CN101992063B - Method for preparing carbon nano hollow grid capable of adsorbing harmful ingredients in tobacco - Google Patents
Method for preparing carbon nano hollow grid capable of adsorbing harmful ingredients in tobacco Download PDFInfo
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- CN101992063B CN101992063B CN2010102973657A CN201010297365A CN101992063B CN 101992063 B CN101992063 B CN 101992063B CN 2010102973657 A CN2010102973657 A CN 2010102973657A CN 201010297365 A CN201010297365 A CN 201010297365A CN 101992063 B CN101992063 B CN 101992063B
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Abstract
The invention relates to a method for preparing a carbon nano hollow grid, which comprises the following steps of: mixing ferrous oxalate and alcohol evenly, loading in a high-pressure autoclave, sealing, and reacting at 530-560 DEG C; after the reaction, cooling to room temperature; washing products respectively by using alcohol, acid and water till pH is neutral; and finally filtering and drying. Raw materials used in the method can be obtained easily, and the prepared carbon nano hollow grid has the particle size of 50-500nm, the specific surface area of 5-50m<2>/g, good adsorbability to ammonium and phenolic compounds and total particle matters in combustion smoke of tobacco and excellent heat stability and can exist stably in air at below 500 DEG C.
Description
Technical field
The invention belongs to the carbon nanomaterial preparing technical field, particularly the preparation method of carbon nano-hollow grid belongs to new material technology field.
Background technology
Harmfulness of smoking health is the well-known fact, and this mainly is owing to can discharge thousands of kinds of harmful chemical substances during result of combustion of tobacco.The harmful substance that discharges when how more effectively to reduce result of combustion of tobacco is absorbed by the body, and is that Jiao's very important link in the research field of removing the evil falls in cigarette.In the present bibliographical information, in the filter tip of cigarette, insert the material that zeolite or active carbon etc. have certain absorption property, can effectively reduce the transmitance of harmful components in the tobacco, to reduce the absorption of human body harmful chemical; Referring to document Micropor.Mesopor.Mater., 60,125 and carbon, 47,1005.
Carbon nanomaterial has bigger specific area and excellent absorption property usually; Based on these advantages; Have in the filter tip that is reported in cigarette and insert CNT, discover that the CNT of inserting is superior to active carbon and zeolite to the absorption property of nicotine and tar, referring to document Appl.Surf.Sci.; 252,2933.
Employing current discharge methods such as Saito Y. have been synthesized carbon nano-hollow grid first, referring to document Nature, and 1998,392,237.Zhang etc. utilize gold nano grain to do template in special electron microscope, and the heating carbon source has obtained uniform carbon nano-hollow grid, referring to document Carbon, 2010,48,424.Wang etc. under the protection of inert gas, under 600～900 ℃ of heating conditions, pyrolytic [Fe (CO)
5] and the mixture of ethanol, made the carbon nano-hollow grid that is of a size of 30～50nm, referring to document Chem.Mater., 2007,19,453.But carry out in the temperature that above-mentioned preparation process often need be higher or the protection of inert gas, and the output of product is lower, preparation is difficulty relatively, and the large-scale preparation of carbon nano-hollow grid also is unrealized.
Summary of the invention
In order to remedy the deficiency of prior art; The present invention provides a kind of economical and convenient, is easy to the preparation method of the carbon nano-hollow grid of suitability for industrialized production, and gained carbon nano-hollow grid has the good adsorption performance to the ammonia in the flue gas, phenolic compound and TPM.
Technical scheme of the present invention is following:
A kind of preparation method of carbon nano-hollow grid, step is following:
(1) with ferrous oxalate and alcohol by mass volume ratio 0.5～3 gram: 10～18 milliliters are mixed, and seal in the autoclave of packing into after mixing, and intensification was in 530～560 ℃ of thermotonuses 5～16 hours.
(2) after reaction is accomplished, make autoclave naturally cool to room temperature, collect product.Products therefrom respectively through alcohol wash, pickling, wash to pH neutral again; Conventional suction filtration, drying get carbon nano-hollow grid powdery product.
Alcohol described in the above-mentioned steps (1) is selected from: ethanol, ethylene glycol, propyl alcohol, 1,2-propane diols, isopropyl alcohol, glycerine, n-butanol, cyclohexanol, Macrogol 200, PEG400, Macrogol 600 or polyethylene glycol 800.Wherein with ethanol for most preferably.
Preferably, the heating rate described in the above-mentioned steps (1) is 10 ℃/min, is warmed up to 550 ℃ and insulation reaction 8～13 hours by room temperature.
Preferably, to wash with alcohol be the industrial alcohol with percentage by weight＞90% to the alcohol described in the above-mentioned steps (2).
Preferably, the spent pickling acid described in the above-mentioned steps (2) is the hydrochloric acid of 1mol/L.
The carbon nano-hollow grid particle diameter of gained of the present invention mainly is distributed in 50～500nm scope, and specific area mainly is distributed in 5～50m
2/ g scope has adsorptivity to the ammonia in the result of combustion of tobacco flue gas, phenolic compound and TPM.Gained carbon nano-hollow grid has good heat endurance, but in air equal stable existence below 500 ℃, can be used as the sorbing material of the harmful components that result of combustion of tobacco discharges.
Gained carbon nano-hollow grid powder is placed in the filter tip of cigarette, can effectively adsorb the harmful components that result of combustion of tobacco discharges, the transmitance of the harmful components such as ammonia, phenols and TPM in the tobacco is significantly reduced.
The reducing cigarette tar and reducing experiment of removing the evil
1. cigarette props up dress appearance and preliminary treatment
Accurately taking by weighing 5 milligrams of embodiment, 1 prepared carbon nano-hollow grid dusty material with electronic balance places between cigarette tobacco leaf and the filter tip.At least adorn 8 cigarettes of appearance, be respectively applied for the detection of phenols and ammonia.It is 20 ℃ that the cigarette that installs sample is placed temperature, and humidity is to leave standstill at least 24 hours in the climatic chamber of 60%RH, before carrying out the smoking experiment; Need handle cigarette Zhi Jinhang line; When smoking to line place, test stops automatically, and line place is 33 millimeters with the distance on stub top.
2, smoking experiment
The instrument that the smoking experiment is adopted is the Britain SM450 of a cerulean company automatic smoking machine, and whole test process experimentizes by standard GB/T19609.The major parameter that is provided with has: 35 ± 0.3 milliliters of suction capacity, suction 55 seconds at interval, 2 seconds smoking time, smoking number are 4 cigarettes or the like.
At first, in trap, add cambridge filter, and weigh.Trap is contained on the automatic smoking machine, and test is also regulated the suction capacity.Import sample number into spectrum and smoking machine major parameter then, just can carry out the smoking experiment.Smoking machine needs manual kinking and lights a cigarette, and treats that cigarette props up to remove stub after sucking, and changes a cigarette and continues to test and all test completion up to 4 cigarettes.Take off trap and weigh, weight difference promptly is the quality of the TPM of every cigarette divided by smoking cigarette number (this test is 4) before and after the trap.Cambridge filter in the trap is put into conical flask, wait for next step processing.
3, phenols detects
The detection of phenols mainly is to utilize high performance liquid chromatography (HPLC) to carry out the analysis of qualitative and quantitative.
1) at first will dispose a series of related solution, its concrete grammar is following:
The configuration of
extract
Volume fraction is 1% acetic acid aqueous solution.
The configuration of
standard reserving solution
Take by weighing catechol, the hydroquinones of about 100mg respectively, phenol, orthoresol, metacresol, the resorcinol of about 20mg is to the beaker of 50mL.After the extract of the about 30mL of adding dissolves fully, be transferred in the brown volumetric flask of 100mL, subsequent use with the extract constant volume.
The configuration of
primary standard liquid
Accurately pipette the 10mL standard reserving solution in the brown volumetric flask of 100mL, subsequent use with the extract constant volume.
The configuration of
secondary standard liquid
Accurately pipette in the brown volumetric flask of 10mL primary standard liquid and 100mL, subsequent use with the extract constant volume.
Pipette 1mL, 2mL, 5mL secondary standard liquid respectively, 1mL, 2mL primary standard liquid are settled to scale with extract to the brown volumetric flask of 50mL, wait pending liquid chromatogram experiment.
2) phenols in the cigarette TPM is extracted.Concrete grammar is following:
Cambridge filter after the smoking experiment is placed the 100mL conical flask, accurately add the 50mL extract, under the room temperature ultrasonic 20 minutes; Leave standstill minute; Use the 2mL disposable syringe, get about 2mL extract, filter with 0.45 μ m mocromembrane filter; Solution after the filtration places chromatogram bottle, waits pending liquid chromatogram experiment.
3) parameter of high performance liquid chromatograph is provided with as follows:
Mobile phase A: 1% acetic acid aqueous solution; Mobile phase B: acetate: acetonitrile: water (volume ratio 1/30/69); Column temperature: 30 ℃; Post flow: 1mL/min; Sampling volume: 10 μ L; The flowing phase gradient is as shown in table 1:
Table 1: flowing phase gradient table
4) the fluorescence detector condition is as shown in table 2:
Table 2: fluorescence detector condition
After instrument set, sample is positioned on the auto injection platform of liquid chromatograph and begins test, each sample analysis time is about 45 minutes.
5) the various phenols content in the calculating cigarette mainstream flue gas.
The phenols computing formula is as follows:
m＝(A×L)/n
In the formula:
The content of phenols in m---every cigarette mainstream flue gas, the μ g/cig of unit;
A---the concentration of phenols in the extraction sample, the μ g/mL of unit;
L---extract volume, Unit;
N---test the smoking cigarette number, the cig of unit at every turn.
4, the detection of ammonia
The detecting instrument of ammonia mainly is an ion chromatograph, analyzes with cation-exchange chromatography.The ion chromatograph capital equipment comprises to be worn peace ED-50 electric conductivity detector, wear peace CSRS-II TVS, wears peace IonpacCS12A cation exchange analytical column and wears peace IonpacCS12A cation exchange pre-column.When carrying out the smoking experiment, the absorption bottle that must will fill the 0.005M HCl solution of 20mL is connected between trap and the suction syringe.The smoking cigarette number is 4.
1) at first will dispose a series of related solution, its concrete grammar is following:
0.005M the configuration of HCl absorption liquid: accurately take by weighing the 0.507g volume fraction and be 36% concentrated hydrochloric acid in the 900mL conductivity water, be settled to 1L.
The configuration of flowing phase 0.1M Loprazolam (MSA): accurately take by weighing 9.610gMSA in the 900mL conductivity water, constant volume is to 1L.
The configuration of standard liquid: accurately take by weighing 0.2987g NH
4Cl is in the 1L volumetric flask, with 0.005M HCl absorption liquid dissolving constant volume.Press 5 standard liquids of data configuration in the table 3.
Table 3: standard liquid configuration condition table
2) ammonia in the cigarette TPM is extracted, concrete grammar is following:
After the smoking experiment is accomplished, the cambridge filter in the trap is put in the 50mL conical flask, adds 20mL 0.005M HCl absorption liquid, oscillation extraction 30min.From conical flask and absorption bottle, respectively pipette 5mL solution in the 25mL volumetric flask, and be settled to scale with 0.005M HCl absorption liquid.Use the 2mL disposable syringe, get about 2mL solution liquid, filter with 0.45 μ m mocromembrane filter, the solution after the filtration places chromatogram bottle, waits pending chromatography of ions experiment.
3) the chromatography of ions instrument parameter is provided with as follows:
Dionex ED-50 condition, TVS electric current: 59mA; Scope: 10 μ S; Output; Offset.
Column temperature: room temperature.
Flowing phase: mobile phase A: water; Mobile phase B: 0.1M MSA, gradient condition is as shown in table 4:
Table 4: flowing phase gradient condition table
With 5 standard liquid sample introduction experiments, with NH
4 +Peak area and NH
4 +Concentration drawing curve.
4) ammonia content in the calculating cigarette mainstream flue gas.
The computing formula of ammonia is following:
NH
4 +Content (μ g/cig) * 25mL * 4/4cig that (μ g/cig)=working curve calculates
NH
3(μg/cig)＝NH
4 +(μg/cig)×17/18
5. test result
According to the smoking test that above step is carried out, find that with blank assay (not adding carbon nano-hollow grid in the cigarette filter) contrast the transmitance of ammonia has reduced by 55.89%; TPM has reduced by 56.84%; Hydroquinones has reduced by 57.31%; Resorcinol has reduced by 62.25%; Catechol has reduced by 65.58%; Phenol has reduced by 75.95%; Metacresol has reduced by 54.34%; Orthoresol has reduced by 59.43%.
Technical characterstic of the present invention is:
1, be feedstock production carbon nano-hollow grid with ferrous oxalate and alcohol, raw material is easy to get, low price, and productive rate is high, and technological process is simple, is easy to realize suitability for industrialized production.
2, the inventive method step (2) product is the composite construction of carbon coated ferriferrous oxide before the salt acid elution, after tri-iron tetroxide is removed in the persalt washing, obtains carbon nano-hollow grid, and purity is high.
3, the present invention can obtain the different carbon nano-hollow grid of specific area through the preferred compositions of prescription, and the harmful components in the tobacco are had adsorption effect in various degree, selects according to the actual needs in commercial production and market.
4, the prepared carbon nano-hollow grid of the present invention adds to and carries out the smoking test in the filter tip of cigarette; The result can effectively be adsorbed multiple harmful components such as ammonia, phenols and the TPM in the tobacco, and the adsorption effect of harmful components is far superior to business-like active carbon.This carbon nano-hollow grid is used for the tobacco filter advantages of good adsorption effect, and consumption is few, has further improved the performance of cigarette filter, has very big using value.
Description of drawings
Fig. 1 is the XRD diffraction pattern (product is without peracid treatment) of the product carbon nano-hollow grid of embodiment 1 preparation.
Fig. 2 is the XRD figure (product is through peracid treatment) of the product carbon nano-hollow grid of embodiment 1 preparation.
Fig. 3 is the TEM photo of the product carbon nano-hollow grid of embodiment 1 preparation.
Fig. 4 is the aerial thermal multigraph of product carbon nano-hollow grid of embodiment 1 preparation.
Fig. 5 is the specific area and the graph of pore diameter distribution of the product carbon nano-hollow grid of embodiment 1 preparation.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention., these instances are not used in restriction scope of the present invention but only being used to the present invention is described.After having read the content that the present invention set forth, those skilled in the art can do various changes or modification to the present invention, and these equivalent form of values fall within the application's claims institute restricted portion equally.
Washing is percentage by weight＞90% industrial alcohol with alcohol among the embodiment.Temperature control high heat furnace is that the friendly electric furnace of last Korean pine company produces model: SG2-3-10.
Taking by weighing 2.0g ferrous oxalate and the 15mL absolute ethyl alcohol volume of packing into is in the 20ml stainless steel autoclave, and sealing is placed on reacts carbonization in the temperature control high heat furnace, and heating rate is 10 ℃/min, is warmed up to 550 ℃ by room temperature, and reaction is 12 hours under 550 ℃ of conditions.After reaction stops, making autoclave naturally cool to room temperature, collect product then.Products therefrom is through industrial alcohol washing, 1mol/L salt acid elution, washes to pH neutrally again, and suction filtration is collected product and in drying box under 60 ℃ of conditions dry 6 hours, obtains the black powder product, i.e. carbon nano-hollow grid.
Gained carbon nano-hollow grid particle diameter is distributed in 100～300nm scope, and specific area is 33.84m
2/ g, heat endurance experiment confirm, product obviously not weightless generation the before 500 ℃ in air explain that product can stable existence before 500 ℃, and the while can find out that this product can tolerate and be no more than 500 ℃ hot environment.
Take by weighing 1.5g ferrous oxalate and 12mL polyethylene glycol-400, the volume of packing into is in the 20ml stainless steel autoclave, and sealing is placed on reacts carbonization in the temperature control high heat furnace, and heating rate is 10 ℃/min, is warmed up to 550 ℃ of insulation reaction 8 hours.After reaction stops, making autoclave naturally cool to room temperature, collect product then.Products therefrom is through industrial alcohol washing, 1mol/L salt acid elution, washes to pH neutrally again, and suction filtration is collected product and in drying box under 60 ℃ of conditions dry 6 hours, obtains the black powder product, and can obtain specific area is 12.38m
2/ g carbon nano-hollow grid.
Take by weighing 2.5g ferrous oxalate and 16mL polyethylene glycol-600, the volume of packing into is in the 20ml stainless steel autoclave, and sealing is placed on reacts carbonization in the temperature control high heat furnace, and heating rate is 10 ℃/min, is warmed up to 540 ℃ of insulation reaction 10 hours.After reaction stops, making autoclave naturally cool to room temperature, collect product then.Products therefrom is through industrial alcohol washing, 1mol/L salt acid elution, washes to pH neutrally again, and suction filtration is collected product and in drying box under 60 ℃ of conditions dry 6 hours, obtains the black powder product, and can obtain specific area is 11.62m
2/ g carbon nano-hollow grid.
Claims (5)
1. the preparation method of a carbon nano-hollow grid, step is following:
(1) ferrous oxalate is restrained by mass volume ratio 0.5～3 with alcohol: 10～18 milliliters are mixed, and seal in the autoclave of packing into after mixing, and heating rate is 10 ℃/min, and insulation reaction is 8～13 hours when being warmed up to 550 ℃;
(2) after reaction is accomplished, make autoclave naturally cool to room temperature, collect product; Products therefrom respectively through alcohol wash, pickling, wash to pH neutral again; Conventional suction filtration, drying get carbon nano-hollow grid powdery product.
2. the preparation method of carbon nano-hollow grid as claimed in claim 1; It is characterized in that the alcohol described in the step (1) is selected from: ethanol, ethylene glycol, propyl alcohol, 1; 2-propane diols, isopropyl alcohol, glycerine, n-butanol, cyclohexanol, Macrogol 200; PEG400, Macrogol 600 or polyethylene glycol 800.
3. the preparation method of carbon nano-hollow grid as claimed in claim 1 is characterized in that it is the industrial alcohol with percentage by weight＞90% that the alcohol described in the step (2) is washed with alcohol.
4. the preparation method of carbon nano-hollow grid as claimed in claim 1 is characterized in that the spent pickling acid described in the step (2) is the hydrochloric acid of 1mol/L.
5. the preparation method of carbon nano-hollow grid as claimed in claim 1 is characterized in that gained carbon nano-hollow grid particle diameter 50～500nm, specific area 5～50m
2/ g has adsorptivity to the ammonia in the result of combustion of tobacco flue gas, phenolic compound and TPM.
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| CN102138703B (en) * | 2011-01-07 | 2013-03-27 | 山东中烟工业有限责任公司 | Top modified transitional metal carbon hollow pipe material, and preparation method and application thereof |
| CN104305591B (en) * | 2014-09-23 | 2016-07-20 | 西安交通大学医学院第一附属医院 | A kind of have the haze mask filtered with adsorption dual function based on nanostructured |
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| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN1751989A (en) * | 2004-09-20 | 2006-03-29 | 三星Sdi株式会社 | Method of preparing carbon nanocages |
| CN101049559A (en) * | 2007-05-17 | 2007-10-10 | 上海交通大学 | Method for preparing electrode catalyst of Nano particles of metal platinum under load of Nano carbon cage with thin wall |
| CN101758243A (en) * | 2010-01-28 | 2010-06-30 | 中国科学院长春应用化学研究所 | Preparation method of hollow gold nanometer cage |
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| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN1751989A (en) * | 2004-09-20 | 2006-03-29 | 三星Sdi株式会社 | Method of preparing carbon nanocages |
| CN101049559A (en) * | 2007-05-17 | 2007-10-10 | 上海交通大学 | Method for preparing electrode catalyst of Nano particles of metal platinum under load of Nano carbon cage with thin wall |
| CN101758243A (en) * | 2010-01-28 | 2010-06-30 | 中国科学院长春应用化学研究所 | Preparation method of hollow gold nanometer cage |
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