CN106000316A - Graphene adsorption material, preparation method and application thereof and cigarette filter - Google Patents
Graphene adsorption material, preparation method and application thereof and cigarette filter Download PDFInfo
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- CN106000316A CN106000316A CN201610591211.6A CN201610591211A CN106000316A CN 106000316 A CN106000316 A CN 106000316A CN 201610591211 A CN201610591211 A CN 201610591211A CN 106000316 A CN106000316 A CN 106000316A
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- graphene
- fiber
- adsorbing material
- fiber carrier
- doped chemical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
-
- 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
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
Abstract
The invention provides a graphene adsorption material, and a preparation method and application thereof. The graphene adsorption material is prepared from a fiber carrier, graphene and doping elements, wherein the graphene and the doping elements are loaded on the fiber carrier; the doping elements are prepared from one or multiple of Al, Si and Fe. The invention also provides a cigarette filter. The cigarette filter comprises a fiber section formed by the graphene adsorption material. According to the graphene adsorption material, the preparation method and the application thereof, and the cigarette filter, provided by the invention, through introduction of the graphene and the doping elements in the fiber carrier, polycyclic aromatic hydrocarbons harmful substances such as benzopyrene in smoke can be specifically adsorbed, filtered out and removed; meanwhile, nicotine and other innocuous substances are reserved, and the smoking of the smoke cannot be influenced. According to the cigarette filter provided by the invention, polycyclic aromatic hydrocarbons cancerogenic substances such as the benzopyrene in the smoke can be effectively adsorbed, and the harmfulness of smoking can be reduced; meanwhile, the smoking pleasure and the mellow smoking of the smoke cannot be influenced. In addition, the graphene adsorption material provided by the invention can also be used for preventing the phenomenon of mildewing of the cigarette filter due to factors of a damp environment and the like.
Description
Technical field
The present invention relates to adsorption technology field, particularly relate to a kind of Graphene adsorbing material, its preparation side
Method and application thereof and cigarette filter.
Background technology
Produce the condensed-nuclei aromatics class harmful components such as CO, phenol and benzopyrene during cigarette burning, taking out
Enter human body with flue gas during suction to work the mischief.Filter plug refers to the upper part of Medicated cigarette, is medicated cigarette mainstream smoke
Gas and the bridge of human body, be mainly used to filter a part and suck the harmful substances such as the tar in flue gas, can
Reduce the smoking harm to human body.In order to reach the function of requirement, cigarette filter is gradually from common
Single cellulose acetate filter is to multiple filter tip, and the filter plug direction that multiple material is made is developed.
Prior art discloses multiple cigarette filter, if Authorization Notice No. is in CN 2872872Y
State's patent documentation discloses a kind of expansion graphite composite cigarette filter tip, and it is by filter fiber section, swollen
Swollen graphite section and bag paper are constituted, and filter fiber section and the docking of expanded graphite fillter section, bag paper bag is rolled in
Both outsides.This application scheme uses and adds one section of mistake containing expanded graphite in cigarette filter
Filter section, prepares expansion graphite composite filter plug, can effectively the nicotine gas in filter cigarette flue gas,
The harmful substance such as kerosene and nicotine, but benzopyrene can not be adsorbed.
Application publication number is that the Chinese patent literature of CN 104815630 A discloses a kind of selective absorption
The preparation method of the filter fiber of benzopyrene and phenol, the method mainly with graphene oxide water solution or
Person's graphene oxide is specific decorating liquid with the mixed solution of chitosan aqueous solution, sprays fiber
Paintings etc. process, and process time 5～20 minutes, treatment temperature 25～50 DEG C, the fiber after then processing
It is placed under 80 DEG C of vacuum conditions, is dried 6 hours, prepare the filter fiber after modified liquid processes.
Gained filter fiber is made cigarette filter by above-mentioned application, it is possible to decrease the benzopyrene content in flue gas, but
It is that on the one hand this application relates to other additives such as chitosan and preparation technology is loaded down with trivial details, on the other hand
It is the most to be improved to the adsorption effect of benzopyrene.
Summary of the invention
In view of this, the application provide a kind of Graphene adsorbing material, its preparation method and application thereof and
Cigarette filter, the cigarette filter that the present invention provides can the optionally benzo in adsorption filtration flue gas
While the condensed-nuclei aromatics class materials such as pyrene, retain the nicotine in flue gas and other innocuous substance, and then
Do not affect the fragrant of flue gas and inhale taste.
The present invention provides a kind of Graphene adsorbing material, including:
Fiber carrier；
With the Graphene being supported on described fiber carrier and doped chemical；
Described mineral element includes one or more in Al, Si and Fe.
Graphene of the present invention can be obtained by different preparation methoies, such as mechanical stripping method, outer
Epitaxial growth, chemical vapor infiltration, graphite oxidation reducing process, it is also possible to be by biomass are provided
Source hydrothermal carbonization method, and the Graphene that in prior art prepared by additive method.But, no matter which kind of
Method is all difficulty with preparing the theoretic Graphene of stricti jurise, such as prior art on a large scale
The Graphene prepared can exist some impurity element, other allotropes of carbon or layer
Number non-the monolayer even graphene-structured of multilamellar (such as 3 layers, 5 layers, 10 layers, 20 layers etc.), this
Bright utilized Graphene also includes the Graphene on above-mentioned non-critical theory of meaning.
Preferably, during described fiber carrier includes natural fiber, semisynthetic fibre and synthetic fibers
Plant or several.
Preferably, described Graphene content accounts for the 0.1～10wt% of fiber carrier.
Preferably, described Graphene has loose structure, and porosity is 2%～10%.
Above-mentioned Graphene has loose structure, for having porous distributed architecture on graphene film layer plane.
Preferably, described Graphene is biomass porous graphene.
Preferably, described doped chemical content accounts for the 0.002～1wt% of fiber carrier.
Preferably, described doped chemical also includes in K, Na, Ca, Mg, P, Mn and Co
Plant or several.
The present invention provides the preparation method of a kind of Graphene adsorbing material, comprises the following steps:
Fiber is contacted with Graphene material, loads, obtain Graphene adsorbing material；
Described Graphene material include Graphene and doped chemical, described doped chemical include Al, Si and
One or more in Fe.
Preferably, specifically include:
Fiber is immersed in graphene solution 10～60min, scrubbed, be dried, obtain Graphene and inhale
Enclosure material；
Described graphene solution is disperseed to make by Graphene material in a solvent, and described Graphene material is
Biomass porous Graphene；
Preferably, described graphene solution is also dissolved with coupling agent.
It is further preferred that described coupling agent includes silane coupler, titanate coupling agent and zirconium class
One or more of coupling agent etc.；Coupling agent consumption can be the 1%～10% of Graphene quality.
The present invention also provides for the application in smoke filtration of a kind of above-mentioned Graphene adsorbing material.
Further, above-mentioned Graphene adsorbing material is at cigartte filter tip, air conditioner filter element or car tail
Application in gas exhaust apparatus, the device of the most described smoke filtration includes cigarette filter, air conditioner filter element
Or vehicle exhaust exhaust apparatus.
The present invention also provides for a kind of cigarette filter, and it includes Graphene adsorbing material by mentioned earlier
And the segment of fiber made.
Compared with prior art, the Graphene adsorbing material that the present invention provides includes fiber carrier and load
Graphene on fiber carrier and doped chemical, described doped chemical includes in Al, Si and Fe one
Plant or several.The present invention, can be specifically by Graphene and the introducing of doped chemical in fiber carrier
Adsorb and be filtered to remove in flue gas the condensed-nuclei aromatics class harmful substances such as benzopyrene, retain simultaneously nicotine and
Other innocuous substance, does not affect the suction taste of flue gas.The cigarette filter energy active adsorption that the present invention provides
The condensed-nuclei aromatics class carcinogen such as the benzopyrene in flue gas, reduce harmfulness of smoking；Do not affect flue gas simultaneously
Suction taste, do not reduce the pleasant sensation of smoker.
Additionally, the Graphene adsorbing material that the present invention provides can also prevent because the factor cigarette holders such as humid environment are mouldy
Phenomenon.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that institute
The embodiment described is only a part of embodiment of the present invention rather than whole embodiments.Based on this
Embodiment in invention, those of ordinary skill in the art are obtained under not making creative work premise
The every other embodiment obtained, broadly falls into the scope of protection of the invention.
The invention provides a kind of Graphene adsorbing material, including:
Fiber carrier；With the Graphene being supported on described fiber carrier and doped chemical；Described doping
Element includes one or more in Al, Si and Fe.Preferably, described Graphene and doped chemical are
Introduced by biomass Graphene.Graphene and doped chemical can be introduced separately into, it is also possible to mixing
Introduce and (mix introducing and include mixing in advance introducing, mix introducing in advance and include again building-up process introduces
Inherently have by oneself), and biomass Graphene is exactly the mixture containing Graphene and doped chemical.
Benzopyrene in the Graphene adsorbing material alternative absorption flue gas that the present invention provides, absorption effect
Rate is high, and it is preferable that flue gas inhales taste.
The Graphene adsorbing material that the present invention provides includes that fiber carrier, described fiber carrier can be skies
So one or more mixing in fiber, staple fibre and synthetic fibers, preferably include semisynthetic fibre
With one or more in synthetic fibers.In an embodiment of the present invention, described natural fiber includes planting
Fibres and animal fiber, Plant fiber includes being obtained by seed, fruit, stem, leaf etc. on plant
Fiber, such as cotton fiber, flaxen fiber, animal fiber includes animal hair class or silkworm silk class.At this
In bright embodiment, staple fibre is also referred to as semisynthetic fibre, including viscose rayon, acetate fiber, copper
Ammonia fiber and other semisynthetic fibres of the prior art；Synthetic fibers include polypropylene fibre (polypropylene),
Polyacrylonitrile fibre (acrylon), vinylon (vinylon), Fypro (brocade
Synthetic fibre), polyethylene terephthalate (terylene) etc..In some embodiments of the invention, described fibre
The technical specification of dimension carrier is as follows:
More than fibre length 5mm, fineness does not limits；
Fiber moisture 5%～10%；
More than fibre strength 1 gram force.
In the present invention, described fiber carrier can be any fibre number, further preferred fiber number
Scope is 0.13-10D.Fibre length can be any fibre length, further preferred fibre length
For more than 5mm.Fiber moisture does not limits, and further preferred fiber moisture is 5%～10%.Fine
Dimension intensity does not limits, and further preferred fibre strength is more than 1 gram force.
In an embodiment of the present invention, viscose rayon, acetate fiber, CUP, polypropylene fibre
(polypropylene), polyacrylonitrile fibre (acrylon), vinylon (vinylon), polyamide
Fiber (chinlon), polyethylene terephthalate (terylene) or other synthetic fibers can be commercially available product
Product, it would however also be possible to employ method of the prior art prepares.
In specific embodiment of the present invention, the above-mentioned fiber dimensious of fiber carrier commercially available prod can wrap
Include: 1.5D*38mm or 1.5D*51mm；Moisture content is 7%, and fibre strength is 1.5 gram forces.
The fiber using preparation method of the prior art to prepare is illustrated below:
As a example by preparing viscose rayon, the viscose used in the present invention is the viscose glue known to prior art
Liquid, its preparation method is, with pulp as raw material, carry out impregnating, squeeze, pulverize, aging, yellow,
The operations such as dissolving, maturation, filtration, deaeration.Pulp is water-soluble through the sodium hydroxide that concentration is about 18%
Immersion stain, makes cellulose change into alkali cellulose, hemicellulose dissolution, and degree of polymerization part declines；Again
Unnecessary alkali liquor is removed through squeezing.Block alkali cellulose becomes loose wadding after pulverizing on pulverizer
Shape body, makes later chemical reaction uniformity improve owing to surface area increases.Alkali cellulose is at the work of oxygen
Making average degree of polymerization decline with lower generation oxicracking, this process is the most aging.By alkali fibre after aging
Dimension element and Carbon bisulfide react generation cellulose xanthate and claim yellow, make the hydrogen bond between macromole further
Weaken, due to the hydrophilic of yellow acid group, make cellulose xanthate solubility property in sig water big
For improving.Solid cellulose xanthate acid is dissolved in sig water, is i.e. viscose glue.The viscose glue just made
Because viscosity and higher being difficult to of salt figure shape, it is necessary to placement certain time is referred to as maturation at a certain temperature,
Make sodium cellulose xanthate in viscose glue gradually hydrolyze and saponification, esterification degree reduce, viscosity and to electrolyte make
Stability also with change.Deaeration and filtration should be carried out, to remove bubble and miscellaneous after maturation
Matter.
In an embodiment of the present invention, technological process and the condition of preparing viscose fiber filament are specific as follows:
1. alkali steeping process conditions: alkali liquor (NaOH): concentration is 240g/L, temperature is 20 DEG C, leaching
Stain time: 120min；
The most experienced process conditions: temperature is 25 DEG C, the time is 34h；
3. yellow process conditions: yellow method is wet method yellow, and wherein, alkalization includes: the time is 30min,
Temperature is 21.0 ± 0.5 DEG C；Yellow includes: the time is 120min, and initial temperature is 21.0 ± 0.5 DEG C,
Final temperature is 30.0 ± 0.5 DEG C；CS2Adding quality is 34.5% (fine to first)；Front dissolving includes:
Time is 120min, and temperature is 16.5 ± 0.5 DEG C；Rear dissolving includes: time be 180min, temperature is
16.5±0.5℃；
4., in terms of mass-dispersion, the viscose glue stock solution composition prepared includes:
First fibre 8.30 ± 0.10%；
NaOH 5.80 ± 0.10%；
S 2.25 ± 0.1%；
5. viscose ripening condition: the time is 36h～38h, temperature is 19.0 ± 0.5 DEG C；
6. the spinning glue index obtained: viscosity is 30～40 seconds (20 DEG C, falling ball method)；Degree of ripeness be 7.8～
8.6mL (10%NH4Cl value)；
7. spinning process condition: spin speed for 82m/min；Drawing-off is 25%；Nervous drawing-off is 4.12%；
8. coagulation bath condition is as follows:
Acid bath consists of:
H2SO4132.0±1.0g/L；
ZnSO410.5±0.5g/L；
Na2SO4265.0±5.0g/L；
Temperature is 52.0 ± 1.0 DEG C；Proportion is 1.270 ± 0.005.
On fiber carrier, the Graphene adsorbing material that the present invention provides includes the Graphene of load and mixes
Miscellaneous element, described doped chemical includes one or more in Al, Si and Fe.The present invention passes through fiber
Graphene and the introducing of doped chemical in carrier, can improve adsorbing material further and filter benzo in flue gas
The effect of the harmful substances such as pyrene, ensures that the suction taste of flue gas is good simultaneously.
Graphene is a kind of by monolayer sp2The two-dimensional material of the alveolate texture of hydbridized carbon atoms composition,
There is many excellent performances.The structure of described Graphene is as shown in Equation 1:
Graphene dispersion of the present invention, on fiber carrier, makes fiber carrier contain Graphene.At this
In the preferred embodiment of invention, described Graphene content accounts for the 0.1～10wt% of fiber carrier, is preferably
1～4wt%, such as 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, 5%, 6%, 7.8%, 8.9%,
10% etc..In some embodiments of the invention, described Graphene has loose structure, is specially and passes through
Pretreatment has the micropore being randomly distributed；Porosity can be 2%～10%, preferably 3%～7%；Hole
Footpath scope is 1～20nm.
In the present invention, described Graphene is preferably biomass porous Graphene, the most preferably,
Described Graphene and doped chemical are introduced by biomass Graphene；Biomass Graphene contains 10
The layer lamellar structure of following Graphene, the SP of carbon3Hybrid structure and mineral element；Mineral element includes
Fe, Si and Al element.In an embodiment of the present invention, described mineral element constituent content is biomass
0.5wt%～6wt% of Graphene, preferably 1.5wt%～5wt%.Described mineral element the most also includes
Any one or more in P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co；Described ore deposit
Prime element is presented in simple substance and/or compound, and compound includes oxide, carbide, they
Absorption is in the surface of biomass Graphene or inside.In an embodiment of the present invention, described biomass stone
Carbon element content >=80wt%, preferably greater than 85wt%, still more preferably greater than 90wt% in ink alkene, optimum
Choosing is more than 95wt%.In an embodiment of the present invention, described Graphene for have thickness 100nm with
Under the cellular lamellar structure of hexatomic ring of carbon.In embodiments of the present invention, this porous graphene one side
Face is provided that flue gas and cross-ventilated passage, prevents tobacco shred imperfect combustion, decreases not exclusively combustion
Burn the generation of nuisance；On the other hand this porous graphene has bigger serface characteristic, it is possible to effectively
Ground carries out selective absorption to condensed-nuclei aromatics class material (PAHs) such as carcinogenic benzopyrene.
In the present invention, described doped chemical includes one or more in Al, Si and Fe, preferably wraps
Include Al, Si and Fe.Described doped chemical is dispersed on fiber carrier, makes fiber carrier contain doping unit
Element.In a preferred embodiment of the invention, described doped chemical content accounts for fiber carrier
0.002～1wt%, preferably 0.02～0.8wt%, more preferably 0.2～0.5wt%.Additionally, described doping
Element the most also includes one or more in K, Na, Ca, Mg, P, Mn and Co.
The Graphene adsorbing material that the present invention provides belongs to carbon nanomaterial product, has specific adsorption
Performance, this kind of harmful substance of benzopyrene in energy specific adsorption flue gas, do not affect the suction of flue gas simultaneously
Taste.
Correspondingly, the invention provides the preparation method of a kind of Graphene adsorbing material, including following step
Rapid: fiber to be contacted with Graphene material, loads, obtain Graphene adsorbing material；Described stone
Ink alkene material includes that Graphene and doped chemical, described doped chemical include the one in Al, Si and Fe
Or it is several.
The nuisances such as the benzopyrene in the Graphene adsorbing material energy active adsorption flue gas that the present invention prepares
Matter, and do not affect the suction taste of flue gas.Additionally, the present invention prepares the method operation of Graphene adsorbing material
Simplicity, is suitable to industrialization promotion.
Graphene and doped chemical, with fiber as carrier, are supported on fiber carrier by the present invention, obtain
Graphene adsorbing material.Wherein, the content of described fiber carrier is not as it was noted above, repeat them here.
In a preferred embodiment of the invention, described Graphene content accounts for the 0.1～10wt% of fiber carrier,
Be preferably 1～4wt%, such as 0.1wt%, 0.3wt%, 0.5wt%, 0.7wt%, 1wt%, 3wt%,
5wt%, 6wt%, 7.8wt%, 8.9wt%, 10wt% etc..In some embodiments of the present invention
In, described Graphene has loose structure, is specially and has, through pretreatment, the micropore being randomly distributed；
Porosity can be 2%～10%, preferably 3%～7%；Pore diameter range is 1～20nm.The present invention is to institute
The source stating Graphene is not particularly limited, and can use commercially available prod, it is also possible to prepare；Institute
The Graphene stated can be by mechanically pulling off method, epitaxial growth method, chemical vapor infiltration, graphite oxidation
Reducing process and by biomass resource hydrothermal carbonization method is prepared.
In one embodiment of the invention, described Graphene is preferably biomass Graphene.Described life
Material Graphene contains the SP of the lamellar structure of less than 10 layers Graphenes, carbon3Hybrid structure and mineral nitrogen unit
Element；Described mineral element includes Fe, Si and Al element.In an embodiment of the present invention, described mineral nitrogen
Element constituent content is 0.5wt%～6wt% of biomass Graphene, preferably 1.5wt%～5wt%.Institute
State mineral element the most also to include in P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co
Any one or more；Described mineral element presented in simple substance and/or compound, compound bag
Including oxide, carbide, they absorption are in the surface of biomass Graphene or inside.The present invention's
In embodiment, carbon element content >=80wt%, preferably greater than 85wt% in described biomass Graphene,
Still more preferably greater than 90wt%, most preferably greater than 95wt%.In an embodiment of the present invention, described graphite
Alkene is the cellular lamellar structure of hexatomic ring having thickness at the carbon of below 100nm.
In an embodiment of the present invention, described biomass Graphene may utilize biomass resource hydrothermal carbonization
Method prepares.Specifically, the most only illustrate:
Method 1:
(1) under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtains presoma；
(2) under conditions of protective gas, described presoma is incubated 1.5 at 140 DEG C～180 DEG C
H～2.5h, obtains the first intermediate；
(3) under conditions of protective gas, described first intermediate is warming up to 350 DEG C～450 DEG C
Insulation 3h～4h, obtains the second intermediate；
(4) under conditions of protective gas, described second intermediate is warming up to 1100 DEG C～1300
DEG C insulation 2h～4h, obtain the 3rd intermediate；
(5) by described 3rd intermediate alkali cleaning successively, pickling, washing, Graphene is obtained；
Heating rate in described step (3), (4) is 14 DEG C/min～18 DEG C/min.
Biomass Graphene (the Graphene that prior art prepares prepared in said method 1
Middle can there is some impurity element, other allotropes of carbon or the number of plies non-monolayer even multilamellar
Graphene-structured, and the Graphene that this biomass method is prepared is also for mixture, is Graphene
Material) in, containing Graphene, amorphous carbon and non-carbon nonoxygen element.
Specifically:
First mixing biomass carbon source and catalyst, after stirring carries out catalytic treatment, is dried to obtain forerunner
Body；
Then in protective atmosphere, by presoma at 140～180 DEG C, it is incubated 1.5～2.5h, obtains the
One intermediate；In some embodiments of the invention, described temperature is 142 DEG C, 148 DEG C, 155 DEG C,
1600 DEG C, 172 DEG C or 178 DEG C；Described temperature retention time is 1.6h, 1.8h, 2h, 2.2h or 2.4h.
Temperature programming afterwards, to 350～450 DEG C, is incubated 3～4h, obtains the second intermediate；In the present invention
Some specific embodiment in, described temperature is 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 410 DEG C,
420 DEG C, 430 DEG C or 440 DEG C；Described temperature retention time is 3.1h, 3.3h, 3.5h, 3.8h or 3.9h.
It is warming up to 1100～1300 DEG C the most again, is incubated 2～4h, obtains the 3rd intermediate, i.e. product thick
Product；In some embodiments of the invention, described temperature is 1130 DEG C, 1170 DEG C, 1210 DEG C
Or 1280 DEG C；The described time be 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h or
3.8h。
The heating rate of described temperature programming is 14 DEG C/min～18 DEG C/min, concrete in some of the present invention
In embodiment, described heating rate is 15 DEG C/min, 16 DEG C/min or 17 DEG C/min.
Finally by after the 3rd intermediate (i.e. product crude product) alkali cleaning, pickling, washing, obtain complex.
In the present invention, the mass ratio of described biomass carbon source and catalyst is 1:(0.5～5), preferably 1:
(1～3)；In some embodiments of the invention, described ratio is 1:0.5,1:1 or 1:3.
In the present invention, described catalyst selected from the halogen compounds of manganese, iron containing compounds, containing cobalt chemical combination
Any a kind or the combination of at least 2 kinds in thing and nickel compound containing.
Preferably, the described halogen compounds of iron containing compounds chosen from Fe, the cyanide of ferrum and Fe-laden acid
Any a kind or the combination of at least 2 kinds in salt.Described iron content hydrochlorate is the organic acid containing ferrum element
Salt or the salt of mineral acid containing ferrum element.The halogen compounds of described ferrum can be iron chloride and/or
Ferric bromide.
Preferably, described cobalt compound is selected from the halogen compounds of cobalt and containing any 1 in cobaltatess
Plant or the combination of at least 2 kinds.Described containing the salt that cobaltatess are the organic acid containing cobalt element or containing cobalt
The salt of the mineral acid of element.The halogen compounds of described cobalt can be cobaltous chloride and/or cobaltous bromide.
Preferably, described nickel compound containing selected from nickel chlorate and containing in nickelate any a kind or
The combination of at least 2 kinds.Described containing the salt that nickelate is the organic acid containing nickel element or containing nickel element
The salt of mineral acid.The halogen compounds of described nickel can be Nickel dichloride. and/or nickelous bromide.
Preferably, described catalyst is selected from iron chloride, ferrous chloride, ferric nitrate, ferrous nitrate, sulfur
Acid ferrum, ferrous sulfate, the potassium ferricyanide, potassium ferrocyanide, three oxalic acid close potassium ferrite, cobaltous chloride, nitre
In acid cobalt, cobaltous sulfate, cobalt acetate, Nickel dichloride., nickel nitrate, nickel sulfate and nickel acetate any a kind
Or the combination of at least 2 kinds.
The typical but non-limiting example of combination of catalyst of the present invention has ferrous chloride and iron sulfate
Combination, the potassium ferricyanide and three oxalic acid close the combination of potassium ferrite, cobaltous chloride, cobalt nitrate and iron chloride
Combination, the combination of cobaltous sulfate, cobalt acetate and nickel nitrate, the combination of iron chloride, cobaltous chloride and nickel acetate.
It is 150 DEG C～200 DEG C that described stirring carries out the temperature of catalytic treatment, such as 160 DEG C, 170 DEG C,
180 DEG C, 190 DEG C etc., time >=4h, preferably 4h～14h, in some embodiments of the invention,
The described time is 4.2h, 7h, 9h, 12h, 16h, 19h, 23h.
Preferably, the moisture in described presoma is below 10wt%, at some tool of the present invention
In body embodiment, described moisture is 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%,
7wt%, 8wt%, 10wt% etc..
Preferably, any a kind or at least 2 during described protective atmosphere is nitrogen, helium, argon
The combination planted, preferably nitrogen.
Preferably, described pickling concentration is the aqueous hydrochloric acid solution of 3wt%～6wt%, further preferably
Concentration is the aqueous hydrochloric acid solution of 5wt%；Described washing is preferably used deionized water and/or distilled water；Described
Alkali cleaning concentration is the sodium hydrate aqueous solution of 5wt%～15wt%, and further preferred concentration is 10wt%
Sodium hydrate aqueous solution.
Preferably, the temperature of described washing is 55～65 DEG C, such as 56 DEG C, 57 DEG C, 58 DEG C, 60 DEG C,
63 DEG C etc., preferably 60 DEG C.
Described biomass carbon source is cellulose and/or lignin, preferred cellulose, further preferred porous
Cellulose.
Porous cellulose of the present invention can be obtained by prior art, typical but non-limiting obtains
The prior art obtaining porous cellulose has: method disclosed in such as patent publication No. CN104016341A
Prepare porous cellulose, use method disclosed in CN103898782A to prepare cellulose.
Preferably, described porous cellulose obtains by the following method:
Biomass resource is carried out acid hydrolysis and obtains lignocellulose, obtain through porous post processing afterwards
To porous cellulose；Alternatively, porous cellulose uses after bleaching.
Described biomass resource is selected from any a kind or at least 2 kinds in plant and/or agriculture and forestry organic waste material
Combination；Preferably any a kind or the combination of at least 2 kinds in agriculture and forestry organic waste material.
Preferably, described agriculture and forestry organic waste material is selected from corn stalk, corn cob, kaoliang stalk, megasse, sweet
Any a kind or the group of at least 2 kinds in bagasse, furfural dregs, xylose residue, wood flour, cotton stalk and phragmites communis
Close, preferably corn cob.
The typical but non-limiting example combinations of biomass resource of the present invention includes corn stalk and Semen Maydis
The combination of core, the combination of bagasse, kaoliang stalk and wood flour, the group of megasse, bagasse and corn cob
The combination etc. of conjunction, kaoliang stalk, megasse and xylose residue.
Can also be prepared by following multiple method:
Method disclosed in method 2:CN104118873A.
Method disclosed in method 3:CN104016341A.
Method disclosed in method 4:CN104724696A.
Method disclosed in method 5:CN104724699A.
Method disclosed in method 6:CN105060289A.
In the present invention, described doped chemical includes one or more in Al, Si and Fe, preferably wraps
Include Al, Si and Fe.Described doped chemical is dispersed on fiber carrier, makes fiber carrier contain doping unit
Element.In a preferred embodiment of the invention, described doped chemical content accounts for fiber carrier
0.002～1wt%, preferably 0.02～0.8wt%, more preferably 0.2～0.5wt%.Additionally, described doping
Element the most also includes one or more in K, Na, Ca, Mg, P, Mn and Co.
In the present invention, described doped chemical can introduce by adding the nano material containing doped chemical,
Also can be introduced by the mixed form of Graphene with doped chemical.Described mixed form can be in routine
Prepare in Graphene technical process, be doped the mixture that constituent content controls to be formed；Preferably,
During utilizing graphite to prepare Graphene by oxidation-reduction method, the mineral nitrogen unit existed due to graphite itself
Element, by conservative control element kind and content, the Graphene containing mineral element prepared.
Or utilize biomass resource to prepare Graphene for raw material, and carry out process control doped chemical content；
The present invention preferably by biomass resource, by hydro-thermal charring process prepare containing mineral element
Graphene.Herein, mineral element is doped chemical.
Specifically, fiber is immersed in graphene solution certain time such as by the embodiment of the present invention
10～60min, scrubbed, dry, obtain Graphene adsorbing material；Described graphene solution is by graphite
Alkene material disperses to make in a solvent.Described Graphene material can be by Graphene with containing doped chemical
Material composition, it is also possible to be the Graphene containing doped chemical, the most biomass porous Graphene.
In a preferred embodiment of the invention, described graphene solution is also dissolved with coupling agent.Described
Coupling agent preferably include the one or several of silane coupler, titanate coupling agent and zirconium class coupling agent etc.
Kind；The consumption of described coupling agent is preferably the 1%～10% of Graphene quality.
In some embodiments of the invention, biomass porous graphene uniform is distributed in solvent,
It is made into graphene solution.In other embodiments of the present invention, by Graphene with containing doped chemical
Material evenly spread to, in solvent, be made into graphene solution.Wherein, doped chemical be at least Fe,
Si, Al, also can be containing one or more in K, Na, Ca, Mg, P, Mn and Co.Described
Material containing doped chemical concretely nanometer phosphorus pentoxide, nano silica fume, nanometer aluminium powder, receive
Meter Tie, nanometer Mg powder, nano-calcium carbonate sodium, nano-calcium carbonate potassium, nano-calcium carbonate, nano manganese oxide and
Nanometer cobalt etc..
Graphene of the present invention can be obtained by different preparation methoies, such as mechanical stripping method, outer
Epitaxial growth, chemical vapor infiltration, graphite oxidation reducing process, it is also possible to be by biomass are provided
Source hydrothermal carbonization method, and the Graphene that in prior art prepared by additive method.But, no matter which kind of
Method is all difficulty with preparing the theoretic Graphene of stricti jurise, such as prior art on a large scale
The Graphene prepared can exist some impurity element, other allotropes of carbon or layer
Number non-the monolayer even graphene-structured of multilamellar (such as 3 layers, 5 layers, 10 layers, 20 layers etc.), this
Bright utilized Graphene also includes the Graphene on above-mentioned non-critical theory of meaning.Such as, stone is utilized
Ink ore deposit is in the Graphene that raw material prepares, may be containing some mineral nitrogen that in graphite ore, self exists
Element.The biomass Graphene of indication is the Graphene utilizing biomass resource to prepare for raw material,
May also can exist plant because of self needs absorb from soil the mineral element obtained and carbon other with
Element obform body.Therefore, in the present invention, the Graphene of indication is specially a kind of mixture containing Graphene.
In an embodiment of the present invention, the solvent of described graphene solution is preferably ethylene glycol, dimethyl
One or more mixing in Methanamide (DMF), N-Methyl pyrrolidone (NMP), second alcohol and water.
Described scattered mode is preferably ultrasonic disperse, can be made into the stone that Graphene concentration is 0.1～10mg/mL
Ink alkene solution, its concentration is preferably 0.5～3mg/mL.
Before fiber is loaded by the present invention, the most also include carrying out fiber activation processing, remove and carry
Impurity that body itself contains, miscellaneous QI, drying, obtain the fiber carrier activated.The present invention's
In embodiment, the mode of described activation processing can be that boiling water boils, and preferably boiling water boils 25～30min.
The fiber carrier activated is immersed in graphene solution 10～60min by the embodiment of the present invention, warp
Wash, be dried, obtain Graphene adsorbing material.Wherein, the mode of described submergence preferably includes first to surpass
Sound, rear concussion, stand again.Between submergence and washing, the present invention the most also includes being fixed
Process；It can be chemical method that described immobilization processes, and the reagent of use preferably includes dehydrated alcohol, anhydrous
The combination of one or more in methanol and dust technology.
The Graphene adsorbing material that the present invention prepares includes: fiber carrier；Be supported on described fibre
Graphene on dimension carrier and doped chemical；Described doped chemical include the one in Al, Si and Fe or
Several.The condensed ring such as the benzopyrene in the Graphene adsorbing material alternative absorption flue gas that the present invention provides
Class harmful substance, adsorption efficiency is high, and it is preferable that flue gas inhales taste, can be used as cigarette filter.Additionally, this
The Graphene adsorbing material that invention prepares can also prevent because of the mouldy phenomenon of the factor cigarette holders such as humid environment.
Present invention also offers the application in smoke filtration of a kind of above-mentioned Graphene adsorbing material.Enter one
Step, above-mentioned Graphene adsorbing material fills in cigartte filter tip, air conditioner filter element or vehicle exhaust aerofluxus
Application in putting.The device of described smoke filtration includes cigarette filter, air conditioner filter element or vehicle exhaust
Exhaust apparatus；The present invention can use above-mentioned Graphene adsorbing material to prepare smoke filtration according to a conventional method
Device.
Concrete, present invention also offers a kind of cigarette filter, be called for short filter tip, it includes by above
The segment of fiber that described Graphene adsorbing material is made.The cigarette filter that the present invention provides can effectively be inhaled
The harmful substances such as the benzopyrene in attached flue gas, reduce harmfulness of smoking；Retain nicotine and harmless object simultaneously
Matter, it is ensured that the suction taste of flue gas is good, does not reduce the pleasant sensation of smoker.
The present invention uses convention filter manufacture method, and Graphene adsorbing material mentioned above is made filter
Mouth.In an embodiment of the present invention, the segment of fiber that Graphene adsorbing material by mentioned earlier is made
Thickness is preferably 1～4mm, and the thickness of described segment of fiber is the thickness prolonging filter plug axial direction.At this
In inventive embodiment, described filter tip is binary combined filter tip, and contact tobacco shred end is close to load graphite
Alkene and the segment of fiber of doped chemical, then connect general fibre section.
The present invention carries out same operation by the medicated cigarette making the tobacco cartridge of identical weight on smoking machine
Under the conditions of fume collection, the sample collected is analyzed through gas phase-mass spectrometry tester,
Determine the change of heterogeneity peak shape in flue gas before and after absorption.
The flue gas of described cigarette filter is inhaled taste and is evaluated by the present invention, specifically to its fragrance, miscellaneous
The evaluation of gas, zest and pleasant impression, 300 valuation officers of the Evaluation and Selection of each embodiment carry out blind sample
Test.Evaluation criterion is as shown in table 1 below.
The flue gas of table 1 cigarette filter inhales taste evaluation criterion
Result shows, the benzopyrene etc. in the cigarette filter energy active adsorption flue gas that the present invention provides has
Pest matter, reduces harmfulness of smoking；Do not affect the suction taste of flue gas simultaneously, do not reduce the pleasant sensation of smoker.
In order to be further appreciated by the application, Graphene absorption the application provided below in conjunction with embodiment
Material and preparation method thereof and cigarette filter are specifically described.
Prepare the biomass Graphene of the present invention by the following method:
(1) under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtains presoma；
(2) under conditions of protective gas, by described presoma 140 DEG C～180 DEG C insulations
1.5h～2.5h, obtains the first intermediate；
(3) under conditions of protective gas, described first intermediate is warming up to 350 DEG C～450 DEG C
Insulation 3h～4h, obtains the second intermediate；
(4) under conditions of protective gas, described second intermediate is warming up to 1100 DEG C～1300 DEG C
Insulation 2h～4h, obtains the 3rd intermediate；
(5) by described 3rd intermediate alkali cleaning successively, pickling, washing, complex is obtained；
Heating rate in described step (3), (4) is 14 DEG C/min～18 DEG C/min.Described biomass
Graphene contains the sp of the lamellar structure of less than 10 layers Graphenes, carbon3Hybrid structure and mineral element；
Described mineral element includes Fe, Si and Al element.In an embodiment of the present invention, described mineral element
Constituent content is the 0.5-6wt% of biomass Graphene, such as 1wt%, 2wt%, 3wt%, 4wt%,
5wt% etc.；Described mineral element mainly can include P, Si, Ca, Al, Fe, Mg element.
More specifically, prepare biomass Graphene used herein by following preparation example 1-4.
Preparation example 1
(1) under the effect of ferrous chloride, corn cob fiber element is carried out catalytic treatment, obtains forerunner
Body；
(2) under conditions of nitrogen, described presoma is incubated 2h at 150 DEG C, obtains in first
Mesosome；
(3) under conditions of nitrogen, described first intermediate is warming up to 400 DEG C of insulation 3.5h,
To the second intermediate；
(4) under conditions of nitrogen, described second intermediate is warming up to 1200 DEG C of insulation 3h,
To the 3rd intermediate；
(5) by described 3rd intermediate through salt that over-richness is the sodium hydroxide solution of 10wt%, 4wt%
After acid pickling, washing, obtain biomass Graphene；
Heating rate in described step (3), (4) is 15 DEG C/min～16 DEG C/min.
Detect through XRD, in the biomass Graphene prepared in the preparation example 1 of the present invention, mineral element
Content is the 4wt% of this biomass Graphene；Further, the mineral element in this biomass Graphene is main
Including P, Si, Ca, Al, Fe, Mg element.
Preparation example 2
Biomass Graphene is prepared, except for the difference that: step (1) by the method identical with preparation example 1
Catalyst used by is the mixture (mass ratio is 3:1) of iron chloride and nickel nitrate, biomass carbon source
For the corn cob fiber element through hydrogen peroxide bleaching；Protective gas used in step (2)-(4) is
Argon, presoma 140 DEG C be incubated 2.5h, the first intermediate be warming up to 250 DEG C insulation 4h, second
Intermediate is warming up to 1100 DEG C of insulation 2h；Alkali used in step (5) is 5wt%NaOH aqueous solution,
The used aqueous hydrochloric acid solution that acid is 3wt%.
After testing, in biomass Graphene obtained in the preparation example 2 of the present invention, containing of mineral element
Amount is the 2wt% of this biomass Graphene；Further, the mineral element in this biomass Graphene mainly wraps
Include Si, Al, Fe element.
Preparation example 3
Biomass Graphene is prepared, except for the difference that: step (1) by the method identical with preparation example 1
Catalyst used by is the mixture (mass ratio is 3:1) of ferrous chloride and iron sulfate, biomass carbon
Source is lignocellulose；In step (2)-(4), presoma is incubated 1.5h at 180 DEG C, in first
Mesosome is warming up to 450 DEG C of insulation 4h, and the second intermediate is warming up to 1300 DEG C of insulation 4h；Step (5)
The sodium hydrate aqueous solution that alkali is 15wt% used by, acid used is the aqueous hydrochloric acid solution of 6wt%.
Biomass Graphene obtained in the preparation example 3 of the present invention, the content of its Mineral Elements is for being somebody's turn to do
Biomass Graphene 0.8wt%；After testing, the mineral element in this biomass Graphene mainly include Si,
Fe element.
Preparation example 4
Biomass Graphene is prepared, except for the difference that: step (1) by the method identical with preparation example 1
Catalyst used by is the mixture (mass ratio is 3:1) of nickel nitrate and cobaltous sulfate, biomass carbon source
For reed fiber element.
Biomass Graphene obtained in the preparation example 3 of the present invention, the content of its Mineral Elements
6wt% for this biomass Graphene；After testing, the mineral element in this biomass Graphene mainly wraps
Include Si, Fe, Na, K element.
Embodiment 1
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, is made into 0.5
The graphene solution of mg/mL；
By fiber carrier (use acetate fiber, the most commercially available in prior art, technical specification includes:
1.5D*38mm, moisture content is 7%, and fibre strength is 1.5 gram forces) carry out boiling water and boil process 25min,
Remove impurity, miscellaneous QI that carrier itself contains, dry, obtain the fiber carrier that activation processing is good；
The fiber carrier handled well is immersed into 10min in graphene solution, and submergence includes first ultrasonic, after shock
Swing, stand again；Being fixed of dehydrated alcohol is used to process, scrubbed, dry, obtain Graphene
Adsorbing material；The quality of Graphene is the 1% of fiber carrier quality.That is, the content of Graphene is fine
The 1wt% of dimension carrier, the content of doped chemical accounts for the 0.04wt% of fiber carrier.
Embodiment 2
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, is made into 3mg/mL
Graphene solution；
Fiber carrier (with embodiment 1) is carried out boiling water and boils process 25min, remove carrier itself and contain
Some impurity, miscellaneous QI, dry, obtain the fiber carrier that activation processing is good；
The fiber carrier handled well is immersed into 60min in graphene solution, submergence include first the most ultrasonic, after
Shake, stand again；Being fixed of dehydrated alcohol is used to process, scrubbed, dry, obtain graphite
Alkene adsorbing material；The quality of Graphene is the 4% of fiber carrier quality.That is, the content of Graphene is fine
The 4wt% of dimension carrier, the content of doped chemical accounts for the 0.16wt% of fiber carrier.
Embodiment 3
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, is made into
The graphene solution of 1.5mg/mL；
Fiber carrier (with embodiment 1) is carried out boiling water and boils process 25min, remove carrier itself and contain
Some impurity, miscellaneous QI, dry, obtain the fiber carrier that activation processing is good；
The fiber carrier handled well is immersed into 25min in graphene solution, and submergence includes first ultrasonic, after shock
Swing, stand again；Being fixed of dehydrated alcohol is used to process, drying, obtain Graphene adsorption material
Material；The quality of Graphene is the 2.5% of fiber carrier quality.That is, the content of Graphene is that fiber carries
The 2.5wt% of body, the content of doped chemical accounts for the 0.1wt% of fiber carrier.
Embodiment 4
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, is made into 0.5
The graphene solution of mg/mL；
By fiber carrier (use acetate fiber, the most commercially available in prior art, technical specification includes:
1.5D*38mm, moisture content is 7%, and fibre strength is 1.5 gram forces) carry out boiling water and boil process 25min,
Remove impurity, miscellaneous QI that carrier itself contains, dry, obtain the fiber carrier that activation processing is good；
The fiber carrier handled well is immersed into 10min in graphene solution, submergence include first the most ultrasonic,
Rear concussion, stand again；Being fixed of dehydrated alcohol is used to process, scrubbed, dry, obtain stone
Ink alkene adsorbing material.The content of Graphene is the 0.1wt% of fiber carrier, and the content of doped chemical accounts for fibre
The 0.004wt% of dimension carrier.
Embodiment 5
As different from Example 4: be made into the graphene solution of 3mg/mL；The fiber carrier that will handle well
It is immersed into 60min in graphene solution；The content of Graphene is the 10wt% of fiber carrier, doping unit
The content of element accounts for the 0.4wt% of fiber carrier.
Embodiment 6
As different from Example 4: be made into the graphene solution of 1.5mg/mL；The fiber handled well is carried
Body is immersed into 25min in graphene solution；The content of Graphene is the 5wt% of fiber carrier, doping
The content of element accounts for the 0.2wt% of fiber carrier.
Embodiment 7
As different from Example 4: use the biomass Graphene obtained by preparation example 2；Doping unit
The content of element accounts for the 0.002wt% of fiber carrier.
Embodiment 8
As different from Example 5: use the biomass Graphene obtained by preparation example 2；Doping unit
The content of element accounts for the 0.2wt% of fiber carrier.
Embodiment 9
As different from Example 6: use the biomass Graphene obtained by preparation example 2；Doping unit
The content of element accounts for the 0.1wt% of fiber carrier.
Embodiment 10
As different from Example 4: use the biomass Graphene obtained by preparation example 3；Doping unit
The content of element accounts for the 0.0008wt% of fiber carrier.
Embodiment 11
As different from Example 5: use the biomass Graphene obtained by preparation example 3；Doping unit
The content of element accounts for the 0.08wt% of fiber carrier.
Embodiment 12
As different from Example 6: use the biomass Graphene obtained by preparation example 3；Doping unit
The content of element accounts for the 0.04wt% of fiber carrier.
Embodiment 13
As different from Example 4: use the biomass Graphene obtained by preparation example 4；Doping unit
The content of element accounts for the 0.006wt% of fiber carrier.
Embodiment 14
As different from Example 5: use the biomass Graphene obtained by preparation example 4；Doping unit
The content of element accounts for the 0.6% of fiber carrier.
Embodiment 15
As different from Example 6: use the biomass Graphene obtained by preparation example 4；Doping unit
The content of element accounts for the 0.3% of fiber carrier.
Embodiment 16
Use compared with Example 6 oxidoreduction Graphene and nano silica fume, nano-aluminium oxide,
Nano-iron material mixing substitutes biomass Graphene.
Comparative example 1
Being distributed in ethylene glycol by oxidoreduction graphene uniform, the Graphene being made into 0.5mg/mL is molten
Liquid；
By fiber carrier (use acetate fiber, the most commercially available in prior art, technical specification includes:
1.5D*38mm, moisture content is 7%, and fibre strength is 1.5 gram forces) carry out boiling water and boil process 25min,
Remove impurity, miscellaneous QI that carrier itself contains, dry, obtain the fiber carrier that activation processing is good；
The fiber carrier handled well is immersed into 10min in graphene solution, submergence include first the most ultrasonic,
Rear concussion, stand again；Being fixed of dehydrated alcohol is used to process, scrubbed, dry, obtain stone
Ink alkene adsorbing material.The content of Graphene is the 5% of fiber carrier.
Comparative example 2
Native graphite is evenly spread in ethylene glycol, be made into the graphite solution of 0.5mg/mL；
By fiber carrier (use acetate fiber, the most commercially available in prior art, technical specification includes:
1.5D*38mm, moisture content is 7%, and fibre strength is 1.5 gram forces) carry out boiling water and boil process 25min,
Remove impurity, miscellaneous QI that carrier itself contains, dry, obtain the fiber carrier that activation processing is good；
The fiber carrier handled well is immersed into 10min in graphite solution, submergence include first the most ultrasonic, after
Shake, stand again；Being fixed of dehydrated alcohol is used to process, scrubbed, dry, obtain graphite
Adsorbing material.The content of graphite is the 5% of fiber carrier.
Comparative example 3
Bamboo charcoal is evenly spread in ethylene glycol, be made into the bamboo charcoal solution of 0.5mg/mL；
By fiber carrier (use acetate fiber, the most commercially available in prior art, technical specification includes:
1.5D*38mm, moisture content is 7%, and fibre strength is 1.5 gram forces) carry out boiling water and boil process 25min,
Remove impurity, miscellaneous QI that carrier itself contains, dry, obtain the fiber carrier that activation processing is good；
The fiber carrier handled well is immersed into 10min in bamboo charcoal solution, submergence include first the most ultrasonic, after
Shake, stand again；Being fixed of dehydrated alcohol is used to process, scrubbed, dry, obtain bamboo charcoal
Adsorbing material.The content of bamboo charcoal is the 5% of fiber carrier.
Comparative example 4
Commercially available acetate fiber is used conventional filtration mouth manufacture method, the common cigarette filter made
Mouth.
Below the fiber adsorbing material of preparation in embodiment 1～16 and comparative example 1～4 is used conventional filtration
Mouth manufacture method makes the cigarette filter of a length of 20mm, by above example 1～16 and comparative example
The cigarette filter of 1～4 adsorbs the detection of before and after's smoke components, and concrete grammar is as follows:
Cigarette product uses Mount Taishan board, filter plug be respectively adopted embodiment 1～16 and comparative example 1～4 make
Cigarette filter, a length of 20mm of cigarette filter plug, circumference is 22～25mm；Use before experiment
Artikel-Nr9020-0039 climatic chamber balances under the conditions of (22 ± 1) DEG C, relative humidity (60 ± 2) %
48 hours.Detection cigarette is detected by application Borgwaltdt-KC smoking machine, and every mouthful is aspirated 2 seconds,
Volume is 35mL, and every mouthful is spaced 58 seconds, and temperature is 22 ± 2 DEG C, relative humidity is 60 ± 5%, carries out
Fume collection, the sample collected is analyzed through gas phase-mass spectrometry tester.
Made cigarette filter is carried out flue gas evaluation, and result sees table 2.
Table 2 embodiment 1～16 and the flue gas evaluation result of cigarette filter of comparative example 1～4
The result of embodiment 1～16: carry out smoke components by smoking machine and gas phase-mass spectrometry chromatograph
Analyzing, the chromatographic data finally given shows, the flue gas that equal quality tobacco shred produces is born through Graphene
After carrying fiber filter, TPM and benzopyrene data decline substantially, and other compositions include the things such as nicotine
The data of matter are basically unchanged.And medicated cigarette suction sense is unaffected.
Being contrasted by embodiment 4,7,10, embodiment 5,8,11 contrasts, embodiment 6,9,12
Contrast, it can be seen that in the case of equal Graphene content, the content of doped chemical is in certain limit
The biggest, then be more conducive to TPM and the absorption of benzopyrene.
The data of comparative example 1 show, the most not absorbing nicotine, nor affect on medicated cigarette and absorb sensation,
But absorption TPM and benzopyrene DeGrain.
The data of comparative example 2,3 show, the medicated cigarette adsorption material made after graphite and bamboo charcoal and fiber composite
Expect nicotine, TPM and benzopyrene assimilation effect all fine, and medicated cigarette is inhaled and experienced serious shadow
Ring.
From above example and comparative example, the present invention is by Graphene in fiber carrier and doping unit
The introducing of element, can specifically adsorb and be filtered to remove in flue gas the condensed-nuclei aromatics class nuisances such as benzopyrene
Matter, retains nicotine and other innocuous substances simultaneously, does not affect the suction taste of flue gas.The present invention provides
The condensed-nuclei aromatics class carcinogen such as the benzopyrene in cigarette filter energy active adsorption flue gas, reduce smoking
Harm；Do not affect the suction taste of flue gas simultaneously, do not reduce the pleasant sensation of smoker.
Applicant states, the present invention illustrates the process of the present invention by above-described embodiment, but this
Invention is not limited to above-mentioned processing step, does not i.e. mean that the present invention has to rely on above-mentioned processing step
Could implement.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, right
The equivalence of raw material selected by the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all
Fall within the scope of protection scope of the present invention and disclosure.
Claims (12)
1. a Graphene adsorbing material, including:
Fiber carrier；
With the Graphene being supported on described fiber carrier and doped chemical；
Described doped chemical includes one or more in Al, Si and Fe.
Graphene adsorbing material the most according to claim 1, it is characterised in that described fiber carrier bag
Include one or more in natural fiber, semisynthetic fibre and synthetic fibers.
Graphene adsorbing material the most according to claim 1, it is characterised in that described Graphene content
Account for the 0.1～10wt% of fiber carrier.
Graphene adsorbing material the most according to claim 1, it is characterised in that described Graphene has
Loose structure, porosity is 2%～10%.
Graphene adsorbing material the most according to claim 4, it is characterised in that described Graphene is made a living
Material porous graphene.
Graphene adsorbing material the most according to claim 1, it is characterised in that described doped chemical contains
Amount accounts for the 0.002～1wt% of fiber carrier.
7. according to the Graphene adsorbing material described in any one of claim 1～6, it is characterised in that described in mix
Miscellaneous element also includes one or more in K, Na, Ca, Mg, P, Mn and Co.
8. a preparation method for Graphene adsorbing material, comprises the following steps:
Fiber is contacted with Graphene material, loads, obtain Graphene adsorbing material；
Described Graphene material include Graphene and doped chemical, described doped chemical include Al, Si and
One or more in Fe.
Preparation method the most according to claim 8, it is characterised in that specifically include:
Fiber is immersed in graphene solution 10～60min, scrubbed, be dried, obtain Graphene absorption
Material；
Described graphene solution is disperseed to make by Graphene material in a solvent, and described Graphene material is made a living
Material porous graphene；
Preferably, described graphene solution is also dissolved with coupling agent.
10. arbitrary described Graphene adsorbing material answering in smoke filtration in a claim 1～7
With.
11. application according to claim 10, it is characterised in that the device of described smoke filtration includes
Cigarette filter, air conditioner filter element or vehicle exhaust exhaust apparatus.
12. 1 kinds of cigarette filters, it is characterised in that include by according to any one of claim 1～7
Graphene adsorbing material or by the graphite obtained by preparation method described in claim 8 or 9
Alkene adsorbing material and the segment of fiber made.
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| CN201710764154.1A CN107537439B (en) | 2016-07-25 | 2016-07-25 | A kind of graphene adsorbent material, preparation method and its application and cigarette filter |
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| CN201511033211.6A CN105597675A (en) | 2015-12-31 | 2015-12-31 | Graphene adsorbing material, preparation method and application thereof and cigarette filter tip |
| CN2015110332116 | 2015-12-31 |
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Cited By (4)
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| CN106820261A (en) * | 2017-04-10 | 2017-06-13 | 滁州卷烟材料厂 | A kind of filter tip for selecting to adsorb BaP and phenol in cigarette smoke |
| CN108722350A (en) * | 2018-05-07 | 2018-11-02 | 中国农业科学院油料作物研究所 | A kind of magnetic graphene composite material and preparation method and application |
| CN110680170A (en) * | 2019-09-24 | 2020-01-14 | 华南理工大学 | Screen window or curtain capable of removing formaldehyde and VOCs and preparation method thereof |
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| WO2017114174A1 (en) * | 2015-12-31 | 2017-07-06 | 济南圣泉集团股份有限公司 | Graphene electrothermal material and application thereof |
| CN105919160A (en) * | 2016-05-27 | 2016-09-07 | 阜阳卷烟材料厂 | Composite cigarette filter stick containing graphene material |
| CN111358048B (en) * | 2018-12-25 | 2022-08-30 | 贵州中烟工业有限责任公司 | Cigarette filter stick |
| CN113019322B (en) * | 2021-03-09 | 2022-11-11 | 云南中烟工业有限责任公司 | Graphene smoke adsorbing material for reducing harmful ingredients in cigarette smoke and preparation method and application thereof |
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| CN105597675A (en) | 2016-05-25 |
| CN106000316B (en) | 2019-09-10 |
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