BRPI0615260B1 - METHOD FOR PROCESSING COMPOSITE BIOMATERIALS - Google Patents

Description

(54) Title: METHOD FOR PROCESSING COMPOSITE BIOMATERIALS (73) Holder: GALA INDUSTRIES, INC .. Address: 181 PAULEY STREET, EAGLE ROCK VA 24085, UNITED STATES OF AMERICA (US) (72) Inventor: J. WAYNE MARTIN; ROBERT G. MANN; ROGER B. WRIGHT

Validity Term: 10 (ten) years from 10/02/2018, subject to legal conditions

Issued on: 10/02/2018

Digitally signed by:

Liane Elizabeth Caldeira Lage

Director of Patents, Computer Programs and Topographies of Integrated Circuits

1/22

Descriptive Report of the Invention Patent for METHOD FOR PROCESSING COMPOSITE BIOMATERIALS.

FIELD OF THE INVENTION [001] The present invention generally relates to a method and equipment that uses submerged pelletization and subsequent accelerated drying of polymer composite biomaterials and foamed polymer composite biomaterials to produce pellets with significantly reduced moisture content. More specifically, the present invention relates to a method and equipment for submerged pelletizing of polyolefins, such as polyethylene and polypropylene, substituted polyolefins, such as polyvinyl and polystyrene chloride, polyesters, polyamides, polyurethanes, polycarbonates or copolymers of the foregoing, contain a solid or semi-solid biomaterial component, such as polysaccharides, including cellulosics and starches, or proteinaceous material, including polypeptides, including expandable composites, with subsequent accelerated drying of these pellets and granules, expandable or otherwise, in such a way that the moisture content of these pellets or granules is significantly reduced. The pelletizing and drying process described here produces pellets and granules that have a reduced moisture level reaching one percent (1%) or less.

BACKGROUND OF THE INVENTION [002] The wood products industry has had an extensive focus on polymer composites and wood products for several years. Since high-quality resources for decorative adornments and exposed wooden surfaces have diminished over the years, considerable efforts have been made to find economical alternatives. Much of this interest involved composites of polyethylene, polypropylene and polyvinyl chloride. The latter has also been extensively investigated for use as a foam compound with

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2/22 wood flour and various inorganic fillers.

[003] More recent considerations have extended areas of interest for construction materials such as flooring, recycling concerns for the paper and wood pulp industry, and for residual by-products of fermentation processes. The continued rise in oil prices has also led to additional considerations for sources of recyclable plastics. Additional interests have developed in landscaping applications, automotive components and in animal odor control applications.

[004] The biggest concern is the control of humidity that leads to the final product. High moisture content leads to potential loss of structural integrity in the finished product due to stress cracking and bubble formation. The surface finish can also be compromised by uncontrolled humidity levels. Also of interest are the temperature limitations imposed by the use of cellulosic products that are particularly susceptible to carbonization with the increase in the processing temperature. This concern limited the choice of plastic materials from which composites can be made.

[005] Drying biomaterials is time-consuming and economically expensive. This is further complicated by the possibility of moisture absorption by the composite's biocomponents during storage requiring expensive moisture control or water-impermeable packaging. Processing that leads to the absorption of moisture from the environment or involves direct exposure to water, therefore, has not been attractive to the industry.

[006] Production yield suffers from rate restrictions due to the need to reduce the water content before and / or during the formulation process. To avoid unnecessary storage and minimize undesirable moisture absorption, several industries recorPetição 870170070337, of 20/09/2017, p. 10/37

3/22 proceeded to the composite formulation followed immediately by extrusion or other production techniques to form the final product.

[007] This invention focused on these concerns to provide a technique a technique for forming the polymer composite biomaterial without unnecessary preliminary drying of the components and to speed up processing to prepare suitably dry intermediate pellets for further processing, transportation or multi-stage processing as required. This process involves a sequence of continuous extrusion production, submerged pelletizing and accelerated drying to obtain the desired low moisture content composite.

RELATED PREVIOUS TECHNIQUE

U.S. Patents 5,441,801 August 1995 Deaner et al. 428/326 5,563,209 October 1996 Schumann et al. 524/709 5,714,571 February 1998 Al Ghatta et al 528 / 308.2 5,746,958 May 1998 Gustafsson et al 264/115 5,847,016 December 1988 Cope 521 / 84.1 5,938,994 August 1999 English et al. 264/102 5,951,927 September 1999 Cope 264/54 6,015,612 January 2000 Deaner at al. 428/326 6,066,680 May 2000 Cope 521/79 6,083,601 July 2000 Prince et al. 428/71 6,245,863 June 2001 Al Ghatta 525/437 6,255,368 July 2001 English et al. 524/13 6,280,667 August 2001 Koenig et al. 264/68 6,498,205 December 2002 Zehner 524/14 6,624,237 September 2003 Tong 524/9 6,632,863 October. 2003 Hutchison et al. 524/13 6,685,858 February. 2004 Korney, Jr 264/102

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4/22

6,706,824 March 2004 Pfaendner et al. 524/437 6,737,006 May 2004 Grohman 264 / 211.21 6,743,507 June 2004 Barlow et al. 428/393 6,762,275 July 2004 Rule et al. 528/273 6,790,459 September 2004 Andrews et al. 428 / 36.92 6,797,378 September 2004 Shimizu 428/394

Published U.S. Patent Applications

2002/0106498 August 2002 Deaner et al. 428 / 292.4 2003/0025233 February 2003 Korney, Jr. 264/102 2004/0126568 July 2004 Deaner et al 428/326 2004/0140592 July 2004 Barlow et al. 264/523 2004/0169306 September 2004 Crews et al. 264/140 2005/0075423 April 2005 Riebel et al. 524/17

Other pending U.S. patent applications

20050110182 May 2005 Eloo 264/69 20050110184 May 2005 Eloo 264/143 Patenl requests Foreigners

1467246 January 2004 CN 1470568 January 2004 CN 1515617 July 2004 CN 1603088 April 2005 CN 2005/035134 February 2005 JP 2005/053149 March 2005 JP 2005/060556 March 2005 JP 2005/088461 April 2005 JP 2005/097463 April 2005 JP

Other references

Wood-Filled Plastics by Lilli Manolis Sherman, Senior Editor, July

2004 Plastics Technology.

SUMMARY OF THE INVENTION

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5/22 [009] As used in this application, the term pellets intends to describe the product formed in a submerged pelletizer in its broadest sense and includes granules and any other particles modeled and sized in a submerged pelletizer.

[0010] The present invention is directed to a pelletizing method and equipment that produces polymeric pellet composites with a minimum submersion time such that they retain sufficient heat to self-initiate the drying process and ultimately provide sufficient moisture levels low reaching one percent (1%) or less, without the need for an additional heating step of the polymer composite pellets before further processing. Previous descriptions have demonstrated the effectiveness of pelleting and cooling to obtain properly dry pellets, but typically avoided exposure to moisture, especially direct immersion in water, preventing significant and undesirable water absorption by biomaterials. According to the present invention, it has been discovered that polymeric composite pellets can be obtained in an acceptably dry state when subjected to high heat conditions and benefit from the reduction of the pellets' residence time in the fluid water sludge, thus leaving sufficient heat pellets to effectively reduce the moisture content within the pellets.

[0011] To obtain high latent heat, the pellets must be separated from the water as quickly as possible with a significant increase in the speed at which they flow from the submerged pelletizer outlet into and through the drying equipment. The pellets come out of the dryer retaining much of their latent heat and can be transported as needed over conventional vibrating conveyor conductors or similar vibrating equipment or other handling equipment such that over time the humidity level

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Desired 6/22 is achieved. Storage of the hot pellets in conventional heat-retaining containers or thermally insulated containers is included in the present invention which provides time to complete the desired drying time. The desired moisture level obtained is determined by the permissible levels in the processing or production steps to be followed and can be reached one percent (1%) or less.

[0012] Polymer composite biomaterials that can be pelletized according to the present invention generally include as a basic component a suitable polymer and biomaterial particles. Appropriate additives are also included. The relative percentages of these basic components may vary depending on the selected polymer and the particles of the biomaterial, but it typically has 5% - 95% polymer and 10% - 90% biomaterial particles.

[0013] The separation of the pellets from the water and the subsequent increase in the speed of the pellet for the drying equipment is achieved by a combination of pressurized gas injection with simultaneous aspiration of water. Once the cut pellets leave the pelletizer water tank submerged in the fluid sludge of water, air or other suitable inert gas is injected into the transport pipe that leads from the water tank to the drying equipment. The term air hereinafter is intended to include air, nitrogen or any other suitable inert gas. The injected air serves to aspirate the water in steam effectively separating it from the pellets. The injected air still increases the transport speed of the pellets to, and finally, through the dryer. This increase in the transport speed is fast enough to allow the pellet to remain at a temperature hot enough to start the drying process of the pellets that can be further dried with transport through a central dryer 870170070337, from 20/09/2017 , p. 14/37

7/22 trifuge. Other conventional methods of drying the pellet with comparable efficiency can be employed by the person skilled in the art and are intended to be included here.

[0014] To obtain water aspiration and increase the transport speed from the water tank outlet from the pelletizer to the dryer, the injected air must be at a very high speed. According to the present invention, the volume of the injected air must be at least 100 cubic meters per hour based on injection through a valve for a pipe of 3.80 CM (1.5 inch) in diameter. This flow volume will vary according to the transfer volume, drying efficiency and pipe diameter as will be understood by the person skilled in the art.

[0015] The rate of air injection into the slurry piping is preferably regulated through the use of a ball valve or other valve mechanism located in the slurry transport pipe after the injection point. Regulation through this valve mechanism allows greater control of the pellets' residence time in the transport pipe and drying equipment and serves to improve the suction of the pellet / fluid sludge. Vibration is reduced or eliminated in the transport pipe by using a valve mechanism also after the injection point.

[0016] The regulation of air injection provides the necessary control to reduce the transport time of the pelletizer water tank exit through the dryer, allowing the pellets to retain significant internal heat. Larger diameter pellets do not lose heat as quickly as smaller diameter pellets and therefore can be transported at a lower speed than smaller pellets. Comparable results are obtained by increasing the air injection speed as the diameter of the pellet decreases, as will be understood by those skilled in the art. The reduction in the residence time between the

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8/22 pelletizer water tank and the dryer outlet leaves enough heat in the pellets to obtain the desired moisture level. Heat retention within the pellet can be increased through the use of a heat conserving vibrating conveyor following the release of the pellet from the dryer and / or through the use of conventional storage containers or thermally insulated containers as required. This method and equipment has been found to be effective for the polymers described herein. Moisture levels that reach one percent (1%) and preferably less than one percent (1%) can be obtained by the process and equipment described here. The change in residence time for polymers and polymer mixtures can be adjusted as needed to optimize the results of a particular formulation as will be understood by one skilled in the art. Additional heating steps are eliminated using the process and equipment described here.

BRIEF DESCRIPTION OF THE DRAWINGS [0017] Figure 1 is a schematic illustration of a submerged pelletizing system, including a submerged pelletizer and centrifugal dryer produced and sold by Gala Industries, Inc. (Gala) of Eagle Rock, Virginia, with air injection and vibrating conveyor according to the present invention.

[0018] Figure 2a is a schematic illustration of the side view of the vibrating conveyor in Figure 1.

[0019] Figure 2b is a schematic illustration of the rear view of the vibrating conveyor in Figure 1.

[0020] Figure 3 illustrates the components of the submerged pelletizing system shown in Figure 1 during bypass mode when the process line was disconnected.

[0021] Figure 4 is a schematic illustration showing an equipment for inert gas injection in the slurry line of pePetição 870170070337, of 09/20/2017, p. 16/37

9/22 letizer for the dryer according to the present invention.

[0022] Figure 5 is a schematic illustration showing a preferred equipment for inert gas injection from the pelletizer slurry line to the dryer including an enlarged view of the ball valve in the slurry line.

DETAILED DESCRIPTION OF THE INVENTION [0023] The preferred embodiments of the invention are explained in detail. The prior art has been included here for purposes of clarification and it should be understood that the invention is not limited in scope to the details of construction, arrangement of components or chemical components presented in the description that follows or as illustrated in the drawings. The modalities of the invention are capable of being practiced or carried out in various ways and are within the scope of the invention.

[0024] Descriptions of the modalities that follow use the terminology included for clarification and are intended to be understood in their broadest meaning including all technical equivalents by those skilled in the art. The polymeric components described for this invention provide details to those skilled in the art the extension of the method as described and are not intended to limit the scope of the invention.

[0025] Composite polymer biomaterials are typically formulated from fibrous biomaterial (s), a thermoplastic matrix, a coupling or stabilizing agent, lubricants, fillers, dyes and various processing aids. They can also contain expanding or foaming agents and crosslinking agents as required by the end use and particular application. Formulation components introduced from various recycling processes are within the scope of this invention.

[0026] Biomaterial or fibrous components provide resistance 870170070337, of 20/09/2017, p. 17/37

10/22 material strength and surface properties for a particular product. The dimensions of the biomaterial or fibrous components are limited only by the size of the desired intermediate pellet and to obtain the required surface characteristics. The moisture absorption and retention of the composite is strongly influenced by the choice of biomaterial. The thermal stability of the biomaterial component is important in consideration of the polymeric matrix material. Care must be taken when choosing a polymer with a melting temperature or processing temperature that will not lead to carbonization or degradation of the biomaterial. The formulations typically include 10% to 90% biomaterial and preferably 30% to 70% biomaterial. The balance is formed from the polymeric matrix and other components. Extrusion temperatures are less than 220 Ό (493.15 K) and preferably less than 200 Ό (473.15 K).

[0027] Biomaterials include, but are not limited to polysaccharides, including cellulosics and starches, and proteinaceous materials, including polypeptides. Examples of cellulosic are wood chips, laminated wood, plywood, wood flake, wood fibers, wood particles, crushed wood, sawdust, coconut shells, peanut shells, straw, wheat straw, cotton, shells or shale of rice, alfalfa, ricegrass, wheat bran, wheat pulp, bean stalks, corn (corn / maize), corn cobs, corn stalks, sorghum or corn, sugar cane, orange juice residue, mulch, bamboo ash, fly ash, peat moss, seaweed, chaff, rye, millet, barley, oats, soy, coffee residue, leguminous plants, forage grass, and plant fibers including bamboo, palm, hemp, yucca and jute. In addition, paper products such as computer paper, cardboard, newspapers, magazines, books, milk and beverage packaging and paper pulp find application in this inventionPetition 870170070337, of 20/09/2017, p. 18/37

11/22 tion.

[0028] Examples of starches include potatoes, sweet potatoes, cassava and forage. Proteinaceous materials include fermentation solids, distillers grains and solids, gluten, wheat and rye prolamines as gliadin, corn as zein and sorghum and millet as caffeine.

[0029] The size of the biomaterial particles will vary depending on whether the particles are fibrous or powdered and the size and end use of the pellets. The size of fibrous particles can typically range from 10 to 900 microns, with an aspect ratio of 1 to 50 and more preferably from 2 to 20. For powders, the particle size will typically range from 15 to 425 microns.

[0030] Thermoplastic materials shown in the prior art for use in polymer composite biomaterials include polyethylene or PE, polyvinyl chloride or PVC, polypropylene or PP, and polystyrene or PS with high density polyethylene or HDPE being the most prevalent in use. Within the formulations for expandable applications, significant attention has been in the area of PVC or chlorinated PVC, CPVC. The choice of materials has often been restricted to those that can be processed at temperatures below the degradation point of biomaterials.

[0031] With careful choice of formulations, the range of polymers can be extended to include polyesters, polyamides, polyurethanes and polycarbonates. Thermoplastic materials as well as thermoset polymers are within the scope of this invention. The use of thermosets, such as choices in polymers, requires careful attention to the crosslinking temperatures to allow post-cure crosslinking to be carried out at temperatures or by chemical reactions not obtained or initiated during processes within the scope of this invention.

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12/22 [0032] Polyethylenes for use in this invention include low density polyethylene or LDPE, linear low density polyethylene or LLDPE, medium density polyethylene or MDPE, high density polyethylene or HDPE, and ultra high molecular weight polyethylene or UHMWPE also known as UHDPE ultra-high density polyethylene.

[0033] Also within the scope of this invention are oleophines including polypropylene, or PP, polyalphaoleophins or PAO, including polymers and copolymers, examples of which are polybutene, polyisobutene, polypentenes, polymethylpentenes and polyoxenes. Polystyrene or PS and poly (alpha-methylstyrenes), acrylonitrile-butadiene-styrene or ABS, acrylic-styrene-acrylonitrile or ASA, styrene-acrylonitrile or SAN, and styrenic block copolymers are included here as an example. Amorphous, crystalline and semi-crystalline materials are also included within the scope of this invention.

[0034] Polyvinylchloride or PVC and chlorinated polyvinylchloride or CPVC as described for this invention can be plasticized or nonplasticized and can be used as a homopolymer or in copolymers that incorporate the aforementioned oleophins as well as in polymeric compositions with acrylonitrile, vinylidene dichloride, acrylates , methyl acrylates, methyl methacrylates, hydroxyethylacrylate, vinyl acetate, vinyl toluene, and acrylamide as an example.

[0035] Polyesters, polyamides, polycarbonates and polyurethanes within the scope of this invention must be formulated such that the processing temperature of the material is below the point of degradation of the biomaterial. As is familiar to those skilled in the art, this can be achieved by using copolymers within this broad family of condensation chemistry.

[0036] Polyesters useful for the present invention are of the formula

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13/22 general structural (ORiO) _x . [(C = O) R ₂ (C = 0)] _y and / or [(C = O) RiO] _x [(C = O) R ₂ O] _y . Ri and R ₂ described herein include aliphatic, cycloaliphatic, aromatic or substituted moieties including, but not limited to halogens, nitro functionalities, alkyl and aryl groups and can be the same or different. More preferably, polyesters described herein include poly (ethylene terephthalate) or PET, poly (trimethylene terephthalate) or PTT, poly (butylene terephthalate) or PBT, poly (ethylene naphthalate) or PEN, polylactide or PLA and poly (alpha-hydroxyalkanoates) or PHA and its copolymers.

[0037] Polyamides useful for the treatment of the present invention are of general structural formula [N (H, R) R-ιΝ (H, R)] _x [(C = O) R ₂ (C = O)] _y and / or [(C = O) RiN (H, R)] _x [(C = O) R ₂ N (H, R) _y . R-, and R ₂ described herein include aliphatic, cycloaliphatic, aromatic and substituted moieties including, but not limited to halogens, nitro functionalities, alkyl and aryl groups, and may be the same or different. R described herein includes, but is not limited to, aliphatic, cycloaliphatic and aromatic moieties. More preferably, polyamides include polytetramethylene or nylon adipamide 4,6, polyiexamitylene adipamide or nylon 6, 6, polyoxymethylene sebacamide or nylon 6,10, poly (hexamethylenediamine-co-dodecanedioic acid) or nylon 6, 12, or nylon 6, polieptanolactam or nylon 7, polyundecanolactam or nylon 11, polydodecanolactam or nylon 12 and their copolymers.

[0038] Polycarbonates useful for the present invention are of the general structural formula [(C = O) ORiO] _x . [(C = O) OR ₂ O] _y . Ri and R ₂ described herein include aliphatic, cycloaliphatic, aromatic and substituted moieties including, but not limited to halogens, nitro functionalities, alkyl and aryl groups. More preferably, polycarbonates include, substituted bisphenol and bisphenol carbonates where the bisphenol is of the structural formula HOPhC (CH ₃ ) ₂ PhOH or

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14/22

HOPhC (CH ₃ ) (CH2CH ₃ ) PhOH where Ph describes the phenyl ring and substituents include but are not limited to alkyl, cycloalkyl, aryl, halogen and nitro functionalities. Ri and R ₂ can be the same or different.

[0039] Polyurethanes useful for the present invention are those of the general formula [(C = O) ORiN (H, R)] _x [(C = O) OR ₂ N (H, R) _y . R-, and R ₂ described herein include aliphatic, cycloaliphatic, aromatic and substituted moieties, including, but not limited to halogens, nitro functionalities, alkyl and aryl groups. R described herein includes, but is not limited to, aliphatic, cycloaliphatic and aromatic moieties. More preferably, polyurethanes described herein include copolymers of polyether polyurethane and / or polyester polyurethane including methylenebis (phenylisocyanate). Ri and R ₂ can be the same or different.

[0040] Polyesters and copolymers, polyamide copolymers, polycarbonates and copolymers, and polyurethanes and copolymers can be comprised of at least one diol including ethylene glycol, 1,2 propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol,

1.5-pentanediol, 1,3-hexanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, dodecamethylene glycol, 2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl -1,3-propanediol, 2-ethyl-2-isobutyl-1,3propanediol, 2-methyl-1,4-pentanediol, 3-methyl-2,4-pentanediol, 3-methyl1.5-pentanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2 -cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polytetramethylene glycol, catechol, hydroquinone, isosorbide, 1,4-bis (hydroxymethyl) -benzene, 1,4bis (hydroxyethoxy) benzene, 2,2-bis (4-hydroxyphenyl) propane and isomers thereof.

[0041] Polyesters and copolymers, polyamide copolymers, polyPetition 870170070337, of 20/09/2017, p. 22/37

15/22 carbonates and copolymers and polyurethane and copolymers can be comprised of at least one lactone or hydroxy acid including butyrolactone, caprolactone, lactic acid, glycolic acid, 2-hydroxyethoxyacetic acid, and 3-hydroxypropoxyacetic acid, 3-hydroxybutyric acid, as an example.

[0042] Polyesters and copolymers, polyamides and copolymers, polycarbonate copolymers, and polyurethane copolymers can be comprised of at least one exemplary diacid or that are phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6dicarboxylic acid, and isomers dicarboxylic stilbene acid, 1,3cyclohexanedicarboxylic acid, diphenyldicarboxylic acids, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, pyelic acid, undecanoic acid, octadecanedioic acid, and cycloexanodiacetic acid.

[0043] Polyesters and copolymers, polyamides and copolymers, polycarbonate copolymers, and polyurethane copolymers can be comprised of at least one diester including, for example, dimethyl or diethyl phthalate, dimethyl or diethyl isophthalate, dimethyl or diethyl terephthalate. dimethyl naphthalene-2,6-dicarboxylate.

[0044] Polyamides and copolymers, polyester copolymers, polycarbonate copolymers, and polyurethane and copolymers comprised of diamines including 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanodiamine , 1,10-decanediamine, 1,12-dodecanediamine, 1,16-hexadecanediamine, phenylenediamine, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 2,2dimethyl-1,5-pentanediamine, 2,2,4 -trimethyl-1,5-pentanediamine, and 2,2,4trimethyl-1,6-hexanediamine are included in this invention and are not limited to that described here.

[0045] Polyamides and copolymers, polyester copolymers, polycarbonate copolymers, and polyurethane copolymers can be

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16/22 comprised of at least one lactam, or amino acid, including propiolactam, pyrrolidinone, caprolactam, heptanolactam, caprylactam, nonanolactam, decanolactam, undecanolactam, and dodecanolactam as an example.

[0046] Polyurethanes and copolymers, polyester copolymers, polyamide copolymers, and polycarbonate copolymers can be comprised of at least one isocyanate including, but not limited to, 4,4'-diphenylmethane diisocyanate and isomers, toluene diisocyanate, diisocyanate isophorone, hexamethylene diisocyanate, ethylene diisocyanate, 4,4 ^, -methylenebis (phenylisocyanate) and isomers, xylylene diisocyanate and isomers, tetramethyl xylylene diisocyanate, 1,5, 1,4-diisocyanate, diisocyanate, 1,4-diisocyanate dimethoxy-4,4'-diisocyanate, 1,6-hexane-diisocyanate, 1,6diisocyanate-2,2,4,4-tetramethylexane, 1,3-bis (isocyanatomethyl) cyclohexane, and 1,10-decanodiisocyanate.

[0047] Coupling agents are preferably incorporated into the formulation to provide greater compatibility of resins with more polar biomaterials. Coupling agents effectively bind biomaterials to the plastic matrix and provide increased dimensional stability, greater impact resistance, more efficient dispersion of fibrous materials, reduced deformation, and reduced water absorption and possibly swelling of intermediate pellets as well as final products . Examples of such coupling agents or stabilizers are maleate polypropylene, maleate polyethylene, long-chain chlorinated paraffins or LCCP, paraffin wax, metal soaps, silanes, titanates, zirconates and surfactants.

[0048] Water-soluble binders serve to promote similar adhesion and can be included in polymer composite biomaterials for the present invention. These binders provide greater solubility for biomaterials and are particularly effective for

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17/22 recycling applications as effectively demonstrated in the prior art. Examples of these include polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, substituted cellulose, sodium carboxymethyl cellulose, sodium hydroxyethyl cellulose, sodium hydroxypropyl cellulose, and sodium carboxymethylhydroxyethyl cellulose. [0049] Lubricants are also desirable in the present invention since they also increase the dispersion of biomaterials and reduce overheating due to frictional drag, effectively reducing that drag and the resulting problematic degradation and discoloration. They also facilitate the reduction of agglomeration and agglutination of biomaterials.

[0050] Yield rates and surface properties are significantly modified by the choice of lubricant (s). Silicone oil, paraffin wax, oxidized polyethylene, metal stearates, fatty acid amides, oleyl palmitamide and ethylene bis-stearamide are included here as an example.

[0051] Loads can also be used to reduce costs and serve to modify properties as is readily understood by those skilled in the art and are included within the scope of this invention. Foaming agents including nitrogen, carbon dioxide, butane, pentane, hexane and the well-described chemical foaming agents (CFA) also follow as examples from prior art descriptions.

[0052] Considerations of the previous descriptions demonstrated that high levels of humidity in the biomaterial feed can be reduced by drying techniques familiar to those skilled in the art before introduction into the extruder or can be significantly reduced during the feeding and extrusion processes. Details of this are outside the scope of this invention, but are included here by reference. Moisture levels as high as 40% were inPetition 870170070337, of 20/09/2017, p. 25/37

18/22 translated into the extruder with appropriate ventilation to obtain products with acceptable results.

[0053] A submerged pelletizing system for use in association with the present invention is shown schematically in the Figure

1. The submerged pelletizing system is generally designated by reference number 10 and includes a submerged pelletizer 12, such as the submerged pelletizer Gala, with cutter hub and blades 14 exposed in the separate view of the water tank 16 and a matrix plate ( die plate) 18.

[0054] In the submerged pelletizing system 10, the polymer composite biomaterials to be processed are fed from the top using at least one vat or polymer feeder 160 typically within an extruder 155 and are cut and heated to melt the polymer. Polymer composite biomaterials are typically extruded at temperatures below 220Ό (493.15 K) to prevent degradation of biomaterials. The melt can continue to feed through a gear pump 22 which provides a uniform and controlled flow rate. The molten polymer, as needed, can be fed into filter 20 (Figure 1) to remove any large mass or solid particles or foreign material. The melt flows to a polymer diverter valve 24 and to the mold holes in a die plate 18. The strands of molten polymer formed by extrusion through the mold holes enter the water tank 16 and are cut by the cutter hub and blades pivots 14 to form the desired pellets or granules. The process as described here is exemplary in nature and other configurations that obtain the desired polymer flow, as easily understood by someone skilled in the art, and are included within the scope of this invention.

[0055] The prior art has demonstrated numerous modifications

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19/22 and additions to the extrusion process, which are useful in reducing the degradation of the extruded thermally or oxidatively. These adaptations include vacuum removal of by-products and excess monomers, reduction by hydrolysis, control of catalytic depolymerization, inhibition of polymerization catalysts, protection of the terminal group, increase in molecular weight, extension of the polymer chain and use of purifiers of inert gas.

[0056] The water enters the water tank 16 through a pipe 26 and quickly removes the pellets thus formed from the face of the mold to form a pellet and fluid mud of water. Process water circulated through the pelletizer water tank as included in this invention is not limited in composition and may contain additives, cosolvents, and processing aids as needed to facilitate pelletization, prevent agglomeration, and / or maintain the transport flow. as will be understood by one skilled in the art. The pellet slurry thus formed leaves the water tank through the pipe 28 and is transported towards the dryer 32 through the slurry line

30.

[0057] According to this invention, air is injected into the slurry line 30 at point 70, preferably adjacent to the outlet of the water tank 16 and near the beginning of the slurry line 30. This preferred site 70 for injection of air facilitates the transport of pellets by increasing the transport rate, facilitating the aspiration of water in the slurry, thus allowing the pellets to retain sufficient latent heat to effect the desired drying. High speed air is conveniently and economically injected into the slurry line 30 at point 70 using conventional compressed air lines typically available in manufacturing facilities, such as with a pneumatic compressor. Other inert gases including, but not limited to, nitrogen may be used according to this invention to

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20/22 transport the pellets at high speed as described. This high-speed air is obtained using compressed gas producing a flow volume of at least 100 m ³ / hour using a standard ball valve for regulating a pressure of at least (8 bar) 800 kPa through the slurry line 30 having a standard pipe diameter, preferably a (1.5 inch) 3.80 cm diameter pipe. For those skilled in the art, flow rates and pipe diameters will vary according to the transfer volume, desired unit level, and the size of the pellets. High-speed air effectively contacts the pellet slurry, generating water vapor by aspiration, and disperses the pellets through the slurry line propagating these pellets at increased speed to dryer 32, preferably at a rate of less than than a second from the water tank 16 to the outlet of the dryer 34. The high speed aspiration produces a mixture of pellets and air that can reach 98 - 99% by volume of air.

[0058] Figure 5 shows the preferred arrangement for the injection of air into the slurry line. The water / pellet sludge leaves the pelletizer 102 water tank into the slurry line 106 through the glass sight glass 112 and beyond the angled elbow 114 where compressed air is injected from valve 120 into angled slurry line. The injected air, pellets and vaporized water continue through the elbow 118, through the dryer inlet 110 and into the dryer 108. It is preferred that the injection of air into the inclined elbow 114 is aligned with the axis of the paste line. fluid 116 providing the maximum effect of that air injection on the pellet / water slurry resulting in constant aspiration of the mixture.

[0059] The angle formed between the vertical axis of the slip line 106 and the longitudinal axis of the slip line 116 can decay

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21/22 from 0 ° to 90 ° or more as required by the variation in the height of the pelletizer 102 in relation to the height of the inlet 110 for the dryer. This difference in height may be caused by the physical positioning of the dryer 108 in relation to the pelletizer 102 or it may be a consequence of the difference in the height of the dryer and the pelletizer. The preferred angle range is 30 ° to 60 ° with a more preferred angle of 45 °. The extended elbow 118 inside the inlet of the dryer 110 facilitates the transition of the high-speed aspirated pellet slurry from the slurry line 116 that is approaching the inlet of the dryer 110 and reduces the potential for pellet agglomeration inside the dryer. 108.

[0060] The preferred position of the equipment as described in Figure 5 allows the pelletizer pellets 102 to be transported to the dryer 108 outlet in approximately one second, which minimizes heat loss inside the pellet. This is further optimized by inserting a second valve mechanism or, more preferably, a second ball valve 150 after injecting air into the elbow 114. This additional ball valve 150 allows better regulation of the pellet dwell time within the slurry 116 and reduces any vibration that may occur in the slurry line. The second ball valve 150 allows additional pressurization of the air injected into the chamber and improves the suction of water from the pellet / water slurry. This becomes especially important as the size of the pellets decreases in diameter.

[0061] The pellets are ejected through outlet 126 of dryer 108 and are preferably directed towards a vibrating unit, such as a vibrating conveyor 84 illustrated schematically in Figure 2a and Figure 2b. The agitation that results from the vibrating action of the vibrating conveyor 84 allows heat to be transferred between the pellets as they come into contact with other feet. Petition 870170070337, of 20/09/2017, p. 29/37

22/22 lethes and the components of said vibrating conveyor. This allows temperature uniformity to be achieved and results in improved, smaller and more uniform pellet moisture content. Agitation decreases the tendency of the pellets to adhere to each other and / or to the components of the vibrating conveyor as a consequence of the increased temperature of the pellets.

[0062] The residence time of the pellets on the vibrating conveyor can affect that the desired moisture content is obtained. It is expected that the larger the pellet, the longer the residence time. The dwell time is typically about 20 seconds to about 120 seconds or more, preferably 30 seconds to 60 seconds, and more preferably 40 seconds to allow the pellets to dry to the desired degree and to allow the pellets to cool for handling. Larger pellets will retain more internal heat and dry faster than would be expected for smaller diameter pellets. Conversely, the larger the diameter of the pellet, the longer the residence time required for the pellet to cool for handling purposes. The desired temperature of the pellet for final packaging is typically less than would be required for further processing.

[0063] Methods for cooling or methods other than the vibrating conveyor can be used to allow pellets exiting the dryer to have enough time to dry and subsequently cool for handling. The pellets as released can be packaged, stored or transported as needed for further processing or final product manufacturing including intermediate and final expansion of the pellets where applicable.

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Claims (15)

1. Method for processing polymer composite biomaterials in pellets including the steps of extruding tapes of a polymer composite biomaterial through a matrix plate (18) within a submerged pelletizer (12, 102), cutting the composite tapes in the pelletizer, transport the composite pellets from the pelletizer as a fluid slurry of water and pellet and dry the composite pellets, characterized by the fact that the step of transporting the composite pellets includes injecting air, nitrogen or any other inert gas suitable within the fluid water slurry and pellet to cause the water to be sucked from the pellets and the pellets to retain internal heat, to reduce the absorption of moisture by the pellets and to carry out the transport and drying of the pellets; wherein the polymer biomaterial composite contains one or more coupling agents selected from long-chain chlorinated paraffins (LCCP), metal soaps, silanes, titanates and zirconates. 2. Method, according to claim 1, characterized by the fact that the step of drying the pellets reaches a humidity level close to 1%, and preferably less than 1%. 3. Method according to claim 1, characterized by the fact that the pellets are transported into a dryer (32, 108) after the high-speed inert gas is injected into the fluid slurry of water and pellet. 4. Method according to claim 3, characterized in that the pellets exiting the dryer are kept in motion by a vibrating unit (84) while the pellets continue to dry. 5. Method, according to claim 3, characterizes Petition 870180059843, of 7/11/2018, p. 7/13 2/3 of the fact that the step of injecting inert gas at high speed into the fluid slurry of water and pellet causes the speed of the pellets inside and through the dryer to increase. 6. Method according to claim 1, characterized by the fact that the gas is injected into the fluid slurry of water and pellet at a flow rate of at least 100 m ³ / hour, and preferably 175 m ³ / hour. 7. Method according to claim 1, characterized by the fact that the gas is injected into the fluid slurry of water and pellet in alignment with a flow line of the slurry. 8. Method according to claim 7, characterized by the fact that the flow line of the slurry bends at an angle between 30 ° and 60 ° and gas is injected into the curve. 9. Method, according to claim 8, characterized by the fact that the pellets remain in the passage line is regulated by a ball valve (150) downstream of the air injection. 10. Method according to claim 1, characterized by the fact that the polymer composite biomaterial includes foamed, foamed and non-foamed composites. 11. Method according to claim 1, characterized by the fact that the polymer composite biomaterial has 5% to 95% polymer and 10% to 90% biomaterial, and preferably 30% to 70% biomaterial. 12. Method, according to claim 11, characterized by the fact that the biomaterial is selected from the group consisting of polysaccharides, including cellulosics and starches, and proteinaceous materials, including polypeptides, and any combination of the above. 13. Method, according to claim 11, characteristic 870180059843, of 11/07/2018, p. 8/13 3/3 due to the fact that the biomaterial includes fibrous particles of 10 to 900 microns, with an aspect ratio of 1 to 50, and preferably 2 to 20. 14. Method according to claim 11, characterized by the fact that the biomaterial includes powders that have a particle size of 15 to 425 microns. 15. Method according to claim 1, characterized by the fact that the polymer is selected from the group consisting of polyolefins, substituted polyolefins, polyesters, polyamides, polyurethanes and polycarbonates. Petition 870180059843, of 7/11/2018, p. 9/13 1/5 2/5 Μ00 3/5 4/5