Novel wheat milling derivative products, methods of making and uses of the same

Abstract

Novel wheat milling derivative products obtained from one or more non-food wheat milling products are described, as well as methods for making the same. The wheat milling derivative products enable up to 50% by weight of cellulosic fibers in paper or in paper packaging or molded product to be displaced or supplemented, diminishing the negative environmental impacts heretofore associated with the making of these paper and paper packaging products and thus improving the sustainability of these paper and paper packaging products, and derive from non-food wheat milling products already realized in conventional wheat milling.

Description

[0001] NOVEL WHEAT MILLING DERIVATIVE PRODUCTS, METHODS OF MAKING AND USES OF THE SAME TECHNICAL FIELD

[0002] The present invention relates generally to wheat milling, and more particularly to the use of wheat milling products in other than consumable or food- / feed-related contexts.

[0003] BACKGROUND

[0004] The particular non-consumable or non-food / feed related context of interest for the present invention is sustainable paper and paper packaging. Sustainable packaging design has become increasingly important over the past few years, as consumers become more focused on the environment.

[0005] Traditionally, pulp for paper and paper packaging has been derived from trees. With a growing awareness however of the negative environmental impacts of certain aspects of paper manufacturing, for example, in relation to deforestation and the loss of important wildlife habitats as well as protections against erosion, the use of enormous amounts of energy and water, water pollution and air pollution, a number of efforts have been undertaken to improve the sustainability of the paper and paper packaging industries. One such effort has involved the use of recycled virgin fibers in old corrugated container (OCC) material.

[0006] However, OCC frequently requires repulping and de-inking processes which causes the recycled fibers to get weakened over time through successive recycles. The result is a deterioration of critical performance requirements such as strength (compression, grammage, burst, ash retention, internal bond potential, and tensile), moisture resistance and freeze / thaw tolerance. Consequently, a variety of alternative, non-wood fibers have recently been evaluated for displacing virgin wood fibers from trees. These alternative, non-wood fiber sources - for example, bagasse from sugar cane refining, hemp and wheat straw among others - are helpful to the extent they are able to function in place of virgin wood fibers from trees, but do not overcome or resolve other negative environmental impacts in that all still undergo the same energy- and water-intensive (and waste intensive) physical and chemical processing used in making paper and paper packaging from trees. Further, all require a certain amount of land to be devoted to their cultivation and sourcing rather than to food production of crops independent of their utility in providing fiber sources for paper and paper packaging, with all of the still-additional offsetting impacts involved in the collection of these materials in lieu of the collection of wood fiber from trees.SUMMARY

[0007] The present invention relates in one aspect to the discovery that certain wheat milling products produced in the normal processing of wheat grain to make wheat flour for breads, pastas and the like can be used to make a suitable material that can serve as a filler, a functional additive, and / or at least a partial replacement for virgin wood fibers and / or OCC material in paper, paper packaging, and molded products, with improved sustainability for the paper, paper packaging, and molded products industries in light of the above-mentioned drawbacks and disadvantages of other alternative, non-wood fiber sources such as bagasse, hemp, wheat straw, com straw, cotton, cotton linter, wheat milling co-products, bamboo, miscanthus, switch grass, arundo, kenaf, hemp, flax, and jute. In this regard, “used” or “useful” in displacement of cellulosic fibers shall be understood to mean that the substitution or supplementation of the cellulosic fibers (virgin or recycled, as the case may be) with an alternative obtained by means of the present invention from the aforementioned wheat milling products from wheat milling as carried out in the usual course of making patent flour, in an equivalent amount by weight up to 50 percent by weight of the finished (dry’) paper sheet, paper packaging, and molded products (or material), yet provides paper sheet, paper packaging, and molded products with commercially acceptable properties, resulting in less than a 20 percent reduction in any relevant finished paper or paper packaging material strength parameter - for example, in regard to paper sheet, the attributes of burst strength, internal bond strength or tensile strength. As will be evident from the working examples below, in a number of these parameters, it is possible by means of the present invention to realize paper sheet and paper packaging materials with very little to no reduction in measured values as compared to products made with no displacement of recycled or virgin cellulosic fibers and, indeed, even to see improvements in these values, and in properties such as hy drophobicity. in certain of embodiments of the more environmentally sustainable paper sheet, paper packaging, and molded products provided by means of our invention.

[0008] It will of course be understood by those of skill in the art that the use of the abovereferenced wheat milling products (as further characterized hereafter) in displacement of cellulosic fibers (whether virgin or recycled) does not by any means exclude the further displacement, in such paper sheet, molded products, and paper packaging materials, of additional cellulosic fibers by means of other alternative, non-wood materials proposed in the art or newly developed - e.g., the non-wood sources already mentioned, or other annual or perennial plants and residues thereof, such as wheat milling products (patent flour or red dog).As background, a wheat kernel is comprised of a number of constituent materials which are broadly classified in the milling literature under the categories of endosperm, bran, brush and germ. A typical wheat milling process employs an array of sorting, grinding, sieving and purification techniques to generate wheat flour, which is a highly purified endosperm fraction referred to by millers as flour or patent flour and which contains starch and varying levels of protein according to its intended use. Through the various grinding and sieving operations, the non-endosperm fractions are systematically fractured or ground and sieved out of the endosperm rich (flour) portion. Since this process occurs over many steps, multiple milling streams are ty pically produced, sometimes referred to as mill feed. Wheat millers may refer to these various milling streams as bran, shorts, red dog, or clear flour, and may further use the terminology bran, fine bran or coarse wearings, fine wearings or shorts, and low grade flour (red dog), though what is signified compositionally by all of these terms of art from one miller or indeed one mill to the next will vary to a degree, so that products or streams from one miller to the next or even from one mill to the next bearing the same descriptor will contain different fractions of endosperm, bran, brush, and germ from the wheat kernel. As well, some millers combine all these nonendosperm materials collected from various places, and will refer to the resulting combined product as ‘'wheat midds” or “wheat middlings”.

[0009] Against this background, the wheat milling products with which the present invention is concerned in this first aspect are especially those non-endosperm-rich, non-patent flour products arising out of the normal processing of wheat grain to make wheat flour or patent flour for foodstuffs, and which may be called “wheat midds” or '‘wheat middlings” in the milling art, but which we will describe compositionally herein in relation to starch, fiber (cellulose and hemicellulose), fat, lignin, and protein content by w eight percentages of what is obtained from a mill for purposes of making the paper and paper packaging compositions of the present invention - so that those of skill in the art will be able to understand with greater clarity the wheat milling products that the present invention employs (according to this first aspect) regardless of how those materials may be described by a particular miller or how and from which milling fractions the materials may be derived by a particular miller or in a particular mill. From this perspective, the wheat milling products with which the present invention is particularly concerned in this first aspect will comprise from 15 to 40 weight percent starch, from 25 to 50 weight percent fiber, from 2 to 11 w eight percent of lignin, from 2 to 10 w eight percent of fat content, and from 10 to 20 weight percent protein - though as already mentioned, the displacement or supplementation of cellulosic fibers by materials made from the wheat milling products so characterized is not to be taken as excluding the further displacement in paper sheet or paper packaging compositionsenabled by the present invention and containing cellulosic fiber alternative materials prepared from wheat midds, of additional cellulosic fibers by other non-wood alternatives, including even other wheat milling products, even those that are endosperm-rich and presently sold into consumable, food- or feed-related applications (such as patent flour).

[0010] As a reference point for those of skill in the milling art considering the potential sourcing of such a wheat milling product from a given mill, a variety of non-endosperm rich, non-patent flour wheat milling products were obtained from a number of mills in the United States under various commonly used mill descriptors and these were compositionally characterized, as follows:

[0011] “Screenings”:

[0012] dry basis, % ash protein starch fat carbs, excluding starch average 7% 14% 39% 3% 38%

[0013] Std dev 2% 2% 2% 0% 3%

[0014] “Shorts”:

[0015] dry basis, % ash protein starch fat carbs, excluding starch

[0016] average 6% 20% 19% 5% 49%

[0017] Std dev 0% 2% 3% 1% 3%

[0018] “Bran”:

[0019] dry basis, % ash protein starch fat carbs, excluding starch average 7% 18% 18% 5% 52%

[0020] Std dev 1% 1% 2% 1% 2%

[0021] “Red dog”:

[0022] dry basis, % ash protein starch fat carbs, excluding starch average 4% 18% 34% 5% 38%

[0023] Std dev 1% 2% 13% 1% 10%

[0024] “Clear Flour”:

[0025] dry basis, % ash protein starch fat carbs, excluding starchaverage 2.7% 20.5% 58.4% 4.4% 14.0%

[0026] Std dev 0.9% 1.5% 6.7% 1.1% 3.4%

[0027] Thus, in this first aspect, the present invention relates to a novel wheat milling derivative product useful for displacing or supplementing virgin wood fibers in paper or in paper packaging from a wheat milling product as characterized above and to a process for making the same, whereby the wheat milling derivative product is obtained by mechanically processing a nonendosperm rich, non-patent flour wheat milling product as characterized above by shearing, grinding / milling or a combination of shearing and grinding.

[0028] In one embodiment, the wheat milling product as characterized above compositionally is processed in or through a device that produces shear forces to produce a sheared pre-product, and the sheared pre-product is ground or milled to form the wheat milling derivative product. In another embodiment, the wheat milling product as characterized above compositionally is processed by grinding, milling, and the like, to produce a reduced particle size product capable of being added directly to slurry compositions used to make paper, paper packaging, or molded products (e.g., food service items, protective packaging, horticultural trays, and the like). For ground or milled wheat milling products, it has been found that such reduced particle size products can be added directly to the slurry compositions, without processing with additional water or shearing forces, when size reduced to within a particular median particle size range.

[0029] A number of devices are known which could be used for producing the sheared preproduct, including for example, single, double and triple continuous screw extruders in any of their conventional configurations, ribbon and paddle blenders and the like, dependent on whether continuous, semi-continuous or batchwise operation is desired. Likewise, a variety of grinding and milling devices and methods are known which could be employed to produce a wheat milling derivative product of the present invention, which we consider should have a median particle size in the range of from 10 microns to 2200 microns in diameter, or from 200 microns to 500 microns in diameter in direct addition applications.

[0030] As used herein, the term “D## particle size” means that ##% of the particles of the mixture have a maximum dimension that is less than or equal to the noted value (e.g., 10 microns), based on a volume basis. For example. D10, D50, and D90 values refer to the particle size in which 10%, 50%, and 90% of the sampled particles are smaller than, respectively. Particle size distribution of the midds and wheat milling derivative w as measured in its dry state using laser diffraction (Malvern Mastersizer 3000, Aero S accessory), and the D50 was reported (medianparticle size). Air pressure was 1 bar, 75% feed, and the obscuration limits were set between 0% to 15%. A refractive index of 1.52. particle density of 1.05 g / cm3, and absorption index of 0.10 were chosen as the material properties. A homogenous sample was loaded into the sample holder and the height and vibration were adjusted until a steady flow of the sample was achieved and fed into the Malvern Mastersizer. The hopper gap was adjusted as necessary betw een 0.50 and 3 mm to achieve the steady flow.

[0031] In another embodiment, the present invention relates to a novel wheat milling derivative product as alternately made by mixing a non-endosperm rich, non-patent flour wheat milling product as characterized above with water to produce a wet wheat milling product mixture; processing the wet milling product mixture through a device that produces shear forces to produce a sheared pre-product; and grinding the sheared pre-product to form a wheat milling derivative product having a median particle size in the range of from 10 microns to 900 microns in diameter.

[0032] In certain embodiments, the wheat milling derivative products made by a mechanical processing of a wheal milling product as previously described are not chemically or enzy matically modified, while in other, preferred embodiments the wheat milling derivative products have been formed by a method including a chemical or enzymatic modification step. Particularly contemplated are treatments, of the wheat milling product by exposure to an acid, alkali, enzyme, oxidizing agent, cationizing agent or any combination thereof prior to or in the course of the mechanical processing involved in producing a wheat milling derivative product from the wheat milling product, for example, prior to or in the course of carrying out the shearing of the wheat milling product to provide the sheared pre-product (that is then ground as needed to provide a wheat milling derivative product of the prescribed median particle size range).

[0033] In a further aspect, the present invention relates to a method of making a paper sheet that comprises (a) providing a non-endosperm rich, non-patent flour wheat milling product comprising from 15 to 40 w eight percent starch, from 25 to 50 weight percent fiber, from 2 to 11 weight percent lignin, from 2 to 10 weight percent fat, and from 10 to 20 weight percent protein; (b) producing a wheat milling derivative product from at least a portion of the wheat milling product according to a process as described above, the wheat milling derivative product having a median particle size in the range of from 10 microns to 900 microns in diameter; and (c) displacing or supplementing at least some and up to 25 weight percent of cellulosic fibers from virgin wood pulp, up to 50 w eight percent of cellulosic fibers from 100% recycled pulp, or from a combination of recycled and virgin pulp with the wheat milling derivative product.In another aspect, the present invention relates to a paper sheet or paper packaging in which a wheat milling derivative product of the present invention has been incorporated, particularly but without limitation in displacement of cellulosic fibers from wood pulping - as the wheat milling derivative products can be used equally to displace less sustainable non-wood alternatives to such cellulosic fibers, for example, from bagasse, hemp and wheat straw, as well as used alongside such other non-wood alternatives, including other wheat milling products and even including wheat milling products such as patent flour or red dog that have substantial food- or feed-related uses (as a paper or paper packaging manufacturer may desire).

[0034] The paper sheet, paper packaging, and molded products made at least in part using the wheat milling derivative products of the present invention may be used for paper towel applications, in carrier board, for tissues, napkins, wall paper, packaging paper, mailing, fluting, liner board, liquid packaging board, folding box board, chipboard, molded products and goods such as food trays and egg cartons.

[0035] These and other aspects, embodiments, and associated advantages will become apparent from the following Description of Embodiments of the Invention.

[0036] DETAILED DESCRIPTION

[0037] Before describing embodiments of the present invention in detail, it is understood that unless explained otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. The materials, methods, and examples are illustrative only and not intended to be limiting.

[0038] As used in this specification, and the appended claims, the singular forms “a,” “an.’' and “the” include the plural references and the term "comprising" means "including" unless the context clearly indicates otherwise. The term "or" refers to a single element of stated alternative elements or a combination of two or more elements unless the context clearly indicates otherwise. In the context of the present invention, the terms "and / or" includes any single element as well as all possible combinations of the elements cited in the respective list. Unless defined otherwise in context, all technical and scientific terms used herein have their usual meaning, conventionally understood by persons skilled in the art to which the present invention pertains.In the present application, unless otherwise indicated either explicitly or necessarily in context, all temperatures given are in degrees Celsius (degrees C), while all percentages are on the basis of weight as compared to the relevant whole (wt %), and is expressed on a dry matter basis. Other abbreviations in this context include “N%” as the amount of nitrogen present in the material (on a dry solid basis), “DS” degree of substitution, “N / A” not analyzed, and “RE” reaction efficiency. The term "grinding" refers to mechanically breaking down the non-patent flour wheat portion of wheat midds or sheared pre-product into smaller components / particles, whether by devices advertised or labeled as “grinders” or by other devices which will mechanically break down the sheared pre-product or the non-patent flour wheat portion of wheat midds into smaller particle sizes. The term “pre-product” used herein refers to a product obtained prior to grinding. In the context of the present invention, "dry" means that less than 12% of free water is present in the composition the invention notwithstanding that a certain amount of water may nevertheless be bound within the particles of the composition. “Wood pulping” refers to pulp made of traditional methods such as acid modified, kraft, and other known methods to the industry. “Cellulosic fibers” shall be understood as comprising recycled pulp, dark kraft, or any combination thereof. Cellulosic fibers may be obtained from virgin or recycled pulp, a papermill, industrial waste, or paper streams rich in mineral fillers and cellulosic materials from a papermill. “Fibers” or “cellulosic fibers”, in the context of the composition of the non-patent flour wheat portion of wheat midds, refers to cellulose, hemicellulose and other carbohydrates that are not starch.

[0039] As previously summarized, the present invention relates in one aspect to the use of certain wheat milling products comprising from 15 to 40 weight percent starch, from 25 to 50 weight percent fiber, from 2 to 11 weight percent lignin, from 2 to 10 weight percent fat, and from 10 to 20 weight percent protein to make novel wheat milling derivative materials which can in turn be used in displacement of cellulosic fibers (both virgin and recycled) in the making of paper and paper packaging comprising such novel wheat milling derivative materials. Fortuitously, a typical wheat midds or wheat middlings fraction or stream will be of the prescribed character and can be mechanically processed to form a novel wheat milling derivative product suited for use in paper or paper packaging in displacement of cellulosic fibers.

[0040] In certain embodiments, the method of forming a wheat milling derivative product suited for displacement or supplementation of cellulosic fibers in paper or paper packaging comprises some or all of the steps of: (a) size reducing a wheat milling product of the prescribed composition and character to a predetermined median particle size, thereby providing a pre-extrusion mixture; (b) mixing the wheat milling product with water, producing a wet wheat milling product mixture; (c) processing the wet wheat milling product mixture through a device that produces shear forces to produce a sheared pre-product; and (d) grinding the sheared preproduct to produce the wheat milling derivative product. Size reducing the wheat milling product prior to the mixing step facilitates improving the processability of the wheat milling product in the processing step by providing a more uniform particle size distribution of the product, thereby enabling a more constant flow of the product to be provided to the mechanical processor, reducing the likelihood of clogging therein, and reducing wear on the mechanical processor. The wheat milling product of the pre-extrusion mixture may be size reduced (e.g., grinded or milled) to a median particle size in the range from 10 microns or more to 2000 microns or less in diameter. In other embodiments, the wheat milling product is provided from a mill as-is to the shearing device to produce the sheared pre-product or to a grinding or milling device.

[0041] It is believed, without being bound by any particular theory, that mechanically processing (i.e., shearing) the wet wheat milling product mixture pre-gelatinizes the starch component of the product, thereby enabling a paper, paper packing, or molded article to be produced therefrom that meets consumer standards of strength and usability, for example.

[0042] A variety of devices will be recognized by those of skill in the art as useful for the shearing of the wheat milling product or of a slurry of the wheat milling product in water, including thermomechanical devices such as an extruder. The extruder may comprise a screw configuration of a single screw, two or more co-rotating or counter-rotating screws, ram, or other similar extrusion methods as is known in the art. Other examples of suitable devices include mixers, such as paddle mixers or screw mixers, as well as blenders, kneaders, pelletizers, and pumps. Other processing methods may also be used including jet milling, milling, or a combination thereof. Processing may also be used with the introduction of air into the processing system including but not limited to cavitation. The elements of such devices, as well as the conditions used in the shearing of the wheat milling product or aqueous wheat milling product slurry (for example, through adding heat during the shearing), can be varied to modify the operating properties of the device and the properties of the products of the invention.

[0043] Subsequently the sheared pre-product can be broken apart by grinding, roll pressing, milling or similar mechanical action (or a combination of such devices) which have the effect of reducing the sheared pre-product to a smaller median particle size material.In certain embodiments, the method of forming a wheat milling derivative product suited for displacement or supplementation of cellulosic fibers in paper or paper packaging comprises some or all of the steps of: (a) obtaining at least one wheat milling product derived from independent milling streams, including bran, shorts, and red dog; and (b) size reducing the at least one wheat milling product of the prescribed composition and character to a predetermined median particle size. The resulting wheat milling derivative product may be added directly to slurry compositions used to make paper, paper packaging, or molded products. That is, it has been found that the wheat milling products may be mechanically processed in the absence of additional water and shearing forces (i.e., extrusion) and yet still be suitable for direct addition to the slurry compositions.

[0044] It is believed, without being bound by any particular theory, that paper, paper packaging, or molded articles made from non-sheared wheat derivative products have improved hydrophobicity and comparable strength to known articles by not disrupting the fiber structure of the various components (starch, fiber, lignin, and / or protein) of the wheat milling product.

[0045] In any of the embodiments described herein, the at least one wheat milling product may be only bran, such as coarse bran (median particle size 100 to 4000 microns). Alternatively, the at least one wheat milling product may be a mixture of bran and shorts (median particle size 50 to 1000 microns), such as in a bran to shorts ratio of 2: 1 to 1:2, 1.5:1 to 1:1.5, or 1: 1. Alternatively, the at least one wheat milling product may be a mixture of bran, shorts, and red dog, such as in a bran to shorts to red dog ratio of 5:5:1 to 5:1:1, 1:5: 1 to 5:5:1, or 2:2:1.

[0046] In some embodiments, the wheat milling product is first subjected to a chemical or enzymatic treatment prior to or in the course of mechanically processing the wheat milling product in neat form or as slurried with water. Particularly contemplated are treatments of the wheat milling product by exposure to an acid, alkali, enzyme, oxidizing agent, cationizing agent or any combination thereof, with exposure to an alkali or to a cationizing agent being particularly preferred. Suitable cationizing agents can be selected from among the group consisting of the amino ion-, imino ion-, sulfonium ion-, phosphonium ion-, ammonium ioncontaining compounds and mixtures of such compounds.

[0047] In any of the embodiments described herein, the wheat milling derivative product may be blended, coated, or co-processed with polymeric materials such as polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyhydroxy esters, polyamides, or polyvinyl amide; starches such as cationic starch and starches co-extruded with polymers such as polyacrylicacid, polyacrylamide, polyhydroxy esters, polyamides, polyvinyl amide, or polyvinyl alcohol; barrier coatings such as waxes, biowaxes, or polymers; cellulose esters; polylactic acid; polyhydroxyalkanoates; or biogenic additives such as proteins, polysaccharides, enzymes, and microbial-derived materials to modify physical, mechanical, or barrier properties. In other embodiments, the product may be formulated with chemical additives such as crosslinking agents, catalysts, mineral fdlers. or nanomaterials to enhance compatibility, strength, or processing characteristics. Thus, the wheat milling derivative product may serve as a functional fiber substitute or supplement, either in its native form or as part of a composite or hybrid formulation incorporating one or more standard or novel chemical, polymeric, or biogenic additives, to achieve desired performance characteristics in paper, packaging, molded, or engineered materials.

[0048] As previously indicated, a paper, paper packaging, or molded product including the wheat milling derivative products of the present invention can be made in the same manner as currently conventionally practiced, with however displacing or supplementing up to 25 percent by weight of the cellulosic fibers from virgin wood pulp and up to 50 percent by weight of the recycled fibers that would otherwise be used in these methods and in these paper, paper packaging, and molded products, as these cellulosic fibers are conventionally used and without any exceptional or extraordinary adjustments being necessary by reason of the substitution - certainly none that would be beyond the exercise of ordinary skill of those knowledgeable in the paper and paper packaging arts or as requiring anything other than routine optimization.

[0049] Consequently, the wheat milling derivative products of the present invention may be blended with those same additives and classes of additives conventionally known to those in the paper and paper packaging arts as useful from time to time in combination with the cellulosic fibers that our materials are displacing, including, for example, additives to enhance the strengthening properties of the paper sheet - including, but not being limited to, cationic starches, oxidized starches, and crosslinked starches from com, rice, potato, pea and combinations of any thereof by way of non-limiting examples of plant sources - fillers, retention aids, sizing agents, wet and dry' strength agents, defoamers, dyes, and pigments.

[0050] Other components may be added for example to achieve certain additional desired functional attributes in sustainable packaging incorporating the wheat milling derivative products of the present invention. Examples include essential oils, such as terpenes, as well as antibiotics, pharmaceuticals, enzymes, and flavors.In any of the embodiments described herein, the method of forming a wheat milling derivative product suited for displacement of cellulosic fibers in paper or paper packaging comprises: (a) dry blending a mixture of a wheat milling product of the prescribed composition and character with cationic starch; (b) mixing the dry blended mixture with water, producing a wet wheat milling product mixture; (c) processing the wet wheat milling product mixture through a device that produces shear forces to produce a sheared pre-product: and (d) grinding the sheared pre-product to produce the wheat milling derivative product. As will be described in more detail below, the pre-shearing dry blended addition of cationic starch may replace the pre-shearing mixing of the wheat milling product and a cationizing agent, such that the wheat milling derivative product does not contain any cationizing agent, and / or may replace the postshearing addition of cationic starch to the wheat milling derivative product described above.

[0051] In any of the embodiments described herein, the method of forming a wheat milling derivative product suited for displacement of cellulosic fibers in paper or paper packaging comprises: (a) obtaining at least one wheat milling product derived from independent milling streams, including bran, shorts, and red dog; (b) dry blending a mixture of the at least one wheat milling product of the prescribed composition and character with cationic starch; and (c) size reducing the at least one wheat milling product of the prescribed composition and character to a predetermined median particle size. The resulting wheat milling derivative product may be added directly to slurry compositions used to make paper, paper packaging, or molded products. That is. it has been found that the wheat milling products may be mechanically processed in the absence of additional water and shearing forces (i.e., extrusion) and yet still be suitable for direct addition to the slurry compositions.

[0052] Dry blending the cationic starch with the wheat milling products mentioned above provides several advantages relative to pre-sheared mixing of the wheat milling product and a cationizing agent and / or to post-shearing addition of cationic starch to the wheat milling derivative product. For example, the pre-shearing mixing with a cationizing agent produces a cationized, sheared wheat milling derivative product. However, it is generally difficult and expensive to add cationizing agents to the wheat milling product. Specifically, the high temperatures used in step (c) above create processing and air handling difficulties, and the cationizing agent itself is more costly than the use of cationic starch in the paper and / or packaging-making applications described herein. In addition, pre-shearing cationizing agent addition may trigger the need for the resulting product to obtain certain approvals fromgovernmental agencies (e.g., the Food and Drug Administration and / or Environmental Protection Agency) before being sold.

[0053] The post-shearing addition of cationic starch is typically performed by the papermill operator after receiving the wood fiber and / or pulp feedstock from a supplier. However, the cationic starch must be heated and / or activated to gelatinize the starch and impart the desired cationic properties, which can be an energy-intensive and laborious process.

[0054] Dry blending the cationic starch with the wheat milling product facilitates producing a pre-cationized wheat milling derivative product that is ready to use by a papermill operator without the need to acquire their own cationic starch and / or the need for further processing on site at the papermill, such as pre-processing (i.e., gelatinizing) cationic starch prior to mixing with the wheat milling derivative product. Thus, use of the wheat milling derivative product facilitates reducing the processing burden on the papermill operator and energy usage at the papermill. In addition, the pre-shearing addition of cationic starch may exempt this wheat milling derivative product from the same governmental regulations as the products formed by pre-shearing addition of a cationizing agent, further improving the readiness and usability of the wheat milling derivative products described herein.

[0055] Similar to the products described above, aspects of the present disclosure relate to the use of certain wheat milling products comprising from 15 to 40 weight percent starch, or from 20 to 40 weight percent starch, from 25 to 50 weight percent fiber, from 2 to 11 weight percent lignin, from 2 to 10 weight percent fat, and from 10 to 20 weight percent protein to make novel wheat milling derivative materials which can in turn be used in displacement of cellulosic fibers (both virgin and recycled) in the making of paper and paper packaging comprising such novel wheat milling derivative materials. In any of the embodiments described herein, dry blending a mixture of a wheat milling product of the prescribed composition and character with cationic starch modifies the composition of the resulting product. The cationic starch may be blended in amounts that increase the starch content of the pre-shearing feedstock by from 0 to 15 weight percent. Thus, the wheat milling derivative product produced from the blended mixture of wheat milling products and cationic starch may have from 15 to 40 weight percent starch, or from 20 to 40 weight percent starch, from 25 to 50 weight percent fiber, and from 10 to 20 weight percent protein.

[0056] Cationic starch can have varying degrees of substitution (DS), such as from 0.02-0.10. It would be reasonable that cationic starch with a higher DS could be used at a potentially lowerdosing level relative to the milled wheat midds. Conversely, a cationic starch at the lower end range of DS could be used at a higher dosing level relative to the milled wheat midds.

[0057] The cationic starch may be derived from any botanical source including, but not limited to including, com, potato, tapioca, wheat, rice, sorghum, and barley.

[0058] EXAMPLES

[0059] The following examples are provided to further describe the embodiments presented herein but are offered as exemplary only and are not to be considered as limiting of the scope of what we have invented and contributed to the art, as more particularly defined by the claims which follow hereafter.

[0060] The wheat milling products used in the below Examples (all of the composition described herein for the wheat milling product starting materials) were obtained from Archer Daniels Midland Company processing facilities at Quincy. Illinois or Beech Grove, Indiana. The cationic reagent 3-chloro-2 -hydroxypropyltrimethyl ammonium chloride (Quat 188, 60% solution) was obtained from Sigma Aldrich in St. Louis, MO. Terpene, d-limonene was obtained from Archer Daniels Midland Company in Winter Haven, Florida. Cationic com starch was obtained from Archer Daniels Midland Company.

[0061] Example 1

[0062] In this example, a twin screw extruder was used to generate a chemically modified wheat milling derivative product. Specifically, the processor had twin screws (each having a length of 17 inches and a diameter of 2 inches) in a high shear configuration including conveying and mixing elements. First. 0.39 mols of sodium hydroxide as a 19% w / w solution in water was sprayed onto 0.5 kg of wheat milling product which had a moisture content of 7%. After mixing for 10 minutes, 0.15 mols of 3-chloro-2-hydroxypropyltrimethyl ammonium chloride was sprayed onto the mixture as a 60% w / w solution in water (Sigma Aldrich). The mixture was continuously fed into the entrance of the twin screw extruder at a rate of 40 grams per minute with additional water, via peristaltic pump, to bring the moisture content of the mixture to 40% w / w. The mixture was processed with the steam jacket at 19 psi and a screw speed of 40 RPM. Material exited the extruder through its 43 mm diameter exit at 66 degrees C, and was collected and dried at 40 degrees C overnight. A 20% dry solids solution of this material in water was then prepared and neutralized with 10% HC1 (v / v) to pH 6.5. This neutralized mixture was then blended on high (in an Oster home blender) with 600 mL of 200proof ethanol for 5 minutes and vacuum filtered with Whatman filter paper (#54). The filter cakes were air dried and evaluated for N%, while the corresponding DS was calculated to be 0.05.

[0063] Example 2

[0064] The material prepared in Example 1 was milled through a 0.5 mm sieve at 12000 RPM. For the control paper, 88 grams of virgin paper was cut into 5 x 5 cm squares and these were added to the pulper. For the experimental papers incorporating a wheat milling derivative product according to the present invention, a portion of the virgin paper was replaced by the sieved material. Tap water (2 L) at 40°C was added to the pulper in each iteration (resulting in a 4% pulp, labeled thickstock). The pulper was run for 5 minutes at 1400 rpm. The thickstock was transferred to an equalizer and further diluted with tap water to a total of 8 kg (resulting in a 1% pulp, labeled thinstock). The thinstock was homogenized for 5 min and then split into two equal portions (4 kg). Each portion was placed in an equalizer. One portion was used as is to produce hand sheets, while cooked cationic starch was added to the other portion at a final concentration of 1%. This process was repeated for papers wherein in excess of 10% by weight of the virgin paper had been replaced with the sieved material (8.8 grams sieved material with 79.2 grams virgin paper). Wet and dry end performance was evaluated and reported in Figure 1, where the reported values were determined by means of the following instruments and methods:

[0065] Wet End Tests:

[0066] • Zeta Potential - The thinstock (1% consistency) was placed into the measurement cup (500 mL) of a SZP-10 Zeta Potential system (BTG Mutek). The suction tube is lowered, and the streaming potential of the pulp was measured with alternating vacuum pressure. The zeta potential is read from the device after the end point is reached.

[0067] • Drainage - Drainage was measured using a DFR-05 (BTG Mutek) with a sample size of 1000 mL thinstock.

[0068] • Turbidity - Forturbidity measurements, 15 mL of filtered ( 100pm pore size) thinstock is measured using a Hach - 2100Q at 860 nm.

[0069] • PCD - For particle charge demand measurements, 10 mL of filtered (100pm pore size) thinstock is measured using a BTG Mutek PCD-04. The solution is titrated with either a negative or positive titrant, specifically 0.001 N PES-Na or 0.001 N Poly-Dadmac. The titration endpoint is reported as the charge demand.

[0070] Dry End Tests:

[0071] • Grammage - The weight of handsheets are measured on an analytical scale, while the thickness of each sheet was measured on 4 points over the surface of the sheet (Wolf - DM2000P). Grammage was calculated as a basis of grams per sq. meter, reported as an average of 4 replicates.

[0072] • Burst strength - One sheet per series is selected and tested on Burst strength.

[0073] To determine the burst strength, a handsheet is placed on the Burst measuring meter (L&W Bursting Strength Tester SEI 80) and the measurement is started. The process is repeated for six replicates and averaged.

[0074] • Ash retention test - The ash retention test is performed by placing a sample of the handsheet into a ceramic cup. The cup is ashed for 2 hours at 525C (Nabertherm - P330), removed from oven, and placed into a desiccator until cooled. Ash is calculated as a percent of the ashed handsheet weight compared to the initial weight of the handsheet.

[0075] • SCT - short span compression test - also known as STFI. The short span compression test was done on 16 mm wide strips using a L&W Compressive Strength Tester, modified from TAPPI T826. Three measurements were made per strip and values are reported as an average of six measurements.

[0076] • Tensile Strength - Tensile strength was measured using L&W - Tensile Tester SE062, following ISO 1924-3 where the width between the clamps were modified to 10 cm. A 16 mm wide strip is placed in the measurement device and aligned in the sample clamps, and the test is run. Results are reported as an average of 5 measurements.

[0077] • Internal Bond - TAPPI T569 method was used to evaluate the internal bond of the samples (Emco Internal Bond Tester), with strips sized at 2.54 cm wide. Values are reported as an average of 5 measurements.

[0078] Examples 3 and 4:

[0079] A wheat milling product (510 grams. 8% moisture) was sprayed first with 0.41 mols of sodium hydroxide (18.6% w / w solution) and then with 0.15 mols of 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (60% w / w solution). The mixture was homogenously mixed (20% moisture), placed in a sealed container, and placed in a laboratoryoven at 85 degrees C for 24 hours. Half of the mixture was removed from the container after 6 hours of heating, and the second half was removed at 24 hours. DS was measured as described in Example 1, with 6 hours resulting in a DS of 0.027 and 24 hrs resulting in 0.029. Stock solutions and papers were thereafter prepared and evaluated as in Example 2, using the same instruments and methods, to evaluate the util ity of the chemically modified wheat milling derivative product made in this example for displacing virgin cellulosic fiber in a paper sheet product and then for displacing recycled fiber in a recycled paper fiber, paper sheet product. Results from that evaluation are shown in Figures 2 and 3, respectively, for the paper sheets made using virgin fiber and recycled fiber.

[0080] Examples 5 and 6

[0081] Paper sheet products compromised of recycled and virgin cellulosic fibers were prepared with portions of a wheat milling derivative product prepared as in Example 1. except that the wheat milling derivative product was however not chemically modified with the 3-chloro-2-hydroxypropyltrimethyl ammonium chloride in the manner of Example 1. The papers were made and evaluated as in Examples 2, 3 and 4 and using the methods and equipment described therein. The results of the evaluations are found in Figures 4 and 5. respectively, for the recycled and virgin fiber-based paper sheet products including the wheat milling derivative product.

[0082] Examples 7 and 8

[0083] A twin screw extruder was used to modify and for the continuous production of two cationic (chemically modified) wheat milling derivative product samples under two different barrel moisture conditions. Wheat milling product was fed into a top loading hopper of a Wenger X52 Extruder System. The wheat milling product was fed into a preconditioner at a rate of 52.1 kg / hr, with 50% w / w sodium hydroxide at a rate of 3.2 kg / hr. As the combined mixture was fed into the extruder, the cationic reagent (1-Propanaminium, 3-chloro-2-hydroxy-N,N,Ntrimethyl-, chloride, 65% w / w) was injected at a rate of 4.37 Kg / hr. Moisture content of the barrel was 30% in one instance, 40% moisture in the other with additional water injected. Temperature of the barrel reached up to 220 degrees F based on mechanical energy', screw configuration, and circulating jacket temperatures of the extruder. The extruded product was then dried to a moisture content less than 15%by weight and milled to a median particle size less than 800 microns. Degree of substitution was determined by N% incorporation, with the starting material's N% serving as N% initial. The degree of gelatinization was evaluated via polarized light microscopy for the presence of maltese crosses, indicative of uncookedcrystalline starch structures. More specifically in relation to this microscopic evaluation, 1 gram of a sample was diluted with 40 mL of deionized water and mixed with the water using a benchtop vortex mixer. The samples were then stained using 1000 uL of N / 50 iodine solution. Approximately two drops of the mixed, cationic wheat milling derivative product solution were added to a microscope slide via transfer pipette, including as many visible particulates as possible. Images were then taken with polarized light, using an optical microscope (Leica DM2700M) in 20x / 0.40 objective.

[0084] The results of the analysis are reported below in Table 1.

[0085] Table 1

[0086] Gelatinization

[0087] Sample Barrel Moisture (%) DS (microscopy)

[0088] Cationic Wheat Milling

[0089] Derivative #1 30% 0.037 low

[0090] Cationic Wheat Milling

[0091] Derivative #2 40% 0.039 high

[0092]

[0093] Examples 9 and 10

[0094] Using each of the cationic wheat milling derivative products produced and characterized as described above in Examples 7 and 8, 100 gsm recycled cellulosic fiber papers were produced and evaluated as in previous examples, displacing 10 percent by weight of the recycled cellulosic fibers with each of the cationic wheat milling derivative products. The effect of the wheat milling derivative fibers on the wet and dry properties of the papers were evaluated and the measured values are reported below in Table 2 as a percent change from the 100% recycled fiber control paper.

[0095] Table 2

[0096] Zeta Burst

[0097] Potentia Basic (Normalize Scott Short Span Tensile 1 Weight d) Bond Compression Strength Sample

[0098] Cationic Wheat

[0099]

[0100] product #! 54%

[0101]

[0102] -2% % -4% 2%Cationic Wheat 15

[0103] product # 65% -3% 19% % 4% 4%

[0104] Examples 11 and 12

[0105] In these examples, paper products were prepared having a final paper composition in one instance of 60% kraft wood pulp, 30% OCC wood pulp, and 10% cationic wheat milling derivative fiber product and in a second instance 70% kraft wood pulp, 20% OCC wood pulp and 10% cationic wheat milling derivative fiber product. After producing the cationic wheat milling derivative fiber product according to the same process and using the same equipment as used in Example 8 (i.e., at the 40% barrel moisture figure), the resultant wheat milling derivative fiber product was dry blended with powdered citric acid to a neutral pH. 4% consistency stock solutions were then prepared from the various pulp sources in the proportions described, hydropulped at 40 degrees Celsius for 5 minutes, and subsequently mixed and diluted to a final 0.3% consistency. 120 gsm handsheets were then prepared following TAPPI Standard Method T205 and compared to controls omitting the cationic wheat milling derivative product following the same handsheet process. Wet and dry end properties were evaluated for all handsheets following TAPPI Standards (T-227 for drainage, T 807 for burst, T-826 for STFI edgewise compressive strength, T 569 for Scott bond, T 211 for ash). Cationic charge determinations were performed on a Mutek PCD-05. For the charge determinations, the cationic polyelectrolyte used was poly dimethyl diallyl ammonium chloride (poly-DADMAC), 0.01 N and the anionic polyelectrolyte was sodium polyethylene sulphonate (PES-Na), 0.01 N from BTG. Pipette or w eigh 10 g of the sample into the sample cell. Insert the sample cell in the instrument. Place the burette tip above the test portion surface, wait for about 1 min, and start the titration. The time between the titrant additions should be at least 30 s. At the neutral point when mV =0, record the amount of titrant used in meq / 1. Percent changes as reported in Figure 6 are calculated based from the 100% Kraft control.

[0106] Example 13

[0107] Cationic wheat milling derivative fiber product was produced using a B&P Littleford batch, bench scale mixer with steam jacket. Wheat milling product was first milled to a particle size less than 500 microns (63% w / w, 13% moisture) and then dry blended with sodium hydroxide (2% w / w). After the material w as mixed for at least 10 minutes, 1-Propanaminium, 3-chloro-2-hydroxy-N,N,Ntrimethyl-, chloride was added via spraying afine mist at 5% w / w (65% aqueous solution). Additional moisture was added to bring the final moisture content to 40% w / w, and the mixture was mixed and brought to an internal temperature of 150 degrees Fahrenheit. The reaction was held at this condition for 5 hours with constant mixing (at 45 hz). The material was thereafter collected, cooled, washed and characterized for degree of substitution by monitoring N% incorporated. Considering the N% of unwashed raw wheat fiber milling product prior to the reaction, 0.35% N was incorporated after a reaction time of 5 hours, which corresponds to a DS of 0.042.

[0108] Example 14

[0109] A wheat milling product (i.e., wheat midds) was milled to a median particle size of 170 microns and having 8.20% moisture. The milled wheat midds were mixed with cationic com starch having 10.20% moisture and a nitrogen DS of about 0.04. The cationic com starch used here was present in the mixture at 10% by weight. The mixture was fed into a preconditioner at a rate ofl50 Ib / hr and water was added at a rate of 150 mL / min. The hydrated mixture then fed into the twin extruder (Wenger, 52 mm, screw speed of 200 RPM) and additional water was injected at a rate of 85 mL / min. The mixture was extruded after reaching a minimum internal temperature of 95°C. The extrudate was collected, dried, and milled to a median particle size of 200 microns.

[0110] This wheat milling derivative product was then used to produce paper samples. For paper production, the wheat milling derivative product was hydrapulped with OCC pulp, and then mixed with hydrapulped and refined kraft in the blend chest. The combined pulp mixture was approximately 10% wheat milling derivative product, 30% OCC, and 60% kraft, all by weight. The combined pulp mixture was soaked together for at least 4 hours in the machine chest. Separately, a stock of 30% OCC and 70% kraft by weight, was prepared, under the same conditions as the pulp mixture containing cationic com starch, to be used as a control. The respective stocks were then diluted to a consistency of 0.50% dry fiber in water at the headbox. Immediately before running on the paper machine, the machine chest was adjusted to a pH 6.35-6.45 with 50% aluminum sulfate. The stock was fed to the paper machine via the headbox, and paper was produced at a rate of 40 ft / min. Setting parameters of the paper machine were adjusted to produce paper with a basis weight of 110 - 130 g / m2Sections of the paper reels were randomly sampled and evaluated for strength. Specifically, the samples were evaluated for basis weight (Tappi T 410), Scott Bond (Tappi T 569), Mullen Burst (Tappi T 403), STFI (Tappi T 826), and Tensile (Tappi T 494), in both the machine direction (MD) and cross direction (CD). Sample basis weights were used to normalize values.CP.0211A.W001

[0111] Table 3

[0112] 70% Kraft : 30% OCC 6Q% Kraft: 30% OCC: 10% Wheat Milling Derivative Blend Orientation Units Average St. Deviation Average St. Deviation Burst index machine 'KF‘3*tnz / g 2.3.3 0.24 2.99 0.23 cross kPa-W / g 2.57 0.2.4 3.02 0.32 STFI machine N*m / g 24.33 3.05 24.55 2.94 cross 15.32 1.S3 16.08 3.37 Scott Bond machine 2.11 0.09 2.8.3 0.26 cross !Q’,g / m3 2.19 0.14 2.85 0.23 Tensile index machine N*»rt / g 45.41 4.24 47.25 9.48

[0113]

[0114] cross 23.33 0.85 29.64 1.55 Notably, it was found that the paper produced from the wheat milling derivative blend had comparable and / or improved characteristics in all four metrics evaluated, in both the MD and CD.

[0115] Examples 15 and 16

[0116] A direct size reduction by milling of three non-patent wheat flour milling by-product compositions produced three wheat milling derivative product prototypes, Prototype-1, Prototype-2, Prototype-3, each with a median particle size (D50) of approximately 250 pm. The compositions of Prototypes 1-3 are summarized in Table 4. Each wheat milling derivative product was utilized in the production of corrugated paper samples. For paper formation, the wheat milling derivative product and kraft pulp were combined at a weight ratio of 10:90 and subjected to hydropulping using a hydrapulper. The aqueous fiber mixture was refined for 5,250 revolutions to achieve a target Canadian Standard Freeness (CSF) value of approximately 500 mL. On a dry weight basis, the pulp mixture consisted of approximately 10% wheat milling derivative product and 90% kraft fibers. The combined pulp was soaked for a minimum of four hours prior to sheet formation. Paper sheets were prepared following the TAPPI T 205 handsheet preparation method, with the paper machine parameters adjusted to obtain a basis weight of approximately 120 g / m2Sections of the resulting paper reels were randomly sampled and evaluated for mechanical and physical properties. The tests performed included Air Permeability (ASTM D737), Burst Strength (TAPPI / ANSI T 220), Short Span Compression Test (STFI, TAPPI T 826), Tear Resistance (TAPPI / ANSI T 220), Water Drop Absorption Time (TAPPI T 432), and Tensile Strength (TAPPI / ANSI T 220). The resulting papers were compared with a reference paper made entirely from 100% virgin pulp. Table 5 presents a comparison of the dry paper performancebetween the 100% virgin pulp formulation and the formulations in which 10% of the virgin

[0117] fiber was replaced with the mechanically modified wheat milling derivative product

[0118] prototypes. Since the testing was done by producing paper at "hand sheets” scale, there is no directionality (MD or CD) for the data presented below.

[0119] Table 4

[0120] Prototype-1 Prototype-2 Prototype-3

[0121] Constituent Name % Dry Basis % Dry Basis % Dry Basis

[0122] Ash 5.81 5.31 4.92

[0123] Protein 18.59 18.95 18.85

[0124] Fat 5.52 5.54 5.31

[0125] Starch 19.22 21.34 24.60

[0126] Total Lignin 7.23 6.81 6.21

[0127] Hemi-Cellulose 39.07 38.09 35.96

[0128]

[0129] Cellulose 4.16 3.93 4.34

[0130] Table 5

[0131] 100% Fiber 90% Fiber + 10% Prototype Virgin Kraft Prototype-1 Prototype-2 Prototype-3 Test Name Units Mean Stdev Mean Stdev Mean Stdev Mean Stdev Air Permeability Test rnm / s 0.028 0.011 0.034 0.014 0.032 0.014 0.03 0.015 Burst Index kPa*m2 / g 6.94 0.64 6.09 0.48 6.29 0.56 6.02 0.79 Strain at Rupture % 3.96 0.13 3.96 0.13 3.78 0.5 3.94 0.26 Tear Index mN*m2 / g 12.71 0.55 13.65 0.67 12.97 0.74 12.44 0.39 Tensile Index N*m / g 95.68 7.22 88.98 2.39 86.44 6.59 84.16 5.57 Water Drop Absorption

[0132] s 121.5 17.31 304.9 28.98 322.84 24.84 373.3 40.28

[0133]

[0134] time

[0135] Prototypes 1-3, which had minor variations in composition, exhibited correspondingly

[0136] minor differences in the mechanical properties of the resulting dry paper. These results indicate

[0137] that wheat milling derivative products provide robust and consistent performance as fiber

[0138] additives. The dry paper produced by substituting 10 weight percent of kraft fibers with wheat

[0139] milling derivative products demonstrated mechanical properties comparable to paper composed

[0140] entirely of kraft fibers, confirming the suitability of the wheat milling derivatives as partial fiber replacements. Furthermore, incorporation of these derivatives introduced additional fat, lignin,

[0141] and protein components into the fiber matrix, resulting in a significant improvement in the hydrophobicity of the dry paper.Under processing conditions similar to those described in Examples 7 and 8, a wheat milling derivative product. Prototype-3, was produced with a median particle size (D50) of approximately 200 pm. In addition, using comparable twin-screw extrusion parameters, a pregelatinized batch (“Pregel”) of wheat milling derivative extrudates was prepared by omitting the chemical additive step. These pregelatinized extrudates (prototype “Pregel”) were subsequently milled to achieve a median particle size (D50) of approximately 200 pm. Each wheat milling derivative product was utilized in the production of corrugated paper samples. For paper formation, the wheat milling derivative product and kraft pulp were combined at a weight ratio of 10:90 and subjected to hydropulping using a hydrapulper. The aqueous fiber mixture was refined for 5,250 revolutions to achieve a target Canadian Standard Freeness (CSF) value of approximately 500 mL. On a dry weight basis, the pulp mixture consisted of approximately 10% wheat milling derivative product and 90% kraft fibers. The combined pulp was soaked for a minimum of four hours prior to sheet formation. Paper sheets were prepared following the TAPPI T 205 handsheet preparation method, with the paper machine parameters adjusted to obtain a basis weight of approximately 120 g / m2. Sections of the resulting paper reels were randomly sampled and evaluated for mechanical and physical properties. The tests performed included Air Permeability (ASTM D737), Burst Strength (TAPPI / ANSI T 220), Short Span Compression Test (STFI, TAPPI T 826), Tear Resistance (TAPPI / ANSI T 220), Water Drop Absorption Time (TAPPI T 432), and Tensile Strength (TAPPI / ANSI T 220). Table 6 presents a comparison of the dry paper performance between the 100% virgin pulp formulation and the formulations in which 10% of the virgin fiber was replaced with the wheat milling derivative product prototypes. Since the testing was done by producing paper at “hand sheets” scale, there is no directionality (MD or CD) for the data presented below.

[0142] Table 6

[0143] 100% Fiber 90% Fiber + 10% Prototype Virgin Kraft Prototype-3 Pregel Test Name Units Mean Stdev Mean Stdev Mean Stdev Air Permeability Test mm / s 0.028 0.011 0.03 0.015 0.036 0.015 Burst Index kPa*m2 / g 6.94 0.64 6.02 0.79 5.93 0.55 Strain at Rupture % 3.96 0.13 3.94 0.26 3.76 0.4 Tear Index mN*m2 / g 12.71 0.55 12.44 0.39 12.65 0.57 Tensile Index N*m / g 95.68 7.22 84.16 5.57 86.74 6.34 Water Drop Absorption

[0144] s 121.5 17.31 373.3 40.28 312.83 50.48

[0145]

[0146] timeThe pregelatinized (“Pregel”) and non-pregelized (“Prototype-3”) wheat milling derivative products, each having a median particle size (D50) of approximately 200 micrometers, exhi bited comparable mechanical performance in the resulting dry paper when 10 weight percent of kraft fibers was replaced with each respective prototype. These findings indicate that both composition and particle size are primary factors influencing the mechanical properties of paper incorporating wheat milling derivatives. Despite the similarity in strength and stiffness properties, the dry paper produced with the pregelatinized prototype demonstrated a measurable decrease in water resistance relative to the paper prepared w ith the non-pregelized prototype. This observation suggests that the thermal and moisture processing steps associated with pregelatinization alter the surface chemistry and internal structure of the wheat milling derivatives — specifically, by increasing the availability of hydrophilic hydroxyl groups and modifying the starch-protein-fiber interactions. Consequently, the processing conditions used in the preparation of wheat middlings play a role in determining the hydrophobicity and overall moisture barrier performance of paper products incorporating such derivatives.

[0147] The pregelatinized wheat milling derivative product (“Pregel”) and the mechanically modified prototype (“Prototype-3”), each produced as described above, were used to replace 10 to 20 weight percent of the virgin kraft fibers in the production of molded fiber trays. The molded fiber tray had finished overall dimensions of 217 mm in length, 134 mm in width, with a depth of 13.5 mm. The comer radius in the finished state is R20, giving the tray its final rounded edge profile. A 70 / 30 mixture of Sylvamo hardwood and Resolute softwood w as used as the base fiber for the trial. At the end of the trial, unrefined bagasse was run as the base fiber to determine if there was an improvement in final article quality and runability on the KFT Lab machine. The batches w ith the additive fibers w ere soaked for at least 4 hours before refining. All batches were refined at 4% consistency to a target freeness range of 350-400 mL and were run in the KFT Lab machine at 0.5%. Dry molded trays were tested for water resistance (Cobb Test; TAPPI / ANSI T 441), Mullen Burst (TAPPI T 807) and Taber Stiffness (TAPPI / ANSI T 489). Tables 7-9 below summarized the dosing, observations and measured dry mechanical properties of the molded fiber products produced.Table 7: Control

[0148] 100% Kraft Pulp

[0149] MD CD

[0150] Test Name Units Mean Stdev Mean Stdev Taber Stiffness (Bending

[0151] mN*m 53.4 2.98 46 2.19 Moment)

[0152] Taber Stiffness (Resistance to

[0153] mN 60 919 43.8 Bending) 1070

[0154] Mullen Burst psi 195 16 NA NA Burst Index kPa*m2 / g 2.06 0.17 NA NA

[0155]

[0156] Cobb Test g / m2 844 77.6 NA NA

[0157] Table 8: 10% Replacement of Fibers with ‘‘Prototype-3”

[0158] 90% Kraft Pulp and 10% 80% Kraft Pulp and Prototype-3 20%Prototype-3 MD CD MD CD

[0159] Test Name Units Mean Stdev Mean Stdev Mean Stdev Mean Stdev Taber Stiffness

[0160] mN*m 54.4 3.81 41.3 4.45 47.8 1.27 47.7 2.74 (Bending Moment)

[0161] Taber Stiffness

[0162] (Resistance to mN 1090 76 827 88.9 956 25.4 955 54.9 Bending)

[0163] Mullen Burst psi 224 25 NA NA 206 10.1 NA NA Burst Index kPa*m2 / g 3.22 0.359 NA NA 2.95 0.14 NA NA

[0164]

[0165] Cobb Test g / m2 790 78.7 NA NA 830 100.3 NA NA

[0166] Table 9: 10% Replacement of Fibers with “Pregel”

[0167] 90% Kraft Pulp and 10% 80% Kraft Pulp and 20%

[0168] Pregel Pregel

[0169] MD CD MD CD

[0170] Test Name Units Mean Stdev Mean Stdev Mean Stdev Mean Stdev Taber Stiffness

[0171] mN*m 58.3 6.36 45 2.46 44.8 0.95 42.1 2.01 (Bending Moment)

[0172] Taber Stiffness

[0173] (Resistance to mN 1170 127 900 49.2 896 18.9 842 40.3 Bending)

[0174] Mullen Burst psi 198 15.9 NA NA 179 11.6 NA NA Burst Index kPa*m2 / g 2.83 0.23 NA NA 2.53 0.16 NA NA

[0175]

[0176] Cobb Test g / m2 1030 60 NA NA 988 125.7 NA NA

[0177] Molded trays prepared with 10 wt.% of Prototype-3 and wood fibers exhibited superior mechanical properties compared to trays composed solely of wood fibers. Thisimprovement demonstrates that the composition of Prototype-3, as well as its interaction with wood fibers during molding, enhances tray stiffness, resistance to bending, and burst strength. These findings confirm the applicability of wheat milling derivatives in broad fiber replacement processes within paper and packaging materials. Furthermore, trays incorporating Prototype-3 showed reduced water absorption relative to trays made exclusively from wood fibers, indicating that both the composition and mold structure influenced by wheat milling derivatives contribute to improved moisture resistance in paper and packaging applications. In contrast, trays produced using the Pregel form of Prototype-3 displayed enhanced mechanical performance compared to 100% wood fiber trays, but exhibited higher water absorption. This observation highlights the significance of processing conditions and formulation optimization when employing wheat milling derivatives in fiberbased composite materials.

Claims

WHAT IS CLAIMED IS:

1. A wheat milling derivative product useful for displacing or supplementing cellulosic fibers in paper or paper packaging or molded products, comprising from 15 or more to 40 or less weight percent starch, from 25 or more to 50 or less weight percent fiber, from 2 or more to 11 or less weight percent lignin, from 2 or more to 10 or less weight percent fat, and from 10 or more to 20 or less weight percent protein from wheat and characterized by a median particle size in the range of from 10 microns or more to 2200 microns or less in diameter.

2. The wheat milling derivative product of Claim 1. w herein at least a portion of the starch is cationic starch.

3. The wheat milling derivative product of any of Claims 1 or 2, wherein the cationic starch is present in the wheat milling derivative product at from 0 or more to 15 or less w eight percent.

4. The wheat milling derivative product of any of Claims 1-3, wherein the wheat milling derivative product does not contain any cationizing agent.

5. A chemically or enzy matically modified wheat milling derivative product as produced by exposure of the wheat milling derivative product of any of Claims 1-4 to an acid, alkali, enzyme, oxidizing agent, or any combination thereof.

6. A chemically or enzymatically modified wheat milling derivative product according to Claim 5, wherein the exposure to an acid, alkali, enzyme, oxidizing agent, or any combination thereof takes place in a process of forming the wheat milling derivative product from a product having the recited composition.

7. A modified wheat milling derivative product according to Claim 6, wherein the exposure is to an alkali.

8. A paper sheet or paper packaging product or molded product comprised of cellulosic fibers and from 0 or more to 50 or less percent by weight of the wheat milling derivative product of any of Claims 1-4 or of the chemically or enzymatically modified wheat milling derivative product of any of Claims 5-7.

9. The paper sheet or paper packaging product or molded product of Claim 8 further comprising:polymeric materials comprising polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyhydroxy esters, polyamides, or polyvinyl amide, orstarches comprising cationic starch and starches co-extruded with polymers comprising polyacrylic acid, polyacrylamide, polyhydroxy esters, polyamides, polyvinyl amide, or polyvinyl alcohol, orbarrier coatings comprising waxes, biowaxes, or polymers, orcellulose esters, orpolylactic acid, orpolyhydroxyalkanoates, orbiogenic additives comprising proteins, polysaccharides, enzymes, and microbial-derived materials.

10. The paper sheet or paper packaging product or molded product of any of Claims 8-9, at least one other non- wood material in the form of bagasse, wheat straw, hemp, or another wheat milling product.

11. The paper sheet or paper packaging product or molded product of any of Claims 8-10, wherein the another wheat milling product comprises bran, shorts, clear flour, fine bran, coarse weatings, fine weatings, patent flour, red dog, or is a combination of these.

12. A process of making a wheat milling derivative product useful for displacing cellulosic fibers, comprising:subjecting at least one wheat milling product to mechanical processing to provide a wheat milling derivative product comprising from 15 or more to 40 or less weight percent starch, from 25 or more to 50 or less weight percent fiber, from 2 or more to 11 or less weight percent lignin, from 2 or more to 10 or less weight percent fat, and from 10 or more to 20 or less weight percent protein, wherein the wheat milling derivative product is characterized by a median particle size in the range of from 10 microns or more to 2200 microns or less in diameter.

13. The process of Claim 12, wherein prior to subjecting the at least one wheat milling product to mechanical processing, the process further comprises blending the at least one wheat milling product with cationic starch.

14. The process of any of Claims 12-13, wherein the cationic starch is present in the wheat milling derivative product at from 0 or more to 15 or less weight percent.

15. The process of any of Claims 12-14, further comprising mixing the at least one wheat milling product with water to produce a wet wheat milling product mixture, and wherein themechanical processing comprises subjecting the at least one wheat milling product in the form of the wet wheat milling product mixture to shearing forces to provide a sheared pre-product in the presence of water, and grinding or milling the sheared pre-product to 10 microns or more to 900 microns or less to provide the wheat milling derivative product.

16. The process of any of Claims 12-15, wherein prior to subjecting the at least one wheat milling product to mechanical processing, the process further comprises grinding or milling the wheat milling product to provide a pre-extrusion mixture characterized by a median particle size in the range of from 10 microns or more to 2000 microns or less in diameter.

17. The process of any of Claims 12-16, further comprising adding an acid, alkali, enzyme, oxidizing agent, or any combination thereof to a) the wheat milling product of either of Claims 10 or 11 prior to its mixing with water or b) in respect of Claim 11 to the wet wheat milling product mixture, and in either of a) or b) as the case may be, either prior to subjecting the same to the mechanical processing.

18. The process of any of Claims 12-17, wherein the wheat milling derivative product does not contain any cationizing agent.

19. The process of any of Claims 12-14, wherein the mechanical processing comprises grinding or milling the at least one wheat milling product to a median particle size in the range of from 200 microns or more to 500 microns or less in diameter to provide the wheat milling derivative product.

20. The process of Claim 19, wherein the mechanical processing is performed in the absence of additional water and shearing forces.

21. The process of any of Claims 19-20, wherein the at least one wheat milling product is only bran.

22. The process of any of Claims 19-20, wherein the at least one wheat milling product is a mixture of bran and shorts.

23. The process of Claim 22, wherein the mixture of bran and shorts is defined by a bran to shorts ratio of 2: 1 to 1 :2.

24. The process of any of Claims 19-20, wherein the at least one wheat milling product is a mixture of bran, shorts, and red dog.

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