first mixture may be about 0.2% to about 1.0% by weight, at least about 0.1 % by weight, at least about 0.17% by weight, at least about 0.2% by weight, at least about 0.25% by weight, at least about 0.27% by weight, at least about 0.3% by weight, at least about 0.35% by weight, at least about 0.4% by weight, at least about 0.45% by weight, at least about 0.5% by weight, at least about 0.55% by weight, at least about 0.6% by weight, at least about 0.65% by weight, at least about 0.7% by weight, at least about 0.75% by weight, at least about 0.8% by weight, or at least about 0.85% by weight of the OD fiber feed.
• the liquid to dry fiber ratio (L/W) of the first mixture is the total liquid amount compared to completely dry fiber, e.g., the weight of liquor applied to a unit weight of oven dried digester feed. It includes all liquids involved in cooking, and can be from about 4, 5, 6, 7, 8, or 9 to about 0, about 7, or about 8.
• the cooking conditions may be at a cooking temperature and a cooking pressure.
• the cooking temperature may be from about 120 °C to about 200 °C, about 150 °C to about 190 °C, or about 165 °C to about 185 °C, about 175 °C, lower than about 175 °C, no higher than 175 °C, about 165 °C, lower than about 165 °C, or no higher than 165 °C.
• the cooking pressure may be from about 60 psi/g to about 150 psi/g, 120 psi/g to about 150 psi/g, or about 130 psig to about 140 psig.
• the cooking time sufficient to form the first pulp at a cooking condition depends on the condition, and may be from about 15 minutes to about 180 minutes, from about 15 minutes to about 120 minutes, from about 15 minutes to about 90 minutes, from about 30 to about 90 minutes, from about 30 to about 60 minutes, about 53 minutes, about 50 minutes, about 40 minutes, about 35 minutes, or about 34 minutes at the
• the first mixture is heated from a lower temperature to a desired temperature during a first cooking time, and is maintained at the desired temperature for a second cooking time.
• a desired temperature may be about 90 °C to about 200 °C, about 120 °C to about 200 °C, about 150 °C to about 190 °C, or about 165 °C to about 185 °C, about 185 °C, about 175 °C, or about 165 °C.
• the lower temperature may be about room temperature, about 90 °C, about 120 °C, about 150 °C, or about 165 °C.
• the first cooking time may be about 1 minute to about 120 minutes, about 1 minute to about 90 minutes, about 1 minute to about 60 minutes, about 5 minute to about 120 minutes, about 5 minute to about 90 minutes, about 5 minute to about 60 minutes, or about 60 minutes.
• the second cooking time may be about 15 minutes to about 180 minutes, about 15 minutes to about 120 minutes, about 15 minutes to about 90 minutes, from about 30 to about 90 minutes, from about 30 to about 60 minutes, about 53 minutes, about 50 minutes, about 40 minutes, about 35 minutes, or about 34 minutes.
• the cooking condition is at a cooking pressure of about 130 psi/g to about 140 psi/g and the desired
• the temperature is about 175 °C.
• the lower temperature is about 90 °C, the first cooking time is 60 minutes, and the second cooking time is about 40 minutes.
• the cooking temperature is from about 20 °C to about 200 °C, and the cooking time is from about 15, 20, or 30 to about 45, 50, 60, 70, 80, or 90 minutes. In certain embodiments, the cooking temperature is from about 150 °C to about 190 °C, and the cooking time is from about 30 to 60 minutes. In certain embodiments, the cooking temperature is from about 165 °C to about 185 °C, and the cooking time is from about 35 to about 45 minutes. [0042] In certain embodiments, the temperature of the first mixture is dropped in to a digester simulation at the desired temperature.
• a second mixture having every ingredient of the first mixture except ARFs may be prepared at the desired temperature, then ARFs are added into the second mixture to form the first mixture.
• the cooking time at the desired temperature may be about 15 minutes to about 180 minutes, about 15 minutes to about 120 minutes, about 15 minutes to about 90 minutes, from about 30 to about 90 minutes, from about 30 to about 60 minutes, about 53 minutes, about 50 minutes, about 40 minutes, about 35 minutes, or about 34 minutes.
• a pulp made from a first cooking step usually has a higher Kappa number or has damaged or destroyed the desired properties of the cellulose.
• pulp made from bagasse known in the art generally has a Kappa number of about 20 or higher.
• Such pulp must be further delignified to reduce the Kappa number (e.g., oxygen delignification and/or ozone treatment), and/or bleached by chlorine.
• delignification and/or chlorine treatment are likely to damage the strength and other parameters of the obtained pulp and increase process costs.
• the Kappa number of the first pulp is about 5 or lower, about 7 or lower, about 10 or lower, or about 15 or lower.
• the first pulp having a Kappa number of 5 or lower can be bleached by TCF or ECF to obtain pulp that is suitable for making paper with desired brightness (e.g. ISO brightness of less than 50%, about 60% or higher, about 70% or higher, about 80% or higher, about 84% or higher, about 88% or higher, about 80 to about 90%, or about 90% or higher).
• desired brightness e.g. ISO brightness of less than 50%, about 60% or higher, about 70% or higher, about 80% or higher, about 84% or higher, about 88% or higher, about 80 to about 90%, or about 90% or higher.
• the Kappa number of the first pulp decreases as the amount of AQ applied to the cooking process increases ( Figure 1 ).
• H-factor indicates relative speed of lignin dissolution. It depends on cooking time and temperature. H-factor's dependency on temperature is very strong due to delignification temperature dependency. Even a difference of couple of degrees in cooking temperature can make a significant difference in pulp quality. H-factor has been defined so that 1 hour in 100 °C is equivalent with H-factor 1. Generally a higher H-factor in the cooking process is more likely to provide a lower Kappa number of the first pulp.
• H-factor can be calculated by
• the pulping process is performed at a H-factor of about 20 or higher, about 50 or higher, about 100 or higher, about 200 or higher, about 300 or higher, about 400 or higher, about 1000 or higher, about 200, about 300, about 400, about 1000, about 1 100 or higher, about 1400 or higher, about 1700 or higher, about 2000 or higher, about 2500 or higher, about 3000 or higher, about 2000 to about 3000.
• the cooking condition is a pressurized cooking condition.
• the pulping method further comprises cooling the first pulp to lower than its boiling point before the first pulp is released from the pressurized cooking condition.
• Cellulose fibers in an alkaline matrix released to atmospheric pressure while still above the boiling point of weak black liquor will suffer damage. The damage may be severe. To avoid such damage, the first pulp may be cooled to within the
• the blowline is cooled to lower than its boiling point before the first pulp is released from the pressurized cooking condition.
• the first pulp is diluted with cooled wash water to lower its temperature to lower than its boiling point before the first pulp is released from the pressurized cooking condition.
• the pulping method further comprises a cleaning step.
• unwanted materials e.g. unwanted mineral material, unwanted cellulosic material, and burned or partially burned fibers
• a pulp obtained after one or more steps of the pulping process e.g. the first pulp, a bleached pulp, and/or a pulp obtained from each stage of bleaching (e.g. chelation, oxygen enriched alkaline peroxide bleaching)).
• Examples of the unwanted mineral material include, without limitation, rocks, sand, rust, soil, tramp metal, trash, and very fine (silicate) particles. These particles may wear out equipment, reduce brightness, affect freeness, and contribute to high ash content.
• the unwanted mineral material may be removed from the fibers before added into the first mixture, from the first mixture and/or from the pulp.
• Examples of the unwanted cellulosic material include, without limitation, pith (parenchyma cells, and other nonfibrous cells).
• the unwanted cellulosic materials have little structural paper-making value, but they may use up chemicals and plug the sheet.
• the unwanted cellulosic materials may be difficult to remove from the pulp. Therefore, removal of the unwanted cellulosic materials as much as is practical from the fibers and/or from the first mixture is desired.
• Examples of the burned or partially burned bagasse particles include, without limitation, carbon and char. Carbon, char, and partially burned bagasse particles may reduce finished pulp brightness if they are microscopic in size. If these particles are large, they will show up as dirt. Removal of these particles from the fibers before added into the first mixture, from the first mixture and/or from the pulp is desired.
• the cleaning steps for raw fibers may comprise a single or multiple cleaning stages. For example, in a first cleaning stage gentle agitation is applied to the raw fibers to provide shear and release some of the pith attached to the fibers.
• the raw fibers are mixed at a first cleaning consistency in water for a first cleaning time to form a first cleaning mixture, then filtered with a first cleaning screen.
• a gentle agitation is optionally applied to the mixing step.
• the first cleaning consistency may be low to moderate, for example, from about 0.5% to about 10%, about 1%, or about 2% by weight.
• the water can be at a temperature of about 20 °C to about 100 °C, about 80 °C to about 100 °C, or about 60 °C.
• the first cleaning time can be from 1 minute to about 1 hour, or about 10 minutes.
• a small quantity of detergent may be used to accelerate wetting.
• the first cleaning screen may be a coarse screen (about 0.5 cm or larger).
• the first cleaning mixture may be poured through the screen. The fibers which are retained on top of the screen are removed often to prevent forming a thick layer (about 1 cm or less in thickness). Much higher consistencies and much thicker layers prevent separation.
• the fiber purification steps for the first pulp involve the separation of the spent chemicals and dissolved non-pulp materials in a process known as washing. Washing is also used to denote using a surfactant then rinsing with water removing small unwanted particles both visible to the naked eye and those particles that are microscopic in size. Cleaning involves the separation of the desired fibers from the undesired fibers and other material such as sand, char or material that was not processed completely in the pulping step with systems known as screens and cleaners. Examples of process equipment of the first type would be rotary drum vacuum washers, wash presses and diffusion washing units. Examples of process equipment of the second type would be pressure pulp screens and centrifugal cleaners.
• unwanted cellulosic and/or mineral materials may be removed from the pulp by actively rinsing the pulp with clean water.
• the pulp may be optionally diluted to form a lower consistency (e.g., about 1.0%) before the rinsing.
• the rinsing step may be carried out in a box with a screen mesh floor, wherein the pulp mat which forms on the mesh is not allowed to accumulate. As soon as a layer of washed pulp begins to form on the mash, it is removed and saved.
• a diffusion washer is a multi stage diffusion unit operating at the cooking conditions to improve the washing efficiency.
• a diffusion unit has 5 or more stages of washing.
• a pressure diffuser is used after each step of washing to allow energy reductions by never cooling the process.
• the pulp mat has a thickness of less than 1 inch, or less than 0.5 inch before it is removed from the screen.
• the size of the holes on a screen may be about 1/8 inch, or about 3/8 inch.
• the screen may be vibrated during the separation.
• the vibration can be from about 0.1 to about 2 inch, about 0.1 to about 1 inch, about 0.1 to about 0.5 inch, about 0.25 to about 0.5 inch.
• the raw fibers, the first mixture, or the pulp is cleaned by dropping to a screen for separation of unwanted materials.
• the raw fibers, the first mixture, or the pulp is dropped at an angle other than 90° to prevent plugging.
• the angle may be about 45° or larger. It is desired to have a consistent pouring speed to feed the screen to keep the material distribution more level and
• unwanted materials are separated from the raw fibers, the first mixture, or the pulp by a vertical hammermill or by a trammel screen. This is the first processing step of preparing the raw bagasse for shipment to the pulp mill and is called moist depithing.
• the pulping method further comprises bleaching the first pulp to provide a bleached pulp.
• the pulp composition has an ISO brightness of about 60% or higher, about 70% or higher, about 80% or higher, about 84% or higher, about 88% or higher, about 80 to about 90%, or about 90% or higher.
• the bleaching step may involve chlorine, chlorine dioxide (ECF techniques) or no chlorine compounds (TCF techniques).
• a bleaching step comprises one or multiple stages. Each stage may or may not include a bleaching agent. Each stage may be performed separately or be performed in combination with another stage at the same time.
• a cleaning step is performed after each stage (e.g., via wash press, diffusion washer, or a diffuser washer).
• a C stage chlorine is applied.
• a PO, Ep, P, P1 or P2 stage hydrogen peroxide is applied.
• an extraction with sodium hydroxide is applied.
• a D, D1 , or D100 stage chloride dioxide is applied.
• Eop stage sodium hydroxide is applied, and hydrogen peroxide and a small amount of oxygen gas is added.
• O stage oxygen gas is applied.
• Q stage a chelating agent is applied to remove metals.
• PO stage alkaline peroxide and oxygen are applied at the same time to improve peroxide efficacy.
• Chelation is a step to protect peroxide used as a bleaching chemical in the next stage.
• chelating agent include, without limitation, ethylenediaminetetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA), and diethylenetriamine penta(methylene phosphonic acid (DTPMPA).
• EDTA ethylenediaminetetraacetic acid
• DTPA diethylene triamine pentaacetic acid
• DTPMPA diethylenetriamine penta(methylene phosphonic acid
• the pH of a pulp to be treated is adjusted to 4.0 to remove calcium and other metals.
• the pulp is treated with a chelating agent (e.g. EDTA, DTPA) and an acid (e.g. H 2 S0 4 ) at a chelation temperature of 80 °C or higher, and for a chelation time of 10 minutes to 30 minutes or longer.
• a chelating agent e.g. EDTA, DTPA
• the target for all the chelants is primarily Mn, which causes catalytic loss of hydrogen peroxide.
• the chemicals may be added via a high shear chemical mixer or any other suitable equipment/method known in the art.
• the pulp is adjusted to a consistency of about 5 to about 30%, about 10 to about 30%, about 15 to about 20%, about 10%, about 15%, or about 20% before the chelation treatment.
• the pulp obtained from the chelation stage is washed before proceeding to the next stage.
• a wash may be performed in a wash press which presses then dilutes and represses the pulp for wash. The wash may be
• a chlorine bleaching approach may be first applied to the first pulp to reduce the Kappa value to lower than about 5-15 (C stage), and then the less harmful hydrogen peroxide may substitute for hypochlorite if desired.
• C stage a C/Eop/PO or a C/Ep/PO bleach sequence may be applied for the bleaching step replacing prior art sequence C/E/H or C/EOP/H or C/EP/H.
• the first pulp has a Kappa number of about 5-15 or less, an ECF or TCF approach is applicable.
• An ECF approach comprises one or more stages selected from the group consisting of D, D100, D1 , Ep, D, PO, and Eop.
• ECF means that at least some chlorine dioxide is used.
• the ⁇ " in ECF stands for "Elemental” meaning that no chlorine gas perse is applied.
• a TCF approach commonly comprises one or more stages selected from the group consisting of Q, P, PO, and O.
• the "T” in TCF stands for Totally.
• TCF sequences might also include a variety of other chemistries such as ozone "Z", peracetic acid, Caro's acid, sodium hydrosulfite, among others.
• a TCF approach comprises a Q stage followed by multiple atmospheric peroxides stages or by a single atmospheric P stage followed by a PO stage.
• Q stage chelation is performed as described supra, with 0.5% chelating agent and 0.4% H 2 S0 4 at 80 °C for 30 minutes, and no H 2 S0 4 but applying the same conditions if DTPMPA is used.
• PO stage bleaching is accomplished in a single extreme alkaline peroxide bleaching stage that is enriched with oxygen to improve peroxide efficacy. Most or even all the brightness gain may be accomplished in the P/PO stage.
• the pulp e.g., about 5 to about 30%, about 10 to about 30%, about 15 to about 20%, about 10%, about 15%, or about 20%
• the pulp is mixed with steam, caustic (NaOH, about 2.6% by weight of the dry pulp), oxygen (pressure of 60 psi/g), hydrogen peroxide (about 6.0% to about 9.0 percent, about 6.0% or about 7.0% by weight of the dry pulp), sodium silicate (about 4.0% by weight of the dry pulp), magsulfate (about 0.3% by weight of the dry pulp) at a temperature of about 120 °C for about 120 minutes.
• This stage may be performed in a high shear pulp/steam/chemical mixture, or any other suitable equipment/method known in the art.
• the ISO ISO
• brightness of the bleached pulp is about 60% or higher, about 70% or higher, about 80% or higher, about 84% or higher, about 88% or higher, about 80 to about 90%, or about 90% or higher.
• the yield may be about 90% of feed fiber or higher, about 94% of feed fiber or higher, about 95% of feed fiber or higher.
• a TCF approach has a sequence of Q/P1/Q/P2 and Q/P1/PO and Q/P1/Q/PO, and Q/PO wherein the Q stage and the P and PO stages are the same as described supra.
• the pulp obtained from a first Q stage (optionally washed, consistency being about 5 to about 30%, about 10 to about 30%, about 15 to about 20%, about 10%, about 15%, or about 20%) is treated with caustic (NaOH, about 0.7% by weight of the dry pulp), hydrogen peroxide (about 1.0% by weight of the dry pulp), sodium silicate (about 4.0% by weight of the dry pulp), magnesium sulfate (about 0.3% by weight of the dry pulp) at a temperature of about 80 °C for about 30 minutes, and the final pH is about 10.6.
• the ISO brightness of the bleached pulp is about 60% or higher.
• the obtained pulp is then treated with another Q stage and a P2/PO stage as described supra.
• a pulping method is carried out as shown in the flow chart of Figure 2.
• the bagasse starting materials are washed with white water, i.e., the process water obtained from a paper making system such as process water obtained from different washes as shown in the figure, to provide washed bagasse (which is used for cooking in the digester step) and bagasse wash water effluent (which is lead to the drain), as described supra.
• the resulted pulping mixture is sent for washes by different wash methods as described supra.
• the obtained wash water effluent is sent for further treatments.
• the washed bagasse is chelated as described supra, washed as described supra, and then bleached in the bleaching step.
• bleaching box Although only one bleaching box is shown in the figure, a single or multiple stage of bleaching may be incorporated, as described supra. In certain embodiments, the washing between the steps may be optional. After the pulp is bleached, it is washed, cleaned, and dried & bailed.
• Bagasse was used as an example of raw fibers. Bagasse was first hydrated for 10 minutes with hot clean water (temperature of water was above room temperature, about 40 °C, or 60 °C), under moderate agitation, at a consistency of 0.5% to 2.0%. Pith and sand were separated from the fibers in a Trammel Screen, which was a rotating drum that lifted and dropped the material and accepted water and pith through 1/8 th inch holes up to 1 ⁇ 2" holes. The rejected material was collected and removed from the screen to prevent accumulation, and disposed, and was dried before added into the pulping process. The washing yield was about 80% or higher, or about 85.9%, depending on quality of the bagasse starting material.
• OD bagasse (cleaned as described in Example 1 , Kappa number was 89) was treated with sodium hydroxide (20% by weight of the OD bagasse) and AQ (0.3% by weight to the dry weight of OD bagasse) at a liquid to dry fiber ratio of 7 (consistency of about 12.5%), at maximum temperature of about 175 °C for 35 or 40 minutes. Time to the maximum temperature was 60 minutes.
• the target H-factor was 1060, as low as 20, and as high as 3000, and the temperature of the pulping reaction was 120 °C to 185 °C.
• the Kappa number of the obtained pulp was 4.5.
• Example 3 Washing of pulp
• a pulp obtained from Example 2 was washed in a pressure diffuser washer designed specifically to accomplish all washing with a single unit without introducing undesired modifications to the pulp.
• the temperature of the wash water was chosen to cool the pulp temperature to about 100 °C, 95 °C, 90 °C, 85 °C, 80 °C or lower.
• the output went to a bleaching step and was cooled to 100 °C or less to prevent flashing.
• the washed pulp obtained from Example 4 was adjusted to a consistency of 15% and proceeding to the P2/PO stage.
• the pulp (15% consistency) was mixed with steam, caustic (NaOH, 2.6% by weight of the dry pulp), oxygen (pressure of 60 psig), hydrogen peroxide (7.0% by weight of the dry pulp), sodium silicate (about 4.0% by weight of the dry pulp), magnesium sulfate (about 0.3% by weight of the dry pulp) at a temperature of about 120 °C for about 120 minutes in a high shear pulp/steam/chemical mixture.
• the ISO brightness of the bleached pulp was 86% or higher, and was up to 89.2.
• the yield was about 94% of feed fiber or higher.
• the terminal pH was 10.2.
• the bleached pulp obtained from Example 5 was diluted to ⁇ 2% consistency, and processed through centrifical cleaners to remove sand, soil particles and other dirt and unwanted materials. These cleaners had a 20 psig differential at the cleaner. A 1% yield loss occurred at this stage.
• the bleached pulp was cleaned, it was formed into a sheet and pressed to 50% dry solid before drying in an air impingement dryer. The minimum dryness was 92%. The sheets were cut to desired size and stacked into bales of desired dimensions and weight. These bales were wrapped and tied and stored for shipment.
• Example 7 ECF bleaching of a pulp obtained from Example 3
• D100 stage low pH, about 2.4, ECF stage to delignify pulp
• a pulp having consistency of 10% was treated at 50 °C for 60 minutes at a Kappa factor of 0.25.
• the final pH was 2.5, and residual chlorine was small to non-detectable.
• Ep stage The pulp obtained from the D100 stage was treated with hydrogen peroxide (0.50% to 0.8% by weight of the weight of the dry pulp) at 80 °C for 60 minutes.
• the final pH was 10.5-1 1 .0, and the final ISO brightness of the obtained pulp was about 80-82%.
• the viscosity of the bleached pulp was high.
• D stage The pulp obtained from Ep stage was treated with chlorine dioxide (1 .2% by weight of the weight of the dry pulp) at 80 °C for 150 minutes.
• the final pH was 3.5-4.0, the residual chloride dioxide was 0.05%, and the final ISO brightness of the bleached pulp was about 89%.
• the viscosity of the bleached pulp was high.
• Example 8 TCF bleaching of a pulp obtained from Example 3
• a TCF bleaching having a sequence of Q/P/PO having the following reaction condition was performed on a pulp having Kappa number of 5 or lower.
• Q stage A pulp having a consistency of 10% was treated with DTPMPA (0.5-0.7% by weight of the weight of the dry pulp) at 80 °C for 30 minutes. The final pH was 7.
• P stage The pulp obtained from the Q stage was treated with hydrogen peroxide (2.0% by weight of the weight of the dry pulp), sodium hydroxide (1.0-1 .1 % by weight of the weight of the dry pulp), DTPMPA (0.25% by weight of the weight of the dry pulp), MgSO 4 (0.60% by weight of the weight of the dry pulp), NaSiO 3 (0.50% by weight of the weight of the dry pulp) at 85 °C for 60 minutes.
• the final pH was 10.5-11.0, and the final ISO brightness of the obtained pulp was about 80%.
• the residual was about 0.05%.
• the viscosity of the bleached pulp was high.
• PO stage The pulp obtained from the P stage can be treated with hydrogen peroxide (5% by weight of the weight of the dry pulp), DTPMPA (0.25% by weight of the weight of the dry pulp), MgSO 4 (0.60% by weight of the weight of the dry pulp), NaSiO 3 (0.50% by weight of the weight of the dry pulp) at 120 °C for 120 minutes.
• a final ISO brightness of the bleached pulp can be 88.00%.
• a viscosity of the bleached pulp can be high.
• Example 9 Benchmark strength of a pulp product made from bagasse
• Bagasse # 1 1 was cleaned by the same procedure as described in Example 1 except that a 3/8" sieve was used instead of the 1/8" sieve.
• the cleaned bagasse was treated with sodium hydroxide (22% by weight of the OD bagasse) and AQ (0.2% by weight to the dry weight of OD bagasse) at a liquid to dry fiber ratio of 8.0 (consistency of about 12%), at a maximum temperature of about 165 °C for 35 minutes. Time to the maximum temperature from 90 °C was 60 minutes.
• the target H-factor was 452.
• the Kappa number of the screened and quick dried pulp was 5.0, the cooking yield was 56.8%, the yield of the screened pulp was 55.8%, total rejects was 1.0% (+ 0.010"), and the viscosity of the pulp was 44.0 mPa.s.
• the pulp obtained was box-washed pulp by first diluting the pulp to a consistency of 1.0%, and then rinsing the pulp in a box with a screen mesh floor, wherein the pulp mat which forms on the mesh was not allowed to accumulate of more than 1 inch. As soon as a layer of washed pulp began to form on the mash, it was removed and saved for the next step of process.
• the washed pulp was bleached by an ECF sequence of D100/Ep/D1 to provide pulp A4420-1-D1 box washed.
• a duplicate washed pulp sample was bleached by a TCF sequence of Q/P1/PO to provide pulp A4420-2-PO box washed.
• D100 stage A pulp having consistency of 10% was treated with C!0 2 (1 .15%) as CI2) at 50 °C for 60 minutes using a Kappa factor of 0.25 The final pH was 2.0, and the residual chlorine was 0.02 g/L (as avail Ci 2 ).
• Ep stage The pulp obtained fro the D100 stage was treated with hydrogen peroxide (0.5% by weight of the weight of the dry pulp), NaOH (0.7% by weight of the weight of the dry pulp), and MgSO 4 (0.1 % by weight of the weight of the dry pulp), at 80 °C for 60 minutes.
• the final pH was 1 1.2, and the final ISO brightness of the obtained pulp was about 75.6%.
• the viscosity of the bleached pulp was very 21.4 mPa.s
• D stage The pulp obtained from Ep stage was treated with chlorine dioxide (1 .5 to 1.7% by weight of the weight of the dry pulp) and NaOH (0.70% by weight of the weight of the dry pulp), at 80 °C for 150 minutes.
• the final pH was 4, the residual chloride dioxide was 0.09%, and the final ISO brightness of the bleached pulp was about 88.4%.
• P1 stage The pulp obtained from the Q stage was treated with hydrogen peroxide (2.0% by weight of the dry pulp), sodium hydroxide (1.1 % by weight of the dry pulp), DTPMPA (0.5% by weight of the dry pulp), agsulfate (0.6% by weight of the dry pulp), Sodium Silicate ( .0% by weight of the dry pulp) at 85C for sixty minutes.
• the final pH was 1 1.2 and the ISO brightness of the pulp was about 67.7%.
• the residual peroxide was 1.25%.
• PO stage The pulp obtained from the P1 stage was treated with hydrogen peroxide (6.0% by weight of the weight of the dry pulp), sodium hydroxide (2.8% by weight of the weight of the dry pulp),
• DTPMPA (0.5% by weight of the weight of the dry pulp
• MgSO 4 0.60% by weight of the weight of the dry pulp
• NaSiO3 3.0% by weight of the weight of the dry pulp
• the final pH was 1 1 .2, and the final ISO brightness of the obtained pulp was about 86%.
• the residual hydrogen peroxide was about 0.39%.
• Table 1 shows the Kappa number and ISO brightness of pulp A4420-1-D1 box washed (pulp 9-1 ) and pulp A4420-2-Po box washed (pulp 9-2).
• Table 2 shows benchmark strength of pulp A4420-1-D1 box washed (pulp 9-1 ) and pulp A4420-2-Po box washed (pulp 9-1) compared with bagasse pulp obtained from a Thailand mill (pulp 9-3), and standard pulps from bagasse (pulp 9-4, bleached bagasse pulp, pulp atlas pulp #60) at 0 revolution in a TAPPI standard PFI analysis, and standard pulps from wood (pulp 9-5, eucalyptus bleached Kraft cenrti coastl. Brazil pulp, pulp atlas pulp #35) at revolutions of 0, 1000, and 2000 in a TAPPI standard PFI analysis,.
• a standard PFI mill method (TAPPI Test Method T-248) was used to evaluate pulp quality for papermaking.
• a pulp was "beaten” or “refined” in a laboratory setting for certain revolutions to reflect further processing of the pulp in a mill.
• a zero revolution number meant no further process was done to the pulp.
• the data of a standard wood pulp (pulp 9-5) showed that further processing of the pulp lowers the freeness, but improves strength parameters such as burst, tear and tensile parameters.
• the bagasse pulps obtained from this embodiment (pulps 9- 1 and pulp 9-2) with no revolutions had higher freeness, tensile and burst parameters than those of the standard hardwood pulp (pulp 9-5) with or without revolutions.
• pulps 9-1 and pulp 9-2) were also compared with those of known bagasse pulps (pulp 9-3 obtained from a Thailand mill and pulp 9- 4, a standard bagasse pulp from the Pulp Atlas) at different revolutions (Table 3).
• Table 3 shows selected parameters of bagasse pulps produced from different sources with different resolutions.
• the freenesses of the pulps obtained from the embodiment ⁇ pulp 9-1 and pulp 9-2) were about 10% to about 18% higher than those of the bagasse pulps obtained from other sources (pulp 9-3 and pulp 9-4) when revolutions were 0.
• the burst indexes of pulp 9-1 and pulp 9-2 were about 60% to 150% higher than those of pulp 9-3 and pulp 9-4 when revolutions were 0. Although the burst indexes of pulp 9-3 and pulp 9-4 increased at higher revolutions, the burst index of pulp 9-3 at 1000 revolutions and the burst index of pulp 9-4 at 750 revolutions were still lower than that of pulp 9-1 or pulp 9-2 at zero revolutions.
• the tensile parameters of pulp 9-1 and pulp 9-2 were about 54% to about 100% higher than those of pulp 9-3 and pulp 9-4 when revolutions were 0. Although the tensile parameters of pulp 9-3 and pulp 9-4 increased at higher revolutions, the tensile parameters of pulp 9-3 at 1000 revolutions and the tensile parameters of pulp 9-4 at 750
• the pulp obtained from the embodiment had significantly higher burst index than that of the reference bagasse pulps, about 60% to about 150% higher.
• the improved strength parameters of pulp 9-1 and pulp 9-2 compared to the reference bagasse pulps were significant and
• Example 10 Effect of cleaning in the pulp process on benchmark strength of the final pulp products obtained from soda AQ process
• Bagasse # 6 was cleaned according to the procedure as described in Example 1.
• the cleaned bagasse was treated with sodium hydroxide (20% by weight of the OD bagasse) and AQ (0.3% by weight to the dry weight of OD bagasse) at a liquid to dry fiber ratio of 7.0 (consistency of about 12.5%), at a maximum temperature of about 175 °C for 34 minutes. Time to the maximum temperature was 60 minutes.
• the target H-factor was 1056, temperature pulping reaction was 175 °C.
• the Kappa number of the screened pulp was 4.1 , the cooking yield was 57.9%, the yield of the screened pulp was 56.6%, total rejects was 1.3% (+ 0.010"), and the viscosity of the pulp was 38.3 mPa.s.
• Pulp A4354-1 -P was obtained by bleaching the pulp obtained from the cooking step by a TCF bleaching having a sequence of Q/P having the following reaction condition.
• Q stage A pulp having a consistency of 10% was treated with DPTA (0.5-0.7% by weight of the weight of the dry pulp) at 80 °C for 30 minutes.
• the pH was 4.
• P stage The pulp obtained from the Q stage was treated with hydrogen peroxide (2.0% by weight of the weight of the dry pulp), sodium hydroxide (1.0-1.1 % by weight of the weight of the dry pulp), DTPMPA (0.25% by weight of the weight of the dry pulp), MgS0 (0.60% by weight of the weight of the dry pulp), NaSi0 3 (0.50% by weight of the weight of the dry pulp) at 85 °C for 60 minutes.
• the final pH was 10.5-1 1 .0, and the final ISO brightness of the obtained pulp was about 84.75%.
• the residual was about 0.05%.
• Pulp A4354-2-P was obtained from the same process as the pulp A4354-1-P, further including cleaning the pulp obtained from the cooking step by box-washing before the TCF bleaching.
• Box-washed pulp was obtained by first diluting the pulp to a consistency of 1 .0%, and then rinsing the pulp in a box with a screen mesh floor, wherein the pulp mat which forms on the mesh was not allowed to accumulate of more than 1 inch. As soon as a layer of washed pulp began to form on the mash, it was removed and saved for the next step of process.
• Pulp 11 Pulp L1503-2-Po was made from corn stover by the following procedures:
• Aged damp corn stover was soaked in cold water for 1 hour, refined at 0.080" gap with standard plates, washed on a 4.75 mm sieve, and then washed on a 1.4 m screen.
• the cleaned corn stover was treated with sodium hydroxide (20% by weight of the OD corn stover) and AQ (0.2% by weight to the dry weight of OD corn stover) at a liquid to dry fiber ratio of 7.0 (consistency of about 12.5%), at a maximum temperature of about 165 °C for 8 minutes. Time to the maximum temperature was 48 minutes.
• the target H-factor was 200, temperature pulping reaction was 165 °C .
• the Kappa number of the screened pulp was 5.0, the cooking yield was 56.8%, the yield of the screened pulp was 56.5%, total rejects was 0.2% (+ 0.0 0" screen), and the viscosity of the pulp was 101.2 mPa.s.
• the pulp obtained from the cooking step was cleaned with a centricleaner using a consistency of 1.0%, 30 gpm flow, and pressure of 34 psi with lightning mixer.
• the cleaned pulp was further cleaned by water at a consistency of 0.05%, 30 gpm flow, and pressure of 34 psi with lightning mixer.
• Pulp L1503-2-Po was obtained by bleaching the cleaned pulp by a TCF bleaching having a sequence of QP QPO having the following reaction condition.
• Q stage A pulp having a consistency of 10% was treated with DTP PA (0.5% by weight of the weight of the dry pulp) and H 2 SO 4 (0.35%) at 80 °C for 30 minutes. The initial pH was 4.0.
• P1 stage The pulp obtained from the Q stage was treated with hydrogen peroxide (1 .0% by weight of the weight of the dry pulp), sodium hydroxide (0.8% by weight of the weight of the dry pulp), MgSO (0.3% by weight of the weight of the dry pulp), NaSiO 3 (4.0% by weight of the weight of the dry pulp) at 85 °C for 60 minutes. ISO brightness of the obtained pulp was 73.5%, yield of P1 stage was 98.2%.
• Q-Stage The pulp obtained from the P1 Stage having a consistency of 10% was treated with DTP M PA (0.5% by weight of the weight of the dry pulp) and H 2 S0 (0.35%) at 80 °C for 30 minutes. The initial pH was 4.0.
• PO stage The pulp obtained from the Q Stage was treated with hydrogen peroxide (6.0% by weight of the weight of the dry pulp), sodium hydroxide (2.8% by weight of the weight of the dry pulp), NaSi0 3 (4.0% by weight of the weight of the dry pulp), 0 2 (pressure measured as 60 psi) at 120 °C for 120 minutes. Final pH was 10.5, residual H 2 0 2 was 0.37%, and ISO brightness was 90.8%, stage yield was 95.9%.
• Example 12 Effect of AQ concentration in the cooking process for ARF pulping
• Example 13 Articles of Manufacture Made from Agricultural Renewable Fiber Pulp
• ARF pulp made as described supra was made having a fiber count per milligram of 19,000.
• a premium grade bath tissue meeting North American Premium Specifications was manufactured using the ARF Pulp by directly substituting minimal amounts of NBSK with the ARF pulp without any refining.
• Examples of other articles of manufacture that can be made from the pulps set forth herein by partially or entirely substituting a prior art wood pulp with an ARF pulp or other pulp composition as described herein include, tissue, printing and writing papers, communication papers, bleached board, food contact packaging papers such as OGR, bleached packaging grades, liquid packaging, the more exotic papers such as wet strength papers and release liner, recycled linerboard and molded packaging products.

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