CN104525126B - Biopolyamines modified graphite alkenes sorbing material and its preparation method and application - Google Patents
Biopolyamines modified graphite alkenes sorbing material and its preparation method and application Download PDFInfo
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- CN104525126B CN104525126B CN201410794573.6A CN201410794573A CN104525126B CN 104525126 B CN104525126 B CN 104525126B CN 201410794573 A CN201410794573 A CN 201410794573A CN 104525126 B CN104525126 B CN 104525126B
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- 239000000463 material Substances 0.000 title claims abstract description 52
- -1 modified graphite alkenes Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 235000019504 cigarettes Nutrition 0.000 claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000021523 carboxylation Effects 0.000 claims abstract description 17
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 claims description 16
- 150000001718 carbodiimides Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229940063673 spermidine Drugs 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 28
- 239000003546 flue gas Substances 0.000 abstract description 26
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 241000208125 Nicotiana Species 0.000 abstract description 12
- 235000002637 Nicotiana tabacum Nutrition 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 8
- 241000894007 species Species 0.000 abstract description 7
- 238000004939 coking Methods 0.000 abstract description 4
- 230000003247 decreasing effect Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- PFNFFQXMRSDOHW-UHFFFAOYSA-N Spermine Natural products NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008030 elimination Effects 0.000 abstract description 3
- 238000003379 elimination reaction Methods 0.000 abstract description 3
- 229940063675 spermine Drugs 0.000 abstract description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 abstract 2
- 238000001514 detection method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000011160 research Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 230000000391 smoking effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 238000007689 inspection Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960002715 nicotine Drugs 0.000 description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 2
- 150000004291 polyenes Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000019505 tobacco product Nutrition 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
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241001456108 Castilla Species 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000037273 Pathologic Processes Diseases 0.000 description 1
- 102000001253 Protein Kinase Human genes 0.000 description 1
- 108700005075 Regulator Genes Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 201000011510 cancer Diseases 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 210000004081 cilia Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
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- 231100000516 lung damage Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009054 pathological process Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
It is used for Biopolyamines modified graphite alkenes sorbing material of phenol and its preparation method and application in selective absorption cigarette mainstream flue gas the invention discloses a kind of.The raw materials by weight portion of the sorbing material is made up of than counting 1 part of graphite powder, 5~50 parts of inorganic acid, 30~100 parts of oxidizing species, 5~20 parts of Biopolyamines and 0.3~1 part of 1 ethyl (3 dimethylaminopropyl) carbodiimide.This method graphite powder is made first Carboxylation graphene crude product, then adds and adds polyamines and EDC, and purifying obtains spermine modified graphite alkenes sorbing material, is added into acetate filter cigarette during use.Modification is used for tobacco lowering harm and decreasing coking field by the present invention with the modified graphene of functional form polar group first, have considerably beyond in the adsorption efficiency of 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.
Description
Technical field
The present invention relates to the sorbing material technology for subtracting burnt drop evil for belonging to tobacco industry, it is used for selectivity in particular to one kind
Adsorb Biopolyamines modified graphite alkenes sorbing material of phenol and its preparation method and application in cigarette mainstream flue gas.
Background technology
Formulated with the World Health Organization (WHO)《The Framework Convention on Tobacco Control》Formal startup in China, Yi Jishe
Can be with consumer to the growing of " smoking and health " problem attention rate, " lowering harm and decreasing coking " has become World tobacco industry height
The operative orientation paid attention to is spent, the burst size of the harmful components efficiently, in the reduction cigarette mainstream flue gas of selectivity turns into tobacco
The strategic research problem of scientific research, to reduce harm of the tobacco product to human health, tobacco business is preferably fulfiled to society
Responsibility.
Volatile phenolics are during cigarette smoking, as caused by the burning cracking of various precursor components, are
Very important a kind of harmful components in cigarette mainstream flue gas, phenol particularly therein, it is most important seven in main flume
One of kind of harmful components, the control ingredients list for being put into WHO " tobacco product control research group " suggestions and 46 kinds have
In evil composition list, cell can be made to lose activity, there is strong corrosiveness to mucous membrane, while nervous centralis, damage can be suppressed
Evil hepatic and renal function etc., and after being inhaled into lung damage can be produced to bronchus cilium, so as to extend tar in the stop of lung
Between, there is rush carcinogenesis.In addition, aldehydes matter can also influence the suction taste of flue gas, so as to which the sensory evaluation generation to cigarette is bad
Influence.Therefore, the selective burst size for reducing phenol in cigarette smoke, reduce harm of the cigarette smoke to health with
And improve cigarette suck impression in terms of, there is very great meaning.
Polyamines is distributed widely in organism, mainly including butanediamine, pentanediamine, spermidine and spermine etc., between them
It can mutually convert, and may participate in many biological processes in regulation and control animal body, process after transcribing and transcribe such as regulatory gene,
The structure of modulation of ion channels keying, protein kinase bioactivity, cell cycle, membrane structure and function and nucleic acid and steady
Qualitative grade (PEGG A E, CASERO R A, Jr.Current status of the polyamine research field
[J].Methods in Molecular Biology,2011,720:3-35.).Recent studies indicate that polyamines is for device
The physiology such as official's development, breeding, aging, immune, cancer and pathologic process have important regulating and controlling effect.In addition, polyamines is rich in just
Electric charge, charge adsorption can be carried out in harmful ingredients in flue gas such as the phenol of negative electrical charge with surface and combined, meanwhile, the amino on polyamines surface
Strong hydrogen bonding absorption can be formed with the hydroxyl of phenol, be harmful into so as to phenol in the selection absorption main flume of duality etc.
Point.
Graphene is a kind of two-dimensional nano material for being made up of cellular regular hexagon lattice with sp2 hybridized orbits carbon atom
Material, (Novoselov K S, Geim A K, Morozov S V, et after successfully being peeled off and being observed first from 2005
al.Electric fieldeffect in atomically thin carbon films[J].Science,2004,306
(5296):666-669.), caused a sensation in chemistry, physics and material educational circles.The high intensity of graphene, high chemical stability,
The specific surface area of unique lamellar structure, nano level size and super large, becomes the new adsorbent being possessed of good qualities,
It is widely used in every field.The suction-operated of nano-graphene mainly includes two kinds of physical absorption and chemisorbed.Thing
The active force of reason absorption mostlys come from the Van der Waals force between graphene and adsorbed composition, and the active force of chemisorbed then takes
The property for the chemical group certainly modified in graphenic surface.There are some researches show (Carlos Moreno-
Castilla.Adsorption of organic molecules from aqueous solutions on carbon
materials[J].Carbon,2004,42(1):83-94.), because graphene has positive six side of plane formed with carbon atom
Shape stratiform polyene structure, makes its sheet surfaces be rich in pi-electron, and this special construction similar to phenyl ring causes graphene and phenyl ring
Between there is stronger π-pi-electron conjugation.This strong π-pi-conjugated effect can make graphene to containing in cigarette mainstream flue gas
The harmful substance of phenyl ring such as phenols, BaP etc. have stronger suction-operated.And chemistry is carried out to the molecular surface of graphene
Modification, after making the Biopolyamines such as the connection of its lamellar structure upper butanediamine, pentanediamine, spermidine, it is easier to by Hydrogen Binding Adsorption and
Charge adsorption double action and specific retention is carried out to the aldehydes matter with polarity in cigarette mainstream flue gas, it is further strong
The function of phenol content in its selectivity reducing cigarette main flume is changed.Therefore, develop with selectivity reducing cigarette master
The functional form graphite alkenes nano material of phenol release amount in flue gas is flowed, horizontal for the technical research of tobacco business lowering harm and decreasing coking
Raising has positive impetus.
At present, the modified graphite alkenes nano adsorption material after being modified using Biopolyamines is used for selectivity reducing cigarette master
The research in flue gas in terms of the burst size of phenol is flowed there is not yet Patents and document report.
The content of the invention
The technical problems to be solved by the invention be just to provide a kind of Biopolyamines modified graphite alkenes sorbing material and its
Preparation method and application.The present invention use that efficient, easily method is to control the microscopic appearance of grapheme material and structure, simultaneously
Biopolyamines class modification is carried out to graphene molecules surface, further to improve the material to phenol in cigarette mainstream flue gas
The selection performance of absorption, while have the advantages that quick, efficient, usage amount is small.
In order to solve the above technical problems, a kind of Biopolyamines modified graphene sorbing material provided by the invention, the absorption
The raw materials by weight portion of material is than counting by 1 part of graphite powder, 5~50 parts of inorganic acid, 30~100 parts of strong oxidizing property thing
Matter, 5~20 parts of Biopolyamines and 0.3~1 part of 1- ethyls-(3- dimethylaminopropyls) carbodiimide composition.
Further, the raw materials by weight portion of the sorbing material is than counting graphite powder by 1 part, 20~30 parts inorganic
Acid, 60~80 parts of oxidizing species, 12~18 parts of Biopolyamines and 0.3~0.8 part of 1- ethyls-(3- dimethylaminos
Base propyl group) carbodiimide composition.
Yet further, the Biopolyamines are any one or a few in spermidine, butanediamine and pentanediamine, its
In, the concentration of Biopolyamines is 0.3~1.0g/ml.
Yet further, the graphite powder is mono-layer graphite powder and the mixture of Multi-layer graphite powder its particle diameter is 0.5~2 μ
m。
Yet further, the inorganic acid is any one in concentrated nitric acid, the concentrated sulfuric acid and concentrated hydrochloric acid.
Yet further, the oxidizing species are that component A forms with B component, wherein, component A is concentrated nitric acid, dense sulphur
Acid and any one in concentrated hydrochloric acid, B component are any one or two kinds in potassium permanganate and hydrogen peroxide.
Yet further, the quality of the potassium permanganate and the volume ratio of component A are：3~8g: 15~100mL.
Or quality and the volume of hydrogen peroxide, the volume ratio of component A of the potassium permanganate are：1~3g: 5mL: 30~
50mL。
Yet further, the graphite powder of 1 part than meter composition of the raw materials by weight portion of the sorbing material, 25 parts of dense nitre
Acid, 5 parts potassium permanganate, 72.8 parts of nitric acid, 15 parts of spermidine and 0.5 part of 1- ethyls-(3- dimethylaminopropyls) carbon
Diimine forms.
Present invention also offers a kind of preparation method of modified polyamine graphite alkenes sorbing material, comprise the following steps：
1) by it is above-mentioned by ratio of weight and the number of copies based on weigh graphite powder, inorganic acid, oxidizing species, Biopolyamines and 1- second
Base-(3- dimethylaminopropyls) carbodiimide, it is standby；
2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water to stir, be ultrasonically treated 12~36h, then
45~60 DEG C are warming up to, 3~6h is reacted under constant temperature, reaction suspension is filtered with miillpore filter, washs to filtrate and is changed into
Neutrality, the graphite powder purified；
3) oxidizing species are added into the obtained graphite powder of step 2) purifying, adds water to stir, it is warming up to 50~
120 DEG C, 8~24h of reaction is stirred at reflux under constant temperature, is filtered with miillpore filter, obtains Carboxylation graphene crude product；
4) step 3) is obtained into Carboxylation graphene crude product to wash to neutrality, then washed 3~5 times with absolute ethyl alcohol, put
36~48h of vacuum drying under the conditions of 40~60 DEG C, the Carboxylation graphene oxide purified；
5) step 4) is obtained adding Biopolyamines in Carboxylation graphene oxide, is ultrasonically treated 1~3h, adds 1-
Ethyl-(3- dimethylaminopropyls) carbodiimide (EDC), 24~48h of stirring reaction at a temperature of 25~50 DEG C, by reaction solution
Filtered with miillpore filter, obtain Biopolyamines modified graphene crude product；
6) Biopolyamines modified graphene crude product is washed to neutrality, then washed 3~5 times with absolute ethyl alcohol, it is placed in 40~
36~48h is dried in vacuo under the conditions of 60 DEG C, obtains Biopolyamines modified graphite alkenes sorbing material.
Present invention also offers a kind of Biopolyamines modified graphite alkenes sorbing material to prepare the group for absorbing phenol
Application in compound, comprises the following steps：
1) appropriate Biopolyamines modified graphite alkenes sorbing material is weighed, adds ice-bath ultrasonic 30min in redistilled water
Make its dispersed, the Biopolyamines modified graphene dispersion liquid that concentration is 1mg/mL is made, it is standby；
2) acetate filter cigarette of the quality at 0.75-0.85 grams every is chosen, with adding for 0.5~4mg/ branch cigarette
Dosage, Biopolyamines modified graphene dispersion liquid is added into cigarette filter rod, 50min is dried at 80 DEG C, be placed in constant temperature perseverance
After being balanced 48 hours in wet tank, the cigarette sample with composite adsorbing material filter tip is obtained.
The beneficial effects of the present invention are：
1) modification is used for tobacco lowering harm and decreasing coking field by the present invention with the modified graphene of functional form polar group first, will
Research and development for new Less harmful cigarette technology bring new breakthrough.After carrying out oxidation carboxylated to graphene molecules surface, then by its
Biopolyamines modified graphene obtained by introducing Biopolyamines is individual layer two-dimensional nanostructure, has very big ratio surface
Product, have considerably beyond in the adsorption efficiency of conventional bulk phase sorbing material and three-dimensional manometer sorbing material, increasing substantially pair
The elimination efficiency of harmful substance in cigarette mainstream flue gas.
2) Biopolyamines modified graphene Pyrogentisinic Acid has the absorption of p keys conjugation, Hydrogen Binding Adsorption and charge adsorption etc. multiple
Specific adsorption effect.First, the phenyl ring of the hexatomic ring polyene structure in the lamella molecule of Biopolyamines modified graphene and phenol
Configuration is similar, and there is stronger π-pi-conjugated adsorption effect；Secondly, amino that its lamella molecular structure surface is modified and
The groups such as barish carboxyl, hydroxyl easily produce stronger Hydrogen Binding Adsorption with the hydroxy groups in phenol and acted on；It is in addition, raw
The lamella molecular structure surface aggregation cation of thing modified polyamine graphene, stronger electricity easily occurs with the phenol of anionic
Lotus suction-operated.This multiple suction-operated highly significant improves Biopolyamines modified graphene in cigarette mainstream flue gas
The selective adsorption capacity of phenol, meanwhile, to other harmful components and HCN containing phenyl ring, the crotonaldehydes such as BaP, benzanthracene
Harmful components Deng anionic also have preferable elimination effect.
3) Biopolyamines modified graphene material with mouth rod fibre bundle due to that with abundant polar group, can produce strong
Hydrogen Binding Adsorption is acted on and difficult for drop-off, and traditional fiber-like sorbing material can be overcome to be used to make and raise caused by composite tip stick
Grey phenomenon, it is avoided that the toxic action produced to environment and human body.
4) efficiency of the filter rod selectivity reducing tar and reducing harm of addition Biopolyamines modified graphene of the invention is very high, this
Amination graphene material used in invention, under every 0.5~4mg of filter tip adding proportion scope, it is possible to reach selection
Property reduce main flume in harmful components phenol release amount more than 30%.
5) dissolubility of the grapheme material after Biopolyamines modifying and decorating in water and alcohols solvent greatly improves, addition
Implementation is simpler, without changing existing production of cigarettes processing technology, simplifies technological process, reduces production cost.
Brief description of the drawings
Fig. 1 is several polyamines type grapheme material drop phenol effect assessment；
Fig. 2 is the drop phenol effect for spermidine modified graphene material Different adding amount in cigarette that embodiment 7 obtains
Evaluation
Embodiment
In order to preferably explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
Present disclosure is not limited solely to following examples.
Raw material according to required for preparing Biopolyamines modified graphite alkenes sorbing material, it is as shown in table 1 to prepare proportioning：
The raw material proportioning list of table 1.
Note：Concentrated nitric acid mass fraction is about that 65% (density is about 1.4g/cm3), concentrated sulfuric acid mass fraction be 98.3% (close
Spend for 1.84g/cm3), concentrated hydrochloric acid mass fraction is 37.5% (density 1.116g/cm3), hydrogen peroxide mass fraction is 30%
(density 1.11g/cm3)。
According to above-mentioned formula, modified polyamine graphite alkenes sorbing material is obtained with reference to its preparation method, step is as follows：
1) by it is above-mentioned by ratio of weight and the number of copies based on weigh graphite powder, inorganic acid, oxidizing species, Biopolyamines and 1- second
Base-(3- dimethylaminopropyls) carbodiimide, it is standby；
2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water until stirring, supersound process 12~
36h, then 45~60 DEG C are warming up to, 3~6h is reacted under constant temperature, reaction suspension is filtered with miillpore filter, washed to filter
Liquid is changed into neutral, the graphite powder purified；
3) oxidizing species are added in the graphite powder obtained to step 2) purifying, adds water until stirring, be warming up to
50~120 DEG C, 8~24h of reaction is stirred at reflux under constant temperature, is filtered with miillpore filter, obtains Carboxylation graphene crude product；
4) step 3) is obtained into Carboxylation graphene crude product to wash to neutrality, then washed 3~5 times with absolute ethyl alcohol, put
36~48h of vacuum drying under the conditions of 40~60 DEG C, the Carboxylation graphene oxide purified；
5) step 4) is obtained adding Biopolyamines in Carboxylation graphene oxide, is ultrasonically treated 1~3h, adds 1-
Ethyl-(3- dimethylaminopropyls) carbodiimide (EDC), 24~48h of stirring reaction at a temperature of 25~50 DEG C, by reaction solution
Filtered with miillpore filter, obtain Biopolyamines modified graphene crude product；
6) Biopolyamines modified graphene crude product is washed to neutrality, then washed 3~5 times with absolute ethyl alcohol, it is placed in 40~
36~48h is dried in vacuo under the conditions of 60 DEG C, obtains Biopolyamines modified graphite alkenes sorbing material.
The response parameter for optimizing each embodiment according to above-mentioned steps is as shown in table 2：
The response parameter list of the embodiment of table 2.
Modified polyamine graphite alkenes sorbing material is added into performance comparison test in cigarette
1st, the contrast experiment of several embodiment modified polyamine graphite alkenes sorbing materials
Several modified polyamine graphite alkenes sorbing materials that above-described embodiment 2,3,7 is obtained, rolled up respectively with 0~2mg/ branch
The addition of cigarette, add in cigarette filter rod, carry out suction fuel test, according to standard and the general flue gas inspection method of tobacco business,
Required to collect flue gas sample according to different detection projects, then carry out the analysis detection of flue gas correlation harmful components.Phenol content
Detection is carried out according to tobacco business standard YC/T 255-2008；Nicotine and moisture are examined using chromatography of gases-MS
Survey；Tar content detection is carried out by standard GB/T/T 19609-2004；Carbon monoxide content in smoking machine aspiration procedure from
Dynamic detection.The specific data result of cigarette mainstream flue gas composition coherent detection is shown in Table 3.Biopolyamines modified graphene is to cigarette main flow
The impact effect evaluation of phenol content is as shown in Figure 1 in flue gas.
The cigarette mainstream flue gas fractions of table 3. detect data
2nd, the contrast test for the spermidine modified graphite alkenes sorbing material Different adding amount that embodiment 7 obtains
The spermidine modified graphite alkenes sorbing material that above-described embodiment 7 is obtained, with the addition of 0.5~4mg/ branch cigarette
Amount, add in cigarette filter rod, suction fuel test is carried out, according to standard and the general flue gas inspection method of tobacco business, according to difference
Detection project requires collection flue gas sample, then carries out the analysis detection of flue gas correlation harmful components.Phenol content detection according to
Tobacco business standard YC/T 255-2008 are carried out；Nicotine and moisture are detected using chromatography of gases-MS；Tar
Content detection is carried out by standard GB/T/T 19609-2004；Carbon monoxide content automatic detection in smoking machine aspiration procedure.
The specific data result of cigarette mainstream flue gas composition coherent detection is shown in Table 4.Spermidine modified graphene is to benzene in cigarette mainstream flue gas
The impact effect evaluation of phenol content is as shown in Figure 2.
The cigarette mainstream flue gas fractions of table 4. detect data
Other unspecified parts are prior art.Although above-described embodiment is made that to the present invention and retouched in detail
State, but it is only part of the embodiment of the present invention, rather than whole embodiments, people can also according to the present embodiment without
Other embodiment is obtained under the premise of creativeness, these embodiments belong to the scope of the present invention.
Claims (4)
- A kind of 1. Biopolyamines modified graphite alkenes sorbing material, it is characterised in that：The raw materials by weight portion of the sorbing material Than counting by 1 part of graphite powder, 20~30 parts of inorganic acid, 60~80 parts of oxidizing species, 12~18 parts of Biopolyamines With 0.3~0.8 part of 1- ethyls-(3- dimethylaminopropyls) carbodiimide composition；Wherein,The Biopolyamines are any one or a few in spermidine, butanediamine and pentanediamine, wherein, the concentration of Biopolyamines For 0.3~1.0g/ml；The graphite powder is the mixture of mono-layer graphite powder and Multi-layer graphite powder, and its particle diameter is 0.5~2 μm；The inorganic acid is any one in concentrated nitric acid, the concentrated sulfuric acid and concentrated hydrochloric acid；The oxidizing species are that component A forms with B component, wherein, component A is in concentrated nitric acid, the concentrated sulfuric acid and concentrated hydrochloric acid Any one, B component is any one or two kinds in potassium permanganate and hydrogen peroxide,The quality of the potassium permanganate and the volume ratio of component A are：3~8g: 15~100mL；Or quality and the volume of hydrogen peroxide, the volume ratio of component A of the potassium permanganate are：1~3g: 5mL: 30~50mL；Above-mentioned sorbing material is prepared by following steps：1) by it is above-mentioned by ratio of weight and the number of copies based on weigh graphite powder, inorganic acid, oxidizing species, Biopolyamines and 1- ethyls-(3- Dimethylaminopropyl) carbodiimide, it is standby；2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water to stir, be ultrasonically treated 12~36h, then heat up To 45~60 DEG C, under constant temperature react 3~6h, reaction suspension is filtered with miillpore filter, wash to filtrate be changed into neutrality, The graphite powder purified；3) oxidizing species are added in the graphite powder obtained to step 2) purifying, adds water to stir, be warming up to 50~120 DEG C, 8~24h of reaction is stirred at reflux under constant temperature, is filtered with miillpore filter, obtains Carboxylation graphene crude product；4) step 3) is obtained into Carboxylation graphene crude product to wash to neutrality, then washed 3~5 times with absolute ethyl alcohol, be placed in 40 36~48h of vacuum drying under the conditions of~60 DEG C, the Carboxylation graphene oxide purified；5) step 4) is obtained adding Biopolyamines in Carboxylation graphene oxide, is ultrasonically treated 1~3h, adds 1- second Base-(3- dimethylaminopropyls) carbodiimide, 24~48h of stirring reaction at a temperature of 25~50 DEG C, by reaction solution micropore Filter membrane filters, and obtains Biopolyamines modified graphene crude product；6) Biopolyamines modified graphene crude product is washed to neutrality, then washed 3~5 times with absolute ethyl alcohol, be placed in 40~60 DEG C Under the conditions of be dried in vacuo 36~48h, obtain Biopolyamines modified graphite alkenes sorbing material.
- 2. modified polyamine graphite alkenes sorbing material according to claim 1, it is characterised in that：The original of the sorbing material Material count by ratio of weight and the number of copies by 1 part of graphite powder, 25 parts of concentrated nitric acid, 5 parts of potassium permanganate, 72.8 parts of concentrated nitric acids, 15 parts Spermidine and 0.5 part of 1- ethyls-(3- dimethylaminopropyls) carbodiimide composition.
- A kind of 3. preparation method of modified polyamine graphite alkenes sorbing material described in claim 1, it is characterised in that：Including following Step：1) by it is above-mentioned by ratio of weight and the number of copies based on weigh graphite powder, inorganic acid, oxidizing species, Biopolyamines and 1- ethyls-(3- Dimethylaminopropyl) carbodiimide, it is standby；2) graphite powder is placed in reaction vessel, and adds inorganic acid, add water to stir, be ultrasonically treated 12~36h, then heat up To 45~60 DEG C, under constant temperature react 3~6h, reaction suspension is filtered with miillpore filter, wash to filtrate be changed into neutrality, The graphite powder purified；3) oxidizing species are added in the graphite powder obtained to step 2) purifying, adds water to stir, be warming up to 50~120 DEG C, 8~24h of reaction is stirred at reflux under constant temperature, is filtered with miillpore filter, obtains Carboxylation graphene crude product；4) step 3) is obtained into Carboxylation graphene crude product to wash to neutrality, then washed 3~5 times with absolute ethyl alcohol, be placed in 40 36~48h of vacuum drying under the conditions of~60 DEG C, the Carboxylation graphene oxide purified；5) step 4) is obtained adding Biopolyamines in Carboxylation graphene oxide, is ultrasonically treated 1~3h, adds 1- second Base-(3- dimethylaminopropyls) carbodiimide, 24~48h of stirring reaction at a temperature of 25~50 DEG C, by reaction solution micropore Filter membrane filters, and obtains Biopolyamines modified graphene crude product；6) Biopolyamines modified graphene crude product is washed to neutrality, then washed 3~5 times with absolute ethyl alcohol, be placed in 40~60 DEG C Under the conditions of be dried in vacuo 36~48h, obtain Biopolyamines modified graphite alkenes sorbing material.
- 4. the Biopolyamines modified graphite alkenes sorbing material described in a kind of claim 1 is preparing the combination for absorbing phenol Application in thing, it is characterised in that：Comprise the following steps：1) appropriate Biopolyamines modified graphite alkenes sorbing material is weighed, adding ice-bath ultrasonic 30min in redistilled water makes it It is dispersed, the Biopolyamines modified graphene dispersion liquid that concentration is 0.5~2mg/mL is made, it is standby；2) acetate filter cigarette of the quality at 0.75~0.85 gram every is chosen, with the addition of 0.5~4mg/ branch cigarette Amount, Biopolyamines modified graphene dispersion liquid is added into cigarette filter rod, 50min is dried at 80 DEG C, is placed in constant temperature and humidity After being balanced 48 hours in case, the cigarette sample with composite adsorbing material filter tip is obtained.
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