CN106000316B - A kind of graphene adsorbent material, preparation method and its application and cigarette filter - Google Patents
A kind of graphene adsorbent material, preparation method and its application and cigarette filter Download PDFInfo
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- CN106000316B CN106000316B CN201610591211.6A CN201610591211A CN106000316B CN 106000316 B CN106000316 B CN 106000316B CN 201610591211 A CN201610591211 A CN 201610591211A CN 106000316 B CN106000316 B CN 106000316B
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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
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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
- A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
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- 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
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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
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- 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
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- 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
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- 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
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Abstract
The present invention provides a kind of graphene adsorbent material, preparation method and its application, which includes: fiber carrier;With the graphene and doped chemical being supported on the fiber carrier;The doped chemical includes one or more of Al, Si and Fe.The present invention also provides a kind of cigarette filters comprising segment of fiber made of graphene adsorbent material by mentioned earlier.The present invention can be adsorbed specifically by the introducing of graphene and doped chemical in fiber carrier and be filtered to remove the condensed-nuclei aromatics such as BaP class harmful substance in flue gas, while retain nicotine and other innocuous substances, not influence the suction taste of flue gas.Cigarette filter provided by the invention can effectively adsorb the condensed-nuclei aromatics class carcinogen such as BaP in flue gas, reduce harmfulness of smoking;The pleasant sensation of smoking and the alcohol fragrant smell of flue gas are not influenced simultaneously.In addition, graphene adsorbent material provided by the invention can also prevent the phenomenon mouldy because of the factors cigarette holder such as humid environment.
Description
Technical field
The present invention relates to adsorption technology field more particularly to a kind of graphene adsorbent materials, preparation method and its application
And cigarette filter.
Background technique
The condensed-nuclei aromatics class harmful components such as CO, phenol and BaP are generated during cigarette burning, in suction with flue gas
It causes damages into human body.Filter tip refers to the upper part of cigarette, is the bridge of cigarette main flume and human body, is mainly used to filter
Except a part sucks the harmful substances such as the tar in flue gas, the harm smoked to human body can be reduced.In order to reach the function of requirement,
Cigarette filter is gradually from common single cellulose acetate filter to filter tip side made of multiple filter tip and multiple material
To development.
Prior art discloses a variety of cigarette filters, such as the Chinese patent literature that Authorization Notice No. is CN 2872872Y
A kind of expansion graphite composite cigarette filter tip is disclosed, is made of filter fiber section, expanded graphite section and packet paper, is filtered
Segment of fiber and the docking of expanded graphite fillter section, packet paper bag are rolled in the outside of the two.This application scheme uses in cigarette filter
One section of fillter section containing expanded graphite is added, expansion graphite composite filter tip is made, it can effectively filter cigarette flue gas
In the harmful substances such as nicotine gas, kerosene and nicotine, but BaP cannot be adsorbed.
The Chinese patent literature that application publication number is 104815630 A of CN disclose a kind of selective absorption BaP and
The preparation method of the filter fiber of phenol, this method is mainly with graphene oxide water solution or graphene oxide and chitosan water
The mixed solution of solution is specific decorating liquid, carries out the processing such as spraying to fiber, handle the time 5~20 minutes, treatment temperature
25~50 DEG C, then by treated, fiber is placed under 80 DEG C of vacuum conditions, 6 hours dry, is prepared and is handled through decorating liquid
Filter fiber afterwards.Cigaratte filter is made in gained filter fiber by above-mentioned application, can reduce the BaP content in flue gas, but
It is that one side this application is related to other additives such as chitosan and preparation process is cumbersome, on the other hand its suction to BaP
Attached effect is still to be improved.
Summary of the invention
In view of this, the application provides a kind of graphene adsorbent material, preparation method and its application and cigarette filter,
While cigarette filter provided by the invention can selectively absorb and filter the condensed-nuclei aromatics substances such as the BaP in flue gas,
Retain the nicotine and other innocuous substances in flue gas, and then does not influence the fragrant smell of flue gas.
The present invention provides a kind of graphene adsorbent material, comprising:
Fiber carrier;
With the graphene and doped chemical being supported on the fiber carrier;
The mineral element includes one or more of Al, Si and Fe.
Graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, change
Vapor deposition method is learned, graphite oxidation reduction method can also be by biomass resource hydrothermal carbonization method, and in the prior art
The graphene of other methods preparation.But no matter which kind of method large scale preparation all difficult to realize obtains stricti jurise theoretically
Graphene, such as to have certain impurity elements, other homoatomics of carbon in the obtained graphene of prior art preparation different
Body or the non-single layer of the number of plies even graphene-structured (such as 3 layers, 5 layers, 10 layers, 20 layers etc.) of multilayer, what the present invention was utilized
Graphene also includes the graphene on above-mentioned non-critical theory of meaning.
Preferably, the fiber carrier includes one or more of natural fiber, semisynthetic fibre and synthetic fibers.
Preferably, the graphene content accounts for 0.1~10wt% of fiber carrier.
Preferably, the graphene has porous structure, and porosity is 2%~10%.
Above-mentioned graphene has porous structure, is to have porous distributed architecture on graphene film layer plane.
Preferably, the graphene is biomass porous graphene.
Preferably, the doped chemical content accounts for 0.002~1wt% of fiber carrier.
Preferably, the doped chemical further includes one or more of K, Na, Ca, Mg, P, Mn and Co.
The present invention provides a kind of preparation method of graphene adsorbent material, comprising the following steps:
Fiber is contacted with graphene material, is loaded, obtains graphene adsorbent material;
The graphene material includes graphene and doped chemical, and the doped chemical includes one of Al, Si and Fe
Or it is several.
Preferably, it specifically includes:
Fiber is immersed in 10~60min in graphene solution, it is washed, dry, obtain graphene adsorbent material;
The graphene solution is dispersed to be made in a solvent by graphene material, and the graphene material is biomass porous
Graphene;
Preferably, the graphene solution is also dissolved with coupling agent.
It is further preferred that the coupling agent includes silane coupling agent, titanate coupling agent and zirconium class coupling agent etc.
It is one or more of;Coupling agent dosage can be the 1%~10% of graphene quality.
The present invention also provides a kind of application of above-mentioned graphene adsorbent material in smoke filtration.
Further, above-mentioned graphene adsorbent material is in cigartte filter tip, air conditioner filter element or vehicle exhaust exhaust apparatus
In application, i.e., the device of the described smoke filtration includes cigarette filter, air conditioner filter element or vehicle exhaust exhaust apparatus.
The present invention also provides a kind of cigarette filters comprising graphene adsorbent material and manufactured fibre by mentioned earlier
Tie up section.
Compared with prior art, graphene adsorbent material provided by the invention includes fiber carrier and is supported on fiber carrier
On graphene and doped chemical, the doped chemical include one or more of Al, Si and Fe.The present invention is carried by fiber
The introducing of graphene and doped chemical in body, can specifically adsorb and be filtered to remove the condensed-nuclei aromatics class such as BaP in flue gas has
Evil substance, while retaining nicotine and other innocuous substances, the suction taste of flue gas is not influenced.Cigarette filter energy provided by the invention
The condensed-nuclei aromatics class carcinogens such as the BaP effectively in absorption flue gas, reduce harmfulness of smoking;Do not influence the suction taste of flue gas simultaneously,
The pleasant sensation of smoker is not reduced.
In addition, graphene adsorbent material provided by the invention can also prevent from showing because the factors cigarette holder such as humid environment is mouldy
As.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of graphene adsorbent materials, comprising:
Fiber carrier;With the graphene and doped chemical being supported on the fiber carrier;The doped chemical include Al,
One or more of Si and Fe.Preferably, the graphene and doped chemical are introduced by biomass graphene.Graphite
Alkene and doped chemical can be introduced separately into, and can also mixing introducing, (it includes that mixing in advance introduces that mixing, which introduces, and mixing introduces in advance
Again include introducing and inherently having by oneself in synthesis process), and biomass graphene is exactly containing graphene and doped chemical
Mixture.
BaP in graphene adsorbent material alternative absorption flue gas provided by the invention, adsorption efficiency is high, flue gas
It is preferable to inhale taste.
Graphene adsorbent material provided by the invention includes fiber carrier, and the fiber carrier can be natural fiber, people
The mixing of one or more of fiber and synthetic fibers is made, one of semisynthetic fibre and synthetic fibers or several are preferably included
Kind.In an embodiment of the present invention, the natural fiber includes plant fiber and animal origin, and plant fiber includes by plant
The fiber that seed, fruit, stem, leaf etc. obtain, such as cotton fiber, flaxen fiber, animal origin includes animal hair class or silk class.
In an embodiment of the present invention, staple fibre is also referred to as semisynthetic fibre, including viscose rayon, acetate fiber, copper ammonia fiber and existing
There are other semisynthetic fibres in technology;Synthetic fibers include polypropylene fibre (polypropylene fibre), polyacrylonitrile fibre (acrylic fibers), poly- second
Enol formal fiber (vinylon), Fypro (polyamide fibre), polyethylene terephthalate (terylene) etc..Of the invention
In some embodiments, the technical indicator of the fiber carrier is as follows:
Fibre length 5mm or more, fineness are unlimited;
Fiber moisture 5%~10%;
It is more than 1 gram force of fibre strength.
In the present invention, the fiber carrier can be any fibre number, and further preferred Denier range is 0.13-
10D.Fibre length can be any fibre length, and further preferred fibre length is 5mm or more.Fiber moisture is unlimited,
Further preferred fiber moisture is 5%~10%.Fibre strength is unlimited, further preferred fibre strength be 1 gram force with
On.
In an embodiment of the present invention, viscose rayon, acetate fiber, copper ammonia fiber, polypropylene fibre (polypropylene fibre), polypropylene
Nitrile fiber (acrylic fibers), vinylon (vinylon), Fypro (polyamide fibre), polyethylene terephthalate
(terylene) or other synthetic fibers can be commercial product, can also be prepared using method in the prior art.
In specific embodiment of the present invention, the above-mentioned fiber dimensious of fiber carrier commercial product may include: 1.5D*
38mm or 1.5D*51mm;Moisture content is 7%, and fibre strength is 1.5 gram forces.
It is illustrated below using fiber made from preparation method in the prior art:
For preparing viscose rayon, viscose used in the present invention is viscose known to the prior art, preparation
Method is, using pulp as raw material, is impregnated, is squeezed, crushed, aging, yellow, dissolution, maturation, filtering, the processes such as deaeration.Slurry
The dregs of rice are impregnated through the sodium hydrate aqueous solution that concentration is 18% or so, and cellulose is made to be converted to alkali cellulose, and hemicellulose dissolution gathers
Right part decline;Extra lye is removed through squeezing again.Block-like alkali cellulose becomes loose after crushing on pulverizer
Flock, since surface area increase improves later chemical reaction uniformity.Alkali cellulose aoxidizes under the effect of the oxygen
Cracking declines average degree of polymerization, this process is known as aging.Alkali cellulose is reacted with carbon disulfide after aging and generates fiber
Plain xanthate acid claims yellow, weakens the hydrogen bond between macromolecular further, due to the hydrophily of yellow acid group, makes cellulose xanthate
Solubility property in sig water greatly improves.Solid cellulose xanthate acid is dissolved in sig water, is viscose glue.Just it is made
Viscose glue is because of viscosity and salt figure is higher is not easy to shape, it is necessary to place certain time at a certain temperature and be known as maturation, make in viscose glue
Sodium cellulose xanthate is gradually hydrolyzed and is saponified, esterification degree reduce, viscosity and to electrolyte effect stability also with change.?
Deaeration and filtering should be carried out after maturation, to remove bubble and impurity.
In an embodiment of the present invention, process flow and the condition for preparing viscose fiber filament are specific as follows:
1. alkali steeping process conditions: lye (NaOH): concentration 240g/L, temperature are 20 DEG C, dip time: 120min;
2. experienced process conditions: temperature is 25 DEG C, time 34h;
3. yellow process conditions: yellow method is wet process yellow, wherein it is 30min that alkalization, which includes: the time, and temperature is
21.0±0.5℃;Yellow includes: the time for 120min, and initial temperature is 21.0 ± 0.5 DEG C, and final temperature is 30.0 ± 0.5
℃;CS2It is 34.5% (to first fibre) that quality, which is added,;Preceding dissolution includes: the time for 120min, and temperature is 16.5 ± 0.5 DEG C;It is molten afterwards
It is 180min when solution includes:, temperature is 16.5 ± 0.5 DEG C;
4. in terms of mass-dispersion, viscose glue stoste composition obtained 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, and temperature is 19.0 ± 0.5 DEG C;
6. obtained spinning glue index: viscosity is 30~40 seconds (20 DEG C, falling ball method);Degree of ripeness is 7.8~8.6mL
(10%NH4Cl value);
7. spinning process condition: spinning speed is 82m/min;Drawing-off is 25%;Nervous drawing-off is 4.12%;
8. coagulation bath condition is as follows:
Acid bath composition are as follows:
H2SO4132.0±1.0g/L;
ZnSO410.5±0.5g/L;
Na2SO4265.0±5.0g/L;
Temperature is 52.0 ± 1.0 DEG C;Specific gravity is 1.270 ± 0.005.
On fiber carrier, graphene adsorbent material provided by the invention includes the graphene and doped chemical of load, institute
Stating doped chemical includes one or more of Al, Si and Fe.The present invention passes through graphene in fiber carrier and doped chemical
It introduces, can be further improved the effect of the harmful substances such as BaP in adsorbent material filtering flue gas, while guaranteeing the suction taste of flue gas
Well.
Graphene is one kind by single layer sp2The two-dimensional material of the honeycomb structure of hydbridized carbon atoms composition, has many excellent
Different performance.The structure of the graphene is as shown in Equation 1:
Graphene dispersion of the present invention makes fiber carrier contain graphene on fiber carrier.Of the invention preferred
In embodiment, the graphene content accounts for 0.1~10wt% of fiber carrier, 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,
The graphene has porous structure, specially has the micropore of irregular distribution by pretreatment;Porosity can for 2%~
10%, preferably 3%~7%;Pore diameter range is 1~20nm.
In the present invention, the graphene is preferably biomass porous graphene, in other words preferably, the graphene and
Doped chemical is introduced by biomass graphene;Biomass graphene contains the lamellar structure of 10 layers or less graphenes, carbon
SP3Hybrid structure and mineral element;Mineral element includes Fe, Si and Al element.In an embodiment of the present invention, the mineral
Element constituent content is the 0.5wt%~6wt%, preferably 1.5wt%~5wt% of biomass graphene.The mineral element
It is also preferable to include any one or more in P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co;The mineral element with simple substance and/
Or the form of compound exists, compound includes oxide, carbide, they are adsorbed on the surface or interior of biomass graphene
Portion.In an embodiment of the present invention, carbon element content >=80wt%, preferably greater than 85wt% in the biomass graphene, then
Preferably greater than 90wt%, most preferably greater than 95wt%.In an embodiment of the present invention, the graphene is to exist with thickness
The hexatomic ring honeycomb lamellar structure of 100nm carbon below.In embodiments of the present invention, on the one hand which can provide
Flue gas and cross-ventilated channel, prevent pipe tobacco imperfect combustion, reduce the generation of imperfect combustion nuisance;On the other hand
The porous graphene has bigger serface characteristic, can be effectively to the condensed-nuclei aromatics such as carcinogenic BaP substance (PAHs)
Carry out selective absorption.
In the present invention, the doped chemical includes one or more of Al, Si and Fe, preferably includes Al, Si and Fe.
The doped chemical is dispersed on fiber carrier, and fiber carrier is made to contain doped chemical.In a preferred embodiment of the invention, institute
State 0.002~1wt% that doped chemical content accounts for fiber carrier, preferably 0.02~0.8wt%, more preferably 0.2~
0.5wt%.In addition, it is also preferable to include one or more of K, Na, Ca, Mg, P, Mn and Co for the doped chemical.
Graphene adsorbent material provided by the invention belongs to carbon nanomaterial product, has specific adsorption performance, can be special
This kind of harmful substance of BaP in opposite sex absorption flue gas, while the suction taste of flue gas is not influenced.
Correspondingly, the present invention provides a kind of preparation methods of graphene adsorbent material, comprising the following steps: by fiber with
The contact of graphene material, is loaded, obtains graphene adsorbent material;The graphene material includes graphene and doping member
Element, the doped chemical include one or more of Al, Si and Fe.
The graphene adsorbent material that the present invention prepares can effectively adsorb the harmful substances such as the BaP in flue gas, and not shadow
Ring the suction taste of flue gas.In addition, the method that the present invention prepares graphene adsorbent material is easy to operate, it is suitable for industrialization promotion.
Graphene and doped chemical are supported on fiber carrier by the present invention using fiber as carrier, obtain graphene absorption
Material.Wherein, the content of the fiber carrier is as it was noted above, details are not described herein.
In a preferred embodiment of the invention, the graphene content accounts for 0.1~10wt% of fiber carrier, and preferably 1
~4wt%, for example, 0.1wt%, 0.3wt%, 0.5wt%, 0.7wt%, 1wt%, 3wt%, 5wt%, 6wt%, 7.8wt%,
8.9wt%, 10wt% etc..In some embodiments of the invention, the graphene has porous structure, specially by pre- place
Manage the micropore with irregular distribution;Porosity can be 2%~10%, preferably 3%~7%;Pore diameter range is 1~20nm.
The present invention is not particularly limited the source of the graphene, can use commercial product, can also prepare;The stone
Black alkene can be by mechanically pulling off method, epitaxial growth method, chemical vapor infiltration, graphite oxidation reduction method and by biomass
Resource hydrothermal carbonization method is prepared.
In one embodiment of the invention, the graphene is preferably biomass graphene.The biomass graphene
The SP of lamellar structure, carbon containing 10 layers or less graphenes3Hybrid structure and mineral element;The mineral element includes Fe, Si
With Al element.In an embodiment of the present invention, the mineral element constituent content be biomass graphene 0.5wt%~
6wt%, preferably 1.5wt%~5wt%.It is also preferable to include P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co for the mineral element
In any one or more;The mineral element exists in the form of simple substance and/or compound, compound include oxide,
Carbide, they are adsorbed on the surface or inside of biomass graphene.In an embodiment of the present invention, the biomass graphene
Middle carbon element content >=80wt%, preferably greater than 85wt%, still more preferably greater than 90wt%, most preferably greater than 95wt%.In this hair
In bright embodiment, the graphene is the hexatomic ring honeycomb lamellar structure with thickness in 100nm carbon below.
In an embodiment of the present invention, the biomass graphene can be made using biomass resource hydrothermal carbonization method.Tool
Body, below only for example:
Method 1:
(1) under the effect of the catalyst, biomass carbon source is subjected to catalytic treatment, obtains presoma;
(2) it under conditions of protective gas, by the presoma in 140 DEG C~180 DEG C heat preservation 1.5h~2.5h, obtains
First intermediate;
(3) under conditions of protective gas, first intermediate is warming up to 350 DEG C~450 DEG C heat preservation 3h~4h,
Obtain the second intermediate;
(4) under conditions of protective gas, by second intermediate be warming up to 1100 DEG C~1300 DEG C heat preservation 2h~
4h obtains third intermediate;
(5) by the third intermediate successively alkali cleaning, pickling, washing, graphene is obtained;
Heating rate in the step (3), (4) is 14 DEG C/min~18 DEG C/min.
The biomass graphene being prepared in the above method 1 (can have certain in the graphene that prior art preparation obtains
A little impurity elements, other allotropes of carbon or the non-single layer of the number of plies even graphene-structured of multilayer, and this biomass
The graphene that method is prepared also is mixture, as graphene material) in, it is non-oxygen containing graphene, amorphous carbon and non-carbon
Element.
Specifically:
Mixing biomass carbon source and catalyst first are dried to obtain presoma after stirring carries out catalytic treatment;
Then in protective atmosphere, by presoma at 140~180 DEG C, 1.5~2.5h is kept the temperature, the first intermediate is obtained;
In some embodiments of the invention, the temperature is 142 DEG C, 148 DEG C, 155 DEG C, 1600 DEG C, 172 DEG C or 178 DEG C;Institute
Stating soaking time is 1.6h, 1.8h, 2h, 2.2h or 2.4h.
Temperature programming later keeps the temperature 3~4h, obtains the second intermediate to 350~450 DEG C;Of the invention certain specific
In embodiment, the 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;The heat preservation
Time is 3.1h, 3.3h, 3.5h, 3.8h or 3.9h.
Then it is warming up to 1100~1300 DEG C again, keeps the temperature 2~4h, obtains third intermediate, i.e. product crude product;In the present invention
Certain specific embodiments in, the temperature be 1130 DEG C, 1170 DEG C, 1210 DEG C or 1280 DEG C;The 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 program heating is 14 DEG C/min~18 DEG C/min, in some embodiments of the invention
In, the heating rate is 15 DEG C/min, 16 DEG C/min or 17 DEG C/min.
Finally by after third intermediate (i.e. product crude product) alkali cleaning, pickling, washing, compound is obtained.
In the present invention, the mass ratio of the biomass carbon source and catalyst is 1:(0.5~5), preferred 1:(1~3);At this
In certain specific embodiments of invention, the ratio is 1:0.5,1:1 or 1:3.
In the present invention, the catalyst is selected from halogen compounds, iron containing compounds, cobalt compound and the nickeliferous chemical combination of manganese
Any a kind or at least two kinds of of combination in object.
Preferably, halogen compounds of the iron containing compounds selected from iron, iron cyanide and iron content hydrochlorate in any 1
Kind or at least two kinds of combinations.The iron content hydrochlorate is the salt of the organic acid containing ferro element or the inorganic acid containing ferro element
Salt.The halogen compounds of the iron can be iron chloride and/or ferric bromide.
Preferably, halogen compounds of the cobalt compound selected from cobalt and containing any a kind or at least two kinds of in cobaltatess
Combination.It is described containing cobaltatess be the salt of the organic acid containing cobalt element or the salt of the inorganic acid containing cobalt element.The cobalt
Halogen compounds can be cobalt chloride and/or cobaltous bromide.
Preferably, chlorate of the nickel compound containing selected from nickel and containing any a kind or at least two kinds of of group in nickelate
It closes.It is described containing nickelate be the salt of the organic acid containing nickel element or the salt of the inorganic acid containing nickel element.The halogen of the nickel
Compound can be nickel chloride and/or nickelous bromide.
Preferably, the catalyst be selected from iron chloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate,
The potassium ferricyanide, potassium ferrocyanide, three oxalic acid close potassium ferrite, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, nickel chloride, nickel nitrate,
Any a kind or at least two kinds of of combination in nickel sulfate and nickel acetate.
The typical but non-limiting example of combination of catalyst of the present invention has the combination of frerrous chloride and ferric sulfate, iron
Potassium cyanide and three oxalic acid close the combination of potassium ferrite, the combination of cobalt chloride, cobalt nitrate and iron chloride, cobaltous sulfate, cobalt acetate and nitric acid
The combination of nickel, the combination of iron chloride, cobalt chloride and nickel acetate.
The temperature that the stirring carries out catalytic treatment is 150 DEG C~200 DEG C, such as 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C
Deng, time >=4h, preferably 4h~14h, in some embodiments of the invention, the time be 4.2h, 7h, 9h, 12h,
16h、19h、23h。
Preferably, the moisture content in the presoma is 10wt% hereinafter, in some embodiments of the invention,
The moisture content is 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 10wt% etc..
Preferably, the protective atmosphere is nitrogen, helium, any a kind or at least two kinds of of combination in argon gas, preferably
Nitrogen.
Preferably, the aqueous hydrochloric acid solution that the pickling is 3wt%~6wt% using concentration, further preferred concentration are
The aqueous hydrochloric acid solution of 5wt%;It is preferable to use deionized water and/or distilled water for the washing;The alkali cleaning is 5wt% using concentration
The sodium hydrate aqueous solution of~15wt%, further preferred concentration are the sodium hydrate aqueous solution of 10wt%.
Preferably, the temperature of the 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
℃。
The biomass carbon source is cellulose and/or lignin, preferred cellulose, further preferred porous cellulose.
Porous cellulose of the present invention can be obtained by the prior art, typical but non-limiting acquisition porous fibre
The prior art of element has: method disclosed in such as patent publication No. CN104016341A prepares porous cellulose, uses
Method disclosed in CN103898782A prepares cellulose.
Preferably, the porous cellulose obtains by the following method:
Biomass resource progress sour water solution is obtained into lignocellulosic, post-processes to obtain porous fibre by porous later
Element;Optionally, porous cellulose uses after bleaching.
Any a kind or at least two kinds of of combination of the biomass resource in plant and/or agriculture and forestry organic waste material;It is preferred that
Any a kind or at least two kinds of of combination in agriculture and forestry organic waste material.
Preferably, the agriculture and forestry organic waste material is selected from cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, wood
Any a kind or at least two kinds of of combination in sugar residue, sawdust, cotton stalk and reed, preferably corncob.
The typical but non-limiting example combinations of biomass resource of the present invention include the combination of cornstalk and corncob,
The combination of bagasse, kaoliang stalk and sawdust, megasse, the combination of bagasse and corncob, kaoliang stalk, megasse and xylose residue
Combination etc..
It can also be prepared by following a variety of methods:
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, the doped chemical includes one or more of Al, Si and Fe, preferably includes Al, Si and Fe.
The doped chemical is dispersed on fiber carrier, and fiber carrier is made to contain doped chemical.In a preferred embodiment of the invention, institute
State 0.002~1wt% that doped chemical content accounts for fiber carrier, preferably 0.02~0.8wt%, more preferably 0.2~
0.5wt%.In addition, it is also preferable to include one or more of K, Na, Ca, Mg, P, Mn and Co for the doped chemical.
In the present invention, the doped chemical can be introduced by adding the nano material containing doped chemical, can also be passed through
Graphene and the mixed form of doped chemical introduce.The mixed form can be to prepare in graphene technical process routinely,
It is doped constituent content and controls the mixture to be formed;Preferably, graphene process is prepared by oxidation-reduction method using graphite
In, due to mineral element existing for graphite itself, by reasonable control element type and content, what is be prepared is first containing mineral
The graphene of element.Or graphene is prepared for raw material using biomass resource, and carry out process control doped chemical content;This hair
It is bright preferably by biomass resource, the graphene containing mineral element being prepared by hydro-thermal charring process.Herein, mineral
Element is doped chemical.
Specifically, fiber is immersed in certain time such as 10~60min in graphene solution by the embodiment of the present invention, through washing
It washs, dry, obtain graphene adsorbent material;The graphene solution is dispersed to be made in a solvent by graphene material.The stone
Black alkene material can the material by graphene and containing doped chemical form, be also possible to the graphene containing doped chemical, it is excellent
It is selected as biomass porous graphene.
In a preferred embodiment of the invention, coupling agent is also dissolved in the graphene solution.The coupling agent is excellent
Choosing includes the one or more of silane coupling agent, titanate coupling agent and zirconium class coupling agent etc.;The dosage of the coupling agent is preferred
It is the 1%~10% of graphene quality.
In some embodiments of the invention, biomass porous graphene uniform is distributed in solvent, is made into graphene
Solution.In other embodiments of the invention, graphene and the material containing doped chemical are evenly spread in solvent, matched
At graphene solution.Wherein, doped chemical is at least Fe, Si, Al, can also contain one of K, Na, Ca, Mg, P, Mn and Co
Or it is several.The material containing doped chemical concretely nanometer phosphorus pentoxide, nano silica fume, nanometer aluminium powder, Nanoscale Iron,
Nanometer Mg powder, nano-calcium carbonate sodium, nano-calcium carbonate potassium, nanometer calcium carbonate, nano manganese oxide and nanometer cobalt etc..
Graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, change
Vapor deposition method is learned, graphite oxidation reduction method can also be by biomass resource hydrothermal carbonization method, and in the prior art
The graphene of other methods preparation.But no matter which kind of method large scale preparation all difficult to realize obtains stricti jurise theoretically
Graphene, such as to have certain impurity elements, other homoatomics of carbon in the obtained graphene of prior art preparation different
Body or the non-single layer of the number of plies even graphene-structured (such as 3 layers, 5 layers, 10 layers, 20 layers etc.) of multilayer, what the present invention was utilized
Graphene also includes the graphene on above-mentioned non-critical theory of meaning.For example, being the graphite that raw material is prepared using graphite ore
In alkene, itself existing certain mineral element in graphite ore may be contained.Signified biomass graphene is provided using biomass
Source is the graphene that raw material is prepared, and can may also have the mineral element that plant needs to absorb from soil because of itself
With other allotropes of carbon.Therefore, graphene signified in the present invention is specially a kind of mixture containing graphene.
In an embodiment of the present invention, the solvent of the graphene solution is preferably ethylene glycol, dimethylformamide
(DMF), one or more of N-Methyl pyrrolidone (NMP), second alcohol and water mix.The mode of the dispersion is preferably ultrasound
Dispersion can be made into the graphene solution that graphene concentration is 0.1~10mg/mL, and concentration is preferably 0.5~3mg/mL.
Before the present invention loads fiber, it is also preferable to include fiber to be activated, removal carrier itself contains
Impurity, miscellaneous gas, drying obtains activated fiber carrier.In an embodiment of the present invention, the mode of the activation processing
It can be boiled for boiling water, preferably boiling water boils 25~30min.
Activated fiber carrier is immersed into 10~60min in graphene solution by the embodiment of the present invention, washed, dry
It is dry, obtain graphene adsorbent material.Wherein, the mode of the submergence preferably includes first ultrasound, rear concussion, stands again.It is submerging
Between washing, it is also preferable to include immobilize processing by the present invention;The immobilization processing can be chemical method, the reagent used
Preferably include the combination of one or more of dehydrated alcohol, anhydrous methanol and dust technology.
The graphene adsorbent material that the present invention is prepared includes: fiber carrier;Be supported on the fiber carrier
Graphene and doped chemical;The doped chemical includes one or more of Al, Si and Fe.Graphene provided by the invention is inhaled
Enclosure material alternative adsorbs the condensed ring class harmful substances such as the BaP in flue gas, and adsorption efficiency is high, and flue gas suction taste is preferable, can use
Make cigarette filter.In addition, graphene adsorbent material produced by the present invention can also be prevented because the factors cigarette holder such as humid environment is mouldy
The phenomenon that.
The present invention also provides a kind of application of above-mentioned graphene adsorbent material in smoke filtration.Further, above-mentioned
Application of the graphene adsorbent material in cigartte filter tip, air conditioner filter element or vehicle exhaust exhaust apparatus.The smoke filtration
Device include cigarette filter, air conditioner filter element or vehicle exhaust exhaust apparatus;Above-mentioned graphene adsorption material can be used in the present invention
The device of smoke filtration is made in material according to a conventional method.
Specifically, the present invention also provides a kind of cigarette filter, abbreviation filter tip comprising graphene by mentioned earlier
Segment of fiber made of adsorbent material.Cigarette filter provided by the invention can effectively adsorb the nuisances such as the BaP in flue gas
Matter reduces harmfulness of smoking;Retain nicotine and innocuous substance simultaneously, guarantees that the suction taste of flue gas is good, do not reduce the fast of smoker
Sense.
The present invention uses convention filter production method, and filter tip is made in graphene adsorbent material described above.In this hair
In bright embodiment, the thickness of segment of fiber made of graphene adsorbent material by mentioned earlier is preferably 1~4mm, the fibre
Tie up section with a thickness of the thickness for prolonging filter tip axial direction.In an embodiment of the present invention, the filter tip is binary combined filter tip,
Contact pipe tobacco end is close to the segment of fiber for loading graphene and doped chemical, then connects general fibre section.
Present invention cigarette made of the tobacco cartridge to identical weight on smoking machine carry out same operation under the conditions of
Fume collection analyzes the sample being collected by gas phase-mass spectrometry tester, determines different in the flue gas of absorption front and back
The variation of ingredient peak shape.
The present invention inhales taste to the flue gas of the cigarette filter and evaluates, specifically to its fragrance, miscellaneous gas, irritation and
The evaluation of the evaluation of pleasant impression, each embodiment selects 300 valuation officers to carry out blind sample test.Evaluation criterion is as shown in table 1 below.
The flue gas of 1 cigarette filter of table inhales taste evaluation criterion
The results show that cigarette filter provided by the invention can effectively adsorb the harmful substances such as the BaP in flue gas, subtract
Small harmfulness of smoking;The suction taste for not influencing flue gas simultaneously, does not reduce the pleasant sensation of smoker.
For a further understanding of the application, below with reference to embodiment to graphene adsorbent material provided by the present application and its system
Preparation Method and cigarette filter are specifically described.
Prepare biomass graphene of the invention by the following method:
(1) under the effect of the catalyst, biomass carbon source is subjected to catalytic treatment, obtains presoma;
(2) it under conditions of protective gas, by the presoma in 140 DEG C~180 DEG C heat preservation 1.5h~2.5h, obtains
First intermediate;
(3) under conditions of protective gas, first intermediate is warming up to 350 DEG C~450 DEG C heat preservation 3h~4h,
Obtain the second intermediate;
(4) under conditions of protective gas, by second intermediate be warming up to 1100 DEG C~1300 DEG C heat preservation 2h~
4h obtains third intermediate;
(5) by the third intermediate successively alkali cleaning, pickling, washing, compound is obtained;
Heating rate in the step (3), (4) is 14 DEG C/min~18 DEG C/min.The biomass graphene contains
The sp of the lamellar structures of 10 layers or less graphenes, carbon3Hybrid structure and mineral element;The mineral element includes Fe, Si and Al
Element.In an embodiment of the present invention, the mineral element constituent content is the 0.5-6wt% of biomass graphene, such as
1wt%, 2wt%, 3wt%, 4wt%, 5wt% etc.;The mineral element mainly may include P, Si, Ca, Al, Fe, Mg element.
More specifically, preparing biomass graphene used herein by following preparation example 1-4.
Preparation example 1
(1) under the action of frerrous chloride, corn cob fiber element is subjected to catalytic treatment, obtains presoma;
(2) under conditions of nitrogen, by the presoma in 150 DEG C of heat preservation 2h, the first intermediate is obtained;
(3) under conditions of nitrogen, first intermediate is warming up to 400 DEG C of heat preservation 3.5h, obtains the second intermediate;
(4) under conditions of nitrogen, second intermediate is warming up to 1200 DEG C of heat preservation 3h, obtains third intermediate;
It (5) is the sodium hydroxide solution of 10wt%, the chlorohydric acid pickling of 4wt%, water through over-richness by the third intermediate
After washing, biomass graphene is obtained;
Heating rate in the step (3), (4) is 15 DEG C/min~16 DEG C/min.
It is detected through XRD, in preparation example 1 of the invention in biomass graphene obtained, the content of mineral element is should
The 4wt% of biomass graphene;Also, the mineral element in the biomass graphene mainly includes P, Si, Ca, Al, Fe, Mg member
Element.
Preparation example 2
Biomass graphene is prepared by method identical with preparation example 1, unlike: step is urged used in (1)
Agent is the mixture (mass ratio 3:1) of iron chloride and nickel nitrate, and biomass carbon source is that the corncob through hydrogen peroxide bleaching is fine
Dimension element;Protective gas used in step (2)-(4) is argon gas, and presoma is in 140 DEG C of heat preservation 2.5h, the heating of the first intermediate
To 250 DEG C of heat preservation 4h, the second intermediate is warming up to 1100 DEG C of heat preservation 2h;Alkali used in step (5) is that 5wt%NaOH is water-soluble
Liquid, acid used are the aqueous hydrochloric acid solution of 3wt%.
Through detecting, in preparation example 2 of the invention in obtained biomass graphene, the content of mineral element is the life
The 2wt% of substance graphene;Also, the mineral element in the biomass graphene mainly includes Si, Al, Fe element.
Preparation example 3
Biomass graphene is prepared by method identical with preparation example 1, unlike: step is urged used in (1)
Agent is the mixture (mass ratio 3:1) of frerrous chloride and ferric sulfate, and biomass carbon source is lignocellulosic;Step (2)-
(4) in, for presoma in 180 DEG C of heat preservation 1.5h, the first intermediate is warming up to 450 DEG C of heat preservation 4h, and the second intermediate is warming up to 1300
DEG C heat preservation 4h;Alkali used in step (5) is the sodium hydrate aqueous solution of 15wt%, and acid used is that the hydrochloric acid of 6wt% is water-soluble
Liquid.The obtained biomass graphene in preparation example 3 of the invention, the content of Mineral Elements are the biomass graphene
0.8wt%;Through detecting, the mineral element in the biomass graphene mainly includes Si, Fe element.
Preparation example 4
Biomass graphene is prepared by method identical with preparation example 1, unlike: step is urged used in (1)
Agent is the mixture (mass ratio 3:1) of nickel nitrate and cobaltous sulfate, and biomass carbon source is reed fiber element.
The obtained biomass graphene in preparation example 3 of the invention, the content of Mineral Elements are the biomass
The 6wt% of graphene;Through detecting, the mineral element in the biomass graphene mainly includes Si, Fe, Na, K element.
Embodiment 1
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, the graphene of 0.5mg/mL is made into
Solution;
Fiber carrier (is used into acetate fiber, commercially available in the prior art, technical indicator includes: 1.5D*38mm, is contained
Water rate is 7%, and fibre strength is 1.5 gram forces) it carries out boiling water and boils processing 25min, the impurity, miscellaneous that removal carrier itself contains
Gas, drying, obtains the fiber carrier being activated;
The fiber carrier handled well is immersed into 10min in graphene solution, submergence includes first ultrasound, rear concussion, quiet again
It sets;Processing is immobilized using dehydrated alcohol, it is washed, dry, obtain graphene adsorbent material;The quality of graphene is fibre
Tie up the 1% of carrier quality.That is, the content of graphene is the 1wt% of fiber carrier, the content of doped chemical accounts for fiber carrier
0.04wt%.
Embodiment 2
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, the graphene for being made into 3mg/mL is molten
Liquid;
Fiber carrier (with embodiment 1) progress boiling water is boiled into processing 25min, the impurity, miscellaneous that removal carrier itself contains
Gas, drying, obtains the fiber carrier being activated;
The fiber carrier handled well is immersed into 60min in graphene solution, submergence includes first ultrasound, rear concussion, quiet again
It sets;Processing is immobilized using dehydrated alcohol, it is washed, dry, obtain graphene adsorbent material;The quality of graphene is fibre
Tie up the 4% of carrier quality.That is, the content of graphene is the 4wt% of fiber carrier, the content of doped chemical accounts for fiber carrier
0.16wt%.
Embodiment 3
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, the graphene of 1.5mg/mL is made into
Solution;
Fiber carrier (with embodiment 1) progress boiling water is boiled into processing 25min, the impurity, miscellaneous that removal carrier itself contains
Gas, drying, obtains the fiber carrier being activated;
The fiber carrier handled well is immersed into 25min in graphene solution, submergence includes first ultrasound, rear concussion, quiet again
It sets;Processing is immobilized using dehydrated alcohol, drying obtains graphene adsorbent material;The quality of graphene is fiber load
The 2.5% of weight.That is, the content of graphene is the 2.5wt% of fiber carrier, the content of doped chemical accounts for fiber carrier
0.1wt%.
Embodiment 4
Biomass graphene uniform obtained by preparation example 1 is distributed in ethylene glycol, the graphene of 0.5mg/mL is made into
Solution;
Fiber carrier (is used into acetate fiber, commercially available in the prior art, technical indicator includes: 1.5D*38mm, is contained
Water rate is 7%, and fibre strength is 1.5 gram forces) it carries out boiling water and boils processing 25min, the impurity, miscellaneous that removal carrier itself contains
Gas, drying, obtains the fiber carrier being activated;
The fiber carrier handled well is immersed into 10min in graphene solution, submergence includes first ultrasound, rear concussion, quiet again
It sets;Processing is immobilized using dehydrated alcohol, it is washed, dry, obtain graphene adsorbent material.The content of graphene is fibre
The 0.1wt% of carrier is tieed up, the content of doped chemical accounts for the 0.004wt% of fiber carrier.
Embodiment 5
As different from Example 4: being made into the graphene solution of 3mg/mL;The fiber carrier handled well is immersed into graphite
60min in alkene solution;The content of graphene is the 10wt% of fiber carrier, and the content of doped chemical accounts for fiber carrier
0.4wt%.
Embodiment 6
As different from Example 4: being made into the graphene solution of 1.5mg/mL;The fiber carrier handled well is immersed into stone
25min in black alkene solution;The content of graphene is the 5wt% of fiber carrier, and the content of doped chemical accounts for fiber carrier
0.2wt%.
Embodiment 7
As different from Example 4: using biomass graphene obtained by preparation example 2;The content of doped chemical accounts for fibre
Tie up the 0.002wt% of carrier.
Embodiment 8
As different from Example 5: using biomass graphene obtained by preparation example 2;The content of doped chemical accounts for fibre
Tie up the 0.2wt% of carrier.
Embodiment 9
As different from Example 6: using biomass graphene obtained by preparation example 2;The content of doped chemical accounts for fibre
Tie up the 0.1wt% of carrier.
Embodiment 10
As different from Example 4: using biomass graphene obtained by preparation example 3;The content of doped chemical accounts for fibre
Tie up the 0.0008wt% of carrier.
Embodiment 11
As different from Example 5: using biomass graphene obtained by preparation example 3;The content of doped chemical accounts for fibre
Tie up the 0.08wt% of carrier.
Embodiment 12
As different from Example 6: using biomass graphene obtained by preparation example 3;The content of doped chemical accounts for fibre
Tie up the 0.04wt% of carrier.
Embodiment 13
As different from Example 4: using biomass graphene obtained by preparation example 4;The content of doped chemical accounts for fibre
Tie up the 0.006wt% of carrier.
Embodiment 14
As different from Example 5: using biomass graphene obtained by preparation example 4;The content of doped chemical accounts for fibre
Tie up the 0.6% of carrier.
Embodiment 15
As different from Example 6: using biomass graphene obtained by preparation example 4;The content of doped chemical accounts for fibre
Tie up the 0.3% of carrier.
Embodiment 16
It is mixed using redox graphene and nano silica fume, nano-aluminium oxide, nano-iron material compared with Example 6
Close substitution biomass graphene.
Comparative example 1
Redox graphene uniform is distributed in ethylene glycol, the graphene solution of 0.5mg/mL is made into;
Fiber carrier (is used into acetate fiber, commercially available in the prior art, technical indicator includes: 1.5D*38mm, is contained
Water rate is 7%, and fibre strength is 1.5 gram forces) it carries out boiling water and boils processing 25min, the impurity, miscellaneous that removal carrier itself contains
Gas, drying, obtains the fiber carrier being activated;
The fiber carrier handled well is immersed into 10min in graphene solution, submergence includes first ultrasound, rear concussion, quiet again
It sets;Processing is immobilized using dehydrated alcohol, it is washed, dry, obtain graphene adsorbent material.The content of graphene is fibre
Tie up the 5% of carrier.
Comparative example 2
Natural graphite is evenly spread in ethylene glycol, the graphite solution of 0.5mg/mL is made into;
Fiber carrier (is used into acetate fiber, commercially available in the prior art, technical indicator includes: 1.5D*38mm, is contained
Water rate is 7%, and fibre strength is 1.5 gram forces) it carries out boiling water and boils processing 25min, the impurity, miscellaneous that removal carrier itself contains
Gas, drying, obtains the fiber carrier being activated;
The fiber carrier handled well is immersed into 10min in graphite solution, submergence includes first ultrasonic, rear concussion, stands again;
Processing is immobilized using dehydrated alcohol, it is washed, dry, obtain graphite adsorbent material.The content of graphite is fiber carrier
5%.
Comparative example 3
Bamboo charcoal is evenly spread in ethylene glycol, the bamboo charcoal solution of 0.5mg/mL is made into;
Fiber carrier (is used into acetate fiber, commercially available in the prior art, technical indicator includes: 1.5D*38mm, is contained
Water rate is 7%, and fibre strength is 1.5 gram forces) it carries out boiling water and boils processing 25min, the impurity, miscellaneous that removal carrier itself contains
Gas, drying, obtains the fiber carrier being activated;
The fiber carrier handled well is immersed into 10min in bamboo charcoal solution, submergence includes first ultrasonic, rear concussion, stands again;
Processing is immobilized using dehydrated alcohol, it is washed, dry, obtain bamboo Charcoal Adsorption material.The content of bamboo charcoal is fiber carrier
5%.
Comparative example 4
Commercially available acetate fiber is used into conventional filtration mouth production method, manufactured common cigarette filter.
The fiber adsorbing material prepared in embodiment 1~16 and comparative example 1~4 is used into conventional filtration mouth production side below
The cigarette filter that length is 20mm is made in method, and the cigarette filter of above embodiments 1~16 and comparative example 1~4 is inhaled
The detection of attached front and back smoke components, the specific method is as follows:
Cigarette product uses Mount Taishan board, and cigarette mistake made of embodiment 1~16 and comparative example 1~4 is respectively adopted in filter tip
Filter tip, a length of 20mm of cigarette filter tip, circumference are 22~25mm;Artikel-Nr9020-0039 climatic chamber is used before experiment
It is balanced 48 hours under the conditions of (22 ± 1) DEG C, relative humidity (60 ± 2) %.Using Borgwaltdt-KC smoking machine to detection cigarette
Zhi Jinhang detection, every mouthful is aspirated 2 seconds, volume 35mL, every mouthful and is spaced 58 seconds, temperature is 22 ± 2 DEG C, relative humidity be 60 ±
5%, fume collection is carried out, the sample being collected into is analyzed by gas phase-mass spectrometry tester.
Made cigarette filter is subjected to flue gas evaluation, as a result referring to table 2.
The flue gas evaluation result of the cigarette filter of 2 embodiment 1~16 of table and comparative example 1~4
The result of embodiment 1~16: fume component analysis is carried out by smoking machine and gas phase-mass spectrometry chromatograph, most
The chromatographic data obtained eventually show equal quality pipe tobacco generate flue gas after graphene-supported fiber filter total granules and
The decline of BaP data is obvious, and other compositions include that the data of the substances such as nicotine are basically unchanged.And cigarette inhales and feels unaffected.
It is compared by embodiment 4,7,10, embodiment 5,8,11 compares, and embodiment 6,9,12 compares, it can be seen that same
In the case where graphene content, the content of doped chemical is bigger in a certain range, then is more conducive to total granules and BaP
Absorption.
Comparative example 1 statistics indicate that, do not absorb nicotine substantially, nor affect on cigarette and absorb and feel, but adsorb total grain
Phase object and BaP effect are unobvious.
Comparative example 2,3 statistics indicate that, after graphite and bamboo charcoal and fiber composite manufactured cigarette adsorbent material to nicotine,
Total granules and BaP assimilation effect are all fine, and cigarette is inhaled to experience and be seriously affected.
By above embodiments and comparative example it is found that the present invention passes through the introducing of graphene and doped chemical in fiber carrier,
Can specifically adsorb and be filtered to remove the condensed-nuclei aromatics such as BaP class harmful substance in flue gas, at the same retain nicotine and other
Innocuous substance does not influence the suction taste of flue gas.It is thick that cigarette filter provided by the invention can effectively adsorb BaP in flue gas etc.
Cyclophane hydro carbons carcinogen reduces harmfulness of smoking;The suction taste for not influencing flue gas simultaneously, does not reduce the pleasant sensation of smoker.
The Applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention not office
It is limited to above-mentioned processing step, that is, does not mean that the present invention must rely on the above process steps to be carried out.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (11)
1. a kind of graphene adsorbent material, comprising:
Fiber carrier;
With the graphene and doped chemical being supported on the fiber carrier;
The doped chemical includes Al, Si and Fe;
The doped chemical content accounts for 0.002~1wt% of fiber carrier;
Wherein, the graphene and doped chemical are introduced by biomass graphene;
The biomass graphene is made with the following method:
(1) under the action of frerrous chloride, corn cob fiber element is subjected to catalytic treatment, obtains presoma;
(2) under conditions of nitrogen, by the presoma in 150 DEG C of heat preservation 2h, the first intermediate is obtained;
(3) under conditions of nitrogen, first intermediate is warming up to 400 DEG C of heat preservation 3.5h, obtains the second intermediate;
(4) under conditions of nitrogen, second intermediate is warming up to 1200 DEG C of heat preservation 3h, obtains third intermediate;
(5) by the third intermediate after over-richness is the sodium hydroxide solution of 10wt%, the chlorohydric acid pickling of 4wt%, washing,
Obtain biomass graphene;
Heating rate in the step (3), (4) is 15 DEG C/min~16 DEG C/min.
2. graphene adsorbent material according to claim 1, which is characterized in that the fiber carrier include natural fiber,
One or more of semisynthetic fibre and synthetic fibers.
3. graphene adsorbent material according to claim 1, which is characterized in that the graphene content accounts for fiber carrier
0.1~10wt%.
4. graphene adsorbent material according to claim 1, which is characterized in that the graphene has porous structure, hole
Gap rate is 2%~10%.
5. graphene adsorbent material according to any one of claims 1 to 4, which is characterized in that the doped chemical is also wrapped
Include one or more of K, Na, Ca, Mg, P, Mn and Co.
6. a kind of preparation method of graphene adsorbent material, comprising the following steps:
Fiber is contacted with graphene material, is loaded, obtains graphene adsorbent material;
The graphene material includes graphene and doped chemical, and the doped chemical includes Al, Si and Fe, the doped chemical
Content accounts for 0.002~1wt% of the fiber;
Wherein, the graphene and doped chemical are introduced by biomass graphene;
The biomass graphene is made with the following method:
(1) under the action of frerrous chloride, corn cob fiber element is subjected to catalytic treatment, obtains presoma;
(2) under conditions of nitrogen, by the presoma in 150 DEG C of heat preservation 2h, the first intermediate is obtained;
(3) under conditions of nitrogen, first intermediate is warming up to 400 DEG C of heat preservation 3.5h, obtains the second intermediate;
(4) under conditions of nitrogen, second intermediate is warming up to 1200 DEG C of heat preservation 3h, obtains third intermediate;
(5) by the third intermediate after over-richness is the sodium hydroxide solution of 10wt%, the chlorohydric acid pickling of 4wt%, washing,
Obtain biomass graphene;
Heating rate in the step (3), (4) is 15 DEG C/min~16 DEG C/min.
7. preparation method according to claim 6, which is characterized in that specifically include:
Fiber is immersed in 10~60min in graphene solution, it is washed, dry, obtain graphene adsorbent material;
The graphene solution is dispersed to be made in a solvent by graphene material;
8. preparation method according to claim 6, which is characterized in that be also dissolved with coupling agent in the graphene solution.
9. application of any graphene adsorbent material in smoke filtration in a kind of Claims 1 to 5.
10. application according to claim 9, which is characterized in that the device of the smoke filtration includes cigarette filter, sky
Adjust filter core or vehicle exhaust exhaust apparatus.
11. a kind of cigarette filter, which is characterized in that including by graphene adsorption material according to any one of claims 1 to 5
Material passes through the manufactured segment of fiber of graphene adsorbent material obtained by the described in any item preparation methods of claim 6~8.
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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 |
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CN108722350B (en) * | 2018-05-07 | 2021-01-01 | 中国农业科学院油料作物研究所 | Magnetic graphene composite material and preparation method and application thereof |
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