WO2017221055A1 - Material compuesto de celulosa obtenida a partir de cascarilla de café o cacao, artículo que comprende el mismo y proceso de obtención - Google Patents
Material compuesto de celulosa obtenida a partir de cascarilla de café o cacao, artículo que comprende el mismo y proceso de obtención Download PDFInfo
- Publication number
- WO2017221055A1 WO2017221055A1 PCT/IB2016/053837 IB2016053837W WO2017221055A1 WO 2017221055 A1 WO2017221055 A1 WO 2017221055A1 IB 2016053837 W IB2016053837 W IB 2016053837W WO 2017221055 A1 WO2017221055 A1 WO 2017221055A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cocoa
- coffee
- cellulose
- husk
- allows
- Prior art date
Links
- 235000009470 Theobroma cacao Nutrition 0.000 title claims abstract description 34
- 239000001913 cellulose Substances 0.000 title claims abstract description 34
- 229920002678 cellulose Polymers 0.000 title claims abstract description 34
- 239000010903 husk Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 244000240602 cacao Species 0.000 title abstract 2
- 235000019568 aromas Nutrition 0.000 claims abstract description 10
- 244000299461 Theobroma cacao Species 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229920001222 biopolymer Polymers 0.000 claims description 10
- 238000013270 controlled release Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000008393 encapsulating agent Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 2
- 239000007844 bleaching agent Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000010297 mechanical methods and process Methods 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- 239000011111 cardboard Substances 0.000 abstract description 20
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- 238000012856 packing Methods 0.000 abstract description 2
- 235000010980 cellulose Nutrition 0.000 description 26
- 239000010410 layer Substances 0.000 description 26
- 238000004806 packaging method and process Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 238000009516 primary packaging Methods 0.000 description 9
- 239000002699 waste material Substances 0.000 description 8
- 235000013305 food Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 7
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- 238000001125 extrusion Methods 0.000 description 3
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- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005354 coacervation Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000012978 lignocellulosic material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- 239000005913 Maltodextrin Substances 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 241001494501 Prosopis <angiosperm> Species 0.000 description 1
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- 244000269722 Thea sinensis Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 230000000295 complement effect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
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- 229920000591 gum Polymers 0.000 description 1
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- 238000003475 lamination Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940035034 maltodextrin Drugs 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000009518 tertiary packaging Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
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- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C1/00—Pretreatment of the finely-divided materials before digesting
- D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
-
- D—TEXTILES; PAPER
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- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
- D21C3/022—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of S-containing compounds
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- D—TEXTILES; PAPER
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- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/02—Open containers
- B32B2439/06—Bags, sacks, sachets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/62—Boxes, cartons, cases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Definitions
- the present invention belongs to the technical field of materials obtained from cellulose. More specifically, the present invention discloses a cellulose composite material, obtained from the coffee or cocoa husk and the process of obtaining it. Additionally, the present invention discloses a laminated article composed of said cellulose composite material, which also emits aromatic odors.
- Paper and cardboard are some of the most important packaging materials in the world. To meet the growing demand for paper pulp and conserve non-renewable timber resources, there is great interest in replacing virgin raw materials to obtain different types of paper and cardboard. Likewise, there is a special interest towards raw materials and alternative manufacturing processes for cellulose pulp, which generate lower environmental impacts, compared to the raw materials and processes traditionally used.
- patent application US2003213573 proposes a container made from rice husk, wheat, wood dust, milk powder and clay, as secondary food packaging. This package is formed from the agglomeration of the recycled material, which is fluidized, pressed, dried and glued until a waterproof and hygienic packaging material is obtained.
- Patent CN103571166 mentions a composite material of polypropylene carbonate (PPC), cellulose or microcrystalline cellulose, a lubricating agent, an antioxidant, a heat stabilizer, a plasticizer and a biodegradation promoting agent. This document also proposes a method of preparing the composite material by extrusion granulation and subsequent hot pressing.
- the application DE3937168 (Al) describes a material for food packaging based on cellulose, shells, bran, husk, barley edges, fibers, hops, finely ground straw, sawdust and animal material, byproduct of slaughterhouses A waterproof coating is applied to the packaging surface.
- the packaging material contains 30-50% of a cellulosic type material and 30-70% of a starch and / or protein material, providing a biodegradable packaging material.
- Patent CN102712409 (A) describes the manufacture of reinforced biodegradable cardboard from starch and cellulose fibers from recycled paper waste. This document discloses the use of a hard outer shell and a foamed interior, and a reinforcement that is achieved by means of a multilaminate or corrugated structure by means of an extrusion process.
- a composite material made from cellulose from the coffee or cocoa husk that can be used in food packaging, medical materials, engineering plastics and the like in the field of art.
- there is no material in the state of the art made from alternative sources of cellulose pulp which has increased flexural strength compared to the flexural strength of widely used materials such as PPC.
- biodegradable articles have also been reported for use in food packaging, which are manufactured with multiple layers or sheets. Below are some prior art documents referring to this type of invention.
- Patent application CN202115856 U discloses a disposable paper cup made of layers. These layers are structured as follows: laminar polyurethane (inner layer), paper holding layer, a layer of printing ink and a surface layer of PE laminate. The surface layer of PE laminate is used to cover the printing ink layer, so that the printing ink is isolated from the outside. Thus, a consumer does not come into direct contact with the printing ink when the disposable paper cup is used.
- EP05781356A1 mentions a sheet composed of several layers made from thermoplastic polyglycolic acid resin, laminated with aqueous adhesives with the possibility of use in food packaging and storage.
- WO1999035049 discloses a biodegradable disposable container, for food or medicine, made from bean, fiber and plant residues and a carboxymethyl cellulose, starch and water adhesive. These elements are mixed, pressed into a mold and dried to deposit a thin layer of wax on the surface of the container.
- the present invention relates to a composite material, made from cellulose from coffee husk or cocoa, for the manufacture of a laminated article for the preparation of containers or packaging.
- the present invention provides an alternative source of cellulose pulp never before used, whereby materials with improved flexural strengths are developed, which allow the manufacture of cellulose composite sheets from waste material for subsequent processing of packaging or containers, biodegradable and compostable, with controlled emanation of coffee and cocoa aroma.
- Coffee and cocoa husks are lignocellulosic materials, of agroindustrial waste. These husks are an important source of cellulose fiber.
- the present invention uses this type of waste as an alternative raw material for the manufacture of cellulose pulp. This pulp can be used to obtain paper, cardboard and / or cardboard. Additionally, the invention discloses a composite material manufactured from this cellulose pulp, which has a flavor release functionality. In addition, the present invention relates to a laminated article made from the composite material, which can be used for making packages or containers. The composite material can be used both in the manufacture of primary packaging, and in the preparation of secondary and / or tertiary packaging.
- the present invention also relates to the method that includes obtaining cellulose pulp from the coffee or cocoa husk (by the "kraft” method) and the subsequent addition of a material that allows the controlled release of aromas.
- Figure 1 Illustrates the laminated article manufactured from the composite material obtained from coffee husk or cocoa.
- Figure 2 Illustrates a container that can be made using the laminated article.
- the present invention relates to the extraction of cellulose from coffee husk or cocoa husk residues.
- Obtaining cellulose can lead to out through a chemical process.
- This method consists of two phases, the first is to introduce the waste into an airtight container where it is subjected to superheated steam at a pressure between 1500 to 2500 psi (10343 to 17237 kPa), for two hours, to remove lignin and achieve an initial separation of the fibers.
- the second phase is to cook the waste in a controlled pressure vessel between 1000 to 2000 psi (6895 to 13790 kPa), with a temperature between 200 to 250 ° C, in an alkaline solution based on sodium hydroxide (NaOH) and sodium sulfide (Na 2 S).
- This process allows the extraction of lignin present in the coffee and cocoa husk.
- a separation of the sulphide-based gases and a filtrate is performed, to perform a separation of the residues that were not degraded in the process.
- a cellulose pulp is obtained, which is classified, washed and bleached in different proportions. Finally the obtained paste is dried.
- This mixture can be made by extrusion, mechanical mixing or in solution, generating the final composite material.
- the material that allows the controlled release of aromas can be obtained by encapsulating an aromatic compound of coffee or cocoa, which is carried out by dispersing the aromatic compound (active agent) in an encapsulating agent, among which rubber can be cashew, gum arabic, mesquite gum, maltodextrin, chitosan.
- This dispersion is carried out by physical methods such as: spray drying, extrusion and spray coating.
- chemical methods such as simple coacervation, complex coacervation and liposome entrapment can be used.
- physicochemical methods such as interfacial polymerization and molecular inclusion. The above allows controlling the volatility and reactivity of the active agent, increasing its stability to achieve a longer duration of aroma in the composite.
- the composite material of the present invention can be used in the preparation of primary, secondary and tertiary packages.
- Primary packaging means that packaging that is directly in contact with the product; It contains the product and also protects it.
- the primary packaging can cover the product entirely or only partially, but prevents the modification of the contents without opening or modifying said package.
- Some examples of primary packaging are plastic bags, bottles, tetra-brick, canned and bottles, among others.
- Primary packaging must contain fundamental data that includes the name of the product, brand, weight, variety, producer and country of origin. Also, the primary packaging must include the production date and the expiration date. Some products warn about their toxicity, handling and storage conditions.
- Primary packaging may also comprise a UPC, an acronym for Universal Product Code or Universal Product Code. In the middle it is known as the Bar Code, which translates into a series of digits that present information about the producer and the product as such.
- the secondary packaging is an external complement that groups several samples of primary packaging, its function is to protect it in quantities that simplify its distribution, storage and inventory.
- the second level are the cardboard boxes, guacales (crates), baskets, trays and perforated boxes (lugs), among others. These must orderly contain the units.
- the boxes must be duly marked indicating the number of units, their maximum resistance at the time of stacking, the brand of the product and its basic characteristics.
- Tertiary packing or transport packaging is used in order to integrate uniform quantities of the product, already arranged in secondary packaging.
- tertiary packages are hoppers, wired or nailed guacales, pallets, baskets and containers among others.
- dividers or partitions of cardboard or plastic Inside the big Shipping containers are added dividers or partitions of cardboard or plastic, in order to divide and secure the merchandise.
- the load is previously provided with reinforcements at the sides and at the ends to increase its resistance to compression.
- This laminated article has three layers made of composite material and is illustrated in Figure 1.
- the difference between the layers lies in the percentage by weight of biodegradable biopolymer with cellulosic material (amount of cellulose pulp) comprising the composite material with the one that each one of the layers is elaborated.
- the union of the different layers is obtained by passing the different layers through rollers at a controlled pressure, speed and temperature.
- This lamination can be done by incorporating adhesives, which can be dry or emulsion, or by thermal methods where heat is applied to seal the different layers.
- External layer (1) comprising up to 100% by weight biodegradable biopolymer with cellulosic material obtained from coffee husk or cocoa. This high biodegradable biopolymer content from the coffee or cocoa husk allows printing on the outer layer.
- Intermediate layer (2) which comprises between 5% and 10% by weight of biodegradable biopolymer with cellulosic material obtained from coffee husk or cocoa. This intermediate layer has mechanical stability.
- Internal layer (3) which comprises between 2% and 5% by weight of biodegradable biopolymer with cellulosic material obtained from coffee husk or cocoa. This layer acts as a liquid barrier, it is safe to allow contact with drinks and food.
- the outer layer (1) of the laminated article comprises up to 100% by weight of biodegradable biopolymer with cellulosic material obtained from coffee husk or cocoa.
- the laminated article allows the printing of information on the packaging, which is of utmost importance in its commercial application as explained above.
- the article can be composted after use, reducing the solid waste associated with this type of packaging, whether primary, secondary or Tertiary Additionally, this article may release aromas.
- the composite material has an improved flexural strength.
- the flexural strength of the composite material of the present invention is increased between 2 to 38 times compared to the flexural strength of the PPC. It also has a density between 0.4 and 0.8 g / cm 3 , a tension index between 300 to 600 Nm / g, a tear index with a range of 200 to 300 mNm 2 / g, explosion rate and performance of the order 40 to 60 %.
- the lignocellulosic material obtained from the coffee and cocoa husks under the procedure described above can also be used to obtain paper, cardboard and cardboard.
- the difference between these products lies in the weight.
- the paper has a weight of up to 130 g / m 2
- the cardboard a weight between 130 to 240 g / m 2
- the compact cardboard a weight of more than 240 g / m 2 .
- Example 1 Manufacture of a glass from the laminated article of the present invention.
- a glass (primary packaging) was obtained, with aroma release, composed of the laminated article obtained from coffee husk or cocoa cellulose.
- This vessel is illustrated in Figure 2. It has (1) outer layer, (2) intermediate layer, (3) inner layer, with a weight between (18 to 250) g / m 2 , a caliber of 180 Um . Its specific properties are reported below:
- Example 2 Manufacture of cardboard, cardboard and corrugated cardboard of the present invention.
- a material consisting of several superimposed layers of the biodegradable and compostable material is obtained, with a weight of 100 and 800 g / m 2 onwards , from which cardboard, cardboard and corrugated cardboard are obtained.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Materials Engineering (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
La presente invención se refiere a la obtención de celulosa a partir de la cascarilla de café o cascarilla de cacao. La celulosa extraída puede ser empleada para la obtención de papel, cartulina y cartón. Igualmente, con esta celulosa se fabrica un material compuesto que adicionalmente comprende un material que permite la liberación de aromas. Con este material se fabrica un artículo laminado para ser utilizado en aplicaciones de empaques primarios, secundarios y terciarios. Este tipo de articulo permite la impresión en su superficie externa, es biodegradable y biocompostable.
Description
MATERIAL COMPUESTO DE CELULOSA OBTENIDA A PARTIR DE CASCARILLA DE CAFÉ O CACAO, ARTÍCULO QUE COMPRENDE EL MISMO Y PROCESO DE OBTENCIÓN
1. CAMPO DE LA INVENCIÓN
La presente invención pertenece al campo técnico de los materiales obtenidos a partir de celulosa. Más específicamente, la presente invención divulga un material compuesto de celulosa, obtenido a partir de la cascarilla de café o cacao y el proceso de obtención del mismo. Adicionalmente, la presente invención divulga un artículo laminado compuesto de dicho material compuesto de celulosa, que además emite olores aromáticos.
2. ANTECEDENTES DE LA INVENCIÓN
El papel y el cartón son algunos de los materiales de empaque de mayor importancia en el mundo. Para satisfacer la creciente demanda de pulpa de papel y conservar los recursos madereros no renovables, existe un gran interés en la sustitución de materia prima virgen para la obtención de diferentes tipos de papel y cartón. Así mismo, existe un especial interés hacia las materias primas y procesos alternativos de fabricación de pulpa de celulosa, los cuales generan menores impactos ambientales, en comparación con las materias primas y los procesos tradicionalmente empleados.
Como parte de estas fuentes alternativas de pulpa de celulosa para la obtención de papel y cartón, se han utilizado residuos agrícolas y agroindustriales. Entre estos residuos se encuentran el bagazo de caña de azúcar, la cascarilla de arroz, el papel reciclado, entre otros. En particular, el papel y el cartón obtenidos a partir de estas materias primas alternativas, son empleados en la elaboración de empaques.
En el estado de la técnica, se ha reportado la fabricación de materiales biodegradables para envasado, que son compatibles con el medio ambiente y son producidos a partir de mezclas que comprenden residuos fibrosos reciclados.
Por ejemplo la solicitud de patente US2003213573 (Al), propone un envase a partir de cascara de arroz, de trigo, polvo de madera, polvo de leche y arcilla, como empaque secundario para alimentos. Este envase está formado a partir de la aglomeración del material reciclado, el cual es fluidizado, prensado, secado y revestido con cola hasta obtener un material de envasado impermeable e higiénico.
La patente CN103571166 (A), se menciona un material compuesto de polipropileno carbonato (PPC), celulosa o celulosa microcristalina, un agente lubricante, un antioxidante, un estabilizador de calor, un plastificante y un agente de promoción de la biodegradacion. Este documento también propone un método de preparación del material compuesto mediante la granulación por extrusión y posterior prensado en caliente.
Por su parte, la solicitud DE3937168 (Al), describe un material para embalaje alimenticio a base de celulosa, conchas, salvado, cascarilla, aristas de cebada, fibras, pasó lúpulo, paja finamente molida, aserrín y material de origen animal, subproducto de mataderos. Se aplica a la superficie de envasado un recubrimiento impermeable al agua. El material de envasado contiene 30-50% de un material de tipo celulósico y 30- 70% de un almidón y/o material proteínico, proporcionando un material de embalaje biodegradable.
La patente CN102712409(A), describe la fabricación de cartón biodegradable reforzado a partir de almidón y fibras de celulosa provenientes de residuos de papel reciclado. Este documento divulga el uso de una cáscara exterior dura y un interior espumado, y un refuerzo que se logra por medio de un multilaminado o estructura corrugada mediante un proceso de extrusión.
Sin embargo, no existe aún en el campo de la técnica un material compuesto fabricado a partir de celulosa proveniente de la cascarilla de café o de cacao, que pueda ser empleado en el envasado de alimentos, materiales médicos, plásticos de ingeniería y similares. Adicionalmente, no existe en el estado de la técnica un material fabricado a partir de fuentes alternativas de pulpa de celulosa, que presente resistencia a la flexión incrementada en comparación con la resistencia a la flexión de materiales ampliamente empleados como el PPC.
Adicionalmente, vale la pena tener en cuenta que en el estado de la técnica también se han reportados artículos biodegradables para ser utilizados en empaques de alimentos, los cuales son fabricados con múltiples capas o láminas. A continuación se mencionan algunos documentos del arte previo referentes a este tipo de invenciones.
La solicitud de patente CN202115856 (U), divulga un vaso desechable de papel fabricado por capas. Estas capas se encuentran estructuradas de la siguiente manera: poliuretano laminar (capa interior), capa de sujeción de papel, una capa de tinta de impresión y una capa superficial de laminado PE. La capa superficial de laminado PE se utiliza para cubrir la capa de tinta de impresión, de modo que la tinta de impresión está aislada del exterior. Así, un consumidor no entra en contacto directo con la tinta de impresión cuando se utiliza el vaso desechable de papel.
Por su parte, la solicitud EP05781356A1 , menciona una lámina compuesta por varias capas fabricadas a partir de resina termoplástica de ácido poliglicólico, laminadas con adhesivos acuosos con posibilidad de uso en empaques y almacenamiento de alimentos.
La patente WO1999035049, describe un recipiente desechable biodegradable, para alimentos o medicamentos, fabricado a partir de residuos de frijol, fibras y plantas y un adhesivo de carboximetil celulosa, almidón y agua. Estos elementos son mezclados,
prensados en un molde y se secados para depositar una fina capa de cera en la superficie del recipiente.
Sin embargo, no existe aún en el arte previo un material laminado para ser empleado en empaques, fabricado a partir de la celulosa obtenida de la cascarilla de café o cacao.
Además, otras invenciones previamente reportadas en el estado de la técnica se encuentran relacionadas con la emisión de olores aromáticos, como por ejemplo la patente CN103054421(A). Este documento describe un dispositivo tipo cápsula o ampolleta, colocado en la parte inferior de un vaso desechable de papel, que al entrar en contacto con bebidas calientes se activa, permitiendo la difusión tanto del aroma como del sabor a té.
Sin embargo, no existe en el arte previo un artículo que permita la liberación de aromas de café o cacao que adicionalmente esté fabricado a partir de celulosa proveniente de la cascarilla de café o cacao.
De manera que a diferencia del arte previo, la presente invención se refiere a un material compuesto, fabricado a partir de celulosa proveniente de cascarilla de café o cacao, para la fabricación de un artículo laminado para la elaboración de contenedores o empaques. Así, la presente invención proporciona una fuente alternativa de pulpa de celulosa nunca antes empleada, mediante la cual se logran desarrollar materiales con resistencias a la flexión mejoradas, que permiten la fabricación de láminas compuestas de celulosa proveniente de material de desecho para la posterior elaboración de empaques o recipientes, biodegradables y compostables, con emanación controlada de aroma de café y cacao.
3. DESCRIPCIÓN GENERAL DE LA INVENCIÓN
Las cascarillas de café y cacao son materiales lignocelulósicos, de residuo agroindustrial. Estas cascarillas son una fuente importante de fibra de celulosa. La presente invención emplea este tipo de residuos como materia prima alternativa para la fabricación de pulpa de celulosa. Esta pulpa puede ser empleada para la obtención de papel, cartulina y/o cartón. Adicionalmente, la invención divulga un material compuesto fabricado a partir de esta pulpa de celulosa, que tiene una funcionalidad de liberación de aromas. Además, la presente invención se refiere a un artículo laminado fabricado a partir del material compuesto, el cual puede ser empleado para la elaboración de empaques o contenedores. El material compuesto puede ser empleado tanto en la fabricación de empaques primarios, como en la elaboración de empaques secundarios y/o terciarios.
La presente invención también se refiere al método que incluye la obtención de la pulpa de celulosa a partir de la cascarilla de café o cacao (por el método "kraft") y la posterior adición de un material que permite la liberación controlada de aromas.
4. BREVE DESCRIPCIÓN DE LAS FIGURAS
Figura 1 - Ilustra el artículo laminado fabricado a partir del material compuesto obtenido a partir de cascarilla de café o cacao.
Figura 2 - Ilustra un recipiente que puede ser elaborado mediante el artículo laminado.
5. DESCRIPCIÓN DETALLADA DE LA INVENCIÓN
En primer lugar, la presente invención se refiere a la extracción de celulosa de residuos de cascarilla de café o de cascarilla de cacao. La obtención de celulosa puede llevarse a
cabo por medio de un proceso químico. Este método consiste en dos fases, la primera es introducir los residuos en un recipiente hermético donde se somete a vapor sobrecalentado a una presión entre 1500 a 2500 psi (10343 a 17237 kPa), durante dos horas, para retirar lignina y lograr una separación inicial de las fibras. La segunda fase es realizar la cocción de los residuos en un recipiente a presión controlada entre 1000 a 2000 psi (6895 a 13790 kPa), con temperatura entre 200 a 250°C, en una solución alcalina basada en hidróxido de sodio (NaOH) y sulfuro de sodio (Na2S). Este proceso permite la extracción de la lignina presente en la cascarilla de café y cacao. Posteriormente, se realiza una separación de los gases a base de sulfuro y un filtrado, para realizar una separación de los residuos que no se degradaron en el proceso. Como resultado de este proceso se obtiene una pasta de celulosa, la cual es clasificada, lavada y blanqueada en diferentes proporciones. Finalmente se seca la pasta obtenida.
A esta pasta de celulosa se le adiciona el material que permite la liberación controlada de aromas. Esta mezcla puede ser realizada mediante extrusión, mezclado mecánico o en solución, generando el material compuesto final.
El material que permite la liberación controlada de aromas puede ser obtenido mediante el encapsulamiento de un compuesto aromático de café o cacao, que se lleva a cabo mediante la dispersión del compuesto aromático (agente activo) en un agente encapsulante, entre los cuales pueden estar goma cashew, goma arábica, goma de mezquite, maltodextrina, quitosano. Esta dispersión se lleva a cabo mediante métodos físicos como: secado por aspersión, extrusión y recubrimiento por aspersión. Igualmente, se pueden emplear métodos químicos como coacervación simple, coacervación compleja y atrapamiento en liposomas. También es posible emplear métodos físico-químicos como polimerización interfacial e inclusión molecular. Lo anterior permite controlar la volatilidad y reactividad del agente activo, incrementando su estabilidad para lograr una mayor duración del aroma en el material compuesto.
El material compuesto de la presente invención puede ser empleado en la elaboración de empaques primaros, secundarios y terciarios.
Se entiende por empaque primario aquel empaque que está directamente en contacto con el producto; contiene el producto y además lo protege. El empaque primario puede recubrir el producto por entero o solo parcialmente, pero previene la modificación del contenido sin abrir o modificar dicho envase. Algunos ejemplos de empaques primarios son las bolsas plásticas, botellas, sistema tetra-brick, enlatados y frascos entre otros. Los empaques primarios deben contener datos fundamentales en los que se incluyen el nombre del producto, marca, peso, variedad, productor y país de origen. Asimismo, los empaques primarios deben incluir la fecha de producción y la de vencimiento. Algunos productos advierten acerca de su grado de toxicidad, forma de manipulación y condiciones de almacenamiento. Los empaques primarios pueden también comprender un UPC, sigla en inglés de Universal Product Code o Código Universal de Productos. En el medio es conocido como el Código de Barras, que se traduce en una serie de dígitos que presentan información acerca del productor y del producto como tal.
El empaque secundario es un complemento externo que agrupa varias muestras de empaques primarios, su función es resguardarlo en cantidades que simplifiquen su distribución, almacenamiento e inventario. Dentro del segundo nivel se encuentran las cajas de cartón, guacales (crates), canastas, bandejas y cajas agujereadas (lugs), entre otros. Éstas deben contener ordenadamente las unidades. Las cajas deben ir debidamente marcadas indicando la cantidad de unidades, su resistencia máxima al momento de apilarlas, la marca del producto y sus características básicas.
El empaque terciario de embalaje o transporte se utiliza con el fin de integrar cantidades uniformes del producto, ya dispuesto en empaques secundarios. Entre los empaques terciarios más utilizados se encuentran las tolvas, guacales alambrados o clavados, tarimas, canastas y contenedores entre otros. Dentro de los grandes
contenedores de embarque se agregan divisores o tabiques de cartón o plástico, con el fin de dividir y asegurar la mercancía. La carga es provista previamente de refuerzos a los costados y en los extremos para aumentar su resistencia a la compresión.
Con el material compuesto, que comprende pulpa de celulosa obtenida a partir de cascarilla de café o cacao y el material que permite la liberación controlada de aromas, es posible obtener un artículo laminado para la elaboración de empaques primarios, secundarios o terciarios. Este artículo laminado cuenta con tres capas hechas de material compuesto y se encuentra ilustrado en la Figura 1. La diferencia entre las capas radica en el porcentaje en peso de biopolímero biodegradable con material celulósico (cantidad de pulpa de celulosa) que comprende el material compuesto con el que cada una de las capas es elaborada. La unión de las diferentes capas, se obtiene al hacer pasar las diferentes capas por rodillos a una presión, velocidad y temperatura controlada. Esta laminación se puede dar incorporando adhesivos, los cuales pueden ser secos o en emulsión, o por métodos térmicos donde se aplica calor para el sellado de las diferentes capas.
A continuación, se relacionan las características de cada una de las capas que componen al artículo laminado:
• Capa externa (1), que comprende hasta un 100% en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o cacao. Este alto contenido de biopolímero biodegradable proveniente de la cascarilla de café o cacao permite la impresión sobre la capa externa.
• Capa intermedia (2), que comprende entre 5% y 10% en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o cacao. Esta capa intermedia cuenta con estabilidad mecánica.
• Capa interna (3), la cual comprende entre 2% y 5% en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o
cacao. Esta capa actúa como barrera a líquidos, es inocuo para permitir el contacto con bebidas y alimentos.
En una modalidad preferida de la invención, la capa externa (1) del artículo laminado comprende hasta un 100 % en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o cacao.
Así, el artículo laminado permite la impresión de información sobre el empaque, el cual es de suma importancia en su aplicación comercial como se ha explicado anteriormente. Además, al comprender altas proporciones de componentes biodegradables (celulosa obtenida a partir de la cascarilla de café o cacao), el artículo puede ser compostado después de su utilización, reduciendo los residuos sólidos asociados a este tipo de empaques, ya sean primarios, secundarios o terciarios. Adicionalmente, este artículo puede liberar aromas.
El material compuesto tiene una resistencia a la flexión mejorada. Particularmente, la resistencia a la flexión del material compuesto de la presente invención se incrementa entre 2 a 38 veces en comparación con la resistencia a la flexión de la PPC. También presenta una densidad entre 0.4 y 0.8 g/cm3, un índice de tensión entre 300 a 600 Nm/g, un índice de rasgado con rango de 200 a 300 mNm2/g, índice de explosión y rendimiento del orden 40 a 60 %.
El material lignocelulósico obtenido a partir de las cascarillas de café y cacao bajo el procedentito anteriormente descrito, puede ser también utilizado para la obtención de papel, cartulina y cartón. La diferencia entre estos productos radica en el gramaje. El papel tiene un gramaje de hasta 130 g/m2, la cartulina un gramaje entre 130 a 240 g/m2 y el cartón compacto un gramaje de más de 240 g/m2.
EJEMPLOS
Ejemplo 1 - Fabricación de un vaso a partir del artículo laminado de la presente invención.
Se obtuvo un vaso (empaque primario), con liberación de aroma, compuesto por el artículo laminado obtenido a partir de celulosa de cascarilla de café o cacao. Este vaso se ilustra en la Figura 2. El mismo cuenta con (1) capa externa, (2) capa intermedia, (3) capa interna, con un gramaje entre (18 a 250) g/m2, un calibre de 180 Um. Sus propiedades específicas se reportan a continuación:
Ejemplo 2 - Fabricación de cartulina, cartón y cartón corrugado de la presente invención.
Utilizando el método de la presente invención, bajo el proceso de compresión, aplicando una presión y temperatura controlada, se obtiene un material formado por varias capas superpuestas, del material biodegradable y compostable, con un gramaje de 100 y 800 g/m2 en adelante, del cual se obtienen cartulina, cartón y cartón corrugado.
Claims
1. Un método para la obtención de un material compuesto de celulosa proveniente de cascarilla de café o cacao, caracterizado porque comprende los pasos de:
a. Someter a vapor sobrecalentado residuos de cascarilla de café o cacao;
b. Cocer los residuos de cascarilla de café o cacao en una solución alcalina basada en hidróxido de sodio (NaOH) y sulfuro de sodio (Na2S), obteniendo una pasta de celulosa;
c. Separar los residuos que no fueron degradados mediante separación de gases a base de sulfuro y filtrado;
d. Clasificar, lavar, blanquear y secar la pasta de celulosa obtenida en el paso b);
e. Obtener un material que permite la liberación controlada de aromas;
f. Mezclar el material que permite la liberación controlada de aromas con la pasta de celulosa obtenida en el paso b).
2. El método de la reivindicación 1, caracterizado porque el paso a) se lleva a cabo a una presión entre 10343 a 17237 kPa, durante 2 horas.
3. El método de la reivindicación 1, caracterizado porque el paso b) se lleva a cabo a una presión de entre 6895 a 13790 kPa y a una temperatura de entre 200 a 250°C.
4. El método de la reivindicación 1, caracterizado porque la obtención de un material que permite la liberación controlada de aromas en el paso e), se lleva a cabo dispersando el compuesto aromático de café o cacao, en un agente encapsulante, mediante métodos mecánicos o químicos.
Un artículo laminado caracterizado porque comprende una lámina externa (1), una lámina intermedia (2) y una lámina interna (3), dichas láminas están elaboradas a partir del material compuesto de cascarilla de café o cacao y de un material que permite la liberación controlada de aromas, obtenido mediante el método de la reivindicación 1, en donde:
la lámina externa (1) comprende hasta un 100% en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o cacao;
la capa intermedia (2), comprende entre 5% y 10% en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o cacao; y
la capa interna (3), comprende entre 2% y 5% en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o cacao.
El artículo laminado de la reivindicación 5, en donde la lámina externa (1) comprende entre 70% y 90% en peso de biopolímero biodegradable con material celulósico obtenido a partir de cascarilla de café o cacao.
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WO2020167807A1 (en) * | 2019-02-11 | 2020-08-20 | Schweitzer-Mauduit International, Inc. | Cocoa wrapper for smoking articles |
FR3109091A1 (fr) * | 2020-04-11 | 2021-10-15 | Miral | Diffuseur de parfum |
WO2021260429A1 (en) * | 2020-06-26 | 2021-12-30 | Kraft Foods Schweiz Holding Gmbh | Biodegradable boards and methods of making the same |
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US20230145256A1 (en) * | 2020-04-01 | 2023-05-11 | Novadelta - Comércio E Indústria De Cafés, Lda | Confinements of composite materials including affinity of substances |
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