CN104522885A - Adsorbing agent capable of reducing phenol release amount in mainstream cigarette smoke and preparation method and application thereof - Google Patents
Adsorbing agent capable of reducing phenol release amount in mainstream cigarette smoke and preparation method and application thereof Download PDFInfo
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- CN104522885A CN104522885A CN201410795388.9A CN201410795388A CN104522885A CN 104522885 A CN104522885 A CN 104522885A CN 201410795388 A CN201410795388 A CN 201410795388A CN 104522885 A CN104522885 A CN 104522885A
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- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 81
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000779 smoke Substances 0.000 title abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000000463 material Substances 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 53
- 239000003546 flue gas Substances 0.000 claims description 50
- 239000003463 adsorbent Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 239000012043 crude product Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 17
- 230000021523 carboxylation Effects 0.000 claims description 16
- 238000006473 carboxylation reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- HOGDNTQCSIKEEV-UHFFFAOYSA-N n'-hydroxybutanediamide Chemical compound NC(=O)CCC(=O)NO HOGDNTQCSIKEEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 239000000306 component Substances 0.000 claims description 3
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- 238000000502 dialysis Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- 241000208125 Nicotiana Species 0.000 description 12
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- 238000001514 detection method Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000004567 concrete Substances 0.000 description 7
- -1 1-ethyl Chemical group 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000000391 smoking effect Effects 0.000 description 6
- PFNFFQXMRSDOHW-UHFFFAOYSA-N Spermine Natural products NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000002296 dynamic light scattering Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229940063675 spermine Drugs 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
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- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000001427 coherent effect Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 229960002715 nicotine Drugs 0.000 description 3
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 210000000780 bap Anatomy 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 210000004072 lung Anatomy 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000621 bronchi Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 210000004081 cilia Anatomy 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an adsorbing agent capable of reducing the phenol release amount in mainstream cigarette smoke and a preparation method and application of the adsorbing agent. The adsorbing agent comprises, by weight, 1 part of graphite powder, 5 parts to 50 parts of inorganic acid, 30 parts to 100 parts of strong oxidizing substances, 5 parts to 20 parts of bis(3-aminopropyl)polyethylene glycol and 0.3 part to 1 part of condensing agent. The method comprises the steps that firstly, the graphite powder is carboxylated to obtain oxidized graphene, and the condensing agent and the bis(3-aminopropyl)polyethylene glycol are added to obtain polyethylene glycol modified graphene. The efficient and convenient method is adopted for controlling the microstructure and the structure of the graphene material, and meanwhile bio-polyamine modification is carried out on the surface of the graphene, so that the performance of the adsorbing agent for selectively adsorbing phenol in the mainstream cigarette smoke is further improved, and meanwhile the adsorbing agent has the advantages of being fast, efficient, small in using amount and the like.
Description
Technical field
Harmful technical field falls in Jiao that subtracts that the present invention relates to tobacco industry, refers to particularly a kind ofly reduce adsorbent of phenol release amount in cigarette mainstream flue gas and its preparation method and application.
Background technology
Cigarette smoke is produced by result of combustion of tobacco, cracking and distillation in cigarette smoking process, is a kind of extremely complicated mixture, is made up of, wherein has quite a few harmful nearly 4000 kinds of compounds.Because main flume directly contacts with smoker, the research enthusiasm of people to wherein harmful components has never gone down since 20th century, the sixties lighted.Especially the proposition of " smoking with healthy " problem, society and consumer's " subtract Jiao and fall evil " attention rate to cigarette growing, the burst size how reducing the harmful components in cigarette mainstream flue gas has become the great research theme of tobacco business.
Volatile aldehydes matter is very important class harmful components in cigarette mainstream flue gas, wherein phenol is one of most important seven kinds of harmful components in main flume, it is a kind of protoplasmic toxin thing causing protein denaturization and precipitation, animal skin and respiratory tract are had to intense stimulus effect, as one of 46 kinds of harmful components in Hoffmann list, endanger initiatively and involuntary smoker healthy.There are some researches show, phenol in cigarette mainstream flue gas not only has strong impulse effect to skin and respiratory mucosa, but also there is tumor promotion, the existence of phenol can significantly improve the carcinogenic activity of polycyclic aromatic hydrocarbon, and after being inhaled into lung, damage is produced to bronchus cilium, thus extend the time of staying of tar in lung.In addition, aldehydes matter also can affect the suction taste of flue gas, thus produces harmful effect to the sensory evaluation of cigarette.Therefore, the reduction of the burst size of phenol in cigarette mainstream flue gas, reduce cigarette smoke to the harm of health and improve cigarette suck in impression, there is very great meaning.
With the material that material with carbon element class porous adsorbent is representative, the specific area huge with it and high efficiency adsorption capacity, good elimination effect is had to the harmful components in cigarette mainstream flue gas, as a kind of functional form filter stick material, in reducing tar and reducing harm effect, there is larger potential quality, be subject to the favor of tobacco scientific workers always.Graphene is a kind of New Two Dimensional plane nano material be just found for 2004, by one deck intensive, carbon atom in cellular regular hexagon crystal lattice forms with sp2 hybridized orbit, be two-dimensional material the thinnest in the world, its thickness is only 0.35nm.This special construction with very bigger serface, Graphene is made to show excellent absorption property, particularly it is with the planar regular hexagonal sheet layer unit of carbon atom composition, similar to the structure of phenyl ring, rich surface is containing pi-electron, make between Graphene and phenyl ring, to there is stronger π-pi-electron conjugation, thus specific absorption can contain the material of benzene ring structure, as multiring aromatic hydrocarbon harmful components such as the phenol in main flume, BaPs, in reduction cigarette mainstream flue gas, there is larger potential quality in phenol content.
Except the porous class sorbing material of main flow, in recent years, based on the strong hydrogen bonding suction-operated that phenolic hydroxy is all, tobacco tar-reducing harm reduction workers are also increasing turns to the sorbing material with strong hydrogen bonding effect, as polyhydroxy material, hydrophilic colloid molecule etc. by research emphasis.
Publication number is that the Chinese invention patent of CN202774108U discloses a kind of syllogic functional form filter rod formed with the triacetyl glycerine tow of variable concentrations, this filter rod material can the content of phenol in selectivity reducing cigarette fume, there is good physical property and outward appearance simultaneously, can not product quality be affected.Publication number is that the Chinese invention patent of CN103141939A discloses a kind of trapping agent reducing phenol content in cigarette smoke, this trapping agent is by water, after glycerine and essence are allocated with the ratio that volume ratio is 2.5 ︰ 1.2 ~ 5 ︰ 0.1 ~ 0.125, capsule for medicine inside is wrapped in as capsule core, finally add in filter rod, total addition level is that 0.01 ~ 0.5mg/ often props up, result shows, this trapping agent can significantly reduce phenol content in cigarette smoke, cigarette smoke moisture can be improved simultaneously, strengthen flue gas moist feeling, improve exhaust gas volumn and flue gas matter, give the special fragrance of flue gas and jealous.Polyethylene glycol is a kind of nontoxic, extraordinary hydrophilic material of nonirritant, biocompatibility, have in biology, medical science, pharmacy, food etc. and apply very widely, its rich surface hydroxyl group, there is good surfactant property, the Hydrogen Binding Adsorption effect that easy formation is stronger, in recent years also by the scientific workers of association area as primary study object.
Based on excellent surface activation capacity and the strong hydrogen bonding suction-operated of polyethylene glycol, and Graphene and aromatic compound specific strong π-pi-conjugated adsorption effect, we carry out chemical modification to the molecular surface of Graphene at design, make the polyethylene glycol branch its lamellar structure chemical bonding being rich in oh group, carry out specificity more easily by Hydrogen Binding Adsorption effect to the aldehydes matter with polarity in cigarette mainstream flue gas to retain, further enhance the function of phenol content in its selectivity reducing cigarette main flume.At present, use polyethyleneglycol modified after modified graphene class nano adsorption material there is not yet Patents and bibliographical information for the research of the burst size aspect of phenol in selectivity reducing cigarette main flume.
Summary of the invention
Technical problem to be solved by this invention is just to provide and a kind ofly reduces adsorbent of phenol release amount in cigarette mainstream flue gas and its preparation method and application.The present invention adopts efficiently, method to be to control microscopic appearance and the structure of grapheme material easily, Biopolyamines class modification is carried out to graphene molecules surface simultaneously, to improve the selectivity of this material to Adsorption of Phenol in cigarette mainstream flue gas further, there is the advantages such as quick, efficient, use amount is little simultaneously.
For solving the problems of the technologies described above, a kind of adsorbent reducing phenol release amount in cigarette mainstream flue gas provided by the invention, described adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the inorganic acid of 5 ~ 50 parts, the oxidizing species of 30 ~ 100 parts, two (3-aminopropyl) polyethylene glycol of 5 ~ 20 parts and 0.3 ~ 1 part of condensing agent.
Further, described adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the inorganic acid of 20 ~ 30 parts, the oxidizing species of 60 ~ 80 parts, two (3-aminopropyl) polyethylene glycol of 10 ~ 16 parts and 0.3 ~ 0.6 part of condensing agent.
Again further, described stone mill powder is the mixture of mono-layer graphite powder and Multi-layer graphite powder, and its particle diameter is 0.5 ~ 2 μm.
Again further, described condensing agent is any one or a few in dicyclohexylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide and N-hydroxy-succinamide.
Again further, described inorganic acid be in red fuming nitric acid (RFNA), the concentrated sulfuric acid and concentrated hydrochloric acid any one.
Again further, described oxidizing species is that component A and B component form, and wherein, component A is any one in red fuming nitric acid (RFNA), the concentrated sulfuric acid and concentrated hydrochloric acid, and B component is any one or two kinds in potassium permanganate and hydrogen peroxide.
Again further, the quality of described potassium permanganate and the volume ratio of component A are: 3 ~ 8g: 15 ~ 100mL.
Or the volume of the quality of described potassium permanganate and hydrogen peroxide, component A volume ratio be: 1 ~ 3g: 5mL: 30 ~ 50mL.
Again further, described adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the red fuming nitric acid (RFNA) of 25 parts, the potassium permanganate of 5 parts, 72.8 parts of nitric acid, two (3-aminopropyl) polyethylene glycol of 15 parts and 1-ethyl-(3-dimethylaminopropyl) carbodiimides of 0.5 part.
Present invention also offers a kind of sorbent preparation method reducing phenol release amount in cigarette mainstream flue gas, comprise the following steps:
1) graphite powder, inorganic acid, oxidizing species, two (3-aminopropyl) polyethylene glycol and condensing agent is taken by ratio of weight and the number of copies by above-mentioned, for subsequent use;
2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water and stir, ultrasonic process 12 ~ 36h, then be warming up to 45 ~ 60 DEG C, react 3 ~ 6h under constant temperature, by reaction suspension miillpore filter suction filtration, wash and become neutrality to filtrate, obtain the graphite powder of purifying;
3) to step 2) add oxidizing species in the graphite powder that obtains of purifying, add water and stir, be warming up to 50 ~ 120 DEG C, under constant temperature, stirring and refluxing reaction 8 ~ 24h, uses miillpore filter suction filtration, obtains Carboxylation Graphene crude product;
4) by step 3) obtain Carboxylation Graphene crude product washing to neutral, then use absolute ethanol washing 3 ~ 5 times, be placed in the vacuum drying 36 ~ 48h under 40 ~ 60 DEG C of conditions, obtain the Carboxylation graphene oxide of purifying;
5) by step 4) obtain Carboxylation graphene oxide and carry out pickling impurity removal, then ultrasonic process at ambient temperature, until solid matter is all soluble in water, add condensing agent and ultrasonic process 10 ~ 30min, then add two (3-aminopropyl) polyethylene glycol, after ultrasonic process 10 ~ 30min, transfer on oscillator, shaken at room temperature reaction 8 ~ 24 hours, obtains reactant liquor, reactant liquor is used miillpore filter suction filtration, obtain the poly ethyldiol modified Graphene crude product of purifying;
6) by absolute ethanol washing step 5) the poly ethyldiol modified Graphene crude product that obtains, repeats 2 ~ 5 times, then poly ethyldiol modified Graphene crude product is placed in bag filter, take deionized water as dislysate dialysis 24 ~ 48 hours, use AgNO
3solution is monitored, until without Cl in dislysate
-exist, by dislysate at-10 DEG C after freezing 24 hours, frozen dried in freeze drier, namely obtains poly ethyldiol modified Graphene solid.
Present invention also offers a kind of application of adsorbent in the composition for the preparation of absorption phenol reducing phenol release amount in cigarette mainstream flue gas, comprise the following steps:
1) take appropriate poly ethyldiol modified Graphene class sorbing material, add ice-bath ultrasonic 30min in redistilled water and make it dispersed, obtained concentration is the poly ethyldiol modified graphene dispersing solution of 1mg/mL, for subsequent use;
2) the acetate filter cigarette that quality is often propped up at 0.75 ~ 0.85 gram is chosen, the addition of cigarette is propped up with 0.5 ~ 4mg/, poly ethyldiol modified graphene dispersing solution is added in cigarette filter rod, dry 50min at 80 DEG C, be placed in climatic chamber balance after 48 hours, obtain the cigarette sample with composite adsorbing material filter tip.
Beneficial effect of the present invention is:
1) modification is used for tobacco lowering harm and decreasing coking field with the modified graphene of functional form polyhydroxy group by the present invention first, and the research and development for novel Less harmful cigarette technology are brought new breakthrough.After the modification of polyethylene glycol chemistry is carried out to graphene molecules surface, the poly ethyldiol modified Graphene obtained is individual layer two-dimensional nanostructure, there is very large specific area, oh group is also rich in its surface, have considerably beyond the adsorption efficiency in conventional bulk phase sorbing material and three-dimensional manometer sorbing material, the elimination efficiency to harmful substance in cigarette mainstream flue gas can be increased substantially.
2) poly ethyldiol modified Graphene Pyrogentisinic Acid has p key conjugation to adsorb and strong hydrogen bonding adsorption dual Specific adsorption effect.On the one hand, the hexatomic ring polyene structure in the lamella molecule of poly ethyldiol modified Graphene is similar to the phenyl ring configuration of phenol, there is stronger π-pi-conjugated adsorption effect; On the other hand, in the polyglycol chain that its lamella molecular structure surface is modified, the abundant oh group of oh group easily and in phenol produces stronger Hydrogen Binding Adsorption effect.This dual suction-operated highly significant improves the selective adsorption capacity of poly ethyldiol modified Graphene to the phenol in cigarette mainstream flue gas, meanwhile, good elimination effect is also had to other harmful components that there is Hydrogen Binding Adsorption effect containing harmful components of phenyl ring and HCN, crotonaldehyde etc. such as BaP, benzanthracene.
3) poly ethyldiol modified grapheme material is owing to having abundant hydrophilic radical, strong hydrogen bonding suction-operated and difficult drop-off can be produced with mouth rod fibre bundle, the dust phenomenon produced when can overcome traditional fiber-like sorbing material for making composite tip stick, can avoid the toxic action produced environment and human body.
4) efficiency of the selective reducing tar and reducing harm of filter rod of the poly ethyldiol modified Graphene of interpolation of the present invention is very high, poly ethyldiol modified grapheme material used in the present invention, claim often prop up the adding proportion scope of filter tip only 1 ~ 5mg under, just can reach harmful components phenol release amount more than 30% in selective reduction main flume.
5) dissolubility of grapheme material in water and alcohols solvent after poly ethyldiol modified modification significantly improves, and adding implementation more simply, without the need to changing existing production of cigarettes processing technology, simplifying technological process, reduce production cost.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of Graphene raw material and poly ethyldiol modified Graphene;
Fig. 2 is particle size and the breadth coefficient figure of the rare sample liquid of poly ethyldiol modified graphite;
Fig. 3 is the zeta potential energy diagram of the rare sample liquid of poly ethyldiol modified graphite;
Fig. 4 is the transmission electron microscope picture of the rare sample liquid of poly ethyldiol modified graphite;
Fig. 5 is poly ethyldiol modified Graphene stability change tendency chart
A. sample liquid Average Particle Diameters variation diagram;
B particle diameter polydispersity coefficient variation diagram is figure;
Fig. 6 is that the obtained adsorbent of embodiment 1 ~ 7 adds and falls phenol effect assessment in cigarette filter rod;
Fig. 7 is that the obtained adsorbent of embodiment 7 adds and falls phenol effect assessment in cigarette filter rod.
Detailed description of the invention
In order to explain the present invention better, illustrate main contents of the present invention further below in conjunction with specific embodiment, but content of the present invention is not only confined to following examples.
Reduce an adsorbent for phenol release amount in cigarette mainstream flue gas, described adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the inorganic acid of 5 ~ 50 parts, the oxidizing species of 30 ~ 100 parts, two (3-aminopropyl) polyethylene glycol of 5 ~ 20 parts and 0.3 ~ 1 part of condensing agent.
Adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the inorganic acid of 20 ~ 30 parts, the oxidizing species of 60 ~ 80 parts, two (3-aminopropyl) polyethylene glycol of 10 ~ 16 parts and 0.3 ~ 0.6 part of condensing agent.
Stone mill powder is the mixture of mono-layer graphite powder and Multi-layer graphite powder, and its particle diameter is 0.5 ~ 2 μm.
Condensing agent is any one or a few in dicyclohexylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide and N-hydroxy-succinamide.
Inorganic acid be in red fuming nitric acid (RFNA), the concentrated sulfuric acid and concentrated hydrochloric acid any one.
Oxidizing species is that component A and B component form, and wherein, component A is any one in red fuming nitric acid (RFNA), the concentrated sulfuric acid and concentrated hydrochloric acid, and B component is any one or two kinds in potassium permanganate and hydrogen peroxide.
The quality of potassium permanganate and the volume ratio of component A are: 3 ~ 8g: 15 ~ 100mL.
Or the volume of the quality of described potassium permanganate and hydrogen peroxide, component A volume ratio be: 1 ~ 3g: 5mL: 30 ~ 50mL.
Adsorbent material is counted by ratio of weight and the number of copies by the graphite powder of 1 part, the red fuming nitric acid (RFNA) of 25 parts, the potassium permanganate of 5 parts, 72.8 parts of nitric acid, two (3-aminopropyl) polyethylene glycol of 15 parts, and the 1-ethyl of 0.5 part-(3-dimethylaminopropyl) carbodiimide composition.
The sorbent preparation method of phenol release amount in cigarette mainstream flue gas can be reduced, comprise the following steps:
1) graphite powder, inorganic acid, oxidizing species, two (3-aminopropyl) polyethylene glycol and condensing agent is taken by ratio of weight and the number of copies by above-mentioned, for subsequent use;
2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water and stir, ultrasonic process 12 ~ 36h, then be warming up to 45 ~ 60 DEG C, react 3 ~ 6h under constant temperature, by reaction suspension miillpore filter suction filtration, wash and become neutrality to filtrate, obtain the graphite powder of purifying;
3) to step 2) add oxidizing species in the graphite powder that obtains of purifying, add water and stir, be warming up to 50 ~ 120 DEG C, under constant temperature, stirring and refluxing reaction 8 ~ 24h, uses miillpore filter suction filtration, obtains Carboxylation Graphene crude product;
4) by step 3) obtain Carboxylation Graphene crude product washing to neutral, then use absolute ethanol washing 3 ~ 5 times, be placed in the vacuum drying 36 ~ 48h under 40 ~ 60 DEG C of conditions, obtain the Carboxylation graphene oxide of purifying;
5) by step 4) obtain Carboxylation graphene oxide and carry out pickling impurity removal, then ultrasonic process at ambient temperature, until solid matter is all soluble in water, add condensing agent and ultrasonic process 10 ~ 30min, then add two (3-aminopropyl) polyethylene glycol, after ultrasonic process 10 ~ 30min, transfer on oscillator, shaken at room temperature reaction 8 ~ 24 hours, obtains reactant liquor, reactant liquor is used miillpore filter suction filtration, obtain the poly ethyldiol modified Graphene crude product of purifying;
6) by absolute ethanol washing step 5) the poly ethyldiol modified Graphene crude product that obtains, repeats 2 ~ 5 times, then poly ethyldiol modified Graphene crude product is placed in bag filter, take deionized water as dislysate dialysis 24 ~ 48 hours, use AgNO
3solution is monitored, until without Cl in dislysate
-exist, by dislysate at-10 DEG C after freezing 24 hours, frozen dried in freeze drier, namely obtains poly ethyldiol modified Graphene solid.
Poly ethyldiol modified Graphene solid sample (hereinafter referred to as sample) obtained by above-mentioned any component and preparation method, carry out characterizing and Performance Detection, Detection results is as follows:
1. infrared spectrum (FTIR) characterizes
The mensuration of the infrared spectrum of poly ethyldiol modified Graphene sample obtains modified graphene sample solid piece, at 25 DEG C by pellet technique, through Bio-Rad FTS 6000 spectrometer (Bio-Rad Company, Hercules, California, USA) characterize.Concrete steps are:
Under room temperature, the sample powder of getting 1mg inserts mortar, add the potassium bromide powder of 150mg drying, under infrared lamp baking, grinding is even rapidly, mixing smalls is evenly added in compression mold, 1min is suppressed under 1000MPa pressure, obtain transparent solid brominated potassium compressing tablet, after infrared spectrometer carries out background scans, sample compressing tablet is inserted in spectral instrument sample room, adjustment position makes light path by fixing behind transparent place, compressing tablet middle, and close sample room rapidly, again Infrared spectra adsorption scan value is carried out to sample, obtain the FTIR spectrum of poly ethyldiol modified Graphene solid sample, as shown in Figure 1.
The infrared spectrum spectrogram of Graphene raw material (collection of illustrative plates A) and poly ethyldiol modified graphite (collection of illustrative plates B) can be seen respectively from Fig. 1.At Fig. 1. in (A), 3400cm
-1neighbouring without significant spike, and Fig. 1. the 3435cm in (B)
-1there is more sharp-pointed absworption peak in place, this is the stretching vibration peak of peg molecule terminal hydroxyl (-OH); At Fig. 1. 2000 ~ 3000cm in (A)
-1locate without obvious absorption peaks, Fig. 1. 2000 ~ 3000cm in (B)
-1there is a larger blunt peak at place, and this is the stretching vibration peak of a large amount of ehter bond (-O-) in peg molecule chain; In addition, at Fig. 1. peak value is less or not have and at Fig. 1 in (A). the 1574cm occurred in (B)
-1, 1194cm
-1the absworption peak at place also belongs to the characteristic absorption peak of ehter bond in peg molecule and hydroxyl respectively, and above these all demonstrate the generation of poly ethyldiol modified Graphene.
2. dynamic light scattering luminosity (DLS) measures
The particle size and distribution coefficient of above-mentioned poly ethyldiol modified Graphene solid sample is at 25 DEG C, survey instrument ZETA-SIZER Nano Series Nano-ZSZEN3600 (Malvern Instruments Ltd., UK) through dynamic light scattering luminosity to record.Concrete steps are as follows:
The sample of 1mg drying is added in 10mL redistilled water, ice-bath ultrasonic 30min makes it dispersed, use liquid-transfering gun to measure 0.2mL dispersion liquid and be placed in 10mL colorimetric cylinder, re-use redistilled water constant volume, and ice-bath ultrasonic 30min makes it fully dissolve, obtain poly ethyldiol modified graphene dispersing solution.Get this dispersion liquid of 2mL and be placed in glass cuvette, measure under 25 DEG C of conditions with equilibration time 1min to its average grain diameter and the coefficient of dispersion, each mensuration is all repeated 3 times, and acquired results as shown in Figure 2.
Same, the zeta current potential of sample, at 25 DEG C, is surveyed instrument through dynamic light scattering luminosity and is recorded, and poly ethyldiol modified graphene solution is to test after 10 times amount redistilled water dilutions again.Zeta potentiometric detection range set is-150V to 150V.Basic parameter is set as follows: stroboscopic postpones-1.00, start-up time 200.00 milliseconds, shut-in time 1.00 milliseconds.Each mensuration all repeats 3 times to average, and acquired results as shown in Figure 3.
From Fig. 3 the data obtained, the Average Particle Diameters of sample dispersion liquid is 189.8nm, polydispersity coefficient is 0.177, and show that the domain size distribution of this sample is comparatively even, distributed area is more concentrated, basic one-tenth Unimodal Distribution, symmetry is better, and from distribution curve, the domain size distribution of its Major particle is in the interval of 100nm ~ 400nm, only have distribution of particles that a small amount of particle diameter is less in the interval of 7-10 μm, the dispersiveness describing this dispersion liquid is better.
Zeta current potential be microparticle surfaces the sign of electrically charged quantity, the electrical potential difference that microparticle surfaces charge density distribution difference is brought, make to avoid near assembling between particulate due to repulsion, therefore the numerical value of electrical potential difference is the important indicator of characterizing particles dispersion liquid system stability, also can the surface charge property of characterizing particles comparatively intuitively.From Fig. 3 the data obtained, the surface potential value of the rare sample dispersion liquid of poly ethyldiol modified graphite is 2.57mV, describes the surface that polyethylene glycol has successfully been modified at graphene film Rotating fields, makes its surface become neutral by negative electrical charge sex reversal.
3. transmission electron microscope (TEM) observation
The microscopic pattern of above-mentioned sample dispersion liquid carries out observation by TEM and obtains.Concrete steps are as follows:
The poly ethyldiol modified Graphene solid sample of 1mg drying adds in 10mL redistilled water, ice-bath ultrasonic 30min makes it dispersed, use liquid-transfering gun to measure 0.2mL dispersion liquid and be placed in 10mL colorimetric cylinder, re-use redistilled water constant volume, and ice-bath ultrasonic 30min makes it fully dissolve, obtain poly ethyldiol modified graphene solution.Get this solution appropriate to drip on micro-grid.After forming sample thin layer, under being statically placed in infrared lamp, dry 20min.Under 100KV accelerating potential, observe through Jeol JEM-2100F type transmission electron microscope (Tokyo, Japan).The micromorphology observed result of sample liquid as shown in Figure 4.
The structure of sample particulate can be seen in the diagram comparatively clearly, its thinner individual layer laminated structure is comparatively unfolded, only there is a little overlap, demonstrate polyethylene glycol preferably and can increase the sterically hindered of its microparticle surfaces to the modification of graphenic surface, expand the distance between lamellar structure, thus improve the specific area of Graphene particulate and dispersed and stability further.
4. stability study
At 4 ± 2 DEG C of temperature, the dispersion liquid of sample is left standstill and keeps in Dark Place 28 days, and measured the average grain diameter of this sample liquid respectively at the the the the the 0th, 1,3,7,14,21,28 day.Particle size and domain size distribution state all measure with DLS, with the physical dispersion variation tendency of the rare sample liquid of poly ethyldiol modified graphite in 28 days obtained.The dispersion liquid Average Particle Diameters variation diagram of sample is Fig. 4. (A), particle diameter polydispersity coefficient variation diagram is Fig. 4. (B).
From Fig. 5. (A), in 28 days, the average grain diameter of the dispersion liquid of sample all remains between 180 ~ 200nm, in first 3 days, the grain size stability of the dispersion liquid of sample is very good, maintains about 189nm, only has 1 ~ 2nm to float, and during 3 ~ 28 days, the average grain diameter of sample liquid fluctuates between 180 ~ 195nm, and in the later stage, particle size change tends towards stability, and stablizes gradually; The average grain diameter entire change amplitude of dispersion liquid in 28 days of sample is less, is all no more than 4%.From Fig. 5. (B), in 28 days, the particle diameter polydispersity coefficient of the rare dispersion liquid of spermine modified graphite all remains within 0.4, in 24 hours, the polydispersity coefficient of sample liquid increases to more than 0.2 rapidly, and in 1st ~ 7 days, amplitude of variation is less subsequently, and polydispersity coefficient slowly changes between 0.23 ~ 0.25, but between 7 ~ 28 days, the particle diameter polydispersity coefficient of the dispersion liquid of sample is again gradually in regular increase, finally reaches about 0.39.According to DLVO (Derjaguin, Landan, Verwey, Overbeek) theoretical (HoekEM, Agarwal GK.Extended DLVO interactions between sphericalparticles and rough surfaces [J] .Journal of Colloid and Interface Science.2006,298 (1): 50-58.), can colloidal sol under certain condition stable existence, depends on interactional potential energy between micelle.Total potential equals the Coulomb repulsion potential energy sum that Van der Waals attracts potential energy and caused by electric double layer, and these two kinds of potential energies are all the functions of micelle spacing, attracts 6 powers of potential energy and distance to be inversely proportional to, and Coulomb repulsion potential energy then increases exponentially function with distance and declines.These two kinds of potential energies come from Van der Waals'attractive force and electrostatic repulsion forces respectively, and these two kinds of opposite effect power determine the stability of colloid.The molecular structure rare from poly ethyldiol modified graphite, the surperficial polyethylene glycol owing to introducing of micrograined texture in its sample dispersion liquid creates larger space steric hindrance, distance between its particulate is increased, Coulomb repulsion potential energy sharply reduces as the exponential function of distance thereupon, and owing to attracting 6 powers of potential energy and distance to be inversely proportional to, potential energy is now attracted also significantly to decline, after the fall of electrostatic repulsion forces exceedes the fall attracting potential energy, inter particles distance is from reducing to some extent again, the change of these active forces makes the total potential between particulate fluctuate to some extent within the specific limits, may be that within sample liquid after the production 24 hours, the change of particle diameter polydispersity coefficient is comparatively remarkable, and the reason that in after sample preparation 3 ~ 28 days, the Average Particle Diameters of particulate and polydispersity coefficient tend towards stability gradually.Average grain diameter within final 200nm and the polydispersity coefficient of about 0.39 show, this sample liquid still maintains the dispersity compared with stable uniform after the production for 28 days, and the electrostatic repulsion forces of the particulate also in interpret sample liquid finally reaches poised state with attracting potential energy.Above phenomenon and data show again, and poly ethyldiol modified graphene dispersing solution is a more stable dispersion.
According to above-mentioned four Detection results com-parison and analysis, again in actual mechanical process, the technological parameter of the composition of raw materials that Selection effect is good and preparation carries out suitability for industrialized production, concrete pulp furnish table 1 and process parameter table 2 as follows: according to the raw material required for the poly ethyldiol modified Graphene sorbing material of preparation, preparation proportioning table 1:
The list of table 1. pulp furnish
Note: red fuming nitric acid (RFNA) mass fraction is about 65%, and (density is about 1.4g/cm
3), concentrated sulfuric acid mass fraction is that 98.3% (density is 1.84g/cm
3), concentrated hydrochloric acid mass fraction be 37.5% (
close degree1.116g/cm
3), hydrogen peroxide mass fraction is that 30% (density is 1.11g/cm
3).
According to above-mentioned formula, obtain poly ethyldiol modified Graphene class sorbing material in conjunction with its preparation method, step is as follows:
1) graphite powder, inorganic acid, oxidizing species, two (3-aminopropyl) polyethylene glycol and 1-ethyl-(3-dimethylaminopropyl) carbodiimide, dicyclohexylcarbodiimide, N-hydroxy-succinamide is taken by ratio of weight and the number of copies by above-mentioned, for subsequent use;
2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water until stir, ultrasonic process 12 ~ 36h, then be warming up to 45 ~ 60 DEG C, react 3 ~ 6h under constant temperature, by reaction suspension miillpore filter suction filtration, wash and become neutrality to filtrate, obtain the graphite powder of purifying;
3) to step 2) add oxidizing species in the graphite powder that obtains of purifying, add water until stir, be warming up to 50 ~ 120 DEG C, under constant temperature, stirring and refluxing reaction 8 ~ 24h, uses miillpore filter suction filtration, obtains Carboxylation Graphene crude product;
4) by step 3) obtain Carboxylation Graphene crude product washing to neutral, then use absolute ethanol washing 3 ~ 5 times, be placed in the vacuum drying 36 ~ 48h under 40 ~ 60 DEG C of conditions, obtain the Carboxylation graphene oxide of purifying;
5) by step 4) obtain in Carboxylation graphene oxide, adding two (3-aminopropyl) polyethylene glycol, ultrasonic process 1 ~ 3h, add appropriate condensing agent again, stirring reaction 24 ~ 48h at 25 ~ 50 DEG C of temperature, reactant liquor is used miillpore filter suction filtration, obtain poly ethyldiol modified Graphene crude product;
6) by the washing of poly ethyldiol modified Graphene crude product to neutral, then use absolute ethanol washing 3 ~ 5 times, be placed in vacuum drying 36 ~ 48h under 40 ~ 60 DEG C of conditions, obtain poly ethyldiol modified Graphene class sorbing material.
The response parameter optimizing each embodiment according to above-mentioned steps is as shown in table 2 below:
The response parameter list of table 2. embodiment
1, the sorbing material that above-described embodiment 1 ~ 7 obtains is carried out suction fuel test:
The spermine modified graphene class sorbing material that above-described embodiment 1 ~ 7 obtains adds in cigarette filter rod, and step is as follows:
1) take appropriate spermine modified graphene class sorbing material, add ice-bath ultrasonic 30min in redistilled water and make it dispersed, obtained concentration is the spermine modified graphene dispersion liquid of 1mg/mL, for subsequent use;
2) the acetate filter cigarette that quality is often propped up at 0.75 ~ 0.85 gram is chosen, the addition of cigarette is propped up with 1mg/, spermine modified graphene dispersion liquid is added in cigarette filter rod, dry 50min at 80 DEG C, be placed in after climatic chamber balances 48h, obtain the cigarette with composite adsorbing material filter tip.
The above-mentioned cigarette obtaining 7 composite adsorbing material filter tips carries out suction fuel test, according to standard and the general flue gas inspection method of tobacco business, requires to collect flue gas sample according to different test item, then carries out the be correlated with analysis of harmful components of flue gas and detects.Phenol content detects and carries out according to tobacco business standard YC/T255-2008; Nicotine and moisture use chromatography of gases-MS to detect; Tar content detects and is undertaken by standard GB/T/T19609-2004; Carbon monoxide content automatically detects in smoking machine aspiration procedure.
The concrete data result of cigarette mainstream flue gas composition coherent detection is in table 3.The poly ethyldiol modified Graphene class sorbing material that embodiment 1 ~ 7 obtains to the impact effect evaluation of phenol content in cigarette mainstream flue gas as shown in Figure 6.Phenol content detection method detailed process is as follows:
Collect the cambridge filter that main flume passes through, with isopyknic 1% Extraction of Acetic Acid liquid, with shaking table, 40min is extracted at normal temperatures to the cambridge filter of each sample respectively again, after filtering with microporous membrane, high performance liquid chromatography is used to detect the content of phenol in each sample extraction liquid.After calculating formula according to the test result of phenol Standard solution, sample measurement is substituted into, thus calculates phenol growing amount in single sample cigarette smoke respectively, then compare with reference cigarette.
Table 3. cigarette mainstream flue gas fractions detects data
2, according to above-mentioned test result, select the embodiment 7 gained poly ethyldiol modified Graphene class sorbing material falling phenol best results, investigation is selective further falls phenol effect:
According to said method, the addition of cigarette is propped up with 0.5 ~ 4mg/, poly ethyldiol modified for above-described embodiment 7 gained Graphene sorbing material is added in cigarette filter rod, carry out suction fuel test, according to standard and the general flue gas inspection method of tobacco business, require to collect flue gas sample according to different test item, then carry out the be correlated with analysis of harmful components of flue gas and detect.Phenol content detects and carries out according to tobacco business standard YC/T255-2008; Nicotine and moisture use chromatography of gases-MS to detect; Tar content detects and is undertaken by standard GB/T/T19609-2004; Carbon monoxide content automatically detects in smoking machine aspiration procedure.The concrete data result of cigarette mainstream flue gas composition coherent detection is in table 4.Poly ethyldiol modified Graphene to phenol content in cigarette mainstream flue gas impact effect evaluation as shown in Figure 7.Phenol content detection method detailed process is as follows:
Collect the cambridge filter that main flume passes through, with isopyknic 1% Extraction of Acetic Acid liquid, with shaking table, 40min is extracted at normal temperatures to the cambridge filter of each sample respectively again, after filtering with microporous membrane, high performance liquid chromatography is used to detect the content of phenol in each sample extraction liquid.After calculating formula according to the test result of phenol Standard solution, sample measurement is substituted into, thus calculates phenol growing amount in single sample cigarette smoke respectively, then compare with reference cigarette.
3, cigarette mainstream flue gas composition influence research
At 25 DEG C of temperature, take poly ethyldiol modified Graphene sample appropriate, add ice-bath ultrasonic 30min in redistilled water and make it dispersed, obtained concentration is the poly ethyldiol modified graphene dispersing solution of 1mg/mL.Choose quality 0.75 ~ 0.85 gram of acetate filter cigarette often propped up five groups, often organize ten, be numbered 1 ~ 5, in the cigarette filter rod of 1 ~ 5 group, add the poly ethyldiol modified graphene dispersing solution (1 group is blank group) of 0mL, 0.5mL, 1mL, 2mL, 4mL respectively.By five groups of cigarette samples at 80 DEG C after dry 50min, be placed in climatic chamber balance after 48 hours, SM450 linear pattern smoking machine is used to carry out suction fuel under standard aspiration condition, according to standard and the general flue gas inspection method of tobacco business, require to collect flue gas sample according to different test item, then carry out the be correlated with analysis of harmful components of flue gas and detect.Phenol content detects and carries out according to tobacco business standard YC/T255-2008; Nicotine and moisture use chromatography of gases-MS to detect; Tar content detects and is undertaken by standard GB/T/T19609-2004; Carbon monoxide content automatically detects in smoking machine aspiration procedure.The concrete data result of cigarette mainstream flue gas composition coherent detection is in table 4.Poly ethyldiol modified Graphene to phenol content in cigarette mainstream flue gas impact effect evaluation as shown in Figure 7.
(phenol content detection method detailed process: collect the cambridge filter that main flume passes through, with isopyknic 1% Extraction of Acetic Acid liquid, with shaking table, 40min is extracted at normal temperatures to the cambridge filter of each sample respectively again, after filtering with microporous membrane, high performance liquid chromatography is used to detect the content of phenol in each sample extraction liquid.After calculating formula according to the test result of phenol Standard solution, sample measurement is substituted into, thus calculates phenol growing amount in single sample cigarette smoke respectively, then compare with reference cigarette.)
Table 4. cigarette mainstream flue gas fractions detects data
Other unspecified part is prior art.Although above-described embodiment is to invention has been detailed description; but it is only the present invention's part embodiment; instead of whole embodiment, people can also obtain other embodiments according to the present embodiment under without creative prerequisite, and these embodiments all belong to scope.
Claims (10)
1. can reduce an adsorbent for phenol release amount in cigarette mainstream flue gas, it is characterized in that: described adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the inorganic acid of 5 ~ 50 parts, the oxidizing species of 30 ~ 100 parts, two (3-aminopropyl) polyethylene glycol of 5 ~ 20 parts and 0.3 ~ 1 part of condensing agent.
2. can reduce the adsorbent of phenol release amount in cigarette mainstream flue gas according to claim 1, it is characterized in that: described adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the inorganic acid of 20 ~ 30 parts, the oxidizing species of 60 ~ 80 parts, two (3-aminopropyl) polyethylene glycol of 10 ~ 16 parts and 0.3 ~ 0.6 part of condensing agent.
3. can reduce the adsorbent of phenol release amount in cigarette mainstream flue gas according to claim 1 or 2, it is characterized in that: described graphite powder is the mixture of mono-layer graphite powder and Multi-layer graphite powder, its particle diameter is 0.5 ~ 2 μm.
4. can reduce the adsorbent of phenol release amount in cigarette mainstream flue gas according to claim 1 or 2, it is characterized in that: described condensing agent is any one or a few in dicyclohexylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide and N-hydroxy-succinamide.
5. can reduce the adsorbent of phenol release amount in cigarette mainstream flue gas according to claim 1 or 2, it is characterized in that: described inorganic acid be in red fuming nitric acid (RFNA), the concentrated sulfuric acid and concentrated hydrochloric acid any one.
6. the adsorbent of phenol release amount in cigarette mainstream flue gas can be reduced according to claim 1 or 2, it is characterized in that: described oxidizing species is that component A and B component form, wherein, component A is any one in red fuming nitric acid (RFNA), the concentrated sulfuric acid and concentrated hydrochloric acid, and B component is any one or two kinds in potassium permanganate and hydrogen peroxide.
7. can reduce the adsorbent of phenol release amount in cigarette mainstream flue gas according to claim 6, it is characterized in that: the quality of described potassium permanganate and the volume ratio of component A are: 3 ~ 8g: 15 ~ 100mL.
Or the volume of the quality of described potassium permanganate and hydrogen peroxide, component A volume ratio be: 1 ~ 3g: 5mL: 30 ~ 50mL.
8. can reduce the adsorbent of phenol release amount in cigarette mainstream flue gas according to claim 1 or 2, it is characterized in that: described adsorbent material is counted by ratio of weight and the number of copies and is made up of the graphite powder of 1 part, the red fuming nitric acid (RFNA) of 25 parts, the potassium permanganate of 5 parts, 72.8 parts of nitric acid, two (3-aminopropyl) polyethylene glycol of 15 parts and 1-ethyl-(3-dimethylaminopropyl) carbodiimides of 0.5 part.
9. can reduce a sorbent preparation method for phenol release amount in cigarette mainstream flue gas described in claim 1, it is characterized in that: comprise the following steps:
1) graphite powder, inorganic acid, oxidizing species, two (3-aminopropyl) polyethylene glycol and condensing agent is taken by ratio of weight and the number of copies by above-mentioned, for subsequent use;
2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water and stir, ultrasonic process 12 ~ 36h, then be warming up to 45 ~ 60 DEG C, react 3 ~ 6h under constant temperature, by reaction suspension miillpore filter suction filtration, wash and become neutrality to filtrate, obtain the graphite powder of purifying;
3) to step 2) add oxidizing species in the graphite powder that obtains of purifying, add water and stir, be warming up to 50 ~ 120 DEG C, under constant temperature, stirring and refluxing reaction 8 ~ 24h, uses miillpore filter suction filtration, obtains Carboxylation Graphene crude product;
4) by step 3) obtain Carboxylation Graphene crude product washing to neutral, then use absolute ethanol washing 3 ~ 5 times, be placed in the vacuum drying 36 ~ 48h under 40 ~ 60 DEG C of conditions, obtain the Carboxylation graphene oxide of purifying;
5) by step 4) obtain Carboxylation graphene oxide and carry out pickling impurity removal, then ultrasonic process at ambient temperature, until solid matter is all soluble in water, add condensing agent and ultrasonic process 10 ~ 30min, then add two (3-aminopropyl) polyethylene glycol, after ultrasonic process 10 ~ 30min, transfer on oscillator, shaken at room temperature reaction 8 ~ 24 hours, obtains reactant liquor, reactant liquor is used miillpore filter suction filtration, obtain the poly ethyldiol modified Graphene crude product of purifying;
6) by absolute ethanol washing step 5) the poly ethyldiol modified Graphene crude product that obtains, repeats 2 ~ 5 times, then poly ethyldiol modified Graphene crude product is placed in bag filter, take deionized water as dislysate dialysis 24 ~ 48 hours, use AgNO
3solution is monitored, until without Cl in dislysate
-exist, by dislysate at-10 DEG C after freezing 24 hours, frozen dried in freeze drier, namely obtains poly ethyldiol modified Graphene solid.
10. can reduce the application of adsorbent in the composition for the preparation of absorption phenol for phenol release amount in cigarette mainstream flue gas described in claim 1, it is characterized in that: comprise the following steps:
1) take appropriate poly ethyldiol modified Graphene class sorbing material, add ice-bath ultrasonic 30min in redistilled water and make it dispersed, obtained concentration is the poly ethyldiol modified graphene dispersing solution of 1mg/mL, for subsequent use;
2) the acetate filter cigarette that quality is often propped up at 0.75 ~ 0.85 gram is chosen, the addition of cigarette is propped up with 0.5 ~ 4mg/, poly ethyldiol modified graphene dispersing solution is added in cigarette filter rod, dry 50min at 80 DEG C, be placed in climatic chamber balance after 48 hours, obtain the cigarette sample with composite adsorbing material filter tip.
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| CN108077994A (en) * | 2017-12-21 | 2018-05-29 | 中国烟草总公司郑州烟草研究院 | The coating fluid of phenol release amount in a kind of filter stick type cigarette mainstream flue gas for reducing paper |
| CN111743192A (en) * | 2020-07-10 | 2020-10-09 | 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 |
| CN115177018A (en) * | 2022-07-13 | 2022-10-14 | 广西中烟工业有限责任公司 | Directional essence using method based on flue gas transfer behavior of roasted sweet and fragrant raw materials |
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