CN104489922B - A kind of preparation and application of graphene oxide bonded silica gel composite - Google Patents
A kind of preparation and application of graphene oxide bonded silica gel composite Download PDFInfo
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- CN104489922B CN104489922B CN201410766164.5A CN201410766164A CN104489922B CN 104489922 B CN104489922 B CN 104489922B CN 201410766164 A CN201410766164 A CN 201410766164A CN 104489922 B CN104489922 B CN 104489922B
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- graphene oxide
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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
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
Abstract
The present invention provides a kind of preparation method of graphene oxide bonded silica gel composite, comprises the following steps：1）Sodium nitrate and the concentrated sulfuric acid are added in graphite powder and carries out pre-oxidation treatment, is added after potassium permanganate stirring, continues to stir after being diluted with water, add warm water and hydrogen peroxide stir after centrifugation, filtering, dried after finally cleaning, produce graphene oxide powder；2）Graphene oxide powder is added in N, N dimethylformamides and carries out ultrasonic disperse, alkylamino silica gel is added and after dicyclohexylcarbodiimide is heated to reflux, centrifugation, filtering are dried after cleaning, produce graphene oxide bonded silica gel composite.The present invention still further provides the cigarette filter rod of addition graphene oxide bonded silica gel composite.A kind of graphene oxide bonded silica gel composite that the present invention is provided, can effectively reduce TSNAs contents in cigarette mainstream flue gas, with very good effect.
Description
Technical field
The invention belongs to cigarette material technical field, be related to the functional material in a kind of cigarette field prepare and its should
With a kind of, and in particular to the preparation of graphene oxide bonded silica gel composite and its it is added to reduction cigarette master in cigarette filter rod
Flow the application of nitrosamine in flue gas.
Background technology
Cigarette can produce rush cancer and carcinogen, such as peculiar nitrous of condensed-nuclei aromatics, aldehydes matter, tobacco in combustion
Amine (TSNAs) and free radical etc..Wherein, tobacco-specific nitrosamine (TSNAs) it is reported that identified 8 kinds at present.But in cigarette
In main have 4 kinds：N- nitrosonornicotines (NNN), 4- (methyl nitrous ammonia) -1- (3- pyridine radicals) -1- butanone (NNK), N-
Nitrosoanatabine (NAT), N- nitrosos anabasine (NAB).Wherein NNN and NNK had been demonstrated with animal carcinogenicity,
Lung cancer is induced to the golden vole of mouse, rat and Syria.In metabolic activity, NNN and NNK can make living animal and in vitro
Tissue in DNA methylation, 07- methyl guanines and 06- methyl birds that the result is isolated from tissue
It can be proven in purine.
At present, in reduction cigarette there be much the method for harmful substance, including added in filter stick punching, formula expanded cut tobacco,
Expanded cut stem and mix reconstituted tobacoo etc..But most of these methods are in the reduction harmful substance such as releasing content of coke tar or nicotine content
While, have a great impact to the fragrance and mouthfeel of cigarette.
Recent years, nano material has the absorption property that unique texture is brought by it, is considered as can be used as cigarette
Filter stick additive.Wherein, graphene is a kind of two-dimension nano materials of an only carbon atom thickness, miscellaneous with sp2 by carbon atom
Change track and constitute cellular regular hexagon lattice configuration, in addition to the property with common nano material, also moved with high electronics
Shifting rate, unique pi bond conjugation suction-operated.Graphene oxide (GO) is the presoma that chemical method prepares graphene, and its surface contains
There are abundant hydroxyl, carboxyl and epoxy functionality, easily with other polar groups formation chemical bond, and with well hydrophilic
Property.Therefore, it is highly desirable to carry out further investigated and research to application of the grapheme material in terms of Harm reduction techniques tar reduction.
The content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of graphene oxide bonded silica gel
The preparation and application of composite, by the way that graphene oxide (GO) is loaded on silica-gel carrier, prepare graphene oxide
Bonded silica gel (GO/ silica gel) composite, is added in cigarette filter rod, can effectively reduce TSNAs in cigarette mainstream flue gas and contain
Amount.
In order to achieve the above objects and other related objects, the present invention provides a kind of graphene oxide bonded silica gel composite
Preparation method, comprise the following steps：
1) sodium nitrate is added in graphite powder and the concentrated sulfuric acid carries out pre-oxidation treatment, is added after potassium permanganate stirring, plus
Continue to stir after water dilution, add warm water and hydrogen peroxide stir after centrifugation, filtering, dried after finally cleaning, produce oxygen
Graphite alkene (GO) powder；
Preferably, the addition weight ratio of the graphite powder and sodium nitrate is：2：0.9-1.1.
It is preferred that, the addition weight ratio of the graphite powder and sodium nitrate is：2：1.
Preferably, the addition weight of the graphite powder and the solid-to-liquid ratio of addition volume of the concentrated sulfuric acid are：1：21-25(g/
ml)。
It is preferred that, the solid-to-liquid ratio of the addition weight of the graphite powder and the addition volume of the concentrated sulfuric acid is：1：23(g/ml).
Preferably, the pre-oxidation treatment condition is：Reaction temperature：0-5℃；Reaction time：20-40 minutes；Stirring time
Number：150-250 beats/min.
It is preferred that, the pre-oxidation treatment condition is：Reaction temperature：0℃；Reaction time：30 minutes；Stir number of times：200
Beat/min.
Preferably, the addition weight ratio of the graphite powder and potassium permanganate is：1：2.8-3.2.
It is preferred that, the addition weight ratio of the graphite powder and potassium permanganate is：1：3.
Preferably, the stirring condition of the potassium permanganate is：Whipping temp：Room temperature；Mixing time：110-130 minutes；Stir
Mix number of times：100-150 beats/min.
It is preferred that, the stirring condition of the potassium permanganate is：Whipping temp：20-25℃；Mixing time：120 minutes；Stir
Mix number of times：120 beats/min.
After the addition potassium permanganate stirring, mixture can become brown slurry.It is described produce brown slurry principle be
Graphite powder is oxidized, and the functional group such as Surface Creation hydroxyl, carboxyl, epoxy radicals, big conjugatedπbond system is broken, spectral absorption
Change, therefore color is changed into brown from black.
Preferably, the addition weight of the graphite powder and the solid-to-liquid ratio of addition volume of water are：1：48-52(g/ml).Institute
State to be diluted with water and be conducive to discharging heat, be easy to oxidation.
It is preferred that, the solid-to-liquid ratio of the addition weight of the graphite powder and the addition volume of water is：1：50(g/ml).
Preferably, the stirring condition that adds water is：Mixing time is 110-130 minutes；Stir number of times：150-250 times/
Point.
It is preferred that, the stirring condition that adds water is：Mixing time is 120 minutes；Stir number of times：200 beats/min.
Preferably, the warm water is the deionized water of 30-50 DEG C of water temperature.The warm water, which is added, to be conducive to preventing sinking in reaction
Shallow lake is regenerated, and increases solute effect.
Preferably, the addition weight of the graphite powder and the solid-to-liquid ratio of addition volume of warm water are：1：95-105(g/ml).
It is preferred that, the solid-to-liquid ratio of the addition weight of the graphite powder and the addition volume of warm water is：1：100(g/ml).
Preferably, the hydrogen peroxide is 30% hydrogen peroxide (v/v).
Preferably, the addition weight of the graphite powder and the solid-to-liquid ratio of addition volume of hydrogen peroxide are：1：9.5-10.5(g/
ml)。
It is preferred that, the solid-to-liquid ratio of the addition weight of the graphite powder and the addition volume of hydrogen peroxide is：1：10(g/ml).
Preferably, warm water and hydrogen peroxide stirring condition are：Mixing time is 15-25 minutes；Stir number of times：150-250 times/
Point.
It is preferred that, warm water and hydrogen peroxide stirring condition are：Mixing time is 20 minutes；Stir number of times：200 beats/min.
Preferably, the centrifugation, filtering refer to that solvent will be filtered out after reactant centrifugation layering, retain solid powder.
It is preferred that, the centrifugal condition is：Centrifugation time：9.5-10.5min；Rotating speed：4800-5200rpm/min.
More excellent, the centrifugal condition is：Centrifugation time：10min；Rotating speed：5000rpm/min.
Preferably, the cleaning is will to filter out cleaning agent after the reactant centrifugation layering for adding cleaning agent, retain solid
Powder.
It is preferred that, the cleaning agent is watery hydrochloric acid or water.
It is preferred that, the cleaning way is：First cleaned twice, then cleaned twice with water with watery hydrochloric acid.It is described
Plus watery hydrochloric acid cleaning is conducive to removing the metal oxide of material surface.
More excellent, the watery hydrochloric acid is 5% watery hydrochloric acid (v/v).
More excellent, each cleaning volumetric usage of the watery hydrochloric acid and the addition weight ratio of graphite powder are：95-105：1
(ml/g)。
Optimal, each cleaning volumetric usage of the watery hydrochloric acid and the addition weight ratio of graphite powder are：100：1(ml/
g)。
More excellent, each cleaning volumetric usage of the water and the addition weight ratio of graphite powder are：95-105：1(ml/
g)。
Optimal, each cleaning volumetric usage of the water and the addition weight ratio of graphite powder are：100：1(ml/g).
Preferably, the drying mode is to dry sample with vacuum drying oven at room temperature.
It is preferred that, the drying condition is：Reaction temperature：Room temperature；Reaction vessel：Vacuum drying oven；Container power：1.8-
2.0kW；Drying time：23.5-24.5 hours.
More excellent, the drying condition is：Reaction temperature：20-25℃；Reaction vessel：Vacuum drying oven；Container power：
1.9kW；Drying time：24 hours.
2) graphene oxide powder is added in DMF and carries out ultrasonic disperse, add alkylamino silica gel
After being heated to reflux with dicyclohexylcarbodiimide, centrifugation, filtering are dried after cleaning, produce graphene oxide bonded silica gel
Composite.
Preferably, the graphene oxide powder addition weight and DMF addition volume solid-liquid
Than for：2：4.8-5.2(g/ml).
It is preferred that, the solid-liquid of the addition weight of the graphene oxide powder and the addition volume of DMF
Than for：2：5(g/ml).
Preferably, the ultrasound condition is：Ultrasonic time：20-40 minutes；Ultrasonic power：480-520W；Ultrasonic temperature：
Room temperature.
It is preferred that, the ultrasound condition is：Ultrasonic time：30 minutes；Ultrasonic power：500W；Ultrasonic temperature：20-25℃.
Preferably, the graphene oxide powder, alkylamino silica gel, dicyclohexylcarbodiimide addition weight ratio are：1：
23-27：0.9-1.1.
It is preferred that, the graphene oxide powder, alkylamino silica gel, dicyclohexylcarbodiimide add weight ratio and are：1：
25：1.
Preferably, the heated reflux condition：Heating-up temperature：50±0.5℃；Return time：30 ± 0.1 hours.
It is preferred that, the heated reflux condition：Heating-up temperature：50℃；Return time：30 hours.
Preferably, the centrifugation, filtering refer to that solvent will be filtered out after reactant centrifugation layering, retain solid powder.
It is preferred that, the centrifugal condition is：Centrifugation time：9.5-10.5min；Rotating speed：4800-5200rpm/min.
More excellent, the centrifugal condition is：Centrifugation time：10min；Rotating speed：5000rpm/min.
Preferably, the cleaning is will to filter out cleaning agent after the reactant centrifugation layering for adding cleaning agent, retain solid
Powder.
It is preferred that, the cleaning agent is methanol or water.
It is preferred that, the cleaning way is：First eccentric cleaning is carried out with water twice, again with methanol carries out eccentric cleaning two
It is secondary.
More excellent, each cleaning volumetric usage of the water and the addition weight ratio of graphite powder are：2300-2700：1
(ml/g)。
Optimal, each cleaning volumetric usage of the water and the addition weight ratio of graphite powder are：2500：1(ml/g).
More excellent, each cleaning volumetric usage of the methanol and the addition weight ratio of graphite powder are：2300-2700：1
(ml/g)。
Optimal, each cleaning volumetric usage of the methanol and the addition weight ratio of graphite powder are：2500：1(ml/
g)。
More excellent, the methanol is absolute methanol.
Preferably, the drying mode is to dry sample with vacuum drying oven at room temperature.
It is preferred that, the drying condition is：Reaction temperature：Room temperature；Reaction vessel：Vacuum drying oven；Container power：1.8-
2.0kW；Drying time：29.5-30.5 hours.
More excellent, the drying condition is：Reaction temperature：20-25℃；Reaction vessel：Vacuum drying oven；Container power：
1.9kW；Drying time：30 hours.
Preferably, the water used in the present invention is deionized water.
The invention also discloses a kind of graphene oxide bonded silica gel composite obtained using the above method.
Preferably, the specific surface area of the graphene oxide composite material is 280-295m2/g。
It is preferred that, the specific surface area of the graphene oxide composite material is 287m2/g。
Preferably, the specific surface area of the graphene oxide bonded silica gel composite is 330-340m2/g。
It is preferred that, the specific surface area of the graphene oxide bonded silica gel composite is 336m2/g。
The present invention further discloses the volume that with the addition of graphene oxide bonded silica gel composite as described above
Cigarette filter.
Preferably, the graphene oxide bonded silica gel composite propped up in the cigarette filter rod containing 3-8mg/.It is preferred that,
The graphene oxide bonded silica gel composite propped up in the cigarette filter rod containing 5mg/.
Preferably, the cigarette filter rod is including two sections of acetate fiber sections positioned at pipe tobacco end and mouth end and positioned at described two sections
Graphene oxide bonded silica gel composite section in the middle of acetate fiber section.
Rolled up present invention also offers a kind of cigarette filter rod that with the addition of graphene oxide bonded silica gel composite in reduction
Application in cigarette main flume in nitrosamine.
As described above, the graphene oxide bonded silica gel of nitrosamine is combined in a kind of reduction cigarette mainstream flue gas of the present invention
The preparation and application of material, graphene oxide (GO) is prepared by using Hummer method principles, further according to GO surfaces carboxyl with
The amino bonded route of Silica Surface, graphene oxide (GO) is loaded on silica-gel carrier, graphite oxide ethylene linkage is prepared
Silica gel (GO/ silica gel) composite is closed, is added in cigarette filter rod, have studied it reduces the filter of TSNAs in cigarette mainstream flue gas
Except effect, the deep application for being newest nanometer technology in terms of Harm reduction techniques tar reduction provides effective reference.
The GO/ material silica gel composites that preparation method of the present invention is obtained have larger specific surface area, easily and cigarette
TSNAs in gas is fully contacted, with very strong adsorption capacity.Meanwhile, GO/ material silica gel composites also have carboxyl functional group,
Nitrogen-atoms in TSNAs molecules can ultimately form amido link by the carbon atom in nucleophilic substitution attack carboxyl, so that
Effectively adsorbed on GO/ material silica gel composites surface, without being entered by cigarette filter rod in smoker's body.The present invention is made
Standby GO/ material silica gel composites can effectively reduce NAB, NAT, NNK, NNN in main flume respectively reach 18.95%,
16.33%th, 26.55%, 6.43%, with very good effect.
Brief description of the drawings
Fig. 1 is shown as a kind of X-ray diffractogram of GO/ material silica gel composites of the present invention
Fig. 2 is shown as a kind of Raman spectrograms of GO/ material silica gel composites of the present invention
Fig. 3 is shown as a kind of N2 adsorption isothermal curve figure of GO/ material silica gel composites of the present invention
Fig. 4 is shown as a kind of transmission electron microscope picture of GO/ material silica gel composites of the present invention
Embodiment
The present invention is expanded on further with reference to specific embodiment, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Following reagents and equipment that following examples are used
1. reagent
Graphite powder (commercially available)；The concentrated sulfuric acid, sodium nitrate, potassium permanganate, hydrogen peroxide, methanol, hydrochloric acid, ammonium acetate (analyze pure, state
Medicine company)；N,N-dimethylformamide, alkylamino silica gel, dicyclohexylcarbodiimide (analyzing pure, Agilent company)；Deionization
Water (water purification machine self-control)
2. equipment
D8 types X-ray diffractometer (X-ray be Cu targets,German Bruker companies)；RM2000 type spectrum
Instrument (Renishw companies of Britain)；The type high resolution transmission electron microscopies of JEM 2010 (Japanese JEOL companies)；The types of ASAP 2010
N2 adsorption is than Surface Tester (Merck ＆ Co., Inc)；The linear smoking machines of SM450 (Cerulean companies of Britain)；VD-115 type vacuum
Baking oven (BINDER companies)；KH5200DE types ultrasonic washing instrument (Kunshan He Chuan companies)；2487 type high performance liquid chromatography mass spectrums
Combined instrument (Water companies)
Embodiment 1
1.GO preparation
By 10g graphite powders, 5gNaNO3It is added to the 230ml concentrated sulfuric acids in the large beaker that volume is 2L, 30 points is stirred at 0 DEG C
Clock carries out pre-oxidation treatment.After pre-oxidation treatment, by 30g KMnO4Be slowly added into, then mixture be stirred at room temperature until
It is changed into brown slurry.After stirring 120 minutes, 500ml deionized waters are slowly added into brown slurry, now reaction temperature is anxious
Play rises, and continues to stir 120 minutes.Add 1L warm water and 100ml30%H2O2, centrifuge, filter after stirring.Filtering
The sample obtained afterwards is first cleaned twice with watery hydrochloric acid, is then cleaned twice, is dried at room temperature with vacuum drying oven with deionized water,
Finally give GO powder.
The preparation of 2.GO/ material silica gel composites
200mgGO powder is taken to be distributed in 500mlN, N-dimethylformamide, ultrasound adds 5g amino silicone after 30 minutes
Glue and 200mg dicyclohexylcarbodiimides, are heated to reflux 30 hours at 50 DEG C.Centrifugation, filtering, are obtained after filtering after reaction terminates
The sample obtained is first cleaned twice with deionized water, is then cleaned twice, is dried at room temperature with vacuum drying oven with methanol, final
To GO/ material silica gel composites.
3. the preparation of cigarette filter rod
By the GO/ material silica gel composites of acquisition, it is added to the 5mg/ contents propped up in cigarette filter rod, then be prepared into cigarette sample
Product (addition sample), it is to be measured.The cigarette filter rod is including two sections of acetate fiber sections positioned at pipe tobacco end and mouth end and positioned at described two
Graphene oxide bonded silica gel composite section in the middle of section acetate fiber section.Meanwhile, prepare and contain without there is graphite oxide
Ethylene linkage closes the cigarette sample (control sample) of the cigarette filter rod of material silica gel composite, to be measured.
Embodiment 2
1.GO preparation
By 10g graphite powders, 4.5gNaNO3It is added to the 210ml concentrated sulfuric acids in the large beaker that volume is 2L, 20 is stirred at 0 DEG C
Minute carries out pre-oxidation treatment.After pre-oxidation treatment, by 28g KMnO4It is slowly added into, then mixture is stirred at room temperature directly
To being changed into brown slurry.After stirring 110 minutes, 480ml deionized waters are slowly added into brown slurry, now reaction temperature
Steeply rise, continue to stir 110 minutes.Add 950ml warm water and 95ml30%H2O2, centrifuge, filter after stirring.
The sample obtained after filtering is first cleaned twice with watery hydrochloric acid, is then cleaned twice with deionized water, vacuum drying oven is used at room temperature
Dry, finally give GO powder.
The preparation of 2.GO/ material silica gel composites
200mgGO powder is taken to be distributed in 480mlN, N-dimethylformamide, ultrasound adds 4.6g amino after 20 minutes
Silica gel and 180mg dicyclohexylcarbodiimides, are heated to reflux 29.9 hours at 49.5 DEG C.Centrifugation, filtering, mistake after reaction terminates
The sample obtained after filter is first cleaned twice with deionized water, is then cleaned twice, is dried at room temperature with vacuum drying oven with methanol,
Finally give GO/ material silica gel composites.
3. the preparation of cigarette filter rod
By the GO/ material silica gel composites of acquisition, it is added to the 3mg/ contents propped up in cigarette filter rod, then be prepared into cigarette sample
Product (addition sample), it is to be measured.The cigarette filter rod is including two sections of acetate fiber sections positioned at pipe tobacco end and mouth end and positioned at described two
Graphene oxide bonded silica gel composite section in the middle of section acetate fiber section.Meanwhile, prepare and contain without there is graphite oxide
Ethylene linkage closes the cigarette sample (control sample) of the cigarette filter rod of material silica gel composite, to be measured.
Embodiment 3
1.GO preparation
By 10g graphite powders, 5.5gNaNO3It is added to the 250ml concentrated sulfuric acids in the large beaker that volume is 2L, 40 is stirred at 5 DEG C
Minute carries out pre-oxidation treatment.After pre-oxidation treatment, by 32g KMnO4It is slowly added into, then mixture is stirred at room temperature directly
To being changed into brown slurry.After stirring 130 minutes, 520ml deionized waters are slowly added into brown slurry, now reaction temperature
Steeply rise, continue to stir 130 minutes.Add 1L warm water and 105ml30%H2O2, centrifuge, filter after stirring.Cross
The sample obtained after filter is first cleaned twice with watery hydrochloric acid, is then cleaned twice with deionized water, dry with vacuum drying oven at room temperature
It is dry, finally give GO powder.
The preparation of 2.GO/ material silica gel composites
200mgGO powder is taken to be distributed in 520mlN, N-dimethylformamide, ultrasound adds 5.4g amino after 40 minutes
Silica gel and 220mg dicyclohexylcarbodiimides, are heated to reflux 30.1 hours at 50.5 DEG C.Centrifugation, filtering, mistake after reaction terminates
The sample obtained after filter is first cleaned twice with deionized water, is then cleaned twice, is dried at room temperature with vacuum drying oven with methanol,
Finally give GO/ material silica gel composites.
3. the preparation of cigarette filter rod
By the GO/ material silica gel composites of acquisition, it is added to the 8mg/ contents propped up in cigarette filter rod, then be prepared into cigarette sample
Product (addition sample), it is to be measured.The cigarette filter rod is including two sections of acetate fiber sections positioned at pipe tobacco end and mouth end and positioned at described two
Graphene oxide bonded silica gel composite section in the middle of section acetate fiber section.Meanwhile, prepare and contain without there is graphite oxide
Ethylene linkage closes the cigarette sample (control sample) of the cigarette filter rod of material silica gel composite, to be measured.
Embodiment 4
1. constituent analysis
The processing of 1.1 testing samples
Addition sample prepared by clause 3 in above-described embodiment 1, according to standard ISO3308-2000《Cigarette smoke routinely divides
Parser is defined and standard conditions》, aspirated (pumping volume 35ml/min) using the linear smoking machines of SM450, and using straight
Footpath is the TPM in Φ 44mm glass fiber filter trapping cigarette mainstream flue gas, and every filter disc collects the flue gas of 5 cigarettes
Granule phase substance, each sample answers parallel determination 2 times.
After cigarette smoking is finished, glass fiber filter is placed in 50ml conical flasks, the accurate 100mM for adding 20ml
(mol/L) ammonium acetate solution, at room temperature after ultrasonic extraction 30 minutes, then crosses aqueous phase membrane filtration by extract, takes 1ml to filter
Liquid, it is to be measured.
1.2 instruments are detected
Filtrate is determined using high performance liquid chromatography GC-MS (HPLC-MS/MS).
Wherein, the analysis condition of high performance liquid chromatography is：Chromatographic column：C18 posts (3.2 × 100mm i.d.1.7 μm)；Stream
Speed：0.25ml/min；Column temperature：50℃；Sample size：10μl；Mobile phase：A phases are 10mM Acetic Acid-Water solution, and B phases are 10mM vinegar
Acid-methanol solution；Analysis time：10min；Linear gradient elution.
The A phases：The graded elution of B phases meets following condition：
0-4min A phases：B phase volume ratios：92：8—40：60；
4-5min A phases：B phase volume ratios：40：60—40：60；
5-8min A phases：B phase volume ratios：40：60—5：95；
8-10min A phases：B phase volume ratios：5：95—92：8.
Wherein, Mass Spectrometry Conditions are：
Mass ion source parameter：Ion gun：Electron spray ionisation source；Scan mode：Cation is scanned；Detection mode：It is more anti-
It should monitor；Electron spray voltage：5000V；Ion source temperature：600℃；Aid in gas Gas1 pressure：35psi；Aid in gas Gas2 pressure：
35psi。
In addition, object mass spectrometry parameters are shown in Table 1.
Table 1 is mass spectrometer parameters setting value
2. result is with discussing
The detection of 2.1GO/ material silica gel composites
GO/ material silica gel composites are determined using D8 types X-ray diffractometer, the X-ray diffraction of GO/ material silica gel composites is obtained
Fig. 1.As shown in Figure 1, there is diffraction maximum near 10 DEG C, illustrate that original graphite powder is oxidized, generate oxygen-containing functional group, cause crystalline substance
Interplanar distance expands, and GO is successfully synthesized.
Using RM2000 type spectrophotometer GO/ material silica gel composites, the Raman spectrum of GO/ material silica gel composites are obtained
Fig. 2.As shown in Figure 2, D bands and G etc. are occurred in that in Raman spectrum, further illustrates that GO is successfully synthesized.
GO/ material silica gel composites are determined than Surface Tester using the type N2 adsorptions of ASAP 2010, GO/ silica gel is obtained and is combined
N2 adsorption isothermal curve Fig. 3 of material.From the figure 3, it may be seen that GO/ material silica gel composites have big specific surface area, it is theoretically excellent
Good sorbing material.
GO/ material silica gel composites are determined using the type high resolution transmission electron microscopies of JEM 2010, GO/ silica gel is obtained and is combined
Transmission electron microscope Fig. 4 of material.As shown in Figure 4, GO is that Silica Surface is bonded in the form of monolithic, maintains big ratio surface
Product, is suitable for absorption.
The detection of 2.2TSNAs contents
Addition GO/ silica gel in the filter stick prepared in above-described embodiment 1 is determined according to above-mentioned 1.2 using HPLC-MS/MS to be combined
The cigarette sample (addition sample) of material.Similarly, determine what is prepared in above-described embodiment 1 using HPLC-MS/MS according to above-mentioned 1.2
Without the cigarette sample (control sample) of GO/ material silica gel composites in filter stick.Specific testing result is shown in Table 2.
4 kinds of TSNAs result in the composite filter of table 2 reduction main flume
As shown in Table 2, GO/ material silica gel composites are added in cigarette filter rod as adsorbent, what is prepared is compound
Filter stick cigarette, can substantially reduce the TSNAs in cigarette mainstream flue gas.This filter stick to NAB in cigarette mainstream flue gas, NAT,
NNK, NNN range of decrease respectively reach 18.95%, 16.33%, 26.55%, 6.43%.
2.3 sensory evaluating smoking
In addition, to prepared in embodiment 1 sample progress sensory evaluating smoking's result show, the filter stick to smoking property of cigarette quality without
Harmful effect, the results are shown in Table 3.As shown in Table 3, compared to the cigarette sample (control in filter stick without GO/ material silica gel composites
Sample), cigarette sample (addition sample) smoking result of addition GO/ material silica gel composites is close with it in filter stick, it is seen that add GO/ silicon
Glue composite, does not influence, can apply in practice substantially on smoking property of cigarette quality.
The Sensory Quality of Cigarette of table 3 examines record sheet
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (7)
1. a kind of preparation method of graphene oxide bonded silica gel composite, comprises the following steps：
1) sodium nitrate is added in graphite powder and the concentrated sulfuric acid carries out pre-oxidation treatment, adds after potassium permanganate stirring, adds water dilute
Continue to stir after releasing, add warm water and hydrogen peroxide stir after centrifugation, filtering, dried after finally cleaning, produce oxidation stone
Black alkene powder；
2) graphene oxide powder is added in DMF and carries out ultrasonic disperse, add alkylamino silica gel and two
After carbodicyclo hexylimide is heated to reflux, centrifugation, filtering are dried after cleaning, are produced graphene oxide bonded silica gel and are combined
Material；
Step 1) in, the pre-oxidation treatment condition is：Reaction temperature：0-5℃；Reaction time：20-40 minutes；Stir number of times：
150-250 beats/min；
Step 1) in, the stirring condition of the potassium permanganate is：Whipping temp：Room temperature；Mixing time：110-130 minutes；Stirring
Number of times：100-150 beats/min；The stirring condition that adds water is：Mixing time is 110-130 minutes；Stir number of times：150-250
Beat/min；Warm water and the hydrogen peroxide stirring condition is：Mixing time is 15-25 minutes；Stir number of times：150-250 beats/min；
Step 2) in, the ultrasound condition is：Ultrasonic time：20-40 minutes；Ultrasonic power：480-520W；Ultrasonic temperature：Room
Temperature；The heated reflux condition：Heating-up temperature：49.5-50.5℃；Return time：29.9-30.1 hours.
2. a kind of preparation method of graphene oxide bonded silica gel composite according to claim 1, it is characterised in that
Step 1) in, the cleaning is will to filter out cleaning agent after the reactant centrifugation layering for adding cleaning agent, retain solid powder；Institute
Cleaning agent is stated for watery hydrochloric acid or water；The cleaning way is：First cleaned twice with watery hydrochloric acid, then carry out with water cleaning two
It is secondary.
3. a kind of preparation method of graphene oxide bonded silica gel composite according to claim 1, it is characterised in that
Step 2) in, the cleaning is will to filter out cleaning agent after the reactant centrifugation layering for adding cleaning agent, retain solid powder；Institute
Cleaning agent is stated for methanol or water；The cleaning way is：First eccentric cleaning is carried out with water twice, again with methanol carries out eccentric cleaning
Twice.
4. a kind of graphene oxide bonded silica gel composite, any described method is made in claim 1-3.
5. a kind of cigarette filter rod, added with graphene oxide bonded silica gel composite as claimed in claim 4.
6. a kind of cigarette filter rod according to claim 5, it is characterised in that propped up in the cigarette filter rod containing 3-8mg/
Graphene oxide bonded silica gel composite；The cigarette filter rod include positioned at pipe tobacco end and mouth end two sections of acetate fiber sections and
Graphene oxide bonded silica gel composite section in the middle of two sections of acetate fiber sections.
7. a kind of cigarette filter rod that with the addition of graphene oxide bonded silica gel composite according to claim 5-6 is in drop
Application in low cigarette mainstream flue gas in nitrosamine.
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| EP3332868A4 (en) * | 2015-08-09 | 2019-01-02 | Jinan Shengquan Group Share Holding Co., Ltd | Graphene adsorbing material, preparation method therefor and application thereof, and cigarette filter tip and cigarette |
| CN106690404B (en) * | 2015-11-18 | 2018-07-27 | 中国烟草总公司郑州烟草研究院 | Tobacco shred additive and its preparation method and application based on graphene nanocomposite material |
| CN105533802A (en) * | 2016-01-18 | 2016-05-04 | 张麟德 | Smoke filtering device and tobacco product |
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| ES2896761T3 (en) * | 2016-04-29 | 2022-02-25 | Log 9 Materials Scient Private Limited | A graphene-based tobacco smoke filter and a method for synthesizing the graphene composition |
| CN108160061A (en) * | 2016-12-07 | 2018-06-15 | 中国石油化工股份有限公司 | Band amino Ionic Liquid Modified graphene oxide package silica gel base chromatograph packing material |
| CN111743192B (en) * | 2020-07-10 | 2022-05-17 | 湖北中烟工业有限责任公司 | Preparation method of geraniol-graphene oxide slow-release heat-conducting composite material for cigarettes |
| CN113633021B (en) * | 2021-08-25 | 2023-10-13 | 上海烟草集团有限责任公司 | Method for reducing butyric acid in cigarette smoke |
| CN113693278B (en) * | 2021-08-26 | 2023-11-07 | 上海烟草集团有限责任公司 | Composite filter stick for reducing propionic acid in cigarette smoke and cigarette |
| CN113598412B (en) * | 2021-08-31 | 2023-10-13 | 上海烟草集团有限责任公司 | Composite filter tip for adsorbing 2-acetylpyridine in cigarette smoke and cigarette |
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