KR20140068093A - Articles of manufacture made from pulp composition - Google Patents

Abstract

One aspect of the invention relates to an article of manufacture made from a pulp composition comprising ARF pulp. In one embodiment, the pulp composition is made from agriculturally renewable fibers (ARF), which have a low kappa value with sufficient unexpected quality (e.g., high strength parameters and high freeness) for the papermaking. In another embodiment, the ARF pulp has an ISO whiteness of 60% or greater and has a quality (e.g., high intensity parameter and high degree of freeness) sufficient for papermaking. In another embodiment, the ARF pulp is produced from a pulping process involving the use of a high concentration of anthraquinone (AQ).

Description

[0001] ARTICLES OF MANUFACTURE MADE FROM PULP COMPOSITION [0002]

The present invention relates to articles of manufacture made from pulp compositions.

Pulp is a lignocellulosic fibrous material made by chemically or mechanically separating cellulose fibers from a wood or non-wood fiber source.

"Pulping" generally refers to the breaking down of bulk fiber source material into its component fibers. Wood and other plant materials used to make pulp generally contain three main components: cellulose fibers (needed for papermaking), lignin (a three-dimensional polymer that binds cellulose fibers together) ) And hemicellulose (short branched carbohydrate polymer). The purpose of pulping is to break down the bulk structure of the fiber source into constituent fibers, whether it be chips, stalks or other plant parts.

Chemical pulping accomplishes this by decomposing lignin into small water-soluble molecules that can be washed away from them without depolymerizing the cellulose fibers and hemicellulose fibers. The depolymerization of cellulose weakens the fiber and lowers the strength of the resulting pulp. Although lignin in the pulp can improve the strength, pulp with a high degree of delignification can facilitate the bleaching process.

In general, current pulping processes do not provide pulp with a sufficiently reduced kappa value without the use of many delignification processes and / or unacceptable destruction or weakening of the cellulose in the pulp. Thus, there is a need for an improved pulping process that is capable of achieving pulps of the desired properties while eliminating many of the steps required in the current art.

In addition, agricultural renewable fiber (ARF) is an environmentally friendly alternative to the use of wood as a fiber source. ARF represents an economically promising source of non-wood fiber. However, given the fragile nature of agricultural residues, ARF pulp available on the market today does not have sufficient strength for many industrial applications, for example, for the production of printing and record grade paper. Thus, there is a need for high quality, consistent ARF pulp that can replace pulp produced from wood fibers for the production of articles of manufacture.

One aspect of the invention relates to an article of manufacture made from a pulp composition comprising ARF pulp.

In one embodiment, the ARF pulp has an unbleached Kappa number of about 15 or less and a strength parameter sufficient for papermaking.

In another embodiment, the ARF pulp is prepared by mixing a first mixture comprising fiber, water, alkali, and a delignification selectivity enhancing chemical with a desired kappa value of about 15 or less and sufficient strength parameters to the paper And cooking at a cooking condition for a sufficient period of time to form the first pulp having the first pulp.

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Figure 1: Effect of the concentration of anthraquinone (AQ) applied to the cooking process on the kappa value of the pulp obtained in high H-factor and low H-factor processes.
2,
2 is a flow chart of a pulping process according to an embodiment of the present invention;

One aspect of the invention relates to an article of manufacture made from a pulp composition comprising ARF pulp.

Examples of articles of manufacture made from pulp compositions comprising ARF pulp include, without limitation, tissue, printed and recorded paper, communication paper, bleached boards, food contact packaging paper, For example, OGR paper, bleached packaging grade paper, liquid packaging paper, more exotic paper such as wet strength paper and release liner, recycled liner board, linerboard) and molded packaging products.

The ARF pulp may be bleached pulp or unbleached pulp. Examples of articles of manufacture made from pulp compositions comprising bleached ARF pulp include, but are not limited to, tissue, printed and recorded paper, telecommunication paper, bleached cardboard, food contact wrappers such as oil and grease resistant "OGR") paper, bleached packaged grade paper, liquid wrapping paper, and more exotic paper such as wetted paper and release liner. Examples of articles of manufacture made from pulp compositions comprising unbleached ARF pulp include, without limitation, recycled liner boards and molded packaging products. In certain embodiments, the use of bleached or unbleached ARF pulp may improve the performance of the article of manufacture.

ARF includes fibers obtained from agricultural production. Examples of ARFs include, without limitation, bagasse, straw, rice straw, corn stover (stem, leaf, and skin), soy residue, coconut tissue, cotton stalks, palm baskets, For example, kenaf, industrial hemp, seed flax straw, textile flax straw, sisal, hesperaloe, rye grass, , And mixtures thereof. In one embodiment, the ARF is a barge or corn.

The ARF pulp as disclosed herein exhibits exceptional binding properties. Fibers in ARF pulp are generally short fibers, but due to their excellent bonding properties, the fibers behave like unexpectedly long fibers, exhibit physical dimensions similar to those of hardwood fibers, and are characterized by a northern bleached softwood kraft ; NBSK), etc., can be partially substituted, if not all. This coupling characteristic leads to outstanding final paper sheet strength to meet today's demanding customer specifications. This sheet strength is achieved using some of the usual refining energy required for wood fibers and is a significant cost savings to tissue applications that require the refinement of wood pulp to develop strength. In some embodiments, the fiber count per milligram is 19,000.

Premium grade bath tissues were prepared using the minimal amount of NBSK by direct replacement with ARF pulp without any further purification, meeting the North American Premium Specifications.

In one embodiment, the ARF pulp has an unbleached kappa value of about 15 or less and sufficient strength parameters for the papermaking.

The Kappa number reflects the hardness, bleachability, or degree of delignification of the pulp. In general, pulp with a kappa value of about 5 or less is bleached (no elemental chlorine free (ECF) technology) or without chlorine compounds (completely chlorine free (TCF) technology) (e.g., less than 50% ISO whiteness, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 84%, greater than about 88%, greater than about 80 to about 90% % ≪ / RTI > ISO whiteness). In general, one or more pulping steps (sometimes referred to as cooking or delignification) are required to lower the kappa value while maintaining the strength parameters of the pulp. Pulp with a higher kappa value will make ECF or TCF bleaching difficult, requiring oxygen delignification and / or ozone, and / or more peroxide. Alternatively, a pulp with a higher kappa value may be bleached by chlorine. Therefore, ARF pulps with sufficiently low kappa values and sufficiently high intensity parameters will be appreciated in the art.

Many methods for measuring the degree of delignification have been developed in the art, but most are variants of the permanganate test. The normal permanganate test provides a permanganate or "kappa value", which is the cubic centimeters of a 1/10 normal (0.1 N) potassium permanganate solution consumed by 1 gram of oven-dried pulp under certain conditions. For example, this can be determined by the TAPPI Standard Test T-236. Acceptable kappa values will vary depending on the intended use of the pulp (e.g., the kappa value requirement for brown paperboard may vary from about 50 to about 90, while the requirement for a white paper stock may be less than 5 ).

Tensile, tear index, and burst index are examples of strength parameters of the pulp to be used to produce articles such as, for example, paper or paper products. In general, higher strength parameters of the pulp are needed to provide higher strength to articles made from the pulp. Pulps obtained from wood fibers generally exhibit better strength parameters as compared to pulps obtained from non-wood fibers (e.g. ARF such as Burgess). However, some of the strength parameters (e.g., tensile strength) of the pulp compositions disclosed herein are similar or better than those of pulp produced from wood, unexpectedly (see, e.g., Example 9, Table 2).

Examples of sufficient pulp strength parameters for paper include, without limitation, a tensile strength of about 5.50 km or more, 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 do.

In some embodiments, the pulp composition has a kappa value of about 15 or less, about 10 or less, or about 5 or less.

In some embodiments, the pulp composition also has a high freeness.

The term " water solubility, " as used herein, refers to "pulp freeness" or to the rate of water drainage, or how "free" If the freeness is too low, the freeness is important for papermaking in that it is not possible to remove enough water from the paper machine to achieve good sheet structure and strength. Often, mechanical pulps have low water solubility due to the coarse action imparted to the raw material, which creates fine fines and particles that clog the drainage paper mat. Many of the chemical pulping processes that use non-wood fiber source materials, such as whole-stalk, have the problem of having poor freeness due to the characteristics of the grained portions.

Some embodiments do not suffer from the problems of prior art processes. Indeed, some of the ARF pulps described herein have a high degree of freeness. Yeosu is much higher than traditional non-wood pulp, so there is no problem with table capacity in the paper machine when replacing wood-based pulp. As used herein, the term "high degree of freeness" refers to a degree of freeness of at least about 400 mL CSF.

In certain embodiments, the ARF pulp described herein has a freeness of about 400, 425, 450, 475, 500, 525, or 550 mL CSF.

In some embodiments, the ARF pulp has an ISO whiteness of at least about 60% and sufficient strength parameters for the papermaking.

There are a number of ways to measure pulp whiteness. This parameter is usually a measure of the reflectivity, which is typically expressed as a percentage of a certain scale. In this specification, the International Standards Organization (ISO) whiteness test is used. In certain embodiments, the ARF pulp of the present invention has an ISO whiteness of less than 50%. In certain embodiments, the ARF pulp of the present invention should have an ISO whiteness of at least about 60% (suitable for use in the manufacture of printed and record grade paper).

In certain embodiments, the ARF pulp has an ISO whiteness of greater than about 60%, greater than about 70%, greater than about 80%, greater than about 84%, greater than about 88%, greater than about 80 to about 90%, or greater than about 90%.

In another embodiment, the ARF pulp comprises a first mixture comprising an ARF fiber, water, an alkali, and a delignification selectivity enhancing chemical to a first pulp having a desired kappa value of about 15 or less and a strength parameter sufficient for the papermaking And cooking at a cooking condition for a sufficient period of time to form a pulp. The cooking step may include a single cooking step to achieve the desired pulp.

In one embodiment, the fiber used in the pulping process is ARF. In another embodiment, the ARF is bergasin or corn bovine. In another embodiment, the fibers used in the pulping process are wood fibers, for example, hard or softwood fibers.

Examples of the parameters without sufficient strength to the paper, limiting, even greater than or equal to about 5.50 km tensile, about 6.00 mN.m ² / g or more of tear index, of about 3.00 kPa.m ² / g or more burst index-cooked before sijae fee Kappa value About 60 or more - and combinations thereof.

The concentration of the alkali in the first mixture may range from about 10% to 30%, from about 15% to about 25%, from about 20% to about 22%, from about 20% to about 20% About 22.5 wt%, about 20 wt%, about 21 wt%, about 22 wt%, about 22.5 wt%, about 24%, or about 27 wt%. Examples of alkalis include, without limitation, sodium hydroxide or potassium hydroxide, which may also contain sulfur chemicals. As used herein, "OD" and "OD" are "oven-dried". Other examples of suitable alkali additives include ammonia and ethanolamine or derivatives thereof.

Examples of delignification selectivity enhancing chemicals include, without limitation, anthraquinone (AQ) or derivatives thereof. The concentration of the AQ or derivative thereof in the first mixture may range from about 0.2 wt% to about 1.0 wt%, at least about 0.1 wt%, at least about 0.17 wt%, at least about 0.2 wt%, at least about 0.25 wt% At least about 0.25 weight percent, at least about 0.3 weight percent, at least about 0.35 weight percent, at least about 0.4 weight percent, at least about 0.45 weight percent, at least about 0.5 weight percent, at least about 0.55 weight percent, at least about 0.6 weight percent, , At least about 0.7 wt%, at least about 0.75 wt%, at least about 0.8 wt%, or at least about 0.85 wt%.

The ratio of the liquid to the dry fibers of the first mixture (L / W) is the sum of the liquids compared to the fully dried fibers, for example the liquor applied to the unit weight of the oven dried digester feed ). This may include all liquids involved in cooking and may be about 4, 5, 6, 7, 8, or 9 to about 10, about 7, or about 8.

The term "consistency " as used herein to refer to" reaction led, "" mixed led, "and" pulp led "refers to percent (%) solids , For example, the weight percent of fibers (usually pulp, not raw fibers) in the pulp / water slurry.

The cooking condition may be the cooking temperature and the cooking pressure. The cooking temperature may range 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, less than 175 ° C, Or 165 < 0 > C or less. The cooking pressure may be from about 0.41 MPa to about 1.03 MPa, from about 0.83 MPa to about 1.03 MPa, or from about 0.89 MPa to about 0.97 MPa (from about 60 psig to about 150 psig, from about 120 psig to about 150 psig, or from about 130 psig to about 140 psig ).

The cooking time sufficient to form the first pulp under the cooking conditions depends on the conditions and may range 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 minutes About 90 minutes, about 30 to about 60 minutes, about 53 minutes, about 50 minutes, about 40 minutes, about 35 minutes, or about 34 minutes.

In certain embodiments, the first mixture is heated from a lower temperature to a desired temperature during the first cooking time, and is maintained for a cooking time of 2 seconds at the desired temperature. For example, the desired temperature may be from about 90 캜 to about 200 캜, from about 120 캜 to about 200 캜, from about 150 캜 to about 190 캜, or from about 165 캜 to about 185 캜, from about 185 캜 to about 175 캜, 165 [deg.] C. The lower temperature may be about room temperature, about 90 占 폚, about 120 占 폚, about 150 占 폚, or about 165 占 폚. The first cooking time may be from about 1 minute to about 120 minutes, from about 1 minute to about 90 minutes, from about 1 minute to about 60 minutes, from about 5 minutes to about 120 minutes, from about 5 minutes to about 90 minutes, 60 minutes, or about 60 minutes. The second cooking time is 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 minutes to about 90 minutes, from about 30 minutes to about 60 minutes, , About 40 minutes, about 35 minutes, or about 34 minutes. In some embodiments, the cooking condition is a cooking pressure of about 130 psig to about 140 psig, and the desired temperature is about 175 ° C. The lower temperature is about 90 占 폚, the first cooking time is 60 minutes, and the second cooking time is about 40 minutes.

In certain embodiments, the cooking temperature is from about 120 캜 to about 200 캜, 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 캜 to about 190 캜, and the cooking time is from about 30 to 60 minutes. In some embodiments, the cooking temperature is from about 165 캜 to about 185 캜, and the cooking time is from about 35 to about 45 minutes.

In certain embodiments, the temperature of the first mixture is lowered to the simulant simulator at the desired temperature. For example, at a desired temperature, a second mixture having all components of the first mixture except for ARF can be prepared, and then ARF is added to the second mixture to form the first mixture. The cooking time at the desired temperature ranges 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 minutes to about 90 minutes, from about 30 minutes to about 60 minutes, 50 minutes, about 40 minutes, about 35 minutes, or about 34 minutes.

In the prior art, the pulp produced from the first cooking step usually had a higher kappa value, or damaged or destroyed the desired properties of the cellulose. For example, pulps made from burgers known in the art generally have a kappa value of about 20 or greater. Such pulp should be further delignified (e.g., by oxygen delignification and / or ozone treatment) to reduce / reduce the kappa value or bleach with chlorine. Such delignification and / or chlorination can compromise the strength and other parameters of the resulting pulp and increase the cost of the process.

The kappa value of the first pulp is about 5 or less, about 7 or less, about 10 or less, or about 15 or less. The first pulp with a kappa value of 5 or less is bleached with TCF or ECF to provide the desired whiteness (e.g., less than 50%, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 84% %, More preferably about 80% to about 90%, or about 90% or more ISO whiteness).

In certain embodiments, the kappa value of the first pulp decreases as the amount of AQ applied to the cooking process increases (FIG. 1).

The H-coefficient represents the relative lignin dissolution rate. This depends on the cooking time and temperature. Due to the delignification temperature dependence, the dependence of the H-factor on temperature is very strong. Even a difference of 2 degrees in the cooking temperature can make a significant difference in pulp quality. The H-factor is defined such that one hour at 100 캜 is equivalent to the H-factor 1. Generally, the higher H-factor in the cooking process is more likely to provide the first pulp of lower kappa values.

The H-factor can be calculated by:

, Where t is the time and T is the temperature (Calvin temperature).

In some embodiments, the pulping process is performed in a pulping process that includes at least about 20, at least about 50, at least about 100, at least about 200, at least about 300, at least about 400, at least about 1000, at least about 200, at least about 300, at least about 400, A H-factor of at least 1100, at least about 1400, at least about 1700, at least about 2000, at least about 2500, at least about 3000, and from about 2000 to about 3000.

In another embodiment, the cooking condition is a pressurizing cooking condition. The pulping method further comprises cooling the first pulp to below its boiling point before releasing the first pulp from the pressurized cooking condition. The cellulose fibers in the alkaline matrix released above atmospheric pressure while still above the boiling point of the weak black liquor will be damaged. Damage can be serious. To avoid such damage, the first pulp may be cooled to within a temperature range of about 70 to about 95 캜 before release from the pressurized cooking condition. In certain embodiments, the blowline is cooled below its boiling point prior to releasing the first pulp from the pressurized cooking condition. In certain embodiments, prior to releasing the first pulp from the pressurized cooking condition, the first pulp is diluted with the cooled wash water to lower its temperature below its boiling point.

In another embodiment, the pulping method further comprises a cleaning step. In the cleaning step, the fibers are removed from the fibers prior to addition to the first mixture, from the first mixture, or from pulp obtained after one or more steps of the pulping process (e.g., the first pulp, the bleached pulp, and / (E. G., Unwanted mineral material, unwanted cellulose material, and burnt or partially burnt fibers) from the process (e. G., Pulp obtained from the step (e.g., chelation, oxygen-rich alkaline peroxide bleaching)).

Examples of unwanted mineral materials include, without limitation, rock, sand, rust, soil, tramp metal, trash, and very fine (silicate) particles. These particles can wear equipment, reduce whiteness, affect freeness and contribute to high ash content. The unwanted mineral material can be removed from the fibers before being added to the first mixture, from the first mixture, and / or from the pulp.

Examples of unwanted cellulosic materials include, without limitation, pith (parenchyma cells, and other non-fibrous cells). Unwanted cellulose materials have a low structural paper-making value, but can deplete the chemical and clog the sheet. Unwanted cellulose material may be difficult to remove from the pulp. Therefore, unwanted cellulose material needs to be removed from the fibers and / or practically from the first mixture.

Examples of burnt or partially burnt burgez particles include, without limitation, carbon and char. Carbon, char, and partially burnt gas particles can reduce the whiteness of the finished pulp if the size is microscopic. If these particles are large, they will appear as dirt. It is necessary to remove these particles from the fibers before they are added to the first mixture, from the first mixture, and / or from the pulp.

The cleaning step for the raw fibers may also include single or multiple cleaning steps. For example, in the first rinsing step, light agitation is applied to the raw fibers to provide shear and to remove a portion of the pieces attached to the fibers.

In the second rinsing step, the rock and coarse sand are removed from the raw fibers by a centrifugal cleaner.

In the third rinsing step, the raw fibers are mixed in water for a first rinsing time in a first rinsing rinse to form a first rinsing mixture, followed by filtration through a first rinsing screen. Mild agitation is optionally applied to the mixing step. The first cleaning run may be low to medium, for example, from about 0.5 wt% to about 10 wt%, about 1 wt%, or about 2 wt%. The water may be at a temperature of about 20 째 C to about 100 째 C, about 80 째 C to about 100 째 C, or about 60 째 C. The first cleaning time can be from about 1 minute to about 1 hour, or about 10 minutes. Alternatively, a small amount of detergent may be used to promote wetting. The first cleaning screen may be a rough screen (about 0.5 cm or more). The first cleaning mixture can be poured through the screen. The remaining fibers on the screen are often removed to prevent the formation of thick layers (thickness less than about 1 cm). Much larger lead and much thicker layers interfere with separation.

The fiber purification step for the first pulp involves separating spent chemicals and dissolved non-pulp material in a process known as washing. Washing is also used to indicate that a surfactant is used and then rinsed with water to remove both small undesirable and microscopic sized particles visible to the naked eye. Cleaning involves separating the desired fibers from undesirable fibers and other materials, such as sand, char, or materials that have not been completely treated in the pulping step, by a system known as screens and scrubbers. Examples of the first type of process equipment may be a rotary drum vacuum washer, a wash press, and a diffusion washing unit. An example of a second type of process equipment may be a pressure pulp screen and a centrifugal scrubber.

In addition, for example, unwanted cellulose materials and / or mineral materials can be removed from the pulp by aggressively rinsing the pulp with clean water. Prior to rinsing, the pulp may optionally be diluted to form a lower lead (e.g., about 1.0%). The rinsing step may be performed in a box with a screen mesh floor, wherein the pulp matte formed on the mesh is not allowed to accumulate. As soon as a layer of washed pulp begins to form on the mesh, it is removed and stored.

A diffuser washer is a multi-stage diffuser operating under cooking conditions to improve cleaning efficiency. In some embodiments, the diffusion unit has five or more wash steps. Optionally, a pressure diffuser is used after each washing step to enable energy reduction by not cooling the process.

In order to achieve good separation during cleaning, it is desirable to keep the pulp mat formed on the screen thinner. In certain embodiments, prior to removal from the screen, the pulp mat has a thickness of less than 2.54 cm (1 inch), or less than 1.27 cm (0.5 inches). The size of the holes on the screen may be about 0.32 cm, or about 0.95 cm (1/8 inch, or about 3/8 inch).

Optionally, the screen may be vibrated during separation. For example, without limitation, the vibrations may range from about 0.25 to about 5.08 cm, from about 0.25 to about 2.54, from about 0.25 to about 1.27 cm, from about 0.64 to about 1.27 cm (from about 0.1 to about 2 inches, from about 0.1 to about 1 inch, About 0.1 to about 0.5 inches, about 0.25 to about 0.5 inches).

In some embodiments, the first mixture, or pulp, is washed by dropping onto a screen for separation of unwanted material, prior to digesting the raw fibers. The raw fiber, first mixture, or pulp is dropped at an angle other than 90 ° to prevent clogging. The angle may be greater than about 45 degrees. It is desirable to feed the screen at a constant swelling speed to keep the material distribution more uniform and constant across the screen surface.

In certain embodiments, the unwanted material is separated from the raw fiber, the first mixture, or the pulp by a vertical hammer mill or by a trammel screen. This is the first treatment step for producing the raw flue gas for loading on a pulp mill and is referred to as moist depression.

In another embodiment, the pulping method further comprises bleaching the first pulp to provide a bleached pulp. In some embodiments, the pulp composition has an ISO whiteness of greater than about 60%, greater than about 70%, greater than about 80%, greater than about 84%, greater than about 88%, greater than about 80 to about 90%, or greater than about 90%.

The bleaching step may comprise chlorine, may contain chlorine dioxide (ECF technology), or may not contain chlorine compounds (TCF technology). The bleaching step comprises one step or multiple steps. Each step may or may not include bleach. Each step may be performed individually, or concurrently with other steps. Alternatively, a cleaning step is performed after each step (e.g., by a cleaning press, a diffusion washer, or a diffuser washer). For example, in step C, chlorine is applied. In the PO, Ep, P, P1 or P2 step, hydrogen peroxide is applied. In step E, extraction with sodium hydroxide is applied. In step D, D1, or D100, chlorine dioxide is applied. In the Eop step, sodium hydroxide is applied, hydrogen peroxide and a small amount of oxygen gas are added. In the O stage, oxygen gas is applied. In step Q, a chelating agent is applied to remove the metal. In the PO phase, alkaline peroxides and oxygen are applied simultaneously to improve the peroxide efficiency.

Alternatively, washing is performed after each reaction step is completed.

The chelation is a step to protect peroxides used as bleaching chemicals in the next step. Examples of chelating agents include, without limitation, ethylenediaminetetraacetic acid (EDTA), diethylenetraamine pentaacetic acid (DTPA), and diethylenetriamine penta (methylenephosphonic acid) (DTPMPA). In some embodiments, the pH of the 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 SO ₄ ) at a chelation temperature of 80 ° C or higher, for a chelation time of 10 minutes to 30 minutes or more. No pH adjustment is required when DTPMPA is used. The main goal of all chelating agents is Mn, which causes catalytic loss of hydrogen peroxide. The chemical agent may be added via a high shear chemical mixer or any other suitable equipment / method known in the art. In some embodiments, the pulp is adjusted to a degree of about 5 to about 30%, about 10 to about 30%, about 15 to about 20%, about 10%, about 15%, or about 20% prior to the chelation treatment. In certain embodiments, the pulp obtained from the chelation step is washed before proceeding to the next step. The cleaning may be performed in a cleaning press in which the pulp for cleaning is squeezed and then diluted and repressed. Cleaning may be performed by other methods or equipment known in the art.

In some embodiments, for example, if the kappa value of the first pulp is greater than about 5 to 15, the chlorine bleaching approach may be applied to the first pulp to lower the kappa value to less than about 5 to 15 (Step C) Hypo chlorites can then be replaced with less hazardous hydrogen peroxide if desired. For example, the C / Eop / PO or C / Ep / PO bleaching sequence can be applied for the bleaching step in place of the prior art sequence C / E / H or C / EOP / H or C / EP /

In certain embodiments, the first pulp has a kappa value of about 5 to 15 or less, and an ECF or TCF approach is applicable.

The ECF approach includes one or more steps selected from the group consisting of D, D100, D1, Ep, D, PO, and Eop. ECF means that at least some chlorine dioxide is used. In the ECF, "E" refers to "elemental", which means that chlorine gas itself is not applied. This replaced the conventional sequence, which is generally C / E / H or a variant thereof.

The TCF approach generally comprises one or more steps selected from the group consisting of Q, P, PO, and O. In the TCF, "T" means Totally. The TCF sequence may also include various other chemicals, especially ozone "Z ", peracetic acid, Caro's acid, sodium hyposulfate.

In some embodiments, the TCF approach comprises a PO step after the Q step, after the peroxide step of the multi-atmosphere or after the P step of the single atmosphere. In step Q, the chelation is carried out using a 0.5% chelating agent and 0.4% H ₂ SO ₄ at 80 ° C for 30 minutes, no H ₂ SO ₄ , but using the same conditions when DTPMPA is used, Is performed as described above. In the PO step, bleaching is achieved in a mono-polar alkaline peroxide bleaching step enriched with oxygen to improve the peroxide efficiency. Most or even all of the whiteness gain can be achieved at the P / PO stage. In some embodiments, 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% (About 6.0 wt.% To about 9.0 wt.% Of dry pulp) of steam, caustic (NaOH, about 2.6 wt.% Of dry pulp) , About 6.0% or about 7.0% by weight), sodium silicate (about 4.0% by weight of dry pulp), magsulfate (about 0.3% by weight of dry pulp). This step may be performed in a high shear pulp / steam / chemical mixture, or any other suitable equipment / method known in the art. The ISO whiteness of the bleached pulp is greater than about 60%, greater than about 70%, greater than about 80%, greater than about 84%, greater than about 88%, greater than about 80 to about 90%, or greater than about 90%. The yield may be at least about 90% of the feed fiber, at least about 94% of the feed fiber, at least about 95% of the feed fiber.

In some embodiments, the TCF approach has a sequence of Q / P1 / Q / P2 and Q / P1 / PO and Q / P1 / Q / PO and Q / PO, . In the P and PO stages, the pulp obtained from the first Q stage (optionally washed, about 5 to about 30%, about 10 to about 30%, about 15 to about 20%, about 10%, about 15% (About 0.7% by weight of dry pulp), hydrogen peroxide (about 1.0% by weight of dry pulp), sodium silicate (about 4.0% by weight of dry pulp) %), Magnesium sulfate (about 0.3% by weight of dry pulp) and the final pH is about 10.6. The ISO whiteness of the bleached pulp is about 60% or more. The resulting pulp is then treated with another Q step and a P2 / PO step as described above.

In another embodiment, the pulping method is performed as shown in the flow chart of FIG. In the gas scrubbing step, as described above, the gas scrubbing material is separated into white water, i.e., process water obtained from the papermaking system, for example, Washing with process water provides a cleaned baggas (used for cooking in the steaming stage) and a baggas wash water effluent (to be drained). After digestion, the resulting pulping mixture is sent for washing by different washing methods as described above. The obtained wash water waste solution is sent for further treatment. The washed burr gas is chelated as described above, washed as described above, and then bleached in the bleaching step. Although only one bleaching box is shown in the figure, single or multiple bleaching steps may be included as described above. In some embodiments, cleaning between steps may be optional. After bleaching the pulp, it is washed, cleaned, dried and bailed.

Example

Example 1. Cleaning of raw fiber

As an example of the raw fiber, a bag gas was used. At a lead of 0.5% to 2.0%, the bagasse was first hydrated for 10 minutes using hot, clean water (the water temperature was above room temperature, about 40 ° C, or 60 ° C) under moderate agitation. The piece and sand were separated from the fibers on a traverse screen, which was a rotary drum that lifted and dropped the material and allowed the water and the piece to pass through a 1/8 inch (1/8 inch) hole to a maximum of 1.27 cm (1/2 ") hole. The material was collected and removed from the screen to prevent accumulation, placed in place, and dried before being added to the pulping process. The wash yield was about 80% or more, or about 85.9%, depending on the quality of the bergass feedstock.

Example 2 Soda AQ Pulping of Burglass

OD buffer (as cleaned as described in Example 1, having a kappa value of 89) at a maximum temperature of about 175 DEG C at a ratio of liquid to dry fiber of 7 (about 12.5% lead) (20 wt.% Of OD gas) and AQ (0.3 wt.% Based on the dry weight of OD bergas). The time to maximum temperature was 60 minutes.

The target H-factor was 1060, as low as 20 and as high as 3000, and the pulping reaction temperature was 120-185 ° C. The kappa value of the obtained pulp was 4.5.

Example 3. Washing pulp

The pulp from Example 2 was washed in a pressure diffuser washer designed specifically to achieve all washing with a single unit without causing unwanted changes 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 less. The product was sent to a bleaching step and cooled to below 100 ° C to prevent flashing.

Example 4. Pulping step (Q step)

The pulp from Example 3 was adjusted to pH 4 and 15% lead with H ₂ SO ₄ (about 0.4 wt.% Of the dry weight of the pulp) and then dried at 80 ° C for 10 min in DTPA 0.5% by weight). The pulp obtained was washed in a washing press before proceeding to the next step.

Example 5. Alkaline peroxide bleaching of pulp (P2 / PO step)

The washed pulp from Example 4 was adjusted to a 15% lead and proceeded to the P2 / PO step. The pulp (15% lead) was mixed with steam, caustic (NaOH, 2.6% by weight of the dry pulp), oxygen (0.41 MPa (60 psig)) in a high shear pulp / steam / chemical mixture for about 120 minutes at a temperature of about 120 & ), Hydrogen peroxide (7.0 wt% of dry pulp), sodium silicate (about 4.0 wt% of dry pulp), magnesium sulfate (about 0.3 wt% of dry pulp). The ISO whiteness of bleached pulp was more than 86%, and the maximum was 89.2. The yield was about 94% or more of the feed fiber. The final pH was 10.2.

Example 6 Washing and Drying of Bleached Pulp

The bleached pulp from Example 5 was diluted to less than 2% lead and processed through centrifugal scrubbers to remove sand, soil particles, and other debris and unwanted material. These scrubbers had a differential pressure of 0.14 MPa (20 psig) in the scrubber. A 1% yield loss occurred at this stage.

After cleaning the bleached pulp, it was formed into a sheet and pressed into 50% dry solids before drying in an air impingement dryer. The minimum dry rate was 92%. The sheet was cut to the desired size and laminated with a bale of the desired size and weight. These veils were packed and bound and stored for loading.

Example 7. ECF bleaching of the pulp from Example 3

ECF bleaching with an order of D100 / E / D was performed on pulp with a kappa value of 5 or less.

D100 step (low pH, approx. 2.4, ECF step for delignification of the pulp): The pulp with a 10% lead was treated at 50 DEG C for 60 minutes with a Kappa factor of 0.25. The final pH was 2.5, and the residual chlorine was in a small amount or in an undetectable amount.

Ep step: The pulp obtained from step D100 was treated with hydrogen peroxide (0.50% by weight to 0.8% by weight of the dry pulp) at 80 DEG C for 60 minutes. The final pH was 10.5-11.0 and the final ISO whiteness of the pulp obtained was about 80-82%. The viscosity of the bleached pulp was high.

Step D: The pulp obtained from the Ep step was treated with chlorine dioxide (1.2 wt% of the weight of the dry pulp) at 80 DEG C for 150 min. The final pH was 3.5 to 4.0, the residual chlorine dioxide was 0.05%, and the final ISO whiteness of the bleached pulp was about 89%. The viscosity of the bleached pulp was high.

Example 8. TCF bleaching of the pulp from Example 3

TCF bleaching with a sequence of Q / P / PO with the following reaction conditions was performed on pulp with a kappa value of 5 or less.

Step Q: The pulp with a lead of 10% was treated with DTPMPA (0.5 to 0.7 wt% of the weight of the dry pulp) at 80 DEG C for 30 minutes. The final pH was 7.

Step P: The pulp obtained from step Q is pulverized with a mixture of hydrogen peroxide (2.0 wt% of the weight of the dry pulp), sodium hydroxide (1.0-1.1 wt% of the weight of the dry pulp), DTPMPA % by weight), was treated with MgSO ₄ (0.60% by weight of the weight of dry pulp), NaSiO ₃ (0.50% by weight) of the weight of the dry pulp. The final pH was 10.5 to 11.0 and the final ISO whiteness of the pulp obtained was about 80%. The residue was about 0.05%. The viscosity of the bleached pulp was high.

PO: The pulp obtained from step P was treated with hydrogen peroxide (5 wt% of dry pulp weight), DTPMPA (0.25 wt% of dry pulp), MgSO ₄ (0.60 wt% ), NaSiO ₃ (0.50% by weight of dry pulp). The final ISO whiteness of the bleached pulp may be 88.00%. The viscosity of the bleached pulp may be high.

Example 9. Benchmark Strength of Pulp Product Made from Burglass

I) Cleaning of burnt gases.

Buzzer # 11 was washed by the same procedure as described in Example 1 except that 0.95 cm (3/8 ") bodies were used instead of 0.32 cm (1/8") bodies.

II) Cooking

The cleaned bagasse was treated with sodium hydroxide (22 wt% of OD gas) and AQ (OD) at a maximum temperature of about 165 캜 for 35 min, a ratio of liquid to dry fiber of 8.0 0.2% by weight based on the dry weight of the bagasse). The time from 90 DEG C to the maximum temperature was 60 minutes.

The target H-factor was 452. The kappa value of the screened and rapidly dried pulp was 5.0, the cooking yield was 56.8%, the screened pulp yield was 55.8%, the total rejection was 1.0% (+0.025 cm (0.010 ")) Was 44.0 mPa.s.

The pulp thus obtained was diluted first with a lead of 1.0% and then rinsed in a box with screen mesh floors, where the pulp mat formed on the mesh did not accumulate more than 2.54 cm (1 inch) ≪ / RTI > was box-washed pulp. As soon as a layer of washed pulp began to form on the mesh, it was removed and stored for the next step of the process.

III) Bleaching

The washed pulp was bleached by ECF sequence of D100 / Ep / D1 to provide box washed pulp A4420-1-D1. Two duplicate washed pulp samples were bleached by the TCF sequence of Q / Pl / PO to provide box washed pulp A4420-2-PO.

The ECF sequence of D100 / Ep / D1 was performed using the following conditions:

Step D100: The pulp with a 10% lead was treated with ClO ₂ (1.15% as Cl ₂ ) 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 utility Cl ₂ ).

Ep step: The pulp obtained from step D100 is pulverized with hydrogen peroxide (0.5 wt% of the weight of the dried pulp), NaOH (0.7 wt% of the weight of the dried pulp) and MgSO ₄ (0.1 wt% %). The final pH was 11.2 and the final ISO whiteness of the pulp obtained was about 75.6%. The viscosity of the bleached pulp was just 21.4 mPa.s.

Step D: The pulp obtained from the Ep step 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 dry pulp) at 80 DEG C for 150 minutes. The final pH was 4, the residual chlorine dioxide was 0.09%, and the final ISO whiteness of bleached pulp was about 88.4%.

The TCF sequence of Q / PO was performed using the following conditions.

Step Q: The pulp with a lead of 10% was treated with DTPMPA (0.5% by weight of dry pulp) at 80 DEG C for 30 minutes. The final pH was 6.6.

Step P1. The pulp obtained from step Q was pulverized at 85 ° C for 60 minutes in a solution of hydrogen peroxide (2.0 wt% of dry pulp), sodium hydroxide (1.1 wt% of dry pulp), DTPMPA (0.5 wt% of dry pulp) By weight) and sodium silicate (1.0% by weight of dry pulp). The final pH was 11.2 and the ISO whiteness of the pulp was about 67.7%. The residual peroxide was 1.25%.

PO: The pulp from step P1 was treated with hydrogen peroxide (6.0 wt% of dry pulp weight), sodium hydroxide (2.8 wt% of dry pulp weight), DTPMPA (0.5 wt% ), treated with MgSO ₄ (0.60% by weight of the weight of dry pulp), NaSiO ₃ (3.0% by weight) of the weight of the dry pulp. The final pH was 11.2 and the final ISO whiteness of the pulp obtained was about 86%. The residual hydrogen peroxide was about 0.39%.

Table 1 shows the kappa values and ISO whiteness of box washed pulp A4420-1-D1 (pulp 9-1) and box washed pulp A4420-2-Po (pulp 9-2).

Table 2 shows the results of a comparison between standard pulp (pulp 9-4, bleached gauze pulp) from Burgas pulp (pulp 9-3) obtained from Thailand mill and standard pulp from Burgas at 0 revolution of TAPPI standard PFI analysis, , Pulp atlas pulp # 60), and standard pulp from wood at 0, 1000, and 2000 revolutions of the TAPPI standard PFI assay (pulp 9-5, eucalyptus bleached kraft, washed pulp A4420-1-D1 (pulp 9-1) and box-washed pulp A4420-2-Po (pulp 9-1), as compared to the pulp at-cirrtl. coastl. Brazil pulp, pulp atlas pulp # Represents the benchmark strength.

The paper pulp quality was evaluated using a standard PFI mill method (TAPPI Test Method T-248). Quot; beating "or" refining " the pulp in the laboratory settings for a given rotation to reflect further processing of the pulp in the mill. The number of revolutions at 0 means that no further treatment was performed on the pulp. Data from standard wood pulp (Pulp 9-5) showed that further processing of the pulp reduces the freeness but improves strength parameters, such as tear, tear, and tensile parameters. The burgundy pulps (pulp 9-1 and pulp 9-2) obtained from this embodiment without the use of rotation show that the freeness, tensile and rupture parameters are similar to those of standard hard wood pulp (pulp 9-5 ). Buerger pulp (pulp 9-1 and pulp 9-2) obtained from this embodiment without using rotation was higher than standard wood pulp (pulp 9-5) without tilting parameters for tear and elongation. This indicated that the bagasse pulp obtained from this embodiment had very good paper quality without using the additional treatment required for wood pulp.

The characteristics of the bagasse pulp (pulp 9-1 and pulp 9-2) obtained from this embodiment are also compared with those of the known bagasse pulp (pulp 9-3 from pulp mill and pulp 9-4 from pulp atlas) (Table 3). ≪ tb > < TABLE >

Table 3 shows the selected parameters of the bagasse pulp produced from the different feeds using different rotations.

The freeness of the pulp (pulp 9-1 and pulp 9-2) obtained in the embodiment is about 10% higher than the freeness of the bagasse pulp (pulp 9-3 and pulp 9-4) obtained from other sources when the rotation is 0, To about 18% higher.

The burst index of pulp 9-1 and pulp 9-2 was about 60% to 150% higher than the burst index of pulp 9-3 and pulp 9-4 when the rotation was zero. Although the burst index 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 corresponded to pulp 9 -1 or the pulp index of pulp 9-2.

The tensile parameters of pulp 9-1 and pulp 9-2 were about 54% to about 100% higher than the tensile parameters of pulp 9-3 and pulp 9-4 when the rotation was zero. 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 revolutions corresponded to pulp 9 -1 or the tensile parameter of pulp 9-2.

The tear and elongation parameters of pulp 9-1 and pulp 9-2 were also higher than the tear and elongation parameters of pulp 9-3 and pulp 9-4.

The pulp from the embodiment had a significantly higher burst index than the reference burgundy pulp, from about 60% to about 150% higher.

Improvements in the strength parameters of pulp 9-1 and pulp 9-2 compared to reference burgundy pulp were significant and unexpected, and the use of burgers or other fiber sources (e. G. Corn versus Example 11, infra) Lt; RTI ID = 0.0 > pulp < / RTI >

Example 10. Effect of washing in the pulp process on the benchmark strength of the final pulp product from the soda AQ process

I) Cleaning of burrs

Burgus # 6 was cleaned according to the procedure described in Example 1.

II) Cooking

The cleaned bagasse was treated with sodium hydroxide (20 wt.% Of OD gas) and AQ (OD) at a maximum temperature of about 175 DEG C for 34 min, at a ratio of liquid to dry fiber of 7.0 0.3% by weight based on the dry weight of the baggas). The time to maximum temperature was 60 minutes.

The target H-factor was 1056 and the pulping reaction temperature was 175 ° C. The screened pulp had a kappa value of 4.1, a cooking yield of 57.9%, a screened pulp yield of 56.6%, a total rejection rate of 1.3% (+ 0.025 cm (0.010 ")) and a viscosity of 38.3 mPa. s.

III) Bleaching

Pulp A4354-1-P was obtained by bleaching the pulp from the cooking step with TCF bleaching in the order Q / P with the following reaction conditions.

Step Q: The pulp with a lead of 10% was treated with DPTA (0.5 to 0.7% by weight of dry pulp) at 80 DEG C for 30 minutes. The pH was 4.

Step P: The pulp obtained from step Q is pulverized with a mixture of hydrogen peroxide (2.0 wt% of the weight of the dry pulp), sodium hydroxide (1.0-1.1 wt% of the weight of the dry pulp), DTPMPA % by weight), was treated with MgSO ₄ (0.60% by weight of the weight of dry pulp), NaSiO ₃ (0.50% by weight) of the weight of the dry pulp. The final pH was 10.5 to 11.0 and the final ISO whiteness of the pulp obtained was about 84.75%. The residue was about 0.05%.

Pulp A4354-2-P was obtained from the same process as pulp A4354-1-P, further comprising cleaning the pulp from the cooking step by box washing before TCF bleaching.

The pulp was first diluted with a 1.0% lead, followed by a box with a screen mesh floor, where the pulp mat formed on the mesh did not accumulate more than 2.54 cm (1 inch) Pulp was obtained. As soon as a layer of washed pulp began to form on the mesh, it was removed and stored for the next step of the process.

The benchmark strengths of pulp A4354-1-P (pulp 10-1) and pulp A4354-2-P (pulp 10-2) are shown in Table 4 below.

The results show that at zero revolution, both the pulp A4354-1-P and the pulp A4354-2-P are of the desired C.S. It indicates that Yeosu has a degree. The box washing step is a step of washing the final bleached pulp C.S. Increased the freeness and provided more desirable products.

Example 11. Soda AQ pulping of cornstarch

Pulp 11 (pulp L1503-2-Po) was prepared from corn bran by the following procedure:

I) Cleaning of cornstarch

The old moist corn bran was soaked in cold water for 1 hour, purified on a 0.20 cm (0.080 ") gap using a standard plate, washed on a 4.75 mm sieve, and then washed on a 1.4 m screen.

II) Cooking

The rinsed cornstarch was treated with sodium hydroxide (20 wt.% Of OD corn) and AQ (OD corn) at a maximum temperature of about 165 ° C for 8 min, at a ratio of liquid to dry fiber of 7.0 0.2 wt% based on the dry weight of the batch). The time to maximum temperature was 48 minutes.

The target H-factor was 200, and the pulping reaction temperature was 165 ° C. The screened pulp had a kappa value of 5.0, a cooking yield of 56.8%, a screened pulp yield of 56.5%, a total rejection rate of 0.2% (+ 0.025 cm (0.010 ") screen) and a viscosity of 101.2 mPa .s.

III) Pulp cleaning

The pulp from the cooking step was cleaned with a centricleaner using a lightning mixer at a pressure of 1.0 psi, a flow of 30 gpm, and a pressure of 0.23 MPa (34 psi). The cleaned pulp was further rinsed with water at a pressure of 34 psi at a flow of 113.6 L / m (30 gpm) with a lightning mixer at 0.05%.

IV) Bleaching

The washed pulp was bleached by TCF bleaching with an order of QP1QPO with the following reaction conditions to obtain pulp L1503-2-Po.

Step Q: The pulp with a 10% lead was treated with DTPMPA (0.5% by weight of dry pulp) and H ₂ SO ₄ (0.35%) at 80 ° C for 30 minutes. The initial pH was 4.0.

P1: The pulp obtained from step Q is added to a mixture of hydrogen peroxide (1.0 wt% of the weight of the dried pulp), 85 wt% of sodium hydroxide (0.8 wt% of the weight of the dried pulp), MgSO ₄ %), NaSiO ₃ (4.0 wt% of dry pulp weight). The ISO whiteness of the obtained pulp was 73.5%, and the yield of the P1 step was 98.2%.

Q-step. The pulp from step P1 with 10% lead was treated with DTPMPA (0.5% by weight of dry pulp) and H ₂ SO ₄ (0.35%) at 80 ° C for 30 minutes. The initial pH was 4.0.

PO: The pulp from Step Q was treated with hydrogen peroxide (6.0 wt% of dry pulp weight), sodium hydroxide (2.8 wt% of dry pulp weight), NaSiO ₃ (4.0 wt% of dry pulp weight, %), O ₂ (pressure measured at 0.41 MPa (60 psi)). The final pH was 10.5, the residual H ₂ O ₂ was 0.37%, the ISO whiteness was 90.8%, and the step yield was 95.9%.

Benchmarking of pulp 11 is shown in Table 5 below.

The results showed that pulp with a very high ISO whiteness, along with the desired intensity parameters, were obtained from corn.

Example 12. Effect of AQ Concentration in Cooking Process for ARF Pulping

(Low H-factor, Cook numbers L1486-2, L1488-2, L1488-2, L1488-2, L1483-2, L1483-3, 3, A4397, A4400), the raw bagasse was washed as described in Example 1 and cooked as described in Example 2. The effect of the% AQ applied in the cooking process on the kappa values of the pulp shown in Tables 6 and 7 is reflected in Fig.

Example 13. An article of manufacture made from an agriculturally renewable fiber pulp

An ARF pulp, prepared as described above, having 19,000 fibers per milligram was prepared. Premium grade bast tissue that meets the North American premium specification was produced using ARF pulp by directly replacing the minimum amount of NBSK with ARF pulp without any purification.

Examples of other articles of manufacture that can be produced from the pulp described herein by partially or totally replacing prior art wood pulp with ARF pulp or other pulp compositions as described herein include tissue, Paper bags, paper bags, paper bags, paper bags, paper bags, paper bags, paper bags, communication paper, bleaching cartons, food contact wrapping paper such as OGR paper, bleached packaging grade paper, liquid packaging paper, .

Although the present invention has been described with reference to preferred embodiments and specific examples, it will be readily apparent to those skilled in the art that many changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore to be clearly understood that this description is by way of example only and is not intended to limit the scope of the invention. All references in this specification are incorporated herein by reference.

Claims (37)

A pulp composition comprising fibers from an agricultural renewable fiber source, wherein said pulp composition is not bleached, has a Kappa number of about 15 or less, a high freeness, A tensile strength of at least about 5.50 km, a tear index of at least about 6.00 mN.m ² / g, and a burst index of at least about 3.00 kPa.m ² / g. Manufactured goods. The method of claim 1, further comprising the steps of: applying a tissue, a printed and recorded paper, a communication paper, a bleached board, a food contact packaging paper, an OGR paper, a bleached packaging grade paper A liquid packaging paper, a wet strength paper, a release liner, a recycled linerboard, and a molded packaging product. The article of manufacture of claim 1 wherein the kappa value is about 10 or less. The article of manufacture of claim 1, wherein the value of kappa is about 5 or less. The article of manufacture of claim 1, wherein the source of agricultural renewable fiber is a bagasse or a corn stover. 3. The article of manufacture of claim 2, wherein the source of agricultural renewable fiber is a bagasse or corn. 4. The article of manufacture of claim 3 wherein the source of agricultural renewable fiber is a bagasse or corn. A pulp composition comprising fibers from an agricultural renewable fiber source, wherein said pulp composition has an unfolded kappa value of about 15 or less, a high degree of freeness, and sufficient strength parameters for papermaking. The article of manufacture of claim 8, wherein the pulp composition has a tensile strength of at least about 5.50 km, a tear index of at least about 6.00 mN.m ² / g, and a burst index of at least about 3.00 kPa.m ² / g. The article of manufacture of claim 8, wherein the ISO brightness is less than 50% ISO. The article of manufacture of claim 8, wherein the ISO whiteness is greater than or equal to about 70%. The article of manufacture of claim 8, wherein the ISO whiteness is greater than or equal to about 80%. 10. An article of manufacture according to claim 9 wherein the ISO whiteness is at least about 80%. The article of manufacture of claim 8 wherein the ISO whiteness is greater than or equal to about 88%. 10. An article of manufacture according to claim 9, wherein the ISO whiteness is at least about 88%. The article of manufacture of claim 8, wherein the ISO whiteness is greater than or equal to about 90%. 10. An article of manufacture according to claim 9, wherein the ISO whiteness is greater than or equal to about 90%. 9. The article of manufacture of claim 8 wherein the agriculturally renewable fiber is bergas or corn. 10. The article of manufacture of claim 9 wherein the agriculturally renewable fiber is bergas or corn. 14. The article of manufacture of claim 13, wherein the agricultural renewable fiber is bergas or corn. 16. The article of manufacture of claim 15, wherein the agricultural renewable fiber is bergas or corn. 19. The article of manufacture of claim 18, wherein the agriculturally renewable fiber is bergas or corn. 9. The method according to claim 8, wherein the tissue, printed and recorded paper, communication paper, bleaching carton, food contact wrap, OGR paper, bleached packaging grade paper, liquid packaging paper, wet paper, release liner, recycled liner board, ≪ / RTI > 10. The method of claim 9, wherein the tissue, printed and recorded paper, communication paper, bleaching carton, food contact wrap, OGR paper, bleached packaging grade paper, liquid packaging paper, wet grease, release liner, recycled liner board, ≪ / RTI > Agricultural renewable fiber,
water,
An anthraquinone or derivative thereof, wherein the concentration is at least about 0.1% by weight of the dry fiber, and
Wherein the mixture has a ratio of liquid to dry fibers of from about 4 to about 10 and an initial kappa value of greater than or equal to about 60; And
Comprising the step of reacting the first mixture at a cooking time and for a sufficient cooking time to form a second mixture having a kappa value of about 15 or less, a high degree of freeness, and sufficient strength parameters for the papermaking An article of manufacture made from a pulp composition comprising agricultural renewable fiber pulp. 26. The method of claim 25, wherein the sufficient strength parameter for papermaking is from the group consisting of a tensile strength 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, The article of manufacture to be selected. 27. An article of manufacture according to claim 26, wherein the cooking condition and the cooking time provide an H-factor of at least about 200. 28. An article of manufacture according to claim 27, wherein the H-factor is at least about 1000. 27. The article of manufacture of claim 26, wherein the second mixture has a kappa value of about 10 or less. 27. The article of manufacture of claim 26, wherein the second mixture has a kappa value of about 5 or less. 26. An article of manufacture according to claim 25, wherein the agriculturally renewable fiber comprises a bagasse or cornstalk. 27. The article of manufacture of claim 26, wherein the pulping method further comprises bleaching the second mixture. 26. An article of manufacture according to claim 25, wherein the agricultural renewable fiber pulp has an ISO whiteness of about 60% or greater. 26. An article of manufacture according to claim 25, wherein the agricultural renewable fiber pulp has an ISO whiteness of at least about 70%. 26. An article of manufacture according to claim 25, wherein the agriculturally renewable fiber pulp has an ISO whiteness of at least about 80%. 26. The article of manufacture of claim 25, wherein the agriculturally renewable fiber pulp has an ISO whiteness of about 85% or greater. 26. The article of manufacture of claim 25, wherein the agriculturally renewable fiber pulp has an ISO whiteness of about 90% or greater.

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