WO2017124992A1 - 烟气过滤装置和烟草制品 - Google Patents

烟气过滤装置和烟草制品 Download PDF

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Publication number
WO2017124992A1
WO2017124992A1 PCT/CN2017/071331 CN2017071331W WO2017124992A1 WO 2017124992 A1 WO2017124992 A1 WO 2017124992A1 CN 2017071331 W CN2017071331 W CN 2017071331W WO 2017124992 A1 WO2017124992 A1 WO 2017124992A1
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Prior art keywords
graphene
section
flue gas
gas filtering
filtering device
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PCT/CN2017/071331
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English (en)
French (fr)
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张麟德
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张麟德
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Priority to US16/067,595 priority Critical patent/US20190000136A1/en
Publication of WO2017124992A1 publication Critical patent/WO2017124992A1/zh

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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/163—Carbon
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24F—SMOKERS' REQUISITES; MATCH BOXES; SIMULATED SMOKING DEVICES
    • A24F13/00—Appliances for smoking cigars or cigarettes
    • A24F13/02—Cigar or cigarette holders
    • A24F13/04—Cigar or cigarette holders with arrangements for cleaning or cooling the smoke
    • A24F13/06—Cigar or cigarette holders with arrangements for cleaning or cooling the smoke with smoke filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4541—Gas separation or purification devices adapted for specific applications for portable use, e.g. gas masks

Definitions

  • the invention relates to the field of tobacco, in particular to a flue gas filtering device and a tobacco product.
  • Smoking can bring spiritual enjoyment, but smoking is harmful to health because it forms a series of substances that are harmful to the human body during the burning process.
  • tobacco products such as cigars have the same problem. Harmful compounds produced by tobacco during combustion include nicotine (nicotine), nitrosamines, carbon monoxide, polycyclic aromatic hydrocarbons (PAHs), tar, cyanide, formaldehyde, acrolein and heavy metals.
  • nicotine nicotine
  • PAHs polycyclic aromatic hydrocarbons
  • tar cyanide
  • formaldehyde acrolein and heavy metals.
  • current cigarettes are usually provided with a filter, and the filter may specifically be acetate or the like.
  • the filtering effect of the existing filter is not good, and only part of the tar can be intercepted, and most of the harmful substances in the smoke, especially the carcinogen, can still enter the human body and cause harm to the human body.
  • the present invention provides a flue gas filtering device and a tobacco product.
  • the present invention provides a flue gas filtering device formed with a flue gas filtering passage, wherein the flue gas filtering passage is provided with a graphene material segment, the graphene material segment is a graphene material powder segment, and graphite a olefinic material aerogel segment or a graphene material film segment; the graphene material is graphene and/or functionalized graphene; the functionalized graphene is aminated graphene, carboxylated graphene, sulfonated graphene , fluorenated graphene, cyano graphene, nitro graphene, borate-based graphene, phosphate-based graphene, hydroxy Graphene, fluorenated graphene, methylated graphene, allylated graphene, trifluoromethylated graphene, dodecylated graphene, octadecylated graphene, graphite fluoride One or more of alkene,
  • the graphene material segment comprises: graphene, aminated graphene, carboxylated graphene, sulfonated graphene, and fluorenated graphene.
  • the flue gas filtering device includes a casing that forms the flue gas filtering passage; the flue gas filtering device further includes: a first ventilating support section and a second disposed in the flue gas filtering passage a permeable support section; the graphene material section being disposed between the first permeable support section and the second permeable support section.
  • first gas permeable support segment and/or the second gas permeable support segment is a cellulose acetate segment, a polypropylene segment, an alumina segment or a cotton segment.
  • a mouthpiece segment further comprising a mouthpiece segment, the mouthpiece segment communicating with a second end of the flue gas filtering passage of the filter segment; and an outer surface of the mouthpiece segment adjacent to one end of the filter segment, away from the The outer surface of one end of the filter section is a curved surface whose cross section is gradually reduced.
  • the cigarette-selling section is detachably connected to the filter section, and/or the mouthpiece section is detachably connected to the filter section.
  • the weight of the graphene material segment is from 0.5 mg to 50 mg.
  • the present invention also provides a tobacco product comprising: a tobacco segment, and the smoke filtering device according to any one of the above-described first to fifth embodiment, wherein the smoke filtering device and the tobacco One end of the segment is connected.
  • the invention also provides a use of a graphene material for adsorbing polycyclic aromatic hydrocarbons, the graphene material being graphene and/or functionalized graphene; the functionalized graphene being aminated graphene, carboxylated graphite Alkene, sulfonated graphene, fluorenated graphene, cyano graphene, nitrographene, borate-based graphene, phosphate-based graphene, hydroxylated graphene, fluorenated graphene, methylated graphene, allylic Baseline graphene, trifluoromethylated graphene, dodecylated graphene, octadecylated graphene, fluorinated graphene, graphene bromide, graphene chloride and graphene iodide One or several. .
  • the present invention provides a flue gas filtering device using a graphene material as a filter material.
  • the graphene material is a two-dimensional material with a large specific surface area.
  • the present invention directly uses a graphene material as a filter segment, and does not load the graphene material on other materials, thereby making the graphene material two-dimensional. Both surfaces on the plane can exert adsorption and adsorb high amounts of toxic substances in the flue gas.
  • Graphene on the other hand, can be considered as a carbon material composed of sp2 hybridized carbon atoms, wherein each carbon provides a Pz orbital and electrons participating in the formation of a large ⁇ bond on the surface of the graphene.
  • the surface of the entire graphene can be considered to be covered by a large ⁇ bond.
  • the surface of PAHs also has a large ⁇ bond system.
  • the ⁇ bonds of the two systems overlap, thus forming a ⁇ - ⁇ interaction between graphene and PAHs, due to ⁇ - ⁇ .
  • the strong interaction force makes the graphene adsorb large amount of PAHs and adsorbs firmly.
  • functionalized graphene in graphene materials can have a stronger adsorption effect on specific compounds because functional groups on functionalized graphene have directivity and can form chemical bonds with chemical structures of specific structures.
  • the flue gas filtering device has large adsorption amount and strong adsorption, and helps to reduce toxic substances in the flue gas from entering the human body and reducing the harm of smoking to the human body.
  • the flue gas filtering device can achieve a removal rate of PAHs having significant carcinogenic activity of 85% to 100%.
  • FIG. 1 is a schematic structural view of a flue gas filtering device according to a first embodiment of the present invention
  • FIG. 2 is a schematic structural view of a flue gas filtering device according to a second embodiment of the present invention.
  • FIG. 3 is a schematic structural view of a flue gas filtering device according to another preferred embodiment of the present invention.
  • FIG. 4 is a schematic structural view of a tobacco product according to a third embodiment of the present invention.
  • Fig. 5 is a schematic view showing the structure of a detecting device for adsorption test of the present invention.
  • nitrosamines In the process of tobacco burning, a series of complex substances are often formed, including nicotine (nicotine), nitrosamines, carbon monoxide, polycyclic aromatic hydrocarbons (PAHs), tar, cyanide, formaldehyde, acrolein and various heavy metals. . Among them, nitrosamines, PAHs, acrolein, etc. are strong carcinogenic substances.
  • PAHs are actually a general term for a series of polycyclic aromatic hydrocarbons, including benzo[a]pyrene, benzo[e]indole, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo [j]fluoranthene, dibenzo[a,h]indene, dibenzo[a,h]acridine, dibenzo[a,j]acridine,7-H-dibenzo[c,g] Carbazole, Most of them have significant carcinogenic activity, and benzo[a]pyrene is even represented as carcinogenicity.
  • the inventors have found that the reason for the poor filterability of the existing filter mouthpiece is mainly: in the smoke, PAHs It is often dissolved in tar and carried by tar.
  • the existing filter cigarette holder only has adsorption capacity for some tar. After the tar is adsorbed, the PAHs mixed in it can only be temporarily adsorbed in the filter cigarette holder, and then with the smoke. The gas continuously passes through the filter cigarette holder. Because the molecular weight is relatively small, the PAHs will be carried away from the filter cigarette holder and enter the human body under the action of the smoke gas, causing damage to the human body.
  • the PAHs can also be adsorbed from the surface of the particulate matter or directly transferred from the flue gas into the human body in a gaseous form of a certain concentration.
  • either the existing filter mouthpiece has a weak adsorption capacity, or is adsorbed and then dissociated and adsorbed into the human body with the flue gas.
  • the present invention firstly provides a use of a graphene material for adsorbing polycyclic aromatic hydrocarbons (PAHs), wherein the graphene material is graphene and/or functionalized graphene; and the functionalized graphene is aminated graphene and a carboxyl group.
  • PAHs polycyclic aromatic hydrocarbons
  • the graphene material is a two-dimensional material which has an extremely high specific surface area and therefore has an excellent adsorption effect.
  • graphene can be thought of as a carbon material composed of sp2 hybridized carbon atoms, wherein each carbon provides a Pz orbital and electrons participating in the formation of a large ⁇ bond on the surface of the graphene. Therefore, the surface of the entire graphene can be considered to be covered by a large ⁇ bond.
  • the surface of PAHs also has a large ⁇ bond system. When PAHs are in contact with graphene, the ⁇ bonds of the two systems overlap, thus forming a ⁇ - ⁇ interaction between graphene and PAHs, due to ⁇ - ⁇ .
  • the strong interaction force makes the graphene adsorb large amount of PAHs and adsorbs firmly.
  • it can have a stronger adsorption effect on specific chemical species because the functional groups on the functionalized graphene have directivity and can form chemical bonds with chemical species of specific structures (ion bonds).
  • the present invention also provides a novel flue gas filtering device using a graphene material as a filter material.
  • FIG. 1 shows the structure of a flue gas filtering device provided by a first embodiment of the present invention.
  • the flue gas filtering device is formed with a flue gas filtering passage L, and a graphene material segment 1 is disposed in the flue gas filtering passage L.
  • the above graphene material segment 1 is a graphene material powder segment, a graphene material aerogel segment or a graphene material film segment.
  • the graphene material can be graphene and/or functionalized graphene.
  • the graphene may be one or more of a single layer of graphene, an oligo-graphene or a multilayer graphene (one or more layers of oligo-graphene, graphene of three or less layers, and three layers of graphene) Above, ten or less layers of graphene).
  • the functionalized graphene may be aminated graphene, carboxylated graphene, sulfonated graphene, fluorenated graphene, cyano graphene, nitrographene, borate-based graphene, phosphate-based graphene, hydroxylated graphite Alkene, fluorenated graphene, methylated graphene, allylated graphene, trifluoromethylated graphene, dodecylated graphene, octadecylated graphene, graphene fluoride, bromine One or more of graphene, graphene chloride and graphene iodide.
  • a graphene material is used as the filter material.
  • the graphene material is a two-dimensional material with a large specific surface area.
  • the present invention directly uses a graphene material as a filter segment, and does not load the graphene material on other materials, thereby making the ratio of the graphene material.
  • the surface area can exert adsorption, and the amount of toxic substances in the flue gas is highly adsorbed.
  • Graphene on the other hand, can be considered as a carbon material composed of sp2 hybridized carbon atoms, wherein each carbon provides a Pz orbital and electrons participating in the formation of a large ⁇ bond on the surface of the graphene.
  • the surface of the entire graphene can be considered to be covered by a large ⁇ bond.
  • the surface of PAHs also has a large ⁇ bond system.
  • the ⁇ bonds of the two systems overlap, thus forming a ⁇ - ⁇ interaction between graphene and PAHs, due to ⁇ - ⁇ .
  • the strong interaction force makes the graphene adsorb large amount of PAHs and adsorbs firmly.
  • functionalized graphene in graphene materials can have a stronger adsorption effect on specific chemical species because functional groups on functionalized graphene are directional and can form chemical species with specific structures.
  • Chemical bond (ion bond, covalent bond, or secondary bond) to form chemical species of this particular structure
  • Chemical adsorption compared to traditional physical adsorption, chemical adsorption has higher adsorption strength and is also more targeted, so even if there is smoke continuously through the graphene material segment, due to chemical bonds (ion bonds, covalent bonds or times)
  • the grade bond is selective and has a strong adsorption force, so that the target chemical species is less likely to desorb. Therefore, the flue gas filtering device provided by the embodiment of the invention has large adsorption capacity, is targeted, and is firmly adsorbed, and helps to reduce toxic substances in the flue gas from entering the human body, thereby reducing the harm of smoking to the human body.
  • the graphene material has the above-mentioned excellent adsorption performance, it is only necessary to use a small amount of graphite material, and the graphene is light, thereby helping to reduce the weight and volume of the flue gas filtering device, and improving the comfort of the consumer. sense.
  • the graphene material in the above graphene material segment includes: graphene, aminated graphene, carboxylated graphene, sulfonated graphene, and fluorenated graphene.
  • the graphene material is capable of fully adsorbing carcinogens in the flue gas.
  • graphene has a very strong adsorption capacity for PAHs.
  • the aminated graphene is a basic group-modified graphene, and has strong adsorption ability to acidic organic substances (such as formic acid, acetic acid, propionic acid, butyric acid, linolenic acid, linoleic acid, oleic acid, etc.).
  • Carboxylated graphene is a weakly acidic group-modified graphene having a basic substance (mainly a nitrogen-containing compound such as ammonia, nicotine, nornicotine, pseudomycin, neonicotinoid, nitrosamine, etc.) Strong adsorption capacity.
  • Sulfonated graphene is a strongly acidic group-modified graphene adsorbed to basic species (mainly nitrogen-containing compounds such as ammonia, nicotine, nornicotine, pseudomycin, neonicotinoid, nitrosamine, etc.) Very capable.
  • the content of alkaline substances in the flue gas is high, so the carboxylated graphene is combined with the sulfonated graphene to ensure efficient filtration of alkaline harmful substances.
  • Thiolated graphene has strong adsorption capacity for heavy metals (such as lead, mercury, nickel, cadmium, arsenic, antimony) and radioactive materials.
  • heavy metals such as lead, mercury, nickel, cadmium, arsenic, antimony
  • the graphene material including the above materials can simultaneously have good adsorption capacity for PAHs, acids, alkaline substances, and heavy metals in the flue gas.
  • the weight ratio of graphene, carboxylated graphene, sulfonated graphene, aminated graphene and fluorenated graphene is 1: (0.2 to 0.4): (0.15 to 0.4): (0.1 to 0.2): (0.1 to 0.2), wherein the weight ratio of the carboxylated graphene to the sulfonated graphene is preferably (1.5 to 2):1.
  • the energizable graphene is preferably not in direct contact to reduce the probability of both being spontaneously stacked under conditions of moisture.
  • the graphene material segment includes an acidic functional group-modified graphene layer, a basic functional group-modified graphene layer, and other graphene layers (in addition to the acidic functional group-modified graphene layer and the basic functional group-modified graphene remaining graphene in the above graphene material) Material); other graphene layers are disposed between the acidic functional group-modified graphene and the basic functional group-modified graphene.
  • the above graphene material may further include hydroxylated graphene and/or octadecylated graphene.
  • hydroxylated graphene is a relatively polar substance (such as methanol, butanol, pentanol, octanol, n-tetracosyl alcohol, octacosanol, phytol, solanesol, cholesterol, beans)
  • the sterol, ⁇ -sitosterol, etc. have strong adsorption capacity.
  • the octadecylated graphene has a strong adsorption capacity for alkanes, such as C25-C35 linear alkane which is transferred to the gas phase by combustion of tobacco wax.
  • the weight ratio of hydroxylated graphene to graphene may be (0.05 to 0.1): 1.
  • the weight ratio of octadecylated graphene to graphene may be (0.05 to 0.1):1.
  • Alcoholic compounds such as solanesol, benzyl alcohol, phenylethyl alcohol; carboxylic acid compounds such as 3-methylvaleric acid and isovaleric acid; phenolic compounds such as eugenol and isoeugenol) are also filtered, which reduces smoking.
  • the preferred embodiment of the present invention controls the graphene material in an amount of 50 mg or less, more preferably 1 mg to 35 mg.
  • the flue gas filtering passage L in the flue gas filtering device provided in this embodiment is used for collecting flue gas for centralized filtration.
  • the cross-sectional shape of the flue gas filtering passage L may be circular, rectangular, triangular, hexagonal, or the like, and the embodiment of the present invention adopts a circular shape.
  • the flue gas filtration passage L may be formed by an outer casing. Referring to FIG. 1, the flue gas filtering device includes a casing 2 which is formed into the above-mentioned flue gas filtering passage L.
  • the flue gas filtering device may further include: a first venting support segment 31 and a second venting support segment 32 disposed in the flue gas filtering passage L; the graphene material segment 1 is disposed on the first venting support segment 31 and the second venting portion Between the support segments 32.
  • the first gas permeable support section 31 and the second gas permeable support section 32 are used to form a space defining a position of the graphene material to prevent the amorphous form of graphene material (such as powder, aerogel film) from coming out of the filter device with the flue gas.
  • the material of the first gas permeable support section 31 and the second gas permeable support section 32 may be any material having gas permeability and support properties, and a non-toxic material is preferably used. Specifically, it may be cellulose acetate, polypropylene, alumina or cotton.
  • the support section may be a cellulose acetate section, a polypropylene section, an alumina section or a cotton section.
  • the graphene material is only small in size in the thickness dimension, the dimension in the dimension of the length and the width is relatively large, and the material gap on the end face of the support segment in contact with the graphene material segment is not less than 10 ⁇ m.
  • the material acts as a barrier to prevent the graphene material from entering the support section and affecting the adsorption effect.
  • the tobacco filter device provided by the above two embodiments has the advantages of high adsorption amount, strong adsorption, and light weight, and has reusability, which is beneficial to save energy.
  • the outer casing 2 may be a hard material or a soft material.
  • the flue gas filtering device when it is a hard material, the flue gas filtering device may be an external type, that is, a nozzle segment that is sleeved in the cigarette when smoking, and the flue gas filtering device has the advantage of being reusable.
  • FIG 2 there is shown the structure of a flue gas filtering device according to a second embodiment of the present invention.
  • the outer casing in the flue gas filtering device is a hard outer casing which sequentially includes a soot section S1 and a filter section S2 along its axial direction.
  • the filter segment S2 forms the flue gas filtering passage; the S1 flue segment end is formed with a cigarette chamber for accommodating the cigarette, and the flue chamber is in communication with the flue gas filtering passage.
  • the tobacco product such as cigarettes can be placed in the smoking chamber, and when the person smokes, the smoke that is sucked out can be filtered by the filter section S2 and then inhaled by the human body.
  • the flue gas filtering device further preferably includes a mouthpiece segment S1.
  • the mouthpiece segment S1 communicates with the second end of the flue gas filtering channel of the filtering segment S2. That is, the outer casing sequentially includes a cigarette portion S1, a filter segment S2, and a mouthpiece segment S3 along its axial direction.
  • the outer surface of the one end of the mouthpiece segment S3 adjacent to the filter section S2 and the outer surface of the one end away from the filter section S2 are curved surfaces whose cross-section is gradually reduced, thereby improving the comfort of the smoker to smoke.
  • the cigarette portion S1 and the filter segment S2 are preferably Disassemble the connection, such as threaded connection, snap connection, etc.
  • the advantage of such a structure is that, on the one hand, the adaptability of the flue gas filtering device to different types of tobacco products is improved by replacing the different inner diameters of the sock segments S1.
  • a plurality of types of cigarettes S1 of the inner diameter of the smoke chamber can be provided to be compatible with ordinary cigarettes, ladies cigarettes, and different types of cigars.
  • the amount of the graphene material determines the filtering effect, and the excessive or too small has drawbacks.
  • the filter section S2 of the outer casing is preferably provided with The indicating portion is used to indicate the volume in which the graphene material is placed. Since the material volume has a corresponding relationship with the weight, the setting indicating portion can conveniently prompt the amount of the graphene material that the operator should put.
  • the indication portion may be an indication line, an indication groove or an indication protrusion or the like.
  • the mouthpiece segment S3 and the filter segment S2 can also be detachably connected, whereby the life of the smoke filtering device can be extended by replacing the mouthpiece segment S3 when the mouthpiece segment S3 is damaged or insufficiently clean.
  • the outer casing of the tobacco filtering device when the outer casing of the tobacco filtering device is a soft material, it can be integrally formed with tobacco.
  • FIG. 4 there is shown a structure of a tobacco product according to a third embodiment of the present invention.
  • the tobacco product comprises: a tobacco section 4, and the flue gas filtering device provided by the first embodiment, the flue gas filtering device and One end of the tobacco section 4 is connected. Since the tobacco and the flue gas filtering device are integrally formed, the consumer does not need to install an additional filtering device before smoking, and is convenient to use.
  • the above tobacco product may be a cigarette, a cigar or a cigarillo.
  • the flue gas filtering device comprises: a first gas permeable support section 31, a graphene material section 1, a second gas permeable support section 32 and a shell 2; the graphene material section 1 is disposed on the first gas permeable support section 31 and the second Between the venting support sections 32; the first permeable support section 31 is connected to the tobacco section 4.
  • the outer casing 2 of the flue gas filtering device is preferably a gas permeable material, and specifically may be a cellulosic material such as tipping paper, cigarette paper, cellulose fiber mesh paper or the like.
  • the tobacco segment may specifically include a tobacco core 41, and a cigarette paper 42 wrapped around the periphery of the tobacco core 41.
  • the tobacco core may be one or more of tobacco leaf, powdered tobacco, reconstituted tobacco, tobacco stem, tobacco, tobacco sheet or cut tobacco.
  • the tobacco product provided by the third embodiment of the invention has the advantages of high adsorption amount, strong adsorption and light weight. Point and integrated with tobacco, consumers are easy to use.
  • Detecting device as shown in Figure 5, it consists of the following seven parts: receiving cup b1, test cigarette b2 (commercially available type A cigarette), flue gas filtering device b3; U-shaped absorption tube b4; absorption solvent b5; Aluminum sieve plate b6, air sampling pump b7; the functions of each part are as follows:
  • Receiving cup b1 used to undertake the burning of test cigarettes during the test;
  • Test cigarette b2 used to simulate tobacco burning in a real process
  • Flue gas filtering device b3 for filtering flue gas
  • U-shaped absorber tube b4 used to support the absorption solvent b5 and prevent the solvent from being sucked into the air sampler.
  • Absorbing solvent b5 used to dissolve the gas generated after the tobacco is burned.
  • the absorption solvent b5 is n-hexane
  • Alumina sieve plate b6 used to prevent back suction, using the hole of the porous sieve plate as a boiling core, in the process of drawing vacuum, the solvent can be boiled without directly sucking into the atmospheric sampler.
  • Air sampler b7 the atmospheric sampler: is used to extract vacuum and provide negative pressure. In some cases, the test is also used to store atmospheric samples.
  • the flue gas filtering device b3 is set to be empty, and the flue gas generated by the test cigarette b2 is directly absorbed by the absorption solvent b5, and the test is stopped after 5 minutes; the absorption solvent b5 is taken out, and passed through GC-MS, HPLC, ICP. - MS, AAS or other test method tests the content of the compound to be detected in the solvent obtained by absorption as the reference amount t0.
  • the flue gas filtering device was a commercially available filter cigarette holder, material: cellulose acetate, diameter: 1 cm, length: 2 cm.
  • Test example The flue gas filtering device numbered 1 to 20 is provided.
  • the structure in the flue gas filtering device is as shown in Fig. 1.
  • the first gas permeable support segment and the second gas permeable support segment have a diameter of 1 cm and a length of 5 mm.
  • the remaining structural information is listed in Table 1:
  • the flue gas filtering device provided by the present invention has more filtering effect on PAHs than the prior art, and even if it is smoked for a long time, its adsorption amount to PAHs is still high.
  • the organic phase absorption solvent b5 is isopropanol, and the rest is the same as the adsorption PAHs test; the heavy metal partial absorption solvent b5 is 5% nitric acid, and is detected by AAS or ICP-MS, and the rest is the same as the adsorption PAHs test.
  • Test example the flue gas filtering device numbered 21 to 25 is provided, and the structure in the flue gas filtering device is as shown in Fig. 1.
  • the first gas permeable support section and the second gas permeable support section are the same as the test examples in the PAHs test;
  • the structural information is listed in the table below:
  • Test items 1 twenty one twenty two twenty three twenty four 25 Formic acid 40.6% 85% 87.1% 89.4% 95.7% 96.2% Oleic acid 78.6% 87.5% 95.4% 96.2% 95% 97.4% Nicotine 27% 80.3% 86% 86.1% 90.3% 87.6% aniline 85.3% 85.9% 90.9% 92.4% 97.2% 96.9% Nitrosamine 82.6% 85% 90.6% 91.3% 96.9% 95.7% lead 18.6% 84.2% 87.7% 89.3% 90.6% 86.9% HG 17.3% 85.1% 88.1% 90.7% 92.5% 87.4% polonium 13.7% 84.1% 87.2% 90% 90.3% 85.9% C1-C24 alkanol 58.9% 59.3% 60% 58.5% 60.2% 94.6% C28 alkanol 67.3% 67.2% 67.5% 67.3% 68.2% 90.2% C25-C35
  • graphene materials, graphene, aminated graphene, carboxylated graphene, sulfonated graphene and fluorenated graphene help to further improve the acid organic matter, alkaline substances and heavy metals in the flue gas filtering device.
  • Further addition of hydroxylated graphene and octadecylated graphene also contributes to the adsorption of highly polar substances and linear alkanes ability.
  • the absorption solvent b5 was methanol-acetonitrile, and the rest was the same as the adsorption PAHs test. Among them, the PAHs removal index is the average of the indicators in Table 2.
  • the flue gas filtering devices numbered 26 to 31 are provided, and the flue gas filtering devices of samples 26 to 31 differ from the samples only in the weight of the graphene powder in the graphene material segment, and the graphene powder weight in the sample 26 to the sample 31.
  • the order is: 0.2 mg, 0.5 mg, 1 mg, 35 mg, 50 mg, 60 mg.
  • Neophysin 45.1% 41.5% 41.9% 42.6% 50.2% 69.7% 88.9% Solanesol 46.3% 42.2% 42.5% 46.1% 50.6% 70.3% 89% Benzyl alcohol 45.2% 41.4% 41.6% 45% 50.3% 69.8% 88.6% 3-methylpentanoic acid 45.1% 41.1% 41.4% 44.9% 50.2% 69.5% 88.3% Isovaleric acid 45.2% 41.2% 41.5% 45% 50.4% 69.6% 88.5% Eugenol 45% 40.3% 41.2% 44.8% 50.3% 69.6% 88.5% Isoeugenol 45.4% 41.5% 41.7% 45.2% 50.5% 70% 89.1% PAHs 94.8% 85.2% 92.4% 93.9% 96.1% 97.3% 99.1%

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Abstract

一种烟气过滤装置和烟草制品。烟气过滤装置形成有烟气过滤通道（L），烟气过滤通道（L）内设置有石墨烯材料段（1），石墨烯材料段（1）为石墨烯材料粉末段、石墨烯材料气凝胶段或石墨烯材料薄膜段；石墨烯材料为石墨烯和/或官能化石墨烯。烟气过滤装置，吸附量大，并且吸附牢靠，有助于降低烟气中的有毒物质进入人体内，降低吸烟对人体的伤害。

Description

烟气过滤装置和烟草制品
本申请要求于2016年01月15日提交中国专利局，申请号为201610031451.0、发明名称为“不同含氧量的石墨烯量子点的制备方法、石墨烯量子点和荧光材料”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及烟草领域，特别涉及一种烟气过滤装置和烟草制品。
背景技术
吸烟能给人带来精神享受，但由于烟草在燃烧过程中会形成一系列列对人体不利的物质，因此吸烟有害健康。类似的，雪茄等烟草制品也存在同样问题。烟草在燃烧过程中产生的有害化合物有：尼古丁(烟碱)、亚硝胺、一氧化碳、多环芳烃(PAHs)、焦油、氰化物、甲醛、丙烯醛与重金属等。为了减少吸烟者吸入的有害物质量，现在的香烟通常设置有过滤嘴，该过滤嘴具体可以为醋酸纤维等。但是，现有的过滤嘴的过滤效果不佳，仅能对部分焦油进行拦截，烟气中的大部分有害物质，尤其是致癌物质仍可进入人体内，对人体造成伤害。
发明内容
为了解决以上技术问题，本发明提出一种烟气过滤装置和烟草制品。
一方面，本发明提供了一种烟气过滤装置，其形成有烟气过滤通道，所述烟气过滤通道内设置有石墨烯材料段，所述石墨烯材料段为石墨烯材料粉末段、石墨烯材料气凝胶段或石墨烯材料薄膜段；所述石墨烯材料为石墨烯和/或官能化石墨烯；所述官能化石墨烯为氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯、巯基化石墨烯、氰基石墨烯、硝基石墨烯、硼酸基石墨烯、磷酸基石墨烯、羟 基化石墨烯、巯基化石墨烯、甲基化石墨烯、烯丙基化石墨烯、三氟甲基化石墨烯、十二烷基化石墨烯、十八烷基化石墨烯、氟化石墨烯、溴化石墨烯、氯化石墨烯及碘化石墨烯中的一种或几种。
进一步地，所述石墨烯材料段包括：石墨烯、氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯和巯基化石墨烯。
进一步地，所述烟气过滤装置包括外壳，所述外壳形成所述烟气过滤通道；所述烟气过滤装置还包括：设置于所述烟气过滤通道内的第一透气支撑段和第二透气支撑段；所述石墨烯材料段设置在第一透气支撑段和第二透气支撑段之间。
进一步地，所述第一透气支撑段和/或第二透气支撑段为醋酸纤维素段、聚丙烯段、氧化铝段或棉花段。
进一步地，所述外壳为硬质外壳，所述外壳沿其轴向顺次包括过滤段和置烟段；所述过滤段形成所述烟气过滤通道；所述置烟段与所述烟气过滤通道的第一端相通；所述置烟段端形成有容纳香烟的置烟腔。
进一步地，还包括烟嘴段，所述烟嘴段与所述过滤段的烟气过滤通道的第二端相通；并且，所述烟嘴段中靠近所述过滤段的一端的外表面，至远离所述过滤段的一端的外表面为截面逐渐减小的弧面。
进一步地，所述置烟段与所述过滤段可拆卸连接，和/或所述烟嘴段与所述过滤段可拆卸连接。
进一步地，所述石墨烯材料段的重量为0.5mg～50mg。
本发明还提供一种烟草制品，其包括：烟草段，以及上述第1至5项实施方案及第8项实施方案中任意一项的烟气过滤装置，所述烟气过滤装置与所述烟草段的一端相连。
本发明还提供一种石墨烯材料在吸附多环芳烃中的应用，所述石墨烯材料为石墨烯和/或官能化石墨烯；所述官能化石墨烯为氨基化石墨烯、羧基化石墨 烯、磺酸化石墨烯、巯基化石墨烯、氰基石墨烯、硝基石墨烯、硼酸基石墨烯、磷酸基石墨烯、羟基化石墨烯、巯基化石墨烯、甲基化石墨烯、烯丙基化石墨烯、三氟甲基化石墨烯、十二烷基化石墨烯、十八烷基化石墨烯、氟化石墨烯、溴化石墨烯、氯化石墨烯及碘化石墨烯中的一种或几种。。
本发明提供一种烟气过滤装置，该烟气过滤装置用石墨烯材料作为过滤材料。一方面，石墨烯材料是一种二维材料，比表面积大，加之本发明是直接使用石墨烯材料作为过滤段，不是将石墨烯材料负载在其他材料上，由此使得石墨烯材料的二维平面上的两个面都能发挥吸附作用，对烟气中的有毒物质吸附量高。另一方面，石墨烯可以认为是由sp2杂化碳原子组成的碳材料，其中，每个碳都提供一个Pz轨道和电子参与形成石墨烯表面的大π键。因此，整个石墨烯的表面可以被认为是由大π键所覆盖着的。同时，PAHs表面也具有大π键体系，这使PAHs与石墨烯相接触时，两个体系的π键会有所重叠，从而使石墨烯与PAHs间形成π-π相互作用，由于π-π相互作用力强，使得石墨烯对PAHs的吸附量大，吸附牢固。另一方面，石墨烯材料中的官能化石墨烯可以对特定的化合物具有更为牢固的吸附效果，这是因为官能化石墨烯上的官能团具有指向性，能够与一些特定结构的化学物种形成化学键(离子键、共价键或次级键)，从而使该类特定结构的化学物种形成化学吸附，相对于传统的物理吸附，化学吸附的吸附强度更高，也亦具有更强的针对性，因此即使有烟气不断通过石墨烯材料段，由于化学键(离子键、共价键或次级键)具有选择性，同时亦具有强的吸附力，从而使目标的化学物种不易发生脱离吸附。因此，采用本发明提供的烟气过滤装置，吸附量大，并且吸附牢靠，有助于降低烟气中的有毒物质进入人体内，降低吸烟对人体的伤害。另外，由于石墨烯材料具有上述优异的吸附性能，因此只需使用少量的石墨烯材料即可，加之石墨烯质轻，因此有助于减少烟气过滤装置的重量及体积，提高消费者使用的舒适感。实验证明，本发明提供的烟气过滤装置可以使具有显著致癌活性的PAHs的去除率达到85％～100％。
附图说明
构成本发明的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为本发明第一实施例提供的烟气过滤装置的结构示意图；
图2为本发明第二实施例提供的烟气过滤装置的结构示意图；
图3为本发明另一优选实施例提供的烟气过滤装置的结构示意图；
图4为本发明第三实施例提供的烟草制品的结构示意图；
图5为本发明吸附测试用检测装置的结构示意图。
附图标记说明：
1   石墨烯材料段      2   外壳
31  第一透气支撑段    32  第二透气支撑段
4   烟草段            S1  置烟段
S2  过滤段            L   烟气过滤通道
具体实施方式
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
在烟草燃烧的过程中，往往会形成一系列复杂的物质，包括尼古丁(烟碱)、亚硝胺、一氧化碳、多环芳烃(PAHs)、焦油、氰化物、甲醛、丙烯醛与各类重金属等。这当中，亚硝胺、PAHs、丙烯醛等属于强致癌性物质。特别是其中的PAHs，实际上是一系列多环芳烃的统称，包括苯并[a]芘，苯并[e]芘，苯并[b]荧蒽，苯并[k]荧蒽，苯并[j]荧蒽，二苯并[a,h]蒽，二苯并[a,h]吖啶，二苯并[a,j]吖啶，7-H-二苯并[c,g]咔唑，
Figure PCTCN2017071331-appb-000001
茚并芘等，其中绝大部分有显著的致癌活性，苯并[a]芘甚至被作为致癌性的代表。
本发明人发现现有的过滤烟嘴过滤性不佳的原因主要在于：在烟气中，PAHs 往往溶解于焦油中，由焦油携带出，而现有的过滤烟嘴仅对部分焦油有吸附能力，焦油被吸附后，夹杂在其中的PAHs也只能暂时被吸附在过滤烟嘴内，而后随着烟气不断通过过滤烟嘴，PAHs由于分子量相对较小，在烟气的作用下会再次被携带离开过滤烟嘴而进入人体内，对人体造成伤害。另外一个方面，PAHs还可以以颗粒物表面吸附，或直接以一定浓度的气态的形式从烟气中传递进入人体。此外，对于其它的有毒化合物，要么现有的过滤烟嘴对其吸附能力弱，要么被吸附后再次随烟气解离吸附进入人体。
据此，本发明首先提供一种石墨烯材料在吸附多环芳烃(PAHs)中的应用，上述石墨烯材料为石墨烯和/或官能化石墨烯；官能化石墨烯为氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯、巯基化石墨烯、氰基石墨烯、硝基石墨烯、硼酸基石墨烯、磷酸基石墨烯、羟基化石墨烯、巯基化石墨烯、甲基化石墨烯、烯丙基化石墨烯、三氟甲基化石墨烯、十二烷基化石墨烯、十八烷基化石墨烯、氟化石墨烯、溴化石墨烯、氯化石墨烯及碘化石墨烯中的一种或几种。
首先，石墨烯材料作为一种二维材料，其具有极高的比表面积，因此吸附效果优。对于石墨烯来说，石墨烯可以认为是由sp2杂化碳原子组成的碳材料，其中，每个碳都提供一个Pz轨道和电子参与形成石墨烯表面的大π键。因此，整个石墨烯的表面可以被认为是由大π键所覆盖着的。同时，PAHs表面也具有大π键体系，这使PAHs与石墨烯相接触时，两个体系的π键会有所重叠，从而使石墨烯与PAHs间形成π-π相互作用，由于π-π相互作用力强，使得石墨烯对PAHs的吸附量大，吸附牢固。对于官能化石墨烯而言，其可以对特定的化学物种具有更为牢固的吸附效果，这是因为官能化石墨烯上的官能团具有指向性，能够与一些特定结构的化学物种形成化学键(离子键、共价键或次级键)，从而使该类特定结构的化学物种形成化学吸附，相对于传统的物理吸附，化学吸附的吸附强度更高，也亦具有更强的针对性，因此即使有烟气不断通过石墨烯材料段，由于化学键(离子键、共价键或次级键)具有选择性，同时亦具有强的吸附力，从而使目标的化学物种不易发生脱离吸附。因此，上述石墨烯材料对 于PAHs具有吸附量大，吸附牢靠，不易脱离吸附的特点。
本发明还提供一种新型的烟气过滤装置，该烟气过滤装置以石墨烯材料作为过滤材料。具体而言，请参见图1，该图示出了本发明第一实施例提供的烟气过滤装置的结构。该烟气过滤装置形成有烟气过滤通道L，烟气过滤通道L内设置有石墨烯材料段1。上述石墨烯材料段1为石墨烯材料粉末段、石墨烯材料气凝胶段或石墨烯材料薄膜段。石墨烯材料可以为石墨烯和/或官能化石墨烯。上述石墨烯可以为单层石墨烯、寡层石墨烯或多层石墨烯中的一种或几种(寡层石墨烯为一层以上，三层以下的石墨烯，多层石墨烯为三层以上，十层以下的石墨烯)。
上述官能化石墨烯可以为氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯、巯基化石墨烯、氰基石墨烯、硝基石墨烯、硼酸基石墨烯、磷酸基石墨烯、羟基化石墨烯、巯基化石墨烯、甲基化石墨烯、烯丙基化石墨烯、三氟甲基化石墨烯、十二烷基化石墨烯、十八烷基化石墨烯、氟化石墨烯、溴化石墨烯、氯化石墨烯及碘化石墨烯中的一种或几种。
本实施例中采用石墨烯材料作为过滤材料。一方面，石墨烯材料是一种二维材料，比表面积大，加之本发明是直接使用石墨烯材料作为过滤段，不是将石墨烯材料负载在其他材料上，由此使得石墨烯材料的全部比表面积都能发挥吸附作用，对烟气中的有毒物质吸附量高。另一方面，石墨烯可以认为是由sp2杂化碳原子组成的碳材料，其中，每个碳都提供一个Pz轨道和电子参与形成石墨烯表面的大π键。因此，整个石墨烯的表面可以被认为是由大π键所覆盖着的。同时，PAHs表面也具有大π键体系，这使PAHs与石墨烯相接触时，两个体系的π键会有所重叠，从而使石墨烯与PAHs间形成π-π相互作用，由于π-π相互作用力强，使得石墨烯对PAHs的吸附量大，吸附牢固。另一方面，石墨烯材料中的官能化石墨烯可以对特定的化学物种具有更为牢固的吸附效果，这是因为官能化石墨烯上的官能团具有指向性，能够与一些特定结构的化学物种形成化学键(离子键、共价键或次级键)，从而使该类特定结构的化学物种形成 化学吸附，相对于传统的物理吸附，化学吸附的吸附强度更高，也亦具有更强的针对性，因此即使有烟气不断通过石墨烯材料段，由于化学键(离子键、共价键或次级键)具有选择性，同时亦具有强的吸附力，从而使目标的化学物种不易发生脱离吸附。因此，采用本发明实施例提供的烟气过滤装置，吸附量大，具有针对性，并且吸附牢靠，有助于降低烟气中的有毒物质进入人体内，降低吸烟对人体的伤害。另外，由于石墨烯材料具有上述优异的吸附性能，因此只需使用少量的石墨材料即可，加之石墨烯质轻，因此有助于减少烟气过滤装置的重量及体积，提高消费者使用的舒适感。
作为本发明的优选方案，上述石墨烯材料段中的石墨烯材料包括：石墨烯、氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯和巯基化石墨烯。该石墨烯材料能够对烟气中的致癌物质进行全面吸附。具体而言，石墨烯对PAHs具有极强的吸附能力。氨基化石墨烯为碱性基团修饰的石墨烯，对酸性有机物(如甲酸，乙酸，丙酸，丁酸，亚麻酸，亚油酸，油酸等)吸附能力强。羧基化石墨烯为弱酸性基团修饰的石墨烯，对碱性物质(主要是含氮化合物，如氨，烟碱，降烟碱，假木贼碱，新烟草碱，亚硝胺等)具有较强的吸附能力。磺酸化石墨烯为强酸性基团修饰的石墨烯，对碱性物种(主要是含氮化合物，如氨，烟碱，降烟碱，假木贼碱，新烟草碱，亚硝胺等)吸附能力极强。烟气中的碱性物质含量高，因此将羧基化石墨烯与磺酸化石墨烯复合使用，以保证对碱性有害物质的高效过滤。巯基化石墨烯对重金属(如铅、汞、镍、镉、砷、钋)与放射性物质的吸附能力极强。由此，包括有上述材料的石墨烯材料能够同时对烟气中的PAHs、酸、碱性物质以及重金属都具有较好的吸附能力。更优选地，上述石墨烯材料中，石墨烯、羧基化石墨烯、磺酸化石墨烯、氨基化石墨烯和巯基化石墨烯的重量比为1：(0.2～0.4)：(0.15～0.4)：(0.1～0.2)：(0.1～0.2)，其中羧基化石墨烯、磺酸化石墨烯的重量比优选为(1.5～2)：1。
另外，对于同时含有酸性官能团修饰石墨烯(如羧基化石墨烯、磺酸化石墨烯)和碱性官能团修饰石墨烯(氨基化石墨烯)的石墨烯材料，上述两种官 能化石墨烯优选不直接接触，以降低二者在有水汽的条件下自发堆叠的概率。例如，石墨烯材料段包括酸性官能团修饰石墨烯层、碱性官能团修饰石墨烯层和其它石墨烯层(上述石墨烯材料中除了酸性官能团修饰石墨烯层和碱性官能团修饰石墨烯剩余的石墨烯材料)；其他石墨烯层设置在酸性官能团修饰石墨烯和碱性官能团修饰石墨烯之间。
进一步地，上述石墨烯材料还可以包括羟基化石墨烯和/或十八烷基化石墨烯。其中，羟基化石墨烯对极性较大的物质(如甲醇、丁醇、戊醇、辛醇、正二十四烷醇、二十八烷醇、植物醇、茄尼醇、胆甾醇、豆甾醇、β-谷甾醇等)吸附能力强。十八烷基化石墨烯对烷烃吸附能力较强，如烟草蜡经燃烧转移至气相中的C25-C35的直链烷烃等。羟基化石墨烯与石墨烯的重量比可以为(0.05～0.1)：1，十八烷基化石墨烯与石墨烯的重量比可以为(0.05～0.1)：1。
对于石墨烯材料的使用量，由于石墨烯材料的高吸附性，其相对于现有的过滤材料使用量极低，0.5mg以上即可保证较好的吸附效果。当然，本领域技术人员可以理解，石墨烯材料用量越大，吸附量越大。但是，也正是由于石墨烯材料超强的吸附性能，使得其用量过大会导致对烟气中可对人体产生愉悦感且对人体无害的香气成分(例如：新植二烯等烯烃类化合物；茄尼醇，苯甲醇，苯乙醇等醇类化合物；3-甲基戊酸，异戊酸等羧酸类化合物；丁香酚，异丁香酚等酚类化合物)也被过滤，这会降低吸烟者的感官享受。为此，本发明优选实施例控制石墨烯材料的用量为50mg以下，更优选为1mg～35mg。
本实施例提供的烟气过滤装置中的烟气过滤通道L用于将烟气收集，以便进行集中过滤。上述烟气过滤通道L的截面形状可以为圆形、矩形、三角形、六边形等，本发明实施例采用圆形。该烟气过滤通道L可以由外壳形成。请参见图1，该烟气过滤装置中包括有外壳2，该壳形2成上述烟气过滤通道L。另外，烟气过滤装置还可以包括：设置于烟气过滤通道L内的第一透气支撑段31和第二透气支撑段32；石墨烯材料段1设置在第一透气支撑段31和第二透气 支撑段32之间。
上述第一透气支撑段31和第二透气支撑段32用于形成限定石墨烯材料位置的空间，以防止无定形态的石墨烯材料(如粉末、气凝胶薄膜)随烟气带出过滤装置。上述第一透气支撑段31和第二透气支撑段32的材料可以是任何具有透气性，具有支撑性能的材料，最优采用无毒材料。具体可以为醋酸纤维、聚丙烯、氧化铝或棉花等。相应的，上述支撑段可以为醋酸纤维素段、聚丙烯段、氧化铝段或棉花段等。此外，由于石墨烯材料只是在厚度的维度上尺寸很小，长度和宽度的维度上尺寸相对较大，支撑段与石墨烯材料段相接触的端面上的材料间隙不小于10um即可对石墨烯材料起到阻挡作用，防止石墨烯材料进入到支撑段内影响吸附效果。
上述两个实施例提供的烟草过滤装置除具有吸附量高，吸附牢靠，质轻的优点外，还具有可重复使用，有利于节约能源。
上述外壳2可以为硬质材料也可以为软质材料。第一种情况，当为硬质材料时，该烟气过滤装置可以为外置式，即吸烟时套设于烟的吸嘴段，此种烟气过滤装置具有的能够重复使用优点。请参见图2，该图示出了本发明第二实施例提供的烟气过滤装置的结构。该烟气过滤装置中的外壳为硬质外壳，该外壳沿其轴向顺次包括置烟段S1和过滤段S2。其中过滤段S2形成上述烟气过滤通道；S1置烟段端形成有容纳香烟的置烟腔，置烟腔与烟气过滤通道相通。
使用时，可将香烟等烟草制品放入置烟腔内即可，人在吸烟时，吸出的烟气便可通过过滤段S2进行过滤后被人体吸入。
进一步地，为了方便吸烟者含住该烟气过滤装置，该烟气过滤装置还优选包括烟嘴段S1，请参见图3，该烟嘴段S1与过滤段S2的烟气过滤通道的第二端相通，即该外壳沿其轴向顺次包括置烟段S1、过滤段S2和烟嘴段S3。并且，该烟嘴段S3中靠近过滤段S2的一端的外表面，至远离过滤段S2的一端的外表面为截面逐渐减小的弧面，由此提高吸烟者吸烟的舒适度。
上述两个实施例提供的烟嘴过滤装置中，置烟段S1与过滤段S2优选为可 拆卸连接，例如螺纹连接、卡接等。此种结构的优点在于：一方面，通过更换不同内径的置烟段S1来提高该烟气过滤装置对于不同类型的烟草制品的适配性。例如，可以设置多种型号(置烟腔内径)的置烟段S1，使其分别能够与普通香烟，女士香烟，不同型号的雪茄等相适配。另一方面，也方便消费者更换过滤段S2内的过滤材料，进而通过更换过滤材料延长该烟草过滤装置的使用寿命。进一步地，正如前述所述，石墨烯材料的用量决定了过滤效果，过大或者过小都有弊端，为了方便消费者掌握更换时石墨烯材料的用量，上述外壳的过滤段S2上优选设置有指示部，该指示部用来指示石墨烯材料放置的体积，因为材料体积与重量具有对应关系，因此设置指示部可以方便的提示操作者应放入的石墨烯材料的量。该指示部可以是指示线，指示凹槽或者指示凸起等。
另外，烟嘴段S3与过滤段S2也可以可拆卸连接，由此当烟嘴段S3损坏或不够清洁时可以通过更换烟嘴段S3来延长烟气过滤装置的使用寿命。
第二种情况，当上述烟草过滤装置的外壳为软质材料时，其可以与烟草做成一体结构。请参见图4，该图示出了本发明第三实施例提供的烟草制品的结构，该烟草制品包括：烟草段4，以及上述第一实施例提供的烟气过滤装置，烟气过滤装置与烟草段4的一端相连。由于烟草与烟气过滤装置做成一体结构，因此消费者在吸烟前无需再额外安装过滤装置，使用方便。上述烟草制品可以为香烟、雪茄或小雪茄等。
本实施例中，烟气过滤装置包括：第一透气支撑段31、石墨烯材料段1、第二透气支撑段32和外壳2；石墨烯材料段1设置于第一透气支撑段31和第二透气支撑段32之间；第一透气支撑段31与烟草段4相连。
此种烟草制品中，烟气过滤装置的外壳2优选为透气材料，具体可以为纤维素材料，例如水松纸、卷烟纸、纤维素纤维网纸等。烟草段具体可以包括烟草芯41，以及包覆于烟草芯41外围的卷烟纸42。上述烟草芯可以为烟叶丝、粉末状烟草、复原烟草、烟茎、烟纤、烟草片或烟丝中的一种或几种。
本发明第三实施例提供的烟草制品，具有吸附量高，吸附牢靠，质轻的优 点，并且与烟草做成一体结构，消费者使用方便。
下面结合具体的实施例对本发明的方案进一步描述。
【吸附PAHs测试】
检测装置：结构图5所示，其由以下七部分组成：承接杯b1，测试用香烟b2(市售甲类烟)，烟气过滤装置b3；U型吸收管b4；吸收溶剂b5；，氧化铝筛板b6，空气采样泵b7；各部分作用如下：
承接杯b1：用于承接在测试过程中测试用香烟燃烧形成的燃烬；
测试用香烟b2：用于模拟真实过程中燃烧的烟草；
烟气过滤装置b3：用于对烟气进行过滤；
U型吸收管b4：用于支撑吸收溶剂b5，并防止溶剂倒吸入空气采样器中。
吸收溶剂b5：用于溶解烟草燃烧后产生的气体。本测试中吸收溶剂b5为正己烷；
氧化铝筛板b6：用于防止倒吸，利用多孔筛板的孔作为沸腾核，在吸取真空的过程中，可以使溶剂沸腾而不直接吸入大气采样仪。
空气采样器b7，即大气采样仪：用来抽取真空和提供负压，一定情况下的测试也用于储存大气样品。
检测方法：1、设置烟气过滤装置b3为空，测试用香烟b2产生的烟气直接经过用吸收溶剂b5吸收，实验持续5min后停止测试；取出吸收溶剂b5，通过GC-MS、HPLC、ICP-MS、AAS或其他的测试方法测试吸收完成的溶剂中待检测化合物的含量，作为参照量t0。
2、设置不同的烟气过滤装置b3，测试用香烟b2产生的烟气直接经过烟气过滤装置b3后用吸收溶剂b5吸收，实验持续5min后停止测试，取出吸收溶剂b5，通过GC-MS、HPLC、ICP-MS、AAS或其他的测试方法测试吸收完成的溶剂中待检测化合物的含量，作为比对量t1；
3、计算化合物去除率：化合物去除率(％)＝比对量t1/参照量t0。
检测样品：
比较例D：烟气过滤装置为市售的过滤烟嘴，材料：醋酸纤维素，直径：1cm，长度：2cm。
测试例：提供编号为1至20的烟气过滤装置，烟气过滤装置中的结构均如图1所示，第一透气支撑段和第二透气支撑段的直径均为1cm，长度均为5mm；其余结构信息列于表1：
表1吸附PAHs测试用测试例烟气过滤装置结构
Figure PCTCN2017071331-appb-000002
检测结果：列于表2
表2吸附PAHs测试结果(去除率)
Figure PCTCN2017071331-appb-000003
续表2吸附PAHs测试结果
Figure PCTCN2017071331-appb-000004
Figure PCTCN2017071331-appb-000005
由表2可知，相对于现有技术，本发明提供的烟气过滤装置对PAHs的过滤效果更多，即使是长时间吸烟，其对PAHs的吸附量仍很高。
【全面吸附测试】
检测装置：
同吸附PAHs测试。
检测方法：
有机相吸收溶剂b5为异丙醇，其余与吸附PAHs测试相同；重金属部分吸收溶剂b5为5％硝酸，通过AAS或ICP-MS等方法来检测，其余与吸附PAHs测试相同。
检测样品：
比较例：PAHs测试中的样品1
测试例：提供编号为21至25的烟气过滤装置，烟气过滤装置中的结构均如图1所示，第一透气支撑段和第二透气支撑段与PAHs测试中的测试例相同；其余结构信息列于下表：
表3全面吸附测试用测试例烟气过滤装置结构
Figure PCTCN2017071331-appb-000006
检测结果：列于表4
表4全面吸附测试结果(去除率)
检测项目 1 21 22 23 24 25
甲酸 40.6％ 85％ 87.1％ 89.4％ 95.7％ 96.2％
油酸 78.6％ 87.5％ 95.4％ 96.2％ 95％ 97.4％
烟碱 27％ 80.3％ 86％ 86.1％ 90.3％ 87.6％
苯胺 85.3％ 85.9％ 90.9％ 92.4％ 97.2％ 96.9％
亚硝胺 82.6％ 85％ 90.6％ 91.3％ 96.9％ 95.7％
铅 18.6％ 84.2％ 87.7％ 89.3％ 90.6％ 86.9％
汞 17.3％ 85.1％ 88.1％ 90.7％ 92.5％ 87.4％
钋 13.7％ 84.1％ 87.2％ 90％ 90.3％ 85.9％
C1-C24烷醇 58.9％ 59.3％ 60％ 58.5％ 60.2％ 94.6％
C28烷醇 67.3％ 67.2％ 67.5％ 67.3％ 68.2％ 90.2％
C25-C35烷醇 43.9％ 44％ 44％ 43.3％ 44.6％ 93.9％
由表4可知，石墨烯材料采用石墨烯、氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯和巯基化石墨烯有助于提高该烟气过滤装置进一步对酸性有机物、碱性物质以及重金属都的吸附能力，实现有毒物质全面吸附。进一步添加羟基化石墨烯和十八烷基化石墨烯还有助于提高对大极性物质以及直链烷烃的吸附 能力。
【PAHs和香气吸附测试】
检测装置：
同吸附PAHs测试。
检测方法：
吸收溶剂b5为甲醇-乙腈，其余与吸附PAHs测试相同。其中，PAHs去除指标为表2中各项指标的平均值。
检测样品：
比较例：PAHs测试中的样品1。
提供编号为26至31的烟气过滤装置，样品26至样品31的烟气过滤装置与样品的区别仅在于石墨烯材料段中石墨烯粉末的重量不同，样品26至样品31的石墨烯粉末重量依次为：0.2mg、0.5mg、1mg、35mg、50mg、60mg。
检测结果：列于表5
表5PAHs和香气吸附测试结果(去除率)
检测项目 1 26 27 28 29 30 31
新植二烯 45.1％ 41.5％ 41.9％ 42.6％ 50.2％ 69.7％ 88.9％
茄尼醇 46.3％ 42.2％ 42.5％ 46.1％ 50.6％ 70.3％ 89％
苯甲醇 45.2％ 41.4％ 41.6％ 45％ 50.3％ 69.8％ 88.6％
3-甲基戊酸 45.1％ 41.1％ 41.4％ 44.9％ 50.2％ 69.5％ 88.3％
异戊酸 45.2％ 41.2％ 41.5％ 45％ 50.4％ 69.6％ 88.5％
丁香酚 45％ 40.3％ 41.2％ 44.8％ 50.3％ 69.6％ 88.5％
异丁香酚 45.4％ 41.5％ 41.7％ 45.2％ 50.5％ 70％ 89.1％
PAHs 94.8％ 85.2％ 92.4％ 93.9％ 96.1％ 97.3％ 99.1％
由表5可知，石墨烯材料的含量对于PAHs和香气成分均有影响，当石墨烯材料的用量在0.5mg～50mg时，可以兼具PAHs的高去除率和香气成分的保留； 当用量在1mg～35mg时，效果更优。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种烟气过滤装置，其特征在于，其形成有烟气过滤通道，所述烟气过滤通道内设置有石墨烯材料段，所述石墨烯材料段为石墨烯材料粉末段、石墨烯材料气凝胶段或石墨烯材料薄膜段；所述石墨烯材料为石墨烯和/或官能化石墨烯；所述官能化石墨烯为氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯、巯基化石墨烯、氰基石墨烯、硝基石墨烯、硼酸基石墨烯、磷酸基石墨烯、羟基化石墨烯、巯基化石墨烯、甲基化石墨烯、烯丙基化石墨烯、三氟甲基化石墨烯、十二烷基化石墨烯、十八烷基化石墨烯、氟化石墨烯、溴化石墨烯、氯化石墨烯及碘化石墨烯中的一种或几种。
  2. 根据权利要求1所述的烟气过滤装置，其特征在于，所述石墨烯材料段包括：石墨烯、氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯和巯基化石墨烯。
  3. 根据权利要求1所述的烟气过滤装置，其特征在于，所述烟气过滤装置包括外壳，所述外壳形成所述烟气过滤通道；所述烟气过滤装置还包括：设置于所述烟气过滤通道内的第一透气支撑段和第二透气支撑段；所述石墨烯材料段设置在第一透气支撑段和第二透气支撑段之间。
  4. 根据权利要求3所述的烟气过滤装置，其特征在于，所述第一透气支撑段和/或第二透气支撑段为醋酸纤维素段、聚丙烯段、氧化铝段或棉花段。
  5. 根据权利要求3所述的烟气过滤装置，其特征在于，所述外壳为硬质外壳，所述外壳沿其轴向顺次包括过滤段和置烟段；所述过滤段形成所述烟气过滤通道；所述置烟段与所述烟气过滤通道的第一端相通；所述置烟段端形成有容纳香烟的置烟腔。
  6. 根据权利要求5所述的烟气过滤装置，其特征在于，还包括烟嘴段，所述烟嘴段与所述过滤段的烟气过滤通道的第二端相通；并且，所述烟嘴段中靠近所述过滤段的一端的外表面，至远离所述过滤段的一端的外表面为截面逐渐减小的弧面。
  7. 根据权利要求6所述的烟气过滤装置，其特征在于，所述置烟段与所述过滤段可拆卸连接，和/或所述烟嘴段与所述过滤段可拆卸连接。
  8. 根据权利要求1至7任意一项所述的烟气过滤装置，其特征在于，所述石墨烯材料段的重量为0.5mg～50mg。
  9. 一种烟草制品，其特征在于，包括：烟草段，以及权利要求1至5及8中任意一项的烟气过滤装置，所述烟气过滤装置与所述烟草段的一端相连。
  10. 石墨烯材料在吸附多环芳烃中的应用，所述石墨烯材料为石墨烯和/或官能化石墨烯；所述官能化石墨烯为氨基化石墨烯、羧基化石墨烯、磺酸化石墨烯、巯基化石墨烯、氰基石墨烯、硝基石墨烯、硼酸基石墨烯、磷酸基石墨烯、羟基化石墨烯、巯基化石墨烯、甲基化石墨烯、烯丙基化石墨烯、三氟甲基化石墨烯、十二烷基化石墨烯、十八烷基化石墨烯、氟化石墨烯、溴化石墨烯、氯化石墨烯及碘化石墨烯中的一种或几种。
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