WO2011123320A2 - Filtre à cigarette biodégradable et procédés de fabrication associés - Google Patents

Filtre à cigarette biodégradable et procédés de fabrication associés Download PDF

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Publication number
WO2011123320A2
WO2011123320A2 PCT/US2011/029739 US2011029739W WO2011123320A2 WO 2011123320 A2 WO2011123320 A2 WO 2011123320A2 US 2011029739 W US2011029739 W US 2011029739W WO 2011123320 A2 WO2011123320 A2 WO 2011123320A2
Authority
WO
WIPO (PCT)
Prior art keywords
filter
seeds
mixture
biodegradable
paper
Prior art date
Application number
PCT/US2011/029739
Other languages
English (en)
Other versions
WO2011123320A3 (fr
Inventor
Tadas Lisauskas
Xavier Alexander Van Osten
Original Assignee
Greenbutts Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Greenbutts Llc filed Critical Greenbutts Llc
Priority to US13/581,851 priority Critical patent/US20120318286A1/en
Publication of WO2011123320A2 publication Critical patent/WO2011123320A2/fr
Publication of WO2011123320A3 publication Critical patent/WO2011123320A3/fr

Links

Classifications

    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/067Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068Biodegradable or disintegrable
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/08Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A24D3/10Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives

Definitions

  • the present invention relates generally to a biodegradable cigarette filter and more specifically, to a non-synthetic, natural cigarette filter which contains seeds.
  • a filter has a filter tow made from plasticized cellulose acetate and can also include polyhydric alcohols, and the tow is wrapped with an inner and outer layer of cigarette paper.
  • the inner layer is known as the plug wrap and the outer wrapping layer is known as the tipping paper.
  • the description of cigarettes and the various components thereof are set forth in Tobacco Production, Chemistry and Technology, Davis et al. (Eds.) (1999).
  • a cigarette is smoked by a consumer lighting one end and burning the tobacco rod end of the cigarette, opposite from the filter. The smoker then receives mainstream smoke into his mouth by drawing the tobacco smoke through the filter on the opposite end of the cigarette.
  • Certain cigarettes incorporate filter elements having absorbent materials dispersed therein, such as activated carbon or charcoal materials in particulate or granular form.
  • a cigarette filter can possess multiple segments, and at least one of those segments can comprise particles of high carbon-content materials.
  • filters incorporating charcoal particles or activated carbon types of materials are set forth in U.S. Pat. No. 2,881,770 to Touey: U.S. Pat. No. 3,101723 to Seligman et al; U.S. Pat. No. 3,236,244 to Irby et al; U.S. Pat. No. 3,311,519 to Touey et al; U.S. Pat. No. 3,347,247 to Lloyd; U.S.
  • Granules of carbonaceous material can be incorporated into the filter via "dalmation" types of filter regions using the general types of techniques used for traditional dalmation filter manufacture.
  • Prior art has included granules of carbonaceous material that is incorporated into “cavity” types of filter regions using known techniques for producing "cavity” filter manufacture.
  • many techniques, well known in the art are often rudimentary in that particulates or granules of carbonaceous material roughly inserted into the filter element as either a loose powder or a slurry, a process which is often inconsistent and inefficient.
  • cellulose acetate is known and widely used in cigarette filter material.
  • such material is only biodegradable in certain chemical forms, such as in the acetic acid ester form of cellulose. In most forms the biodegradability of cellulose acetate remains relatively low. Further, the biodegradation character of cellulose acetate is most often dependent on the degree of substitution, or the number of acetyl groups per glucose unit of the cellulose acetate molecular structure. For example, if the degree of substitution of cellulose acetate is decreased, the biodegradation rate of cellulose acetate is increased.
  • Patent 6,739,344 describes a biodegradable cellulose acetate filter, which purports to provide excellent biodegradability which includes a "biodegradation promoting agent".
  • the invention describes a cellulose acetate structure comprising at least one compound selected from the group consisting of a salt of an oxygen acid of phosphorus, an ester of an oxygen acid of phosphorus or a salt thereof, carbonic acid and a salt thereof.
  • U.S. Patent No. 6,062,228 discloses biodegradable filter material and method for its manufacture. Specifically, the patent describes a biodegradable filter tow or filter material prepared from renewable raw materials for use as a tobacco filter element of cigarettes. Further, it describes a method of preparing such a filter wherein fibers, films or foams are prepared in an extrusion method from biopolymer based on thermoplastic starch.
  • such methods require an inordinate up front expense in manufacturing costs with methods of preparation often complex and require significant chemical intermediates for production.
  • such methods also do not address the issue of introduction of complex chemical compounds into the environment which leads to pollution.
  • a biodegradable cigarette filter which contains seeds and which comprises a filter tow with at least one layer of filter wrapper paper surrounding the tow.
  • the seeds may be located in the filter tow, in the wrapper paper, or both.
  • the filter may have two separate wrapper layers, comprising an inner layer or plug wrap paper and an outer layer or tipping paper of filter wrapper paper.
  • the seeds are located in both the filter tow and one or both layers of filter wrapper paper surrounding the filter tow. The seeds allow germination of plants when the filter is discarded into a soil medium.
  • the tow may comprise a mixture consisting of hemp, cotton or paper, and a bonding agent.
  • the filter utilizes a starch solution of flour and water which act as a thickening and bonding agent, while the mixture of hemp and cotton or paper act as a filtering matrix for the cigarette smoke when consumed by a user.
  • one or both filter wrapper layers are of biodegradable non-acetate paper embedded with plantable seeds on the outer surface, inner surface, or both, or seeds may be located between the paper layers.
  • the cigarette filter is 100% biodegradable and non-synthetic, with no chemical additives.
  • the seeds embedded in the filter can grow to produce various plants, depending on which seeds are embedded.
  • Seeds located within the filter tow break the filter apart, thus accelerating degradation from the inside.
  • Seeds located within the filter tow can be of a larger diameter than those used within the inner and outer layers of filter wrapper paper, when seeds are located throughout the entire filter. Seeds located within one or both filter wrapper layers break the filter plug wrap and tipping paper apart which then releases the filter tow within, accelerating degradation from an outside in approach. Seeds located within the tipping paper and plug wrap are located outside of the smoke column. Types of seed located within or between the plug wrap and tipping paper layers include smaller diameter seeds or varieties that would be damaged by direct interaction with smoke, impede smoke draw through the filter, or alter smoke taste.
  • the cigarette filter is of a non-synthetic, bio-degradable material that decreases the global environmental impact of the carbon "footprint" of cigarettes, and may assist in providing germination of plants in the environment, further promoting carbon sequestration.
  • This cigarette filter biodegrades at a faster rate and can help to reduce the prevalent problem of litter created by known synthetic, non-biodegradable cigarette filters in the environment.
  • FIG. 1 is perspective cross-sectional view of a cigarette including a first embodiment of a biodegradable cigarette filter
  • FIG. 1A is a cutaway view of part of the filter of FIG. 1 illustrating a modified filter with two wrapper layers;
  • FIG. 2 is a longitudinal cross-sectional view of the cigarette of FIG. 1 including the biodegradable cigarette filter;
  • FIG. 3 is a cross-sectional view on the lines 3-3 of FIG. 2.
  • Embodiments described herein provide a biodegradable filter for cigarettes that significantly decreases the amount of litter and pollution in the environment due to the brief period of time required for the filters to break down and decompose, as well a method of manufacture for producing the filters. Embodiments described herein further provide a filter that, when discarded, acts to germinate plants into the environment into which it is discarded.
  • FIGS. 1 to 3 illustrate a cigarette 20 incorporating a first embodiment of a filter 10 at one end.
  • the remainder of the cigarette contains cigarette tobacco 2 surrounded by an elongated cylindrical tube 1 of cigarette paper.
  • the filter 10 is adhered to the remainder of the cigarette and comprises two parts, specifically an interior filter body or filter tow 3 of filter material and one or more outer wrapper layers 4.
  • the filter material 3 includes a number of ingredients including a biodegradable and compostable combination of hemp, cotton and/or paper fibers bound together with a starch solution.
  • wrapper layers 4 comprise an inner wrapper layer or plug wrap 4A and an outer wrapper layer or tipping paper 4B.
  • the paper is wrapped around the hemp/cotton material 3 and glued along the longitudinal seam 8 using any appropriate liquid starch adhesive.
  • the filter has recessed ends 7.
  • one or both outer wrapper layers 4 contain small diameter plantable seeds 6 in one embodiment of the filter.
  • the seeds may be provided on the outer surface, the inner surface, or both, or may be located between the wrapper layers.
  • the filter may have a single outer wrapper layer which optionally contains seeds.
  • the filter tow 3 also contains larger diameter plantable seeds 5 which are encapsulated within the interior of the filter tow, as illustrated in FIGS. 1 to 3.
  • Seeds 5 can be of any variety appropriate for containment in the filter. However, inclusion of seeds in the filter tow 3 is optional, and seeds 5 may be eliminated in alternative embodiments, with seeds 6 provided in one or both outer wrapper layers 4 only.
  • the filter tow 3 comprises a mixture of hemp and a second fibrous material such as cotton or paper, and a binding agent.
  • the ratio of the ingredients in the filter tow can be changed to accommodate less or more filtering of the cigarette smoke.
  • a ratio of 25 to 75% hemp/75% to 25% cotton or paper fiber is used to prepare the filter tow.
  • a mixture of flour and water is used in the production process as a binding and thickening agent to provide pliability, as described in more detail below.
  • the size and shape of the filter body or filter tow may be the same as a standard cigarette filter as to accommodate current cigarette specifications and existing manufacturing processes.
  • the filter tow is produced from a mixture of de-gummed hemp with cotton or paper and flour and water as the binding and thickening agent. Any appropriate liquid starch as known in the art can be used in lieu of the flour and water mixture.
  • 25 to 75% de-gummed hemp is placed into a blending apparatus. Thereafter, 25 to 75% cotton or paper is added and blended with the hemp until the mixture of fibers appears to be uniform.
  • cotton or paper, or both cotton and paper are mixed with the hemp. After blending, 0.25 to 2.5 teaspoons of flour is added to 1 to 4 cups of water and thoroughly mixed. After mixing, the hemp based mixture is immersed into the flour/water mixture.
  • a starch-based mixture may be employed in place of the flour/water mixture.
  • a ratio of 0.1 to 1 cup cornstarch or cornstarch- like product is added to every 0.5 to 2 cups of water, followed by mixing. While continuing to mix the solution, 0.5 to 5 cups of 100 degrees Celsius or higher water is added.
  • Other starch based mixtures as known in the art may be employed.
  • the water is removed. While the blended mixture is damp, seeds are added and the material is once again placed in a blending device or a device used in the production of non-woven fabrics, such as a hydro entangler, until the material is relatively uniform.
  • the material is removed and allowed to dry in a ventilated area. Seeds may also be added to the mixture during the drying process as needed. Without using a heat source, approximately 24-48 hours is allowed for complete drying depending on drying conditions and humidity.
  • the blended filter material is set on an assembly line with a constant and uniform heat source, reducing the time to dry the mix. The steps are repeated to form a stack of sheets or a continuous roll of filter tow. The aforementioned process is adaptable to mass production scale and such processes are encompassed within the scope of the invention
  • a simpler method of manufacture may be employed eliminating the process of blending the hemp based mixture before adding the starch solution.
  • the specified ratio of hemp with cotton, paper, or both cotton and paper, along with a starch solution is placed into a blending apparatus or a device used in the production of nonwoven fabrics such as a hydro entangler and blended until mixture appears uniform.
  • the material is blended with the addition of seeds, the material is removed and allowed to dry in a ventilated area. Seeds may also be added to the mixture during the drying process as needed. Without using a heat source, approximately 24-48 hours is allowed for complete drying depending on drying conditions and humidity.
  • the blended filter material is set on an assembly line with a constant and uniform heat source, reducing the time to dry the mix. The steps are repeated to form a stack of sheets or a continuous roll of filter tow.
  • the aforementioned process is adaptable to mass production scale and such processes are encompassed within the scope of the invention.
  • the dry hemp and cotton and/or paper blend filter tow in sheets or continuous roll form, is compacted into or extruded through a cylinder shaped form or die to form a filter rod.
  • the filter rods are then cut into individual filters which are each the length of a typical cigarette filter.
  • Filter tipping paper or plug wrap is made of a biodegradable material such as, for example, wood pulp with the option of plantable seeds imbedded into the paper during the paper making process.
  • the hemp-based filter tow is wrapped in the tipping paper and plug wrap and is recessed from both the mouth or smoking end and the opposite end, as seen in Fig. 1 and 2.
  • the tipping paper and plug wrap seams are glued using a liquid starch or other adhesive materials as are known in the art.
  • the outer tipping paper and plug wrap surrounding the filter tow are each comprised of a biodegradable non-acetate paper and act both to contain the filter tow and attach to the cigarette.
  • Various seeds including grass seeds, flower seeds and even fruit and vegetable seeds may be embedded into the filter tow as well as in within the tipping paper/plug wrap 6.
  • seeds may be provided only in the filter tow 3, in one or both of the wrapper layers 6, or between the wrapper layers.
  • Methods for producing paper embedded with plantable seeds are known in the art. Briefly, the paper is made by first placing wood shavings in a blending instrument and filling with heated water. The material is blended with increasing blending speed until the pulp appears smooth and uniform. A basin is filled with water with the pulp added therein. Seeds may be added to the solution and the contents of the basin are mixed. A mold is then utilized to remove the paper pulp from the water.
  • the filter tow is made into the shape of a standard cigarette filter.
  • the tipping paper/plug wrap is wrapped around the filter tow to encapsulate the filter tow with both ends of the filter tow recessed from the respective ends of the paper wrapper and exposed at either end.
  • One end is attached to the cigarette body 1 , 2 and the other is used to intake smoke by the smoker.
  • This filter performs the same function as a standard cigarette filter but lacks the chemical toxins used in the existing process and the unpleasant taste ordinarily produced by standard cigarette filters.
  • hemp fiber is mixed with cotton or paper fiber, or both, in a blending device until the fibers are uniformly mixed to form a hemp-based mixture.
  • Flour is added to water in a ratio of one part flour to ten to forty parts water, followed by mixing to form a flour/water mixture.
  • the hemp-based mixture is then immersed into the flour/water mixture, followed by removal of the water from the hemp- based mixture by wringing, spinning, ventilating, or heating.
  • the hemp-based mixture is combined with plantable seeds and then placed in a blending device or a device used in the production of non-woven fabrics, such as a hydroentangler, until the material is relatively uniform.
  • the hemp-based mixture is removed and allowed to dry.
  • the mixture is laid into molds for creating stacks of sheet filter tow, or onto a moving belt or production line to form large continuous rolls of filter tow.
  • the sheet filter tow is extruded or drawn through a die to form an extrudate.
  • the extrudate then called a filter rod, is wrapped with one or two layers of a non-acetate paper to form a single filter element, which is cut to appropriate size.
  • the filter described above can be produced and configured to fit larger smoking devices such as cigars, hookah hoses, or any number of smoking devices as known in the art.
  • the stand-alone filter tow may also be used in a roll-your-own cigarette device as a simple, bullet-shaped insert.
  • flour refers to either white or wheat flour as is known in the art.
  • the term also includes flour generated from sources other than wheat such as, for example, corn, soy or the like.
  • starch refers to a naturally abundant nutrient carbohydrate, found chiefly in the seeds, fruits, tubers, roots, and stem pith of plants, notably in corn, potatoes, wheat, and rice, and varying widely in appearance according to source but commonly prepared as a white amorphous tasteless powder.
  • hemp refers to soft, durable fiber that is cultivated from plants of the Cannabis genus, cultivated for industrial and commercial (non-drug) use.
  • Examples of modern industrial use of hemp include production of paper, textiles, and biodegradable plastics, used in construction, health food, fuel and in the medical industry.
  • Advantages of the present invention over the known art include the ability to provide a cigarette filter that is biodegradable and hence, does not harm the environment.
  • the invention also provides a method of manufacturing free of the complex and often harmful chemical components of standard cigarette filters. Further, the present invention capitalizes on the harmful impact of cigarette butt littering by providing the user a filter containing seeds that will grow in whatever location it is discarded.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
  • Paper (AREA)
  • Nonwoven Fabrics (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

La présente invention concerne un filtre à cigarette biodégradable qui comporte une mèche de filtre entourée par une ou plusieurs couches d'emballage. La mèche de filtre est un mélange de chanvre, un second matériau fibreux qui comprend du coton, du papier, ou un mélange de coton et de papier, et un agent épaississant et liant qui comprend de la farine ou de l'amidon ajouté initialement au mélange sous forme de solution dans de l'eau. Le mélange de chanvre et du second matériau fibreux dans la mèche de filtre sert de matrice de filtrage pour la fumée de cigarette lorsqu'elle est consommée par un utilisateur. Dans un exemple, deux couches d'emballage, y compris un papier pour filtre et un papier de manchette, entourent la mèche de filtre. La mèche de filtre ou une ou les deux couches d'emballage, ou la mèche ainsi que les couches d'emballage, peuvent contenir des graines qui peuvent être plantées.
PCT/US2011/029739 2010-03-31 2011-03-24 Filtre à cigarette biodégradable et procédés de fabrication associés WO2011123320A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/581,851 US20120318286A1 (en) 2010-03-31 2011-03-24 Biodegradable cigarette filter and methods for making same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31953710P 2010-03-31 2010-03-31
US61/319,537 2010-03-31

Publications (2)

Publication Number Publication Date
WO2011123320A2 true WO2011123320A2 (fr) 2011-10-06
WO2011123320A3 WO2011123320A3 (fr) 2012-02-02

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WO (1) WO2011123320A2 (fr)

Cited By (7)

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CN102657382A (zh) * 2012-04-27 2012-09-12 云南烟草科学研究院 一种卷烟嘴棒
EP2712510A1 (fr) * 2012-09-28 2014-04-02 Reemtsma Cigarettenfabriken GmbH Article à fumer
RU2575068C1 (ru) * 2011-12-09 2016-02-10 Джапан Тобакко Инк. Курительное изделие и фильтр
CN105942579A (zh) * 2016-06-16 2016-09-21 湖南中烟工业有限责任公司 一种含有植物种子的卷烟滤嘴及其制备方法
WO2018006148A1 (fr) * 2016-07-05 2018-01-11 Amaral Deyse Suellem Felipe Capsule jetable et procédé de culture de plantes
CN111205494A (zh) * 2020-03-04 2020-05-29 昆明理工大学 一种烟秆再生纤维素抗菌膜的制备方法及应用
WO2020155337A1 (fr) * 2019-02-01 2020-08-06 福建绿色黄金生物科技有限公司 Pointe de filtre et produit de tabac

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US10076135B2 (en) 2014-05-23 2018-09-18 Greenbutts Llc Biodegradable cigarette filter tow and method of manufacture
US10724224B2 (en) 2016-03-31 2020-07-28 Frog Creek Partners, LLC Storm drain grate and filter apparatus and method
US10334839B2 (en) 2016-03-31 2019-07-02 Frog Creek Partners, LLC Removable catch basin filter insert and lifting apparatus
WO2018132693A1 (fr) 2017-01-16 2018-07-19 Diem, Llc Élément de filtre magnétique flexible non linéaire
CA2999135A1 (fr) * 2017-03-24 2018-09-24 David Cappelucci Appareil de fumage
WO2019018196A1 (fr) 2017-07-17 2019-01-24 Freelander Innovations USA, LLC Emballage biodégradable pour cartouches
AU2020221789A1 (en) 2019-02-11 2021-08-19 Swm Luxembourg Filler containing blends of aerosol generating materials
US11388925B2 (en) 2019-02-11 2022-07-19 Schweitzer-Mauduit International, Inc. Cannabis wrapper for smoking articles
JP2022520187A (ja) 2019-02-11 2022-03-29 エスダブリュエム ルクセンブルク 喫煙物品用のカカオ包装材料
AU2020221787A1 (en) 2019-02-11 2021-08-26 Swm Luxembourg Reconstituted cannabis material for generating aerosols
DE202019001738U1 (de) 2019-04-18 2019-05-14 Wintersun Co., Ltd Zigarette mit einem aus Polylactid (PLA) aufgebauten Zigaretten-Filter
CN110279145A (zh) * 2019-06-14 2019-09-27 广东精彩国际生物科技有限公司 一种封堵装置以及封堵工艺
WO2023083719A1 (fr) * 2021-11-11 2023-05-19 Philip Morris Products S.A. Article de génération d'aérosol comprenant une cavité avec des graines de plante susceptibles de germer
WO2023149875A1 (fr) * 2022-02-03 2023-08-10 Attilio Tebano Filtre de cigarette en cire naturelle

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US20040003822A1 (en) * 2002-03-26 2004-01-08 Godfrey Phillips India Limited Biodegradable dual density filter cigarette
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2575068C1 (ru) * 2011-12-09 2016-02-10 Джапан Тобакко Инк. Курительное изделие и фильтр
CN102657382A (zh) * 2012-04-27 2012-09-12 云南烟草科学研究院 一种卷烟嘴棒
EP2712510A1 (fr) * 2012-09-28 2014-04-02 Reemtsma Cigarettenfabriken GmbH Article à fumer
WO2014048533A1 (fr) * 2012-09-28 2014-04-03 Reemtsma Cigarettenfabriken Gmbh Article à fumer
CN105942579A (zh) * 2016-06-16 2016-09-21 湖南中烟工业有限责任公司 一种含有植物种子的卷烟滤嘴及其制备方法
WO2018006148A1 (fr) * 2016-07-05 2018-01-11 Amaral Deyse Suellem Felipe Capsule jetable et procédé de culture de plantes
WO2020155337A1 (fr) * 2019-02-01 2020-08-06 福建绿色黄金生物科技有限公司 Pointe de filtre et produit de tabac
CN111205494A (zh) * 2020-03-04 2020-05-29 昆明理工大学 一种烟秆再生纤维素抗菌膜的制备方法及应用

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US20120318286A1 (en) 2012-12-20

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