CN105597675A - Graphene adsorbing material, preparation method and application thereof and cigarette filter tip - Google Patents
Graphene adsorbing material, preparation method and application thereof and cigarette filter tip Download PDFInfo
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- CN105597675A CN105597675A CN201511033211.6A CN201511033211A CN105597675A CN 105597675 A CN105597675 A CN 105597675A CN 201511033211 A CN201511033211 A CN 201511033211A CN 105597675 A CN105597675 A CN 105597675A
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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 invention provides a graphene adsorbing material and a preparation method and application thereof. The adsorbing material comprises a fiber carrier, graphene and doped elements, wherein the graphene and the doped elements are carried by the fiber carrier; the doped elements include one or more of Al, Si and Fe. The invention also provides a cigarette filter tip which comprises a fiber section made from the graphene adsorbing material. According to the cigarette filter tip, by introducing the graphene and the doped elements in the fiber carrier, benzopyrene and other polycyclic aromatic hydrocarbon harmful substances in smoke can be specifically adsorbed, filtered and removed, nicotine and other harmless substances are reserved at the same time, and therefore the smoking taste of a cigarette is not affected. The cigarette filter tip can effectively adsorb benzopyrene and other polycyclic aromatic hydrocarbon cancerogenic substance in the smoke to reduce harm of smoking; meanwhile, the pleasure of smoking and the mellow taste of the smoke are not affected. Besides, the graphene adsorbing material can prevent the phenomenon that a cigarette holder is moldy due to environment dampness and other factors.
Description
Technical field
The present invention relates to adsorption technology field, relate in particular to a kind of Graphene sorbing material, its preparation methodAnd application and cigarette filter.
Background technology
In cigarette burning process, produce the condensed-nuclei aromatics class harmful components such as CO, phenol and BaP, in suctionIn time, enters human body with flue gas and works the mischief. Filter tip refers to the upper part of cigarette, be cigarette main flume withThe bridge of human body, is mainly used to a filtering part and sucks the harmful substances such as tar in flue gas, can reduce to inhaleThe harm of cigarette to human body. In order to meet the requirements of function, cigarette filter is gradually from common single acetic acidFiber filter tip is to multiple filter tip, and the filter tip future development made of multiple material.
Prior art discloses multiple cigarette filter, if Granted publication number is the China of CN2872872YPatent documentation discloses a kind of expansion graphite composite cigarette filter tip, and it is by filter fiber section, expansion stoneChina ink section and bag paper form, filter fiber section and the docking of expanded graphite fillter section, and bag paper bag is rolled in bothOutside. This application scheme adopts and in cigarette filter, adds one section of fillter section that contains expanded graphite, systemObtain expansion graphite composite filter tip, effectively nicotine gas, kerosene and the Buddhist nun in filter cigarette flue gasThe harmful substances such as Gu Ding, but BaP can not be adsorbed.
Application publication number is that the Chinese patent literature of CN104815630A discloses a kind of selective absorption benzeneAnd the preparation method of the filter fiber of pyrene and phenol, the method is mainly with graphite oxide aqueous solution or oxygenThe mixed solution of functionalized graphene and chitosan aqueous solution is specific decorating liquid, and fiber is sprayed etc. to placeReason, in 5～20 minutes processing times, 25～50 DEG C for the treatment of temperatures, are then placed in 80 DEG C by fiber after treatmentUnder vacuum condition, dry 6 hours, prepare modified liquid filter fiber after treatment.
Gained filter fiber is made cigaratte filter by above-mentioned application, can reduce the BaP content in flue gas,But, on the one hand this application relate to other additives such as shitosan and preparation technology loaded down with trivial details, on the other handIt is still to be improved to the adsorption effect of BaP.
Summary of the invention
In view of this, the application provides a kind of Graphene sorbing material, its preparation method and application and volumeTobacco filters, cigarette filter provided by the invention is BaP in adsorption filtration flue gas etc. optionallyWhen condensed-nuclei aromatics class material, retain nicotine and other innocuous substance in flue gas, and then do not affectThe perfume (or spice) of flue gas is inhaled taste.
The invention provides a kind of Graphene sorbing material, comprising:
Fiber carrier;
With the Graphene and the doped chemical that load on described fiber carrier;
Described mineral element comprises one or more in Al, Si and Fe.
Graphene of the present invention can obtain by different preparation methods, for example mechanical stripping method, extensionGrowth method, chemical gaseous phase deposition method, graphite oxidation reducing process, can also be by biomass resource waterHot carbonizatin method, and the Graphene that in prior art prepared by additive method. But which kind of method allVery difficult realization prepares the theoretic Graphene of stricti jurise on a large scale, and for example prior art preparesGraphene in can there is other allotropes of some impurity element, carbon or the non-individual layer of the number of plies veryFor example, to the graphene-structured of multilayer (3 layers, 5 layers, 10 layers, 20 layers etc.), the present invention utilizesGraphene also comprises the theoretic Graphene of above-mentioned non-stricti jurise.
Preferably, described fiber carrier comprises the one in natural fiber, semisynthetic fibre and synthetic fibersOr several.
Preferably, described Graphene content accounts for 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 living beings porous graphene.
Preferably, described doped chemical content accounts for 0.002～1wt% of fiber carrier.
Preferably, described doped chemical also comprises the one in K, Na, Ca, Mg, P, Mn and CoOr several.
The preparation method who the invention provides a kind of Graphene sorbing material, comprises the following steps:
Fiber is contacted with Graphene material, carry out load, obtain Graphene sorbing material;
Described Graphene material comprises Graphene and doped chemical, and described doped chemical comprises Al, Si and FeIn one or more.
Preferably, specifically comprise:
Fiber is immersed in to 10～60min in graphene solution, through washing, dry, obtains Graphene absorptionMaterial;
Described graphene solution is disperseed in solvent by Graphene material to make, and described Graphene material is made a livingMaterial porous graphene;
Preferably, described graphene solution is also dissolved with coupling agent.
Further preferably, described coupling agent comprises that silane coupler, titanate coupling agent and zirconium class are evenOne or more of connection agent etc.; Coupling agent consumption can be 1%～10% of Graphene quality.
The present invention also provides the application of a kind of above-mentioned Graphene sorbing material in smoke filtration.
Further, above-mentioned Graphene sorbing material is at cigartte filter tip, air conditioner filter element or vehicle exhaustApplication in exhaust apparatus, the device of described smoke filtration comprises cigarette filter, air conditioner filter element or vapourTail gas exhaust apparatus.
The present invention also provides a kind of cigarette filter, and it comprises Graphene sorbing material system by mentioned earlierThe segment of fiber becoming.
Compared with prior art, Graphene sorbing material provided by the invention comprises fiber carrier and loads onGraphene on fiber carrier and doped chemical, described doped chemical comprise a kind of in Al, Si and Fe orSeveral. The present invention, by the introducing of Graphene in fiber carrier and doped chemical, can be adsorbed also specificallyRemove by filter the condensed-nuclei aromatics class harmful substance such as BaP in flue gas, retain nicotine and other is harmless simultaneouslyMaterial, does not affect the suction taste of flue gas. Cigarette filter provided by the invention can effectively adsorb the benzene in flue gasAnd the condensed-nuclei aromatics class carcinogen such as pyrene, reduce harmfulness of smoking; The suction taste that does not affect flue gas, does not subtract simultaneouslyFew smoker's pleasant sensation.
In addition, Graphene sorbing material provided by the invention can also prevent from sending out because of factor cigarette holders such as humid environmentsMould phenomenon.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, institute retouchesThe embodiment stating is only the present invention's part embodiment, instead of whole embodiment. Based on the present inventionIn embodiment, those of ordinary skill in the art are not making the institute obtaining under creative work prerequisiteThere are other embodiment, all belong to the scope of protection of the invention.
The invention provides a kind of Graphene sorbing material, comprising:
Fiber carrier; With the Graphene and the doped chemical that load on described fiber carrier; Described doping is firstElement comprises one or more in Al, Si and Fe.
BaP in the alternative absorption of Graphene sorbing material provided by the invention flue gas, adsorption efficiencyHeight, it is better that flue gas is inhaled taste.
Graphene sorbing material provided by the invention comprises fiber carrier, and described fiber carrier can be naturalOne or more in fiber, staple fibre and synthetic fibers are mixed, and preferably include semisynthetic fibre and closeBecome one or more in fiber. In an embodiment of the present invention, described natural fiber comprises stringAnd animal origin, string comprises by seed, fruit, stem, leaf etc. on plant locates the fiber obtaining,As cotton fiber, flaxen fiber, animal origin comprises animal hair class or silk class. At embodiments of the inventionIn, staple fibre also claims semisynthetic fibre, comprises viscose rayon, acetate fiber, CUP and existingOther semisynthetic fibres in technology; Synthetic fibers comprise polypropylene fibre (polypropylene fibre), polyacrylonitrile fibreDimension (acrylic fibers), vinylon (vinylon), Fypro (polyamide fibre), poly-rightEthylene diester (terylene) etc. In some embodiments of the invention, the skill of described fiber carrierArt index is as follows:
More than fibre length 5mm, fineness is not limit;
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 modelEnclose for 0.13-10D. Fibre length can be any fibre length, and further preferred fibre length is 5mmAbove. Fiber moisture is not limit, and further preferred fiber moisture is 5%～10%. Fibre strength is notLimit, further preferred fibre strength is more than 1 gram force.
In an embodiment of the present invention, viscose rayon, acetate fiber, CUP, polypropylene fibre (thirdSynthetic fibre), polyacrylonitrile fibre (acrylic fibers), vinylon (vinylon), polyamide fibreDimension (polyamide fibre), PET (terylene) or other synthetic fibers can be commercially available prod,Also can adopt method of the prior art to prepare.
In specific embodiment of the present invention, the above-mentioned fiber dimensious of fiber carrier commercially available prod can comprise:1.5D*38mm or 1.5D*51mm; Moisture content is 7%, and fibre strength is 1.5 gram forces.
The fiber that adopts preparation method of the prior art to make illustrates below:
Taking Making viscose fiber as example, the viscose using in the present invention is the viscose that prior art is known,Its preparation method is, taking pulp as raw material, flood, squeezing, pulverizing, aging, yellow, dissolving,The operations such as maturation, filtration, deaeration. Pulp is the sodium hydrate aqueous solution dipping of 18% left and right through concentration,Make cellulose conversion become alkali cellulose, hemicellulose stripping, degree of polymerization part declines; Remove through squeezing againUnnecessary alkali lye. Block alkali cellulose becomes loose flock after pulverizing on pulverizer, due to tableArea increases improves later chemical reaction uniformity. Under the effect of oxygen, there is oxidation and split in alkali celluloseSolution declines average degree of polymerization, and this process is called aging. After aging by anti-to alkali cellulose and carbon disulfideShould generate cellulose xanthate and claim yellow, large intermolecular hydrogen bond further be weakened, due to yellow acid groupHydrophily, the solubility property of cellulose xanthate in sig water greatly improved. Solid celluloseXanthate acid is dissolved in sig water, is viscose glue. The viscose glue of just having made is difficult for into because viscosity and salt figure are higherShape, must place at a certain temperature certain hour and be called maturation, makes in viscose glue sodium cellulose xanthate graduallyHydrolysis and saponification, esterification degree reduce, viscosity and to the stability of electrolyte effect also along with change. RipeAfter becoming, should carry out deaeration and filtration, to remove bubble and impurity.
In an embodiment of the present invention, the technological process of Making viscose fiber filament and condition are specific as follows:
1. alkali steeping process conditions: alkali lye (NaOH): concentration is 240g/L, temperature is 20 DEG C, dippingTime: 120min;
2. experienced process conditions: temperature is that 25 DEG C, time are 34h;
3. yellow process conditions: yellow method is wet method yellow, and wherein, alkalization comprises: the time is 30min,Temperature is 21.0 ± 0.5 DEG C; Yellow comprises: the time is 120min, and initial temperature is 21.0 ± 0.5 DEG C, eventuallyOnly temperature is 30.0 ± 0.5 DEG C; CS2Adding quality is 34.5% (to first fibre); Front dissolving comprises: timeBetween be 120min, temperature is 16.5 ± 0.5 DEG C; Rear dissolving comprises: time be 180min, temperature is 16.5±0.5℃；
4. disperse in quality, the viscose glue stoste composition making comprises:
First fibre 8.30 ± 0.10%;
NaOH5.80±0.10％；
S2.25±0.1％；
5. viscose ripening condition: the time is 36h～38h, temperature is 19.0 ± 0.5 DEG C;
6. the spinning glue index obtaining: 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: 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, Graphene sorbing material provided by the invention comprises Graphene and the doping of loadElement, described doped chemical comprises one or more in Al, Si and Fe. The present invention passes through fiber carrierThe introducing of middle Graphene and doped chemical, can further improve sorbing material and filter in flue gas BaP etc. and haveThe effect of harmful substances ensures that the suction taste of flue gas is good simultaneously.
Graphene is a kind of two-dimensional material of the alveolate texture being made up of individual layer sp2 hydridization carbon atom, toolThere is the performance of many excellences. The structure of described Graphene is as shown in Equation 1:
Graphene of the present invention is dispersed on fiber carrier, makes fiber carrier contain Graphene. At thisIn bright preferred embodiment, described Graphene content accounts for 0.1～10wt% of fiber carrier, is preferably1～4wt%, for example 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 through in advanceProcessing has the micropore of irregular distribution; Porosity can be 2%～10%, is preferably 3%～7%; Aperture modelEnclosing is 1～20nm.
In the present invention, described Graphene is preferably biomass porous Graphene; Living beings Graphene containsThe lamellar structure of 10 layers of following Graphene, SP3 hybrid structure and the mineral element of carbon; Mineral element comprisesFe, Si and Al element. In an embodiment of the present invention, described mineral element constituent content is living beings stone0.5wt%～the 6wt% of China ink alkene, is preferably 1.5wt%～5wt%. Described mineral element preferably also comprise P,Any one in Ca, Na, Ni, Mn, K, Mg, Cr, S and Co or multiple; Described mineral unitElement exists with the form of simple substance and/or compound, and compound comprises oxide, carbide, and they are adsorbed onThe surface of living beings Graphene or inner. In an embodiment of the present invention, carbon in described living beings GrapheneConstituent content >=80wt%, is preferably greater than 85wt%, then is preferably greater than 90wt%, is most preferably greater than 95wt%.In an embodiment of the present invention, described Graphene is the hexatomic ring honeybee with the carbon of thickness below 100nmNest shape lamellar structure. In embodiments of the present invention, this porous graphene can provide flue gas and air on the one handThe passage of convection current, prevents pipe tobacco imperfect combustion, has reduced the generation of imperfect combustion nuisance; AnotherThis porous graphene of aspect has bigger serface characteristic, can be effectively to condensed ring such as carcinogenic BaPsAromatic hydrocarbon substance (PAHs) carries out selective absorption.
In the present invention, described doped chemical comprises one or more in Al, Si and Fe, preferably includesAl, Si and Fe. Described doped chemical is dispersed on fiber carrier, makes fiber carrier contain doped chemical.In a preferred embodiment of the invention, described doped chemical content accounts for 0.002～1wt% of fiber carrier, excellentElect 0.02～0.8wt% as, more preferably 0.2～0.5wt%. In addition, described doped chemical preferably also comprise K,One or more in Na, Ca, Mg, P, Mn and Co.
Graphene sorbing material provided by the invention belongs to carbon nanomaterial product, has specific adsorptionCan, this class harmful substance of BaP in energy specific adsorption flue gas, the while does not affect the suction taste of flue gas.
Correspondingly, the invention provides a kind of preparation method of Graphene sorbing material, comprise the following steps:Fiber is contacted with Graphene material, carry out load, obtain Graphene sorbing material; Described Graphene thingMaterial comprises Graphene and doped chemical, and described doped chemical comprises one or more in Al, Si and Fe.
The Graphene sorbing material that the present invention prepares can effectively adsorb the nuisances such as the BaP in flue gasMatter, and do not affect the suction taste of flue gas. In addition, the present invention prepares the method operation letter of Graphene sorbing materialJust, be suitable for industrialization promotion.
The present invention, taking fiber as carrier, loads on Graphene and doped chemical on fiber carrier, obtains stoneChina ink alkene sorbing material. Wherein, the content of described fiber carrier as mentioned before, does not repeat them here.
In a preferred embodiment of the invention, described Graphene content accounts for 0.1～10wt% of fiber carrier, excellentElect 1～4wt% as, for example 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, concreteFor there is the micropore of irregular distribution through pretreatment; Porosity can be 2%～10%, is preferably 3%～7%;Pore diameter range is 1～20nm. The present invention is not particularly limited the source of described Graphene, can adopt citySell product, also can prepare; Described Graphene can pass through mechanical stripping method, epitaxial growth method,Chemical gaseous phase deposition method, graphite oxidation reducing process and by biomass resource hydrothermal carbonization method is prepared intoArrive.
In one embodiment of the invention, described Graphene is preferably living beings Graphene. Described biologyThe lamellar structure that matter Graphene contains 10 layers of following Graphene, SP3 hybrid structure and the mineral element of carbon;Described mineral element comprises Fe, Si and Al element. In an embodiment of the present invention, described mineral element unitCellulose content is the 0.5wt%～6wt% of living beings Graphene, is preferably 1.5wt%～5wt%. Described mineral unitElement preferably also comprise in P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co any one orMultiple; Described mineral element exists with the form of simple substance and/or compound, and compound comprises oxide, carbonCompound, they are adsorbed on the surperficial or inner of living beings Graphene. In an embodiment of the present invention, described inCarbon element content >=80wt% in living beings Graphene, is preferably greater than 85wt%, then is preferably greater than 90wt%,Most preferably be greater than 95wt%. In an embodiment of the present invention, described Graphene is for having thickness at 100nmThe cellular lamellar structure of hexatomic ring of following carbon.
In an embodiment of the present invention, described living beings Graphene can utilize biomass resource hydrothermal carbonization methodMake. Particularly, below, only illustrate:
Method 1:
(1) under the effect of catalyst, living beings carbon source is carried out to catalytic treatment, obtain presoma;
(2) under the condition of protective gas, by described presoma 140 DEG C～180 DEG C insulations1.5h～2.5h, obtains the first intermediate;
(3), under the condition of protective gas, described the first intermediate is warming up to 350 DEG C～450 DEG C guarantorsTemperature 3h～4h, obtains the second intermediate;
(4), under the condition of protective gas, described the second intermediate is warming up to 1100 DEG C～1300 DEG CInsulation 2h～4h, obtains the 3rd intermediate;
(5) by described the 3rd intermediate alkali cleaning successively, pickling, washing, obtain Graphene;
Heating rate in described step (3), (4) is 14 DEG C/min～18 DEG C/min.
The living beings Graphene preparing in said method 1 is (in the Graphene that prior art preparesCan there is other allotropes or the even stone of multilayer of the non-individual layer of the number of plies of some impurity element, carbonChina ink alkene structure, and the Graphene that this living beings method is prepared is also mixture) in, contain Graphene,Amorphous carbon and non-carbon nonoxygen element.
The disclosed method of method 2:CN104118873A.
The disclosed method of method 3:CN104016341A.
The disclosed method of method 4:CN104724696A.
The disclosed method of method 5:CN104724699A.
The disclosed method of method 6:CN105060289A.
In the present invention, described doped chemical comprises one or more in Al, Si and Fe, preferably includesAl, Si and Fe. Described doped chemical is dispersed on fiber carrier, makes fiber carrier contain doped chemical.In a preferred embodiment of the invention, described doped chemical content accounts for 0.002～1wt% of fiber carrier, excellentElect 0.02～0.8wt% as, more preferably 0.2～0.5wt%. In addition, described doped chemical preferably also comprise K,One or more in Na, Ca, Mg, P, Mn and Co.
In the present invention, the nano material that described doped chemical can contain doped chemical by interpolation is introduced,Also can introduce by the mixed form of Graphene and doped chemical. Described mixed form can be in routine systemIn standby Graphene technical process, carry out the mixture that the control of doped chemical content forms; Preferably, utilizeGraphite is prepared in Graphene process by oxidation-reduction method, due to the mineral element that graphite itself exists, logicalCross reasonable control element contamination, the Graphene that contains mineral element preparing. Or utilizeBiomass resource is that raw material is prepared Graphene, and carries out process control doped chemical content; The present invention is preferredUtilize biomass resource, the Graphene that contains mineral element preparing by hydro-thermal charring process. ThisPlace, mineral element is doped chemical.
Particularly, the embodiment of the present invention is immersed in graphene solution certain hour as 10～60min by fiber,Through washing, dry, obtain Graphene sorbing material; Described graphene solution by Graphene material at solventMiddle dispersion is made. Described Graphene material can be made up of Graphene and the material that contains doped chemical, alsoCan be the Graphene that contains doped chemical, be preferably biomass porous Graphene.
In a preferred embodiment of the invention, in described graphene solution, be also dissolved with coupling agent. DescribedCoupling agent preferably includes one or more of silane coupler, titanate coupling agent and zirconium class coupling agent etc.;The consumption of described coupling agent is preferably 1%～10% of Graphene quality.
In some embodiments of the invention, biomass porous graphene uniform is distributed in solvent, joinsBecome graphene solution. In other embodiment of the present invention, by Graphene and the material that contains doped chemicalMaterial evenly spreads in solvent, is made into graphene solution. Wherein, doped chemical is at least Fe, Si, Al,Also can contain one or more in K, Na, Ca, Mg, P, Mn and Co. The described doping unit of containingThe material of element specifically can be nanometer phosphorus pentoxide, nano silica fume, nanometer aluminium powder, Nanoscale Iron, nanometer MgPowder, nano-calcium carbonate sodium, nano-calcium carbonate potassium, nano-calcium carbonate, nano manganese oxide and nanometer cobalt etc.
Graphene of the present invention can obtain by different preparation methods, for example mechanical stripping method, extensionGrowth method, chemical gaseous phase deposition method, graphite oxidation reducing process, can also be by biomass resource waterHot carbonizatin method, and the Graphene that in prior art prepared by additive method. But which kind of method allVery difficult realization prepares the theoretic Graphene of stricti jurise on a large scale, and for example prior art preparesGraphene in can there is other allotropes of some impurity element, carbon or the non-individual layer of the number of plies veryFor example, to the graphene-structured of multilayer (3 layers, 5 layers, 10 layers, 20 layers etc.), the present invention utilizesGraphene also comprises the theoretic Graphene of above-mentioned non-stricti jurise. For example, utilize graphite ore for raw material systemIn the standby Graphene obtaining, may contain some mineral element self existing in graphite ore. The life of indicationMaterial Graphene is the Graphene that utilizes biomass resource to prepare for raw material, may also can have plantBecause self need to absorb the mineral element that obtains and other allotropes of carbon from soil. Therefore, originallyIn invention, the Graphene of indication is specially a kind of mixture that contains Graphene.
In an embodiment of the present invention, the solvent of described graphene solution is preferably ethylene glycol, dimethyl methylOne or more mixing in acid amides (DMF), 1-METHYLPYRROLIDONE (NMP), second alcohol and water.The mode of described dispersion is preferably ultrasonic dispersion, can be made into the graphite that Graphene concentration is 0.1～10mg/mLAlkene solution, its concentration is preferably 0.5～3mg/mL.
The present invention carries out fiber before load, preferably also to comprise fiber is carried out to activation processing, removes carrierThe impurity itself containing, assorted gas, drying, the fiber carrier that obtains having activated. In enforcement of the present inventionIn example, the mode of described activation processing can be boiling water and boils, and preferably boiling water boils 25～30min.
The fiber carrier having activated is immersed into 10～60min in graphene solution by the embodiment of the present invention, through washingWash, be dried, obtain Graphene sorbing material. Wherein, the mode of described submergence preferably include first ultrasonic,Rear concussion, standing again. Between submergence and washing, the present invention preferably also comprises being fixed processing;Described immobilization processing can be chemical method, and the reagent of use preferably includes absolute ethyl alcohol, absolute methanol and rareThe combination of one or more in nitric acid.
The Graphene sorbing material that the present invention prepares comprises: fiber carrier; With load on described fiberGraphene on carrier and doped chemical; Described doped chemical comprises one or more in Al, Si and Fe.The condensed ring class nuisances such as the BaP in the alternative absorption of Graphene sorbing material provided by the invention flue gasMatter, adsorption efficiency is high, and it is better that flue gas is inhaled taste, can be used as cigarette filter. In addition, the present invention makesGraphene sorbing material can also prevent because of mouldy phenomenons of factor cigarette holder such as humid environments.
The present invention also provides the application of a kind of above-mentioned Graphene sorbing material in smoke filtration. Further, above-mentioned Graphene sorbing material is in cigartte filter tip, air conditioner filter element or vehicle exhaust exhaust apparatusApplication. The device of described smoke filtration comprises cigarette filter, air conditioner filter element or vehicle exhaust exhaust dressPut; The present invention can adopt above-mentioned Graphene sorbing material to make according to a conventional method the device of smoke filtration.
Concrete, the present invention also provides a kind of cigarette filter, is called for short filter tip, and it comprises by institute aboveThe segment of fiber that the Graphene sorbing material of stating is made. Cigarette filter provided by the invention can effectively adsorb cigaretteThe harmful substances such as the BaP in gas, reduce harmfulness of smoking; Retain nicotine and innocuous substance simultaneously, protectThe suction taste of card flue gas is good, does not reduce smoker's pleasant sensation.
The present invention adopts conventional filter tip preparation method, and Graphene sorbing material mentioned above is made to filter tip.The thickness of the segment of fiber that in an embodiment of the present invention, Graphene sorbing material is by mentioned earlier made is excellentElect 1～4mm as, the thickness of described segment of fiber is the thickness that prolongs filter tip axial direction. In reality of the present inventionExecute in example, described filter tip is binary combined filter tip, and contact pipe tobacco end is close to load and Graphene and doping unitThe segment of fiber of element, then connects general fibre section.
The present invention carries out same operation bar by the cigarette that the tobacco cartridge of identical weight is made on smoking machineFlue gas under part is collected, and the sample of collecting is analyzed through gas phase-mass spectrometry tester, determinesThe variation of heterogeneity peak shape in flue gas before and after absorption.
The present invention inhales taste to the flue gas of described cigarette filter and evaluates, specifically to its fragrance, and assorted gas,The evaluation of excitant and pleasant impression, the evaluation of each embodiment selects 30 valuation officers to carry out blind sample test. CommentPrice card standard is as shown in table 1 below.
The flue gas of table 1 cigarette filter is inhaled taste evaluation criterion
Result shows, it is harmful that cigarette filter provided by the invention can effectively adsorb the BaP in flue gas etc.Material, reduces harmfulness of smoking; Do not affect the suction taste of flue gas, do not reduce smoker's pleasant sensation simultaneously.
In order further to understand the application, Graphene adsorption material the application being provided below in conjunction with embodimentMaterial and preparation method thereof is described particularly with cigarette filter.
Embodiment 1
(1) under the effect of catalyst, living beings carbon source is carried out to catalytic treatment, obtain presoma;
(2), under the condition of protective gas, described presoma, at 150 DEG C of insulation 2h, is obtained to firstIntermediate;
(3) under the condition of protective gas, described the first intermediate is warming up to 400 DEG C of insulation 3.5h,Obtain the second intermediate;
(4) under the condition of protective gas, described the second intermediate is warming up to 1200 DEG C of insulation 3h,Obtain the 3rd intermediate;
(5) by described the 3rd intermediate alkali cleaning successively, pickling, washing, obtain Graphene;
Heating rate in described step (3), (4) is 15 DEG C/min～16 DEG C/min.
The lamellar structure that described living beings Graphene contains 10 layers of following Graphene, the SP3 hybrid structure of carbonAnd mineral element; Described mineral element comprises Fe, Si and Al element. In an embodiment of the present invention, instituteState the 4wt% that mineral element constituent content is living beings Graphene; Described mineral element mainly comprise P, Si,Ca, Al, Fe, Mg element.
Embodiment 2
The living beings Graphene that adopts embodiment 1 to make, evenly spreads in ethylene glycol, is made into 0.5mg/mLGraphene solution;
By fiber carrier, (acetate fiber, commercially available, technical indicator comprises: 1.5D*38mm, moisture content is7%, fibre strength is 1.5 gram forces) carry out boiling water and boil and process 25min, remove assorted that carrier itself containsMatter, assorted gas, dry, and obtains the fiber carrier that activation processing is good;
The fiber carrier of handling well is immersed into 10min in graphene solution, and submergence comprises first ultrasonic, after shockSwing, leave standstill again; Adopt being fixed of absolute ethyl alcohol to process, through washing, dry, obtain Graphene and inhaleEnclosure material; The quality of Graphene is 1% of fiber carrier quality.
Described Graphene sorbing material (thickness is 2mm) is adopted to conventional filter tip preparation method, make filterMouth.
Embodiment 3
The living beings Graphene that adopts embodiment 1 to make, evenly spreads in ethylene glycol, is made into 3mg/mLGraphene solution;
Fiber carrier (with embodiment 1) is carried out to boiling water and boil processing 25min, remove carrier itself and containImpurity, assorted gas, dry, obtain the fiber carrier that activation processing is good;
The fiber carrier of handling well is immersed into 60min in graphene solution, and submergence comprises first ultrasonic, after shockSwing, leave standstill again; Adopt being fixed of absolute ethyl alcohol to process, through washing, dry, obtain Graphene and inhaleEnclosure material; The quality of Graphene is 4% of fiber carrier quality.
Described Graphene sorbing material (thickness is 2mm) is adopted to conventional filter tip preparation method, make filterMouth.
Embodiment 4
The living beings Graphene that adopts embodiment 1 to make, evenly spreads in ethylene glycol, is made into 1.5mg/mLGraphene solution;
Fiber carrier (with embodiment 1) is carried out to boiling water and boil processing 25min, remove carrier itself and containImpurity, assorted gas, dry, obtain the fiber carrier that activation processing is good;
The fiber carrier of handling well is immersed into 25min in graphene solution, and submergence comprises first ultrasonic, after shockSwing, leave standstill again; Adopt being fixed of absolute ethyl alcohol to process, drying, obtains Graphene sorbing material;The quality of Graphene is 2.5% of fiber carrier quality.
Described Graphene sorbing material (thickness is 2mm) is adopted to conventional filter tip preparation method, make filterMouth.
Comparative example 1
According to the method for embodiment 4, do not add Graphene, make filter tip.
Embodiment 5
According to method mentioned above, the filter tip that embodiment 2～4 and comparative example 1 are made carries out flue gas suctionTaste is evaluated, and result is referring to table 2.
The flue gas of the filter tip that table 2 embodiment 2～4 and comparative example 1 are made is inhaled taste evaluation result
| Sequence number | Fragrance score value | Assorted gas | Excitant | Pleasant impression |
| Embodiment 2 | 30 | 11 | 20 | 24 |
| Embodiment 3 | 30 | 12 | 20 | 25 |
| Embodiment 4 | 30 | 12 | 20 | 25 |
| Comparative example 1 | 28 | 10 | 17 | 21 |
The detection of smoke components before and after above embodiment 2～4 and comparative example 1 are adsorbed, concrete grammarAs follows:
Cigarette product uses Bei Dai River board, the filter that filter tip adopts respectively embodiment 2～4 and comparative example 1 to makeMouth, cigarette filter tip is long is 20mm, circumference is 22～25mm; Before experiment, use Artikel-Nr9020-0039 perseveranceConstant temperature and humidity case balance 48 hours under (22 ± 1) DEG C, relative humidity (60 ± 2) % condition. ApplicationBorgwaltdt-KC smoking machine detects detecting cigarette, and every mouthful is aspirated 2 seconds, and volume is 35mL,58 seconds, every mouthful of interval, temperature is that 22 ± 2 DEG C, relative humidity are 60 ± 5%, carries out flue gas collection, collectsTo sample analyze through gas phase-mass spectrometry tester. Main result is as follows:
Embodiment 2 results: by preparation graphene-supported fiber and pipe tobacco by conventional cigarette process systemStandby one-tenth cigarette with filter tip, carries out fume component analysis by smoking machine and gas phase-mass spectrometry chromatograph,The chromatographic data obtaining eventually shows, the graphene-supported fiber filter of flue gas process that equal quality pipe tobacco producesRear BaP peak value declines 85%, and the peak shape that other compositions comprise the materials such as nicotine is constant, and peak height reducesBe no more than 2%. It is unaffected that cigarette is inhaled sense.
Embodiment 3 results: by preparation graphene-supported fiber and pipe tobacco by conventional cigarette process systemStandby one-tenth cigarette with filter tip, carries out fume component analysis by smoking machine and gas phase-mass spectrometry chromatograph,The chromatographic data obtaining eventually shows, the graphene-supported fiber filter of flue gas process that equal quality pipe tobacco producesRear BaP peak value declines 95%, and the peak shape that other compositions comprise the materials such as nicotine is constant, and peak height reducesBe no more than 2%. It is unaffected that cigarette is inhaled sense.
Embodiment 4 results: by preparation graphene-supported fiber and pipe tobacco by conventional cigarette process systemStandby one-tenth cigarette with filter tip, carries out fume component analysis by smoking machine and gas phase-mass spectrometry chromatograph,The chromatographic data obtaining eventually shows, the graphene-supported fiber filter of flue gas process that equal quality pipe tobacco producesRear BaP peak value declines 90%, and the peak shape that other compositions comprise the materials such as nicotine is constant, and peak height reducesBe no more than 2%. It is unaffected that cigarette is inhaled sense.
Comparative example 1 result: commercially available acetate fiber and pipe tobacco are prepared into filtration by conventional cigarette processMouth cigarette, carries out fume component analysis by smoking machine and gas phase-mass spectrometry chromatograph, finally obtainsChromatographic data shows, the flue gas of equal quality pipe tobacco generation BaP peak after commercially available acetate fiber filtersHigh reduction is no more than 2%, and the peak shape that other compositions comprise the materials such as nicotine is constant, and peak height reduction is no more than2%. It is unaffected that cigarette is inhaled sense.
From above embodiment and comparative example, the present invention is by Graphene and doped chemical in fiber carrierIntroducing, can adsorb specifically and remove by filter the condensed-nuclei aromatics class harmful substance such as BaP in flue gas,Retain nicotine and other innocuous substance simultaneously, do not affect the suction taste of flue gas. Cigarette mistake provided by the inventionFilter tip can effectively adsorb the condensed-nuclei aromatics class carcinogens such as the BaP in flue gas, reduces harmfulness of smoking; WithTime do not affect the suction taste of flue gas, do not reduce smoker's pleasant sensation.
Applicant's statement, the present invention illustrates process of the present invention by above-described embodiment, but thisBrightly be not limited to above-mentioned processing step, do not mean that the present invention must rely on above-mentioned processing step abilityImplement. Person of ordinary skill in the field should understand, any improvement in the present invention, to the present inventionThe selections of the equivalence replacement of selected raw material and the interpolation of auxiliary element, concrete mode etc., all drop on thisWithin bright protection domain and open scope.
Claims (12)
1. a Graphene sorbing material, comprising:
Fiber carrier;
With the Graphene and the doped chemical that load on described fiber carrier;
Described doped chemical comprises one or more in Al, Si and Fe.
2. Graphene sorbing material according to claim 1, is characterized in that, described fiber carrierComprise one or more in natural fiber, semisynthetic fibre and synthetic fibers.
3. Graphene sorbing material according to claim 1, is characterized in that, described Graphene containsAmount accounts for 0.1～10wt% of fiber carrier.
4. Graphene sorbing material according to claim 1, is characterized in that, described Graphene toolHave loose structure, porosity is 2%～10%.
5. Graphene sorbing material according to claim 4, is characterized in that, described Graphene isBiomass porous Graphene.
6. Graphene sorbing material according to claim 1, is characterized in that, described doped chemicalContent accounts for 0.002～1wt% of fiber carrier.
7. according to the Graphene sorbing material described in claim 1～6 any one, it is characterized in that, described inDoped chemical also comprises one or more in K, Na, Ca, Mg, P, Mn and Co.
8. a preparation method for Graphene sorbing material, comprises the following steps:
Fiber is contacted with Graphene material, carry out load, obtain Graphene sorbing material;
Described Graphene material comprises Graphene and doped chemical, and described doped chemical comprises Al, Si and FeIn one or more.
9. preparation method according to claim 8, is characterized in that, specifically comprises:
Fiber is immersed in to 10～60min in graphene solution, through washing, dry, obtains Graphene absorptionMaterial;
Described graphene solution is disperseed in solvent by Graphene material to make, and described Graphene material is made a livingMaterial porous graphene;
Preferably, in described graphene solution, be also dissolved with coupling agent.
10. the application of the arbitrary described Graphene sorbing material of a claim 1～7 in smoke filtration.
11. application according to claim 10, is characterized in that, the device bag of described smoke filtrationDraw together cigarette filter, air conditioner filter element or vehicle exhaust exhaust apparatus.
12. 1 kinds of cigarette filters, is characterized in that, comprise by described in claim 1～7 any oneThe Graphene sorbing material system that preparation method described in Graphene sorbing material or claim 8 or 9 makesThe segment of fiber becoming.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511033211.6A CN105597675A (en) | 2015-12-31 | 2015-12-31 | Graphene adsorbing material, preparation method and application thereof and cigarette filter tip |
| JP2018526981A JP6790095B2 (en) | 2015-08-09 | 2016-07-25 | Graphene adsorbent, its manufacturing method and its application, and tobacco filter and tobacco |
| PCT/CN2016/091497 WO2017024933A1 (en) | 2015-08-09 | 2016-07-25 | Graphene adsorbing material, preparation method therefor and application thereof, and cigarette filter tip and cigarette |
| CN201610591211.6A CN106000316B (en) | 2015-12-31 | 2016-07-25 | A kind of graphene adsorbent material, preparation method and its application and cigarette filter |
| US15/751,700 US11006664B2 (en) | 2015-08-09 | 2016-07-25 | Graphene adsorbing material, preparation method therefor and application thereof, and cigarette filter tip and cigarette |
| EP16834557.7A EP3332868A4 (en) | 2015-08-09 | 2016-07-25 | Graphene adsorbing material, preparation method therefor and application thereof, and cigarette filter tip and cigarette |
| KR1020187006746A KR102177137B1 (en) | 2015-08-09 | 2016-07-25 | Graphene adsorbent, its manufacturing method and use, and cigarette filter tips and tobacco |
| PCT/CN2016/110136 WO2017114174A1 (en) | 2015-12-31 | 2016-12-15 | Graphene electrothermal material and application thereof |
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| CN106000316A (en) | 2016-10-12 |
| CN106000316B (en) | 2019-09-10 |
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